NICE 2018 Book of Abstracts PDF

th
4 International Conference on
Bioinspired and Biobased
Chemistry and Materials
#NICEConference2018
Nice, France ©2018 H.S. Salapare III
www.unice.fr/nice-conference
Welcome to N.I.C.E. Conference 2018
Dear colleagues,
Today, we are facing the consequences of the over-exploitation of

our natural resources. Pollution, reduction of the ozone layer,
decline in biodiversity and the reduction of natural habitats are
becoming even more worrying where climate change is
concerned. We urgently need a turnaround for a more sustainable
development.
Nature has developed processes and robust materials, which possess superior
physical, chemical and electromagnetic properties that can withstand the most
extreme conditions. We need to take inspiration from nature to obtain a more
sustainable development. By combining our knowledge of processes and the
knowledge of natural systems, we can create “biomimetic” solutions to our problems.
Velcro®, inspired by the burdock burrs, is amongst some of the bioinspired invention,
as well as artificial spider silk made from Kevlar and carbon fiber, which mimics the
hardness and elasticity of spider silk. Other applications are the development of a
drug-reducing pattern called rib-lets inspired from the shark’s skin and the spider web
glass that reflects UV light and can prevent birds from accidental suicide into glassy
buildings.
Nice, France, the capital city of the French Riviera, once again welcomes the 4th
edition of the International Conference on Bioinspired and Biobased Chemistry and
Materials (“Nature Inspires Creativity Engineers” or N.I.C.E. 2018 Conference) from
14 to 17th of October 2018. As in the previous editions, hundreds of scientists and
engineers are going to share the latest developments in the growing field of
bioinspired and biobased chemistry and materials. In this edition, aside from usual
main themes (NanoTech, BioTech, SmartTech), there will be six special thematic
sessions, namely, (1) Bioinspired Chemistry and Materials for Sustainable Energy,
(2) Biomass Valorization : Catalysis, New Materials, and Applications, (3) Bioinspired
2D and 3D Molecular and Hybrid Architectures, (4) Plasma and Laser Processing of
Bioinspired and Biobased Materials, (5) 3D Printing of Bioinspired Materials, and (6)
Bio-inspired Adhesion. It is a unique opportunity to understand the new challenges,
to initiate new collaborations and to envisage sustainable solutions for the future.
Welcome to N.I.C.E. Conference 2018!

Prof. Frédéric Guittard
Conference Chair
i
TABLE OF CONTENTS
International Scientific Committee p. iii
Organizing Scientific Committee p. v
Organizing Committee p. vi
Sponsors p. vii
Partners and Endorsers p. ix
Supporting Journals p. x
Main Conference Themes p. xi
Special Thematic Sessions p. xii
Plenary speakers p. xv
Keynote speakers p. xvii
Program summary p. 1
Conference program p. 2
Workshops program p. 44
Poster session p. 45
Plenary Abstracts p. 52
Keynote Abstracts p. 57
Oral Abstracts p. 152
Poster Abstracts p. 286
ii
INTERNATIONAL SCIENTIFIC COMMITTEE
Michele ARESTA (University of Bari)
Matthias BALLAUFF (Humboldt University Berlin)
Georges BELFORT (Rensselaer Polytechnic Institute)
Gabriele CENTI (University of Messina, Chair - Editorial Board - ChemSusChem)
Xiaodong CHEN (Nanyang Technological University, Advisory board of Advanced

Materials)
Tao DENG (Shangai Jiao Tong University)
John DUTCHER (University of Guelph)
Julian EASTOE (University of Bristol, Co-editor Journal of Colloid and Interface

Science)
Catarina ESTEVES (Technische Universiteit Eindhoven)
Michele FERRARI (Consiglio Nazionale delle Ricerche)
Justin GOODING (University of New South Wales)
Nicholas KOTOV (University of Michigan)
Chao-Jun LI (McGill University, Associate editor of Green Chemistry)
Feng-Huei LIN (National Taiwan University)
Federica LO VERSO (University of Southern Denmark)
Cefe LOPEZ (Instituto de Ciencia de Materiales de Madrid, Advisory board –

Advanced Materials)
Avi MARMUR (Technion Israel Institute of Technology)
Elena MARTÍNEZ (Institute of Bioengineering of Catalonia)
Christopher K. OBER (Cornell University)
Roshan PAUL (University of Beira Interior)
Frank QUINA (University of São Paulo)
Anupama SHARMA (Panjab University)
iii
Yury SHCHIPUNOV (Russian Academy of Sciences)
Alina SIONKOWSKA (Nicolaus Copernicus University)
Richard SPONTAK (North Carolina State University)
Nicolas VOELCKER (Monash University)
Silvia VIGNOLINI (Cambridge University)
Valentine VULLEV (University of California, Riverside)
Kristina WANIECK (Deggendorf Institute of Technology)
Françoise WINNIK (University of Montreal, Editor-in-chief - Langmuir)
Bai YANG (Jilin University)
Peidong YANG (University of California, Berkeley, Associate Editor - JACS)
iv
ORGANIZING SCIENTIFIC COMMITTEE
NanoTech
Dr. Caroline SZCZEPANSKI – Northwestern University – USA
Dr. Thierry DARMANIN – Université Nice-Sophia Antipolis – France
BioTech
SmartTech
Dr. Caroline SZCZEPANSKI – Northwestern University – USA
Bioinspired Chemistry and Materials for Sustainable Energy

Prof. Valentine VULLEV – University of California, Riverside, USA
Biomass Valorization: Catalysis, New Materials and Applications (HUGS)

Dr. Nathanaēl GUIGO – Université Nice-Sophia Antipolis – France
Ed DE JONG – Avantium – Netherlands
Bioinspired 2D and 3D Molecular and Hybrid Architectures

Prof. Damien PRIM – University of Versailles – France
Dr. Anne GAUCHER – University of Versailles – France
Plasma and Laser Processing of Bioinspired and Biobased Materials (PLASMAT 2018)
Dr. Hernando S. SALAPARE III – Université Nice-Sophia Antipolis – France and University of the
Philippines Open University – Philippines
3D Printing of Bioinspired Materials

Dr. Arnaud ZENERINO – Université Nice-Sophia Antipolis – France – France
Guillaume CABRIÉ – LEMANTEK CEO & Co-founder Pangloss Labs Ferney – France
Dr. Frédéric PRATE – CHU of Nice-Director of Health, Aging and Wellbeing Center – France
Laurianne ALAOUCHICHE – IMREDD- Université Nice-Sophia Antipolis – France – France
Bio-inspired Adhesion
Dr. Kalina RASKIN – Ceebios – France
Laura MAGRO – Ceebios – France
v
ORGANIZING COMMITTEE
Frédéric GUITTARD
Conference Chair
Univ. Nice-Sophia Antipolis, Nice – France
University of California, Riverside – U.S.A.
Hernando S. SALAPARE III

Conference Secretary
University of the Philippines Open University, Philippines
Sonia AMIGONI
Conference Treasurer
Arnaud ZENERINO
Webmaster
Thierry DARMANIN
Odile GIORGI
Caroline SZCZEPANSKI
Northwestern University, USA
Damien PRIM
University of Versailles, France
Anne GAUCHER
University of Versailles, France
vi
SPONSORS
GOLD SPONSOR
BRONZE SPONSOR
EXHIBITORS
vii
viii
PARTNERS AND ENDORSERS
ix
SUPPORTING JOURNALS
CONFERENCE PROCEEDINGS
MEDIA PARTNERS
x
MAIN CONFERENCE THEMES
BIOTECH
Green Chemistry, Tissue, Biofouling, Membrane, Biobased Chemicals and Materials,
Bioadhesion, Water Technologies, Building Blocks, (Anti)bioadhesion,
Bioengineering, Biomanufacturing
NANOTECH
Nanostructured Materials, Polymer Nanotechnologies, (Anti)Adhesive Materials,
Mineralization, Nanocomposites, Micro and Nanofluidics, Nanomanufacturing,
Nanochemistry, Nanostructured Devices, Nanoparticles, Fluorinated Materials
SMARTTECH
Functional Polymers, Self-Healing, Biosensors, Renewable Energies, Stimuli
Responsive Materials (Photochromic, pH-sensitive, Thermochromic), Interactive &
Autonomous Materials, Sensors, Batteries, Solar Cells, Optical Devices, Polymer
Brushes
xi
SPECIAL CONFERENCE THEMES
Bioinspired Chemistry and Materials for Sustainable
Energy
This symposium will bring chemists and engineers with diverse expertise who have a
common interest in employing ideas from biology to address pending challenges of solar and
other forms of sustainable energy. The symposium will focus on key challenges pertinent to
the impacts from energy production and consumption on the environment, the addressing of
which requires not only innovative technological developments, but also unprecedented
fundamental paradigms. Therefore, this symposium will provide a platform for interfacing
basic science with applied engineering as a driving force for innovation, which will be in
concord with the theme of the conference.
SYMPOSIUM CHAIR
Prof. Val Vullev ([email protected])
University of California, Riverside – USA
Biomass Valorization: Catalysis, New Materials, and

Applications (HUGS)
Pollution, climate change, depletion of traditional feedstocks, and intensification of the world-
wide population density, thus increasingly stringent energy and food demands, call for the
development of truly sustainable industrial processes and practices.
Biomass valorization is taking a hold of the scientific community as the renewable alternative
to fossil resources for the sustainable production of fine and bulk chemicals. In particular, the
chemical processing of biomass can open a wide range of possibilities for new platform
chemicals and materials, including materials, fuels, and pharmaceuticals.
This is where the HUGS consortium finds inspiration: easily harvested plants and their by-
products can find a suitable place in the chemical industry, largely increasing the future’s
sustainability. In collaboration with the N.I.C.E. conference 2018, the HUGS consortium will
xii
host five sessions on different strategies for a truly sustainable development. The
consortium’s efforts are focused on the safe development of new (catalytic) processes for
biomass conversion and new bio-based materials for a variety of applications including
catalysis, polymers and adsorbents.
Sustainability is a joint global effort, ranging from political to scientific development. Focusing
on the science, we hope to inspire, discuss and develop with you a greener and brighter
future.
SYMPOSIUM CHAIRS
Nathanaël Guigo, Université Nice-Sophia Antipolis, France
Ed de Jong, Avantium, Netherlands
Contact people:
Nathanaël Guigo, PhD ([email protected])
Anna Sangregorio ([email protected])
Bioinspired 2D and 3D Molecular and Hybrid Architecture
To shed light on emerging bio inspired nanostructures, emerging strategies and applications
SYMPOSIUM CHAIRS
Anne Gaucher, PhD ([email protected])
Damien Prim, PhD ([email protected])
Institut Lavoisier de Versailles. University of Versailles-St Quentin (France)
Bioinspired Adhesion
From biological adhesion (model identification and characterization) to artificial bio-inspired
adhesive systems
SYMPOSIUM CHAIR/S AND CONTACT PERSON/S

Kalina RASKIN, PhD ([email protected]), Ceebios, Senlis, France
Laura MAGRO ([email protected]), Ceebios, Senlis, France
xiii
Plasma and Laser Processing of Bioinspired and Biobased
Materials (PLASMAT 2018)
This symposium at the 4th International Conference on Bionspired and Biobased Chemistry
and Materials will draw together scientists and technologists working on the plasma
chemistry, plasma physics, and laser processing of bioinspired and biobased materials. The
symposium will highlight the advances in the field and will challenge the boundaries of
mimicking nature through the use of plasma science and technology and/or laser technology.
This symposium will also be an avenue for the participants to formulate the technological
roadmap on this very important and highly specialized field.
SYMPOSIUM CHAIR
Hernando S. SALAPARE III, PhD ([email protected])
Université Côte d’Azur, NICE Lab, IMREDD, Nice, France
3D Printing of Bioinspired Materials

This symposium will highlight the state-of-the-art researches and innovations on bioinspired
materials and related themes such as technical materials, construction materials and
practical applications, using 3D printing technologies.Research scientists, engineers (design,
mechanical, industrial, aerospace and construction), architects, innovators, and technologists
will have a great opportunity to exchange knowledge about innovative process and materials
using 3D printing in the field such as engineering and construction, automotive, aerospace,
industrial design, architecture, dental, medical industries.This event would also bring
international academic and industrial experts to discuss the key challenges and opportunities
in the field of 3D printing that would go beyond the “overhype” media attention on this
technology.
SYMPOSIUM CHAIRS
Arnaud Zenerino, PhD ([email protected]), IMREDD-University of Nice,
Nice, France
Guillaume Cabrié, LEMANTEK CEO & Co-founder Pangloss Labs Ferney, Ferney-Voltaire,
France
Frédéric Prate, CHU of Nice-Director of Health, Aging and Wellbeing Center, Cimiez,
Nice, France
Laurianne Alaouchiche, IMREDD-University of Nice, Nice, France
xiv
PLENARY SPEAKERS
XIANG ZHANG, University of California, Berkley, USA
“Soft metamaterials: Self-gauged assembly, non-equilibrium matters, and
3D super-resolution imaging”
Professor Xiang Zhang was appointed the 16th President and Vice-
Chancellor of the University of Hong Kong (HKU) on December 15, 2017.
Prior to joining HKU, he was the inaugural Ernest S. Kuh Endowed Chair
Professor at the University of California, Berkeley, and the Director of the
Nano-scale Science and Engineering Center (SINAM). He has also
served as the Director of Materials Science Division at Lawrence Berkeley
National Laboratory (LBNL).
Professor Zhang is an elected member of the US National Academy of Engineering (NAE) and of
Academia Sinica, a foreign member of the Chinese Academy of Sciences, and a Fellow of the
American Physical Society (APS), the Optical Society of America (OSA), the American Association for
the Advancement of Science (AAAS), and the International Society of Optical Engineering (SPIE).
Professor Zhang received his PhD from UC Berkeley (1996), MS from the University of Minnesota and
MS/BS from Nanjing University, China. He was an assistant professor at Pennsylvania State
University (1996-1999), and associate professor and full professor at UCLA (1999-2004) prior to
joining Berkeley's faculty in 2004.
Professor Zhang's current research focuses on materials physics, metamaterials and nano-photonics.
He has published over 340 journal papers including 70 publications in Science and Nature family
series. He has given over 330 Keynote, Plenary and Invited talks at international conferences and
institutions. He was a Co-Chair of the NSF Nano-scale Science and Engineering Annual Grantee
Conferences in 2004 and 2005, and has served as Chair of the Academic Advisory Board for the
Research Center for Applied Science (RCAS), Academia Sinica.
In 2008, Professor Zhang's research was selected by Time Magazine as one of the "Top Ten
Scientific Discoveries of the Year" and "50 Best Inventions of the Year", Discover Magazine's "Top
100 Science Stories" in 2007, and R&D Magazine's top 25 Most Innovative Products of 2006. His
research has been frequently featured in international media, including the BBC, CNN, ABC, New
York Times, and Wall Street Journal.
JOSEP SAMITIER, Barcelona Institute of Science and Technology,

SPAIN
“Mimicking Spleen Organ in vitro”
Background in Physics (M.S. Degree in Physics, University of Barcelona

and Ph.D. in Physics, University of Barcelona). Full Professor of
Electronics and Biomedical Engineering. Engineering Department.
(Electronics). Faculty of Physics. University of Barcelona (UB). Group
leader of the Nanobioengineering Group at IBEC. His main research areas
are Biosensors, Microfluidics and Organ-on-chip. Prof. Samitier also is
member of the EIT Health Supervisory Board, coordinator of the Spanish Nanomedicine Platform
(NanomedSpain), spanish delegate in the Working Party on Biotecnology (OECD) and president of the
Catalan Association of Research Centres (Associació Catalana d'Entitats de Recerca - ACER). Prof
Samitier is currently serving as the Editor-in-Chief of the open-access journal Biomimetics.
xv
VALENTINE VULLEV, University of California Riverside, USA
“From Biomimicry to Biological Inspiration : Path to Discovery Beyond
What Nature Offers”
Prof. Val Vullev completed his undergraduate education in chemistry
and physics at Keene State College, New Hampshire. For his graduate
education, Prof. Vullev went to Boston University where he obtained his
Ph.D. degree in chemistry with emphasis on physical organic chemistry,
photochemistry and charge transfer. To expand his expertise in surface
science, Val Vullev moved to Harvard University as a postdoctoral
fellow. His postdoctoral research was in the areas of optomocrofluidics,
molecular electronics and single-molecule biophysics. In 2006, Val
Vullev moved from the Northeast part of U.S.A. to Southern California
to assume a faculty position at the University of California, Riverside (UCR), and rose through the
ranks to Full Professor in about 10 years. Presently, he is a Professor of Bioengineering, Chemistry,
Biochemistry, and Materials Science and Engineering at UCR. His research employs bioinspired
approaches to charge transfer and interfacial science. In parallel, Prof. Vullev pioneered print-and-peel
microfabrication; invented dynamic staining; and developed space-domain time-resoled spectroscopy.
Most importantly, he pioneered the concept of bioinspired molecular electrets and introduced it to
charge transfer. Electrets possess ordered electric dipoles making them the electrostatic analogues of
magnets. The molecular electrets have allowed Prof. Vullev to spearhead the research field of dipole
modulated charge transfer, leading to discoveries of new phenomena.
STEPHEN WEINER, Weizmann Institute of Science,

ISRAEL
“Minerals and Crystals in Biology: Inspirations for New
Materials”
Steve Weiner (1948) was born in Pretoria, South Africa. He
obtained a BSc degree in chemistry and geology at the
University of Cape Town, an MSc in geochemistry at the
Hebrew University of Jerusalem, and a PhD at the California
Institute of Technology in Pasadena, USA in 1977 working in
the field of mineral formation in biology. In the same year he
joined the faculty of the Weizmann Institute. Steve Weiner
carries out research in two fields: biomineralization and archaeological science. In 1989 he published
a book entitled “On Biomineralization” with the late Prof H.A. Lowenstam, and in 2010 he published
another book entitled “Microarchaeology: Beyond the Visible Archaeological Record”.
He is the recipient of the 2010 prize of the Israel Chemical Society, the 2011 Aminoff Prize for
Crystallography from the Royal Swedish Academy of Sciences and he received the 2013 Pomerance
Award for Scientific Contributions to Archaeology from the Archaeological Institute of America.
xvi
KEYNOTE SPEAKERS
Maria Abrahamsson Igor Alabugin Florent Allais

Chalmers University of
Florida State University AgroParisTech
Technology
Wendel A. Alves Katalin Barta Nuno Basílio

Universidade Federal do ABS -
University of Groningen Universidade Nova de Lisboa
UFABC
Erick L. Bastos Ilker Bayer Mikhael Bechelany

University of São Paulo Instituto Italiano di Tecnologia Institut Européen des
Membranes – University of
Montpellier
Emmanuel Belamie Sidi Bencherif Laurent Billon

Institut Charles Gerhardt de
University of Pau and Pays de
Montpellier EPHE, PSL Northeastern University
l’Adour
University
xvii
Hugues Brisset Sylvain Caillol Felix N. Castellano
University of Toulon University of Montpellier North Caroline State University
Caroline Chaix Chang-Hwan Choi Insung S. Choi

Claude Bernard Korea Advanced Institue of
Stevens Institute of Technology
University Lyon 1 Science and Technology
Thierry Darmanin Thierry DELAIR Tao Deng

Claude Bernard
University of Nice Shanghai Jiao Tong University
University Lyon 1
Marc Dubois Catarina Esteves Maria Luisa Ferrer

Eindhoven University of Instituto de Ciencia de
University of Clermon Auvergne
Technology Materiales de Madrid
Patrick Flammang Malcom Forbes Tristan Gilet
Université de Mons Bowling Green State University University of Liège
xviii
Ksenija Glusac Dorota Gryko Zhiguang Guo
University of Illinois at Chicago /
Polish Academy of Sciences Chinese Academy of Sciences
Argonne National Laboratory
Karsten Haupt Chaobin He Soon Hyung Hong

Korea Advanced Institute of
Compiègne University of
National University of Singapore Science and Technology
Technology
(KAIST)
Dominique Hourdet Atsushi Hozumi Nathaniel Hwang

National Institute of Advanced
University of Pierre and Marie
Industrial Science and Seoul National University
Curie
Technology
Masato Ikeda Pascal Jonkheijm Marleen Kamperman

Wageningen University and
Gifu University University of Twente
Research
Vadim Kessler Anne Kietzig Beatrice Labat

Centre Universitaire d’Evreux –
BioCenter SLU McGill University
University of Rouen Normandie
xix
Martine Largeron Alan Le-Goff Kesong Liu
Paris Descartes University Université Grenoble Alpes Beihang University
Federica Lo Verso Pascal Jean Lopez Xuehong Lu

Muséum nation d’Histoire Nanyang Technological
University of Southern Denmark
naturelle/ Sorbonne Univ. University
João F. Mano Guy Marlair Angel Marti
University of Aveiro INERIS Rice University
Glen McHale Isabelle Michaud-Soret Philippe Miele

Laboratory of Chemistry and
Institut Européen des
Biology of Metals (LCBM)/
Northumbria University Membranes – University of
Biosciences and Biotechnology
Montpellier
Institute of Grenoble
Amar Mohanty Gary Moore Maryline Moreno-Couranjou
Luxembourg Institute of Science

University of Guelph Arizona State University
and Technology
xx
Jean-Marie Nedelec Christoph Neinhuis Ralph Nuzzo
Institut de Chimie de Clermont-
California Institute of
Ferrand – University of Technische Universitat Dresden
Technology
Clermont Auvergne
Pola G. Oppenheimer Julia Ortony Cornelia G. Palivan

Massachusetts Institute of
University of Birmingham Universität Basel
Technology
Alyssa Panitch Carole Perry Céline Pochat-Bohatier

University of California Davis Nottingham Trent University Montpellier University
Oleg G. Poluektov Frank Quina Marc Robert

Argonne National Laboratory University of São Paulo Paris Diderot Université
Masanobu Sagisaka Thomas Scheibel Caroline Szczepanski

Hirosaki University Universität Bayreuth Northwestern University
xxi
Anupama Sharma Yury Shchipunov Richard Spontak
Panjab University Russian Academy of Sciences North Carolina State University
Nathalie Steunou Michael Therien Christophe Thomas

Institut Lavoisier de Versailles Institut de Recherche de Chimie
Duke University
University Paris, CNRS, Chimie ParisTech
Magdalena Titirici Vladimir V. Tsukruk Rein V. Ulijn

Queen Mary University of
Georgia Institute of Technology City University of New York
London
Rajender S. Varma Tuan Vo-Dinh Dean Webster

US Environmental Protection
Duke University North Dakota State University
Agency
Jonathan J. Wilker Juyoung Yoon Liqun Zhang

Beijing University of Chemical
Purdue University EWHA Womans University
Technology
xxii
Yong-Lai Zhang Yongmei Zheng Feng Zhou
Jilin University Beihang University Chinese Academy of Sciences
xxiii
October 14
PROGRAM SUMMARY
Sunday, October 14
- Registration
- Social Event : NICE City and Museum Tour
Location :
Negresco Hotel
37 Promenade des Anglais - 06000 Nice
Monday, October 15
- Welcome Remarks/Opening Ceremony

- Plenary session
- Conference session
- Poster session
Location :
Negresco Hotel
Tuesday, October 16
- Plenary session
- Workshops
- Social Event : Conference Gala Dinner
Location :
Negresco Hotel
Wednesday, October 17
- Plenary session
- Closing and Award Ceremony
Location :
Negresco Hotel
1
October 14
CONFERENCE PROGRAM
Sunday, October 14
Opening registration: 13:00 – 18:00
Social Event – Nice City and Museum Tour: 13:00-18:00
2
October 15
CONFERENCE PROGRAM
Monday, October 15
8:00 – 8:45: Welcome Remarks and Opening Ceremony (Salon Royal)
Plenary Lectures (Salon Royal):
Session Chair: Frédéric GUITTARD
8:45 – 9:30 : Xiang ZHANG – Soft metamaterials: Self-gauged assembly, non-equilibrium matters,
and 3D super-resolution imaging (PL01)
Abstract:
Metamaterials are artificial composite structures that lead to many exciting

applications beyond nature such as imaging objects below the diffraction limit, optical
clocking, sensing and communications. Traditional metamaterials are considered as
“hard” materials that structural units cannot be tailored after their formation which
limits their material responses and applications. It remains a critical and unsolved
problem to design “soft metamaterials” that can spontaneously self-adapt to changes
in the source wavelength or the environment.
We explore “soft metamaterials” with building blocks that have a strong propensity for
self-assembly/re-assembly. In this regards, the structure units can be artificially
evolving during the formation of soft metamaterials. Particularly, we explore the self-
feedback mechanism between structures and properties for self-selective assembly of
complex metamaterial nanoarchitectures with tailored symmetries. We expand
structural design using soft metamaterial approach to achieve isotropic negative index
metamaterials and Brownian optical imaging. We also explore approach for realizing
bandgap materials that reside far from equilibrium and emerge enslaved to an external
drive. Experimental results are providing supports as well as new insights into such
new type of soft metamaterials that facilitate self-responsive material applications.
9:30 – 10:15 : Josep SAMITIER – Mimicking spleen organ in vitro (PL02)
Abstract:
The spleen is a secondary lymphoid organ specialized in the filtration of senescent,

damaged, or infected red blood cells, facilitating the recognition and posterior
destruction of unhealthy Red Blood Cells by specialized macrophages.
Through a complex organizational architecture, the spleen is perfectly adapted to

selectively filter and eliminate senescent Red Blood Cells as well as blood-borne
infectious organisms. Such complex architecture includes the splenic white pulp, red
3
October 15
pulp, and the marginal zone. The filtering capacity of the spleen is inherently linked to
the complex vasculature of the organ, controlling events such as blood passage
through the reticular meshwork of the red pulp; entry into the marginal sinuses or the
marginal zone; drainage through perimarginal cavernous sinuses or capillary
branches; or entry into the white pulp.
With the aim of studying RBCs filtration in the spleen, here it is presented a
multilayered microengineered device of the human splenon-on-a-chip. With this
device, engineered to mimic the splenic closed-fast and open-slow microcirculations,
the reticular meshwork and the Interendothelial slits filtering capacity, hopefully it
would be possible to advance in the knowledge of the spleen’s function in malaria and
other haematological disorders.
Moreover, another goal is to demonstrate the practicality of the platform for both
structure-function studies. Some 3D culture models fail to reconstitute features of
living organs that are crucial for their function, such as blood–tissue interfaces. In this
regard, the proposed system takes advantage of co-flow phenomena, in order to
properly coat and culture the different sections of the device, when needed, with
splenic human cells.
To complete the system, it is introduced an autonomous closed-loop pumping

machinery, connected to the splenon-on-a-chip to simulate human blood flowing with
physiological conditions.
Coffee Break: 10:15 – 10:30
Exhibitor Set-up (Salon Royal): 12:30 - 14:30
Poster Set-up (Salon Royal): 12:30 - 14:30
Coffee Break: 16:00 - 16:15
Poster Session (Salon Royal): 16:00 - 18:00
4
October 15, BIOTECH
Monday, October 15
BIOTECH SESSION
BIOTECH 1 – Masséna Room

Session Chair: Thomas Scheibel
10:30 Thomas Scheibel
Biofabrication with bioinks made of rekombinant spider silk
BIOTECH-KN06
10:55 Emmanuel Belamie
Biosourced polysaccharide nanocrystals to template hybrid materials
BIOTECH-KN10
11:20 Alyssa Panitch
Development of a Glycocalyx Mimetic
BIOTECH-KN05
11:45 Aad Lansbergen
Renewable alkyds based on Citraconic anhydride Diels Alder adducts
BIOTECH-OR17
12:00 Giulia Scoponi
Tuning the properties of poly(lactic acid)-based biomaterials by green blending of linear
PLLA and star-shaped PDLLA
BIOTECH-OR32
12:15 Samira Benali
Processable and fully biodegradable Poly(ɛ-caprolactone)/Laccase materials for food
packaging application
BIOTECH-OR04
12:30 Guillaume Riviere
Structure-Property Relationship for Fabricating Colloidal Lignin Particles from Various
Sources for Biomedical Applications
BIOTECH-OR23
12:45 Lunch Break
(poster set-up for presenters in Salon Royal)
14:30
5
October 15, BIOTECH

Session Chair: Dean Webster
14:30
Dean Webster
Thermosets from Highly Functionalized Bio-Based Resins
BIOTECH-KN09
14:55
Acerina Trejo-Machin
Synthesis of fully bio-based polybenzoxazine resins by solvent-free method
BIOTECH-OR37
15:10 Jozef Kollár

Betaine-based materials – preparation and their tunable properties
BIOTECH-OR30
15:25 Claudio Gioia
Tunable Thermosetting Epoxies Based on Fractionated and Well Characterized Lignins
BIOTECH-OR11
15:40 Free Time
16:00
Coffee break
Salon Royal room
16:15
16:00 Poster session
Salon Royal room
6
October 15, BIOTECH

Session Chair: Nathaniel S. Hwang
18:00 Mikhael Bechelany

Engineering of bionanomaterials and biointerfaces: design, properties and applications
BIOTECH-KN08
18:25 Nathaniel S. Hwang

Bioinspired Inorganic Nanoparticles for Bone Remodeling Control
BIOTECH-KN13
18:50 Sanghoon Kim
Sustainable polysaccharide-derived mesoporous carbons (Starbon®) as additives for
negative electrodes of lithium-ion batteries
BIOTECH-OR14
19:05 Giuseppina Luciani
Ceramic templated melanin nanostructures: a biomimetic synthesis approach to bio-
functional hybrid materials
BIOTECH-OR22
19:20 Naresh D. Sanandiya
3D bioprinting of stimuli-responsive cell-laden cellulosic hydrogel
BIOTECH-OR40
19:35
7
October 15, NANOTECH
NANOTECH SESSION
NANOTECH 1 – Baie des Anges A Room

Session Chair – Federica Lo Verso
10:30 Federica Lo Verso
Computational Investigation of Microgels: Effect of the Microstructure on the
Deswelling Behavior
NANOTECH-KN12
10:55 Solene Fleutot

Versatile capped superparamagnetic iron oxide nanoparticles
NANOTECH-OR10
11:10 Sara Kawrani
Studying CaCu3Ti4O12 behavior after adding the boron nitride nanosheets
NANOTECH-OR18
11:25 Radek Bombera

Characterisation of functional layers and biomolecular interactions using Multi-
Parametric Surface Plasmon Resonance (MP-SPR)
NANOTECH-OR32
11:40 Lunch Break


Session Chair: Caroline Szczepanski
14:30 Thierry Darmanin
Homogeneous and templateless growth of conducting polymer nanotubes with
special wetting properties
NANOTECH-KN05
14:55 Caroline Szczepanski
Design of biomimetic polymer interfaces: using photopolymerization techniques to
simultaneously control surface chemistry and topography
NANOTECH-KN19
15:20
Eui-Sung Yoon
Correlation studies of nanoscale adhesion and friction using mushroom-shaped
and cylindrical pillar patterns of varying physico-chemical characteristics
NANOTECH-OR22
15:35 Jérôme Fresnais

Making superhydrophobic surfaces with magnetic elastomer: towards controlled
droplet movement
NANOTECH-OR03
15:50 Jimmy Faivre
Towards the Fabrication of a Bioinspired Fluid for Biotriblogical Applications
NANOTECH-OR02
8
16:05
Coffee Break
Salon Royal Room
16:15
16:00 Poster Session
Salon Royal Room

Session Chair: Christoph Neinhuis
18:00
Christoph Neinhuis
Plant Biomimetics - From basic principles to applications
NANOTECH-KN08
18:25 Yongmei Zheng

Bioinspired surfaces with wettability from design to functions
NANOTECH-KN23
18:50 Xuan Chen
Effect of Air Contamination on The Wettability of Mono and Few-layered InSe
Films
NANOTECH-OR06
19:05
9
October 15, SMARTTECH
SMARTTECH SESSION
SMARTTECH 1 – Versailles Room
Session Chair: Atsushi Hozumi
10:30 Atsushi Hozumi
Bio-inspired Surfaces Showing Reversible/Repeatable Thermo-responsive Anti-icing/Snow
Properties
SMARTTECH-KN07
10:55
Dominique Hourdet
Sol-Gel transitions of modified polysaccharides under temperature and salt control
SMARTTECH-KN06
11:20 Masayoshi Higuchi

Metallo-Supramolecular Polymer: Stimuli-Responsive Properties and Smart Window
Device Application
SMARTTECH-OR10
11:35 Julien Dupré de Baubigny
Redox triggered peel-off of antifouling polymer layers for on demand activation of
surface patterns.
SMARTTECH-OR07
11:50 Emmanuelle Marie
Mixed AD Layers of Poly(Lysine)-Based Copolymers to Dynamically Control Cell
Adhesion/Migration
SMARTTECH-OR17
12:05 Dasom Jeon
Tailored Assembly of Biomimetic Nacre-like Catalytic Multilayers for Artificial
Photosynthesis
SMARTTECH-OR24
12:20 Lunch Break
Bioinspired Molecular Electrets

SMARTTECH-KN19
Session Chair: Dominique Hourdet
14:30
Sophie Groult
Pectin aerogels: structure-properties correlations and use for drug controlled-release
SMARTTECH-OR22
14:45 Albane Birault

pH-Responsive Mesoporous Silica Nanoparticles for Combination Cancer Therapy
SMARTTECH-OR12
15:00 Mihai Lomora

Mussel-bioinspired polydopamine coated coccoliths as novel therapeutic carriers
SMARTTECH-OR16
15:15
Eda Cagli
Antibiotic Releasing Multilayers of Poly(2-isopropyl 2-oxazoline) and Tannic Acid
SMARTTECH-OR04
10
15:30
Free Time
16:00
Coffee break
16:15 “Salon Royal” room
"Salon Royal" room

Session Chair: Nathalie Steunou
18:00 Nathalie Steunou
Design of Hybrid Materials based on Metal Organic Frameworks for bioimaging and
biodetection applications
SMARTTECH-KN08
18:25 Remi Merindol
Combining DNA phase transition and hybridization to form all-DNA colloids and
superstructures
SMARTTECH-OR27
18:40 Aude Falcimaigne-Cordin
New delivery system for crop protection based on biosourced molecularly imprinted
polymers
SMARTTECH-OR18
18:55 Habib Belaid
Development of a 3D printed scaffold allowing multiple drug delivery for the treatment
of bone metastasis in breast cancers
SMARTTECH-OR01
19:10
11
October 15, HUGS
HUGS SESSION
HUGS 1 – Baie des Anges B Room
Session Chair: Nathanaël Guigo
10:30 Symposium on Biomass Valorization: Catalysis, New Materials, and
Applications
Welcome Remarks – Nathanaël Guigo (Chair)
10:35 Amar Mohanty
Going Green: Circular Economy in Exploring Innovation of Biobased Materials
HUGS-KN08
11:00 Rajender Varma

Biomass Bounty: Carbonaceous Magnetic Materials in Sustainable Chemical
Transformations
HUGS-KN12
11:25 Anupama Sharma
Comprehensive Utilization of various Lignocellulosic biomass as a sustainable
precursor for high performance materials
HUGS-KN13
11:50
Layla Filiciotto
Catalytic approaches for biorefinery’s waste valorization: The humins challenge
HUGS-OR07
12:05 Daniele Padovan

Preventing the deactivation of Sn-containing zeolites during continuous biomass
processing
HUGS-OR09
12:20 Shi Jiang

Unveiling the role of choline chloride on furfural synthesis from a highly
concentrated xylose
HUGS-OR12
12:35 Robin White
Is Doping Performance Enhancing? Hydrothermal Carbons in Catalyst
Development.
HUGS-OR24
12:50 Lunch Break

Session Chair: Katalin Barta
14:30
Katalin Barta
Cleave and Couple: Catalytic Pathways to Value Added Products from Renewables
HUGS-KN02
12
October 15, HUGS
14:55
Christophe M. Thomas
Polymerization of Heterocycles using Organometallic Complexes: A Simple
Approach to Sequence Control in Polymer Synthesis
HUGS-KN10
15:20 Fatima El Ouahabi

Caprolactam precursors from biomass-derived levulinic acid
HUGS-OR06
15:35 François Jérôme

Selective conversion of concentrated feeds of furfuryl alcohol to alkyl levulinates
catalyzed by metal triflates
HUGS-OR11
15:50
Sergey Tin
Synthesis of HHD and HHD-derived chemicals from HMF
HUGS-OR21
16:05
Coffee break
Salon Royal Room
16:15
Salon Royal Room

Session Chair: Marc Dubois
18:00
Marc Dubois
From hydrophilic to hydrophobic wood using direct fluorination
HUGS-KN05
18:25 Yury Shchipunov

Cellulose Functionalization through its Mineralization
HUGS-KN09
18:50 Feng Chen
From Cellulose Fibers Dissolution and Swelling toward Manufacturing All Cellulose
Composites
HUGS-OR03
19:05 Eero Kontturi
Solid State Assembly of Cellulose Nanocrystals in the Template of a Fiber Cell Wall
HUGS-OR14
19:20 Lifeng Yan
Fluorescent/Transparent Wood based Composite Materials
HUGS-OR25
19:35

SMARTTECH-KN19
13
October 15, ENERGY
ENERGY SESSION
ENERGY 1 – Nations Room

Session Chair: Valentine Vullev
10:30
Symposium on Bioinspired Chemistry and Materials for Sustainable Energy
Welcome Remarks – Valentine Vullev (Chair)
10:35 Ksenija Glusac

Metal-free Electro- and Photocatalysis
ENERGY-KN08
11:00 Dorota Gryko
Bioinspired catalysis with porphyrinoids
ENERGY-KN09
11:25 Gary F. Moore
Nature Inspired Surface Coatings for Applications in Photoelectrosynthesis
ENERGY-KN12
11:50 Jungki Ryu
Enabling Solar-Fuel Production with Biomimetic Architectures
ENERGY-OR07
12:05 Thierry Tron
Photocatalytic O2 Reduction at a Laccase
ENERGY-OR08
12:20 Lunch Break
14
October 15, ENERGY

Session Chair: Oleg Poluektov
14:30 Maria Abrahamsson
Solar Energy Conversion Materials: Charge and Energy Transfer Approaches to
High(er) Efficiencies
ENERGY-KN01
14:55 Tao Deng
Bioinspired Solar Thermal Conversion at Interface and in Bulk
ENERGY-KN06
15:20 Oleg Poluektov
Bioinspired Systems for Solar Fuel Production: Advanced EPR/DFT Biohybrid
Characterization
ENERGY-KN13
15:45 Lin Wang
Cross-Species Inspired Patterned Slippery Surfaces for Fog Harvesting
ENERGY-OR10
16:00
Coffee break
Salon Royal room
16:15
16:00
Poster Session
Salon Royal room

Session Chair: Frank Quina
18:00 Angel Martí
Light-Driven Processes in Nanomaterials of Multiple Dimensions
ENERGY-KN11
18:25 Frank Quina

Nature-Inspired Fruit and Flower Chromophores for Collection and Dissipation of
the Energy of Absorbed Light
ENERGY-KN14
18:50
15
October 15, 2D3D
2D3D SESSION
2D3D 1 – Louis XVI Room
Session Chair: Anne Gaucher
10:30
Symposium on Bioinspired 2D and 3D Molecular and Hybrid Architecture
Welcome Remarks – Anne Gaucher (Chair)
10:35
Carole Perry
Experimental and Computational Studies of (Nano)particle-biotic interfaces
2D3D-KN07
11:00 Carole Chaix

Stimuli-responsive DNA structures grafted on biosensing surfaces
2D3D-KN01
11:25 Maya Abdallah
Controlling the Stiffness and Porosity of Polyacrylamide Hydrogel Matrices and
Evaluating their Effect on Podocyte-Behavior
2D3D-OR01
11:40 Eduardo Anaya-Plaza
Electrostatic protein-phthalocyanine assemblies towards biohybrid photoactive
materials
2D3D-OR02
11:55 Lunch Break
14:30
16
October 15, PLASMAT
PLASMAT SESSION
PLASMAT 1 – Louis XVI Room
Session Chair: Hernando S. Salapare III
14:30
Symposium on Plasma and Laser Processing of Bioinspired and Biobased
Materials (PLASMAT 2018)
Welcome Remarks – Hernando S. Salapare III (Chair)
14:35 Anne-Marie Kietzig

Engineering nature-inspired surfaces by femtosecond laser micromachining
PLASMAT-KN01
15:00 Kesong Liu
Bio-Inspired Superwetting Materials
PLASMAT-KN02
15:25
Po-Yu Chen
Synthesis of Transparent, Omniphobic, Self-cleaning Surfaces by Silanization and
Atmospheric Plasma-assisted Metal-oxide Coatings Inspired from Lotus Leaves
PLASMAT-OR01
15:40 Sameer F. Hamad

Low Voltage-SEM insights into Nanoscale Surface Modification of Ramie Plant
Fibers by Plasma Treatment
PLASMAT-OR02
15:45
Free Time
16:00
Coffee break
Salon Royal Room
16:15
16:00
Poster Session
Salon Royal Room
17
October 15, 3D
3D SESSION
3D 1 – Louis XVI Room
Session Chair: Ralph Nuzzo
18:00
Symposium on 3D Printing of Bioinspired Materials
Welcome Remarks – Arnaud Zenerino (Chair)
18:05 Ralph Nuzzo

Printing 4D Gradient Hydrogel Scaffolds for Programmable Cellular Dynamics
and Patterned Biogenic Mineralization
3D-KN01
18:30 Angelo Accardo
3D hydrogel neuronal microenvironments fabricated by two-photon
lithography
3D-OR01
18:45 Leonid Ionov
4D Biofabrication by Shape-Morphing Polymers
3D-OR02
19:00
18
October 16
CONFERENCE PROGRAM
Tuesday, October 16
Coffee Break and Group Photo: 9:15 – 9:30
Plenary Lecture (Masséna Room)
Session Chair: Felix N. Castellano
9:30 – 10:15 : Valentine VULLEV – From Biomimetics to Biological Inspiration: Path to Discovery
Beyond What Nature Offers (PL03)
Abstract
Life on Earth offers an amazing diversity of paradigms and lessons that have
withstood the test of time for 3.8 billion years of evolution. Biomimetic and bioinspired
approaches, therefore, are profoundly important for advancing science and
engineering [1]. While the terms “biomimetic” and “bioinspired” appear
interchangeable, they carry different denotations and truly different connotations, and
as such, their implications for science and engineering also differ. Biomimicry
involves sheer imitation of biological systems where resemblance of structural feature
does not necessarily ensure attainment of functionality [1,2]. Biomimesis takes the
process of mimicking biology to the next level. In addition to perfecting the structural
imitations, biomimesis also aims at attaining functionalities comparable to those of the
natural systems [1,2]. Bioinspiraton goes beyond what nature offers, by taking
concepts found in biology and employing them in manners optimal for the targeted
applications without necessarily resembling the living systems [1,2]. As such,
biomimetics (encompassing biomimicry and biomimesis) takes the first steps toward
taking lessons from Nature. Mimicking Nature with the aim to attain functionality based
on structural resemblance of biology is invaluable for testing our knowledge of how
living systems work [1]. Biomimentics, therefore, proves crucial for basic science.
Conversely, bioinspiration provides paths for taking biomimetic advances to applied
science and engineering. Bioinspiration can also reveal the emergence of new
properties leading to unprecedented scientific discoveries. The development of
charge-transfer (CT) molecular electrets illustrates perfectly the evolution from
biomimicry, through biomimesis, to bioinspiration [1]. (Electrets are systems with
ordered electric dipoles, i.e., they are the electrostatic analogues of magnets.) Electric
dipoles are everywhere, and the importance of understanding how they affect
chemical, physical and biological processes cannot be overstated. CT is essential for
sustaining life and for making energy conversion possible. Molecular dipoles present
important, but underutilized, paradigms for guiding CT processes. Protein helices are
the best-known molecular electrets with immensely large macrodipoles. Using
synthetic biomimetic polypeptide helices to guide long-range electron transfer (ET)
19
October 16
has proven the feasibility of the idea for using molecular dipoles for guiding CT.
Polypeptides, however, mediate ET via tunneling with limited efficiency to about 2 nm,
rendering such biological and biomimetic helices impractical for electronic
applications. Therefore, we develop bioinspired molecular electrets that like the
protein helices possess enormous macrodipoles, but unlike the biological and
biomimetic polypeptides, the bioinspired electrets can efficiently mediate long-range
CT via electron or hole hopping [3-6]. In addition to their promise for electronic
applications, the bioinspired molecular electrets reveal the emergence of new
properties, such as the synergy between electronic-coupling and the Franck-Condon
contribution to ET kinetics [4]. The bioinspired electrets provide the first evidence that
molecular dipoles can profoundly affect the donor-acceptor electronic coupling and the
ET rates. These discoveries illustrate how the evolution from biomimetics to biological
inspiration can profoundly impact science and engineering.
Coffee Break: 14:45 – 15:00
Workshops :
15:00 – 17:45 : Interactive Session on Wetting – Abraham Marmur
16:05 – 17:45 : HUGS - Industrial Sustainable Development – Nathanaël Guigo
Social Event :
20:00 – 23:00 : Conference Gala Dinner (Salon Royal Room)
20
October 16, BIOTECH
Tuesday, October 16
BIOTECH SESSION

Session Chair: Soon Hyung Hong
08:00 Jean-Marie Nedelec
Cationic substitutions in calcium phosphate bioceramics: toward mimicking natural bone and
beyond
BIOTECH-KN04
08:25
Soon Hyung Hong
Bioinspired BNNS/Gelatin Nanocomposite with Nacre-mimetic Structure for Bone Substitute
Application
BIOTECH-KN12
08:50 Franck Cleymand

New free standing "green" biomembranes for tissue engineering
BIOTECH-OR31
09:05
Free Time
09:15
Coffee Break & Group Photo
Salon Royal Room
09:30
21
October 16, BIOTECH

Session Chair: Insung Choi
10:15 Insung Choi
Artificial Spores: Chemical Sporulation and Germination
BIOTECH-KN02
10:40
Louis Gangolphe
Absorbable and bio-inspired materials dedicated to soft-tissue reconstruction
BIOTECH-OR09
10:55 Audrey Tourrette

Biopolymer based smart wound dressing for surgical application
BIOTECH-OR26
11:10
Lunch Break

Session Chair: Vladimir Tsukruk
13:30 Vladimir Tsukruk

Flexible Bioenabled Nanocomposites
BIOTECH-KN16
13:55 Claudio Gioia

Valorization of ferulic acid from wheat bran to obtain bio-based polymers for
packaging applications
BIOTECH-OR10
14:10 Maria Elena Antinori
Mycelium-based materials: a broad spectrum of tunable properties
BIOTECH-OR01
14:25 Ana Isabel Quilez
One-Pot Fabrication and Characterization of Antioxidant Polymers from Tea Waste
Extracts
BIOTECH-OR29
14:45 Coffee Break
Salon Royal Room
22
October 16, BIOTECH

Session Chairs: Ilker S. Bayer and Laurent Billon
15:00 Ilker S. Bayer

Engineering Bio-based Composites for Intelligent and Functional Applications
BIOTECH-KN03
15:25 Laurent Billon

Bio-inspired polymer materials: From the monomer chemical nature to hierarchically
structured functional films
BIOTECH-KN11
15:50 Lucile Druel
New aerogel-like materials: lightweight and mesoporous cellulose xerogels
BIOTECH-OR05
16:05 Oona Korhonen
All-Cellulose Composites via Short-Fiber Distribution Approach
BIOTECH-OR16
16:20 Anna Laromaine

From novel structuration to functional composites of bacterial cellulose
BIOTECH-OR18
16:35 Claude Grison

Putting Waste to Work through a Bio-inspired Approach
BIOTECH-OR13
16:50 Giacomo Tedeschi
Bioinspired sodium alginate-tomato peel composites with enhanced hydrodynamic
properties
BIOTECH-OR36
17:05 Annie Chimphango
Sequential fractionation of mango peels for anthocyanins, polyphenols and pectin
BIOTECH-OR24
17:20 Fawzi Banat
Exploitation of waste date seeds as sustainable source of high quality bio-oil
BIOTECH-OR02
17:35
23
SMARTTECH SESSION
Session Chair: Karsten Haupt
08:00
Karsten Haupt
Molecularly Imprinted Polymer Nanocomposites as Synthetic Antibody Mimics for
Biomedicine
SMARTTECH-KN02
08:25 Vaishakh Nair

Selective Photooxidation of Lignin Model Compound- Benzyl Alcohol in a ZnO Coated
Microfluidic Reactor
SMARTTECH-OR30
08:40 Remi Merindol
Macroscopic DNA hydrogels that sense mechanical strain
SMARTTECH-OR28
08:55 Alejandra Mier Gonzalez

Application of Molecularly Imprinted Polymers in Cosmetics: A New Deodorant Principle
SMARTTECH-OR29
09:15
Coffee Break & Group Photo
Salon Royal Room
09:30

Session Chair: Martine Largeron
10:15
Martine Largeron
Aerobic Catalytic Systems Inspired by Copper Amine Oxidases
SMARTTECH-KN05
10:40 Nuno Basílio

Stimuli-Responsive Supramolecular Systems Bio-Inspired in Anthocyanins
SMARTTECH-KN14
11:05 Juyoung Yoon
Recent Progress Activatable Photosensitizers and Fluorescent Probes
SMARTTECH-KN10
11:30 Andrea Belluati
Compartments and cascades: a model reaction for complex nanoscale systems
SMARTTECH-OR09
11:45
Lunch Break
24

Session Chair: Feng Zhou
13:30 Feng Zhou
Bioinspired wet-lubricious materials
SMARTTECH-KN11
13:55 Omar Chaalal
Novel Surfactant made of plants from the United Arab Emirates to remove zinc from
wastewater
SMARTTECH-OR13
14:10
Annie Chimphango
Enzymatic transformation of biopolymers to produce nanohydrogels as surface
modifiers and slow release devices for bioactive substances
SMARTTECH-OR15
14:25 Emilie Forestier

Stretching of biosourced polyethylene 2,5-furandicarboxylate above its glass transition
and associated microstructural development
SMARTTECH-OR20
14:45 Coffee Break

Salon Royal Room

Session Chair: Juyoung Yoon and Gabriela Ramos Chagas
15:00 Jorge Royes Mir
Nanocapsules with functional (T switchable) polymer corona produced by microbial cell
factories
SMARTTECH-OR34
15:15
Sagana Thamboo
Biomimetic Assemblies based on Subcompartmentalized Giant Polymersomes
SMARTTECH-OR36
15:30 Lilia Clima

Polymeric supramolecular transporters for nucleic acids delivery
SMARTTECH-OR06
15:45
Shengchang Zhang
The structural and morphological controlling of Polycaprolactone microspheres via
electrospraying and selecting green solvent
SMARTTECH-OR23
16:00
Christian Sproncken
PVA-based polymer micelles for ice recrystallization inhibition
SMARTTECH-OR19
25
16:15 Isis Castro-Cabrera

The role of interface functionalization on self-healing and relaxation properties of
vitrimer nanocomposites
SMARTTECH-OR05
16:30 Florent Malloggi
Self-rolled polymeric thin film: toward fully functionalized microsystems
SMARTTECH-OR25
16:45 Elena Orlenko
Effect of the Space Dimension upon the Spin Magnetic Ordering in the Electron Fermi-
Gas
SMARTTECH-OR31
17:00
26
NANOTECH SESSION

Session Chair: Chang-Hwan Choi
08:00 Chang-Hwan Choi
Bioinspired Slippery Surfaces: Oil-Impregnated Nanoporous Alumina Coating for
Anticorrosion and Antibiofouling
NANOTECH-KN03
08:25 Glen McHale
Droplets on Smart Slippery Surfaces
NANOTECH-KN07
08:50 Alla Synytska
Bio-inspired Strategies for Design of Ice-Resistant Materials based on Polymeric
Janus Colloids
NANOTECH-OR15
09:05 Federico Veronesi
Liquid-repellent coatings for friction and drag reduction in industrial applications
NANOTECH-OR16
09:20 Coffee Break & Group Photo
Salon Royal Room

09:30

Session Chair: Catarina Esteves
10:15 Catarina Esteves

Tailor-made hydrophilic polymer networks with biomimetic functions: anti-fouling,
self-healing and low-friction
NANOTECH-KN01
10:40 Zhiguang Guo
Bionic Materials of Tribology
NANOTECH-KN02
11:05
Himanshu Mishra
Coatings-free Desalination Membranes from Bio-inspiration
NANOTECH-OR13
11:20 Olivier Felix

Engineering the properties of self-assembled bio-inspired nanocomposite
materials
NANOTECH-OR09
11:35
Lunch Break
27

Session Chair: Jonathan Wilker
13:30 Jonathan Wilker

How Far Can We Push the Performance of Polymers Mimicking Mussel Adhesive
Proteins?
NANOTECH-KN20
13:55 Marleen Kamperman
Bioinspired Ionic Adhesives
NANOTECH-KN04
14:20 Charlotte Vendrely
Identification of the molecular bases of arthropod natural glues
NANOTECH-OR29
14:35
Seethalakshmi Chandramouli
Wettability assisted selective deposition of nanoparticles on patterned glass fibers
NANOTECH-OR05
14:50 Coffee Break

Salon Royal Room

Session Chair: Richard Spontak
Richard Spontak
15:00
Block Copolymer Hierarchical Morphologies and Customized Functionality Inspired
by Nature
NANOTECH-KN11
15:25 Philippe Miele
Nanostructured materials based on boron nitride for energy, environmental and
health applications
NANOTECH-KN14
15:50 Celine Pochat-Bohatier
Emulsion templating to prepare porous polymeric membrane
NANOTECH-KN16
16:15 Pola Goldberg Oppenheimer
Hierarchical Electrohydrodynamic Lithography for Advanced Micro-Engendered
Devices
NANOTECH-KN06
16:40 Hyunjung Shin
Stable New Polymorph Gold and Silver Nanowires Fabricated in Nanoscale
Confinement
NANOTECH-OR25
16:55 Luxiao Chai
Rapid Access to Functional Oil-Filled poly(vinyl alcohol)-based Glyconanocapsules
through Nanoprecipitation
NANOTECH-OR04
17:10
28
October 16, HUGS
HUGS SESSION

Session Chair: Magdalena Titirici
08:00 Magdalena Titirici
The green black: Sustainable Carbon Materials for Renewable Energy Applications
HUGS-KN11
08:25 Wahiba Ramdani
Catalytic glycosylation of glucose with alkyl alcohols over sulfonated mesoporous
carbons
HUGS-OR10
08:40
Ana Belen Jorge-Sobrido
Biomass-derived electrodes for flexible supercapacitors
HUGS-OR13
08:55 Pierluigi Tosi

New rigid foams based on industrial humins
HUGS-OR22
Salon Royal Room
09:30

Session Chair: Chaobin He
10:15
Chaobin He
Lignin as Useful Biomass for Composites and Carbon Materials
HUGS-KN07
10:40
Manju Misra
Opportunity of Biocarbon in Next Generation Materials Application
HUGS-KN14
11:05 Remo Merijs Meri

On the oat husks modified polypropylene composite for injection molding
applications
HUGS-OR15
11:20 Anna Sangregorio
Fully biobased composites by humins valorization
HUGS-OR20
11:35 Gianni Girotti
Platform technology for a guayule biorefinery
HUGS-OR26
11:50
Lunch Break
29
October 16, HUGS

Session Chair: Guy Marlair
13:30 Guy Marlair
Alternative solvents such as ionic liquids or deep eutectic solvents: are they green or
not?
HUGS-KN06
13:55 Sylvain Brohez
Flame retardant behavior of PLA containing phosphorus and nitrogen chemically
modified lignin
HUGS-OR01
14:10 Anitha Muralidhara
Importance of safety considerations of furanics compounds and their side streams in
advanced biorefineries
HUGS-OR17
14:25 Alexis Vignes

Nanomaterials and biorefineries: inspiring some safety thoughts
HUGS-OR23
14:45 Coffee Break
Salon Royal Room

Session Chair: Florent Allais
15:00 Florent Allais
Chemo-enzymatic synthesis, biological properties, functionalizations and
polymerizations of biobased bisphenols derived from ferulic and sinapic acids
HUGS-KN01
15:25 Sylvain Caillol

Synthesis of biobased building blocks from cashew nutshell liquid: a chemical
platform approach for polymer synthesis
HUGS-KN03
15:50
Alain Graillot
Biobased Building-Blocks for Thermosets Epoxy Resins
HUGS-OR08
16:05
30
October 16, PLASMAT
PLASMAT SESSION
PLASMAT 2 – Louis XVI Room

Session Chair: Maryline Moreno
08:00 Maryline Moreno
Pulsed atmospheric pressure plasma: An elegant route for the deposition of tunable
bioinspired and smart thin polymer films
PLASMAT-KN04
08:25 Sidi Bencherif
Injectable cryogels for biomedical applications
PLASMAT-KN03
08:50 Yong-lai Zhang
Laser processing of biomimetic graphene surfaces
PLASMAT-KN05

Salon Royal Room
09:30
31
October 16, 3D
3D SESSION
3D 2 – Louis XVI Room
Session Chair: Liqun Zhang
10:15
Liqun Zhang
Novel Bio-based Elastomers with tunable properties
3D-KN02
10:40 Elena Martínez

Dynamic polymerization photolithography yields 3D biomimetic models of small
intestine in a simple fabrication process
3D-OR03
10:55 Laurine Valot
3D-bioprinting of peptide based hybrid organic-inorganic hydrogels : Encapsulation
of mesenchymal stem cells for cartilage repair
3D-OR04
11:10
Lunch Break
13:30
32
October 16, BIOADHESION
BIOADHESION SESSION
BIOADHESION 1 – Louis XVI Room
Session Chair: Laura Magro
13:30 Symposium on Bio-inspired Adhesion
Welcome Remarks – Laura Magro (Chair)
13:35
Patrick Flammang
In the footsteps of sea stars: Proteins for temporary adhesion
BIOADH-KN02
14:00 Amanda Andersen

Metal Ion Interactions in Protein- and Protein-Inspired Materials
BIOADH-OR01
14:15 Alessandra Griffo

Adhesive and elastic fusion proteins toward nanocomposites materials: a single
molecule study
BIOADH-OR02
14:30
Free Time
14:45 Coffee Break

Salon Royal Room
BIOADHESION 2 – Louis XVI Room

Session Chair: Tristan Gilet
15:00 Tristan Gilet
The hairy adhesive pads: wet and compliant
BIOADH-KN03
15:25 Vincent Bels
Lingual adhesion in Tetrapods: Why and how in lizards?
BIOADH-KN01
15:50 Pascal-Jean Lopez
Tube formation in polychaetes: a proteomic and genomic perspective
BIOADH-KN05
16:15
Dong Woog Lee
Bio-inspired adhesives triggered by polyelectrolyte complexation and surface priming
BIOADH-OR03
16:30 Kathrina Lois Taaca

Development and evaluation on the surface properties of polyaniline – chitosan bio-
inspired adhesive: Experimental study and numerical molecular dynamics simulation
BIOADH-OR04
16:45
33
October 16, 2D3D
2D3D SESSION
2D3D 2 – Nations Room
Session Chair: Masato Ikeda
08:00 Masato Ikeda
Bioinspired supramolecular nanofiber
2D3D-KN03
08:25 Christian Hamm
Nanostructures of diatom silica: how biominerals adapt to high- performance
lightweight geometries
2D3D-OR04
08:40
Free Time

Salon Royal Room
09:30
34
October 16, ENERGY
ENERGY SESSION
Session Chair: Erick L. Bastos
10:15
Erick L. Bastos
Advances in betalain chemistry: from fluorescent flowers to technological applications
ENERGY-KN04
10:40 Felix N. Castellano

Triplet Energy Transfer Across Quantum Dot – Molecular Interfaces
ENERGY-KN05
11:05
Lunch Break

Session Chair: Igor Alabugin
13:30 Igor Alabugin
From Carbon-Rich Molecules to Carbon-Rich Materials
ENERGY-KN02
13:55 Marc Robert
Solar fuels production from CO2 Catalytic Reduction with Bioinspired Fe Molecular
Complexes
ENERGY-KN15
14:20 Jieun Choi
Mussel-inspired hydrophilic polymer binder for cathode in seawater batteries
ENERGY-OR02
14:35
Free Time
14:45 Coffee Break

Salon Royal Room
15:00
35
October 17
CONFERENCE PROGRAM
Plenary Lecture (Masséna Room)
Session Chair: Julia Ortony
10:15 – 11:00 : Stephen WEINER – Minerals and Crystals in Biology: Inspirations for New Materials
(PL04)
Abstract
Organisms produce many minerals and crystals, but the choice of minerals is based
on their evolutionary history. As organisms need to constantly adapt to a changing
environment, they also need to adapt the minerals they form, and this leads to
interesting solutions to challenging problems.
One “unconventional” approach adopted by many different invertebrate taxa as well

as vertebrates that produce mineralized materials, is to first form a highly disordered
precursor phase inside vesicles within cells, and then to extrude these minerals into
the extracellular space and induce them to crystallize to greater or lesser extents. In
fact control over the extent of atomic disorder is the hallmark of many biogenic
minerals. We have developed a valuable and relatively simple technique for assessing
atomic disorder using infrared spectrometry. Bone mineral is also formed via a
disordered precursor mineral phase, and the pathway of mineral formation in bone is
relatively well documented.
A variety of organisms produce minerals for light manipulation. The most commonly
documented example is the organic crystal guanine. Guanine has an unusually high
refractive index in one direction and this is exploited by organisms for producing
structural colors, including both the silvery iridescence of fish scales, and the bright
colors in various marine copepods. The latter can be tuned to the local environment in
which they live. Guanine crystals are also used in vision, such as in the eyes of
scallops where they produce a back reflecting mirror for focusing light. A recently
discovered additional function of guanine crystals is to enhance photosynthesis in the
marine protozoans called dinoflagellates by the back scattering of light.
Many of the minerals and crystals produced by organisms have shapes and
mechanical properties that are adapted to their functions. Some of the mechanisms
used for their formation and function may well be applicable to synthetic materials.
Coffee Break : 10:00 – 10:15
Coffee Break : 16:00 – 16:15
16:15 – 17:00 : Closing and Awards Ceremony – Masséna Room
36
October 17, BIOTECH
BIOTECH SESSION

Session Chair: Thierry Darmanin
08:00 Tamaki Naganuma
The Correlation between Cell Adhesion Force Activation on Nano/Micro-Topographical
PLLA Surfaces and Temporal Dependence of Cell Morphology
BIOTECH-OR25
08:15 Virginie Sottile
Live quantitative monitoring of mineral deposition in human stem cells using an antibiotic
molecule
BIOTECH-OR33
08:30 Franck Cleymand
BIOTECH-OR38
08:45 Yuya Tachibana
Bio-based poly(Schiff-base) comprising bifurfural
BIOTECH-OR35
09:00 Viktor Kochkodan
Surface Coating of Polymer Membranes for Water Treatment: a New Approach to
Mitigate Biofouling
BIOTECH-OR41
09:15 Free Time
10:00 Coffee Break
Salon Royal Room
10:15

SessionChair: Pascal Jonkheijm
11:00 Pascal Jonkheijm
Dynamic cell-instructive coatings
BIOTECH-KN14
11:25 Francisco Fernandes
Freeze casting biopolymers for 3D cell culture systems
BIOTECH-OR08
11:40 Kankan Qin
Freezing living cells: understanding the impact of the physical cell environment on
survival
BIOTECH-OR28
37
October 17, BIOTECH
11:55 Paulina Ximena Medina Rangel

Molecularly Imprinted Polymer Nanoparticles as Synthetic Antibody Mimics for Cell
Targeting and Imaging
BIOTECH-OR19
12:10 Lunch Break
BIOTECH 10 – Masséna Room BIOTECH 11- Versailles Room

Session Chair: Béatrice Labat Session Chair: João Mano
14:30 Béatrice Labat 14:30
Versatile biomimetic chondroitin-sulfate- Thierry Delair
based matrix for tissue repair and From chitosan to biomaterials
mechanobiology BIOTECH-KN17
BIOTECH-KN15
14:55 João Mano 14:55
Bioinspired methodologies for the
Kathrina Lois Taaca
preparation and fixation of soft
In vitro anti-diabetic activity of Philippine
spherical polymeric devices for the
Mulberry leaves (Morus alba Linn.) extract
encapsulation of cells and therapeutic
BIOTECH-OR34
molecules
BIOTECH-KN18
15:10 Tristan Baumberger 15:20
Samir Bkhaït
Complex, flow-induced organization of
Antibiofouling surface modifications
dense collagen solutions during
using bioactive molecules
microfluidic fibre extrusion
BIOTECH-OR27
BIOTECH-OR03
15:25 15:35
Free Time
16:00
16:00 Coffe Break
Salon Royal Room
38
NANOTECH SESSION

Session Chair: Rein V. Ulijn
08:00 Rein V. Ulijn

Guiding principles for peptide-based, life-like nanotechnology
NANOTECH-KN21
08:25 Julia Ortony
Molecular motion in self-assembled nanostructures
NANOTECH-KN15
08:50 Mondem Sudhakara Reddy

Microbial concrete provides resistance to concrete structures exposed to severe sulfate
attacks
NANOTECH-OR14
09:05 Habib Belaid
Development of an injectable cement allowing multiple drug delivery for the treatment of
breast cancer bone metastasis
NANOTECH-OR31
09:20
Free Time
10:00 Coffe Break

“Salon Royal” Room
10:15

Session Chair: Isabelle Michaud-Soret
11:00 Isabelle Michaud-Soret
Ecoconception of metallic nanoparticles with bioinspired coatings: a safer-by-design
approach
NANOTECH-KN24
11:25
Yingying Liu
Hydrophobin-polymer bioconjugate for antifouling and low non-specific binding surfaces
NANOTECH-OR12
11:40 Antje Clasen

Microstructural surface properties of drifting seeds – a model for non-toxic antifouling
agents
NANOTECH-OR01
11:55 Solenne Fleutot
Facile one-step synthesis of polyoxazoline coated iron oxide nanoparticles
NANOTECH-OR11
12:10 Lunch Break
14:30
39
SMARTTECH SESSION

Session Chair: Hugues Brisset
08:00 Hugues Brisset
Advanced molecularly imprinted polymer as electrochemical sensor interfaces
SMARTTECH-KN03
08:25 Nofar Pinker
Porous Silicon Optical Biosensors for Detection of Subclinical Mastitis Biomarkers in
Bovine Milk
SMARTTECH-OR32
08:40 Mike Bismuth
Porous Silicon Optical Biosensors for Rapid Environmental Monitoring of Trace Heavy
Metals
SMARTTECH-OR03
08:55 Volkan Kilinc
Supported lipid monolayer with unprecedented mechanical and dielectric properties:
Application to ISFET sensors
SMARTTECH-OR11
09:10 Iryna Polishchuk
A Biological Strategy for Presstressing Crystalline Calcite Lenses
SMARTTECH-OR33
09:25 Free Time
10:00
Coffee Break
Salon Royal Room
10:15

SMARTTECH-KN19
SMARTECH 9 – Versailles Room
Session Chair: Tuan Vo-Dinh
11:00
Tuan Vo-Dinh
Nanoplasmonic Bioprobes: Golden Prospects for Biosensing, Diagnostics and Immunotherapy
SMARTTECH-KN09
11:25 Vadim Kessler

Molecular mechanisms in mineral nanoparticle interactions with proteins
SMARTTECH-KN04
11:50
Gulaim A. Seisenbaeva
Specific functionalization of the surface –key for molecular recognition approach
SMARTTECH-OR35
12:05 Octavio Graniel

Atomic layer deposition for biosensing applications
SMARTTECH-OR37
12:20 Lunch Break
Bioinspired Molecular Electrets 40

SMARTTECH-KN19
October 17, ENERGY
ENERGY SESSION
ENERGY 6 – Baie des Anges B Room
Session Chair: Malcom Forbes
08:00 Malcolm Forbes
Light-Responsive Iron(III)–Polysaccharide Coordination Hydrogels: Evidence for a Radical
Mechanism
ENERGY-KN07
08:25 Alan Le Goff
From enzymes to bioinspired catalysts for noble-metal-free hydrogen fuel cells
ENERGY-KN10
08:50
Sang-Yup Lee
Self-assembly of Amino Acidic Bolaamphiphiles for Building Enzyme-mimetic Catalysts
ENERGY-OR05
09:05
Free Time
10:00 Coffee Break

Salon Royal Room
10:15
ENERGY 7 – Baie des Anges B Room

Session Chair: Michael Therien
11:00
Michael Therien
U-Turn Electron Transfers in Chemistry and Biology
ENERGY-KN16
11:25 Laura Puchot

From biophenols to fully biobased thermosets: focus on benzoxazine resins
ENERGY-OR09
11:40 Zhao Wang

Design, synthesis, and properties of several new bio-based elastomers
ENERGY-OR11
11:55
Lunch Break
41
October 17, 2D3D
2D3D SESSION
Session Chair: Xuehong Lu
08:00 Xuehong Lu
Mussel-Inspired Approaches to Core-Shell and Dual Metal-Doped Hybrid Nanospheres for
Energy and Environmental Applications
2D3D-KN04
08:25 Masanobu Sagisaka
Dynamic Aggregation Behavior of Hybrid Surfactants to Generate Quasi Ion-Channels
for Bioinspired Bilayers
2D3D-KN08
08:50 María Luisa Ferrer
Bioinspired Features of Three-Dimensional Porous Carbon Structures
2D3D-KN11
09:15 Patrick Di Martino

Identification of amyloid motifs in the protein TasA of Bacillus subtilis
2D3D-OR03
09:30 Katja Heise
Janus-type nanorods by surface-initiated polymer grafting from the reducing end-
groups of cellulose nanocrystals
2D3D-OR05
09:45
Free Time
10:00 Coffee Break

“Salon Royal” Room
10:15

Session Chair: Wendel A. Alves
11:00 Wendel A. Alves
Supramolecular Engineering of Peptides for Aldol Reactions
2D3D-KN10
11:25 Kwang Hui Jung

Robust Superhydrophobic Surfaces via Concave pillar
2D3D-OR06
11:40 Laureen Moreaud
Artificial repeat protein as in-situ capping agents of 2D gold nanocrystals for a single
particle sensing platform
2D3D-OR07
11:55
Lunch Break
42
October 17, 2D3D

Session Chair: Damien Prim
14:30
Cornelia Palivan
Bioinspired molecular factories with architecture and in vivo functionality as cell mimics
2D3D-KN06
14:55 Sakthivel Nagarajan

2D nanosheets; novel candidate to improve the mechanical property of polymer fiber for
tissue engineering application
2D3D-OR08
15:10
Katsiaryna Prudnikova
Biomimetic Proteoglycans Enhance Type I Collagen Fibrillogenesis
2D3D-OR09
15:25
Free Time
16:00 Coffee Break

Salon Royal Room
16:15
43
WORKSHOPS
WORKSHOP PROGRAMS
WORKSHOP – HUGS Industrial Sustainable Development
Date: Tuesday, October 16
Room : Baie des Anges B Room
Scheduled time : 16:15 – 17:45
Moderator: Nathanaël Guigo
Industrial Speakers: Paul Mines, CEO - Biome Technologies; Gianni Girotti, Green Chemistry R&D
Manager - ENI Versalis; Peter Mangnus, VP Partnering & Commercialization – Synvina; Ed de Jong,
VP Development – Avantium
This session is dedicated to the industrial panel and workshop. Key exponents of leading chemical
companies involved in innovation and sustainability will give their opinion on challenges, hopes, and
controversies on the biomass conversion strategies, as well as address the public's doubts and
concerns. The focus will be on the way different companies are engaged in topics as biomass
conversion and valorization, catalysis for green chemistry, development of new building blocks for
biobased materials and clean technologies. Each industrial speaker would have the possibility to give
a short introduction about the sustainability commitment of their own company followed by an open
discussion involving the audience, a moderator and the industrial speakers.
WORKSHOP –The simple but complicated world of wetting: from fundamentals

to applications
Date: Tuesday, October 16

Room : Nations Room
Scheduled time : 15:00 – 17:45
Organizers: Alidad Amirfazli, York University, Canada; Abraham Marmur, Technion, Israel Institute of
Technology; and Anish Tuteja, University of Michigan, USA
This session is intended to present an overview of wetting and nonwetting in a systematic way, from
fundamentals to applications. This is an attempt to develop an interactive session, where the audience
actively participates in the discussion.
Three general themes are planned: Fundamentals of wetting and non-wetting, contact angle
measurement, and design of super-hydrophobic surfaces. The first theme will include discussion of
questions such as the definition of surface tension, calculations of interfacial tension, wetting on rough
and heterogeneous surfaces. The second theme will comprise discussions of the difficulties in
measuring contact angles and ways to solve them. The last theme will consist of presentations and
discussions of the biomimetics of super-hydrophobicity and beyond.
44
POSTER SESSION
POSTER SESSION
BIOTECH
Ayache
P01 Algeria Application of Rare Aquatic Plants (Salvinia Natans) for Wastewater
LAABASSI
Treatment under Algerian Semi-Arid Climate
Ahmed Petroselinum crispum as biosorbent for the removal of metallic trace

P02 Algeria
BAHLOUL elements
Hocine Synthesis and characterization of new analogues of Azomethin-β-D-

P03 Algeria
BOULEGHLEM Glucosamines
Xavier
P04 Belgium Textos: Improvement of the interface between tissues and scaffolds
CARETTE
Frankje
P05 Netherlands Edible colloidal colorants from water insoluble proteins
DE BOER
Production of Halomonas Levan and Polymethylsilsesquioxane

Tugce
P06 Turkey Nanofibres With Co-Axial Electrospinning For Wound Healing
DOGRUEL
Applications
Merve
P07 ERGİNER Turkey Halomonas Levan as a Bioactive Cosmetic Ingredient
HASKÖYLÜ
Karol Catalytic Olefin Metathesis for Preparation of Macrocyclic Musks and

P08 Poland
GRELA Fine Chemicals from Biomass
Sabine Phage Display Derived Short Peptides for the Recovery of Valuable
P09 Germany
MATYS Metal Ions from Water Streams
Tofik Coherent-synchronized oxidation reaction of 3-picolin by nitrous

P10 Azerbaijan
NAGIEV oxide
Falko Synthesis and Characterization of Functional Polyamides from

P11 Slovakia
PIPPIG Tulipalin A
The characterization and testing of dermal scales of Scophthalmus

Chloe
P12 Ireland rhombus for application in antifouling technology
RICHARDS
Greta
P13 Romania
SOCOTEANU Spherical Zinc Oxide Materials with Antimicrobial Activity
Hideki Green polymer chemistry : Approach to artificial “urushi” via oxidative

P14 Japan
YAMANE polymerization of cardanol in w/o emulsion
45
POSTER SESSION
Paolo Silica fumed as a carrier for synthetic metalloporphyrins emulating

P16 Italy
ZUCCA ligninolytic peroxidases: the effect of ligands
Fahima
P17 Algeria Synthesis Of Some Glycosteroidal Bolaphiles
ALI-RACHEDI
Janis Characterization of oat and spelt husks for development of

P18 Latvia
ZICANS polypropylene based composites
Liliane Samara Bionanocomposites based on gelatin and cellulose nanocrystals

P19 Brazil
FERREIRA LEITE obtained by continuous casting
Soumeya Phytochemical and analysis of hydromethanolic extracts and their

P20 Algeria
KRIMAT fractions from three lamiaceae species
Pablo
P21 Netherlands Fully bio-based epoxy resins from fractionated BCD lignin
ORTIZ
Enio N. Mixotrophic cultivation of Chlorella sorokiniana and Chlorella vulgaris

P22 Brazil
OLIVEIRA JUNIOR using cheese whey as carbon source
Nicolette United
P23 Bio-Inspired Hybrid Systems: A Route to Self-Healing Materials
MOREAU Kingdom
Agata Plasmonic Fluorescent Assay for molecular lipid membrane binging,

P24 Ireland
STEPLEWSKA Permeation and dynamics of permeation.
Wahiba Catalytic glycosylation of glucose with alkyl alcohols over sulfonated

P25 France
RAMDANI mesoporous carbons
Monika
P26 Germany Sustainable hydrothermal Carbons for Biorefinery-related Catalysis
BOSILJ
NANOTECH
Luca Supramolecular engineering of 1-D nanomaterials by self-assembly

P01 France
ALBERTIN of artificial amyloid proteins
Ahmed Preparation of a new material composite film (polybithiopene-MnO2

P02 Algeria
BAHLOUL nanoparticles) and their photocurrent properties.
Abbdesselam Characterization of CuGaxIn1-xSe2 Nanoparticles synthesized by

P03 Algeria
BOULOUFA one-step green hydrothermal route
46
POSTER SESSION
Kirill E. Synthesis and study of the repellent properties of fluorine-

P04 Russia
CHEKUROV containing diblock copolymer films
Using Internal Light Sources for Localized Photopolymerization of

Bilal
P05 France MIP Shells Around Carbon Dots: Plastic Antibodies for Targeted
DEMIR
Bioimaging
Amar Structural properties and catalytic activity of bulk and supported iron
P06 Algeria
DJADOUN cobaltite spinel oxide FeCo2O4
Deok-Jin Bioinspired Blue Coloration Approach Based on Alcedo Atthis

P07 South Korea
JEON Feather’s Structural Color
K.P. Simple and Facile Approach To Create Charge Reversible Pores

P08 India
SONU via Hydrophobic Anchoring of Ionic Amphiphiles
Mrah Polystyrene Nanocomposites: Preparation, Characterization and

P09 Algeria
LAHOUARI Investigation of Mechanical Properties
Randy Towards the fabrication of nanocomposite films with bio-inspired

P10 France
MUJICA complex reinforcing architectures.
Enio N.
Development of nanostrutured coatings of chitosan for postharvest
P11 OLIVEIRA Brazil
preservation of guavas 'Pedro Sato'
JUNIOR
Morphology and thermal properties of poly (alkyl

Kamal
P12 Algeria methacrylates)/bentonite nanocomposites prepared via in situ
OUAAD
polymerization initiated by Ni (II) α-Benzoinoxime (NBO) complex.
Elaboration and thermal analysis of blends and nanoblends based
Kamal
P13 Algeria on poly (methyl methacrylate–co-4-vinylpyridine)/cellulose acetate
OUAAD
butyrate and Maghnia bentonite.
Poly(ethylene terephthalate)/poly(ɛ-caprolactone) blend
Dalila
P14 Algeria nanocomposites : A ‘green’ route compatibilization using a reduced
SAAOUI
graphene properly functionalized
Tomáš Czech Comprehensive evaluation of biomimetic nanocomposite scaffolds

P15
SUCHÝ Republic for bone surgery
Kin-ya
P16 Japan Peptide Self-Assembly-Directed Gold Nanocrystal Synthesis
TOMIZAKI
Aleksandr Composite materials and coatings based on polytetrafluoroethylene

P17 Russia
TSVETNIKOV nanofilms of different temperature fractions
Eui-Sung Experimental and modelling studies on wetting of nanoscale bio-

P18 South Korea
YOON inspired pattern shapes and contours
Rahima Optical Proprieties of CdxZn1-xS Thin Films Deposed by Chemical

P19 Algeria
ZELLAGUI Bath Deposition
47
POSTER SESSION
Yuna In vivo Two-photon Imaging of Tumor with Porous Silicon

P20 South Korea
JUNG Nanoparticles
NaHee Development of a Molecular Photoacoustic Imaging Agent

P21 South Korea
KIM Encapsulated Porous Silicon Nanoparticle Formulation
Nanofibrous surfaces with high hydrophobicity from

Omar
P22 Senegal electrodeposited poly(3,4-ethylenedioxypyrrole) and poly(3,4-
SANE
propylenedioxypyrrole) films substituted by alkyl chains
Synthesis of a novel 3,4-ethylenedioxypyrrole (EDOP) and 3,4-

Djibril
P23 Senegal propylenedioxypyrrole (ProDOP) monomers for special wetting
DIOUF
properties
Maria Teresa Electrodeposition Mechanism and Morphological Analysis of A

P24 Philippines
PULIDO Highly Ordered Structure Polyaniline (PAni)
Katharina Lois Bentonite Activated by Copper and Nickel: Cytotoxicity Testing and
P25 Philippines
TAACA Antimicrobial Activity Studies
Omar Study of the wettability and morphology of parahydrophobic

P26 Senegal
THIAM surfaces made of polymers with hyperbranched alkyl chains
Doebner Von Electrodeposition Mechanism and Morphological Analysis of A

P27 Philippines
TUMACDER Highly Ordered Structure Polyaniline (PAni)
Ouahiba
P29 Algeria Synthesis and characterisation of nanomaterials dawson type
BECHIRI
El Hadji Yade
P30 Sénégal Synthesis and characterization of new superhydrophobic polymers
THIAM
Salima
P31 SAIDI- Algeria Design and development of bionanocomposites for food packaging
BESBES applications
Salima
P32 SAIDI- Algeria Iron oxide based magnetic nanomaterials for water remediation
BESBES
Aline Connecting structural, optical, and electronic properties and
P33 BARRIOS Brazil photocatalytic activity of Ag3PO4:Mo complemented by DFT
TRENCH calculations
Mária Czech
P34 Microsphere lithography in diamond technology
DOMONKOS Republic
Muhamad Synthesis and Properties of Activated Nano

P35 Indonesia
NASIR Carbon/Collagen/Cellulose Acetate Nanofiber by Electrospinning
Raja
P36 Germany Biomass-derived Carbon Dots (C-Dots) for multi-color imaging
SEBASTIAN
Grzegorz Inulin-based nanosensors for enhanced detection of tumorigenic

P37 Poland
BAZYLAK ioxynil residues in garlic
48
POSTER SESSION
Kaibi Microstructure Evolution and Magnetic Properties of Nanocrystalline

P38 Algeria
AMEL Ni75Fe25 Thin Films: Effects of Substrate and Thickness.
Ananya
P39 France Crack pattern formation in plasma-treated TiO2 thin films
SATHANIKAN
Léo Cupric oxide (CuO) nanoparticle formation from plasma surface

P40 France
CLERC modification of copper
SMARTTECH
Patrycja Czech Lignin/polypyrrole biocomposites and their carbonized analogues

P01
BOBER Republic as materials for supercapacitors
Pascal
P02 France Local scale characterizations of smart interface in thin coatings
CARRIERE
Sonata Novel 1’,3,3’,4-Tetrahydrospiro[chromene-2,2’-indole] Based Azo

P04 Lithuania
KRIKŠTOLAITYTĖ Dyes for Naked Eye Detection of Cyanide Ion
Hybrid Material of Bacterial Cellulose Nanocrystals
Hathaikarn Based Surface-Loaded Silver Nanoparticles and
P05 Thailand
MANUSPIYA Alginate-Molybdenum Trioxide Nanoparticles Film with
Hydrogen Sulfide Gas Sensor Ability
Josipa Bioinspired tyrosine photo-crosslinked gels for the enhanced
P06 Croatia
MATIĆ properties of supramolecular systems
Sinem Selvin
P07 Turkey Halomonas Levan Based Hydrogels
SELVI
SINEM Layer-by-Layer Modification of Surfaces Using Zwitterionic Block

P08 Turkey
ULUSAN Copolymer Micelles for Preparation of Anti-adhesive Coatings
Mohamed-Zine
Removal of directs dyes from textile wastewater
P09 MESSAOUD- Algeria
by coton fiber waste
BOUREGHDA
Nathalie Amphiphilic covalent hybrid hydrogels from PEG/PLA-based

P10 France
MIGNARD thermoreversible networks.
Changoon
P11 South Korea DNA Supercoiling Inspired Fiber Conductors
CHOI
Selen Design and Synthesis of Novel pH-sensitive Fluorescence Polymer

P12 Bulgaria
ISMAIL Structures For Biomedical Applications
Stéphane Double-oriented micrometric surface texturing: a way to antifogging

P13 France
VALETTE through filmwise condensation
Guilherme K.
P14 Brazil Surface Modification of 3D-Printed PBAT by Ultraviolet Radiation
BELMONTE
49
POSTER SESSION
Stefan
P15 Germany Bioinspired hairy surfaces
MÜLLERS
Pinar
Synthesis and characterization of molecularly imprinted polymers
P16 CAKIR Turkey
for solid phase extraction of quercetin
HATIR
Gabriela
Polypyrene films and their potential applications: superhydrophobic,
P17 RAMOS France
fluorescent, anti-bacterial and pH-sensitive coatings
CHAGAS
ENERGY
Kadda The influence of the heating on the nanostructure of the ZnO and
P01 Benmokhtar Algeria the characterization by spectroscopy (AES, XPS, UPS) detecting a
BENSASSI gas
Hyeonmyeong
P02 South Korea Electrochemical Oxidation of Biomass for Solar Fuel Production
OH
Aleksandr Cathode materials for high-energy lithium electrochemical systems

P03 Russia
TSVETNIKOV based on fluorinated wood and lignin
Discounted Cash Flow (DCF) valuation for an assessment of

Jonni Guiller
P04 Brazil strategic investments in a hydrogen production and distribution
MADEIRA
center
Said Natural thermal-insulation materials composed of renewable

P05 Morocco
SABIR resources: characterization of local date palm fibers (LDPF)
Lauri Effect of pH and Oxidant on the First Steps of Polydopamine

P06 Finland
MARTTILA Formation: A Thermodynamic Approach
You
Techno-economic evaluation of solar fuels production system using
P07 CHANHEE South Korea
CO2 hydrogenation with a fibrous Cu/Zn/Al/Zr catalyst
Jiseon United
P08 Study of custom-made ceramic membranes for microbial fuel cells
YOU Kingdom
3D
Edina
P01 Turkey 3D Printed Levan Scaffolds for Cardiac Regeneration
EMINAGIC
50
POSTER SESSION
2D3D
Hui Xian Towards a better understanding of nature inspired Aquaporin

P01 Singapore
GAN biomimetic membrane
Ville Heat-induced reversible stiffening and liquid crystallinity in cellulose

P02 Finland
HYNNINEN composite hydrogels
Valérie Ruthenium complex-DNA conjugates and their linear and 2D-

P03 France
SARTOR nanoassemblies
Mercedes
P04 Germany Capillary nanostamping with spongy mesoporous silica stamps
SCHMIDT
3D Polymer Gels as Matrices of Solid-phase Sensors

Tatiana
P05 Russia for the Determination of Neuromediators: Catecholamines
SHEKHOVTSOVA
and Their Metabolites
Amel DFT studies on vibrational spectra, HOMO-LUMO and NBO of

P06 Algeria
BOUTASTA Tetrodoxine
PLASMAT
Structural, electronic, optical, elastic, mechanical and

Moufdi
P01 Algeria thermodynamic properties of zincblende III-X ( X= As, Sb): ab-initio
HADJAB
calculations
Yu-Qing
P02 China Laser-structured Janus wire mesh for efficient oil-water separation
LIU
Irina Plasma activated water - a new and effective alternative for

P03 Romania
ROSCA duodenoscope reprocessing
Elena-Laura Carbon dimers enrichment in excimer laser generated graphite

P04 Romania
URSU plasma
51

PLENARY ABSTRACTS
52
PL01
Soft metamaterials: Self-gauged assembly, non-equilibrium

matters, and 3D super-resolution imaging
Xiang Zhang
University of California, Berkeley, USA
Metamaterials are artificial composite structures that lead to many exciting applications
beyond nature such as imaging objects below the diffraction limit, optical clocking, sensing
and communications. Traditional metamaterials are considered as “hard” materials that
structural units cannot be tailored after their formation which limits their material responses
and applications. It remains a critical and unsolved problem to design “soft metamaterials”
that can spontaneously self-adapt to changes in the source wavelength or the environment.
We explore “soft metamaterials” with building blocks that have a strong propensity for self-
assembly/re-assembly. In this regards, the structure units can be artificially evolving during
the formation of soft metamaterials. Particularly, we explore the self-feedback mechanism
between structures and properties for self-selective assembly of complex metamaterial
nanoarchitectures with tailored symmetries. We expand structural design using soft
metamaterial approach to achieve isotropic negative index metamaterials and Brownian
optical imaging. We also explore approach for realizing bandgap materials that reside far from
equilibrium and emerge enslaved to an external drive. Experimental results are providing
supports as well as new insights into such new type of soft metamaterials that facilitate self-
responsive material applications.
53
PL02
Mimicking spleen organ in vitro

1 1 1 1,2,3
L. G. Rigat-Brugarolas , A. Homs-Corbera , M. J. Lopez , J. Samitier *

1
Nanobioengineering group, Institute for Bioengineering of Catalonia (IBEC) Barcelona Institute of
Science and Technology (BIST), 12 Baldiri Reixac 15-21, Barcelona 08028, Spain
2 Centro de Investigación Biomédica en Red en Bioingeniería, Biomateriales y Nanomedicina
(CIBER-BBN), Monforte de Lemos 3-5. Pabellón 11, 28029 Madrid, Spain
3 Department of Electronics and Biomedical engineering, University of Barcelona,

Keywords: Organ on a chip, microfluidics, nanomedicine
The spleen is a secondary lymphoid organ specialized in the filtration of senescent, damaged, or
infected red blood cells, facilitating the recognition and posterior destruction of unhealthy Red Blood
Cells by specialized macrophages.
Through a complex organizational architecture, the spleen is perfectly adapted to selectively filter and
eliminate senescent Red Blood Cells as well as blood-borne infectious organisms. Such complex
architecture includes the splenic white pulp, red pulp, and the marginal zone. The filtering capacity of
the spleen is inherently linked to the complex vasculature of the organ, controlling events such as
blood passage through the reticular meshwork of the red pulp; entry into the marginal sinuses or the
marginal zone; drainage through perimarginal cavernous sinuses or capillary branches; or entry into
the white pulp.
With the aim of studying RBCs filtration in the spleen, here it is presented a multilayered
microengineered device of the human splenon-on-a-chip. With this device, engineered to mimic the
splenic closed-fast and open-slow microcirculations, the reticular meshwork and the Interendothelial
slits filtering capacity, hopefully it would be possible to advance in the knowledge of the spleen’s
function in malaria and other haematological disorders.
Moreover, another goal is to demonstrate the practicality of the platform for both structure-function
studies. Some 3D culture models fail to reconstitute features of living organs that are crucial for their
function, such as blood–tissue interfaces. In this regard, the proposed system takes advantage of co-
flow phenomena, in order to properly coat and culture the different sections of the device, when
needed, with splenic human cells.
To complete the system, it is introduced an autonomous closed-loop pumping machinery, connected

to the splenon-on-a-chip to simulate human blood flowing with physiological conditions.
54
PL03
From Biomimetics to Biological Inspiration:

Path to Discovery Beyond What Nature Offers

Valentine I. VULLEV

Departments of Bioengineering, Chemistry and Biochemistry, and
Materials Science and Engineering Program, University of California, Riverside, CA 92521, USA

Keywords: biomimicry, biomimesis, bioinspiration, electrets, charge transfer
Life on Earth offers an amazing diversity of paradigms and lessons that have withstood the test of time
for 3.8 billion years of evolution. Biomimetic and bioinspired approaches, therefore, are profoundly
important for advancing science and engineering [1]. While the terms “biomimetic” and “bioinspired”
appear interchangeable, they carry different denotations and truly different connotations, and as such,
their implications for science and engineering also differ. Biomimicry involves sheer imitation of
biological systems where resemblance of structural feature does not necessarily ensure attainment of
functionality [1,2]. Biomimesis takes the process of mimicking biology to the next level. In addition to
perfecting the structural imitations, biomimesis also aims at attaining functionalities comparable to
those of the natural systems [1,2]. Bioinspiraton goes beyond what nature offers, by taking concepts
found in biology and employing them in manners optimal for the targeted applications without
necessarily resembling the living systems [1,2]. As such, biomimetics (encompassing biomimicry and
biomimesis) takes the first steps toward taking lessons from Nature. Mimicking Nature with the aim to
attain functionality based on structural resemblance of biology is invaluable for testing our knowledge
of how living systems work [1]. Biomimentics, therefore, proves crucial for basic science. Conversely,
bioinspiration provides paths for taking biomimetic advances to applied science and engineering.
Bioinspiration can also reveal the emergence of new properties leading to unprecedented scientific
discoveries. The development of charge-transfer (CT) molecular electrets illustrates perfectly the
evolution from biomimicry, through biomimesis, to bioinspiration [1]. (Electrets are systems with
ordered electric dipoles, i.e., they are the electrostatic analogues of magnets.) Electric dipoles are
everywhere, and the importance of understanding how they affect chemical, physical and biological
processes cannot be overstated. CT is essential for sustaining life and for making energy conversion
possible. Molecular dipoles present important, but underutilized, paradigms for guiding CT processes.
Protein helices are the best-known molecular electrets with immensely large macrodipoles. Using
synthetic biomimetic polypeptide helices to guide long-range electron transfer (ET) has proven the
feasibility of the idea for using molecular dipoles for guiding CT. Polypeptides, however, mediate ET
via tunneling with limited efficiency to about 2 nm, rendering such biological and biomimetic helices
impractical for electronic applications. Therefore, we develop bioinspired molecular electrets that like
the protein helices possess enormous macrodipoles, but unlike the biological and biomimetic
polypeptides, the bioinspired electrets can efficiently mediate long-range CT via electron or hole
hopping [3-6]. In addition to their promise for electronic applications, the bioinspired molecular
electrets reveal the emergence of new properties, such as the synergy between electronic-coupling
and the Franck-Condon contribution to ET kinetics [4]. The bioinspired electrets provide the first
evidence that molecular dipoles can profoundly affect the donor-acceptor electronic coupling and the
ET rates. These discoveries illustrate how the evolution from biomimetics to biological inspiration can
profoundly impact science and engineering.
[1]. V. I. Vullev, J. Phys. Chem. Lett. 2011, 2, 503-508.

[2]. E. M. Espinoza, et al., Pure Appl. Chem. 2017, 89, 1777-1797.
[3]. B. Xia, et al., J. Org. Chem. 2013, 78, 1994-2004.
[4]. D. Bao, et al., J. Am. Chem. Soc. 2014, 136, 12966-12973.
[5]. E. M. Espinoza, et al., J. Phys. Chem. Lett. 2016, 7, 758-764.
[6]. J. M. Larsen-Clinton, et al., Phys. Chem. Chem. Phys. 2017, 19, 7871-7876.
55
PL04
Minerals and Crystals in Biology: Inspirations for New Materials
Steve WEINER and Lia ADDADI
Department of Structural Biology, Weizmann Institute of Science, Rehovot, Israel
Keywords: biomaterials, biomineralization, precursor phases, guanine crystals
Organisms produce many minerals and crystals, but the choice of minerals is based on their
evolutionary history. As organisms need to constantly adapt to a changing environment, they also
need to adapt the minerals they form, and this leads to interesting solutions to challenging problems.
One “unconventional” approach adopted by many different invertebrate taxa as well as vertebrates
that produce mineralized materials, is to first form a highly disordered precursor phase inside vesicles
within cells, and then to extrude these minerals into the extracellular space and induce them to
crystallize to greater or lesser extents. In fact control over the extent of atomic disorder is the hallmark
of many biogenic minerals. We have developed a valuable and relatively simple technique for
assessing atomic disorder using infrared spectrometry. Bone mineral is also formed via a disordered
precursor mineral phase, and the pathway of mineral formation in bone is relatively well documented.
A variety of organisms produce minerals for light manipulation. The most commonly documented
example is the organic crystal guanine. Guanine has an unusually high refractive index in one
direction and this is exploited by organisms for producing structural colors, including both the silvery
iridescence of fish scales, and the bright colors in various marine copepods. The latter can be tuned
to the local environment in which they live. Guanine crystals are also used in vision, such as in the
eyes of scallops where they produce a back reflecting mirror for focusing light. A recently discovered
additional function of guanine crystals is to enhance photosynthesis in the marine protozoans called
dinoflagellates by the back scattering of light.
Many of the minerals and crystals produced by organisms have shapes and mechanical properties
that are adapted to their functions. Some of the mechanisms used for their formation and function
may well be applicable to synthetic materials.
56
KEYNOTE ABSTRACTS
57
BIOTECH-KN02
Artificial Spores: Chemical Sporulation and Germination

Insung S. CHOI*
Center for Cell-Encapsulation Research, Department of Chemistry, KAIST, Daejeon 34141, Korea
Keywords: Artificial Spores, Cell-in-Shell Structures, Micrometric Iron Men
Nature has developed a fascinating strategy of cryptobiosis for counteracting the stressful, and often
lethal, environmental conditions that fluctuate sporadically over time. For example, certain bacteria
sporulate to transform from a metabolically active, vegetative state to an ametabolic endospore state.
The bacterial endospores, encased within tough biomolecular shells, withstand the extremes of
harmful stressors, such as radiation, desiccation, and malnutrition, for extended periods of time and
return to a vegetative state by breaking their protective shells apart when their environment becomes
hospitable for living. Inspired by cryptobiosis in nature, researchers have sought to chemically control
and tailor the metabolic behaviors of non-spore-forming cells as well as enhancing their viability
against adverse environmental conditions, by forming thin (< 100 nm), tough artificial shells. These
living “cell-in-shell” structures, called artificial spores, enable chemical control of cell division,
protection against physical and chemical stresses, and cell-surface functionalizability, armed with
exogenous properties that are not innate to the cells but are introduced chemically. The field has
further advanced to the stage of chemical sporulation and germination, where cytoprotective shells
are formed on living cells and broken apart on demand. The (degradable) cell-in-shell hybrids are
anticipated to find their applications in various biomedical and bionanotechnological areas, such as
cytotherapeutics, high-throughput screening, sensors, and biocatalysis, as well as providing a
versatile research platform for single-cell biology. In this sense, the artificial spore can be considered
[1]
as a micrometric Iron Man: what is important is not the shell but the cell inside the shell.
[1]. J. H. Park, D. Hong, J. Lee, I. S Choi, Acc. Chem. Res. 2016, 49, 792-800.
58
BIOTECH-KN03
Engineering Bio-based Composites for Intelligent and Functional

Applications

1
Ilker S. BAYER
1
Smart Materials, Istituto Italiano di Tecnologia, Genova, 16163, Italy.
Keywords: all-green biocomposites, graphene, flexible electronics, cellulose
Biopolymers can be obtained either from petroleum resources or from different forms of biomass.
Recently, production of biopolymers have been categorized as materials from “bio-replacement”
approach, in which synthetic biology and catalysis are combined to obtain petrochemical monomers
from sugars and lignocellulosic feedstocks that can be polymerized into a number of common plastics;
such as metabolic engineering of bacteria as a viable route to monomers like butadiene, isoprene,
styrene, acrylic acid, etc. The other approach is referred to as the “bio-advantage” strategy, where an
abundant number of naturally available multifunctional “monomers” are transformed into new polymers
or bio-composites. The bio-advantaged approach may be more cost-effective than the bio-
replacement processes as many plants produce pre-polymeric or polymeric materials that require little
or no post modification to extract and make use of these compounds.
In this presentation, we will demonstrate fabrication and characterization of real or “all green”
functional bio-composites produced by both approaches and present novel applications ranging from
biodegradable GHz antennas to flexible electrodes for electromyography. As such our aim is to offer
alternative green substitutes to address electronic waste, or commonly referred to as e-waste. As a
first example, functional bio-composites produced via a simple bio-replacement strategy are discussed
first. Light weight all cellulose based conductive bio-composites with graphene nanoplatelets were
fabricated. The bio-composites demonstrated remarkable THz EMI shielding capabilities. Due to their
low sheet resistance, they functioned as efficient as expensive and bulky titanium electrodes for
electromyography signal acquisition. In comparison to conductive paper, these bio-composites feature
isotropic bulk conductivity and resist dissolution in water due to cellulose acetate. Moreover, they
demonstrate remarkable robust mechanical resistance against severe (weight pressed) folding
unfolding cycles as well as wear abrasion under 20 kPa. Due to their light weight, biodegradability,
flexibility but at the same time mechanical robustness and quasi metal conductivity levels, these bio-
composites can be used in many diverse technological applications ranging from wearable
electronics, electro-diagnostic medicine, aerospace and security.
As the bio-advantaged approach, we investigated electrical performance and electronic
applications of flexible biodegrading conductors produced by dispersing graphene nano-platelets
(GnPs) in a zein-polyaleuritate (both plant extracts) matrix that is embedded in a cellulose fiber
support. The cellulose fiber support ensures that the resulting biomaterial is flexible and mechanically
stable under severe folding and twisting conditions. Zein, aleuritic acid and GnPs were dispersed in
an organic solvent and the resulting ink was spray coated on both sides of a pure cellulose
membrane. The coated membrane was hot-pressed at temperatures sufficient to polymerize aleuritic
acid in situ resulting in a flexible composite. We also show that in situ formed polyaleuritate binds zein
with the cellulose, mimicking the composite plant cell wall composition (protein, polysaccharides and
hydroxyl fatty acids) and the bio-composites fully biodegrade in sea waters under dark. Various high
performance electronic applications of these folding and twisting resistant green conductors were
demonstrated such as sub-millimeter (microwave) electromagnetic interference (EMI; 500-750 GHz)
shielding, efficient GHz antennas adaptable to Wi-Fi applications and flexible electrode for organic
photovoltaics.
59
BIOTECH-KN04
Cationic substitutions in calcium phosphate bioceramics: toward

mimicking natural bone and beyond

1 1 1 1 1,2 1
A Jacobs , G. Renaudin , S. Gomes , C. Vichery , S. Descamps , J.-M. Nedelec*
1
Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand,
F-63000 Clermont-Ferrand, France
2
CHU Clermont-Ferrand, Clermont-Ferrand, France
Keywords: bioceramics, calcium phosphates, bone substitutes, multifunctional materials
Introduction
Human allograft is by far the best solution for repairing and reconstructing human skeleton. Upon
trauma or as a consequence of a disease, clinical situations where the surgeon needs bone defect
filling materials are very frequent. In many cases neither autograft nor allograft is possible and the
surgeon has to use synthetic bone filling materials, either because the volume to be filled is too
important or the co-morbidity an issue. Among all potential materials, calcium phosphate bioceramics
are the most interesting and commonly used materials due to their osteointegrative and osteoinductive
properties.
Results and Discussion

Beyond these remarkable properties, it is highly desirable to bring multifunctionality to the bioceramic.
Chemical doping though ionic substitution is a very efficient and convenient way to do it. In this
lecture, we will focus on cationic substitution in hydroxyapatite and tricalcium phosphate. We will try to
demonstrate how fine knowledge of crystallo-chemistry taking place in these materials is necessary to
fully understand the material behaviour. Using the example of zinc, iron and copper doping in biphasic
1,2
calcium phosphates , we will show that unsuspected doping mechanisms can be put forward. In this
example, bioceramics with anti-inflammatory property can then be produced with a fine-tuning of the
3
material. Other examples concerning materials with luminescent properties for diagnostic ,
antibacterial activity, anti-osteoporosis property and others will be presented.
3+ 2
Fig. 1: Insertion scheme of Fe ion in Hydroxyapatite
Conclusion
The take home message of this lecture is that upon thorough knowledge of materials chemistry taking
place upon doping, it is now possible to reach on demand design of multifunctional biomaterials with
improved properties.
References.
[1] S. Gomes, C. Vichery, S. Descamps, H. Martinez, A. Kaur, A. Jacobs, J.-M. Nedelec, G. Renaudin
Acta Biomaterialia 65, (2018) 462-474
[2] S. Gomes, A. Kaur, J.-M. Greneche, J.-M. Nedelec, G. Renaudin, Acta Biomaterialia 2017, 50, 78-
88
[3] P. Sobierajska, R. Pazik, K. Zawisza, G. Renaudin, J.-M.Nedelec, R. Wiglusz, Cryst. Eng. Comm,
2016, 18, 3447-3455.
60
BIOTECH-KN05
Development of a Glycocalyx Mimetic

1 1,2,3 1 2 2
Alyssa Panitch , James Wodicka , Vasilios Morikis , Andrea Chambers , Gurneet Sangha , Craig
2 1
Goergen , Scott Simon
1
University of California, Davis, USA;
2
Purdue University, West Lafayette, USA
Keywords: glycosaminoglycan, selectin, endothelial dysfunction,

Introduction: Endothelial cell (EC) dysfunction is associated with many cardiovascular diseases
including atherosclerosis, thrombosis, and sepsis. Loss of the glycocalyx is a key feature of EC
dysfunction and increases exposure of adhesion molecules such as E- and P-selectin, which initiate
binding of platelets and leukocytes to the ECs. Bound platelets and leukocytes can cause thrombosis
and increased inflammation. Current treatments for EC dysfunction remain limited. Therefore, a
glycocalyx mimetic (EC-SEAL), consisting of a dermatan sulfate (DS) backbone and multiple selectin-
binding peptides was developed to bind to inflamed ECs and prevent platelet/leukocyte binding. EC-
SEAL inhibited platelet binding and activation in a dose-dependent manner and reduced thrombus
formation in a murine model of deep vein thrombosis. EC-SEAL also reduced leukocyte interactions
on both E- and P-selectin substrates, and inflamed ECs, under physiologically relevant shear stress.
Methods: DS was oxidized using sodium meta-periodate. Oxidized DS was reacted with N-[β-
maleimidopropionic acid] hydrazide, trifluoroacetic acid salt, to which the selectin-binding peptide,
IELLQARGC, was conjugated. Human microvascular endothelial cells (HMVEC) were activated with
2.5 ng/ml TNFα and 2.5 ng/ml IL-1β. They were then used untreated or treated with EC-SEAL. For
platelet activation, fresh human platelets were seeded on the surfaces for one hour. The media was
then examined for neutrophil activating peptide-2 and platelet factor-4. To assess neutrophil-
1,2
endothelial interactions, HMVECs were seeded on microfluidic devices, and treated with EC-SEAL
3
or GMI-1070, a small molecule selectin inhibitor. Human neutrophils were pumped at physiological
shear rates across the ECs. Phase contrast images of neutrophils interacting with the substrate were
taken in the middle of each channel every 3 seconds for 10 minutes. Rolling velocities, percentage of
rolling neutrophils transitioning to arrest, and
subsequent migration were calculated. A murine
model of deep vein thrombosis consisting of a 90%
ligation of the inferior vena cava (IVC) to create a
region of disrupted flow and thrombus formation
were treated with heparin, saline or EC-SEAL
immediately following ligation. 6-hour ultrasound
images were taken to asses thrombus formation
and size.
Results: EC-SEAL bound preferentially to
inflamed ECs, primarily through interactions with
E- and P-selectin. EC-SEAL suppressed platelet
binding and activation on inflamed endothelium by
Figure 1. Neutrophil transition from rolling to 80% as compared to controls. Regarding
arrest on HMVECs. neutrophils, Figure 1 shows data obtained from
activated fresh human neutrophils flowing across
inflamed HMVEC treated with PBS, EC-SEAL or GMI-1070. With respect to both neutrophil arrest and
migration, (a measure of neutrophil diapedesis), EC-SEAL significantly decreased both arrest and
migration as compared to untreated controls (p<0.05) and was equivalent to the inhibition seen using
GMI-1070. In vivo data suggests that EC-SEAL suppresses thrombus formation by acting locally at
4
the vascular wall, and is equivalent to the antithrombotic effects of systemic heparin.
Conclusions: EC-SEAL is a promising therapeutic for treatment of endothelial dysfunction. It
can be delivered systemically and act locally to inhibit thrombosis and inflammation.
References: [1] Schaff UY. Lab Chip 2007;7:448-56. [2] Gower RM. SWorld Scientific Publishing
Co Pte Ltd; 2010:313-29. [3] Chang J. Blood 2010;116:1779-86. [4] Wodicka JR. Pharmaceuticals
(Basel) 2017;10.
61
BIOTECH-KN06
Biofabrication with bioinks made of rekombinant spider silk
Thomas Scheibel
Lehrstuhl Biomaterialien, Universitätsstraße 30, Universität Bayreuth, Bayreuth D-95447, Germany
Keywords: spider silk, hydrogels, 3D-printing, biofabrication
Biological materials often exceed the characteristics and properties of man-made ones. One well-
known example is spider silk with superior mechanical properties such as strength and toughness,
another one is collagen with excellent biocompatibility. Here, recombinant spider silk proteins will be
introduced as one material to be used in bioinks for biofabrication.
Proteins reflect one fascinating class of natural polymers with huge potential for technical as well as
biomedical applications. We have developed biotechnological methods using bacteria as production
hosts which produce structural proteins mimicking the natural ones [1]. Besides the recombinant
protein fabrication, we analyzed the natural assembly processes [2; 3] and we have developed
spinning techniques to produce protein threads closely resembling natural fibers. In addition to fibers,
we employ structural proteins in other application forms such as hydrogels, particles or films with
tailored properties [4]. Especially hydrogels can be employed as new bioinks for biofabrication [5; 6].
Their elastic behavior dominate over the viscous behavior over the whole angular frequency range
with a low viscosity flow behavior and good form stability. No structural changes occur during the
printing process, and the hydrogels solidify immediately after printing by robotic dispensing. Due to the
form stability it is possible to directly print multiple layers on top of each other without structural
collapse. Cell-loaded spider silk constructs can be easily printed without the need of additional cross-
linkers or thickeners for mechanical stabilization. Encapsulated cells show good viability in such spider
silk hydrogels.
[1]. Vendrely C. & Scheibel T. Macromol. Biosci. 2007, 7, 401-409

[2]. Heim, M. et al. Angew. Chem. Int. Ed 2009, 48, 3584-3596
[3]. Hagn F. et al. Nature 2010, 465, 239-242
[4]. Hardy J. & Scheibel T. Polymer 2008, 49, 4309-4327
[5]. Schacht K., et al. Angew. Chem. Int. Ed. 2015, 54, 2816-2820
[6]. DeSimone, E., et al Biofabrication 2017, 9, 044104

62
BIOTECH-KN08
Engineering of bionanomaterials and biointerfaces: design,

properties and applications
1
Mikhael BECHELANY *
1
Institut Européen des Membranes, IEM – UMR 5635, ENSCM, CNRS, Univ Montpellier, Montpellier,
France
Keywords: Atomic Layer Deposition, Electrospinning, 3D printing, Graphene, bionanocomposites,

tissue engineering, drug delivery, biosensing, biofuel cells, DNA sensing
Nanostructure science and technology are a broad and interdisciplinary area of research and
development that has been exponentially growing in the past few years. Engineered nanomaterials
are resources designed at the molecular (nanometer) scale to take advantage of their small size and
novel properties which are generally not seen in their conventional bulk counterparts. The two main
reasons why nanomaterials can have different properties are: (i) the increase of relative surface area
and (ii) the quantum confinement effects leading to novel optical, electrical and magnetic behaviors. In
order to apply these nanomaterials in biofields and to increase the throughput of biobased
nanostructured materials and devices for energy, environmental and health applications, an efficient
immobilization of the biomolecules is needed by the control of the interfaces between the
nanostructures and the immobilized biomaterials.
Here, we used different synthesis techniques such as atomic layer deposition (ALD),[1]
electrospinning, 3D printing and the exfoliation of Graphene and BN like Graphene etc. as the main
tools for the creation of controlled nanostructured materials and interfaces in which the geometry can
be tuned accurately and the dependence of the physical-chemical properties on the geometric
parameters can be studied systematically in order to investigate their performances in energy,
environmental and health applications. We will show examples of how these methods can be used to
create biofuel cells, [2] single nanopores for sensing, membrane for gas purification, osmotic energy
harvesting [3] and water treatment, optical sensors and biosensors [4], and bionanocomposites
materials for packaging, drug delivery and tissue engineering[5] in which the performance varies with
the nanostructures/interfaces.
Fig. 1: Design of bionanomaterials for energy, environmental and health applications
[1]. C. Marichy, M. Bechelany, N. Pinna, Advanced Materials, 2012, 24, 1017

[2]. T. X. H. Le, R. Esmilaire, M. Drobek, M. Bechelany, C. Vallicari, D. L. Nguyen, A. Julbe, S. Tingry,
M. Cretin Journal of Materials Chemistry A, 2016, 4, 17686-17693
[3]. M. Weber, B. Koonkaew, S. Balme, I. Utke, F. Picaud, I. Iatsunskyi, E. Coy, P. Miele, M.
Bechelany, ACS Appl. Mater. Interfaces, 2017, 9, 16669–16678
[4]. A. Tereshchenko, V. Fedorenko, V. Smyntyna, I. Konup, A. Konup, M. Eriksson, R. Yakimova, A.
Ramanavicius, S. Balme, M. Bechelany, Biosensors and Bioelectronics, 2017, 92, 763–769
[5]. S. Nagarajan, H. Belaid, C. Céline Pochat-Bohatier, C. Teyssier, I. Iatsunskyi, E. Coy, S. Balme,
D. Cornu, P. Miele, N. S. Kalkura, V. Cavaillès, M. Bechelany, ACS Appl. Mater. Interfaces, 2017,
9, 33695-33706
63
BIOTECH-KN10
Thermosets from Highly Functionalized Bio-Based Resins

1 1 1 1 1
Dean WEBSTER,* Songqi MA, Arvin YU, Eric KRALL, Adlina PARAMARTA

1
Coatings and Polymeric Materials, North Dakota State University, Fargo, North Dakota, USA;
A challenge faced with transitioning from polymer materials derived from petrochemical sources to bio-
based sources is in designing materials having the performance properties required for today’s
applications. High performance thermoset polymers are used in applications such as coatings,
composites, and adhesives and are made in-situ from the crosslinking reactions of functional low
molecular weight resins or functional oligomers. While vegetable oils are a readily available and
amenable to functionalization to be used in thermosets, their long aliphatic hydrocarbon chains tend to
result in materials that are soft and flexible. However, we have found that by creating multifunctional
resins from vegetable oil fatty acids and a highly functional polyol, thermosets can be formed that have
the strength and stiffness for use in high performance coatings and composites. For example,
epoxidized sucrose esters of vegetable oil fatty acids, such as epoxidized sucrose soyate (ESS,
Figure 1) crosslinked with cyclic anhydrides yield thermosets having high modulus, solvent resistance,
and hardness. Methacrylated epoxidized sucrose esters can be used to form high performance resins
that can be cured with free radicals and used in composites using either glass or natural fibers. It has
also been discovered that 100% bio-based thermosets can be made from the water-catalyzed
crosslinking of epoxidized sucrose soyate with naturally-occurring acids such as citric or tartaric acids.
Conversion of the epoxy groups into cyclic carbonate groups leads to highly functional resins that can
be cured using multifunctional amines to yield polyurethanes without using isocyanates. Methacrylated
and acrylated resins can also be cured with multifunctional amines via the Michael reaction. In all of
these examples, the thermosets formed have properties far superior to their triglyceride oil
counterparts and equivalent or superior to current petrochemical resins. This approach is also applied
to lignin, where a green process for direct functionalization of lignin has been discovered. Thermosets
from functionalized lignin can be made which are strong and tough.
Figure 1. Structure of epoxidized sucrose soyate (ESS)

64
BIOTECH-KN10
Biosourced polysaccharide nanocrystals to template hybrid

materials

1,2 1 2 3
Emmanuel BELAMIE *, Bruno ALONSO , Laura CARDOSO, Krassimir KOSTOV, Alexander
1
SACHSE

1
ICGM-MACS (CNRS-UM-ENSCM), Montpellier France
2
EPHE – PSL Research University, Paris, France
3
Bulgarian Academy of Science, Sofia, Bulgaria

Keywords: polysaccharide nanocrystals, chitin, sol-gel, hybrid, mesoporous, catalysis
Chitin crystalline nanorods are found in many natural nanocomposites associated with an inorganic
phase like CaCO3 in crustaceans and silica in the skeleton of glass sponges. Such organic-inorganic
association at the nanoscale in physiological conditions served as an inspiration for new materials
synthesis routes compliant with green chemistry principles. In addition, polysaccharide nanocrystals
are renewable organic precursors readily prepared from industrial waste biomass. A new family of
hybrid organic-inorganic nano-composites has been synthesized based on a versatile colloid-based
approach, which allows for a high level of control over materials texture and morphology [1].
This approach combines the self-assembly properties of polysaccharide α-chitin nanorods (bundles of
monocrystals (D = 3.2 ± 0.6 nm) [2] with the flexibility of sol-gel processes involving siloxane
oligomers. The formation of hybrid colloidal species was assessed by a combination of spectroscopy
(NMR, XPS), diffusion techniques (SAXS, DLS), rheology, and visualized by TEM (Figure 1). The
hybrid suspensions undergo an isotropic / nematic transition in ethanol at concentrations beyond ca.
2%. The ordered phase is highly responsive to the application of external fields (shearing, electric,
magnetic) and the suspensions' 3D organization can be transferred to the solids by solvent
evaporation across the sol-gel transition [2].
Hybrid materials can be obtained by sol-gel processing into microparticles by spray-drying, fibers by
electro-spinning and thin films by spin-coating. The characteristics of the silica-chitin nano-composites
can be transferred to their mesoporous counterpart by simple calcination [1,2]. The porous materials
2 -1
have pore diameters in the 5-20 nm range and specific surface areas up to 500 m .g . For
heterogeneous catalysis applications (selective oxidation), titanium alkoxides have been introduced to
form mixed oxides SiO2-TiO2. The dispersion of Ti sites can be tuned through synthesis conditions [3].
Fig. 1: Colloidal assembly of polysaccharide nanocrystals and inorganic precursors and sol-
gel materials processing
[1]. B. Alonso and E. Belamie, Angew. Chem. Int. Ed. 2010, 49, 8201-8204.
[2]. E. Belamie, M. Y. Boltoeva, K. Yang, T. Cacciaguerra and B. Alonso, J. Mater. Chem. 2011, 21,
16997-17006.
[3]. A. Sachse, V. Hulea, K.L. Kostov, E. Belamie and B. Alonso, Catal. Sci. Technol. 2015, 5, 415-
427.
65
BIOTECH-KN11
Bio-inspired polymer materials:

from the monomer chemical nature to hierarchically structured
functional films
Laurent BILLON
Université de Pau & Pays Adour UPPA, IPREM CNRS UMR 5254
Bio-inspired Materials Group: Functionalities & Self-assembly
Hélioparc, 2 avenue Angot, 64053 Pau Cedex 09, France
The present talk aims at designing bio-inspired polymer materials by chemical natures, structures and
architectures of the living as a source of innovation and engineering. The combination of these
inspiration sources can lead to functional building blocks and then materials by directed self-assembly.
New (meth)acrylic monomers with 100% bio-based carbons and their controlled polymerizations will
1, 2
be described for the elaboration of thermoplastic and elastomeric block copolymers.
The intimately association between natural “Breath Figure”, as a bottom-up solvent evaporation
process and the self-assembly of a building blocks panel based on soft matter will be also discussed.
3
Hierarchically structured honeycomb films, as porous surface , from well-defined macromolecular
4
structures will be first described for a number of applications including iridescence , bioactivity & cells
5 5-6 7
adhesion , CO2/pH-responsive reversible wettability , photocatalysis or for light extraction in an
8
Organic Light Emitting Diode .
2
Then, photonic crystals over 100 cm elaborated by extrusion or pressure casting processes from
9
latexes or from water-based microgels building blocks will be shown. Finally, a fully bio-sourced
formulation mimicking nacre will be demonstrated as an efficient flame retardant coating for ligno-
10
cellulosic building insulation materials for a sustainable transition.
REFERENCES
[1] S. Noppalit, J. Asua, L. Billon, to be submitted, 2018.
,
[2] F. Dergal, A. Khoukh, I. Chikhi, D. Lerrari, K. Bachari, L. Billon, to be submitted 2018.
[3] a) A. Munoz-Bonilla, M. Save, L. Billon, J. Rodriguez-Hernandez Polymer Surfaces in Motion:
Unconventional Patterning Methods, Ed. Springer USA, 2015, Chapter 10, p 219-256. b) P.
Escalé, M. Save, L. Billon, J. Ruokolainen, L. Rubatat Soft Matter 2016, 12, 790-797. c) A.
Bertrand, A. Bousquet, C. Dagron-Lartigau, L. Billon Chem Comm, 2016, 52, 9562-9565. d) E. Ji,
V. Pellerin, F. Ehrenfeld, A. Laffore, A. Bousquet, L. Billon Chem Comm, 2017, 53, 1876-1879.
[4] L. Billon, M. Manguian, V. Pellerin, M. Joubert, O. Eterradossi, H. Garay Macromolecules 2009,
42, 345.
[5] a) H. Yin, A.L. Bulteau, Y. Feng, L. Billon Adv. Mat. Interfaces 2016, 3, 1500623. b) H. Yin, Y.
Feng, L. Billon Chem Eur J, 2018, 24, 425-433.
[6] a) P. Escalé, L. Rubatat, C. Derail, M. Save, L. Billon Macro. Rapid. Comm 2011, 32, 1072-1076.
b) P. Escalé, W. Van Camp, F. DuPrez, L. Rubatat, L. Billon, M. Save, Polymer Chemistry, 2013,
4, 4710-4717.
[7] L. Pessoni, S. Lacombe, L. Billon, R. Brown, M. Save Langmuir 2013, 29, 10264−10271.
[8] A. Bertrand, F. Dumur, M. Perrin, M. Mruczkiewicz, C. Dagron-Lartigau, A. Bousquet, L. Vignau,
L. Billon, S. Fasquel, Organic Electronic : Physics, materials, applications, 2018, 52, 222-229.
[9] a) M. Boularas, E. Gombart, J.F. Tranchant, L. Billon, M. Save Macro. Rapid. Comm. 2015, 36,
79−83. b) M. Boularas, E. Deniau-Lejeune, V. Alard, J.F. Tranchant, L. Billon, M. Save Polym
Chem. 2016, 7, 350-363. c) M. Boularas, L. Billon, E. Gombard, M. Save, JF Tranchant
PCT/FR/050009, WO2016110615 A1, 2015 d) G. Aguirre, A. Khoukh, K. Chougrani, V. Alard, L.
Billon Polym. Chem, 2018, DOI: 10.1039/C7PY02111A.
[10] C. Baguenard, G. Labat, L. Billon, Patent FR1660640, 2017.
66
BIOTECH-KN12
Bioinspired BNNS/Gelatin Nanocomposite with Nacre-mimetic

Structure for Bone Substitute Application
1* 2 1
Soon Hyung, Hong, Hojin, Ryu , Sung Chan, Yoo
1
Department of Material Science and Engineering,
Korea Advanced Institute of Science and Technology, Daejeon, Republic of Korea
2
Department of Nuclear and Quantum Engineering,
Korea Advanced Institute of Science and Technology, Daejeon, Republic of Korea
Nacre exhibits surprisingly high mechanical properties with elegant simplicity in structure consisting
of a brick-and-mortar assembly of inorganic and organic constituents. With the recent development in
functional nanomaterials, the bio-inspiration has been considered as a key aspect of the next-
generation material design to simultaneously achieve excellent mechanical properties and functional
properties in the synthetic materials.
BNNS/Gelatin Nanocomposite film consisted of hierarchically aligned layered boron nitride
nanosheets (BNNSs) bonded by gelatin, a biocompatible and biodegradable natural polymer, were
fabricated by a vacuum filtration-assisted self-assembly of BNNSs and gelatin suspension. The
microstructure of the resulting BNNS/gelatin nanocomposite film showed distinct layered alignment of
BNNS bonded by gelatin similar to the brick-and-mortar hierarchical structure found in the natural
nacre. The mechanical properties of the nacre-mimetic BNNS/gelatin nanocomposite film can be
controlled by changing the composition of BNNS in the artificial nacre. The mechanical properties can
be tailored to resemble that of the human cortical bone. The biocompatibility of the BNNS/gelatin
nanocomposite nacre was characterized using adipose-derived mesenchymal stem cell (ADMSCs). In
vitro cell viability experiment revealed that the BNNS/gelatin nanocomposite film supports cell
adhesion, viability, and proliferation, which were enhanced with the increase in the amount of BNNSs
in the nanocomposite paper. These results demonstrate the potential of BNNP-based artificial nacre
material as a new material for tissue regeneration, especially for load bearing tissues and bones.
Keywords: Bioinspired, Boron Nitride Nanosheet, BNNS/Gelatin Nanocomposites, Artificial Nacre,

Mechanical Properties, Cell Viability
Fig. 1: Fabrication processes of bioinspired BNNS/Gelatin nanocomposite
[1]. S.H. Hong et al. Nano letters 2015, 1238-1244.

[2]. B. Lee et al. Scientific reports 2016, 27609
67
BIOTECH-KN13

Bioinspired Inorganic Nanoparticles for Bone Remodeling Control

,1,2
Nathaniel S. Hwang*

1
School of Chemical and Biological Engineering, Seoul National University, Seoul, Republic of Korea;
2
Interdisciplinary Program in Bioengineering, Seoul National University, Seoul, Republic of Korea

Keywords: Inorganic nanoparticle, bone, tissue regeneration, nature inspired
Bone remodeling process relies on complex signaling pathway between osteoblasts and osteoclasts
and control mechanisms to achieve homeostasis of their growth and differentiation. Despite previous
achievements in understanding complicated signaling pathways between cells and bone extracellular
matrices during bone remodeling process, a role of local ionic concentration remains to be elucidated.
Here, we demonstrate that synthetic whitlockite (WH: Ca18Mg2(HPO4)2(PO4)12) nanoparticles can
recapitulate early-stage of bone regeneration through stimulating osteogenic differentiation, prohibiting
osteoclastic activity, and transforming into mechanically enhanced hydroxyapatite (HAP)-neo bone
3- 2+
tissues by continuous supply of PO4 and Mg under physiological conditions. In addition, based on
their structural analysis, the dynamic phase transformation from WH into HAP contributed as a key
factor for rapid bone regeneration with denser hierarchical neo-bone structure. Our findings suggest a
groundbreaking concept of 'living bone minerals' that actively communicate with the surrounding
system to induce self-healing, while previous notions about bone minerals have been limited to
passive products of cellular mineralization.
Fig. 1: Overall effects of nature-inspired synthetic nanoparticles (whitlokcite) on bone

remodeling process [1]
[1]. HD Kim, HL Jang, YH Ahn, HK Lee, J Park, ES Lee, YH Jeong, DG Kim, KT Nam, NS Hwang.
Biomaterials. 2017, 112:31-43
68
BIOTECH-KN14
Dynamic cell-instructive coatings

1,2
Pascal JONKHEIJM,*,

1
MIRA Institute for Biomedical Technology and Technical Medicine, Enschede, Netherlands;
2
MESA+ Institute for Nanotechnology, Enschede, Netherlands

Keywords: supramolecular chemistry, self-assembly, surfaces, biomimetic, cell-surface interactions
Supramolecular chemistry provide nowadays an excellent prospect to construct reversible biological

interfaces that can be employed for supramolecular cell manipulation experiments.[1] Making use of
supramolecular chemistry is rewarding to develop functional materials and devices. Knowing the
limitations involved in ordering proteins at different length scales will surely hasten developing future
applications, supramolecular bionanotechnology being the most prominent. The construction of
synthetic supramolecular assemblies of proteins provides an excellent tool to fabricate organized
bioactive components at surfaces. I will present new synthetic procedures for site-specific noncovalent
anchoring of proteins to surfaces and polymers.[2, 3] Special attention is paid to orientational and
conformational aspects at the surface and will be demonstrated. Using concepts of multivalency the
interactions between proteins and surfaces can be modulated by design. Many of the protein
complexes were patterned on surfaces using microcontact printing or nanolithography and visualized
using fluorescence microscopy. Furthermore, supramolecular linkers that are sensitive to remote
electrochemical stimuli will be presented, using cucurbituril (CB) and cyclodextrin (CD)-modified
surfaces.[2, 4] Electrochemical switching was studied using surface embedded electrodes.[4] Cell
release was studied in detail in the case of cell-adhesive peptides and growth factors. Lastly,
supramolecular linkers were compared to reversible covalent linkers, providing insight in the cell
receptor signaling pathway.[5] With the development of reversible bioactive platforms on surfaces
serving as a reversible dynamic interfaces to cells, improved scaffolds for tissue regeneration will
become in hand. First steps into this directions will be introduced as well.
Fig. 1: Supramolecular platform for cell adhesion employing host-guest chemistry suitable for
electro-responsive cell manipulation
[1]. J. Brinkmann, E. Cavatorta, S. Sankaran, B. Schmidt, J. van Weerd, P. Jonkheijm, Chem. Soc.
Rev. 2014, 43, 4449.
[2]. L. Yang, A. Gómez-Casado, J.F. Young, H.D. Nguyen, J. Cabanas-Danés, J. Huskens, L.
Brunsveld, P. Jonkheijm, J. Am. Chem. Soc. 2012, 134, 19199.
[3]. D. Wasserberg, J. Cabanas-Danés, J. Prangsma, S. O’Mahony, E. Tromp, C. Blum, D.
Thompson, J. Huskens, V. Subramaniam, P. Jonkheijm, ACS Nano 2017, 11, 9068.
[4]. Q. An, J. Brinkmann, J. Huskens, S. Krabbenborg, J. de Boer, P. Jonkheijm, Angew. Chem. Int.
Ed. 2012, 51, 12233.
[5]. S. Sankaran, L. Jaatinen, J. Brinkmann, T. Zambelli, J. Vӧrӧs, P. Jonkheijm, ACS Nano 2017, 11,
3867.
69
BIOTECH-KN15
Versatile biomimetic chondroitin-sulfate-based matrix

for tissue repair and mechanobiology
1 1 2 1
Fabien GAUDIERE , Sandrine MORIN-GROGNET , Nimrod BUCHBINDER , Guy LADAM , Jean-
2 1 1
Pierre VANNIER , Hassan ATMANI , Béatrice LABAT *
1
PBS UMR CNRS 6270 – Team BioMMAT (Biomaterials and Matrix Models for Tissue Adaptation),
University of Rouen Normandie, 55 rue St Germain, CS40486, 27004 Evreux Cedex, France.
2
PANTHER INSERM U1234, Faculty of Medicine and Pharmacy, University of Rouen Normandie,
22 Bd Gambetta, 76183 Rouen Cedex, France.

Keywords: Biomimetic ECM, topography, mechanobiology
The design of bio-inspired extracellular matrices (ECMs) is an up-to-date trend (i) to improve tissue
integration of implants and (ii) to offer in vitro models for a better understanding of cell behavior in
healthy or pathological tissues, as they can mimic the complex cell niche microenvironment by a
multifactorial approach combining bio-chemico-physical properties of cell substrates.
Following this line, we developed a versatile biomimetic ECM-like platform, based on polyelectrolyte
multilayer films (PEMs) [1], composed of a natural anionic glycosaminoglycan (chondroitin sulfate A
(CSA)), and a cationic polypeptide (poly-L-lysine (PLL)), stiffened by genipin, a biocompatible bio-
sourced crosslinker [2].
In a first approach (Fig. 1 left), we applied these PEMs for the surface functionalization of bone
biomaterials after a topomimetic surface roughening at a nano-to-micro-scale, to improve pre-
osteoblasts adhesion, proliferation and long-term differentiation. We observed a favourable synergistic
influence of as-designed topography and PEMs microenvironment for osteogenesis [3].
In a second approach (Fig. 1 right), we studied the combination of the mechanical properties of these
PEMs (mimicking healthy or tumorous tissues) and their use as nano-reservoirs. In particular, we
studied the differentiation of neuroblastoma cells (neurite extension) upon the elasticity of the films
and the release of retinoic acid (RA) from the reservoir. We found that an appropriate mechanical
environment combined to the release of RA can enhance the maturation of neuroblastoma cells by
remarkable neurite extensions.
Fig. 1: CSA-based ECM-like matrices - Osteoblast differentiation (left) revealed by Raman

microspectrocopy of hydroxyapatite-containing nodules (green) – Neuroblastoma
differentiation (right) with fluorescence of neurite extensions (green).
[1]. G. Decher, G., Science, 1997, 277, 1232.

[2]. F. Gaudière, et al., Biomacromolecules 2014, 15, 1602.
[3]. B. Labat et al., J. Biomed. Mater. Res. – Part A, 2016, 104A, 1988.
70
BIOTECH-KN16
Flexible Bioenabled Nanocomposites

Vladimir TSUKRUK

Georgia Institute of Technology, Atlanta, GA, USA

Keywords: natural polymers, graphene oxides, cellulose nanocrystals, flexible bionanocomposites,
printing and sensing

I discuss recent results from our research group on designing soft and strong responsive polymer and
biopolymer nanocomposite materials and structures at biological interfaces and for biosensing as
summarized in our recent reviews [1, 2]. Ultrathin silk fibroin proteins and cellulose
nanocrystals/nanofibers are combined with functionalized graphene oxide sheets for prospective
applications functional nanocomposites. Ultrathin films and membranes are fabricated by layer-by-
layer assembly of various functional components in order to create tough, ultrastrong, and flexible
freely-standing materials with electronic-based sensing capabilities. We discuss laminated
bionanocomposites from silk, cellulose nanocrystals, graphene oxide and reduced graphene oxide
components, which were found to possess extremely high elastic modulus around 200 GPa, ultimate
mechanical strength, and toughness as well as ability for ambient, electrochemically-enabled
conductive patterning on large spatial scale (1-3]. Such patterned graphene oxide-graphene films
show the ability to detect of bio-tactile events as triggered by the bio-electrolyte injection during
touching that can be exploited as artificial electronic skin that discriminates against human and “dry”
touching events [4]. Electrochemical-assisted photolithography has been utilized for high spatial
resolution conductive patterning of these nanocomposites with high local electrical conductivity, sharp
boundaries, and optical transparency. We observed that combining of biological components such as
silks and cellulose nanofibers can result in formation of peculiar shish-kebab nanostructures for
functional porous robust membranes [5] and controlled drying of cellulose nanocrystals can lead to the
fabrication of uniform chiral nematic-like structure with peculiar biophotonic properties [6].
[1] R. Xiong, A. M. Grant, R. Ma, S. Zhang, V. V. Tsukruk, Naturally-derived polymers and

bionanocomposites, Mat. Sci.&Eng. Reports, 2018, 125, 1.
,
[2] S. Zhang, R. Geryak, J. Geldmeier, S. Kim, V. V Tsukruk, Synthesis, assembly, and applications of
hybrid nanostructures for biosensing, Chem. Rev. 2017, 117, 12942
[3] R. Ma, V. V. Tsukruk, Seriography-Guided Fabrication of Graphene Oxide Biopapers for Wearable
Sensory Electronics, Adv. Funct. Mater., 2017, 27, 1604802.
,
[4] K. Hu, R. Xiong, H. Guo, R. Ma, S. Zhang, Z. L. Wang, V. V. Tsukruk, Self-Powered Electronic
Skin with Bio-Tactile Sensitivity, Adv. Mater. 2016, 28, 3549.
[5] R. Xiong, H. S. Kim, S. Zhang, S. Kim, V. F. Korolovych, R. Ma, Y. Yingling, C. Lu, V. V. Tsukruk,
Template-Guided Assembly of Silk Fibroin on Cellulose Nanofibers for Robust Nanostructures
with Ultrafast Water Transport, ACS Nano, 2017, 11, 12008.
[6] V. Cherpak, V.F. Korolovych, T. Turiv, D. Nepal, J. Kelly, T.J. Bunning, O.D. Lavrentovich, V.V.
Tsukruk, Uniform Chiral Organization of Cellulose Nanocrystals in Capillary Confinement, 2018,
submitted
71
BIOTECH-KN17
From chitosan to biomaterials.

Thierry DELAIR*
Université de Lyon, F-69003 Lyon ; CNRS, UMR 5223, Ingénierie des Matériaux Polymères,
Université de Lyon1, F-69622 Villeurbanne, France

Keywords: chitosan, polysaccharides, biomass, biomaterials, drug delivery, tissue regeneration.
Biomaterials are materials suitable for introduction into living tissues and thus, for these medical
applications, the safety issue is critical. Polysaccharides from biomass such as chitosan, alginates,
hyaluronic acids etc are materials generally regarded as safe and that is why many investigations
have been carried out to process them into devices like fibers, films, hydrogels, nanoparticles,
microspheres. Most of these devices were designed for a great variety of purposes in medicine such
as wound dressing, drug or gene delivery, cosmetics, cell culture, tissue replacement/regeneration
etc. Most naturally occurring polymers are water soluble and so are processed as solutions in water,
the safest media that can be used for manufacturing medical devices. That also suggests that the final
properties of the devices will be highly impacted by the physic-chemical properties of the parent
solution
Fig. 1: Chitosan chemical structure

Chitosan is a polysaccharide composed of D-glucosamine and N-acetyl D- glucosamine residues and
the molar fraction of N-acetyl D - glucosamine moieties is called the Degree of Acetylation (DA).
Chitosa is soluble in slightly acidic media thans to the protonation of the primary amine groups. In the
past we have extensively investigated the physic-chemical properties of chitosan solutions and the DA
and the degree of polymerization of chitosan have proven essential parameters [1].
In this presentation we will report our latest results on the elaboration of chitosan-based biomaterials.
We will detail the various processes we developed to obtain nanoparticles [2, 3], films [4], hydrogels
[5], of pure chitosan or chitosan-based blends. We will detail an innovative process based on the
controlled polyelectrolyte complex formation [6] that led to materials with outstanding properties like
hyper strechable hydrogels [7], and will illustrate their applications in the field of drug/vaccine
delivery[8] and tissue regeneration[9].
[1] aC. Schatz, C. Pichot, T. Delair, C. Viton, A. Domard, Langmuir 2003, 19, 9896-9903; bC.
Schatz, C. Viton, T. Delair, C. Pichot, A. Domard, Biomacromolecules 2003, 4, 641-648.
[2] T. Delair, European Journal of Pharmaceutics and Biopharmaceutics 2011, 78, 10-18.
[3] M. Costalat, P. Alcouffe, L. David, T. Delair, Journal of Colloid and Interface Science 2014,
430, 147-156.
[4] J. Becerra, G. Sudre, I. Royaud, R. Montserret, B. Verrier, C. Rochas, T. Delair, L. David,
Aaps Pharmscitech 2017, 18, 1070-1083.
[5] G. Lalevee, G. Sudre, A. Montembault, J. Meadows, S. Malaise, A. Crepet, L. David, T. Delair,
Carbohydrate Polymers 2016, 154, 86-95.
[6] M. Costalat, P. Alcouffe, L. David, T. Delair, Carbohydrate Polymers 2015, 134, 541-546.
[7] G. Lalevee, L. David, A. Montembault, K. Blanchard, J. Meadows, S. Malaise, A. Crepet, I.
Grillo, I. Morfin, T. Delair, G. Sudre, Soft Matter 2017, 13, 6594-6605.
[8] D. Wu, T. Delair, Carbohydrate Polymers 2015, 119, 149-158.
[9] A. Fiamingo, A. Montembault, S.-E. Boitard, H. Naemetalla, O. Agbulut, T. Delair, S. P.
Campana-Filho, P. Menasché, L. David, Biomacromolecules 2016, 17, 1662-1672.
72
BIOTECH-KN18
Bioinspired methodologies for the preparation and fixation of soft

spherical polymeric devices for the encapsulation of cells and
therapeutic molecules

1
João Mano

1
Department of Chemistry, CICECO — Aveiro Institute of Materials, University of Aveiro, 3810-193
Aveiro, Portugal;

Keywords: Biomedical, soft-matter, bioencapsulation, tissue engineering, regenerative medicine, drug
delivery, superhydrophobic surfaces,
The encapsulation of therapeutic molecules in microparticles have been widely used to develop
controlled drug delivery devices. More sophisticated strategies have also been employed to
encapsulate cells in spherical matrices using distinct biomaterials, to be explored in cell and tissue
engineering. We propose distinct enabling technologies that could be used to encapsulate both
molecules and cells in geometrically controlled micro-compartments. Superhydrophobic surfaces
serve as platforms to process basic units of hydrogels in mild conditions, permitting the encapsulation
of living cells and other biological cargo with high efficiency. In another strategy, capsules are
fabricated using the so-called layer-by-layer technology, where the consecutive layers are well
stabilized by electrostatic interactions or other weak forces. By using spherical templates containing
cells it is possible to produce liquefied capsules that may entrap viable cells. The presence of solid
microparticles inside such capsules offers adequate surface area for adherent cell attachment (with
controlled mechanical properties) increasing the biological performance of these hierarchical systems,
while maintain both permeability and injectability. The liquid environment allows for a free-organization
in the space of the cells towards the formation of new microtissues.
73
NANOTECH-KN01
Tailor-made hydrophilic polymer networks with biomimetic

functions: anti-fouling, self-healing and low-friction.

Catarina Esteves
Laboratory of Physical Chemistry, Chemical Engineering and Chemistry, Eindhoven University of
Technology, Eindhoven, the Netherlands.

Keywords: crosslinked polymers, networks, anti-fouling, self-healing, lubricity
Water has naturally a strong affinity to high surface energy surfaces. This favorable interaction leads
to an enduring hydration state (or hydration layer) of the materials which therefore present special
properties such as anti-fouling (AF), biocompatibility or aqueous lubricity [1,2]. These properties are
particularly relevant for applications where materials are in permanent contact with water or aqueous
environments. Some examples are in marine coatings or filtration membranes, which are constantly
subjected to biofouling or in bio-medical devices in contact with tissue-cells or body fluids, e.g.
catheters, contact lenses, guidewires, implants and stents.[3]
In nature, living organisms found strategies to develop such functionalities and many of them rely on
hydrophilic biopolymer-based networks and hydrogels. For instance, many seaweeds, fishes and jelly-
fishes are covered with soft and “wet’ hydrogels to avoid settlement of fouling organisms and provide a
lubricious character. Another example comes from our own cartilage, where a highly hydrophilic
biopolymer-based network provides for lubrication to withstand friction and mechanical loads [3].
Many of the devices we currently use need, however, to be made out of hard materials which should
be mechanical and chemically resistant, hence, they do not possess by default such hydrophilic
surface properties. One way to achieve that is to coat the device or substrate with a crosslinked
hydrophilic polymer layer (coating), which will allow the proper interaction with the aqueous media
while the bulk of the device or material can deliver the other physical/chemical properties required for
a specific application.
In this work, several types of crosslinked polymer networks were designed to obtain specific surface
functionalities, such as anti-fouling (or low protein adhesion) and low wet friction. Additional these
polymer films show also the ability to self-heal, via a self-replenishing mechanism [4,5].
Crosslinked polycarbonate–polyurethane networks were prepared containing mPEG (methyl ether
polypropylene glycol) as dangling chains. The films obtained from these polymers were very
transparent and robust. They showed a remarkable stability while immersed in water and were able to
self-replenish from damages created by wear, recovering totally the surface hydrophilicity upon re-
immersion in water [6].
Model networks consisting of crosslinked PEG-polyurethane hydrophilic polymers were used to study
the wet-friction behavior. The films prepared with these networks had a high water uptake and lrge
swelling ratios. The network architectures were varied by using PEG and PPG precursors with mPEG
or PEG-diols as dangling chains. The role of the dangling chains number and average molecular
weight on the coefficient of friction (CoF) was evaluated, and an optimal network composition for the
highest lubricious behaviour was encountered. At low contact sliding velocities a significant reduction
in CoF was observed upon increasing the water uptake, via changing the network precursor length or
via the introduction of the loose chain ends.
[1] Nurioglu, A.G.; Esteves, A.C.C.; de With, G.; J Mat Chem B 2015, 3, 6547.
[2] Chen, S.; Li, L.; Zhao, C.; Zheng, J. Polymer 2010, 51, 5283.
[3] Greene, G.W.; Banquy, X.; Lee, D.W.; Lowrey, D.D.; Yu, J.; Israelachvili, J. N.; P Natl Acad Sci
USA 2011, 108, 5255.
[4] Dikić. T.; Ming, W.; van Benthem, R.A.T.M.; Esteves, A.C.C.; de With, G.; Adv Mater 2012, 24,
3701.
[5] Esteves, A.C.C.; Luo, Y.; van de Put, M.W.P.; Carcouët, C.C.M.; de With, G. Adv. Funct. Mater.
2014, 24, 986.
[6] Jiménez-Pardo, I.; van der Ven, L.G.J. ; van Benthem, R.A.T.M.; de With, G.; Esteves, A.C.C.,
Coatings 2018, in press.
74
NANOTECH-KN02
Bionic Materials for Tribology

Zhiguang Guo
State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy
of Sciences, Lanzhou 730000, China
Tel: +86-931-4968105, Fax: +86-931-8277088, E-mail: [email protected]
Keywords: Tribology, Friction, Wear, Liquid lubricants, Separation

Friction is two faces, one is helpful for human beings, and the other is harmful, which can make a lot of
loss for materials, energy, sizes and so on. Lubrication is an effective way to reduce friction by various
kinds of lubricants. Among them, liquid lubrications are the most used due to their excellent properties,
compared solid lubricants. Once water was mixed into the liquid lubricant, it will largely reduce the
lubrication efficiency by hindering the formation of lubrication films and forming more serve corrosion
wear for metal frictional pairs. How to remove water from liquid lubricants is still a challenge for us.
Herein, some interesting researches will be introduced, which were done in our research group in the
past six years. This will open a new route for the separation of oil/water mixtures.
1. B. Wang, W. X. Liang, Z. G. Guo,* W. M. Liu. Biomimetic super-lyophobic and super-lyophilic

materials applied for oil/water separation: a new strategy beyond nature. Chem. Soc. Rev. 2015,
44, 336.
2. L. Tie, Z. G. Guo*, W. M. Liu. Ph-manipulated underwater-oil adhesion wettability behavior on the
micro/nanoscale semicircular structure and related thermodynamic analysis. ACS Applied
Materials & Interfaces 2015, 7, 10641.
3. Y. Dong, J. Li*, L. Shi, X. B. Wang, Z. G. Guo*, W. M. Liu. Significant advantages of low-oxygen
graphene nanosheets. J. Mater. Chem. A 2015, 3, 9738.
4. Y. F. Si, Z. G. Guo*, W. M. Liu. A robust epoxy resins@stearic acid-Mg(OH)2 Micronanosheet
superhydrophobic omnipotent protective coating for real-life applications. ACS Appl. Mater.
Interfaces 2016, 8, 16511-16520.
5. Y. B. Peng, Z. G. Guo*. Recent advances in biomimetic thin membranes applied in emulsified
oil/water separation. J. Mater. Chem. A. 2016, 4, 15749-15770.
6. M. M. Liu, J. Li,* Y. Y. Hou, Z. G. Guo.* Inorganic adhesives for robust superwetting surfaces. ACS
Nano 2017, 11, 1113-1119.
7. L. W. Chen, Y. F. Si, Z. G. Guo*, W. M. Liu. Superhydrophobic sand: a hope for desert water
storage and transportation projects. Journal of Materials Chemistry A 2017, 5, 6416-6423. (Cover
paper)
75
NANOTECH-KN03
Bioinspired Slippery Surfaces: Oil-Impregnated Nanoporous

Alumina Coating for Anticorrosion and Antibiofouling

1,2 ,1
Junghoon Lee , Chang-Hwan Choi*

1
Department of Mechanical Engineering, Stevens Institute of Technology, Hoboken NJ, United States;
2
Department of Metallurgical Engineering, Pukyong National University, Busan, South Korea

Keywords: Anodic aluminum oxide; oil-impregnated surface; anticorrosion; antibiofouling
Engineered by the inspiration from nature’s Nepenthes pitcher plant, slippery liquid-infused porous
surfaces (so-called SLIPS) have demonstrated the configuration of unique liquid-solid-liquid composite
interface at the surfaces, which leads to water-repelling and omniphobic properties [1, 2]. Such
surfaces have aroused significant attention in a wide range of applications to overcome the issues of
the other types of water-repelling surfaces, e.g., superhydrophobic surfaces inspired by nature’s Lotus
leaf, which include the depletion of air from the surfaces and the loss of superhydrophobicity.
Especially, oil-impregnated nanoporous surfaces of metal oxide have shown remarkable anticorrosion
[3] and antibiofouling properties [4] for metallic substrates, which were more effective than
superhydrophobic surfaces. In this presentation, we demonstrate the realization of oil-impregnated
nanoporous surfaces of aluminum oxide on aluminum substrates and their efficacy in the anticorrosion
and antibiofouling applications. High-aspect-ratio dead-end nanopore structures of oxide on aluminum
were first fabricated by anodizing processes, followed by the hydrophobization with a thin (a couple of
nanometers) Teflon film. A lubricating water-immiscible perfluorinated oil was then impregnated into
the high-aspect-ratio dead-end nanopores by a novel solvent exchange method [3]. The contact and
imbibition of corrosive liquids can significantly be inhibited by the oil impregnated in the nanoporous
oxide surface. Especially, the disconnected high-aspect-ratio dead-end nanopore geometry allows the
robust retention of oil within the pores, showing superior corrosion resistance to superhydrophobic
surfaces. Moreover, the impregnated liquid oil naturally permeates into defects or damaged areas and
ultimately inhibits the exposure of the aluminum surface to the corrosive media, exhibiting an effective
self-healing capability. In addition, the oil-impregnated nanoporous aluminum oxide surfaces prevent
the adhesion of bacteria more effectively than superhydrophobic surfaces and bare aluminum. The
anodizing and oil-impregnation processes that we have developed are scalable and readily applicable
to current industrial manufacturing processes to potentially provide the industry-relevant metallic
substrates with such multifunctional surface properties with great durability and self-healing capability.

References
[1]. T.-S. Wong, S. H. Kang, S. K. Y.Tang, E. J. Smythe, B. D. Hatton, A. Grinthal, J. Aizenberg,

Nature 2011, 477, 443-447.
[2]. A. K. Epstein, T.-S. Wong, R. A. Belisle, E. M. Boggs, J. Aizenberg, Proc. Natl. Acad. Sci. U.S.A.
2012, 109, 13182-13187.
[3]. J. Lee, S. Shin, Y. Jiang, C. Jeong, H. A. Stone, C.-H. Choi, Adv. Funct. Mater 2017 27 1606040.
[4]. G.-H Ban, J. Lee, C.-H. Choi, Y. Li, S. Jun, LTW - Food Sci. Technol. 2017 84 359-363.
76
NANOTECH-KN04
Bioinspired Ionic Adhesives

1,
Marleen Kamperman *
1
Physical Chemistry and Soft Matter, Wageningen University, Wageningen, the Netherlands;

Keywords: Bio-inspiration, adhesives, complex coacervation, polymer chemistry, wet adhesion
Biology provides numerous stimulating illustrations of successful design strategies. As biology evolved
to complex designs, synthetic mimics are evolving towards new levels of complexity achieving larger
combinations of properties within one material. In my group we utilize biologically inspired strategies to
develop polymeric materials for next generation adhesives and functional materials.
In this talk I will present recent developments in mimicking the adhesive secretions of marine animals
such as P. californica and M. edulis by creating fully synthetic polymeric systems. Characteristic of the
proteins found in the adhesive plaque of mussels and sandcastle worms is a high proportion of
cationic, anionic and catecholic residues (hydroxylated tyrosine, DOPA). DOPA is involved in a
versatile combination of functions: covalent crosslinking, complexation to mineral substrates, and
bonding to hydrophobic (fouled) surfaces. The anionic and cationic residues are often said to be
involved in a secondary interaction that aids cohesion, namely complex coacervation. This is an
attractive phase separation of mixtures of polyanions and polycations that results in a highly
polyelectrolyte-rich phase in equilibrium with almost pure solvent. Complex coacervates have very low
surface tensions and are water insoluble, which makes them highly desirable for underwater
adhesives. Additionally, they are mechanically well-suited for adhesion due to their high storage and
loss moduli that provide, respectively, bonding strength and dissipation of strain energy. We aim to
reproduce the working mechanism of mussels and sandcastle worms by developing a new class of
underwater adhesives based on complex coacervates reinforced with physical interactions.
77
NANOTECH-KN05
Homogeneous and templateless growth of conducting polymer

nanotubes with special wetting properties

1 1 1
Thierry DARMANIN, Sonia AMIGONI, Frédéric GUITTARD*,

1
NICE Lab, IMREDD, Université Côte d’Azur, Parc Valrose, 06200, Nice, France

Keywords: Bioinspiration, Superhydrophobic, Nanostructures, Electrochemistry.
The control of surface structures is fundamental for many applications such as in the wetting
properties. Inspired by natural species found in Nature, the presence of surface structures plays a very
1
important role in the enhancement of hydrophobic properties with various water adhesion properties.
In particular, nanotubes were found to be excellent candidates because the surface properties are
highly dependent on their diameter, the height or their porosity, for example. The preparation of highly
ordered nanotubes often needs complex processes such as the use the template or lithographic
process.
The templateless electropolymerization is an excellent alternative for the formation of porous
structures such as nanotubes. In 2003, Shi et al. reported for the first time the formation of nanotubes
2
by electropolymerization of pyrrole in an aqueous solution containing a surfactant. In this process,
gas bubbles released from water (O2 and/or H2 following the polymerization process) are responsible
of the formation of nanotubes. Very recently, we show this possibility in organic solvent (trace water is
sufficient) and without surfactant. The monomer plays a special role in the stabilization of gas bubbles
and the formation of porous structures. Here, I will present most of the results obtained in our group in
this domain.
Fig. 1: Nanotubes and nanorings obtained by templateless electropolymerization.
[1]. T. Darmanin, F. Guittard, Mater. Today 2015, 18, 273-285.

[2]. L. Qu, G. Shi, F. Chen, J. Zhang, Macromolecules 2003, 36, 1063-1067.
[3]. T. Darmanin, F. Guittard, J. Mater. Chem. A 2016, 4, 3197-3203.
[4]. C. R. Szczepanski, I. M’Jid, T. Darmanin, G. Godeau, F. Guittard, J. Mater. Chem. A 2016, 4,
17308-17323.
[5]. A. Gbilimou, T. Darmanin, G. Godeau, F. Guittard, ChemNanoMat 2018, 4, 140-147.
78
NANOTECH-KN06
Hierarchical Electrohydrodynamic Lithography for Advanced

Micro-Engendered Devices

1,*
Pola GOLDBERG OPPENHEIMER

1
School of Chemical Engineering, University of Birmingham, Edgabston, Birmingham, B15 2TT, UK

Keywords: Electrohydrodynamic Patterning, Thin Films, Hierarchical Micro-Nanostructures
High resolution lithography is one of the cornerstones of electronic technologies. While these are
based on conventional optical projection methods, a range of alternative techniques have emerged
over the past 10 years for the control of pattern replication on the 10 nm to 1 µm length scale.
Electrohydrodynamic (EHD) patterning takes lithography to a new level by the development of
techniques that control structure formation within the replicated material down to the atomic level. This
results in the controlled manufacture of design patterns with hierarchical feature sizes.
[1]
This overview is centred on the electro-hydrodynamic lithography (EHL) technique, in which a
design electrode pattern is replicated into a polymeric resist by electric field-gradient forces. This
method reliably produces faithful replicas of a master-pattern with feature sizes down to 100 nm. This
well-established EHL process provides additional handles that permit control over the arrangement of
the material within the lithographically produced structures. We develop several hierarchical pattern
[2]
replication methods, demonstrating the creation of functional thin films with 3D design patterns. EHL
contributes to a fundamental understanding how electric fields can be used to control the arrangement
of material down to the nanometre length scale and demonstrates the promise of electric field-assisted
techniques in the control of a range of functional materials.
The central part of the EHD lithography will be concerned with the structure formation of conducting
and semiconducting materials by EHL, which is challenging because of the high electric fields
employed in this method and the associated risk of short-circuiting the devices. The EHD
demonstrates successful structure control in semiconducting polymers, block-copolymers, and
polymers loaded with carbon nanotubes. In addition to the control over the distribution of
optoelectronically active materials in thin films, the work also shows how nanometre-sized conducting
domains within these materials can be aligned. In addition, other uses of EHL are explored, such as
the control over crystallinity within the replicated material and in particular, the use of submicrometre-
sized design topographies for sensing by means of surface-enhanced Raman scattering.
[1] P. Goldberg Oppenheimer, Springer, 2013.

[2]. J.J.S. Rickard et al., ACS Nano, 2016, 10, 3865.

79
NANOTECH-KN07
Droplets on Smart Slippery Surfaces

1 1 1 1 1 2
Glen McHale, Y.Q. Fu, N.R. Geraldi, J.H. Guan, R. Ledesma-Aguilar, J.T. Luo, É. Ruiz-
1 1 1 1 1 1
Gutiérrez, J. Martin, C. Semprebon, G.G. Wells, D. Wood and B.B. Xu

1
Smart Materials & Surfaces Laboratory, Northumbria University, Newcastle upon Tyne NE1 8ST, UK
2
College of Physics and Energy, Shenzhen Key Laboratory of Sensor Technology,
Shenzhen University, Shenzhen 518060, People’s Republic of China
Keywords: SLIPS, Lubricant Impregnated Surfaces, Droplets
Recent focus on superhydrophobic surfaces has been due to their ability to create almost complete
non-wetting by balling-up droplets of water. Their slipperiness is a by-product of the reduced liquid-
solid contact area. An alternative strategy is to reduce contact angle hysteresis. In this work, we
consider lubricant impregnated surfaces, also known as slippery liquid-infused porous surfaces
(SLIPS), which create slipperiness by removing contact line pinning and increasing the mobility of
sessile droplets. We first show that diffusion-limited droplet evaporation corresponds to a constant
apparent contact angle mode [1]. We then argue that droplet position and motion on slippery
lubricated surfaces, can be controlled using a SLIPS Cheerios effect induced by structuring the
underlying surface or by droplets in close proximity to each other [2]. As a specific example, we show
that a droplet on a SLIPS surface with a V-shaped groove has three equilibrium states and that droplet
motion on the surface towards an equilibrium state occurs when the droplet-lubricant meniscus
overlaps with the lubricant-surface meniscus caused by surface features. We then consider an
alternative configuration of a droplet confined in a wedge between two slippery surfaces. We show the
droplet can be continuously translated in an energy invariant manner by reconfiguring the boundaries
[3,4]. As an alternative actuation method, we show that the large footprint of a droplet on a SLIPS
surface allows easy droplet transport using energy coupled via a surface acoustic wave (SAW) [5].
Fig. 1: Transportation and positioning of droplets using slippery surfaces: (a) Droplet Cheerios
effect to control droplet position, and (b) Reconfigurable boundaries to actuate droplet motion
Acknowledgement. This work has been financial supported by the UK Engineering & Physical
Sciences Research Council (EPSRC) and Reece Innovation Ltd.
[1]. J.H. Guan, G.G. Wells, B. Xu, G. McHale, D. Wood, J. Martin, S. Stuart-Cole, Langmuir 2015, 31,
11781-11789.
[2]. J.H. Guan, É. Ruiz-Gutiérrez, B.B. Xu, D. Wood, G. McHale, R. Ledesma-Aguilar, G.G. Wells, Soft
Matter 2017, 13, 3404-3410.
[3]. É. Ruiz-Gutiérrez, J.H. Guan, B. Xu, G. McHale, G.G. Wells, R. Ledesma-Aguilar, Physical
Review Letters 2017, 118, 218003.
[4]. É. Ruiz-Gutiérrez, C. Semprebon, G. McHale, R. Ledesma Aguilar, Journal of Fluid Mechanics
2018, accepted.
[5]. J.T. Luo, N.R. Geraldi, J.H. Guan, G. McHale, G.G. Wells, Y. Q. Fu, Physical Review Applied,
2017, 7, 014017.
80
NANOTECH-KN08
Plant Biomimetics - From basic principles to applications.
Christoph NEINHUIS,

Technische Universität Dresden, Dresden, Germany;

Keywords: Plants, functional morphology, biomechanics, Cactaceae, Lotus-Effect, Martyniaceae,
Plant served as indispensable resource all through the history mankind. Food, fibres, building
materials, fuel or secondary metabolites for medical treatments are only a few examples for the
importance of plants in everyday life. In recent decades, plants have gain increasing interest as
models for improved components or materials in engineering, if not as key to completely novel
solutions for certain problems. One of the most prominent examples deals with plant surfaces the
properties of which, especially regarding attachment of insects, wetting with water, or the application
of chemicals have been a research topic for almost one hundred years. However, the publication
about the connection between wetting properties and the removal of contaminating particles 1997 [1],
that became popular under name “Lotus-Effect” initiated a new interest in functional surfaces resulting
in a boost of investigations dealing with self-cleaning properties and related phenomena [2]. Despite
the vast amount of research, the number of commercially successful applications is still limited. Here,
a short overview is given about the basis for water-repellency in plants and animals, examples for the
successful transfer from a biological into a technical system and finally results will be presented of
recent research activities.
The second part deals with the particular role of cell walls and their contribution to mechanical stability
and function of the whole plant body or individual organs. Examples will be given from Cactaceae [3]
and Martyniaceae [4]. In columnar Cactaceae the sophisticated arrangement of fibres not only results
in a very thin walled tubular wood tissue but more specifically in a highly resilient connection between
stem and branch that finally served as inspiration for newly designed light weight carbon and glass
fibre reinforced components. In Martyniaceae, the fruits develop into a highly specialised capsule
adapted to the dispersal by large animals. Fruit development, especially the formation of sclerenchy-
matous tissue combined with the unusual arrangement of fibres and its implication for the mechanical
properties will be discussed.
Fig. 1: the stem branch junction of columnar Cactaceae (left) served as model for a novel
carbon fibre reinforced component in light weight construction (center). The fruits of
Proboscidea (right) consist of sclerenchymatous fibres only, but exhibit superior mechanical
properties und different load conditions.
[1]. W. Barthlott, C. Neinhuis Planta 1997, 202 (1), 1-8.

[2]. W. Barthlott, M. Mail, C. Neinhuis 2016 Phil. Trans. Roy. Soc. A, 374, 2073
[3]. H. Schwager, T. Masselter, T. Speck, C. Neinhuis, Proc. Roy. Soc. B. 2013, 280.
[4]. M. Horbens, M. Eder, C. Neinhuis, Acta Biomaterialia 2015, 28, 13-22.
83
NANOTECH-KN11
Block Copolymer Hierarchical Morphologies and Customized

Functionality Inspired by Nature

1
Richard J. Spontak*

1
North Carolina State University, Raleigh, NC, USA

Keywords: block copolymer, directed self-assembly, gel networks, responsive polymers, dielectric
elastomers, anti-bacterial
As one of the most extensively investigated and employed classes of synthetic macromolecules, block
copolymers afford numerous opportunities for designer soft materials with tremendous structure and
property versatility. For instance, crystallization-directed self-assembly can proceed by heterogeneous
nucleation with block copolymers in a selective solvent and generate nearly monodisperse nanofibers,
with some measuring several micrometers in length. Such nanofibers can then be strategically
arranged into hierarchical nonwoven-like superstructures [1]. Similarly, coordination-driven self-
assembly of functionalized toroids yields multicompartmental hierarchical superstructures that can be
subsequently merged to form 2D/3D mesoscale meshes for size-regulated filtration purposes. The
importance of a selective solvent in block copolymer morphological development is further established
with multiblock copolymer gels wherein a new morphology naturally found at nanoscale dimensions in
various oxides has been identified to form at mesoscale dimensions [2]. Efforts to elucidate the onset
of network formation along with network properties that generate electroactive dielectric elastomers
capable of emulating mammalian skeletal muscle utilize Monte Carlo and Dissipative Particle
Dynamics simulations in conjunction with a detailed topological analysis of various chain
conformations. In all these cases mentioned thus far, the polymers have been relatively nonpolar. In
the case of block ionomers, that is, block copolymers with one or more charged blocks, polar solvents
can be introduced into the morphology of microphase-separated block copolymers to facilitate the
development of hydrogel [3] and dye-sensitized [4] solar cells, in addition to membranes for selective
removal of amphoteric gases (e.g., ammonia and carbon dioxide) [5]. The materials to be discussed
are also found to be naturally antibacterial, not requiring any additives or further chemical
functionalization. Taken together, the topical vignettes presented here establish the remarkable utility
of block copolymers, including ionomers, in terms of hierarchical morphologies and customized
functionality gleaned from nature.
Fig. 1: Monte Carlo simulation of the truncated octahedron morphology in a selectively

solvated triblock copolymer [2].
[1]. D.J. Lunn, O.E.C. Gould, G.R. Whittell, D.P. Armstrong, K.P. Mineart, M.A. Winnik, R.J. Spontak,
P.G. Pringle, I. Manners, Nat. Commun. 2016, 7, 12371.
[2]. S. Woloszczuk, M.O. Tuhin, S.R. Gade, M.A. Pasquinelli, M. Banaszak, M., R.J. Spontak, ACS
Appl. Mater. Interfaces 2017, 9, 39940.
[3]. H.A. Al-Mohsin, K.P. Mineart, R.J. Spontak, Adv. Energy Mater. 2015, 5, 1401941.
[4]. H.A. Al-Mohsin, K.P. Mineart, D.P. Armstrong, A. El-Shafei, R.J. Spontak, Sol. RRL 2018, 2,
1700145.
[5]. L. Ansaloni, Z. Dai, J.J. Ryan, K.P. Mineart, K.T. Saud, Q. Yu, M.-B. Hägg, R.J. Spontak, L. Deng,
Adv. Mater. Interfaces 2017, 4, 1700854.
84
NANOTECH-KN12
Computational Investigation of Microgels:

Effect of the Microstructure on the Deswelling Behavior
1 2,
Federica Lo Verso, Angel J. Moreno,
1
Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55,
5230 Odense, Denmark
2
Centro de Física de Materiales (CSIC, UPV/EHU) and Materials Physics Center MPC, Paseo Manuel
de Lardizabal 5, 20018 San Sebastián, Spain
Keywords: Polymers, Computational Synthesis, Deswelling kinetics, Microstructure
Microgels represent unique systems due to their tunability in terms of architecture, softness, permeability and
deformability. Their conformational changes in solution can be e.g. achieved by changing temperature and pH.
The importance of these molecules relies on their huge amount of possible applications such as drug delivery,
photonic crystals or purification technologies, just to name a few. [1-2]
Unlike regular network frameworks, usually assumed in microgel computational studies, we modeled and
simulated a very realistic and efficient synthesis, mimicking cross-linking of functionalized chains inside a cavity.
This model is inspired, e.g., by microfluidic fabrication of microgels from macromolecular precursors [3] and is
different from polymerization routes [4]. The assembly of the chains is mediated by a low fraction of interchain
crosslinks. The microgels are polydisperse in size and shape but globally quite spherical objects.
In order to deeply understand their structure and eventually improve the synthesis protocol we characterize the
equilibrium structure and deswelling kinetics and compare them with the results found for microgels obtained via
underlying regular structures. The specific microstructure of the microgel has no significant effect on the locus of
the deswelling transition but strongly affects its kinetics. The coarsening process during the deswelling and
collapse of the microgel is apparently given by two universal time scaling laws: stretched exponential for the
regular networks and power-law for the disordered ones.
Fig. 1: Snapshots of a middle-size disordered microgel during the collapse. Blue beads are
reactive monomers.
[1]Lopez, V. C.; Snowden, M. Drug Delivery Syst. Sci. 2003, 3, 19

[2] Murthy, N. et al., Proceedings of the National Academy of Sciences 2003, 100, 4995
[3] Seiffert, S.; Weitz, D. A.; Soft Matter 2010, 6, 3184
[4] Gnan, N. et al.,Macromolecules, 2017, 50, 8777
85
NANOTECH-KN14
Nanostructured materials based on boron nitride for energy,

environmental and health applications

1,2 1 1
Philippe MIELE *, Mikhael BECHELANY, Danae GONZALEZ ORTIZ, Céline POCHAT-
1
BOHATIER,

1
Institut Européen des Membranes (UMR ENSCM/UM/CNRS 5635)
IEM/Université de Montpellier, Montpellier, France
2
Institut Universitaire de France
Paris, France
Keywords: boron nitride, porous materials, Pickering emulsions
The development of new materials for near-future technological challenges is strongly dependent
on the elaboration of ceramics with suitable morphologies, shapes and properties. This goal can be
achieved by both the utilization of non-conventional chemical methods and the related preparation of
tailored precursors.
In the case of non-oxide ceramics, the pyrolysis of preceramic precursors is a useful process for
preparing materials with a controlled chemical composition and in complex shapes. The general
strategy can be described as a molecule-to-ceramic conversion, involving a complex sequence of
physical and chemical modifications. In this contribution, several examples of Polymer Derived nano-
Ceramics will illustrate this elegant method as well as their use in energy applications, particularly for
Hydrogen storage. We will focus on boron-based PDCs displaying various forms and sizes.
On another hand, 2D material such as graphene and boron nitride nanosheets are very attractive
for many applications particularly as sensors, electronics, adsorbents and catalysis devices. In the
case of boron nitride, novel properties can arise from BN nanosheets (BNNS) due to the high surface
area and the edge structures. Here, we used the exfoliation as the main tool for the creation of
controlled two-dimensional nanostructured interfaces in order to investigate their performances in
energy, environmental and health applications. We will show examples of how these methods can be
used to create membranes for osmotic energy harvesting and water treatment, optical sensors and
biosensors, and bio-nanocomposites materials for packaging. Recent works using the Pickering
emulsions technique for the preparation of porous materials will be described.
86
NANOTECH-KN15
Molecular motion in self-assembled nanostructures

1 1 1
Jia TIAN, William R. LINDEMANN, Julia H. ORTONY *

1
Massachusetts Institute of Technology, Cambridge, MA, USA

Keywords: Self-assembly, nanofiber, dynamics
The chemistry of natural phospholipids is highly evolved, leading to membranes with thermal phase
behaviors and packing parameters perfect for their function. Synthetic chemists have mimicked
1
amphiphilic self-assembly to form nano-objects for a variety of applications. An important missing
aspect of synthetic systems, however, has been control over the internal molecular motion of
nanostructured materials. We synthesize amphiphilic nanostructures and use our recently developed
methodology based on EPR spectroscopy to measure the internal dynamics with sub-nanometer
2-
resolution. We find that self-assembly leads to an extraordinary degree of internal dynamic structure.
3
Further, we show quantitatively that the 7-nanometer cross-section of a peptide-based nanostructure
exhibits an incredible range of dynamics, from a viscous liquid core to a solid-like shell. We show that
cross-sectional dynamics can be controlled by tuning molecular design and explore the implications of
dynamic control at sub-nanometer length scales.
Fig. 1: A supramolecular nanofiber exhibits a range of internal dynamics from liquid-like to

solid-like through its 7-nm cross-section.
[1]. N. Stephanopoulos, J.H. Ortony, S.I. Stupp, Acta materialia. 2013, 61, 912-930.
[2]. J.H. Ortony, C.J. Newcomb, J.B. Matson, L.C. Palmer, P.E. Doan, B.M. Hoffman, S.I. Stupp,
Nature mater. 2014, 13, 812-816.
[3]. J.H. Ortony, B. Qiao, C.J. Newcomb, T.J. Keller, L.C. Palmer, E. Deiss-Yehiely, M. Olvera de la
Cruz, S. Han, S.I. Stupp, J. Am. Chem. Soc. 2017, 139, 8915-8921.
87
NANOTECH-KN16
Emulsion templating to prepare porous polymeric membrane

Céline POCHAT-BOHATIER

IEM (Institut Européen des Membranes) UMR 5635, Univ. Montpellier, CNRS, ENSCM, Montpellier,
France

Keywords: Pickering emulsion, porous structure, polymer, membrane, elaboration process.
Basically, porous polymeric membranes used in water and filtration treatments are mainly prepared by
phase separation processes induced in polymer solution by the modulation of a thermodynamic
parameter (e.g. solubility parameter, temperature). The demixtion of the homogeneous polymer
solution gives rise to two phases: the polymer-rich phase solidifies quickly after the phase separation
and forms the matrix of the membrane, whereas the polymer-poor phase gives the membrane voids
and pores. The mechanisms of the membrane morphology formation are very complex but they are
now well controlled to produce commercially membranes made of synthetic polymers. Developing
membranes with bio-sourced polymers is an alternative to petroleum-based materials, due to
renewable origin of raw materials. However it is not possible to transpose directly the usual processes
to induce phase separation to bio-sourced polymer because of their specific properties. One of the
novel methods that can be used to prepare porous structure is based on emulsion templating. In
Nature, emulsions are complex colloidal systems (milk, vegetal lattices) where two immiscible liquid
phases co-exist. Pickering emulsions are colloidal emulsions stabilized by solid nanoparticles
adsorbed at Oil/Water interface instead of organic surfactants. These emulsions are extremely stable
due to the quasi-irreversible anchorage of particles at the interface between the dispersed and
continuous phase. Our recent works focus on the preparation of bio-based membranes with porous
structure made with gelatin [1] or polyvinyl alcool using emulsion templating. We used 2-D materials
(graphene oxide or boron nitride [2]) as nanoparticles. The challenge is to control the moment when
the polymer reach the gel point in order to overcome droplet coalescence after casting, but still
allowing the formation of highly interconnected, open-cell, emulsion template porous structure.
Fig. 1: Emulsion template procedure to form porous polymeric membrane
[1]. N. Sakthivel, D. Abessolo Ondo, S. Gassara, M. Bechelany, S. Balme, P. Miele, N. Kalkura, C.

Pochat-Bohatier, Langmuir 2018, 34, 1542–1549.
[2]. D. Gonzalez Ortiz, C. Pochat-Bohatier, J. Cambedouzou, S. Balme, M. Bechelany, P. Miele,
Langmuir 2017, 33 13394-13400.
88
NANOTECH-KN19
Design of biomimetic polymer interfaces: using

photopolymerization techniques to simultaneously control surface
chemistry and topography

1 2 2,3 1
Caroline SZCZEPANSKI,* Thierry DARMANIN, Frédéric GUITTARD, John TORKELSON

1
Department of Chemical and Biological Engineering, Northwestern University, Evanston IL, USA;
2
NICE Lab, Université Côte d’Azur, Nice, France
3
Department of Bioengineering, University of California Riverside, Riverside CA, USA

Keywords: wettability, photopolymerizations, surfaces, interfaces
There exist numerous examples of natural surfaces with unusual interfacial behaviors, such as the
extreme water repellency of the lotus leaf, to the shell of the Namib desert beetle which facilitates
water capture and collection in arid climates. These interfacial designs are valuable for engineering
applications such coating development, water purification, and beyond. Through observations of
natural surfaces, it has been established that both surface chemistry as well as topological features
ranging in scale from nanometers to microns play an equally significant role in interfacial interactions.
However, knowing the importance of these combined influences, the current challenge is identifying
versatile and efficient methods for materials development that afford control over both surface
chemistry and topography. Developed techniques such as templating or nanolithography are often
employed, particularly towards controlling topographical features, but are lacking as they cannot be
used to manipulate surface chemistry nor are they appropriate for applications where in situ polymer
formation is necessary. Here we explore the use of photopolymerization-based approaches to
engineer surfaces that address the need for both topological features and chemical patterning during
in situ material formation. To manipulate surface chemistry and the patterning thereof, we designed
multi(acrylate)/polystyrene and multi(acrylate)/polyvinylidene fluoride (PVDF) copolymer resins that
undergo thermodynamically driven de-mixing across an interface, allowing for local variations in
composition of the surface material. We show how polymer/substrate interactions as well as polymer
macromolecular structure can be engineered to manipulate the segregation of certain moieties
towards the air/polymer interface, further demonstrating control over the surface chemistry.
Additionally, we show how polymerization-induced shrinkage can be exploited to create structures on
a surface, addressing the need for topological features in addition to chemical patterning (Figure 1,
below) and significantly altering the wettability of such materials. This work is particularly relevant as
photopolymerizations are an attractive approach to address the need for robust and complex
interfacial development. Photopolymerizations offer both spatial and temporal control over surface
fabrication and are energy efficient, particularly when compared to thermal-based processes. These
advantages, along with the fact that both the need for specific chemistries and three-dimensional
features are necessary for efficient surface design, make photopolymerizations a viable alternative
when addressing large scale materials needs.
Fig. 1: AFM image of a rough, photopolymerized interface and associated wettability

(polymer matrix: hexanediol diacrylate-co-octyl acrylate, modified with 20wt% PVDF)
89
NANOTECH-KN20

How Far Can We Push the Performance of Polymers Mimicking
Mussel Adhesive Proteins?
1,2
Jonathan Wilker
Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, Indiana 47907, USA
and School of Materials Engineering, Purdue University, West Lafayette, Indiana, 47907, USA
Keywords: Adhesive, biomimetic, marine, mussel, polymer
A visit to the beach will show barnacles, oysters, sea grasses, and several other organisms
sticking themselves to rocks. These creatures adhere with unique classes of proteins. In recent
[1]
years, there has been a great deal of research effort devoted to mimicking the adhesive of mussels.
[2]
The 3,4-dihydroxyphenylalanine (DOPA) amino acid is present to confer cross-linking and adhesion.
Exciting progress is being made with regard to new surface coatings, hydrogels, drug delivery
matrices, sensors, and nanoparticle functionalization, amongst several applications.
Our research group is particularly interested in using biomimetic principles to develop high
strength adhesive materials. A hydrophobic, polystyrene-based system bonds strongly both dry and
underwater. One polymer family with varying amounts of polyethylene glycol demonstrates tunable
[3]
flexibility. A bio-based adhesive system can be made by catechol functionalizing of polylactic acid.
We have even been able to generate adhesives from select components of foods. In the best of
cases, dry adhesion can be greater than that of commercial products such as Super Glue
(cyanoacrylate). Underwater adhesion can also exceed the performance of commercially available
systems. In side-by-side comparisons, one biomimetic polymer adheres underwater with over ten
[4]
times the strength of adhesive generated by live mussels.
Mimicking intricate details of biological materials may still be beyond our reach. However, with
judicious choices of chemistry, methods, and targets, we are reaching a point at which some of the
more impressive aspects of biological adhesives can be achieved synthetically. These results will be
discussed in the context of future applications development including manufacturing, cosmetics, and
biomedical repair of tissues.
Fig. 1: A small amount of a mussel mimicking polymer is used to hold up a pot of live mussels.
[1]. J. Sedó, J. Saiz-Poseu, F. Busqué, D. Ruiz-Molina Adv. Mater. 2013, 25, 653− 701.
[2]. A. Hagenau, M. H. Suhre, T. R. Scheibel, Prog. Polym. Sci. 2014, 39, 1564-1583.
[3]. C. L. Jenkins, H. M. Siebert, J. J. Wilker, Macromolecules 2017, 50, 561-568.
[4]. M. A. North, C. A. Del Grosso, J. J. Wilker, ACS Appl. Mat. Inter. 2017, 9, 7866-7872.
90
NANOTECH-KN21
Guiding principles for peptide-based, life-like nanotechnology

1,2,3,4
Rein V. ULIJN*

1
Advanced Science Research Center (CUNY ASRC) of the Graduate Center, City University of New
York, New York, USA;
2
Department of Chemistry & Biochemistry, Hunter College, CUNY, New York, USA.
3
PhD programs in Chemistry and Biochemistry, Graduate Center, CUNY, New York, USA.
Keywords: systems chemistry, supramolecular materials, catalytic self-assembly, peptide

nanotechnology
Life’s diverse molecular functions are largely based on only a small number of highly conserved
building blocks- the twenty canonical amino acids. These building blocks are chemically simple, but
when they are organized in three-dimensional structures of tremendous complexity, new properties
emerge, giving rise to the extraordinary machinery of life. So, if just twenty simple building blocks-
when appropriately assembled - give rise to the complexity and functionality that can sustain life- then
this is clearly a very versatile construction set.
Our overall goal is conceptually simple: to figure out how to make nanoscale systems and
materials from biology’s building blocks, and to apply these materials to diverse problems, that require
them to be interfaced, ideally seamlessly, with living systems, or the natural environment.
Different from other research groups, we have an unbiased approach, that is not guided by copying
biological systems, and we keep these systems as simple as possible, which lowers barriers to
application. The talk will focus on our latest results in three areas: (i) directed discovery of peptide
nanostructures with new functions, by searching the sequence space (1,2); (ii) application of peptide
nanostructures as functional materials (including customizable melanin pigments (3) and cell culture
matrices (4)). (iii) actively assembling systems, that continuously turn over chemical fuels, enabling
dynamic changes in structure and function (5).
Fig. 1: Searching the peptide sequence space for new functions
[1]. C.G. Pappas, et al., Dynamic Peptide Libraries for the Discovery of Supramolecular
Nanomaterials, 2016 Nature Nanotechnol., 11 , 960.
[2]. P.W.J.M. Frederix, et al. Exploring the Sequence Space for (Tri-)peptide Self-Assembly to Design
and Discover New Hydrogels, 2015 Nature Chem., 7, 30-37.
[3]. A. Lampel, et al., Polymeric Peptide Pigments with Sequence-encoded Properties, 2017Science,
356, 1064.
[4]. E.V. Alakpa, et al. Tunable Supramolecular Hydrogels for Selection of Lineage-Guiding
Metabolites in Stem Cell Cultures, 2016 Chem, 1, 298.
[5]. M. Kumar, et al., Amino Acid-Encoded Biocatalytic Self-Assembly Enables the Formation of
Transient Conducting Nanostructures, 2018 Nature Chem. accepted.
91
NANOTECH-KN23
Bioinspired Surfaces with Wettability from Design to Functions

YONGMEI ZHENG*

Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology of Ministry of Education,
School of Chemistry, and Beijing Advanced Innovation Center for Biomedical Engineering, Beihang
University, Xueyuan Road 37, Haidian District, Beijing, China. *email:[email protected]
Keywords: Gradient, Micro- and Nanostructures, Bioinspired, Wettability, Droplet
Biological surfaces provide endless inspiration for design and fabrication of smart materials. It has
recently been revealed to have become a hot research area in materials and science world. For
instance, the capture silk of the cribellate spider Uloborus walckenaerius collects water through a
combination of multiple gradients in a periodic spindle-knot structure after rebuilding. Inspired by the
roles of micro- and nanostructures in the water collecting ability of spider silk, a series of bioinspired
gradient fibers has been designed by integrating fabrication methods and technologies such as dip-
coating, Rayleigh instability break-up droplets, phase separation, strategies of combining
electrospinning and electrospraying, and web-assembly. Based on such fabrications above, the
“spindle-knot/joint” structures can be tailored to demonstrate the mechanism of multiple gradients
(e.g., roughness, smooth, temperature-respond, photo-triggering, etc.,) in driving tiny water drops. A
water capturing ability can be developed by the combination of “slope” and “curvature” effects on
spindle-knots on bioinspired fiber, including heterostructured fibers to respond environmental humidity,
temperature-responsive fiber for directional transport of droplet effectively, multi-geometric gradient
fiber for the droplet target transport in a long range along as-designed bioinspired gradient fiber.
Otherwise, biological surfaces such as plant leaves and butterfly wings with gradient structure features
display the effect of water repellency. Smart bioinspired surfaces can be fabricated by combining
machining, electrospinning, soft lithography, and nanotechnology. The gradient surfaces exhibit robust
transport and controlling of microdroplets. These bioinspired gradient surfaces would be promising
applications.
Fig. 1: Bioinspired surfaces with wettability from design to functions.
[1]. Y. Zheng et al, Nature 2010, 463, 640-643.

[2].Y. Zheng, Bioinspired wettability surfaces. Pan Stanford Publishing. 2015, 0-216
[3].M. Zhang, L. Wang, Y. Hou, S. Feng, Y. Zheng. Adv. Mater. 2015, 27, 5057-5062.
[4].T. Xu, Y. Lin, M. Zhang, W. Shi, Y. Zheng. ACS Nano 2016, 10, 10681-10688.
[5].L. Wang, Q. Gong, S. Zhan, L. Jiang, Y. Zheng. Adv. Mater. 2016, 28, 7729-7735.
[6].M. Zhang, L. Wang, S. Feng, Y. Zheng. Chem. Mater., 2017, 29, 2899-2905.
92
NANOTECH-KN24
Ecoconception of metallic nanoparticles with bioinspired coatings:

a safer-by-design approach
1*
Isabelle MICHAUD-SORET
1
Univ. Grenoble Alpes, CNRS, CEA, BIG-LCBM, 38000 Grenoble, France
Keywords: metallic nanoparticle; titanium dioxide, silver, safer-by-design
Due to their unique intrinsic properties nanomaterials (NMs) have a significant technological impact.
As an example, NMs such as Ag or TiO2 nanoparticles are already used in paints for their
antimicrobial and self-cleaning properties, respectively. Nowadays, more than 1 800 nano-products
are on the market [1] and the production of NMs is predicted to increase exponentially to reach several
millions of tons in 2024 for TiO2 [2]. Consequently, the question of their release in the environment by
weathering or mechanical stress and the growing risk of human exposure have become a major
concern. A safer-by-design approach e.g. a responsible development of NMs through all the life cycle
(manufacture, use and end of life) must be taken into account. The objective was to develop a novel
nanocomposites via a “Safer-By-Design” approach in order to reduce drastically the release in the
environment and the risk of human exposure. The work of our group concerns silver Nanoparticles
(NP) [3] and titanium oxide nanoparticles. Concerning Ag-NP we develop a concept of NP assembly.
Concerning TiO2-NP, our collaborators, B. Fiorentino et al. [4] have shown a rapid and intense
degradation of the paint due to very small uncoated nanoparticles of TiO2 presenting very efficient
photo-catalytic properties compared to micrometric TiO2 traditionally used as pigment. The aim of our
work was to modify the surface of the TiO2 nanoparticles used by a paint manufacturer with a bio-
inspired approach in order to reduce the degradation of the organic part of the paint while maintaining
an appropriate photo-catalytic effect. We will present our strategy to disperse and stabilize the
particles in aqueous media with the use of bio-inspired ligands (amino-acids, iron chelators,
biodegradable polymers) as electrostatic and steric stabilizers. The photocatalytic activity of the new
composites materials was investigated under UV irradiation. Finally, the best candidates have been
dispersed in paints in order to evaluate their release during ageing.
[1] Project on Emerging Nanotechnlogies http://nanotechproject.org/cpi/.

[2] C.O. Robichaud, A.E. Uyar, M.R. Darby, L.G. Zucker, M.R. Wiesner, Env.Sci.Technol, 2009, 43,
12.
[3] M. Marchioni, T. Gallon, I. Worms, P.-H. Jouneau, C. Lebrun, G. Veronesi, D. Truffier-Boutry, E.
Mintz, P. Delangle, A. Deniaud, Isabelle Michaud-Soret. Insights into polythiol-assisted AgNP
dissolution induced by bio-relevant molecules. Environ. Sci.: Nano, 2018, 5, 1911-1920.
[4] B. Fiorentino, L. Golanski, A. Guiot, J.F. Damlencourt, D. Boutry, Journal of Nanoparticle Research,
2015, 17, 149.

93
SMARTTECH-KN02
Molecularly Imprinted Polymer Nanocomposites as Synthetic

Antibody Mimics for Biomedicine

Karsten HAUPT, Bernadette TSE SUM BUI, Paulina MEDINA RANGEL, Alejandra MIER

1
Université de Technologie de Compiègne, Compiègne, France;

Keywords: Biomimicry, functional polymers, synthetic antibodies, inhibitors, bioimaging
Molecularly imprinted polymers (MIPs) are synthetic antibody mimics that specifically recognize
molecular targets [1,2]. They are highly cross-linked polymers synthesized in the presence of the
target molecule acting as a molecular template. This templating induces three-dimensional binding
sites in the polymer that are complementary to the template in size, shape and chemical functionality.
The synthetic antibody can recognize and bind its target with an affinity and selectivity similar to a
biological antibody.
We present here new approaches for the synthesis of MIP, by localized polymerization at the
nanoscale. Photoinduced living radical polymerization using a dendritic multiiniferter was used to
synthesize protein-size, soluble MIP nanogels with a homogeneous size distribution [3]. Their mean
diameter is 17 nm and the average molecular weight 97 kDa, thus their size and density are very close
to those of biological antibodies. The MIP nanogels show specific binding of their targets, small
organic molecules or proteins, with a nanomolar affinity and a good selectivity. In addition, the direct
coating of thin MIP films around fluorescent nanoparticles [4,5] by localized photopolymerization using
the particles as individual internal light sources (Fig. 1), are described. The targets of these MIPs are
cell surface glucosides, and peptide epitopes of cell surface proteins.
The use of these functional nanomaterials as antibody-mimicking inhibitors of biological functions, for
bioassays [6] as well as for cell and tissue imaging [5,7] by fluorescence microscopy will be
demonstrated on fixated and living keratinocytes, and on tissue samples.
Fig. 1. Left: Localized photopolymerization of MIP nanocomposites with quantum dots.

Right: Confocal fluorescent microscopy imaging with MIPs as antibody mimics.
[1] R. Arshady, K. Mosbach, Makromol. Chem. 1981, 182, 687-692.

[2] K. Haupt, et al., Top. Curr. Chem. 2012, 325, 1-28.
[3] P. Çakir, et al. Adv. Mater. 2013, 25, 1048-1051.
[4] S. Beyazit, et al. Angew. Chem. Int. Ed. 2014, 53, 8919-8923.
[5] M. Panagiotopoulou et al. Angew. Chem. Int. Ed. 2016, 55, 8244-8248.
[6] J. Xu, K. Haupt, B. Tse Sum Bui, ACS Appl. Mater. Interfaces 2017, 9, 24476-24483.
[7] M. Panagiotopoulou et al. Biosensors & Bioelectronics, 2017, 88, 85-93.
94
SMARTTECH-KN03
Advanced molecularly imprinted polymer as electrochemical

sensor interfaces

Catherine Branger, Hugues Brisset

Université de Toulon, Laboratoire MAPIEM, Toulon, France

Keywords: molecularly imprinted polymer (e-MIP), ferrocene, electrochemistry
Molecularly Imprinted Polymers (MIPs) are three-tridimensional polymers network prepared around a
molecular template. The release of template leads to polymers with binding cavities, which retain
shape, size and orientation of the target molecule. Due to their simple synthesis, high stability and low
cost MIPs can advantageously replace natural receptors in biosensor devices [1].
Based on this, we developed since few years electrochemical molecularly imprinted polymers (e-MIP)
specially designed to detect organic molecules thanks to the electrochemical answer of a redox probe
inserted inside the binding cavities of cross-linked MIPs during synthesis (figure 1) [2].
Fig. 1: concept of e-MIP detection
This new concept was first established for the detection of benzo[a]pyrene with vinyl-ferrocene using
as redox probe and as functional monomer [3]. More recently we have extended this strategy to the
detection of Bisphenol A from ferrocenylmethyl methacrylate as functional redox tracer. In this case e-
MIP microbeads particles were incorporated in a graphite paste to prepare screen-printed carbon
electrodes. Electrochemical properties these new sensors revealed a highly sensitivity in the presence
of BPA in aqueous medium compared to the corresponding non imprinted polymer with a limit of
detection (LOD) of 0.06 nM [4].
References
[1] K. Haupt, K. Mosbach, Chem. Rev. 2000, 100, 2495–2504
[2] C. Branger, H. Brisset, D. Udomsap, French patent FR 1262617 ; PCT/IB2013/ 061196
[3] D. Udomsap, C. Branger, G. Culioli, P. Dollet, H. Brisset, Chem. Comm. 2014, 50, 7488–7491
[4] V. Mba Ekomo, C. Branger, R. Bikanga, A.-M. Florea, G. Istamboulie, C. Calas-Blanchard, T.
Noguer, A. Sarbu, H. Brisset, Biosens. Bioelectron. 2018, under revision
95
SMARTTECH-KN04
Molecular mechanisms in mineral nanoparticle interactions with

proteins

1 1 2 1
Vadim KESSLER*, Gustav NESTOR, Nicholas KOTOV, Gulaim SEISENBAEVA

1
Department of Molecular Sciences, BioCenter SLU, Box 7015, 75007 Uppsala, Sweden;
2
Department of Chemical Engineering, Michigan University, Ann Arbor, MI 48109-2800, USA

Keywords: mineral oxide nanoparticles, solution reactivity, wound healing, tissue engineering, hybrid
materials
Broadly recognized health effects of metal oxide nanoparticles (NP) are caused by their “protein
corona”. Interaction of NPs with blood proteins can, dependent on the nature of metal oxide, result
either in enhanced hydrolysis of peptide bonds or, on the contrary, in enhanced aggregation and
clotting. In both cases appreciable effects can be observed on the immune recognition and tissue
regeneration [1-3].
In the present contribution some advanced applications of mineral nanoparticle dispersions for
regulating immune reactions and for creation of new advanced hybrid biomaterials will be presented.
Interaction of mineral nanoparticles with peptides and proteins will be discussed based on, on one
hand, partly experimental investigation of specific adsorption of proteins on nanostructured surfaces,
and, on the other hand on experimental structure determination of peptide and protein complexes with
nano-sized oxide clusters, polyoxometallate compounds (POMs). Structural studies of
Polyoxometallate (POM) ions binding to biomolecules when carried out with atomic resolution offer a
key to understanding of potential chemical mechanisms in metal oxide nanoparticle-protein
interactions. These compounds, even when produced from chemically different but structurally
identical spherical POMs, demonstrate appreciable difference in the crystal structures and in the
chemical behavior especially in relation to the bonding between POMs and the peptide and the
hydrolysis mechanisms for POMs in the presence of peptide. These observations have potential to
unveil possibly diverse effects of chemically different NPs on the body fluids.
3−
Fig. 1: One of the bonding modes of a protonated GlyGly peptide to the [PW12O40] anion.
[1]. G.A. Seisenbaeva, K. Nilsson Ekdahl, V.G. Kessler et al., Sci. Rep., Nature PG, 2017, 7,
15448.
[2] G.A. Seisenbaeva, V.G. Kessler, I.S. Choi, et al., Angew. Chem. Int. Ed., 2017, 56, 10702-
10706.
[3] K. Nilsson Ekdahl, Seisenbaeva G.A, Kessler V.G, Nilsson B., et al. Nanomedicine:
Nanotechnology, Biology and Medicine, 2017, 14, 735-744.

96
SMARTTECH-KN05
Aerobic Catalytic Systems Inspired by Copper Amine Oxidases

Martine LARGERON

UMR 8638 CNRS−Université Paris Descartes, Paris, France
Keywords: amine; bioinspired catalyst; imine; metalloenzyme; purpurogallin.
The development of biomimetic methods that utilize environmentally benign oxidants such
as molecular oxygen or, much better, ambient air at room temperature, and avoid deleterious
side reactions, is one of the most promising goals in oxidation chemistry today.
Recently, there has been a boost in the development of various catalytic methods for the
aerobic oxidation of amines to imines given the widespread importance of imines as pivotal
synthetic intermediates in a plethora of reactions such as reduction, addition, condensation
and cycloaddition [1]. Imines also serve as essential pharmacophores in numerous biologically
active compounds.
Natural copper amine oxidase (CuAO) enzymes have revealed their efficiency as catalysts
to perform controlled aerobic oxidation of amines under mild conditions. These enzymes
couple the oxidation of primary amines to aldehydes with the reduction of O 2 to H2O2, through
the synergistic action of a quinone-based cofactor (topaquinone) and a copper ion. As a
consequence, researchers have begun to realize that CuAOs could constitute a rich source of
inspiration for the rational design of small-molecules catalysts for the oxidation of amines to
imines. They have designed biomimetic “first-order” quinone-based catalysts with two
objectives: 1) to achieve controlled sustainable aerobic amine oxidation reactions; 2) to expand
the scope of possible substrates [2].
Recently, the concept of “second-order” biomimicry has been introduced to describe a
system in which in situ modification of precatalyst components affords the biomimetic catalyst
[3]. Such systems may be contrasted with “first-order” biomimicry in which an active biomimetic
catalyst is synthesized directly before its use. As an example of “second-order” biomimicry, a
bioinspired organocatalytic cascade reaction is presented which starts from inexpensive commercially
available pyrogallol and allows, under ambient air, the in situ formation of not easily accessible natural
purpurogallin [4]. This is further engaged in the CuAOs-like catalytic process for producing, under
single turnover conditions, the active biomimetic organocatalyst which mediates the oxidative cross-
coupling of primary amines to imines under exceptionally mild conditions (Fig. 1).
Fig. 1: Example of “second-order” biomimicry (one pot protocol)
[1]. For a review, see: B. Chen, L. Wang, S. Gao, ACS catal. 2015, 5, 5851.
[2]. For a review, see: M. Largeron, Org. Biomol. Chem. 2017, 15, 4722-4730.
[3]. S. D. Mc Cann, J.-P. Lumb, B. A. Arndtsen, S.S. Stahl, ACS Cent. Sci. 2017, 3, 314-321.
[4]. M. Largeron, M.-B. Fleury, Chem. Eur. J. 2017, 23, 6763-6767.
97
SMARTTECH-KN06
Sol-Gel transitions of modified polysaccharides

under temperature and salt control.

1,2 1,2 1,2
Dominique HOURDET* , Guylaine DUCOURET , Hui GUO ,
1,2
Mickaël DE MAGALHAES GONCALVES

1
Laboratoire Sciences et Ingénierie de la Matière Molle, CNRS, ESPCI Paris,
PSL Research University, 10 rue Vauquelin, F-75005 Paris, France;
2
Laboratoire Sciences et Ingénierie de la Matière Molle, Université Pierre et Marie Curie,
Sorbonne-Université, 10 rue Vauquelin, F-75005 Paris, France.

Keywords: Alginates, temperature-responsive, sol/gel transition
Associating polymers have known a large development during the last decades due to their high
performances as thickeners in aqueous media with important applications in various domains like oil
recovery, cosmetics or paints. With time the systems become more efficient, even smart as they are
able to change their properties under controlled environmental conditions. This is the case of
responsive polymers [1] which respond to stimuli like salt, pH, temperature, light or external fields.
Under controlled conditions, these systems readily form physical networks or nanostructures which
offer wide potentialities in biomedical engineering.
In this context, biopolymers have an important role to play and we are currently developing a platform
of responsive polysaccharides [2-3]. In this work, new thermo-associating copolymers have been
prepared by grafting thermoresponsive poly(N-isopropylacrylamide) (PNIPAM), characterized by a
LCST behavior, onto a rich mannuronic alginate backbone (ALG) [4]. Working in semi-dilute solutions,
we show by coupling DSC and viscoelastic measurements that ALG-g-PNIPAM solutions are able to
form gels either by cooling or heating depending on the ionic environment (see Fig.1). As the
aggregation process of ALG and PNIPAM depends mainly and respectively on the nature of the
cations and anions, the choice of the salt is then critical to control the self-assembly behavior.
G’ (Pa) G’’ (Pa)

104
P
N
I PA M P N
A
M
P P
N
P
MMMM
I P
Gel Gel Gel N N
I
MMMM
MMMM
P A MMMM 103 I I
M
P P
MMMM A A Fig. 1: Sol/Gel
MMMM
102 M M transitions of
N I P M
P A
ALG-g-PNIPAM in
P A N I
M P
P
N
I
101
P
MM
M
potassium salt
A
A
MM
P
I
N
P
M M
M
M P solution [1].
100 MM M
M
I
N
M
M
P
M N
A
P M M
Gel Sol Gel

I
P
A
P
MMMM
I
MM M M
M MM A
N
M
10-1 M
P
M
MMMM M
M
0 10 20 30 40 50 60 MM
Temperature °C
M
P
A
N
P
I
I
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A
M
M
M
MM
[1]. H. Guo, A. Brûlet, P. R. Rajamohanan, A. Marcellan, N. Sanson, D. Hourdet D, Polymer 2015, 60,
164-175.
[2]. C. Karakasyan, S. Lack, F. Brunel, P. Maingault, D. Hourdet, Biomacromolecules 2008, 9, 2419-
2429.
[3]. N. R. Gupta, A. Torris, P. P. Wadgaonkar, P. R. Rajamohanan, G. Ducouret, D. Hourdet, C.
Creton, M. V. Badiger, Carbohydrate Polymers 2015, 117, 331–338.
[4]. H. Guo, M. De Magalhaes Goncalves, G. Ducouret, D. Hourdet, Biomacromolecules, 2018, Just
Accepted Manuscript, DOI: 10.1021/acs.biomac.7b01667.
98
SMARTTECH-KN07
Bio-inspired Surfaces Showing Reversible/Repeatable

Thermo-responsive Anti-icing/Snow Properties
Chihiro Urata and Atsushi Hozumi*

National Institute of Advanced Industrial Science and Technology (AIST),
2266-98, Anagahora, Shimoshidami, Nagoya 463-8560, Japan
Keywords: Biomimetics, organogels, anti-icing, micro/nanostrucutres, thermo-responsivity
Anti-icing (icephobic) surfaces possessing ice adhesion strength of less than 10 kPa have
attracted much attention lately for safety purposes with applications in automobiles, aircrafts, power
lines, wind turbines and so on. In this study, we report novel type of organogels, which we have
named SLUG (Self-Lubricating Gels) [1,2], showing reversible/repeatable thermo-responsive anti-
icing/snow properties. We have developed this unique material by mimicking the mucus secretion from
the body surface of slug. Our SLUG can spontaneously release silicone oil from their inner gel
matrices to their outer surfaces in response to changes in ambient temperatures. Utilizing this unusual
phenomenon, that is, syneresis, we achieved excellent thermo-responsive anti-icing/snow properties
[1].
We successfully tuned the syneresis temperatures (-15 ~ 25 °C) to achieve reversible/repeatable
thermo-responsive anti-icing/snow properties. In our present case, the syneresis gradually begins as
the temperature is cooled below 0 °C, and the silicone oil is drawn back into the SLUGs again by
heating it to room temperature. Thanks to this smart thermo-responsive property, an ice-pillar or snow
on SLUG surfaces below 0 °C can easily slide off without any external force. In addition, due to the
addition of nano/microstructures to the SLUG surfaces, the resulting samples also show unique optical
(diffraction and anti-reflection (moth-eye effect)) properties, besides icephobicity. Our thermo-
responsive nanostructured SLUG undoubtedly shows great potential for solar cell applications in
snowy regions.
2 0 0 μm 2 0 0 μm
Fig. 1: Typical SEM images of the micropatterned SLUG surfaces at 25°C (left, no syneresis) and -

15°C (right, syneresis).

References
[1] A. Hozumi et al., J. Mater. Chem. A., 3, 12626 (2015).
[2] A. Hozumi et al., Langmuir, 33, 9972 (2017).
99
SMARTTECH-KN08
Design of Hybrid Materials based on Metal Organic Frameworks for

bioimaging and biodetection applications.

1*
Nathalie STEUNOU

1
Institut Lavoisier, Université Versailles St Quentin-en-Yvelines, Université Paris Saclay, Versailles,
France. Email:[email protected]

Keywords:MOFs, iron oxide, biomedicine, bioimaging, drug delivery, biodetection
In all living organisms, Nature provides a wide range of materials of complex architecture and
functions. One of the remarkable feature of Nature is its ability to combine at the nanoscale
(bio)organic and inorganic components following a clearly defined pattern. These natural materials
present a complex hierarchical microstructure able to accommodate a maximum of elementary and
complementary functions in a small volume. Such observations have motivated materials chemists to
produce a wide range of materials with controlled organic–inorganic interface, porosity and/or texture.
In the domain of biomedicine, the integration of multiple components and thus functionalities into
a single nanomedicine has appeared as a promising strategy, expanding the capabilities of nano-
vectors to perform multiple parallel tasks. In particular, the strategy of combining into a single nano-
object the functions of diagnosis/imaging and therapy (called “theranostics”) has emerged as an
essential breakthrough in nanomedicine, allowing monitoring the treatment in real time rather than
1
performing imaging before or after a treatment.
However, numerous drug delivery carriers reported so far suffer from serious limitations such as :
(1) poor drug loading typically lower than 10 wt% (weight percentage of drug to the carrier material)
inducing both poor efficacy of the active molecule and high toxicity or side-effects, (2) rapid (reported
as « burst release ») or non-specific delivery of the encapsulated drug leading to its poor
biodistribution, (3) difficulty of by-passing physiological barriers and (4) the lack of reproducible scale-
up processes of drug nanocarriers through cost-effective and eco-compatible synthesis routes for an
2
industrial pharmaceutical application. These drawbacks, together with an often insufficient Enhanced
Permeability and Retention effect (EPR) efficacy, are at the origin of the current limited number of
manufactured drug nanomedicines. This justifies the need to design novel, multifunctional and more
efficient nano-objects for nanomedicine.
Nanoparticles of Metal Organic Frameworks (MOFs) have emerged recently as promising drug
3
delivery platforms or stimuli-responsive nano-carriers. They are a class of highly porous hybrid
crystalline materials with a large chemical and structural diversity, most of them exhibiting a very large,
3 -1
tunable and regular porosity with pore sizes and volumes up to 60 Å and 4 cm .g . Their large surface
area, amphiphilic internal microenvironment as well as the possibility to introduce easily in the pores
and frameworks on a spatially controlled way functional groups (e.g. acidic, basic, redox,
hydrophobic…) through the metal or the organic linker make these materials suitable to host a large
4
variety of drugs with a high loading capacity.
The present communication deals with the the design of surface-decorated or core-shell nano-
objects by assembling nanoparticles of mesoporous iron trimesate MOF (i. e.MIL-100(Fe)) and
5
maghemite. Not only is this bimodal nanovector produced through a cost-effective and reliable green
approach, but it also exhibits excellent colloidal stability under simulated intravenous conditions, and
its ability to encapsulate and progressively release drugs is preserved. This nano-object presents a
superparamagnetic behavior characterized by a high saturation magnetization at room temperature.
More importantly, it combines low toxicity with high anti-tumoral activity and can be used in vivo as an
efficient MRI contrast agent because of its excellent relaxivity properties. All these properties make
this nano-object a bimodal therapeutic nanovector coupling drug-delivery and MRI properties.
[1] L. Eun-Kyung, T. Kim, S. Paik, S. Haam, Y.-M. Huh, K. Lee. Chem. Rev. 2015, 115, 327-394.
[2] P. Couvreur, Adv. Drug. Deliver. Rev. 2013, 65, 21-23.
[3] Themed issues: Chem. Soc. Rev. 2017,46, 3104-3481.
[4] P. Horcajada, R. Gref, T. Baati, P. K. Allan, G. Maurin, P. Couvreur, G. Ferey, R. E Morris, C.
Serre, Chem. Rev. 2012, 112, 1232-1268 .
[5] S. Sene, M. T. Marcos-Almaraz, N. Menguy, J. Scola, J. Volatron, R. Rouland, J. – M. Grenèche,
S. Miraux, C. Menet, N. Guillou, F. Gazeau, C. Serre, P. Horcajada, N. Steunou, Chem 2017, 3, 303-
322.
100
SMARTTECH-KN09
Nanoplasmonic Bioprobes: Golden Prospects for Biosensing,

Diagnostics and Immunotherapy
Tuan VO-DINH

Fitzpatrick Institute for Photonics
Departments of Biomedical Engineering
Department of Chemistry
Duke University
Durham, NC 27705-0281, USA
Keywords: biosensor, nanosensor, diagnostics, immunotherapy, plasmonics, surface-enhanced

Raman scattering (SERS), global health, cancer treatment
This lecture presents the development and application of plasmonics-active nanoplatforms for
use in sensing, diagnostics and therapy by integrating several areas of research at the nexus of
engineering, biology, medicine and nanotechnology. A new generation of nanoprobes using plasmonic
nanomaterials including gold nanostars combining bio-recognition and nanotechnology has been
developed for in vivo monitoring of biochemical processes in a single living cell. A unique
nanoplatform based on gold nanostars equipped with nucleic acid biorecognition probes, referred to
as ‘Molecular Sentinel’ nanoprobes, has been developed to detect DNA targets of pathogenic agents
and biomarkers of diseases (cancer, infectious diseases) using surface-enhanced Raman scattering
(SERS) detection scheme. The Molecular Sentinel nanoprobes have been developed to detect DNA
targets of pathogenic agents (e.g., HIV) and biomarkers of diseases (e.g., BRCA1, ERB2 breast
cancer genes). Other plasmonic platforms, such as gold nanostars, offer plasmon properties that
efficiently transduce photon energy into heat for photothermal therapy. Nanostars, with their small core
size and multiple long thin branches, exhibit intense two-photon luminescence, and high absorption
cross sections that are tunable in the near infrared region with relatively low scattering effect,
rendering them efficient photothermal agents in cancer photo-immunotherapy.
SERS-based plasmonic nanoprobes and biochip systems have also been developed for use as
diagnostic systems for point-of-care personalized nanomedicine and global health applications.
Ultrabright SERS-encoded nanorattles using DNA hybridization bioprobes with magnetic beads can be
designed for the detection of plasmodium falciparum malaria parasite using microfluidic chips. In non-
medical research areas, these nanoprobes can also be used for sensing plant cells in biofuel
development. Using nanofabrication, SERS-based plasmonic nanochip systems can also be
developed for use as environmental sensors and diagnostic systems for point-of-care and global
health applications.
In the field of nanobiosensing of individual cells a unique advance has been the development
of optical nanosensors, which have dimensions on the nanometer (nm) size scale. Using lasers as
excitation sources for these nanosensors, it has become possible to probe physiological parameters
(pH), biochemical species (DNA adducts) and monitor molecular pathways (apoptosis) in a single
living cell. These nanosensors lead to a new generation of nanophotonic tools that can detect the
earliest signs of disease at the single-cell level and have the potential to drastically change our
fundamental understanding of the life process itself. Such bioprobes open new horizons to a myriad of
applications ranging from sensing of plant cells for renewable energy research to cancer diagnostics
at the point of care, global health, molecular imaging, and applications to cancer treatment.

101
SMARTTECH-KN10
Recent Progress Activatable Photosensitizers and Fluorescent

Probes

Juyoung YOON *

Department of Chemistry and Nano Science, Ewha Womans University, Seoul, Korea

Keywords: Activatable photosensitizers, phthalocyanines, fluorescent probes
Switchable phototheranostic nanomaterials are of particular interest for specific biosensing, high-
1
quality imaging, and targeted therapy in the field of precision nanomedicine. Here, we develop a “one-
for-all” nanomaterial that self-assembles from flexible and versatile phthalocyanine building blocks.
The nanostructured phthalocyanine assemblies (NanoPcTBs) display intrinsically unique photothermal
2
and photoacoustic properties. Fluorescence and reactive oxygen species (ROS) generation can be
triggered depending on a targeted, protein-induced, partial disassembly mechanism, which creates
opportunities for low-background fluorescence imaging and activatable photodynamic therapy (PDT).
We also recently reported a facile strategy to directly assemble a phthalocyanine photosensitizer
(PcS) with an anticancer drug mitoxantrone (MA) to form uniform nanostructures (PcS-MA), which not
only display nanoscale optical properties but also have the capability of undergoing nucleic acid-
3 4,5
responsive disassembly. Recent progress from our group on the fluorescent probes for HOCl, and
6
GSH will be also presented.
Fig. 1: The structure of PcTB and TEM images of NanoPcTBs before and after adding avidin
[1]. (a) X. Li, S. Lee, J. Yoon, Chem. Soc. Rev. 2018, 47, 1174-1188. (b) X. Li, J. Kim, J. Yoon, X.
Chen, Adv. Mater. 2017, 29, 1606857.
[2]. X. Li, C-y. Kim, S. Lee, D. Lee, H.-M. Chung, G. Kim, S.-H. Heo, C. Kim, K. S. Hong, J. Yoon,
J. Am. Chem. Soc. 2017, 139, 10880–10886.
[3]. X. Li, S. Yu, D. Lee, G. Kim, B. Lee, Y. Cho, B.-Y. Zheng, M.-R. Ke, J.-D. Huang, K. T. Nam,
X. Chen, J. Yoon, ACS Nano 2018, 12, 681-688.
[4]. Y. L. Pak, S. J. Park, D. Wu, BH Cheon, H. M. Kim, J. Bouffard, J. Yoon, Angew. Chem. Int.
Ed. 2018, 57, 1567-1571.
[5]. Q. Xu, C. H. Heo, G. Kim, H. W. Lee, H. M. Kim, J. Yoon, Angew. Chem. Int. Ed. 2015, 54,
4890-4894.
[6]. Z. Liu, X. Zhou, Y. Miao, Y. Hu, N. Kwon, X. Wu, J. Yoon, Angew. Chem. Int. Ed. 2017, 56,
5812–5816.
102
SMARTTECH-KN11
Bioinspired wet-lubricious materials

1
Feng ZHOU,

State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics
18 Middle Tianshui Road, Lanzhou, 730000 China
*email: [email protected]
Keywords: weting, lubrication, drag reduction, adhesion

The translated term of lubrication into Chinese includes two aspects of "wetting" and "lubrication".
However, whether can wetting lead to lubrication has not been systematically elucidated. For solid-
solid friction, only if water or other liquid lubricants completely wet the friction surfaces, can they form
stable liquid film and perform lubrication medium. However, wetting cannot guarantee effective
lubrication due to low viscosity of liquids. The feasible way is to utilize liquid affinity macromolecules to
trap the liquid between sliding pair, which I will present rational design of interfacial materials for ultra-
low friction and antiwear. For solid-liquid interface, reducing the surface wettability indicates a
reduction of the solid-liquid interface molecular interaction and so the solid-liquid interface friction.
Especially when the fluid cannot wet the solid surface (i.e., the super-hydrophobic state), due to
presence of an air layer, the frictional resistance transforms from the solid-liquid interface to solid-gas
interface and so the friction can be greatly reduced. One recent example we’ve achieved recently is to
create alternating hydrophobic/hydrophilic strips to trap air rings as that more than 77% drag reduction
is reached.

-
brushes fiber brushes
spherical brushes hydrogels
-
coatings
Fig. 1: wetting and lubrication and their control; wet-lubricious materials
103
SMARTTECH-KN14
Stimuli-Responsive Supramolecular Systems Bio-Inspired in

Anthocyanins
1 1
Nuno BASÍLIO * and Fernando PINA
1
REQUIMTE – Laboratório Associado para a Química Verde, Departamento de Química, Faculdade
de Ciências e Tecnologia, Universidade NOVA de Lisboa, 2829-516 Monte de Caparica, Portugal,
.
[email protected]
Keywords: Anthocyanins; Photochemistry; Stimuli-Responsive Supramolecular Systems
Anthocyanins and related compounds are involved in a multistate of chemical reactions that in acidic
medium give rise to five different species reversibly interconnect by four chemical reactions, Scheme
1.
OCH3 Proton Transfer OCH3 Hydration OCH3

Tautomerization OCH3
OH Isomerization OCH3
OH ka kh OH
kt OH ki
OH HO OH OH
O HO O+ HO O HO OH O
O OCH3
k-a[H+] OCH3 k-h [H+] OCH3
k-t OCH3
k-i OCH3
+ H+ + H+ GlO O
OGl OGl OGl OGl
Quinoidal base (A) Flavylium cation (AH+) Hemiketal (B2) cis-chalcone (Cc) trans-chalcone (Ct)
kn
Kn= n=a,h,t,i
k-n
Scheme 1. The multistate of chemical species involving anthocyanins and related compounds.
The mechanism depicted in Scheme 1 is followed by all flavylium derivatives obtained from synthetic
or natural sources. The multistate network of chemical reactions can be actuated by external stimuli
such as pH and light conferring responsive properties to the system.[1-2] These properties have been
explored to devised photochromic materials, models for optical memories and molecular systems
capable of mimic elementary properties of neurons.[3] The selective interaction of the multistate
species with water-soluble supramolecular receptors allows the developed of multistimuli-responsive
host-guest systems with potential applications in, for example, drug-delivery and molecular
machines.[4-5] In this presentation the kinetics, thermodynamic and photochemical properties of the
flavylium network of reactions will be discussed and the application of these compounds in the
development of stimuli-responsive supramolecular systems will be highlighted.
[1] F. Pina, Chapter 11, Thermodynamic and kinetic processes of anthocyanins and related
compounds and their bio-inspired applications” Recent Advanced in Polyphenols Research, Vol. 4,
Wiley-Blackwell, 2014.
[2] S. Gago, N. Basílio, A. Moro, F. Pina, Chem. Comm., 2015, 51, 7349-7351.
[3] F. Pina, M. J. Melo, C. A. T Laia, A. J. Parola, J. C. Lima Chem. Soc. Rev. 2012, 41, 869-908.
[4] Basílio, N.; Pischel, U. Chem. - A Eur. J. 2016, 22 , 15208.
[5] A. Zubillaga, P. Ferreira, A. J. Parola, S. Gago, N. Basílio, Chem. Commun. 2018, 54, 2743.

104
HUGS-KN01
Chemo-enzymatic synthesis, biological properties,

functionalizations and polymerizations of biobased bisphenols
derived from ferulic and sinapic acids
1
Florent ALLAIS*
1
Chaire Agro-Biotechnologies Industrielles (ABI) - AgroParisTech, CEBB 3 rue des Rouges Terres
51110 Pomacle, France
Keywords: ferulic acid, sinapic acid, biocatalysis, antioxidants, monomers, polymers, resins
Novel renewable bisphenols were prepared from ferulic and sinapic acids – two biobased p-
hydroxycinnamic acids - through chemo-enzymatic processes under mild conditions. The enzyme-
catalyzed steps have been optimized and lead to high purity grade bisphenols in high to excellent
yields. Estrogenic activity test revealed no endocrine disruption for all the bisphenols.
The antiradical/antioxidant properties of these bio-based bisphenols were investigated and revealed
activities similar or higher than that of current commercially available antiradical/antioxidant additives
®
such as Irganox 1010 .
The bisphenols were used as monomers for the preparation of various types of alternating
aliphatic/aromatic polymers such as copolyesters, polyurethanes, polyolefins, poly(ester-alkenamers),
non-isocyanates polyurethanes (NIPUs) and epoxy resins. The newly obtained materials were then
characterized by NMR, GPC, DSC, TGA and DMA. These analyses revealed not only good thermal
stabilities, a broad range of accessible Tg but also thermo-mechanical properties similar to widely used
materials such as PET and DGEBA-based epoxy-amine resins.
Fig. 1: From phenolic acids to additives, monomers and polymers/resins
105
HUGS-KN02

Cleave and Couple: Sustainable pathways to value added
chemicals from renewable resources
Katalin Barta
Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The
Netherlands
[email protected]
Lignocellulose is a promising renewable raw material that is produced as part of agricultural and
forestry waste streams in large enough quantities globally to cover a substantial demand on chemical
[1]
building blocks. However in order to achieve true economic feasibility of future biorefineries, it should
[2]
be ensured that maximum value is derived from all individual lignocellulose components. This
requires novel catalytic strategies that are able to convert even the most challenging component,
[3,4]
lignin to (preferably) aromatic building blocks. Furthermore, the downstream processing of the
platform chemicals obtained, still needs significant improvement in order to access sufficient diversity
of products, ultimately covering an entire value pyramid of new bio-based materials.
Importantly, any new technology needs to be feasible for the conversion of large amount of renewable
material. To reach the level of sustainability that is desired here, research questions need to be re-
designed to maximize material balance, energy efficiency and sustainability globally. This should be
achieved by implementing highly efficient, waste-free transformations and Earth-abundant metal
catalysts in the individual reaction steps.
In this contribution I will describe our “cleave and couple” strategy, where “cleave” refers to the
[2] [3,4]
catalytic deconstruction of lignocellulose or lignin to aromatic and aliphatic alcohol intermediates,
and “couple” involves the development of novel, sustainable transformations for the formation of C-C
[2,5,6]
and C-N bonds in order to obtain a range of attractive products from lignocellulose.
[1] Chemical Reviews, 2018, 118 (2), 614-678.

[2] Nature Catalysis, 2018, 1 (1), 82-92.
[3] J. Am. Chem. Soc, 2016, 138 (28), 8900–8911; J. Am. Chem. Soc, 2015, 137 (23), 7456–7467.
[4] Green Chemistry, 2017, 19(12), 2774-2782.
[5] Nature Comm., 2014, 5, doi: 10.1038/ncomms6602.
[6] Science Advances, 2017, 3 (12), eaao6494.
106
HUGS-KN03
Synthesis of biobased building blocks from cashew nutshell liquid:

a chemical platform approach for polymer synthesis
Sylvain Caillol
Institute Charles Gerhardt, Montpellier, France
We propose a platform approach for the synthesis of various building blocks from cardanol in one or
two-steps syntheses. Cardanol, which is a natural phenolic oil, is issued from Cashew Nutshell Liquid
(CNSL), a non-edible renewable resource, co-produced from cashew industry in large commercial
volumes (1Mt p.a.). Cardanol is non-toxic and particularly suitable for the addition of aromatic
renewable resources in polymers and materials. Various routes were used for the synthesis of di- and
poly-functional building blocks used thereafter in polymer syntheses. Phenolation was used to
dimerize/oligomerize cardanol to propose increase functionality of cardanol. Thio-ene was used to
synthesize new reactive amines. Epoxidation and (meth)acrylation were also used to insert oxirane or
(meth)acrylate groups in order to synthesize polymers and materials. Finally, we also synthesized a
new radically polymerizable monomer from cardanol. Hence we synthesized cardanol-based aromatic
latex by water emulsion radical polymerization for styrene-free coating applications.
[1] Synthesis of cardanol oil building blocks for polymer synthesis, F Jaillet, E Darroman, A
Ratsimihety, B Boutevin, S Caillol*, Green Materials, 2015, 3, 1-29
107
HUGS-KN06

From hydrophilic to hydrophobic wood using direct fluorination
1,2 1 2 2 3,4
Martial Pouzet , Marc Dubois , Karine Charlet , Alexis Béakou , Jean-Michel. Leban , Mohamed
1
Baba
1
Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, F-
63000 Clermont-Ferrand, France
2
Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut Pascal, F-63000 Clermont-Ferrand,
France
3I
NRA, Biogéochimie des Ecosystèmes Forestiers, 54280 Champenoux
4
IGN, Laboratoire de l’Inventaire Forestier, 54000 Nancy, France
Keywords: surface treatment, fluorination, water absorption, spectroscopy, cellulose, lignin
The main limiting factor for the use of solid wood lies in its highly hydrophilic character which is
associated with the loss of its properties after moisture uptake. Therefore for limiting the negative
impact of moisture in wooden structures, numerous research have been carried out in order to (i)
protect the surface of wood by the addition of varied varnish or protections or to (ii) modify the wooden
surfaces structure by the mean of different technologies such as thermal treatments. The former
present the disadvantage to protect the wood surfaces for a limited period of time while the later
present the disadvantage to reduce the mechanical properties. Investigate how to reduce the
hydrophilic character of wood without reducing physical and mechanical properties is of primary
importance. Gas/solid fluorination was performed to decrease the hydrophilic character of wood.
In a first step, the relationship between the chemical composition of natural fibres and their reactivity
during fluorination have been established [1]. Indeed, on the one hand, the affinity for F2 is improved
by the presence of lignin, leading to a better conversion of COH into CF bonds. On the other hand, a
high cellulose content tends to inhibit the reaction. We use then dynamic fluorination using F2 gas
applied to wood samples (Douglas and silver fir) for reducing the hydrophilic character [2-4]. The
covalent grafting of fluorine atoms on a wood surface was highlighted by Fourier-Transform infrared
19
spectroscopy and F solid state Nuclear Magnetic Resonance. The wood samples acquire a
hydrophobic character comparable to that of Polytetrafluoroethylene, thanks to fluorination. The high
durability of this treatment was also determined by aging tests under ambient atmosphere and UV
irradiation. Moreover, this treatment gives a surface with a hydrophobic character without major
structural (morphology, density and color) and mechanical modifications.
The mechanical properties of wood polyester composites have been enhanced by acting on the
wood/polymer interfaces [3]. X-ray tomography showed that the fluorination of wood flour decreased
the quantity of pores within the composites. Tensile and flexural tests revealed an improvement of the
composite properties through fluorination of the reinforcements. Both the elastic modulus and the
strength were increased. The treatment also improved the creep properties of the wood–polyester
composites, making them less sensitive to temperature. Furthermore, the composite surface energy
and its hydrophilicity were decreased after the treatment of the wood reinforcements. The further
fluorination of a composite made of fluorinated wood led to a contact angle comparable to that of
some metals (steel, gold) due to the etching of the composite surface during fluorination.
[1] M. Pouzet, M. Dubois, K. Charlet, A. Béakou, Mater. Design 2017, 120, 66-74
[2] M. Pouzet, D. Gautier, K. Charlet, M. Dubois, A. Béakou, Applied Surf. Sci. 2015, 353, 30, 1234-
1241
[3] K. Charlet, F. Saulnier, M. Dubois, A. Béakou, Mater. Design, 2015,74, 61-66
[4] F. Saulnier, M. Dubois, K. Charlet, L. Frezet, A. Beakou, Carbohydrate Polymers 2013, 94, Pages
642-646
108
HUGS-KN06

Alternative solvents such as ionic liquids or deep eutectic solvents:

are they green or not?

1 2 1 1
Guy MARLAIR , Christophe LEN , Pascal PANDARD & Anne BADO-NILLES

1 ,
INERIS, Verneuil-en-Halatte, France;
2
Sorbonne Universités, UTC, Compiègne, & Institut de Recherche de Chimie Paris PSL University,
Chimie Paris Tech, Paris, France

Keywords: green chemistry, ionic liquids, deep eutectic solvents, safety aspects, (eco-)toxicity
Whilst ionic liquids based on most common cationic structures as phosphonium, imidazolium and
pyrrolidinium are subject to a strong regain or interest for some time, notably in the domain of
biorefining [1] as well as in the domain of energy storage, early warnings provided in 2006 about
erroneous communication of their properties in relation with their safe use have not stopped regular
release of misleading information about their safety profiles [2/3/4]. Being in close relationship with
these chemicals, so called deep eutectic solvents, also providing interesting functional properties
notably exploitable for biomass pretreatment and conversion [5], would also deserve more attention
towards potential hazardous properties characterization to guarantee their safe and sustainable use.
Accordingly, this presentation aims at demystifying “truths” from “myths” about safety related
properties of these two families of products, with a focus on ionic liquids, based on a literature survey
and fit-for-purpose testing carried out at INERIS in the last decade in the context of various research
projects. Il will be shown, not surprisingly, that many (if not all!) safety related properties may vary with
ionic liquids as do their targeted functional properties according to their chemical structure
characteristics. From recently published research, it can be deducted that flammability and explosive
reactivity may even been targeted as a functional property of some ionic liquids either associated to
the nitrate counter-anion or nitrogen enriched cationic moiety. Adequate testing can be carried out to
rate the level of thermal and fire-induced toxicity from combustion gases making use of the so called
Tewarson apparatus [6]. Moreover, toxic activity is also sometimes focused in synthesizing new ionic
liquids for a potential use as pharmaceutic bi-component drug [7]. Actual properties of ionic liquids
such as volatility, thermal stability, flammability, corrosivity, ecotoxicity, and biodegradability will be
discussed showing appropriate choice of alternative solvents such as ionic liquids and deep eutectic
solvents is typically application dependent. In general, these chemicals may benefit from more or less
marked safety advantages, when adequately selected considering potential trade-off between
functional properties and correctly evaluated instead of postulated safety profiles [8].
[1] A.Stark, Energy Environ. Sci., 2011, 4, 19

[2] M.Smiglack, Chem. Commun., 2006, 2554–2556
[3] M. Deetleft & K.R. Seddon, Chemistry Today, 2006, vol 24, n°2, 16-22
[4] A-O.Diallo et al., Sep. Purif. Tech., 2012, 97, 228 – 234
[5] Q. Zhang et al, Chem. Soc. Rev., 2012,41, 7108-71
[6] A-O. Diallo et al, Energy Environ. Sci., 2013,6, 699-710
[7] K.S. Egorova et al, Chem. Rev. 117, 10, 7132-7189
[8] A. Bado-Nilles et al, J Hazard Mater. 2015;283:202
109
HUGS-KN07

Lignin as Useful Biomass for Composites and Carbon Materials
1 1 1 1 2 2 1,2
Yang Sun , Hui Li , Jiaotong Sun , Du Yuan , Suxi Wang , Xu Li , Chaobin HE*
1
Department of Materials Science & Engineering, National University of Singapore, 9 Engineering
Drive 1, Singapore 1175751
2
Institute of Materials Engineering and Research, A-star, 2 Fusionopolis Way, Singapore 138634
Keywords: Lignin, Composites, Carbon Materials, Biomass
Lignin, a major source of biomass which ranks second as the most abundant biopolymer on earth, is a
long-chain molecule from random polymerization of three aromatic subunits with widely varied
structures, size and shape. It could be considered as a kind of phenolic condensate and is the highest
concentrated carbon source on earth. Lignin is obtained as a by-product of paper manufacturing
industry. However, only less than 2 % of the total lignin production volume is being effectively utilized
in commercial applications, such as preparation of surfactants and adhesives, with the rest destined
as waste or ineffective fuel source. In this keynote presentation, I will highlight some of our research
in utilizing lignin for the synthesis of carbon fiber, and using as carbon source for anode materials in
battery and for supercapacitor, and using lignin as additives for preparation of polymer composites
and as a polyol for polyurethane synthesis. The developed materials also exhibit much better
proprieties, which could potentially be used in composites, and energy materials.
References
[1]. H Li, JT Sun, C Wang, SL Liu, D Yuan, X Zhou, J Tan, LP Stubb, CB He, ACS Sustainable
Chemistry & Engineering 2017, 5 (9), 7942-7949.
[2]. J Sun, C Wang, LP Stubb, CB He, Macromolecular Materials and Engineering 2017, 302
[3]. J Sun, H Li, C Wang, D Yuan, LP Stubbs, CB He, Macromolecular Chemistry and Physics 2016,
217 (9), 1065-1073.
[4]. H Li, D Yuan, C Tang, S Wang, J Sun, Z Li, T Tang, F Wang, H Gong, He CB, Carbon, 2016 100,
151-157.
[5]. X Li, CB He, S Wang, SY Wong, S Chen, US Patent App. 14/890,410
[6]. J Sun, C Wang, JCC Yeo, D Yuan, H Li, LP Stubbs, CB He, Macromolecular Materials and
Engineering, 2015, 301 (3), 328-336.
[7]. Y Sun, L Yang, X Lu, CB He, Journal of Materials Chemistry A 2015, 3 (7), 3699-3709.
[8]. SX Wang, L Yang, LP Stubbs, X Li, CB He, ACS applied materials & interfaces 2013, 5 (23),
12275-12282.
110
HUGS-KN08

Going Green: Circular Economy in Exploring Innovation of

Biobased Materials
Amar K. Mohanty*,
Bioproducts Discovery and Development Centre, Department of Plant Agriculture and School of
Engineering, University of Guelph, ON, Canada N1G 2W1.
(*Email: [email protected])
Keywords: Bioplastics, Biocomposites, Green Materials, Pyrlozed biomass, Recycled plastics
The current linear economy model of “make-use-dispose” is not sustainable given the globe’s
finite reserve. The circular economy concept envisions a close-loop system through “waste
minimization” that fosters social, economic and environmental value. The coproducts and byproducts
from one industry can be used as raw materials for another industry thus in finding their value-added
uses. The current global plastic production exceeding 335 million metric tons per year along with their
increasingly uses in non-durable applications; nurture huge disposal, land-filling and pollution
problems. It is predicted that by 2050 we will have more plastics than fish in oceans. Current waste
management strategies of plastics are focused on recycling and energy recovery. A very small
component of used plastics is recycled and rest ends with landfills. Food waste is another global
concern; around 1/3 of the food we produce is wasted. Food and Agriculture Organization (FAO) of
United Nations estimates that such food waste equates to 1.3 billion tonnes loosing $990 billion US
per year. With proper design and engineering; such undervalued coproducts and wastes can be used
as filler and reinforcement in plastics to innovate biobased composites materials for new industrial
uses. The food processing wastes, the pyrlozed biomass and recycled plastics were used in
engineering a number of green composite materials for their uses in compostable food packaging,
consumer products and light-weight car parts. This presentation will highlight the synergistic effect of
“Circular Economy” strategy in plastic innovation for commercialization success of green composites.
Acknowledgements: Ontario Ministry of Agriculture, Food, and Rural Affairs (OMAFRA) - University
of Guelph Bioeconomy Industrial uses Research Program; Agriculture and Agri-Food Canada and
Competitive Green Technologies through AgriInnovation Program; the Natural Sciences and
Engineering Research Council (NSERC), Canada for the Discovery Grants; and the Ontario Research
Fund, Research Excellence Program; Round-7 (ORF-RE07) from the Ontario Ministry of Research
and Innovation (MRI).
111
HUGS-KN09

Cellulose Functionalization through its Mineralization

Yury SHCHIPUNOV *

Institute of Chemistry, Far East Department, Russian Academy of Sciences
Vladivostok, 690022 Russia

Keywords: Cellulose, Nanofibrillated Aerogel, Mineralization, Silica, Titania, Hydrophobic,
Photocatalytic, Self-cleaning
Cellulose possesses inherent advantages including sustainable sources, recyclability and

processability, low density and cost, nontoxicity, biocompatibility and biodegradability. It is available in
traditional and novel forms, such as fibrils, microfibers, nanofibers, nanocrystals, fabrics, films (paper),
nanosheets (nanopaper), liquid crystals and aerogels. Its excellent properties and availability attract
increasing attention nowadays, but performance characteristics do not satisfy human requirements in
full measure. To extend feasibility and develop a variety of novel materials, cellulose is treated and
modified by various chemical and physical methods. Abundant surface hydroxyl groups and high
hierarchical porous structure make cellulose a suitable substrate for metal and metal oxide deposition
(mineralization), while the diversity of forms allows manipulating their synthesis, size, morphology,
porosity, hierarchy, functionality and performance. The mineralization improves drastically or results in
materials with new properties and subsequently special functionalities, thus expanding applications in
fields in which cellulose has not been used before [1].
Main methods and approaches of the fast-developing and broad area of cellulose mineralization are
reviewed in the lecture. It is illustrated by our own results on superhydrophobic, photocatalytic and
self-cleaning bionanocomposites prepared by the method of sol-gel chemistry by using dimensionally
stable aerogels from nanofibrillated cellulose [2]. To strengthen and protect aerogels against the
microorganisms, fibrils were coated by silica by a method of green chemistry. Superhydrophobic
coating was formed also in aqueous media by means of a new water-soluble precursor with a methyl
group attached to the silicon atom [1]. These aerogels can work as an efficient oil absorbent.
Titania (TiO2) coating was formed by another new route because of essential difference in the sol-gel
chemistry [3]. The mineralization was regulated via limited hydration of cellulosic fibers in nonaqueous
media. This allowed obviating the common precipitation of TiO2 in the solution bulk after the precursor
addition. It was involved into the instant hydrolysis and following condensation reactions where
contacting with the hydrating water serving as a reaction center at which TiO2 formation mainly
occurred. As shown, some samples had a photocatalytic activity comparable with commercial
photocatalysts. Furthermore, cellulose demonstrated significant self-cleaning ability under the outdoor
sunlight irradiation [4]. When polysaccharide scaffold was removed by carbonization, carbonized
aerogels with precipitated titania were fabricated. They demonstrated also high photocatalytic activity.
[1]. Y. Shchipunov, I. Postnova, Adv. Funct. Mater. 2018, DOI: 10.1002/adfm.201705042.

[2]. O. N. Khlebnikov, V. E. Silant’ev, Y. A. Shchipunov, Mendeleev Commun. 2018, 28, 214–215.
[3]. Y. A. Shchipunov, I. V. Postnova, Colloid Surf. B 2009, 74, 172-177.
[4]. I. Postnova,, E. Kozlova, S. Cherepanova, S. Tsybulya, A. Rempel, Y. Shchipunov, RSC Adv.
2015, 5, 8544-8551.
112
HUGS-KN10

Polymerization of Heterocycles using Organometallic Complexes: a
Simple Approach to Sequence Control in Polymer Synthesis
1
Christophe M. Thomas*,
1
Chimie ParisTech, PSL Research University, CNRS, Institut de Recherche de Chimie Paris,
75005 Paris, France
Keywords: Biomass, Catalysis, Biodegradable
There are economic and social issues associated with the depletion of fossil feedstocks and the
accumulation of conventional polyolefin plastics. Given the growing need for inexpensive
biodegradable plastics for use in various applications, the development of synthetic methods for the
polymerization of a wide range of monomers with control over the stereochemistry, molecular weight,
and comonomer incorporation is of particular importance.[1] In this context aliphatic polyesters have
emerged as biodegradable materials with huge potential.
Fig. 1: Synthetic approaches to aliphatic polyesters
We have synthesized polylactide and poly(β-hydroxyalkanoate)s (PHAs) with controlled structures.[2]

By using highly efficient yttrium complexes as initiators, we were able to synthesize highly alternating
PHAs by ring-opening polymerization of a mixture of enantiomerically-pure but different monomers
(Fig. 1). This efficient catalytic system makes copolymers that would be very difficult to make through
any other method. Also we have reported a new strategy to obtain biodegradable polyesters.[3] This
was achieved by tandem catalysis, which confers great interest to this approach.[4] Commercially
available complexes were used as efficient catalysts for cyclization of dicarboxylic acids followed by
alternating copolymerization of the resulting anhydrides with epoxides (Fig. 1). Given an operationally
simple method, this tandem catalysis is an attractive strategy for the production of new renewable
materials.
[1] C. M. Thomas, Chem. Soc. Rev. 2010, 39, 165-173.

[2] a) J. W. Kramer, D. S. Treitler, E. W. Dunn, P. M. Castro, T. Roisnel, C. M. Thomas G. W.
Coates, J. Am. Chem. Soc. 2009, 131, 16042-16044. b) C. Robert, T. E. Schmid, V. Richard,
P. Haquette, S. K. Raman, M.-N. Rager, R. M. Gauvin, Y. Morin, X. Trivelli, V. Guérineau, I.
del Rosal, L. Maron*, C. M. Thomas, J. Am. Chem. Soc. 2017, 139, 6217–6225.
[3] a) C. Robert, F. De Montigny, C. M. Thomas, Nat. Commun. 2011, 2:586, doi:
10.1038/ncomms1596. b) C. Robert, F. De Montigny, C. M. Thomas, ACS. Catal. 2014, 4,
3586-3589.
[4] C. Robert, C. M. Thomas, Chem. Soc. Rev. 2013, 42, 9392-9402.
113
HUGS-KN11

The Green Black: Sustainable Carbon Materials for Renewable

Energy
Magdalena TITIRICI*, Kathrin PREUSS, Mo QIAO, Servann HEROU, Philipp SCHLEE, Ana Belen
JORGE SOBRIDO
Queen Mary University of London, School of Engineering and Materials Science, Mile End Road, E17
3JG, London
Keywords: Hydrothermal Carbonisation, Carbon Dots, Electrocatalysis, Energy Storage
One of the grand challenges facing humanity today is access to sustainable materials and chemicals
which are at the heart of sustainable technologies. The production of materials, chemicals and fuels
from abundant and renewable resources will eliminate our dependence on petroleum/critical metal-
based supplies and will provide access to a new economy based on available reserves.
Carbon is the most versatile element known. It combines with other (carbon) atoms giving rise to new
carbon materials with astonishing properties. The versatility and potential of carbon has attracted top
recognition in the last decade for the work in fullerenes (1996 Nobel Prize in Chemistry), CNTs (2008
Kavli Prize in Nanoscience) and grapheme (2010 Nobel Prize in Physics). However, the mystery and
wonder of carbon offers more to discover.
While carbon is widespread on Earth, it has been mainly synthesised from fossil fuel based precursors
with sophisticated and energy consuming methodologies that generate toxic gases and chemicals.
The preparation of carbon materials from renewable resources is a key research challenge in terms of
sustainability, climate change and economics. Since the beginning Nature created carbon from
biomass.
We have demonstrated that it is possible to mimicking the natural process of carbon formation and
prepare carbon nanomaterials from biomass using mild hydrothermal processes. Along with
amorphous carbon materials (denoted HTC), this procedure also enables biomass transformation into
useful chemicals such as 5-hydroxymethylfurfural (5-HMF) or levulinic acid (LA). Recently, we have
discovered a third product of Hydrothermal Carbonisation - a crystalline form of carbon - arising at the
interface between the amorphous HTC microspheres and the aqueous phase containing the biomass-
derived chemicals.
In this talk I will present some of the fundamentals governing the production of carbon nanomaterials
and chemicals. We will also discuss the application of HTC materials in electrocatalytic reactions such
as Oxygen Reduction Reaction and Oxygen Evolution Reaction.
Finally, some of the photo-physics governing the optoelectronic properties of the new family of
fluorescent hydrothermal carbon nanocrystals and their applications as sensitizers in solar cells will be
presented.
114
HUGS-KN12

Biomass Bounty: Carbonaceous Magnetic Materials in Sustainable

Chemical Transformations

1,2
Rajender S. Varma*

1
Regional Centre of Advanced Technologies and Materials, Palacky University, Olomouc, Czech
Republic;
2
National Risk Management Research Laboratory, US EPA, Cincinnati, Ohio, USA.
Keywords: Biomass upgrading; Magnetic nano-catalysts; Carbonaceous materials; Waste Utilization
Sustainable efforts for the greener synthesis of diverse nanoparticles and their varied applications as
1-5
recyclable and reusable nano-catalysts in eco-friendly medium are important in chemical synthesis;
Pd, Ni, Ru, Ce, Cu etc. immobilized on biodegradable and recyclable earth-abundant supports namely
cellulose, chitosan or on magnetic ferrites via ligands such as dopamine or glutathione will be
1-3
presented. The value of heterogenized bimetallic Ag-Pd nanoparticles on graphitic carbon nitride
(AgPd@g-C3N4) will be underscored in upgrading of biofuel via hydrodeoxygenation of vanillin under
4a
visible light conditions using formic acid as a hydrogen source including direct aminoformylation of
4b 5a
nitroarenes. Photocatalytic C-H activation using VO@g-C3N4 catalyst for direct oxidative
5b 5c
esterification of alcohols, oxygen insertion reaction in hydrocarbons and selective oxidation of
5d 5e
alcohols and hydrogenation of alkenes and alkynes using visible light as the source of energy will
be described; these strategies capitalize on the use of waste that can sustainably generate N-enriched
carbonaceous catalytic materials valuable in executing greener transformations with minimal
6a
environmental impact. Sustainable route to nanoparticles using waste from winery, or biodiesel
6b,c 7
byproduct, glycerol and their applications in catalysis (magnetic nano-catalysts or organocatalysis),
8
toxicity and environmental remediation will be highlighted. The utility of magnetic ZSM-5 zeolite for
9
the valorization of furfuryl alcohol to γ-valerolactone, alkyl levulinates or levulinic Acid and the
prowess of metal-exchanged magnetic β−zeolites for the valorization of lignocellulosic biomass-
10
derived compounds to platform chemicals will be described.
References:
[1] R.S. Varma, Green Chem. 2014, 16, 2027; R.S. Varma, ACS Sustain. Chem. Eng. 2016, 4, 5866.
[2] R.S. Varma, Curr. Opin. Chem. Eng. 2012, 1, 123.
[3] R.B.N. Baig, M. N. Nadagouda, R.S. Varma, Coord. Chem. Rev. 2015, 287, 137.
[4] a) S. Verma, R.B. Nasir Baig, M.N. Nadagouda, R.S. Varma, Green Chem. 2016, 18, 1327;
b) S. Verma, R.B. Nasir Baig, M.N. Nadagouda, R.S. Varma, Green Chem., 2016, 18, 1019.
[5] a) S. Verma, R.B.N. Baig, C. Han, M.N. Nadagouda, R.S. Varma, Chem. Commun. 2015 51,
15554; b) S. Verma, R.B.N. Baig, C. Han, M.N. Nadagouda, R.S. Varma, Green Chem. 2016 18, 251;
c) S. Verma, R.B.N. Baig, M.N. Nadagouda, R.S. Varma, ACS Sustain. Chem. & Eng. 2016 4, 2333;
d) S. Verma, R.B.N. Baig, M.N. Nadagouda, R.S. Varma, ACS Sustain. Chem. & Eng. 2016, 4, 1094;
e) R.B.N. Baig, S. Verma, M.N. Nadagouda, R.S. Varma, ACS Sustain. Chem. & Eng. 2016, 4, 1661.
[6] a) B. Baruwati, R.S. Varma, ChemSusChem, 2006, 2, 1041; b) J. Kou, R.S. Varma, Chem.
Commun. 2013, 49, 692; (c) J. Kou, R.S. Varma, ACS Sustain. Chem. Eng., 2013,1, 810.
[7] R.B.N. Baig, R.S. Varma, Chem. Commun. 2013, 49, 752; Gawande, M.; Branco, P.; Varma, R.S.
Chem. Soc. Rev. 2013, 42, 3317; R.B.N. Baig, R.S. Varma, Green Chem. 2013, 15, 398; R.
Hudson, Y. Feng, R.S. Varma, A. Moores, Green Chem. 2014, 16, 4493; R.B.N. Baig, M.N.
Nadagouda, R. S. Varma, Green Chem. 2014, 16, 2122.
[8] J. Virkutyte, B. Baruwati, R.S. Varma, Nanoscale 2010, 2, 1109; J. Virkutyte, V. Jegatheesan,
R.S. Varma, Bioresource Tech. 2012, 113, 288; M. Pelaez, B. Baruwati, R. S. Varma, R.
Luque, D. D. Dionysiou, Chem. Commun. 2013, 49, 10118; A.D. Dwivedi, S.P. Dubey, M. Sillanpää,
Y.- N. Kwon, C. Lee, R.S. Varma, Coord. Chem. Rev. 2015, 287, 64.
[9] T.M. Lima, C.G.S. Lima, A.K. Rathi, M.B. Gawande, J. Tuček, E.A. Urquieta-González, R. Zbořil,
M.W. Paixão, R.S. Varma, Green Chem. 2016, 18, 5586.
[10] E.Y.C. Jorge, T. de M. Lima, C.G.S. Lima, L. Marchini, W.N. Castelblanco, D.G. Rivera, E.A.
Urquieta-González, R.S. Varma, M. W. Paixão, Green Chem. 2017, 19, 385.
115
HUGS-KN13

Comprehensive Utilization of various Lignocellulosic biomass as a

sustainable precursor for high performance materials
Anupama Kaushik Nee Sharma
Professor, SSB University Institute of Chemical Engineering and Technology, Panjab University,
Chandigarh, India-160014
E-mail: [email protected], [email protected]
Keywords: Lignocellulosic biomass, oxypropylated lignin, magnetic cellulose

Lignocellulosic biomass is a complex biopolymer consisting cellulose fibers embedded in amorphous
matrix of lignin, pectin and hemicelluloses. This research work focuses on simultaneous extraction of
lignin and cellulose nanofibers (CNFs) from waste biomass including groundnut shells, wheat straw
fibers, pine needles, jute fibers and bagasse using chemico-mechanical treatment. The extraction
process was optimized to get high purity lignin and cellulose nanofibers with 98% crystallinity. The
extracted lignin and cellulose nanofibers were further modified to yield high performance materials [1].
The extracted lignin was chemically modified via functionalization of its hydroxyl group using
oxypropylation to synthesize lignopolyol that was used as a precursor for the synthesis of
biodegradable polyurethanes. The polyol and polyurethanes synthesized were characterized using H-
NMR, FTIR, MALDI-ToF, DSC, TGA, Mechanical properties and biodegradability [2]. These
polyurethanes were further reinforced with CNFs to improve their properties.
The second part of the study deals with the isolation of cellulose nanofibers from same lignocellulosic
biowaste using acid hydrolysis followed by high shear homogenization. Extracted Cellulose nanofibers
were subjected to homogeneous and heterogeneous modifications for further applications. The
modified fibers are used for various applications including (i) Developing superhydrophobic cellulose
foam using sol gel technique and their application in oil water separation (ii) Esterification with l-
2+
cysteine to yield thiol and amine functionalized green material (Cys-CNFs) for removal of Hg ions (iii)
developing antimicrobial membranes by subjecting CNFs to periodate oxidation to form dialdehyde
cellulose and further modification by a Schiff base reaction with chitosan (iv) heterogenous phase
indirect modification of CNF fiber surface using propionic anhydride to render the surface hydrophobic
for application as fillers in nanocomposites (v) modifying the surface of CNFs with magnetic and
photocatalytic nanoparticles and for photo-decomposition of industrial pollutants and catalyst for
organic reactions [3].
Fig. 1. Pristine cellulose fibers, hydrophobic cellulose fibers, magnetic cellulose fibers
[1] D. Ahuja, A. Kaushik and M. Singh, Intl. J. Bio. Macromol., 2018, 107, 1294-1301
[2] D. Ahuja, A. Kaushik and G. S. Chauhan, Intl. J. Bio. Macromol., 2017, 97, 403-410
[3] K. Gupta, A. Kaushik, K.B. Tikoo, V. Kumar, S. Singhal, Arabian J. Chem., In press
116
HUGS-KN14

Opportunity of Biocarbon in Next Generation Materials Application

1,2,*
Manju Misra
1
School of Engineering, University of Guelph, Guelph, ON, N1G 2W1, Canada
2
Bioproducts Discovery and Development Centre, Department of Plant Agriculture and School of
Engineering, University of Guelph, ON, Canada N1G 2W1.
(*Email: [email protected])
Keywords: Biomass, natural fibre, supply chain, filler, bioproducts
Sustainable lightweight green composites from renewable resources are attracting increased attention
from manufacturing industries. There is a strong momentum for weight reduction in auto parts,
motivated by need for a better fuel economy. The thermo-chemical conversion of biomass is utilized to
overcome the key challenges associated with the use of traditional natural fibres in melt processed
composites uses. The unwanted odor of natural fibre during melt processing and in finished products,
along with their supply chain concern, their limitation for use in high melt temperature engineering
plastic reinforcements, and their hydrophilicity pose considerable challenges for their widespread
applications. Biocarbon from pyrolysis of inexpensive biomass, such as purpose-grown grasses (e.g.
Miscanthus, switchgrass) and food processing wastes show tremendous potential for new green
3
materials uses. Such biocarbons have a lower density (~1.4 g/cm ) in comparison to glass fibres and
3
mineral fillers (~2.6 g/cm ), are low cost, and have wide supply chain potential. They also have high
thermal stability, which thus broadens their use as reinforcing fillers from traditional thermoplastics like
polypropylene to engineering thermoplastics such as nylon. This presentation aims to highlight the re-
invention of natural fibre composites in advanced bioproducts manufacturing.
Acknowledgements: The Natural Sciences and Engineering Research Council (NSERC), Canada
Discovery Grants (Project # 400320); NSERC Collaborative Research and Development (CRD)
(Project # 401190); the Ontario Centres of Excellence (OCE) (Project # 053035); Competitive Green
Technologies (Project # 053036); the Ontario Research Fund, Ontario Research Fund, Research
Excellence Program, Round-7 (ORF-RE07) from the Ontario Ministry of Research and Innovation,
currently known as the Ontario Ministry of Research, Innovation and Science (MRIS) (Project #
052644, 052665 and 052850) and the Ontario Ministry of Agriculture, Food, and Rural Affairs
(OMAFRA) - University of Guelph Bioeconomy Industrial uses Research Program (Project # 030177).
117
ENERGY-KN01

Solar Energy Conversion Materials: Charge and Energy Transfer

Approaches to High(er) Efficiencies

Maria ABRAHAMSSON*

Chalmers University of Technology, Göteborg, Sweden

Keywords: solar energy conversion, multi-electron transfer, triplet-triplet annihilation, singlet fission
Efficient solar energy conversion, to electricity in a photovoltaic (PV) device or to solar fuels in a dye
sensitized photoelectrosynthetic cell (DSPEC) relies on efficient utilization of the absorbed photons,
either in energy transfer processes or in charge transfer events. The rates for the different energy and
electron transfer processes needs to be controlled and tuned, to avoid destructive pathways and
increase the overall efficiencies of the devices. Furthermore, desirable solar fuels typically require
multi-electron transfer reactions.
To some extent rates can be tuned by molecular design; molecules typically provide excellent
selectivity. However, many actual applications require solid state materials, and a material-oriented
approach is often favorable to stabilize the highly reduced states generated in multi-electron transfer
processes. Here, two examples where the selectivity of molecules is maintained while still taking steps
towards solid state materials.
Herein I will discuss semi-solid state materials and how they csan be used to facilitate the energy
transfer dynamics in assemblies for singlet fission or photon upconversion through triplet-triplet
annihilation. In addition, semiconduction materials like nanocrystals that enable visible to UV photon
upconversion will be discussed. Furthermore, the potential use of patterned dye sensitized mixed-
semiconductor thin films in multi-electron transfer processes will be discussed. We have shown that
using these types of films results in at least a factor of ca 50 longer-lived charge separated state
compared to a single semiconductor thin film. Furthermore, we prove conduction band mediated
electron transfer to a catalyst, and preliminary results indicate that we may have a two-electron
transfer process.
Fig. 1: Patterned semiconductor thin films can be used to prolong the lifetime of the charge
separated state, allowing for conduction band mediated electron transfer
[1] V. Saavedra, E. Sundin, M. Mapar, M. Abrahamsson, PCCP, 2017, 19, 22684

[2] V. Gray, K. Moth-Poulsen. B. Albinsson, M. Abrahamsson, Coord. Chem. Rev. 2018, 362,
54
[3] V. Gray, B. Küçüköz, F. Edhborg, M. Abrahamsson, K. Moth-Poulsen, B. Albinsson PCCP,
2018, 20, 7549
118
ENERGY-KN02

From Carbon-Rich Molecules to Carbon-Rich Materials

Igor V. ALABUGIN
Department of Chemistry and Biochemistry, Florida State University, Tallahassee, USA 32306
Keywords: Carbon-rich structures and materials
Although the high energy and high carbon content render alkynes the perfect precursors for the
preparation of polyaromatic ribbons and other carbon-rich materials with precisely controlled structure
and reactivity, the paradox of alkyne reactivity (alkynes store a lot of energy but are protected
kinetically by their relatively strong π-bonds) requires precise use of stereoelectronic factors for
lowering the activation barriers for alkyne cyclizations. With a judicious choice of supramolecular and
intramolecular effects, efficient and selective cascades form precisely shaped and functionalized
polyaromatic products that do not contain any five-membered defects [1-7].
Top: Practical implementations of the all-exo (A) and all-exo (B) alkyne cyclization cascades.
Bottom: Exploration of benzannulation reactions for the extension of carbon nanostructures
[1]. Alabugin, I.; Gilmore, K.; Manoharan, M. J. Am. Chem. Soc. 2011, 133, 12608–12623.
[2]. Pati, K.; Gomes, G. P.; Harris, T.; Hughes, A.; Phan, H.; Banerjee, T.; Hanson, K.; Alabugin, I. V.
J. Am. Chem. Soc. 2015, 137, 1165-1180
[3]. Pati, K.; Gomes, G.; Alabugin, I. V. Angew. Chem. Int. Ed., 2016, 55, 11633-11636.
[4]. Mohamed, R.; Mondal, S.; Gold, B.; Evoniuk, C. J.; Banerjee, T.; Hanson, K.; Alabugin, I. V. J.
Am. Chem. Soc., 2015, 137, 6335-6349.
[5]. Mohamed, R. K.; Mondal, S.; Guerrera, J. V.; Eaton, T.M.; Albrecht-Schmitt, T. E.; Shatruk, M.;
Alabugin, I. V. Angew. Chem. Int. Ed., 2016, 55, 12054-12058.
[6]. Gomes, G.; Alabugin, I. V. J. Am. Chem. Soc., 2017, 139, 3406–3416.
[7]. Byers, P. M.; Rashid, J. I.; Mohamed, R. K.; Alabugin, I. V. Org. Lett., 2012, 14, 6032–6035.
119
ENERGY-KN04

Advances in betalain chemistry: from fluorescent flowers to

technological applications

Erick L. BASTOS*, Letícia Christina P. GONÇALVES, Nathana B. LOPES,
Ana Clara B. RODRIGUES, Larissa C. ESTEVES, Caroline O. MACHADO, Renan M. PIOLI,
Douglas M. M. SOARES, Frank H. QUINA, and Carlos HOTTA

Institute of Chemistry, University of São Paulo, São Paulo, Brazil;
Among the natural pigments of fruits and flowers, the anthocyanins and the betalains are particularly
noteworthy from the perspective of the range of colors that they are capable of producing in nature as
the result of changes in their chemistry. The betalains range in color from yellow to red-purple, but are
restricted to a single order of flowering plants, the Caryophyllales, which includes cacti, bougainvillea,
carnations, some carnivorous plants and red and yellow beets. The betalains, on the other hand, are
Schiff base adducts of betalamic acid, a fluorescent aldehyde derivative of L-tyrosine, with an amino
acid or amine. When the amino acid is cyclo-DOPA or a glycosylated derivative thereof, the resultant
betalains are reddish-purple in color due to the extended conjugation and designated generically as
betacyanins. With other amino acids or amines, the resultant betains are yellow or yellow-orange and
[1]
generically referred to as betaxanthins . In addition, red beetroot serves as a convenient source of
[2]
appreciable quantities of betanin, which can then be hydrolyzed to betalamic acid . The betalamic
acid thus obtained can then be reacted with amino acids or other ncleophilic compounds to prepare a
wide variety of natural and synthetic non-natural analogs of betalains.
While most betaxanthins are weakly fluorescent in aqueous solution (fluorescence quantum
yields typically less than 0.001), betacyanins are essentially non-fluorescent. The fluorescence
quantum yields of betaxanthins and several different synthetic analogs were found to increase 2-4 fold
in TFE relative to water, probably reflecting the different influence of intermolecular hydrogen bonding
[3]
on the non-radiative deactivation of the singlet excited state of the betalain . Betaxanthins pigments
are responsible for the fluorescence of the petals of the flowers of the yellow varieties of four-o’clock
[4]
(Mirabilis jalapa) and eleven-o’clock (Portulaca grandiflora) under illumination with blue light .
However, this fluorescence, and that of owers in general, is too weak relative to the light reflected
[5]
from the flower to be of appreciable importance in attracting pollinators . Although naturally-occurring
betalains are only weakly or non-fluorescent, betalain analogs with much higher fluorescence
efficiencies can be obtained by conjugating betalamic acid with a highly emissive chromophore such
[6]
as 7-amino-4-methylcoumarin . Non-natural betalains derived from aminocoumarins also show large
[7]
two-photon absorption cross section in water .
[8]
Betalains also have been used as chromophores in dye-sensitized solar cells , presumably
via the interaction of the carboxylate groups of the molecule with the surface of mesoporous TiO2, and
[9,10]
for the generation of H2 using nanoparticles decorated with hydrogenase mimic and betanin .
Finally, in a green chemistry application, beetroot extract has been used as both a reducing agent and
growth-regulator for the controlled preparation of monodisperse silver nanoparticles in a microfluidic
[11]
flow system . In this talk, I will discuss the current and future aspects of research at the frontiers of
investigation of the chemistry and photochemistry of betalains.
Keywords: betalains, fluorescence, natural products, flowers.
[1] D. Strack, T. Vogt, W. Schliemann, Phytochemistry 2003, 62, 247–269.
[2] W. Schliemann, N. Kobayashi, D. Strack, Plant Physiol. 1999, 119, 1217–1232.
[3] F. H. Bartoloni, L. C. P. Gonçalves, A. C. B. Rodrigues, F. A. Dörr, E. Pinto, E. L. Bastos,
Monatshefte für Chemie - Chem. Mon. 2013, 144, 567–571.
[4] F. Gandía-Herrero, F. García-Carmona, J. Escribano, Nature 2005, 437, 334.
[5] M. G. Lagorio, G. B. Cordon, A. Iriel, Photochem. Photobiol. Sci. 2015, 14, 1538–1559.
[6] L. C. P. Gonçalves, R. R. Tonelli, P. Bagnaresi, R. A. Mortara, A. G. Ferreira, E. L. Bastos,
PLoS One 2013, 8, e53874.
[7] A. C. B. Rodrigues, I. de F. A. Mariz, E. M. S. Maçoas, R. R. Tonelli, J. M. G. Martinho, F. H.
Quina, E. L. Bastos, Dye. Pigment. 2018, in press.
[8] C. Qin, A. E. Clark, Chem. Phys. Lett. 2007, 438, 26–30.
[9] M. V Pavliuk, A. M. Cieślak, M. Abdellah, A. Budinská, S. Pullen, K. Sokołowski, D. L. A.
Fernandes, J. Szlachetko, E. L. Bastos, S. Ott, et al., Sustain. Energy Fuels 2017, 1, 69–73.
[10] M. V. Pavliuk, A. B. Fernandes, M. Abdellah, D. L. A. Fernandes, C. O. Machado, I. Rocha, Y.
Hattori, C. Paun, E. L. Bastos, J. Sá, Sci. Rep. 2017, 7, 8670.
[11] D. L. A. Fernandes, C. Paun, M. V. Pavliuk, A. B. Fernandes, E. L. Bastos, J. Sá, RSC Adv.
2016, 6, 95693–95697.
120
ENERGY-KN05

Triplet Energy Transfer Across Quantum Dot – Molecular Interfaces
1 1 1 1 1
Sofia Garakyaraghi, Cedric Mongin, Christopher M. Papa, Daniel Yonemoto, Felix N. Castellano*
1
Department of Chemistry, North Carolina State University, Raleigh, NC 27695-8204, USA
Keywords: triplet energy transfer, quantum dots, photoluminescence, thermally activated delayed
photoluminescence, ultrafast spectroscopy, interfacial energy transfer
The generation and transfer of triplet excitons across semiconductor nanomaterial-molecular

interfaces will play an important role in emerging photonic and optoelectronic technologies and
1
understanding the rules that govern such phenomena is essential. The ability to cooperatively merge
the photophysical properties of semiconductor quantum dots, with those of well-understood molecular
chromophores is therefore paramount. CdSe semiconductor nanocrystals, selectively excited by green
light, engage in interfacial Dexter-like triplet-triplet energy transfer with surface-anchored polyaromatic
2
carboxylic acid acceptors, thereby extending its excited state lifetime by 6 orders-of-magnitude. Net
triplet energy transfer also occurs from surface anchored molecular acceptors to freely diffusing
molecular solutes, further extending the triplet exciton lifetime while sensitizing singlet oxygen in
aerated solution. The successful translation of triplet excitons from semiconductor nanoparticles to
bulk solution implies a general paradigm that such materials are effective surrogates for molecular
triplets.
Inspired by the notion that semiconductor nanocrystals present molecular-like photophysical and
photochemical properties, 1-pyrenecarboxylic acid (PCA)-functionalized CdSe quantum dots are
3
shown to undergo thermally activated delayed photoluminescence. This phenomenon results from a
near quantitative triplet-triplet energy transfer from the nanocrystals to PCA, producing a molecular
triplet-state ‘reservoir’ that thermally repopulates the photoluminescent state of CdSe through
endothermic reverse triplet-triplet energy transfer. The resultant photoluminescence properties are
systematically and predictably tuned through variation of the quantum dot–molecule energy gap,
temperature, and the triplet-excited-state lifetime of the molecular adsorbate. The concepts developed
here appear to be generally applicable to semiconductor nanocrystals interfaced with molecular
chromophores enabling potential applications of their combined excited states. Finally, a curious
supramolecular mechanism for the generation of molecular triplets on the surface of PbS nanocrystals
4
will also be presented. These combined nanoparticle/molecular constructs are currently poised to
sensitize myriad chemical transformations relevant for fields as diverse as optoelectronics, solar
energy conversion, and photobiology.
References
[1] Garakyaraghi, S.; Castellano, F. N. Nanocrystals for triplet sensitization: Molecular behavior from
quantum-confined materials. Inorg. Chem. 2018, 57, 2351-2359.
[2] Mongin, C.; Garakyaraghi, S.; Razgoniaeva, N.; Zamkov, M.; Castellano, F. N. Direct observation
of triplet energy transfer from semiconductor nanocrystals. Science 2016, 351, 369-372.
[3] Mongin, C.; Moroz, P.; Zamkov, M.; Castellano, F. N. Thermally activated delayed
photoluminescence from pyrenyl-functionalized CdSe quantum dots. Nat. Chem. 2018, 10, 225-230.
[4] Garakyaraghi, S.; Mongin, C.; Granger, D. B.; Anthony, J. E.; Castellano, F. N. Delayed molecular
triplet generation from energized lead sulfide quantum dots. J. Phys. Chem. Lett. 2017, 8, 1458-1463.
121
ENERGY-KN06

Bioinspired Solar Thermal Conversion at Interface and in Bulk

Tao DENG*, Wen SHANG, Chengyi SONG, Jianbo WU, Peng TAO

School of Materials Science and Engineering
Shanghai Jiao Tong University, Shanghai, China 200240
Keywords: Bioinspired, Energy Conversion, Solar, Thermal
Solar energy is the most abundant sustainable energy source on earth. Most nature biological
systems rely on solar energy for their survival and growth. One of the basic solar energy utilization
processes within the biological systems involves the solar thermal energy conversion. For example, in
plants the solar thermal conversion process drives the evaporation of water at the leaf surfaces and
helps transport the nutrition from the plant roots to the top of the plants. With billions of years of
evolution, biological systems developed unique structures to achieve efficient solar energy conversion
and utilization. This talk will present the efforts in learning from biological systems for the efficient solar
thermal energy conversion. Specifically, this presentation will discuss the bioinspired solar thermal
conversion both at the interface and in bulk materials (Figure 1) [1-2]. In biological systems, the solar
thermal conversion process at the interface, for example, the solar-driven evaporation at the leaf
surfaces of plants, helps localize the solar heat at evaporation interface and facilitates the efficient
liquid-to-vapor phase change. Such biological interfacial solar thermal conversion helps inspire the
engineered effort in developing solar-driven interfacial evaporation systems that are demonstrated in
numerous applications, including desalination, water purification, energy harvesting, and electricity
generation. Besides the solar thermal conversion process at the interface, biological systems also
develop approaches for solar thermal conversion in bulk. For example, the black butterflies in cold
environment can convert solar energy into heat throughout their wings for quick warming up of their
body. Such solar thermal energy conversion in bulk also helps inspire the development of photon-
based solar thermal energy charging process to enhance the efficiency in solar thermal energy
storage.
Fig. 1: Solar thermal energy conversion at (a) interface; (b) in bulk.
[1]. Wang, Z., Tong, Z.,…, & Deng., T. “Dynamic tuning of optical absorbers for accelerated solar-
thermal energy storage”, Nat. Comm. 2017, 8(1), 1478.
[2]. Meng, F., Hao, W., …, & Deng, T. “Vapor-enabled propulsion for plasmonic photothermal motor at
the liquid/air interface”, J. AM. Chem. Soc., 2017, 139(36), 12362-12365.
122
ENERGY-KN07

Light-Responsive Iron(III)–Polysaccharide Coordination Hydrogels:

Evidence for a Radical Mechanism
Giuseppe E. GIAMMANCO, Christopher T. SOSNOFSKY, Malcolm D. E. FORBES, Alexander D.
BRUGH, And Alexis D. OSTROWSKI
Center for Photochemical Sciences and Department of Chemistry, Bowling Green State University,
Bowling Green, Ohio 43403, United States
Keywords: hydrogels, light-responsive materials, electron paramagnetic resonance spectroscopy, free

radicals
Visible-light responsive gels were prepared from two plant-origin polyuronic acids (PUAs), alginate
and pectate, coordinated to Fe(III) ions. Comparative quantitative studies of the photochemistry of
these systems revealed unexpected differences in the photoreactivity of the materials, depending on
1
the polysaccharide and its composition. The roles that different functional groups play on the
photochemistry of these biomolecules were also examined. Mannuronic-rich alginates were more
photoreactive than guluronic acid-rich alginate and than pectate. The microstructure of alginates with
different mannuronate-to-guluronate ratios changed with polysaccharide composition. This influenced
the gel morphology and the photoreactivity. Coordination hydrogel beads were prepared from both
Fe–alginate and Fe–pectate. The beads were stable carriers of molecules as diverse as the dye
Congo Red, the vitamin folic acid, and the antibiotic chloramphenicol. The photoreactivity of the
hydrogel beads mirrored the photoreactivity of the polysaccharides in solution, where beads prepared
with alginate released their cargo faster than beads prepared with pectate. Spin-trapping studies using
steady-state electron paramagnetic resonance (EPR) spectroscopy show strong evidence that the
mechanism of the reaction involves free radical intermediates, most likely through photo-oxidation of
carboxylate moieties followed by decarboxylation to alkyl radicals on the polysaccharide backbone.
Fig. 1: Light-responsive polysaccharide coordination hydrogels
[1]. Giuseppe E. Giammanco, Christopher T. Sosnofsky, and Alexis D. Ostrowski, ACS Appl. Mater.
Interfaces, 2015, 7 (5), 3068–3076. DOI: 10.1021/am506772x.
123
ENERGY-KN08

Metal-free Electro- and Photocatalysis
1,2
Ksenija GLUSAC*,
1
Department of Chemistry, University of Illinois at Chicago, Chicago, IL 60607, United States
2
Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL 60439, United
States
Keywords: metal-free, OER, electrocatalysis, CO2RR, photocatalysis.
We study conceptually new catalytic approaches for energy storage and solar fuel-forming reactions.
The mainstream research in this area explores transition metal oxides and complexes to catalyze
O2/H2 evolution and O2/CO2 reduction reactions. These catalysts are often made of rare and toxic
metals, which restricts their wide usage. To provide less expensive and more environmentally friendly
alternatives to electro- and photo-catalytic processes, we aim to discover earth-abundant catalytic
motifs that utilize solely organic compounds made of C, H, N and O.
OXYGEN EVOLUTION AND CARBON DIOXIDE REDUCTION CONDUCTIVE CARBON

REDUCTION CATALYSIS CATALYSIS PLATFORMS
ORR/OER
CATALYSTS
CONDUCTIVE
GRAPHENE N N
RIBBON R
N N
R
N N
200 NM X 1 NM
O2 + 4H+ + 4e-
R R
ORR N N N N
OER N N
2H2 O
Fig. 1: Molecular Models for metal-free Catalysis. Left: OER by N-containing aromatic models;
Middle: Photocatalytic CO2 reduction by biomimetic NADH analogs; Right: Conductive
graphene nanoribbon platforms for electrocatalysis.
Three projects are currently under investigation in our labs: (i) Electrocatalytic water oxidation by N-
containing heteroaromatic cations, where we look for metal-free functionalities that can transform
+
water to diatomic oxygen. (ii) Bio-inspired CO2 reduction using metal-free NAD /NADH analogs, where
we look for strong hydride donors that can selectively reduce CO2 to methanol and that can be
recycled photochemically; (iii) Carbon-based platforms for electrocatalysis. In this project, we design
porous and conductive carbon nanotube platforms that contain catalytic motifs relevant to energy
storage applications.
124
ENERGY-KN09

Bioinspired catalysis with porphyrinoids
1 1 1
Katarzyna RYBICKA-JASIŃSKA, Katarzyna ORŁOWSKA, Katarzyna GOLISZEWSKA,
1
Dorota GRYKO*,
1
Institute of Organic Chemistry Polish Academy of Science, Warsaw, Poland
Keywords: catalysis, porphyrins, vitamin B12, radicals
|
„Do as nature, work as nature, and produce as nature" (Bao-Lian Su)
Our life depends on porphyrinoids - pigments of life. They are responsible for oxygen transport
(heam), electron transport (cytochrome c), and photosynthesis (chlorophyll a). Chlorophylls are, in the
first instance, responsible for transforming light energy into the chemical reactivity with the ultimate
production of starch (photosynthesis). We should follow nature and exploit potential of pigments of
life. Photoredox catalysis has recently emerged as powerful tool for the formation of C-C bonds mainly
catalyzed by ruthenium and iridium complexes.[1] But, they are both very expensive and undesirable
by pharmaceutical industry. On the other hand, organic dyes exhibit considerable advantages and in
fact they have been shown to act as photoredox catalysts with eosin Y being the most widely
studied.[2]
Fig. 1. Transfers of electrons in reactions catalyzed by porphyrinoids
This presentation will highlight a successful application of porphyrinoids as catalysts for visible-light
induced selective functionalizations. In particular, these compounds are effective in catalyzing C-C
bond forming reactions involving the reductive or oxidative quenching. Employing dual catalytic
system – photocatalysis merged with enamine-iminium catalysis alkylation of carbonyl compounds at
the α position was accomplished.[3] Porphyrins with tuned physicochemical properties, via tailoring
various substituents at the periphery of the macrocycle, are also effective in catalyzing light-induced
direct arylation of heteroarenes and cumarins with diazonium salts.[4] The reaction afforded arylated
products in good yields and tolerates a wide range of functional groups. Along this line, we have
proposed vitamin B12 photochemical activation in bond forming and cleavage reactions.[5] TiO2 can be
utilized in a catalytic system with vitamin B12, allowing for the efficient photocatalytic reduction of
2
Co(III) to Co(I). Under light irradiation vitamin B12 derivative unusually catalyzes new olefinic sp C-H
alkylation reaction and acylation of activated olefins.[6]
[1]. T. Darmanin, F. Guittard, J. Am. Chem. Soc. 2011, 133, 15627-15634.

[2]. Prier, C. K.; Rankic, D. A.; MacMillan, D. W. C. Chem. Rev. 2013, 113, 5322.
[3]. Nicewicz, D. A.; Nguyen, T. M. ACS Catal. 2014, 4, 355.
[4]. K. Rybicka-Jasińska, W. Shan, K. Zawada, K. M. Kadish, D. Gryko J. Am. Chem. Soc.
2016, 138, 15451-15458.
[5]. K. Rybicka-Jasińska, B. Konig, D. Gryko, Eur. J. Org. Chem. 2017, 2104–2107.
[6]. M. Giedyk, J. Turkowska, S. Lepak, M. Marculewicz, K. ó Proinsias, D. Gryko Org. Lett.
2017, 19, 2670-2673
[7]. M. Ociepa, O. Baka, J. Narodowiec, D. Gryko Adv. Synth. Catal. 2017, 359, 3560-3565.
125
ENERGY-KN10

From enzymes to bioinspired catalysts for noble-metal-free

hydrogen fuel cells
1
Alan LE GOFF *
1
Univ. Grenoble Alpes, CNRS, DCM UMR 5250, F-38000 Grenoble, France
Keywords: Hydrogen, fuel cells, hydrogenases, multicopper oxidases, bioinspired catalysts, oxygen
reduction
Conventional proton-exchange membrane fuel cell (PEMFC) requires noble metal such as platinum to
harvest electrical energy from the electrocatalytic H2 oxidation and O2 reduction. Nature relies on iron,
nickel and copper-based enzymes in order to oxidize H2 or reduce O2 with minimal overpotential
requirement and exceptional catalytic efficiency. The electrical wiring of enzymes on electrode implies
the development of multiscale strategies to maximize catalyst loading and electron transfers between
the surface of the electrode and the enzyme active site. We have especially investigated the
biomimetic wiring of hydrogenases and multicopper oxidases at nanostructured electrodes for their
[1–5]
integration in fuel cell systems. Another strategy lies in the design of novel bioinspired molecular
catalysts and their grafting on electrodes. These catalysts have to be designed by taking into account
the important features of metalloenzymes which are responsible for their exceptional catalytic activity.
This presentation will show our recent advances in the implementation of metalloenzymes and their
synthetic models at fuel cell electrodes. Our efforts in the design of novel bioinspired catalysts for both
H2 oxidation and O2 reduction will be discussed as well as their immobilization on conductive
[6–8]
nanomaterials and their integration in noble-metal-free hydrogen fuel cells.
[1] N. Lalaoui, A. Le Goff, M. Holzinger, M. Mermoux, S. Cosnier, Chem. Eur. J. 2015, 21, 3198–
3201.
[2] N. Lalaoui, P. Rousselot-Pailley, V. Robert, Y. Mekmouche, R. Villalonga, M. Holzinger, S.
Cosnier, T. Tron, A. Le Goff, ACS Catal. 2016, 6, 1894–1900.
[3] N. Lalaoui, A. de Poulpiquet, R. Haddad, A. Le Goff, M. Holzinger, S. Gounel, M. Mermoux, P.
Infossi, N. Mano, E. Lojou, et al., Chem. Commun. 2015, 51, 7447–7450.
[4] L. Altamura, C. Horvath, S. Rengaraj, A. Rongier, K. Elouarzaki, C. Gondran, A. L. B. Maçon,
C. Vendrely, V. Bouchiat, M. Fontecave, et al., Nat Chem 2017, 9, 157–163.
[5] S. Rengaraj, R. Haddad, E. Lojou, N. Duraffourg, M. Holzinger, A. Le Goff, V. Forge, Angew.
Chem. Int. Ed. 2017, 56, 7774–7778.
[6] S. Gentil, D. Serre, C. Philouze, M. Holzinger, F. Thomas, A. Le Goff, Angew. Chem. Int. Ed.
2016, 55, 2517–2520.
[7] A. Le Goff, V. Artero, B. Jousselme, P. D. Tran, N. Guillet, R. Metaye, A. Fihri, S. Palacin, M.
Fontecave, Science 2009, 326, 1384–1387.
[8] S. Gentil, N. Lalaoui, A. Dutta, Y. Nedellec, S. Cosnier, W. J. Shaw, V. Artero, A. Le Goff,
Angew. Chem. Int. Ed. 2017, 56, 1845–1849.
126
ENERGY-KN11

Light-Driven Processes in Nanomaterials of Multiple Dimensions

1
Angel A. Martí *
1
Department of Chemistry & Department of Bioengineering, Rice University, Houston, TX 77005
Keywords: metal complexes, nanotubes, graphene quantum dots, zeolites, photochemistry
Photocatalytic processes are of central importance for sustainable solar energy conversion. Nature
does this with unmatched efficiency during photosynthesis, where energy and electron transfer
reactions occur in multiple dimensions. Understanding how light can drive processes in structures of
varied dimensions is important for modulating and controlling solar energy utilization and conversion.
Along this line, we have been studying photoinduced processes in metal complexes and
nanomaterials of varied dimensions. First, we will show the interactions between metal complexes and
one dimensional nanotubes structures by steady-state and time-resolved absorption and emission
spectroscopies. Two dimensional graphene quantum dots will also be described, particularly their
interaction with lanthanide salts such as terbium. We have found that the photosensitized emission
quantum yield of terbium presents an order of magnitude change when varying the light excitation
wavelength, which is in contrast with the Kasha-Vavilov’s rule. Furthermore, we will present structures
in three dimensions in which metal complexes have been immobilized in a supramolecular framework,
which leads to a remarkable effect on their photoelectronic properties. The unconventional
photochemistry and photophysics of these materials due to the synergy of nanomaterials of varied
dimensions and metals complexes have opened applications in solar energy harvesting,
anticounterfeiting, molecular detection.
127
ENERGY-KN12

Nature Inspired Surface Coatings for Applications in

Photoelectrosynthesis

Gary F. Moore*, Anna M. Beiler, Diana Khusnutdinova, Edgar Reyes, Brian L. Wadsworth

School of Molecular Sciences and the Biodesign Institute Center for Applied Structural Discovery
(CASD), Arizona State University, Tempe, AZ 85287-1604, USA.

Keywords: Catalysis, Semiconductors, Polymers, Surface Coatings, Interfaces
Photoelectrosynthesis provides an approach to capture, convert, and store solar energy as chemical
fuels. However, the ability to effectively interface redox catalysts for activating multi-electron / multi-
proton chemical transformations with materials that absorb light and convert photons to charge
carriers moving through a potential remains an outstanding challenge for science and the imagination.
Using a nature-inspired approach, our research group has developed a synthetic methodology to
chemically graft thin-film polymer coatings onto solid-state (semi)conductor surfaces. [1-5] Taking the
role of the protein environment in biological assemblies as inspiration, the polymer coatings provide a
strategy to direct, template, and assemble molecular catalysts for activating fuel-forming reactions at
appropriate functional groups along the surface-grafted polymer chains. In addition, the three-
dimensional soft-material matrix chemically stabilizes catalysts imbedded within the polymer during
redox cycling. Photoelectrochemical measurements confirm the hybrid assemblies use solar energy to
power reductive fuel-forming transformations in aqueous solutions without the use of sacrificial
chemical reductants, strong acids, or electrochemical forward biasing. This work introduces a highly
useful, yet easily accessible, motif for preparing and studying molecular-modified (semi)conductors.
(Supported by the National Science Foundation under Early Career Award 1653982.)
Fig. 1: Schematic of a polymer-coated (semi)conductor for photoelectrosynthetic applications.
[1] A. M. Beiler, D. Khusnutdinova, S. I. Jacob, G. F. Moore, Ind. & Eng. Chem. Research 2016, 55,
5306-5314. DOI: 10.1021/acs.iecr.6b00478
[2] D. Khusnutdinova, A. M. Beiler, B. L. Wadsworth, S. I. Jacob, G. F. Moore, Chem. Sci. 2017, 8,
253-259. DOI: 10.1039/c6sc02664h
[3] A. M. Beiler, D. Khusnutdinova, B. L. Wadsworth, G. F. Moore, Inorg. Chem. 2017, 56, 12178-
12185. DOI: 10.1021/acs.inorgchem.7b01509
[4] B. L. Wadsworth, A. M. Beiler, D. Khusnutdinova, S. I. Jacob, G. F. Moore, ACS Catal. 2016, 6,
8048-8057. DOI: 10.1021/acscatal.6b02194
[5] A. M. Beiler, D. Khusnutdinova, S. I. Jacob, G. F. Moore, ACS Appl. Mater. Interfaces 2016, 8,
10038-10043. DOI: 10.1021/acsami.6b01557
128
ENERGY-KN13

Bioinspired Systems for Solar Fuel Production:
Advanced EPR/DFT Biohybrid Characterization

Oleg POLUEKTOV, Jens NIKLAS, David TIEDE, Karen MULFORT Lisa UTSCHIG

Argonne National Laboratory, Division of Chemical Science and Engineering
9700 S. Cass Ave., Lemont, IL 60514, USA

Keywords: Biohybrids, Solar fuels, Photosynthesis, Hydrogen production, Electron Paramagnetic
Resonance, Biocatalysis
The two main ways for solar energy conversion are solar-to-electricity and solar-to-fuel. Solar fuels
research aims to mimic photosynthesis and devise integrated systems that can capture, convert, and
store solar energy in high-energy molecular bonds. Currently, we are designing both synthetic
supramolecular photocatalytic systems as well as biohybrids based on natural photosynthetic proteins
that photochemically produce hydrogen. Molecular hydrogen stands out among the solar fuels, since it
can be utilized essentially pollution-free. The two electrons needed to reduce protons to one hydrogen
molecule can be provided by natural and artificial photosensitizers. Using natural photosystems allows
taking advantage of nature’s optimized light-harvesting and electron-transfer capabilities, while
artificial photosensitizers provide a larger choice of chromophores. Independently, the incorporation of
the metalorganic hydrogen catalysts in protein surrounding has the potential to protect and stabilize
them and thus overcome one of their weaknesses – low stability in acidic environment. To achieve
sustainable hydrogen generation, the catalysts should not be rare and expensive, but use earth
abundant elements like first row transition metals. Both cobaloximes and Ni-bis(diphosphine)
complexes are among the best molecular transition metal complexes for the reduction of protons to
molecular hydrogen. The catalytic properties of these systems depend not only on the chemical
structure of the complexes but also on the local surrounding and on the direct ligands to the central
metal ion. Knowledge of the electronic properties is important for an in-depth understanding of the
catalytic properties of the complexes. Multi-frequency Electron Paramagnetic Resonance (EPR)
spectroscopy at X-band (9 GHz), Q-band (34 GHz), and D-band (130 GHz) has been used to
investigate these cobaloxime and Ni-bis(diphosphine) complexes, allowing us to determine the
59 14 1 31
electronic g-tensors and hyperfine interaction with various magnetic nuclei like Co, N, H and P.
The experimental results are supplemented with an extensive set of DFT calculations. The knowledge
gained by these model studies is used to characterize the binding of the hydrogen catalyst to proteins
as well as mechanism of hydrogen generation. The associated complexes are capable of light-induced
molecular hydrogen generation with high yield. Further development and improvement of these
systems relies on understanding the inherent, fundamental mechanisms for coupling captured photons
to fuel generation. This work was supported by the Office of Basic Energy Sciences of the U.S.
Department of Energy through Grant DE-AC02-06CH11357.

Fig. 1: Schematic representation of the Photosystem I based biohybrid. Light induced electron flow
from a donor (plastocyanin) to an acceptor (ferredoxin) is redirected to molecular catalyst.
129
ENERGY-KN14

Nature-Inspired Fruit and Flower Chromophores for Collection and

Dissipation of the Energy of Absorbed Light
1 2 1 2 2
Cassio P. Silva, Gustavo T. M. Silva, Frank H. Quina*, Adilson A. Freitas, Antonio L. Maçanita, Eli
3 3 4 5 5
Espinoza, Valentine Vullev, Vânia M. T. Carneiro, Farhan Siddique, Adelia J. A. Aquino .
1
Instituto de Química, Universidade de São Paulo, São Paulo, Brazil;
2
Instituto Superior Técnico, UNL, Lisbon, Portugal;
3
Materials Science and Engineering, University of California Riverside, Riverside, CA, USA
4
Departamento de Química, Universidade Federal de Viçosa, Viçosa, MG, Brazil
5
School of Pharmaceutical Science and Technology, Tianjin University, Tianjin, China
Keywords: Anthocyanins, Pyanoanthocyanins, flavylium cations, pyranoflavylium cations, time-

resolved spectroscopy, fluorescence, phosphorescence
Anthocyanins are the natural plant pigments responsible for the majority of the red, purple and
blue colors of flowers, fruits and leaves. The colors of anthocyanins in plants are modulated by pH or
substitution and can be stabilized by complexation with metal ions or with colorless organic molecules
(copigments) such as hydroxybenzoic or hydroxycinnamic acids. Weak acids in the ground state (pKa
ca. 4-5), uncomplexed anthocyanins are strong photoacids (pKa* ca. -1) in the singlet excited state
and undergo ultrafast adiabatic deprotonation (5–20 ps) in aqueous solution to give the corresponding
short-lived (about 200 ps) excited quinonoidal base [1]. Anthocyanins complexed with organic
copigments, on the other hand, undergo deactivation that is even faster than deprotonation. All of
these features of anthocyanin chemistry and photophysics can be mimicked and manipulated utilizing
appropriately substituted flavylium cations.
During the maturation of red wine, the anthocyanins present in the grapes (predominantly
malvidin) are transformed into pyranoanthocyanins. As in the case of anthocyanins, the chemistry and
photophysics of pyranoanthocyanins can be inferred from studies of pyranoflavylium cations [2,3].
Pyranoflavylium cations are also weak acids in the ground state (pKa ca. 4) but, compared to flavylium
cations, are less water-soluble, have longer fluorescence lifetimes, less pronounced photoacidity (pKa*
ca. 0.6) and readily observable phosphorescence at 77K. Both excited state proton transfer and
charge-transfer-mediated internal conversion provide efficient ultrafast energy dissipation mechanisms
for anthocyanins and pyranoanthocyanins.
Scheme 1. Typical Flavylium and Pyranoflavylium Cation Chromophores.
The relationship between the chemical and photochemical properties of natural plant pigments and
their chemical structure has important implications for their use as safe dyes or coloring agents and
other practical applications. The relatively facile synthesis of substituted pyranoflavylium cations with
electron-donating and electron-withdrawing substituents or with attached heterocyclic or polycyclic
aromatic rings [3] facilitates manipulation of the ground and excited states of these pyranoanthocyanin
analogs, including color, redox properties and the nature of the lowest excited state (TICT, charge-
transfer or localized). Circumventing the ultrafast energy dissipation pathways that contribute to the
photostability of these pigments in Nature is key to the rational design of fluorescent pigments, probes
and sensors based on flavylium and pyranoflavylium cation chromophores.
[1]. V. O. Silva, A. A. Freitas, A. L. Maçanita, F. H. Quina, J. Phys. Org. Chem. 2016, 29, 594–599.
[2]. A. A. Freitas, C. P. Silva, G. T. M. Silva, A. L. Maçanita, F. H. Quina, Pure Appl. Chem. 2017,
89, 1761-1767.
[3]. C. P. Silva, R. M. Pioli, L. Liu, S. Zheng, M. Zhang, G. T. M. Silva, V. M. T. Carneiro, F. H.
Quina, ACS Omega, 2018, 3, 954-960.
130
ENERGY-KN15

Solar fuels Production from CO2 Catalytic Reduction with

Bioinspired Fe Molecular Complexes
Marc Robert
Laboratoire Electrochimie Moléculaire - UMR CNRS 7591, Université Paris Diderot, Sorbonne Paris
Cité, 15 rue Jean de Baïf, 75013 Paris, France
Keywords: Solar fuels, Fe porphyrins, CO2 reduction, Molecular catalysis
Recent attention aroused by the reduction of carbon dioxide has as main objective the production of
useful organic compounds and fuels − the “solar fuels” − in which solar energy would be stored. One
route to this goal consists in first converting sunlight energy into electricity than could be further used
to reduce CO2 electrochemically.(1-4) Another approach is to directly use the visible photons and
photocatalyze the reduction of the gas in the presence (or not) of an appropriate sensitizer and of a
sacrificial electron donor. (5-8)
By using variously substituted tetraphenyl Fe porphyrins we have recently found that it was possible to
selectively and efficiently convert CO2 with 2 electrons into CO (2-8), in both organic solvent and pure
water, in electrochemical conditions as well as in photochemical conditions. Recently, we have
discovered that the carbon dioxide could be reduced with 8 electrons to methane with a single
molecular porphyrin catalyst. (9) Our most recent results will be presented and discussed.
Fig. 1: Catalytic reduction of CO2 to CO and CH4 with Fe(0) tetraphenyl substituted porphyrins
[1]. A. Tatin, J. Bonin, M. Robert, ACS Energy Lett. 2016, 1, 1062-1064.

[2]. S. Drouet, C. Costentin, M. Robert, J-M. Savéant, Science, 2012, 338, 90-94.
[3]. C. Costentin, M. Robert, J-M. Savéant, Acc. Chem. Res., 2015, 48, 2996-3006.
[4]. I. Azcarate, C. Costentin, M. Robert, J-M. Savéant, J. Am. Chem. Soc. 2016, 138, 16639-16644.
[5]. M. Routier, J. Bonin, M. Robert, J. Am. Chem. Soc., 2014, 136, 16768-16771.
[6]. H. Takeda, C. Cometto, O. Ishitani, M. Robert, ACS Catalysis 2017, 7, 70-88.
[7]. H. Rao, J. Bonin, M. Robert, Chem. Commun. 2017, 53, 2830-2833.
[8]. H. Rao, J. Bonin, M. Robert, ChemSusChem 2017, 10, 4447-4450.
[9]. H. Rao, J. Bonin, M. Robert, Nature 2017, 548, 74-77.
131
ENERGY-KN16

U-Turn Electron Transfers in Chemistry and Biology
Nicholas F. Polizzi, Ting Jiang, David N. Beratan, and Michael J. Therien*
Department of Chemistry, French Family Science Center, 124 Science Drive, Duke University,
Durham, North Carolina 27708, USA
Keywords: High energy photoproducts; opposite singlet and triplet excited state polarization
Efficient energy conversion requires quantitative, light-driven formation of high-energy, charge-

separated states. Conventional artificial photosystem designs seek to promote electron transfer (ET)
by polarizing excited donor electron density toward the acceptor (“one-way” ET). Enigmatically, the
excited donor of the archetypal R. sphaeroides reaction center polarizes its electron density away from
its electron acceptor: light absorption by the reaction center thus triggers a “U-turn” ET event.
Whatever mechanistic importance lies behind this biological U-turn ET has been obscured by the
inability to experimentally reverse donor excited-state polarization within the reaction center. We
describe how U-turn ET produces a strikingly larger yield of high-energy photo-products compared to
a conventional one-way ET scheme, by minimizing intersystem crossing to the donor triplet state. We
directly compare one-way vs. U-turn ET strategies via linked donor-acceptor (DA) assemblies based
on highly conjugated (porphinato)metal-(polypyridyl)metal constructs, in which selective optical
excitation produces donor excited states polarized either toward or away from the acceptor. Ultrafast
spectroscopic studies of these DA assemblies pinpoint the importance of realizing donor singlet and
triplet excited states that have opposite electronic polarizations to shut down intersystem crossing, a
scheme exploited by the reaction center of R. sphaeroides. These results offer an unexpected U-turn
design principle, heralded by Nature, that averts intersystem crossing and dramatically increases the
yield of high-energy photo-products critical for light-driven energy conversion reactions.
132
2D3D-KN01

Stimuli-responsive DNA structures grafted on biosensing

surfaces
1 1 1 1 1
Carole CHAIX, * Carole FARRE, Alice WRIGHT, Romaric BONNET, Gabriel DE CROZALS
1
Institut des Sciences Analytiques, CNRS/Université Claude Bernard Lyon 1, ENS de Lyon, 5 rue de
la Doua, 69100 Villeurbanne
Keywords: Bio-functionalization of surface; DNA nanostructure; Electrochemical biosensors
Biosensor technologies hold great promise for the sensitive detection of specific (bio)-markers in
complex matrices. In this field, electrochemical devices have the advantage of being highly sensitive,
with a low manufacturing cost, a fast response and the potential for miniaturization. In the last few
decades, many DNA-based biosensors have been developed. DNA is now recognized as a novel
material in the field of nanoengineering, as the specific binding of base pairs can be exploited to
elaborate sophisticated 2D and 3D nanostructures that can respond to a specific stimulus. The
conformational change of DNA can be exploited to elaborate sensitive and real-time detection
systems.
In our laboratory, we focused on the design of DNA-based sensitive layers for bio-sensing. Bio-
functionalization of electrodes or nanomaterials was investigated in order to develop DNA
functionalized surfaces with a controlled folding of the DNA structure. Firstly, we developed a strategy
to directly modify the oligonucleotide sequences with many ferrocene (Fc) derivatives during an
1, 2
automated DNA synthesis. Stem/loop oligonucleotides labeled with numerous Fc molecules were
synthesized and used as probes grafted on gold electrode sensors to achieve DNA target detection.
Secondly, we also synthesized tetrathiol modified probes to obtain a strong anchoring of these
compounds on the gold surface. This approach permitted the development of a selective
3
amperometric DNA biosensor for Hepatitis C virus genotyping with a detection limit of 10 fM.
Methylene blue (MB) derivatives were also developed for direct incorporation in oligonucleotidic
4
probes during synthesis. A nanoparticle-based electrochemical sandwich immunoassay was
developed for bacteria detection in platelet concentrates. Innovative methylene blue-DNA/nanoparticle
5
assemblies were designed by exploiting a new technology developed by our group (Fig. 1). First,
oligonucleotide-functionalized nanoparticles were obtained by direct synthesis of the DNA strands on
the nanoparticle surface using an automated oligonucleotide synthesizer. Densely packed DNA
coverage was thus obtained. Then, DNA duplexes were constructed on the NP surface with a
complementary strand bearing a 3 methylene blue tag. This strategy ultimately produced highly
functionalized nanoparticles with electrochemical markers. These assemblies enabled amplification of
the electrochemical signal, resulting in a very good sensitivity. The methylene blue-DNA/nanoparticles
amplify sensitivity x1000 compared with the assay run without NPs for electrochemical detection. A
limit of detection of 10 CFU/mL was achieved for E. coli bacteria.
Fig. 1: Strategy for oligonucleotide solid-phase synthesis on nanosized particles
[1]. G. Chatelain, M. Ripert, C. Farre, S. Ansanay-Alex and C. Chaix, Electrochim. Acta, 2012, 59, 57-63.
[2]. M. Ripert, C. Farre and C. Chaix, Electrochim. Acta, 2013, 91, 82-89.
[3]. M. Lereau, C. Fournier-Wirth, J. Mayen, C. Farre, A. Meyer, V. Dugas, J.-F. Cantaloube, C. Chaix, J.-J. Vasseur and F.
Morvan, Anal. Chem., 2013, 85, 9204-9212.
[4]. G. De Crozals, C. Farre, M. Sigaud, P. Fortgang, C. Sanglar and C. Chaix, Chem. Commun., 2015, 51, 4458-4461.
[5]. G. De Crozals, C. Farre, G. Hantier, D. Léonard, C. Marquette, A., C. Mandon, A., L. Marmuse, C. Louis, J.-J. Toulmé, C.
Billotey, M. Janier and C. Chaix, RSC Advances, 2012, 1-9.
133
2D3D-KN03

Bioinspired supramolecular nanofiber

,1,2,3
Masato IKEDA *

1
Department of Life Science and Chemistry, Graduate School of Natural Science and Technology,
Gifu University, 1-1 Yanagido, Gifu 501-1193, Japan;
2
United Graduate School of Drug Discovery and Medical Information Sciences, Gifu University, 1-1
Yanagido, Gifu 501-1193, Japan;
3
Center for Highly Advanced Integration of Nano and Life Sciences, Gifu University (G-CHAIN), Gifu
501-1193, Japan;

Keywords: Self-assembly, Stimuli-responsiveness, Nanomaterials, Nanofiber, Hydrogel
Soft matters inspired by biological systems such as supramolecular hydrogels composed of self-
assembled nanofibers exhibiting stimuli-response under aqueous conditions are attractive owing to
their numerous potential bio-applications. However, installing response toward structurally complex
biochemical stimuli into them remains a challenge. To overcome the obstacle, we developed simple
strategy to introduce artificial chemical-stimuli-responsive cleavable groups into peptides to develop
self-assembled supramolecular nanofibers capable of showing chemical stimuli-responsive
degradation of the nanofibers and the corresponding hydrogel materials. More importantly, we found
that the rational combination of the stimuli-responsive supramolecular nanofibers (supramolecular
hydrogels) and enzymes enabled us to construct hydrogel materials capable of showing gel
degradation (dis-assembly of supramolecular nanofibers) in response to a wide variety of
[1,2,3]
biomolecules. Very recently, we also applied the same molecular design principle to nucleic acids
[4,5]
for the development of a stimuli-responsive aptamer.
We believe that our simple, but robust strategy and the relevant synthetic molecular tools could
offer a variety of stimuli-responsive and bioinspired supramolecular soft materials.
Fig. 1: Stimuli-responsive supramolecular nanofiber
[1]. M. Ikeda, I. Hamachi et al., Adv. Mater. 2011, 23, 2819–2822.

[2]. M. Ikeda, I. Hamachi et al., Nat. Chem. 2014, 6, 511–518.
[3]. H. Shigemitsu, M. Ikeda, I. Hamachi et al., Nat. Protoc. 2016, 11, 1744–1756.
[4]. M. Ikeda, Y. Kitade et al., ChemBioChem 2016, 17, 1304–1307.
[5]. M. Ikeda et al., Chem. Lett. (Highlight Review) 2017, 46, 634–640.
134
2D3D-KN04

Mussel-Inspired Approaches to Core-Shell and Dual Metal-Doped

Hybrid Nanospheres for Energy and Environmental Applications
Jiaming ANG, Huiqing Wu, Xuehong Lu *
School of Materials Science and Engineering, Nanyang Technological University, Singapore
Keywords: polydopamine, self-assembly, complexation, UV-resistant self-cleaning membrane,

electrocatalysis
Mussel-inspired biomimetic polydopamine (PDA) coating process has been under the spotlight since
2007 [1]. It was found that beside its versatile coating ability, PDA could also self-assemble into
colloidal nanospheres. As the catechol groups in PDA are capable of forming hydrogen bonds, metal-
ligand complexes and quinhydrone charge-transfer complexes with a wide variety of materials, in
particular transition metals and their compounds, the self-assembly process can be utilized to facilely
prepare various types of organic-inorganic hybrid nanostructures [2]. In this keynote talk, some new
developments in this area will be introduced with highlights of two examples.
As the first example, our latest work on one-pot synthesis of Co(II)-Fe(III)-PDA complex nanospheres
will be introduced. Our results show that ferric ions form coordination bonds with dopamine before the
initiation of polymerization, whereas cobalt(II) ions are only able to form coordination bonds with
oxidized dopamine units or oligomers after the initiation of dopamine polymerization. When the two
types of ions are concurrently added into a dopamine solution, ferric ions play a dominant role in
directing the final morphology of the complex nanostructures. From Co(II)-Fe(III)-PDA complex
nanospheres, mesoporous CoFe2O4/CoFe/carbonized PDA (C-PDA) nanospheres with high specific
surface area could be easily obtained via controlled annealing, which show good performance as a
promising low cost, efficient and stable bifunctional oxygen electrocatalyst for zinc-air batteries.
In the second example, PDA/TiO2 core-shell hybrid nanospheres were used as dopants to render
polysulfone (PSf) ultrafiltration membranes simultaneous self-cleaning and self-protection properties
[3]. In the TiO2-PDA nanohybrid, PDA spheres act as adhesive substrates to hold densely covered
photocatalytic TiO2 nanoparticles, and also serve as a free-radical scavenger to protect PSf
membrane from being attacked by free radicals produced by TiO2 during UV irradiation. The hybrid
nanospheres can be easily doped into PSf membrane via phase inversion method, which allows the
hydrophilic hybrid spheres migrating to the surface of the hydrophobic PSf channels without blocking
the open pores. As a result, the hybrid membrane exhibits high performances in separation efficiency,
self-cleaning property, as well as excellent performance stability under UV irradiation.
Fig. 1: Morphologies of (a,b) as synthesized Co(II)-Fe(III)-PDA complex nanospheres, (c)

CoFe/PDA nanospheres and (d) CoFe2O4/CoFe/C-PDA nanospheres.
[1]. H. Lee, S. M. Dellatore, W. M. Miller, P. B. Messersmith, Science 2007, 318 (5849), 426-430.
[2]. J. Ang, Y. Du, B. Y. Tay, C. Zhao, J. Kong, L. P. Stubbs, X. Lu, Langmuir 2016, 32, 9265–
9275.
[3]. H. Wu, Y. Liu, L. Mao, C. Jiang, J. Ang, X. Lu, J. Membrane Sci. 2017, 532, 20-29.
135
2D3D-KN06

Bioinspired Molecular Factories with Architecture and in vivo

Functionality as Cell Mimics

1
Cornelia G. PALIVAN*

1
University of Basel, Chemistry Department, Mattenstr. 24a, Basel, Switzerland

Keywords: artificial cells, artificial organelles, molecular factory, enzymes, giant plasma membrane
vesicles
Abstract: The design of artificial cells and organelles represents a highly promising direction of
development of systems mimicking bio-compartments as it is intended to provide nanometer and
micrometer range compartments with cell-like properties in order to understand fundamental bio-
behavior and processes to eventually offer medical solutions [1]. Even though there are examples of
artificial cells either based on single microcompartments or compartment-in-compartments [2], they
still inherently lack the material variety and responsiveness found in the most basic cellular structures,
and have not yet been investigated in vivo to determine whether they preserve their functionality.
Here, we introduce a general strategy for creating bioinspired molecular factories based on giant
plasma membrane vesicles, GPMVs supplementary equipped with the necessary elements to mimic
the composition and functionality of natural cells, and that are evaluated in vitro and in vivo in terms of
architecture and functionality. Cellular origin of GPMVs has a huge potential for developing a cell-
mimic, because the transfer of the cytoplasm and membrane from the donor cells to GPMVs occurs
spontaneously during their formation and offers the opportunity to supplement them with desired
molecules. Such GPMVs can be equipped with artificial organelles, which have been already proved
to be functional in vitro and in vivo, in Zebra fish [3]. In our strategy, eukaryotic cells are used to: i)
manufacture GPMVs (top-down approach), and ii) simultaneously equip GPMVs with a large variety of
structural and functional elements (bio- synthetic molecules, nanoobjects, and artificial organelles) by
pre-modifying cell composition. The advantage of our strategy is that it goes beyond the insertion of
bio- and synthetic molecules, by supplementing GPMVs with supramolecular assemblies
(nanoparticles, liposomes, polymersomes), and catalytic nanocompartments playing the role of
artificial organelles. Such a molecular factory opens up the possibility to reproduce and study
biological behavior and reactions in a real cell-like environment but less complex and crowded than a
natural cell.
[1]. C.G.. Palivan, R. Goers, A. Najer, X. Zhang, W. Meier, Chem. Soc. Rev. 2016, 45, 377-411.
[2]. R.J. W. Peters, et al., Angew. Chem. Int. Ed. 2014, 53, 146–150.
[3]. T. Einfalt, D. Witzigmann, C. Edlinger, S. Sieber, R. Goers, A. Najer, M. Spulber, O. Onaca-
Fischer, J. Huwyler, C. G. Palivan, Nature Comm., 2018, accepted.
136
2D3D-KN07

Experimental and Computational Studies of (Nano)particle-biotic

interfaces

1 1 1,2 1 1
Carole C. Perry,* Victor V. Volkov, Monika Michaelis , Daniel Oliver , Aneeqa Fayyaz

1
Biomolecular and Materials Interface Research Group, School of Science and Technology,
Nottingham Trent University, Clifton Lane, Nottingham NG11 8NS;
2
Hybrid Materials Interfaces Group, Bremen Center for Computational Materials Science (BCCMS)
and Center for Environmental Research and Sustainable Technology (UFT), Faculty of Production
Engineering, University of Bremen, 28359 Bremen, Germany.
Keywords: silica, metal oxides, metals, molecular dynamics simulations, density functional theory
Events occurring at the solid/ aqueous interface underpin a variety of technologies used in the
biomedical and technological fields. Interactions occurring at interfaces are also used to good effect in
nature where biomolecules guide and control the formation of biominerals. My research group studies
biomineralisation in vivo and transitions the mechanistic information so gained to laboratory-based
reaction systems. A major goal of our research is to develop a detailed understanding of interactions
between biomolecules such as peptides and surfaces including preformed particles in solution. One of
our end goals is to generate novel biomimetic materials using our improved molecular level
understanding.
Using examples from our recent studies, this presentation will describe our current understanding of
the mechanisms of biological-material interactions for a number of inorganic materials and show the
synergy between application of experimental approaches and simulation.
Fig. 1: an example of the data that we are accumulating combining computational analysis and
spectroscopy
137
2D3D-KN08

Dynamic Aggregation Behavior of Hybrid Surfactants to Generate

Quasi Ion-Channels for Bioinspired Bilayers
1 1 1 1
Masanobu SAGISAKA *, Tsuyoshi NARUMI, Hitomi OSHIYAMA, Yayoi FUJITA,
1 2 3
Atsushi YOSHIZAWA, Frédéric GUITTARD, Julian EASTOE,

1
Graduate School of Science and Technology, Hirosaki University, Hirosaki, Japan;
2
Univ. Cote d'Azur, NICE-Lab, Nice, France
3
School of Chemistry, University of Bristol, Bristol, U.K.

Keywords: Micro-segregation, Liquid Crystal, Bilayer, Oxyethylene, Hybrid Surfactant
Surfactants form various kinds of micelles and liquid crystals (i.e. lyotropic assemblies) in solvents,
depending on its solvophobic and solvophilic interactions. Introducing thermotropic liquid crystal
mesogens as a hydrophobic moiety into surfactants often generates unique lyotropic assemblies and
functions by incorporating specific mesogen-mesogen interactions with solvophobic one. On the other
hand, oxyethylene units usually behave as a hydrophilic group at a low temperature but it became
hydrophobic at a high temperature. Mesogens and oxyethylene units are immiscible and can generate
micro-segregation in molecular assemblies if both are in surfactant di-chain. To generate unique
aggregation behaviors and functions of assemblies based on the ethoxylated micro-segregation (quasi
ion channel), this study synthesized a new class of hybrid surfactant, CB-B2ES having mesogenic (6-
[4-(4-cyanophenyl)phenyloxy]hexyl, X1 in Fig.1) and temperature-responsive (butoxyethoxyethyl, X2 in
Fig.1) tails and examined its aggregation behavior and interfacial properties in water [1].
CB-B2ES was found to form lamellar aggregates in water at concentrations higher than 5 wt%.
Interestingly, population of the lamellar aggregates gradually increased with elapsed time, but all the
aggregates were suddenly disappeared in only 1-2 minutes (Fig.1). Such a gradual formation/sudden-
breakdown behavior of lamellar aggregates is not identified as a typical aggregation behavior of
surfactant and did not appear for the CB-B2ES analogues with non-hybrid and/or non-ethoxylated
structures. Therefore, the combination of two unsymmetrical tails, one containing oxyethylene units
and the other cyanobiphenyl terminal tips, must play an important role to promote this unusual
behavior, and formation of the micro-segregated ethoxylated-tail domains (i.e. quasi ion-channels) in
the lamellar aggregates was suggested to be a trigger for the behavior.
Fig. 1: (Left) Schematic models for micro-segregated CB-B2ES bilayers in water. X1 and X2 are
alkyl chains having cyanobiphenyl (X1) and dioxyethylene (X2) units, respectively. (Right) POM
images of 40wt% CB-B2ES/water mixture at 40 ºC after 0, 8, 16 and 19 min.
[1]. M. Sagisaka, Y. Fujita, Y. Nakanishi, H. Takahashi, N. Tsuyoshi, C. James, A. Yoshizawa, A.

Mohamed, F. Guittard, J. Eastoe, Langmuir 2015, 31, 13040-13047.
138
2D3D-KN10

Supramolecular Engineering of Peptides for Aldol Reactions

Wendel Andrade Alves

Federal University of ABC, Santo André, SP, Brazil
([email protected])

Keywords: peptide nanostructures, supramolecular chemistry, catalysis, aldol reaction.

The technological innovations toward the biomaterials have contributed in the research for high-
performance devices with specific functionalities. This work aims the study of self-assembling
molecular processes of amphiphilic peptide compounds seeking their application in catalysis. A
comprehensive review of the self-assembly in water of a lipopeptide consisting of a sequence of L-
proline (P), L-arginine (R), and L-tryptophan (W) with a hydrocarbon chain has been published
1
recently by our group. In this work, we will present other systems involving amphiphilic peptide
compounds containing one or two amphiphilic tails: PRWG-C18, PRWG-(C18)2, PR(GCP)WG-C16,
PR(GCP)W-(C16)2, where W= L-tryptophan, G= L-glycine, and GCP= guanidinocarbonylpyrrole polar
group. They have been synthesized through the solution-phase strategy, and subsequently
nanostructured and evaluated as catalysts for direct aldol reactions in aqueous media, which is very
desirable from an economic and environmental point of view. The choice for these classes relies on
the rich polymorphism of mesophases they are able to form as well as on their ability to establish
biointerfaces through molecular recognition, increasing their range of applications significantly. We
evaluated the formation of these systems and the kind of interactions appearing in their construction to
provide insights on the physicochemical mechanisms implied in the self-assembly, by using several
analytical, microscopic, spectroscopic and structural techniques. The weakly basic GCP groups (pKa
≈7) are key for secondary structure formation as well as they stabilize the β-sheet through mutual
interactions (formation of a “GCP zipper”) by changing pH of solution. In the following, these structures
were successfully applied as a supramolecular catalytic system for direct aldol reactions between
cyclohexanone and p-nitrobenzaldehyde in excess water. Our results show, for the first time, the
viability of L-proline amphiphilic nanostructures as a catalyst with excellent conversion and
stereoselectivity. In contrast, poor results were obtained in the absence of the lipopeptide assemblies.
The excellent results provided by the self-assembled structures demonstrate the potential of
lipopeptide assemblies to catalyze aldol reactions in an environmentally-friendly manner. [FAPESP,
CNPq]
[1] B.M. Soares, A.M. Aguilar, E.R. Silva, M. Coutinho-Neto, I.W. Hamley, M. Reza, J. Ruokolainen,
W.A. Alves. Phys. Chem. Chem. Phys. 2017, 19, 1181-1189.
139
2D3D-KN11

Bioinspired Features of Three-Dimensional Porous Carbon

Structures

,1 1 1 1
María Luisa Ferrer,* Li Zhi Guan, María Concepción Gutiérrez, Francisco del Monte

1
Group of Bioinspired Materials, Instituto de Ciencia de Materiales de Madrid, CSIC. Campus de
Cantoblanco. 28049, Madrid. Spain

Keywords: hierarchical materials, porous materials, electrically conductive materials,
superhydrophobic materials.
The most complex hierarchically organized chemical structures (e.g., from the nanoworld of proteins to
the macroscopic structures of oyster shells, bone and enamel, among others) can be found in nature.
This is why the imitation of Nature has called the attention of numerous research groups during the
last years. The understanding of the processes through which inorganic atoms and organic
macromolecules self-assemble into organized architectures and complex forms must allow for the
design of new bioinspired routes for materials preparation. In this talk, we will describe different
bioinspired approaches providing hierarchical materials. [1, 2] We will also see how the performance
of these materials (irrespective of the particular field of application) depends on the integration of the
individual components into the hierarchical structure. [3, 4] In particular, we will focus on the
preparation of three-dimensional carbon structures with superhydrophobic properties.
[1] F. del Monte and coworkers, Chem. Soc. Rev., 2013, 42, 794
[2] F. del Monte and coworkers, Nature Commun., 2013, 4 , 2683
[3] F. del Monte and coworkers, Energy Environ. Sci., 2011, 4, 4201
[4] F. del Monte and coworkers, Biomaterials 2014, 35, 1543

140
PLASMAT-KN01

Engineering nature-inspired surfaces by femtosecond laser

micromachining

1 1 1
Anne-Marie KIETZIG *, Youssef ASSAF, K M Tanvir AHMMED,

1
Department of Chemical Engineering, McGill University, Montreal, Canada;

Keywords: femtosecond laser, structural colour, surface wetting, superhydrophobicity, drag reduction
Functional surfaces in Nature are often characterized by patterns of similar multi-length scale surface
features of regular but random geometry. In engineering we prefer precise feature geometries that are
accessible by mathematical formulations for kinetic and thermodynamic considerations. Often multi-
length scale features result from complicated multiple processing steps under controlled environments
needing various equipment. Femtosecond (fs) laser machining has emerged in the past decades as a
versatile material processing technique which requires only one single process step to induce either
random multi-length scale features or microstructures of closely controlled geometry. Further, the
short pulse duration results in very localized heat effects which allows structuring material surfaces
without affecting the underlying bulk properties. Although there is no limit to the material type that can
be treated, the topological outcome is a direct response dictated by the respective material properties.
Overall it is an interesting technique for biomimetic surface engineering as highlighted by examples of
structural colour, superhydrophobicity and drag reduction experiments with metals and polymers.
Nano- and micro-scale structures are known to generate structural colours, which is an approach
applied by various natural creatures. Surface structures resulting from fs laser machining often come
along with new shades of colour in comparison to the base material. Yet, in many cases it is not the
structure alone but also changes in surface chemistry that result in the altered colour response. In the
case of metals the oxide layer thickness plays an important role [1], while, when ablating polymers,
changes in the chemical structure also contribute to the final optical result [2].
Many plants provide examples for surface functionality where liquid-solid interactions are of
importance, e.g. lotus leaf, water fern, rose petal, etc.. Fs laser machining can provide air-trapping
surface patterns on metals by producing microstructures that are decorated with sub-micron surface
ripples typical of laser ablation at ambient conditions, and depending on process conditions, a third tier
of structures can be added by redeposited nanoparticles [3]. Such superhydrophobic metal surfaces
have proven successful in reducing drag under internal flow conditions, e.g. in pipelines.
Polymers exhibit a characteristic surface porosity upon fs laser irradiation, where pore size can be
controlled by carefully choosing the material parameters, and superhydrophobic air-trapping structures
able to reduce drag as well as non-adhesive surfaces are readily obtained [4, 5]. We have further
produced drag reducing surface patterns mimicking the mechanism employed by shark skin. Yet our
attempt of combining shark skin and lotus leaf-like patterns showed no synergistic effects [6].
Further, fs-laser machining provides an interesting toolkit for biomimetic surface engineering also
because it allows tuning the wetting response of a surface from non-wetting to wetting by exposing
metallic surfaces to different processing or post-processing environments [7] or by integrating fs laser
ablation with pulsed-laser deposition of metallic nanoparticles for polymeric samples [8].
[1] N. Y. Khafaji, A. G. Demir, et al., Surf. Coat. Technol. 2017, 321, 156-163.
[2] Y. Assaf, A.-M. Kietzig, Mat. Today Comm. 2018, 14, 169-179.
[3] KM T. Ahmmed, A.-M. Kietzig, Soft Matter 2016, 12, 4912-4922.
[4] KM T. Ahmmed, A.-M. Kietzig, Appl. Mat. Interfaces 2016, 8, 27411-27419.
[5] F. Liang, J. Lehr, et. al., Int. J. Mol. Sci. 2014, 15, 13681-13696.
[6] KM T. Ahmmed, J. Montagut, A.-M. Kietzig, Can. J. Chem. Eng. 2017, 9999, 1-9.
[7] J. Lehr, L. Matus, et. al., Appl. Surf. Sci. 2014, 320, 455-465.
[8] Y. Assaf, G. Forstmann, A.-M. Kietzig, Appl. Surf. Sci. 2018, 436, 1075-1082.
141
PLASMAT-KN02

Bio-Inspired Superwetting Materials

Kesong LIU
Email: [email protected]

Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology of Ministry of Education,
School of Chemistry, Beihang University, Beijing 100191, China

Keywords: Superwettability, Multiscale structures, Multifunction materials, Bio-inspired materials
Nature is a school for human beings. Multiscale structures are characteristic for biological materials,
exhibiting inherent multifunctional integration. Learning from nature has long been a source of bio-
inspiration for scientists and engineers [1,2]. Optimized biological solutions provide inspiration for
scientists and engineers to design and to fabricate multiscale structured materials for multifunctional
integration. In recent years, inspired by nature, our research is focused on the design, synthesis, and
application of bio-inspired materials with super-wettability, including (i) clarification of the relationship
between multi-scale micro/nanostructures and special wettability of some biomaterials, providing new
theory for the design of functional materials; (ii) extraction of novel design concept for bio-inspired
materials with multifunction integration; (iii) bio-inspired fabrication of a series of multifunctional
materials with super-wettability; (iv) practical applications of multifunctional materials in the fields of
oil/water separation, water collection, droplet transport, etc. [3-5].
Fig. 1: Typical biological materials with functional integration and corresponding multiscale
structures, which could serve as source of inspiration for the design and fabrication of
multifunction superwetting materials.
[1]. K. Liu, X. Yao, L. Jiang, Chem. Soc. Rev. 2010, 39, 3240-3255.
[2]. K. Liu, M. Cao, A. Fujishima, L. Jiang, Chem. Rev. 2014, 114, 10044-10094.
[3]. S. Yang, J. Du, M. Cao, X. Yao, J. Ju, X. Jin, B. Su, K. Liu, L. Jiang, Angew. Chem. Int. Ed. 2015,
54, 4792-4795.
[4]. M. Cao, X. Jin, Y. Peng, C. Yu, K. Li, K. Liu, L. Jiang, Adv. Mater. 2017, 29, 1606869.
[5]. Y. Zhang, M. Cao, Y. Peng, X. Jin, D. Tian, K. Liu, L. Jiang, Adv. Funct. Mater. 2018, 28,
1704220.
142
PLASMAT-KN03

Injectable Cryogels for Biomedical Applications

1,2,3,4
Sidi A. BENCHERIF

1
Department of Chemical Engineering, Northeastern University, Boston, USA;
2
Department of Bioengineering, Northeastern University, Boston, USA;
3
School of Engineering and Applied Sciences, Harvard University, Cambridge, MA, USA;
4
Sorbonne University, UTC CNRS UMR 7338, UTC, Compiègne, France
Keywords: Biopolymers, Cryogel, Injectable, Tissue Engineering, Drug Delivery, Cancer

Immunotherapy
Injectable biomaterials are increasingly being utilized to limit risks and complications associated
with surgical implantation. We recently developed a strategy for delivery via conventional needle–
syringe injection of large preformed macroporous scaffolds called cryogels with well-defined properties
[1]. These cryogels in the form of elastic sponge-like matrices are prepared by environmentally friendly
cryotropic gelation of alginate giving rise to 3D scaffolds with unique properties as these preformed
biomaterials are injectable (Figure 1-A).
Additionally, these
cryogels have shape-memory A
1 2 3 4
properties and can easily be
molded to a variety of shapes
Seaweeds
and sizes, and may be
optionally loaded with Alginate MA-Alginate Water Cryogel Ice crystals Macropores
therapeutic agents or cells
(Figures 1-B and 1-D). These
scaffolds have the capability to D
withstand reversible B C 1.2
In Vivo Release of BSA
Crosslinked BSA
deformations, and a rapid 1
Encapsulated BSA
(Radiant Efficiency)
0.8
volumetric recovery allows the 0.6
structurally defined scaffolds to 0.4
be injected through a small- 0.2
bore needle with nearly 0

0 20 40 60 80 100 120
complete geometric restoration Time (days)
once delivered (Figure 1-A). Figure 1. Injectable cryogels for controlled drug delivery and cell
These gels demonstrated long- transplantation. (A) An overview of the cryogelation process: alginate is
term release of biomolecules in chemically modified (MA-alginate) to allow radical polymerization (1); MA-
alginate is added to APS/TEMED initiator system before incubation at −20
vivo (Figure 1-C). Furthermore,
°C to allow ice crystal formation (2); the process of cryogelation takes place
cryogels impregnated with via the following steps: phase separation with ice crystal formation, cross-
bioluminescent reporter cells linking, and polymerization followed by thawing of ice crystals (porogens) to
provided enhanced survival, form an interconnected porous cryogel network (3); and conventional
higher local retention, and needle–syringe injection of preformed cryogels (4). (B) Photographs
extended engraftment of showing cryogels prepared with different geometric shapes (disk, pentagon,
transplanted cells at the heart, and star) retained their original shapes after syringe injection. (C) In
injection site compared with a vivo release profiles of cross-linked (chemically anchored) or encapsulated
standard injection technique (physically entrapped) rhodamine-labeled BSA containing injected cryogels.
(D) Noninvasive bioluminescence in vivo imaging of transplanted cells in
(Figure 1-D). Further, cryogels
BALB/c mice 2 days post injection.
can be hybridized with

nanoparticles to enhance their physico-chemical properties such as stimuli responsiveness to their
external environment. Overall, these injectable scaffolds show great promise for various biomedical
applications, including drug delivery, tissue engineering, cell transplantation, and more cancer
immunotherapy [2].
[1] S.A. Bencherif, W.R. Sands, D. Bhatta, P. Arany, C. Verbeke, D.A. Edwards, D.J. Mooney,
PNAS 2012, 109, 19590-19595.
[2] S.A. Bencherif, R.W. Sands, O. Ali, S.A. Lewin, A. Li, T. Braschler, T. Shih, D. Bhatta, G.
Dranoff, D.J. Mooney, Nature Communications 2015, 6:7556 doi: 10.1038/ncomms8556.
143
PLASMAT-KN04

Pulsed atmospheric pressure plasma: An elegant route for the

deposition of tunable bioinspired and smart thin polymer films

Maryline MORENO-COURANJOU
Luxembourg Institute of Science and Technology, Materials Research and Technology departement,
5 Avenue des Hauts-Fourneaux, L-4362 Esch/Alzette, Luxembourg.
Keywords: pulsed atmospheric pressure plasma, nanosecond pulsed discharge, plasma

polymerization, tunable catechol thin films, thermoresponsive polymers
Among various existing technique for coating of a material surface with a functional thin film,
atmospheric-pressure Dielectric-Barrier-Discharge (AP-DBD) have gained considerable interests at
laboratory and industrial levels. Indeed, AP-DBD present several advantages such as solvent-free, up
scalable and substrate independent characters, allowing the fast production of high purity organic
coatings. Considering the deposition of thin polymer films from organic precursors, significant retention
of the monomer features has been achieved using a pulsed DBD approach. Such strategy relies on
the successive switching on and off of the plasma during different periods, namely plasma-on (ton) and
plasma-off (toff) times. The duty cycle (DC) defines the pulsed plasma as the ratio of ton to the total
cycle time. [1] Hence, by promoting long toff over ton (i.e, DC around 0.02), it was shown that free-
radical polymerization and deposition from vinyl-based monomers can be carried out. [2] Later, at
LIST, we successfully exploited pulsed DBD generated from high voltage alternating current chopped
in the millisecond range, for the deposition of common anhydride [3], carboxylic [4] or epoxy [5] -
containing films. Interestingly, it is worth noting that pulsed DBD of thermoresponsive films remain
scarcely reported. Indeed, such smart film properties require the synthesis of conventional-like
polymers, which structure remains difficult to achieve despite limiting the plasma duration (ton ∼1 ms).
Recently, Plasma initiated Chemical Vapor Deposition (PiCVD) was introduced. Relying on low
frequency repetition of nanosecond pulsed discharges (i.e, ton ∼ 100 ns, toff ~ 31.6 ms), PiCVD allowed
the deposition of polymer layers with an unprecedented degree of polymerization coupled to an
outstanding thin film conformality and an excellent chemical functionality retention. [6]
In this communication, the latest developments carried out at LIST in the field of pulsed AP-DBD
will be presented.
In the first part of the presentation, it will be shown how judicious bio-inspired monomer choice
and injection type associated to a fine adjustment of the electrical discharge parameters (i.e, ton and toff
ranging from 1-15 and 15-800ms, respectively) can lead to the simultaneous synthesis and deposition
of catechol-bearing thin films with tunable catechol content, morphology and deposition rates.
In the second part, application of PiCVD copolymerization for smart thermoresponsive polymer
film deposition will be reported.
[1] CVD polymers, Fabrication of organic surfaces and devices Edited by K.K. Gleason, 2015, p.67
[2] C.P. Klages, K. Höpfner, N. Klake, R. Thyen, Plasmas Polym. 2000, 5, 79−89.
[3] M. Moreno-Couranjou, A. Manakhov, N. D. Boscher, J-J. Pireaux, P. Choquet, ACS Appl. Mater.
Interfaces 2013, 5, 8446-5456.
[4] R. Mauchauffé, M. Moreno-Couranjou, N. D. Boscher, C. Van De Weerdt, A-S. Duwez, P,Choquet,
J. Mater. Chem. B, 2014, 2, 5168-5177.
[5] G. Camporeale, M. Moreno-Couranjou, S. Bonot, R. Mauchauffé, N. D. Boscher, C. Bebrone, C.
Van de Weerdt, H-M. Cauchie, P. Favia, P. Choquet, Plasma Processes Polym. 2015, 12, 1208-1219
[6] F. Loyer, G. Frache, P. Choquet, N. D. Boscher, Macromolecules 2017, 50, 4351-4362
144
PLASMAT-KN05

Laser processing of biomimetic graphene surfaces and their

applications

1
Yong-Lai Zhang, *

1
State Key Laboratory of Integrated Optoelectronics, College of Electronic Science and Engineering,
Jilin University, Changchun, China
Keywords: Laser processing, bioinspired structures, graphene, graphene oxide, superhydrophobic
Biomimetic fabrication has long been considered a short cut to the rational design and production of
artificial materials or devices that possess fascinating properties, just like natural creatures.
Considering the fact that graphene exhibits a lot of exceptional properties in a wide range of scientific
fields, biomimetic fabrication of graphene multiscale structures, denoted as biomimetic graphene, is of
great interest in both fundamental research and industrial applications. Especially, the combination of
graphene with biomimetic structures would realize structural and functional integrity, and thus bring a
new opportunity of developing novel graphene-based devices with remarkable performance. In this
[1-10]
regard, we developed a laser processing strategy for producing biomimetic graphene films.
Notably, laser processing enables designable fabrication of various micronanostructures. Meanwhile,
the laser treatments also provide a way to tune the surface energy of materials by selective removal of
special functional groups. Nowadays, the unique laser processing technology has been considered an
enabler for creating bioinspired micronanostructures, revealing great potential for developing
biomimetic materials, especially, graphene and its derivatives. Functionalized graphene films with
multiscale structures inspired from a wide range of biomaterials including rose petals, butterfly wings
have been fabricated and presented. Moreover, both current challenges and future perspectives of
biomimetic graphene are discussed. Although research of the so-called ‘‘biomimetic graphene’’ is still
at an early stage, it might become a ‘‘hot topic’’ in the near future.
Fig. 1: Concept for laser processing of biomimetic graphene surface
[1]. Y. Zhang, et. al., Nanoscale, 2012, 4, 4858.

[2]. Y. Zhang, et. al., Soft Matter, 2012, 8, 11217.
[3]. Y. Zhang, et. al., Adv. Optical Mater. 2014, 2, 10–28.
[4]. H. Jiang, et. al., Laser Photonics Rev. 2016, 10, 441–450.
[5]. Y. Liu, et. al., Nanoscale, 2017, 9, 17933
[6]. J. Wang, et. al., Nanoscale, 2015, 7, 7101.
[7]. Y. Liu, et. al., ACS Appl. Mater. Interfaces 2015, 7, 20930−20936.
[8]. Z. Yan, et. al., ACS Appl. Mater. Interfaces 2015, 7, 27059−27065.
[9]. H. Jiang, et. al., Adv. Funct. Mater. 2014, 24, 4595–4602.
[10]. J. Wang, et. al., Chem. Asian J. 2012, 7, 301 – 304.
145
3D-KN01

Printing 4D Gradient Hydrogel Scaffolds for Programmable Cellular

Dynamics and Patterned Biogenic Mineralization
Ralph G. NUZZO *
Department of Chemistry
University of Illinois at Urbana, Champaign, USA
Keywords: Biomimetic 4D Printing; Biomineralization; 3D Cellular Scaffolds; Gradient Hydrogel

Composites; Cellular Microcultures; 3D Printing.
I will describe temporally-dynamic scaffolds (4D) fabricated using gradient 3D-printing methods that
are capable of programming cellular decision-making in complex microcultures. These structures are
prepared using a Direct Ink Writing technique of DIW, which uses extrusion to precisely pattern
filaments at biologically-relevant diameters (~<100 µm). Here, we incorporate a rheological modifier
LAP into 2-hydroxyethyl methacrylate (HEMA) hydrogels to print gradient composition LAP-HEMA
(LH) gel composites that require no protein treatment to direct the spatio-temporally programmed
attachment/migration/development of fibroblast (3T3) and preosteoblast (E1) cells as well as to direct
long-term osteodifferentiation of the E1 cultures. Cell-to-gel interfacial morphologies are characterized,
and LAP-conferred cellular motility is quantified using Spatial Light Interference Microscopy (SLIM).
Using a combination of HEMA and LH gels, we develop a high-performance, high-resolution
nanocomposite—UniH—that manifests properties of both gels and translates their temporally-dynamic
attributes to dentition-mimetic 3D scaffolds. These analyses confirm that the underlying materials
chemistry of hydrogel nanocomposites, as well as the geometries embedded at the point-of-printing
them, are capable of temporally directing cellular attachment and behavioral outcomes that are robust
in the absence of protein modifications and scalable as biodynamic 4D scaffolds.
146
3D-KN02

Novel Bio-based Elastomers with tunable properties

1 1 1 1 1
Liqun Zhang*, Zhao Wang, Runguo Wang, Yu Gao, Qinan Zhang

1
State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology,
Beijing 100029, P. R. China;
Keywords: bio-based elastomer, functional performance
With extensive interest in sustainable development, the chemical industry is making great attempts to
replace petrochemical-based monomers with natural ones [1]. It is strategically important to construct
novel polymers by renewable resources. We have focused on bio-based elastomers for a dozen
years, and synthesized quite a few new bio-based elastomers with high molecular weight, low glass
transition temperature (Tg), and comprehensive mechanical properties based on renewable
monomers that are produced on a large scale [2], and some of them are approaching industrialization.
There are two representative bio-based elastomers, bio-based polyester elastomer via
polycondensation method [2] and itaconic acid-based elastomers (poly(di-n-butyl itaconate-co-
butadiene), PDII) via emulsion polymerization [3]. The polyester elastomers were designed and
synthesized from large scaled diols and diacids such as butanediol, propanediol, sebacic acid,
succinic acid, itaconic acid, et al. These polyester elastomers could be prepared into oil resistant
rubber products, bio-based and degradable chewing gums, full-bio-based thermoplastic vulcanizate
(TPV) products and used as bio-based plasticizers or tougheners for plastics. The TPV products could
be used as ink for 3D printing, and the digital photos of the 3D printing products were shown below.[4]
PDII reinforced with silica have been successfully prepared into a green tire that has very low roll
resistance and excellent wear-resistance that promote fuel efficiency and our dependence on
petrochemical resources. Bio-based poly(dibutyl itaconate-ter-isoprene-ter-4-vinylpyridine) (PDBIIVP)
elastomers with different 4-vinylpyridine (4-VP) contents were synthesized by redox emulsion
polymerization for the purpose of designing and preparing green graphene oxide (GO)/PDBIIVP
nanocomposites with strong interfacial interaction [5]. For the GO/PDBIIVP with 7.0 wt% of 4-VP and 4
phr of GO, the tensile strength increased by 700%, the volume loss of abrasion decreased by 53%,
and the gas permeability decreased by 63% compared with those of the neat PDBIIVP. This method
may become an important strategy for developing GO-based polymer nanocomposites with high
performance. The bio-based polyester elastomers and itaconic acid-based elastomers are promising
materials for the replacement of the existed elastomers or provide new applications.
Digital photos of soft 3D printing products using bio-based TPV as ink
[1] A. Gandini. Macromolecules 2008, 41, 9491-9504

[2] T. Wei, L.J. Lei, H.L. Kang, B. Qiao, Z. Wang, L.Q. Zhang, P. Coates, K.C. Hua, J. Kulig. Adv.
Eng. Mater. 2012, 14, 112-118
[3] R. Wang, J. Ma, X. Zhou, Z. Wang, H. Kang, L. Zhang, K. Hua, and J. Kulig. Macromolecules
2012, 45, 6830−6839
[4] X.R. Hu, H.L. Kang, M.Q. Li, R.G. WANG, R.W. Xu, H. Qiao, L.Q. Zhang. Polym. Chem. 2015, 6,
8112-8123
[5] H. Qiao, R.G. Wang, H. Yao, X.X. Zhou, W.W. Lei, X.R. Hu, L.Q. Zhang. Polym. Chem. 2015, 6,
6140-6151
147
BIOADH-KN01

Lingual adhesion in Tetrapods: Why and how in lizards?

1 2 2 2
Vincent Bels, Leila Zghikh, Valérie Vangysel, Emeline Paulet, Anne-Sophie Paindavoine,

1
Muséum national d’Histoire naturelle, Sorbonne Université, Institut de Systématique, Evolution,
Biodiversité, 57, rue Cuvier BP 55, F- 75231 Paris CEDEX 05, France.
2
University of Mons, Institute of BioSciences, Faculty of Medicine and Pharmacy, 23, Place du Parc,
B-7000 Mons, Belgium.

Keywords: Adhesion, Tongue, Feeding, Prey capture
Adhesion plays a key role in the predatory behavior of a lot of Tetrapods including amphibians, lizards,
reptiles, birds and mammals. Lingual morphology permitting food/prey adhesion is highly diverse (i.e.,
SEM, histology, histochemistry). However, the mechanisms explaining the efficiency of lingual food
prehension are relatively poorly understood. In a first time, we review the various behavioral and
physical mechanisms suggested in the literature to explain how Tetrapods with highly different lingual
structures (e.g., surface) are able to catch various foods from their natural environment. Within
Tetrapods, Lizards are one of the clades that catch the food with the jaws, the tongue, and both for
same food items. This clade thus provides a key example to analyze the adhesion mechanism in
species able to catch living insects, rodents, and plant material (e.g., fruit) with the tongue. In the
context of understanding the evolutionary scenario to relate tongue structures, and performances with
feeding behavior, we compare empirical data on lingual adhesion in representative species exploiting
various foods (i.e., plant material, living and mobile prey). These mechanisms are examined in
relationship with the selected food and their properties (i.e., texture, size, volume), and the
environmental contexts (e.g., dry versus wet surface) that lizards have to face as proximal factors of
their food/prey in their habitats. Finally, a consideration of the various hypotheses that have been
suggested about the evolution of lingual adhesion in lizards is used to provide new comprehension of
the evolutionary mechanism that governs prey capture in Lizards in various habitats. These behavioral
and evolutionary approaches permit to suggest some preliminary insights of lingual adhesion in lizards
on new finding that might help to design new adhesive system that stick at high speeds.
148
BIOADH-KN03

In the footsteps of sea stars: Proteins for temporary adhesion
1 1 1 2
Patrick FLAMMANG *, Birgit LENGERER, Morgane ALGRAIN, Mathilde LEFEVRE,
2
Elise HENNEBERT
1
University of Mons, Biology of Marine Organisms and Biomimetics Unit, Mons, Belgium;
2
University of Mons, Cell Biology Unit, Mons, Belgium
Keywords: Marine adhesion, Starfish, Recombinant proteins
Marine biological adhesives are a promising source of inspiration for biomedical and industrial
applications. They are environmentally friendly, biodegradable, and adhere to various surfaces under
the challenging conditions of the marine environment. Nevertheless, natural adhesives and especially
temporary adhesion systems are still largely unexplored. Sea stars use their adhesive secretions to
attach strongly to the substratum but also to pry open the mussels on which they feed. They are able
to quickly and repeatedly attach and detach themselves with their hydraulic tube feet. The reversible
adhesion of sea stars relies on a duo-gland adhesive system, where two types of adhesive cells co-
secrete a blend of adhesive proteins and a different gland type produces a de-adhesive substance [1].
Upon voluntary detachment, the adhesive material stays attached to the substrate as a footprint
consisting of a structural meshwork deposited on a thin homogenous film [1]. It has been proposed
that one adhesive cell secretes the material of the meshwork and the other forms the thin film covering
the substrate.
Recently, a tube foot transcriptome and a footprint proteome were combined to obtain the
sequences of all footprint specific proteins in the species Asterias rubens. A list of 34 putative sea star
footprint proteins (Sfps) was retrieved in this way [1]. Whole-mount in situ hybridization (ISH) was
used to confirm their expression in the duo-gland adhesive system. Twenty-two proteins are
specifically expressed in the adhesive epidermis, indicating that sea star temporary adhesion involves
a complex network of proteins. Double ISH experiments were conducted in order to ascribe the
different Sfps to the two adhesive cell types.
To date, only one adhesive protein, Sfp1, has been characterized [1]. This large protein is
translated from a single mRNA and then cleaved into four subunits displaying specific protein-,
carbohydrate- and metal-binding domains (Fig. 1). Originating from one of the two types of adhesive
cells, it is localized at the level of the fibrillar meshwork of footprints after secretion, where it forms the
structural core of the adhesive material. Based on the amino acid sequence of Sfp1, two recombinant
proteins have been designed and produced in the bacterium Escherichia coli (Fig. 1). After
purification, their secondary structure has been characterized by Fourrier transform infrared (FTIR)
and circular dichroism (CD) spectroscopy, and their nanomechanical properties by atomic force
microscopy (AFM).
Unravelling the complex protein network involved in sea star temporary adhesion might facilitate
the development of biomimetic, reversible glues. Indeed, Sfps provide an interesting design paradigm
for engineering specific adhesion between different tissues for potential applications as biomedical
adhesives.
Fig. 1: the four subunits and the main structural domains of Sfp1. Yellow, lectin domain; blue,
von Willebrand factor domain; red, discoidin domain; green, EGF-like domain; purple, C8
domain. Framed parts correspond to produced recombinant proteins
nd
[1]. P. Flammang, M. Demeuldre, E. Hennebert, R. Santos, Biological Adhesives (2 edition), 2016,
Smith A.M. (ed.), Springer International Publishing, Cham.

149
BIOADH-KN03

The hairy adhesive pads: wet and compliant

1
Tristan GILET *,
1
Microfluidics Lab, Dept. Aerospace and Mech. Eng., University of Liège, Liège, Belgium

Keywords: Adhesion, elasto-capillarity, insect locomotion, hairy pads, robotics
The miniaturization of pick-and-place robotics is currently limited by the challenge to control adhesion
forces on a wide variety of substrates and on very short timescales. Insects have already solved this
challenge: most of them can walk on about any substrate in any orientation. Thanks to the adhesive
pads on their tarsi, they must thereby generate appropriate adhesion and friction forces, and cancel
them a fraction of a second later.
Through evolution, insects have converged independently to only two main architectures of adhesive
pads: smooth and hairy. This talk will be focused on the hairy pads of beetles and flies (figure 1). I will
discuss two ingredients that guarantee a robust, efficient and controllable adhesion to different
substrates: 1) compliant microstructures, and 2) the presence of a liquid secretion. Both act in concert
to mediate the contact and provide sufficient adhesion and friction forces [1]. The force level seems to
be controlled through an appropriate leg kinematics [2].

Figure 1: Hairy tarsal segments of the dock beetle Gastrophysa viridula.
[1]. S. Gernay, W. Federle, P. Lambert and T. Gilet, J. R. Soc. Interface 2016, 13, 20160371.
[2]. S. Gernay, S. Labousse, P. Lambert, P. Compère and T. Gilet, J. R. Soc. Interface 2017, 14,
20170493.
150
BIOADH-KN05

Tube formation in polychaetes: a proteomic and genomic
perspective
Buffet JP, Corre E, Duvernois-Berthet E, Fournier J, Luquet G, Bouchon C, Lopez PJ
UMR BOREA CNRS – 7208/ MNHN/ Sorbonne Universités/ IRD-02/ UCN/ UA Muséum National
d’Histoire Naturelle, 43 rue Cuvier 75005 Paris, France
Tube-building polychaetes are hermatypic organisms capable of forming vast reefs in highly turbulent
marine habitats. Among them, Sabellaridae and Terebellidae assemble their tube by gluing together
siliceous and calcareous clastic particles using a polyelectrolytic biocement. Here, we performed
transcriptomic analyses to investigate the genes that are differentially expressed in the parathorax
region, which contains the adhesive gland and tissues, from the rest of the body. We found a large
number of candidate genes to be involved in the composition and formation of biocement in three
species: Sabellaria alveolate, Phragmatopoma caudata and Lanice conchilega. Altogether these new
genomic resources coupled to proteomic analyses, help to identify novel transcripts encoding for
proteins involved in cement and tube formation, but also important enzymes putatively involved in the
chemistry of the adhesion process and may correspond to new targets to develop biomimetic
approaches.
151

ORAL ABSTRACTS
152
BIOTECH-OR01

Mycelium-based materials: a broad spectrum of tunable properties

1,2 1 1
Maria Elena ANTINORI , Laura BERTOLACCI , José Alejandro HEREDIA-GUERRERO ,
1*
Athanassia ATHANASSIOU

1
Smart Materials, Department of Nanophysics, Istituto Italiano di Tecnologia (IIT), Genoa, Italy;
2
DIBRIS, University of Genoa, Genoa, Italy
Keywords: fungi, biocomposites, tunability
Plastics are one of the widest spread materials, being used in the fabrication of most of commodities.
However, conventional plastics are non-biodegradable and still mostly produced from petrochemical
products. Bio-based plastics, produced from renewable resources, seem the best solution to
1
overcome pollution and non-sustainability concerns connecting with synthetic plastics . Among them,
materials which are directly produced by living organisms can benefit from the ability of biological
beings not only to self-grow, but especially to change their properties according to environmental
conditions. Mycelium-based materials are possibly the best representatives of this category, since
2
after their growth they can be entirely recovered as fibrous biocomposites. .
Mycelium-based materials have been employed so far in clothing, packaging and construction
applications usually in the form of composites. The aim of this work is to uncover a broader spectrum
of interesting features owed by mycelium-based materials, even when not combined in composites,
and to find related applications. This objective is pursued by analyzing a high number of
physicochemical properties and further tuning of them through growth in different conditions and post-
3
harvesting processing . In particular, two- and three-dimensional mycelium-based materials obtained
by varying growing time, feeding substrate and post-harvesting processing were compared in terms of
morphological, chemical, mechanical and wettability properties. Kinetics of growth, measured as dry
weight and area increase per day, were also assessed in every condition. Different substrates varying
from Potato Dextrose Broth to vegetable wastes were provided to the mycelia as feeding substrates
4
for their growth .
The chemical composition of the feeding substrates, phase and porosity especially influenced
mechanical and wettability properties of final materials, as well as kinetics of growth: higher
concentrations of polysaccharides in the medium accelerated mycelium growth, leading to thicker
materials, with high static water contact angles (around 120°) and better mechanical properties.
Hyphal morphology and arrangement were also highly affected by substrate chemical composition,
being less entangled and with larger pores when grown onto more hydrophobic substrates; hyphal
dimensions did not show significant changes in the different substrates. Moreover, growth was faster
and more complete in liquid or very porous media, at an initial pH of 4, when substrates with the same
chemical composition were compared.
The wide range of properties owed by mycelium-based materials allows a broad variety of
applications, from nanotechnological devices, by exploiting the hyphal network as a scaffold, to textiles
and medical devices, with the possibility of tuning mycelium features locally just by varying conditions
of growth.
[1]. Iwata, Tadahisa, Angew. Chem. Int. Ed. 2015, 54.11, 3210-3215.
[2]. Jones, Mitchell, et al. J. Bionanosci. 2017,11.4, 241-257.
[3]. Haneef, Muhammad, et al. Sci. rep. 2017, 7, 41292.
[4]. Perotto, Giovanni, et al. Green Chem. 2018, 20.4, 894-902.
153
BIOTECH-OR02

Exploitation of waste date seeds as sustainable source of high

quality bio-oil

1 1 1
Mujeeb Oladipupo KAREEM, Anjali ACHAZHIYATH EDATHIL, Fawzi BANAT*,

1
Department of Chemical Engineering, Khalifa University of Science and Technology (KUST) - SAN
campus, Abu Dhabi, United Arab Emirates

Keywords: Date seed; Phoenix dactylifera; Bio-oil; Soxhlet extraction; FTIR spectroscopy
Date fruit, Phoenix dactylifera, one of the most popularly consumed foods in the world is known for its
nutraceutical, pharmaceutical and medicinal values. In a bid to improve the benefits derivable from the
date fruits, the seeds – commonly viewed as waste accounting for 10-18% of the total fruit mass –
have been studied and exploited as a bio-oil source. The date oil, extracted from ground date seeds
has been found suitable for cosmetic and nutritional applications, but is still of interest to know how
good its quality is for nutrition and what are the other innovative methods that can be used to improve
the yield without compromising the quality. In line with this, the current work focuses on the
exploitation of waste seeds of the Sukkary date fruit type as a cheap feedstock for producing bio-oil
and determine its quality using FTIR spectroscopy. FTIR analysis revealed that the extracted bio-oil
from waste date seed were very much similar to that of olive oil; suggesting its suitable nutritional and
sensory characteristics. To ascertain the conditions that would lead to optimal oil yield, the effect of
grain sizes, drying method, type of solvent and pretreatments were analyzed by carrying out the
extraction in a standard soxhlet apparatus. The highest oil yield was attained by using a grain size of 0
- 200 microns, drying in an oven at 110 ˚C for 24 h and chloroform as solvent. Pretreatment of the
seeds by soaking in sodium chloride (NaCl) solution of varying concentrations showed an
improvement in the oil yield.
154
BIOTECH-OR03

Complex, flow-induced organization of dense collagen solutions

during microfluidic fiber extrusion

1,2 2 3 1
Lise PICAUT , Léa TRICHET , Guillaume DUCOURTHIAL , Olivier RONSIN , Marie-Claire
3 2 1
SCHANN-KLEIN , Gervaise MOSSER , Tristan BAUMBERGER *
1 Institut des Nanosciences de Paris, Sorbonne Universités, UPMC Univ Paris 6 and CNRS-UMR
7588, F-75005 Paris, France,
2 Laboratoire de Chimie de la Matière Condensée de Paris, Sorbonne Universités, UPMC Univ Paris
6 and CNRS-UMR 7574, F-75005 Paris,
3 Laboratoire d'Optique et Biosciences, Ecole Polytechnique, CNRS, INSERM U696, Palaiseau,
France
Keywords: Collagen, Tendon, Crimp, Microfluidics, Extrusion, Flow-Induced crystallization
Fibril-forming collagens are the principal building blocks of the extracellular matrix. In vivo , fibril
organization spans long distances leading to complex, hierachical structures, the archetype of which
are tendons[1]. Reproducing in vitro the large scale, supramolecular alignment and crimp distorsion,
which play a major role in tendon mechanical properties, remains challenging. It has recently been
shown that flow-induced crystallization may occur during fibre drawing at sufficiently high rates, out of
a dense enough collagen solution[2]. Here we show that this strategy may be generalized to
microfluidic threadlike fibre extrusion into a fibrilling bath[3]. Provided that the shear rate at the wall is
larger than some frequency, characteristic of the viscoelastic relaxation in the solution, collagen
monomers tend to align along the fibre axis, exhibiting an unexpected core-shell discontinuous
distribution of the nematic order parameter, as evidenced by polarization-resolved SHG microscopy.
Subsequent fibrillation proceeds onto this anisotropic template. One step further, taking advantage of
our recent study of extrusion instabilities of shear thinning alginate solutions[4], we have succeeded in
forming helicoidally distorted collagen fibres which reveal a birefringence pattern akin to that exhibited
by naturally crimped tendons[5]. Though preliminary, this result suggests a new, fully-rheological way
to imprint a 3D large-scale order into linear collagen scaffolds.
Fig. 1: Bright field (left) and cross-polarization (right) pictures of a helicolidally distorted,
extruded collagen (30 mg/ml) fibre (bar = 200 µ m) [5]. The birefringence pattern is reminiscent
of that of naturally crimped tendons.
[1]. C. Rieu, L. Picaut, G. Mosser, and L. Trichet, Current pharmaceutical design , 2017 , 23 , 3483-
3506.
[2]. J. A. Paten, S. M. Siadat, M. E. Susilo, E. N. Ismail, J. L. Stoner, J. P. Rothstein and J. W. Ruberti,
ACS Nano , 2016 , 10, 5027-5040.
[3]. L. Picaut, L. Trichet, O. Ronsin, B. Haye, I. Génois, T. Baumberger and G. Mosser, Biomed. Phys.
Eng. Express , 2018 , 4, 035008.
[4]. L. Picaut, O. Ronsin, C. Caroli, and T. Baumberger, Phys. Rev. Fluids, 2017 , 2, 083303-17.
[5]. L. Picaut, Synthesis of an artificial tendon , PhD Thesis, Sorbonne Unversity, 2017 .
155
BIOTECH-OR04

Processable and fully biodegradable Poly(ɛ-caprolactone)/Laccase

materials for food packaging application
1 1 3
S. Benali , R. Mincheva , F. Audrit , P. Dubois1, S. Flahaut2, JM. Raquez1
Email : [email protected]
1
Center of Innovation and Research in Materials and Polymers (CIRMAP), Research Institute for
Materials Science and Engineering, University of Mons-UMONS, Place du Parc 20, 7000 Mons,
Belgium
2
Department of Molecular Microbiology and Cellular Biology, LABIRIS, University of Brussels-ULB,
Campus du CERIA, Bât 4B, 1 avenue Emile Gryson B-1070 Bruxelles, Belgium
Keywords: Poly(ɛ-caprolactone), Laccase, Melt Blending.
Laccases (p-diphenol: oxygenoreducdoreductases EC1.10.3.2) is the biggest subgroup of blue multi-

copper oxidases, which directly utilize the redox ability of cupric ions for catalysing the oxidation of
1,2
several aromatic compounds with the reduction of oxygen molecules to water. These enzymes
participate in processes such as biosynthesis and lignin degradation, morphogenesis, and pigment
biosynthesis, among others. Laccases are considered “ideal green” catalysts because they employ O2
3
as a co-substrate and generate H2O as a byproduct.. This ability could be a great potential for fully
biodegradable polymer materials including the high carbon footprint of food packaging application.
However, the greatest limitation of the laccase study into polymer matrices is the loss of their activity
with temperature. One of the challenge is to obtain a thermoresistant laccases to extend their uses to
new applications in biomaterials area. The results presented, here, is the cooperative effort between
microbiologists and polymerists for producing a new processable and fully biodegradable material
based on poly(ε-caprolactone) and Laccase. For this purpose, a new thermoresistant laccase
extracted from coriolopsis gallica fungi has been worked out and successfully melt-blended into a
commercial biodegradable polymer. The enzymatic activity of the final product has been checked as
well as mechanical, thermal and oxygen barrier properties for smart food packaging application.
Fig. 1: Illustration of fully biodegradable material processing based on poly(e-caprolactone)

and fungal laccase
[1] W. Du, C. Sun, Z. Yao, J. Wang, B. Wang, W. Xie, Y. Zhang, D. Duan, X. Liu. Biocatal.
Biotransformation. 2018, 1–8.
[2].A.M. Mayer, R.C.Staples, Phytochemistry. 2002, 60, 551–565 (2002).
[3].C.M. Rivera-Hoyos,. E. D.Morales-Álvarez, R.A Poutou-Piñales, A.M. Pedroza-Rodríguez, R.
RodrÍguez-Vázquez, J.M. Delgado-Boada, Fungal Biol. Rev. 2013, 27, 67–82 .
156
BIOTECH-OR05

New aerogel-like materials: lightweight and mesoporous cellulose

xerogels

1 1
Lucile DRUEL, Tatiana BUDTOVA *,

1
Center for Materials Forming - CEMEF, MINES ParisTech, PSL Research University, UMR CNRS
7635 1, 06904 Sophia Antipolis, France

Keywords: Cellulose, Xerogels, Mesoporous, Low density
Cellulose is a versatile raw material that can be used and shaped in multiple ways depending
on the targeted applications. Recently, cellulose was used to produce a new generation of porous
materials: the aerogels. In the past decades, these cellulose-based, and more widely, bio-based
aerogels, were extensively studied and showed high porosity (> 90 %), high specific surface area (200
2 -1 -3
– 500 m .g ) and low density (around 0.1 g.cm ). Up to now, these outstanding properties were
reached thanks to drying with supercritical CO2. During this drying, the capillary pressure that would
lead to the collapse of the gel pore walls is theoretically zero, and the structure is kept intact. Despite
the remarkable aerogels’ properties, this drying is time consuming, it uses a lot of CO2 and it is rather
expensive.
In this study, we have demonstrated that, by using selected preparation parameters, we can obviate
the CO2 supercritical drying and prepare highly porous, lightweight cellulose “xerogels” with high
specific surface area.
Cellulose xerogels were prepared from microcrystalline cellulose via dissolution-solvent
exchange and vacuum drying. The influence of cellulose solvent, additives and their concentration,
solution gelation or not and the type of non-solvent was studied and correlated with xerogels’
-3
properties. The xerogels’ density varied from 0.14 to 1.12 g.cm , their specific surface area was
2 -1
comparable with that of aerogels: up to 300 m .g . The xerogels’ properties were compared to those
of their aerogels counterparts’ and the use of supercritical CO2 for the drying was proven not to be
necessary to obtain cellulose aerogel-like materials.
Acknowledgements: This project has received funding from the European Union´s Horizon 2020
research and innovation program under grant agreement No 685648.

157
BIOTECH-OR08

Freeze casting biopolymers for 3D cell culture systems

Francisco M. FERNANDES, Corentin ESCHENBRENNER, Sarah CHRISTOPH, Clément RIEU, Clio
1
PARISI, Léa TRICHET, Thibaud CORADIN

Laboratoire Chimie de la Matière Condensée de Paris, Sorbonne Université, Paris, France
Keywords: Freeze-casting, Macroporous materials, Colonization, Encapsulation, 3D culture
Macroporous materials are omnipresent in everyday life. They range from natural examples such as
trabecular bone, balsa wood or cork [1] to man-made materials used in antifrost surfaces [2] or water
harvesting devices [3]. Several processing strategies are available to elaborate such porous
structures, however few are as straightforward as freeze-casting, a technique based on oriented ice
templating that has gained considerable momentum during the last decade [4]. Freeze-casting relies
on the use of ice crystal growth to create porosity. The method presents the advantage of being easy
to implement, cost effective and applicable to a wide range of materials. As the technique relies on the
use of low temperatures it can be particularly relevant in the processing of materials prone to thermal
denaturation such as biopolymers [5].
Here, we report our recent results in the development of new 3D cell culture systems based on freeze
casting of biopolymer solutions. We show how a wide variety of cell types (yeast, bacteria, fibroblasts
and myoblasts) can be successfully hosted in self-supported macroporous materials obtained by
freeze casting. We explore different biopolymer compositions (collagen, alginate, pectin and silk
fibroin) to produce oriented porous scaffolds that promote cell colonization and migration. Moreover,
we report how the freeze casting technique can be modulated to induce the supramolecular assembly
2+
of type I collagen [6] or the Ca crosslinking of alginate [7] without the drying step, opening an exciting
pathway to the elaboration of cell-laden oriented macroporous hydrogels. Finally, the ability of the
freeze casting technique to promote the encapsulation of living cells will be discussed as an
alternative approach for the development of cellularized materials [8].
Fig. 1: Freeze casting (A) allows to structure biopolymer-based macroporous materials (B)
applicable as 3D cell culture systems [6]. In figure C myoblasts colonize a fibrillary collagen
scaffold.
[1]. L.J. Gibson, M.F. Ashby, B.A. Harley, 2010, Cellular Materials in Nature and Medicine, Cambridge
University, Cambridge, UK.
[2]. P. Kim, et al., ACS Nano. 2012, 6, 6569–6577.
[3]. H. Yang, et al., Adv. Mater. 2013, 25 1150–1154.
[4]. S. Deville, et al., Science 2006, 311, 515–518.
[5]. S. Christoph et al., Chem. Eng. J. 2018 (accepted).
[6]. C. Rieu et al. (submitted)
[7]. C. Eschenbrenner et al. (in preparation)
[8]. S. Christoph et al., Macromol Biosci. 2016, 16, 182-187.
158
BIOTECH-OR09

Absorbable and bio-inspired materials dedicated to soft-tissue
reconstruction
1,2 1 2 2 2
Louis Gangolphe , Fréderic Bossard* , Benjamin Nottelet* , Audrey Bethry and Xavier Garric
* [email protected] & [email protected]
1
Univ. Grenoble Alpes, CNRS, Grenoble INP*, LRP, 38000 Grenoble, France * Institute of Engineering
Univ. Grenoble Alpes
2
Department of Artificials Biopolymers, Max Mousseron Institute of Biomolecules (IBMM), UMR CNRS
5247, University of Montpellier, France
Keywords: Biodegradable polymers, Nanostructured materials, Tissue, Functional polymeric materials
Synthetic materials commonly used in soft-tissue engineering have low deformability and are
generally not bioresorbable. Beyond those intrinsic properties, their structuration plays a key role. The
development of efficient bio-inspired scaffolds requires the control of three-dimensional structures
having interconnected pores to promote host-tissue reconstruction [1]. In this work, we evaluate the
impact of various patterns for the electrospinning of architected degradable scaffolds and the
promotion of cellular growth.
In order to reach these specifications, different biodegradable well-defined triblock copolymers

(PLA-PEG-PLA, PLA-Pluronic®F127-PLA) were synthesized via ring-opening polymerization [2].
Polymer solutions were electrospun onto innovative micro-structured collectors whose unit meshes
(square, rectangular, honeycomb) could easily be changed. Beside the modulation of architecture and
mechanical properties (Figure 1-a), this also provides a very good control over pore size of our
scaffolds.
Figure 1: (a) Mechanical properties of architected scaffolds based on PLA-PEG-PLA

biodegradable triblock copolymer (b) L929 cell proliferation on architected scaffolds based on
PCL (preliminary study)
To ensure in vitro compatibility evaluation of our scaffolds, primary cells such as L929 or NHDF
fibroblasts have been used. A preliminary in vitro study with L929 fibroblasts was conducted on
different nano-structured scaffolds based on PCL. It showed that the architecture may influence
cellular growth (Figure 1-b).
Thus, electrospinning combining with micro-structured collectors and biodegradable polymers is

a promising way to develop artificial biomimetic implants fitting with specific host tissues for soft-tissue
reconstruction. A further study on the in-situ photo-crosslinked fiber via functionalized polymers will be
investigated to increase intrinsic scaffolds properties.
[1]. T. Jiang, E. J. Carbone, K. W.-H. Lo, and C. T. Laurencin, Prog. Polym. Sci. 2015, 46,1–24
[2]. A. Leroy et al., Biomater. Sci. 2015, 3, 4, 617–626
159
BIOTECH-OR10

Valorization of ferulic acid from wheat bran to obtain bio-based

polymers for packaging applications

1 1 1 1 1
Claudio GIOIA*, Laura SISTI, Paola MARCHESE, Annamaria CELLI, Maura FERRI, Annalisa
2 1
TASSONI, Giulio ZANAROLI.

1
Department of Civil, Chemical, Environmental, and Materials Engineering, University of Bologna,
Italy;
2
Department of Biological, Geological, and Environmental Sciences, University of Bologna, Italy

Keywords: Ferulic acid, biobased polymer, antioxidant additives.
Every year, in Europe, 90 million tons of food and 700 million tons of crops are wasted. From the point
of view of a circular economy, such gigantic amount of undesired sub-products represents a
completely unexploited opportunity for an industrial point of view, as well as a remarkable academic
challenge. Disposable leftovers from cultivations such as tomato, potato, olives and cereals have the
potential to be the sources of substances and molecules which could be employed for high value
materials or chemicals. [1] In particular, 90-150 Mt of wheat bran are produced globally every year.
Currently, it is mainly used as food additive and feed supplement, however, there is great interest
toward innovative strategies for valorizing this residue through its transformation into added-value
biomolecules. In particular, ferulic acid represents the most abundant phenolic acid in bran (0.2-15
g/Kg). The conjugated phenolic structure of ferulic acid is responsible for peculiar properties such as
antioxidant and antibacterial activity. If properly introduced into a polymeric backbone, its aromatic
character could confer rigidity to the macromolecular structure for the production of industrially
relevant thermoplastic materials.
Here we will report our current advances in the recovery of ferulic acid from industrial bran.
Furthermore, it will be chemically modified and polymerized, by means of sustainable procedures, for
the synthesis of unsaturated and semi-aromatic polyesters suitable for packaging applications.
Fig. 1: Valorization of bran sub-product to produce value added additives and polymeric
materials
[1]. The Agrimax project has received funding from the Bio Based Industries Joint Undertaking under
the European Union’s Horizon 2020 research and innovation programme under grant agreement
No. 720719.
160
BIOTECH-OR11

Tunable Thermosetting Epoxies Based on Fractionated and Well

Characterized Lignins

1 2 2 2
Claudio Gioia*, Giada Lo Re, Martin Lawoko*, Lars Berglund.

1
Department of Civil, Chemical, Environmental, and Materials Engineering, University of Bologna,
Bologna, Italy
2
Wallenberg Wood Science Center, WWSC, Department of Fiber and Polymer Technology, KTH
Royal Institute of Technology, Stockholm, Sweden

Keywords: Industrial lignin refining, characterized fractions, lignin polymer, structure-properties
relationship.
Technical lignin currently presents a huge opportunity for material applications. In particular, the Kraft
process is predominant with a production of about 70 Mton/year of lignin. Such incredibly abundant
source of natural aromatic structures is still poorly exploited in material science due to its variability of
structures, chemical composition and polydispersity. Here we report the synthesis of thermosetting
resins from low molar mass Kraft lignin fractions of high functionality, refined by solvent extraction.
Such fractions were fully characterized by 31P NMR, 2D-HSQC NMR, SEC, and DSC in order to
obtain a detailed description of the structures. Reactive oxirane moieties were introduced on the lignin
1
backbone under mild reaction conditions and quantified by simple H NMR analysis. The modified
fractions were chemically cross-linked with a flexible polyether diamine (Mn ≈ 2000), in order to obtain
epoxy thermosets. Epoxies from different lignin fractions, studied by DSC, DMA, tensile tests, and
SEM, demonstrated substantial differences in terms of thermo-mechanical properties. For the first
time, strong relationships between lignin structures and epoxy properties could be demonstrated. [1]
The suggested approach provides unprecedented possibilities to tune network structure and
properties of thermosets based on real lignin fractions, rather than model compounds.
Fig. 1: General approach toward refining and modification of lignin for the synthesis of tunable
thermosetting materials
[1]. C. Gioia, G. Lo Re, M. Lawoko, L. Berglund, J. Am. Chem. Soc. 2018, 140(11), 4054-4061.
161
BIOTECH-OR13

Putting Waste to Work through a Bio-inspired Approach

1 1 1
Camille BIHANIC, Andrii STANOVYCH, Claude GRISON *

1
Laboratoire de Chimie Bio-inspirée et Innovations Ecologiques UMR 5021 CNRS - Université de
Montpellier, Grabels, France

Keywords: Ecological catalysis, bio-inspired approach, green oxidation, circular economy
Despite the enforcement of European regulations, the dissemination of metal trace elements within
environment is continuing. At the same time, the depletion of mineral resources is alarming.
We propose the implementation of breakthrough innovation and cross-disciplinary research in bio-
inspired chemistry to overcome this paradox. The approach is based on an original concept: that of
turning polluted waste into new, sustainable catalysts through polymetallic catalysis.
The communication will be focused on a representative case using wastes from industrial contexts:
+
polluted effluents from pyrite quarries (Fe/Mn/H ). The acidity of the effluent allowed solubilization of
efficient cations: Mn(II), Fe(II)/Fe(III), Ca(II), Mg(II). This polymetallic composition is an opportunity to
promote innovative oxidative catalysis. The development of a catalytic methodology for soft oxidation
by Mn(IV) is motivating.
It is clear that an efficient Eco-Mn-Ca catalyst can be generated from the pyrite quarries. The
preparation of this catalyst is achieved by the addition of a co-oxidant (H2O2) onto the effluent at
controlled pH, to generate the new oxidative catalytic system. The catalytic activity is based on a
synergistic effect between Mn and Ca, which is the consequence of a cooperative effect between
these two elements for oxidation. Eco-Ca-Mn is a dual illustration of the current developments in
chemistry based on bimetallic catalysis and biomimetic catalysis [1].
The oxidation of alcohols into carbonyl compounds, the epoxidation of alkenes, the oxidative
cleavage of diols will be described. The catalytic activity of Eco-Mn-Ca clusters, which derived from
effluents of pyrite is better than activated MnO2 [2].
In a context of exponentially growing problems of pollution and waste, the design of eco-friendly
processes for transforming contaminated wastes into new catalysts and reagents is a powerful
opportunity. We think that it would be relevant to turn the current treatment of effluents into bio-inspired
promoters of oxidations.
This approach presents a general aspect and can be applied to other industrial effluents.
[1]. Hooley R.J. Nature Chemistry, 2016, 202-204

[2]. Stanovych A., Carrasco D., Grison C., 2017, PCT/FR2017/1752822
162
BIOTECH-OR14

Sustainable polysaccharide-derived mesoporous carbons
(Starbon®) as additives for negative electrodes of lithium-ion
batteries

1,* 1 2 1
Sanghoon KIM, Angel Manuel ESCAMILLA-PEREZ, Mario DE BRUYN, Johan G. ALAUZUN,
1,3 1 2 1,3
Nicolas LOUVAIN, Nicolas BRUN, DUNCAN J. MACQUARRIE, Lorenzo STIEVANO, Bruno
1 1,3 1
BOURY, Laure MONCONDUIT, P. Hubert MUTIN

1
Institut Charles Gerhardt Montpellier, Université de Montpellier, CNRS, Montpellier, France
2
Green Chemistry Centre of Excellence, University of York, York, North Yorkshire, YO10 5DD, UK
3
Réseau sur le Stockage Electrochimique de l'Energie (RS2E), CNRS FR3459, Amiens, France

Keywords: polysaccharide, mesoporous carbon, Li ion batteries, negative electrodes,
For the first time, we have shown that polysaccharide-derived mesoporous carbonaceous materials
(Starbon®)[1,2] are used as carbon additives for negative electrodes of Li-ion batteries. A set of
3 -1
samples with pore volumes ranging from 0 to 0.91 cm g was prepared to evidence the role of
porosity in such sustainable carbon additives. Both pore volume and pore diameter have been found
crucial parameters for improving the electrodes performance e.g. reversible capacity. Mesoporous
carbons with large pore volumes and pore diameters provide efficient pathways for both lithium ions
and electrons as proven by the improved electrochemical performances of Li4Ti5O12 (LTO) and TiO2
based electrodes compared to conventional carbon additives.[3] The mesopores provide easy access
for the electrolyte to the active material surface, and the fibrous morphology favors the connection of
active materials particles. These results suggest that polysaccharide-derived mesoporous
carbonaceous materials are promising, sustainable carbon additives for Li-ion batteries.

Fig. 1. Starbon® can provide efficient pathways for both lithium ions and electrons

[1]. V. Budarin, J. H. Clack, J. J. E. Hardy, R. Luque, K. Milkowski, S. J. Tavener, A. J. Wilson,

Angew. Chem. Int, Ed. 2006, 45, 3782-3786.
[2]. R. J. White, C. Antonio, V. L. Budarin, E. Bergström, J. Thomas-Oates, J. H. Clack, Adv. Funct.
Mater., 2010, 20, 1834-1841.
[3]. S. Kim, A. M. Escamilla-Pérez,M. De bruyn, J. G. Alauzun, N. Louvain, N. Brun, D. J. Macquarrie,
L. Stievano, B. Boury, L. Monconduit, P. H. Mutin, J. Mater. Chem. A, 2017, 5, 24380-24378.
163
BIOTECH-OR16

All-Cellulose Composites via Short-Fiber Distribution Approach

1 1,2
Oona KORHONEN, Tatiana BUDTOVA*

1
Aalto University, Espoo, Finland;
2
Mines ParisTech CEMEF, Sophia Antipolis, France

Keywords: NaOH, biocomposite, green processing
Increasing environmental awareness drives the need for more sustainable materials, which can be
produced from renewable resources via green processing methods and recycled at the end of their
life-cycle. All-cellulose composites (ACC) [1] are self-reinforcing and biodegradable biocomposites,
which originate from renewable raw materials. Since both matrix and reinforcement are made of
cellulose, ACCs have excellent interfacial adhesion and easier recyclability compared to conventional
polymer composites reinforced with natural fibers. ACCs can be produced by dispersing the
reinforcing fibers in cellulose solution followed by coagulation, washing and drying. This approach
mimics the conventional processing of short fiber reinforced polymer composites and is thus an
interesting option for producing strong biodegradable materials.
In this work, we show the production of all-cellulose composites from commercial pulps via short-fiber
dispersion method utilizing NaOH-water as a cellulose solvent. NaOH is a low-cost chemical with
established recycling procedure and it can be considered as “green” solvent. Dissolving pulp was used
as a matrix and softwood kraft fibers as reinforcement. Tensile properties of the all-cellulose
composites were investigated and correlated with the reinforcing fiber content, composite density and
morphology.
[1]. T. Nishino, I. Matsuda, K. Hirao, Macromolecules 2004 37, 7683-7687.
Acknowledgements:
The financial support from Business Finland (former Finnish Funding Agency for Innovation), Stora
Enso Oyj and UPM-Kymmene Oyj is gratefully acknowledged. Additionally, authors wish to thank to
Separation Research Oy Ab and Fibertus Oy for collaboration.
164
BIOTECH-OR17

Renewable alkyds based on citraconic anhydride Diels Alder
adducts

Aad Lansbergen, Cor Koning*, Reinier Smabers, Paul Buijsen, Alwin Papegaaij

DSM Coating Resins, Ceintuurbaan 5, 8022 AW Zwolle, the Netherlands

Keywords: renewable; Diels Alder; citraconic anhydride; alkyds; paint properties
In this paper we will discuss (partially) renewable building blocks for alkyd resins that are based on
certain specific citraconic anhydride Diels Alder adducts. Usually alkyd resins are produced from fossil
based rigid aromatic or cycloaliphatic dicarboxylic acid or anhydride, such as phthalic anhydride or
hexahydrophthalic anhydride, a polyol such as fossil based trimethylolpropane or pentaerythritol, and
one or more bio-based fatty acids (these alkyd resins are mentioned in this work as ‘fossil-based alkyd
resins’). The use of one or more bio-based fatty acids in the manufacturing of a typical fossil-based
alkyd resin, is responsible for attributing a bio-based character of up to 35-40 wt % to such typical
fossil-based alkyd resins. One of the problems for manufacturing 80+ wt % renewable alkyd resins is
the lack of supply on an industrial scale of biorenewable rigid aromatic or cycloaliphatic dicarboxylic
acids and dicarboxylic acid anhydrides that may be used as substitutes for the typically used phthalic
anhydride, isophthalic acid or tetrahydro- or hexahydro-phthalic anhydride. Therefore, we investigated
(partially) renewable rigid dicarboxylic acids in order to enable the development of 80+ wt% renewable
alkyd resins. The raw materials of choice were certain specific citraconic anhydride Diels Alder
adducts as shown in Figure 1. These adducts were prepared from citraconic anhydride (which can be
prepared from renewable itaconic acid) and, either i) a conjugated diene e.g. isoprene (which can be
prepared from biomass) [Figure 1, adduct (a)], or ii) biorenewable conjugated diene functional
terpenes e.g. myrcene, phellandrene, a-terpinene [Figure 1, adducts (b)-(d)]. Given the functionality of
these adducts, they appeared to be good candidates in replacing phthalic anhydride in alkyd
syntheses.
(a) (b) (c) (d)

Fig. 1: Citraconic anhydride Diels Alder adducts of
Isoprene (a), Myrcene (b), α-Phellandrene (c) and α-Terpinene (d)
Novel biorenewable alkyd resins were prepared from these specific citraconic anhydride Diels Alder
adducts, and were compared with fossil-based alkyd resins containing phthalic anhydride. The results
of the paint application tests of the alkyd resins prepared showed that the replacement of the fossil-
based phthalic anhydride by the above mentioned citraconic anhydride Diels Alder adducts, can result
in alkyds with enhanced bio-based content that in addition exhibited better hardness development and
decreased yellowing. This work presents an example of a possible improvement of the performance of
alkyd resins -as to the properties mentioned above- with a simultaneous enhancement of the bio-
based content (above 80 wt%); this was the result of the replacement of phthalic anhydride by certain
specific citraconic anhydride Diels Alder adducts as shown herein.
[1]. Hendriks J. W. M., Koning, C. E., Lansbergen A. J. H., Papegaaij A., WO 2015193493 A1.
165
BIOTECH-OR18

From novel structuration to functional composites of bacterial

cellulose

Soledad Roig, Irene Anton, Anna Roig, Anna Laromaine*

Institut de Ciència de Materials de Barcelona, ICMAB-CSIC. Campus UAB. 08193 Bellaterra,
Barcelona - Spain.

Keywords: bacterial cellulose, biopolymer, biomedical, composites
Looking towards green resources to fabricate advanced functional materials, cellulose seems to be a
good candidate as it constitutes the most abundant renewable biosphere-produced polymer. Specially,
nanocellulose is in the spotlight when designing new functional (bio)nanocomposites due to its
characteristics: hydrophilicity, chirality, biodegradability, high porosity, transparency, high water
holding capacity, chemical tunability and formation of semi-crystalline morphologies.
Cellullose can be synthesized by bacteria or obtained from plants, algae and fungi. In particular,
bacterial cellulose (BC) does not contain lignin and hemicelluloses, potentials sources of toxicity
present in plant cellulose. It also exhibits a higher degree of polymerization (DP 2000-8000) and better
crystallinity (60%-90%). It presents a high elastic modulus (79GPa measured in a single fiber by
AFM) and high tensile strength (200-300MPa). The highly porous matrix created by the nano-fiber
gives to the material its large water holding capacity. Moreover, it offers the possibility to impact on its
micro(nano)structuration and shape during its production.
Due to its properties, BC has an enormous potential in sectors as energy, health and catalysis
although its investigations have steadily increased.
In this presentation I will introduce how we can obtain novel bacterial cellulose nanocomposites with
different types of nanoparticles for biomedical applications. The possibility to control the formation of
the BC and the modification after BC synthesis will be illustrated.
166
BIOTECH-OR19

Molecularly Imprinted Polymer Nanoparticles as Synthetic Antibody

Mimics for Cell Targeting and Imaging

1 1 1
Paulina Ximena MEDINA-RANGEL, Bernadette TSE SUM BUI, Karsten HAUPT*,

1
Sorbonne Universités, Université de Technologie de Compiègne, CNRS Enzyme and Cell
Engineering Laboratory, Rue Roger Couttolenc, Compiègne Cedex, France

Keywords: molecularly imprinted polymers, solid-phase synthesis, cell staining, hyaluronan, growth
factor receptor protein, click chemistry.
Advanced affinity tools for cell imaging are of particular interest as they can detect, localize and
quantify molecular targets. Aberrant glycosylation sites and deregulated expression of growth factor
receptors are promising biomarkers of many human diseases, most notably cancer. However,
targeting these biomarkers is often challenging due to a lack of receptor molecules. Molecularly
imprinted polymers (MIPS) are tailor-made synthetic receptors (antibody mimics), able to specifically
recognize target molecules. They are synthesized by co-polymerizing functional and cross-linking
monomers in the presence of a molecular template, resulting in the formation of binding sites with
affinities and specificities comparable to those of natural antibodies [1]. Herein we demonstrate
biotargeting and bioimaging with fluorescently labeled MIPs on two different cancer biomarkers:
hyaluronan and a growth factor receptor protein. MIPs were synthesized using a solid-phase synthesis
approach in which an epitope of the biomarkers was immobilized on glass beads (as solid support) via
click chemistry. This configuration allows an oriented immobilization of the template upon which
thermo-responsive MIP nanoparticles were synthesized. The binding sites of the resulting MIPs all
have the same orientation, thus MIPs synthesized by the solid-phase approach can be considered
analogous to monoclonal antibodies [2-3]. Hyaluronan imaging was achieved by applying rhodamine-
doped MIPs specific for glucuronic acid (an epitope of hyaluronan) on fixed human keratinocytes [4].
Hyaluronan is composed of alternating units of D-glucuronic acid (GlcA) and N-acetyl-D-glucosamine.
Thus, azide functionalized-glucuronic acid was immobilized on glass beads bearing alkyne groups.
MIP-GlcA (70 nm) as water-soluble particles were found to bind selectively extracellular, intracellular
and nuclear hyaluronan, as imaged by epifluorescence and confocal (Figure 1) microscopies. The
specificity of binding was verified with a non-imprinted control polymer and by comparing the staining
with a hyaluronan binding protein (HABP). For bioimaging the growth factor receptor membrane
protein, a short peptide (terminal alkyne functionalized) was selected as epitope for immobilization on
azide-modified glass beads. The MIP nanoparticles (50 nm) specifically recognized both the template
peptide and the whole protein. Cell imaging studies with fluorescent dye-doped MIPs were performed.
Fig. 1: Confocal microscope images showing extracellular, intracellular and nuclear labeling of
hyaluronan on fixed human keratinocytes by MIP-GlcA (red) (left) and HABP/fluorescent
streptavidin (green) (right), nuclear counterstaining with Hoechst (blue).
[1]. K. Haupt, A. V. Linares, M. Bompart, B. Tse Sum Bui, Top. Curr. Chem. 2012, 325, 1-28.
[2]. S. Ambrosini, S. Beyazit, K. Haupt, B. Tse Sum Bui, Chem. Commun. 2013, 49, 6746-6748.
[3]. J. Xu, P.X. Medina-Rangel, K. Haupt, B. Tse Sum Bui, Methods Enzymol. 2017, 590, 115-141.
[4]. M. Panagiotopoulou, S. Kunath, P. X. Medina-Rangel, K. Haupt, B. Tse Sum Bui, Biosens.
Bioelectron. 2017, 88, 85-93.
167
BIOTECH-OR22

Ceramic templated melanin nanostructures: a biomimetic synthesis

approach to bio-functional hybrid materials

1 1 1 2
Giuseppe Vitiello , Brigida Silvestri , Aniello Costantini , Alessandro Pezzella ,
1*
Marco D’Ischia, Giuseppina Luciani ,

1
DICMaPI- Dept. of Chemical, Materials and Production Engineering, University of Naples Federico II,
Naples, Italy;
2
Dept. of Chemistry, University of Naples Federico II, Naples, Italy;
Keywords: Melanins; Organo-inorganic Hybrids; Bioinspired Synthesis; Antimicrobial nanostructures,

Antioxidant
Organo-inorganic hybrids provide the opportunity to invent a huge set of new multifunctional materials
with a large spectrum of known and as yet unknown properties. Melanins, hydrophobic natural
pigments have been emerging as a powerful organic component for developing biologically active
materials because of their numerous biological functions, such as photo-protection, photosensitization,
free radical quenching, metal ion chelation and even intrinsic antimicrobial behavior. Furthermore, due
to their semiconductor behavior and electrical properties they hold great promise for next-generation
photovoltaics and bioelectronics. Melanins are produced in-vivo by oxidative polymerization of
phenolic or indolic compounds within melanosomes that template melanin formation. Following a
bioinspired approach, herein we propose a novel synthesis approach towards hybrid materials, that
exploits inorganic ceramic systems as catalysts and structure directing agents in melanin biopolymers
building up. In this route we disclosed TiO2 ability to drive 5,6-dihydroxyindole-2-carboxylic acid
(DHICA) polymerization via complex mediated electron transfer (LMCTC) from DHICA to the TiO2
lattice, that enables photo-activation under visible light [1]. This strategy led to eco-friendly, non-
cytotoxic, melanin-TiO2 hybrid nanostructures with unique antimicrobial activity even higher than bare
melanin under visible light and peculiar antimicrobial mechanism (Fig.1A-B) [2,3]. This synthesis
approach was successfully extended to the design of melanin-silica hybrid nanoparticles, integrating
the potent antioxidant properties of DHICA melanin into a stable, bioactive and biocompatible silica
scaffold with high antioxidant and cytoprotective effects associated with a specific subcellular
localization (Fig.1C-D) [4]. Both systems prove that melanin’s biofunctional and physical-chemical
properties can be markedly enhanced through its templated polymerization in the presence of a
ceramic phase, disclosing the manifold potentialities of this approach, that can ultimately lead to
cutting-edge functional hybrid materials featuring relevant biological properties, such as antimicrobial
activity, selective cell interaction and signaling, as well as ionic- and electronic-based charge
transport.
A B A D
C
50 nm

Fig. 1: TEM micrograph (A) and antimicrobial activity (B) of TiO2_Mel nanoparticles; SEM
micrograph (C) and antioxidant properties (D) of SiO2_Mel nanoparticles.
[1]. G. Vitiello, G. Luciani et al., Mater. Sci. Eng. C 2017, 75, 454-462.
[2]. G. Vitiello, G. Luciani et al., J. Mater. Chem. B, 2015, 3, 2808-2815.
[3]. G. Vitiello, G. Luciani et al., J. Phys Chem C, 2016, 120, 6262-6268
[4]. B. Silvestri, A. Pezzella, G. Luciani et al. ACS Appl. Mater. Interfaces 2017, 9, 37615−37622.
168
BIOTECH-OR23

Structure-Property Relationship for Fabricating Colloidal Lignin

Particles from Various Sources for Biomedical Applications
Guillaume RIVIERE, Mika SIPPONEN, Timo LESKINEN, Maija-Liisa MATTINEN, Monika

ÖSTERBERG
Bioproduct Chemistry, Department of Bioproducts and Biosystems, Aalto University, Espoo, Finland
Keywords: Lignin, Colloidal Lignin Particles, Carbohydrates, Self-assembly, Biomedical
Lignin, an underexploited byproduct from biorefineries and pulp and paper industries, has been widely
studied during the last decade for sustainable applications. However, due to its structural
heterogeneity, dark color, unpleasant odor and especially its low aqueous solubility, this main
polyphenolic component of lignocellulosic biomass is still not fully utilized [1].
Conversion into spherical and stable Colloidal Lignin Particles (CLPs) by self-assembly in anti-solvent
system has shown promise to circumvent aforementioned problems and to increase the number of
potential applications. However, development of this method has to date mainly focused on optimizing
CLP production from kraft lignin [2].
Indeed, chemical structure and composition of lignin depends on its source and on its extraction
process. These variations affect solubility of lignin in organic solvent and consequently the CLP
preparation process. Thus, the objective of this work was to elucidate the relationship between lignin
properties and solubility, and to tailor the CLP production process amenable for various lignin sources.
Lignins used in this work contained different amounts of carbohydrates and other impurities.
In an effort to produce particles from these lignins, the presence of smaller particles were detected by
Dynamic Light Scattering measurements despite visually the mixture lignin/solvent did not look at first
as a CLP dispersion but rather as a polymeric lignin solution. UV-visible measurements have been
done to explain this phenomenon. In addition, the effect of carbohydrates in lignin was studied further
by fractionation of lignin samples. Then the antioxidative properties of the CLPs were evaluated as
well as their UV-absorbance. The results obtained during this work confirm the high potential of
biorefinery lignins as a source of CLPs towards sustainable materials especially for biomedical
applications.
[1]. L. Avérous, S. Laurichesse, Prog. Polym. Sci. 2014, 39,1266.

[2]. T. Leskinen, M. Smyth, Y. Xiao, K. Lintinen, M.-L. Mattinen, M. Kostiainen, P. Oinas, M.
Österberg, Nord Pulp Pap. Res. J. 2017, 32, 586-596.
169
BIOTECH-OR24

Sequential fractionation of mango peels for anthocyanins,

polyphenols and pectin
1* 2
Lindleen R. Mugwagwa , Annie F.A. Chimphango
1,2
Department of Process Engineering, Stellenbosch University, Banghoek Rd, Stellenbosch Central,
Stellenbosch, 7599,South Africa
1
[email protected]
2
[email protected]
Keywords: Polyphenols, Pectin, Anthocyanins, Sequential extraction, Optimisation
Red coloured mangoes are the preferred cultivars for the mango processing industry as they are less
fibrous and can be transported for long distances without being damaged. This industry produces a
considerable amount of mango peels as a form of waste (20-40% of total waste). Mango peels have
attracted attention in the past decade as a potential source of polyphenols and pectin. However, the
focus has been on extraction of each product singly without considering the potential of sequential
extraction of multiple products.
This study proposed a bio-refinery set up for fractionation of mango peels to extract anthocyanins,
polyphenols and pectin from the red-coloured mango peels. Anthocyanins extraction conditions acetic
o
acid concentration (0.1-2%), ethanol concentration (50-80%), temperature 25 C and time (60-150 min)
were optimised taking into consideration the properties of pectin (yield, uronic acid content) and
polyphenols (yield, antioxidant activity) in the residue. The residue recovered at optimum conditions
were used as a feedstock for extraction of polyphenols (ethanol concentration (65-85%) time (20-
o o
80mins) temperature (70 C)) prior to pectin extraction (0.25% ammonium oxalate, 1hour, 85 C). The
influence of each extraction step on the properties of the consequent products was investigated.
Optimisation of the sequential extraction was carried out and the optimum conditions for anthocyanins
o
were ethanol concentration 80%, acetic acid concentration 2%, temperature 25 C and time 1hour, and
o
for polyphenols were ethanol concentration 65% time 1hour and temperature 70 C. The sequential
extraction realised an increase in pectin uronic acid content by 35%, 1.6% increase in pectin yield, a
12% reduction in polyphenol yield, a 1% decrease in polyphenol antioxidant activity when compared to
a single stage extraction of each product. The sequential process is a step towards multiple product
bio refinery of mango peel waste for valuable by-products recovery and in the process providing an
alternative disposal method for the waste.
170
BIOTECH-OR25

The Correlation between Cell Adhesion Force Activation
on Nano/Micro-Topographical PLLA Surfaces and
Temporal Dependence of Cell Morphology

1
Tamaki Naganuma *

1
National Institute for Materials Science, Ibaraki, Japan

Keywords: nano-roughness, micro-patterns, cell adhesion and single cell force spectroscopy
Interactions between adherent cells and extracellular matrix / scaffold surface features play a crucial
role in the inducement of signal transduction related to physiological functions. Topographical design
of scaffold surfaces, therefore, has the potential to promote physiological functions such as cell
proliferation and differentiation. This study attempts to quantitatively evaluate cell–material interaction
to identify how temporal dependence of cell morphology impacts cell adhesion force activation on
nano / micro-ordered topographical surfaces. Micro-dot / line-patterned poly-lactic acid (PLLA)
substrates and nano-rough substrates (nanoparticle-dispersed PLLA matrix nanocomposites) were
prepared to assay cell detachment force by single cell force spectroscopy. This study presents
findings regarding the relationship between cell adhesion force activation on nano / micro-
topographical surfaces and temporal dependence of cell morphology [1]. These findings could be
useful to the development of scaffold surface design in tissue engineering.
[1] T. Naganuma, Nanoscale. 2017, 35 [9], 13171-13186.
171
BIOTECH-OR26

Biopolymer based smart wound dressing for surgical application

1 2 2,3 1
G. Conzatti , J. Torrisani , N. Carrère , A. Tourrette
1
CIRIMAT, Université de Toulouse, CNRS, Toulouse, France
2
CRCT, UMR1037 INSERM/Université Toulouse III-Paul Sabatier, Toulouse, France
3
Gastrointestinal Surgery department, Purpan Hospital - CHU de Toulouse, Toulouse, France
[email protected]
Nowadays, the development of new biomaterials with controlled properties on the surface has a strong
impact in the field of Health. The surface of biomaterials takes an active part in cell adhesion and
proliferation. All these phenomena are strongly related to surface / cell interactions. In the field of
wound healing materials, porous scaffold hydrogels, which presents advanced surface properties such
as a controlled bioadhesion are promising biomaterials. The aim of this study is to design and validate
a biomaterial constituted of a biopolymer based matrix that will ensure the dual function of absorbent
and antibacterial agent reservoir, on which a surface modification should allow controlled bioadhesive
properties. Previous studies showed that alginate and chitosan, combined as polyelectrolyte
complexes (PECs) are good candidates to elaborate such a matrix [1-2], whereas poly(N-
isopropylacrylamide), which presents a Lower Critical Solution Temperature (LCST) around 32°C, is
known to confer surfaces thermos-regulated bioadhesion [3]. Hence, this presentation is devoted to
the optimization of PECS matrix and its surface functionalization as well as the study of the surface
thermosensitivity toward cells (in vitro) and organs (ex vivo).Thanks to this study the optimal
alginate/chitosan ratio and the choice of the technic of homogenization have been determined to
prepare PEC films with suitable swelling capacity and stability. Results show also the importance of
the choice of the drying method, which control films physicochemical characteristics (figure 1). The
surface functionalization has been confirmed by X-Ray Photoelectron spectroscopy (XPS) analysis.
No in vitro cytotoxicity was observed for the developed biomaterials. The materials also showed
thermosensitive bioadhesive properties, with a cellular bioadhesion mainly observed above the LCST.
Figure 2 SEM images of a) and b) xerogels, c) and d) lyophilized and e) and f) SCC samples.
Image magnifications are adapted to the different kind of structures and architecture scales
obtained.
REFERENCES
[1]. M.Castel-Molieres, et al. J. Med. Biol. Eng. In press, 2017.
[2]. Conzatti, G. et al. Carbohydr. Polym. 2017, 172, 142–151.
[3]. Conzatti, G. et al. Colloids Surfaces B Biointerfaces 2017, 151, 143–155.
ACKNOWLEDGMENTS
Authors would like to thank the French National Research Agency for its financial support (ANR-14-
CE17-0002-01, FP- BioPrev project).
172
BIOTECH-OR27

Antibiofouling surface modifications using bioactive molecules

1 1 2 1 1
S. BKHAÏT* , B. DESCHAMPS , E. NEUHAUSER , J.-F. LAHITTE , C. CAUSSERAND , C.
1
COETSIER
1
Laboratoire de Génie Chimique, Université de Toulouse, CNRS, INPT, UPS, Toulouse, France
2
Laboratoire de Biotechnologies Agroalimentaire et Environnementale, UPS, Auch, France

Keywords: biofouling, membrane surface modifications, quorum sensing inhibitors
Fouling is the main problem encountered during membrane filtration. It causes a permeability
loss, which means a reduction of the productivity. Chemical cleaning is generally used to restore
performances of the membrane but other approaches are required to limit water contamination. The
development of new biomimetic membranes for water treatment is promising to limit both the fouling
and use of cleaning agent. This work focuses especially on biofouling caused by microorganisms.
Bacteria used a cell-to-cell communication called quorum sensing to form biofilms. This process can
be disrupted by using quorum sensing inhibitors found in the nature in order to prevent biofilm
formation. Surface modification via bioinspired approaches combining a biological activity and the
modification of physico-chemical properties of the material is recommended to limit biofilm
development. In this frame, membrane surface modifications were performed using two approaches,
adsorption of Vanillin and grafting of vanillin methacrylate (VMA) as bioactive molecules that would
1-2
also affect the membrane surface moiety (hydrophilicity) . The aim of this study is to modify
commercial polyethersulfone (PES) membrane typically used for water treatment by these two
approaches. Physico-chemical and antibiofouling properties of the new membrane have been
characterized by adhesion test and quantification of biological products.
®
Vanillin was adsorbed on PES membrane (3M, MicroPES 1F PH) by soaking in 3 g/L vanillin
solution for 3 h. Vanillin methacrylate (VMA) was covalently bonded onto the PES membrane by UV-
grafting. Specific bands of vanillin and grafted VMA have been determined by FTIR-ATR (Nexus
Thermo Nicolet). Biofilms have been developed on membrane surface placed on agar plate for growth
inhibition assays and biofilm development using Pseudomonas aeruginosa (CIP 103467).
Surface characterization using FTIR mapping highlights differences between the modification
approaches. An effective adsorption of vanillin and grafting of VMA at the membrane surface is
observed on FTIR mapping, showing a good homogeneity of the deposit layer. However, the efficiency
in terms of adhesion and biofilm development inhibition is limited due to the instability of the molecule
at the membrane surface. At the contrary, the grafting approach leads to the covalent binding of the
VMA. Impact of the membrane surface modification is observed on the bacterial growth (figure 1). The
effect on the biofilm development has to be further investigated and quantified, especially considering
the grafting approach.

Figure 3: Number of CFU observed on virgin and modified membranes by adsorption of vanillin
(n=2) after 24h bacterial growth
[1] Kumar, S. R.; Arthanareeswaran, G.; Lukka Thuyavan, Y.; Ismail, A. F., Journal of the Taiwan
Institute of Chemical Engineers 2017, 72, 200-212.
[2] Si, X.; Quan, X., International Biodeterioration & Biodegradation 2017, 116, 211-218.
Acknowledgement - The authors would like to thank the ANR for funding of the project BIOCOM <
ANR-17-CE04-0001
173
BIOTECH-OR28

Freezing living cells: understanding the impact of the physical cell

environment on survival

Kankan Qin, Thibaud Coradin and Francisco M. Fernandes

Laboratoire Chimie de la Matière Condensée de Paris, Sorbonne Université, Paris, France

Keywords: Cryopreservation, Ice-front velocity, Freeze casting, Biopolymers
1
Cryopreservation is the use of very low temperatures to preserve structurally intact living cells . This
2
procedure could be used not only in cell storage and cell transfusion , but also in preparing cell–laden
3
scaffolds . In literature, two factors are commonly described as decisive to ensure cell viability during
4 5
cryopreservation process: the use of cryoprotection agents and freezing rate . Control over the
freezing rate could prevent the formation of intracellular ice-crystals, which is a critical condition for cell
6
survival . Freeze casting, an ice-templating method developed for porous materials processing, can
7 8
achieve a well-controlled freezing rate . In our group, Christoph et al. have successfully applied this
technology to build three-dimensional alginate materials with encapsulated cryopreserved cells
(Saccharomyces cerevisiae) while maintaining its metabolic activity.
However, recent results on the same cell model have shown that constant freezing rate translates into
different ice-front velocities. Here, we investigate the impact of ice-front velocity on cell survival. We
freeze-cast a mixture of yeast cells and alginate solution at three freezing rates (-1/10/100 ℃/min)
followed by freeze-drying in order to get cell-laden materials with precisely defined macroporous
structures. The cell viability values were analyzed in light of the local ice-front velocity during the
freezing events. Results indicated that for a constant freezing rate, different ice-front velocities were
9
attained and that these relate to the cell viability . To fully characterize these freezing events and the
resulting macroporous morphology we performed extensive DSC and SEM analysis on samples
obtained under different conditions. We could also show the impact of the drying process on final cell
viability maybe due to stresses caused by the decrease of thickness of pore-walls after freeze-drying.
In conclusion, during cryopreservation process with freeze-casting and subsequent freeze-drying
techniques, ice-front velocity and the drying procedure played an important role for final cell viability of
materials.
The reported results open an exciting pathway to develop pre-cellularized scaffolds for application in
biocatalysis and tissue engineering.
1. Wolkers et al., 2007. Cryopreservation and freeze-drying protocols, Vol 368. Humana press.
2. Stefanic et al., Biomaterials 2017 138-149.
3. Katsen-Globa et al., J Mater Sci Mater Med. 2014, 25, 857-871.
4. Shivakumar et al., Int J Stem Cells 2015, 8, 155-169.
5. Gurina et al., Cell Tissue Bank. 2016, 17, 303-316.
6. Mazur et al., Am J Physiol Cell Physiol. 1984, 247, C125-142.
7. Christoph et al., Chem. Eng. J. 2018 (accepted).
8. Christoph et al., Macromol Biosci. 2016, 16, 182-187.
9. Qin et al, (in preparation)

174
BIOTECH-OR29

One-Pot Fabrication and Characterization of Antioxidant

Polymers from Tea Waste Extracts
1,2 2 2 3
Ana Isabel QUILEZ, Jose Alejandro HEREDIA-GUERRERO, Lara MARINI, Andrea ARMIROTTI,
2 2 2 2
Uttam PAUL, Gianvito CAPUTO, Athanassia ATHANASSIOU, Ilker S. BAYER, .
1
DIBRIS, Università di Genova, Via Opera Pia 13, 16145, Italy
2
Smart Materials, Nanophysics, Istituto Italiano di Tecnologia, Genova, 16163 Italy
3
Drug discovery and Development, Istituto Italiano di Tecnologia, Genova, 16163 Italy
Keywords: Tea waste film, Green tea polyphenols, Antioxidant activity, Food packaging, Balsamic
vinegar waste film
In this study, we describe a facile one-pot synthesis approach to produce transparent,

antioxidant poly(vinyl alcohol) (PVA) films using tea-extract from used tea bags. The films could be
ideal for certain food packaging applications. Formic acid was used as a common solvent for
dissolving the polymer and obtaining the tea extracts. The effect of tea extract concentrations such as
5, 10, 20 and 50% (w/w) was studied in detail. Concentration dependent antiradical and antioxidant
activities was measured using standard radical scavenging methods such as 2,2-Diphenyl-1-
picrylhydrazyl (DDPH) and 2,2-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) assays. The
mechanical properties of PVA films were modified significantly due to the tea extracts inclusions. The
observed antioxidant effects were correlated to the total polyphenol content present in natural tea
products. Moreover, gas barrier properties, particularly oxygen barrier and/or scavenging effects have
been measured and compared to pristine PVA polymer. Moreover, Fourier transform infrared
attenuated total reflectance spectroscopy (FTIR-ATR) measurements indicated that polyphenols and
the PVA matrix form chemical interactions. Further work is underway in order to characterize the
individual antioxidant components within the polymer matrix using high-performance liquid
chromatography (HPLC) along with mass spectrometry (MS).
In parallel, we also produced PVA films containing industrially discarded balsamic vinegar
wastes (known for their antioxidant properties) using a water-based film forming approach and using
concentrations identical to tea. Then, we compared the physicochemical and mechanical properties of
both antioxidant films. Interestingly, it was found that balsamic vinegar waste acted like plasticizer
whereas tea extract as stiffening additive. Moreover, films from tea waste extract displayed stronger
antioxidant effect compared to balsamic vinegar waste (see Figure 1).
Fig. 1: (A) DPPH radical scavenging activity assay of PVA-tea waste film 20% and PVA-
balsamic vinegar waste film 20%. (B) Stress-strain curves of PVA-tea waste film 50% and PVA-
mic vinegar waste film 50%. (C) Inserted photo shows an example of both films.
175
BIOTECH-OR30

Betaine-based materials – preparation and their tunable properties

a a b
Jozef KOLLÁR , Jaroslav MOSNÁČEK , Peter KASÁK
a
Polymer Institute, Slovak Academy of Sciences, Bratislava 845 41, Slovakia
b
Center for Advanced Materials, Qatar University, P.O.Box 2713, Doha, Qatar
Keywords: zwitterion, self-assembled monolayer, modulation of wettability, DNA immobilization.
Zwitterionic compounds containing betaine structure are gaining remarkable interest for the
development of smart materials in biomedical applications. Self-assembled monolayer (SAM) based
on betaine derivatives provides anti-fouling properties and biocompatibility of coated materials.
This contribution describes the synthesis and application of various betaines derived from L-lipoic
acid. Some derivatives such as carboxybetaine esters with positive charge can undergo pH-induced
and controlled hydrolysis of ester moieties and formation of a neutrally charged zwitterionic structure.
Exchange of functionality induces variable properties for tunable wettability and adhesion with noble
nanoparticles. A fast change from superhydrophilic to superhydrophobic behavior of carboxybetaine
-
ester-based SAM on rough Au surface was achieved by a simple exchange of Cl to
perfluorooctanoate counterion [1]. Betaine derivatives were used also for the preparation of SAM on
the gold surface to control the interaction between DNA and gold nanoparticles via pH [2]. SAM
containing a carboxybetaine ester moiety allowed DNA immobilization with pH controlled release.
Furthermore, polymerization of selected betaines was studied in solution as well as on silicon
substrate. Modulated upper critical solution temperature (UCST) of prepared poly(disulfides) was
observed. Moreover, poly(disulfides) were introduced as a material for the immobilization and
subsequent release of DNA in a controlled manner.
Acknowledgement: J.K. and J.M. thank for financial support to APVV grant agency through grant no.
APVV-14-0891 and APVV-15-0296. This contribution was made possible by NPRP grant #6-381-1-
078 from the Qatar National Research Fund (a member of Qatar Foundation). The statements made
herein are solely the responsibility of the authors.
[1] Mosnáček J, Popelka A, Osička J, Filip J, Ilčíková M, Kollár J, Yousaf AB, Bertók T, Tkáč J,
Kasák P., Modulation of wettability, gradient and adhesion on self-assembled monolayer by counterion
exchange and pH, In Journal of Colloid and Interface Science, 512, 2018, 511-521
[2] Filip J, Popelka A, Bertók T, Holazová A, Osička J, Kollár J, Ilčíková M, Tkáč J, Kasák P, pH-
Switchable interaction of a carboxybetaine ester-based SAM with DNA and gold nanoparticles. In
Langmuir, 33, 2017, 6657-6666
176
BIOTECH-OR31


1 2 3 4
Franck CLEYMAND *, Émilie VELOT, Elmira ARAB-TEHRANY, João MANO,

1
Institut Jean Lamour UMR 7198 CNRS/Université de Lorraine, Nancy, France;
2
Ingénierie Moléculaire et Physiopathologie Articulaire (IMoPA), Biopôle de l'Université de Lorraine,
UMR 7365 CNRS/Université de Lorraine, Vandoeuvre-lès-Nancy, France
3
Laboratoire d'Ingénierie des Biomolécules, Nancy-Université, Vandoeuvre-Lès-Nancy, France,
4
Department of Chemistry, CICECO, University of Aveiro, Aveiro, Portugal

Keywords: biomembranes, nanoliposomes, lecithin, chitosan
Advances in Tissue Engineering and Regenerative Medicine (TERM) depend increasingly on the
availability of specific biomaterials that allow controlling biological systems behaviour [1]. Therefore,
many efforts have been devoted in proposing both biologically derived and synthetic materials in
contact with biological materials and new tissue engineering strategies that could enhance the
regenerative potential of the products.
In this work, chitosan membranes, were elaborated and functionalized by incorporating
nanoliposomes based on natural vegetable (soy based) and marine (salmon head) lecithin. The
properties of natural nanoliposomes/chitosan blend membranes were evaluated by multi scale
techniques such as water contact angle (WCA), water uptake ability, Fourier Transform InfraRed
spectroscopy (FT-IR) and Atomic Force Microscopy analysis (AFM). In vitro biocompatibility analysis
of chitosan before and after functionalization with nanoliposomes were performed using human
mesenchymal stem cells (hMSCs). This study provides the information about the potential of natural
nanoliposomes/chitosan blend membranes to be used as multifunctional biomaterials for supporting
cell activity, facilitating regeneration, and guiding tissue repair. Especially, cytotoxic assays showed
-1
that 1) none of the membranes induced any cytotoxic effect and ii) 1mg.mL of salmon nanoliposomes
in the chitosan has the highest potential in the development of chitosan-based biomembranes for
tissue engineering applications [2].
[1] R. Langer, D.A. Tirrell, Nature 2004, 428, 487-492.

[2] F. Cleymand, H. Zhang, G. Dostert, P. Menu, E. Arab-Tehrany, E. Velot, João F. Mano, RCS
Advances 2016, 6, 83626-83637.
177
BIOTECH-OR32

Tuning the properties of poly(lactic acid)-based biomaterials by

green blending of linear PLLA and star-shaped PDLLA

1,2 1 1
Giulia SCOPONI *, Athanassia ATHANASSIOU, José Alejandro HEREDIA-GUERRERO*,

1
Smart Materials, Istituto Italiano di Tecnologia, Genoa, Italy
2
DIBRIS, University of Genoa, Genoa, Italy

Keywords: Poly(lactic acid), Biopolymers, Green Chemistry, Star-shaped poly(lactic acid)
Nowadays, poly(lactic acid) (PLA) is one of the most extensively researched renewable thermoplastic
polyesters. It is a high-strength, high-modulus bio-based biodegradable polymer that can be produced
on large-scale by renewable resources, including potato starch and sugar from beets and sugar cane.
It is also easily processable on already existing standard manufacturing petroleum-based plastic
technologies. Therefore, it holds great potential to replace conventional non-biodegradable plastics for
disposable applications, such as food or cosmetic packaging and biomedical devices. However, many
efforts are still needed in order to achieve equivalent characteristics to petro-plastics.
In the case of PLA, an interesting strategy consists in the use of mixtures of diverse macromolecular
architectures to improve the processability and diffusivity properties, keeping its physical and chemical
properties. In particular, star-shaped polymers can affect the linear matrix in different ways: branching
implies a close proximity between polymer chains (higher density) so that the coils assume a more
compact structure, approximating a hard sphere; moreover, the high likelihood of entanglements
between polymer segments decreases the hydrodynamic size. As a result, the viscosity of star-shaped
1
polymers is typically lower than their linear counterparts . Such rheological and physical properties
make these polymers very promising tools for the releasing of active molecules and for enhancing
melt flow in injection molding process.
In this work, different blends of 3-armed star-shaped poly(d,l-lactic acid) (star-PDLLA) and linear
poly(l-lactic acid) (linear-PLLA) have been produced. Given the low solubility of PLA in non-
halogenated and green solvents, free-standing films with increasing amounts of star-PDLLA have
been obtained by blending the two components in melt by hot-pressing fabrication. Characterization
by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), water contact angle
(WCA), tensile testing, and scanning electron microscopy (SEM) techniques of the new blended
materials have showed that the good mechanical, thermal, hydrophobic properties and surface
homogeneity of the linear matrix have remained practically unchanged. On the other hand, as
expected, the melt viscosity has been shown to decrease along with increasing amounts of star-
PDLLA.
Subsequently, various model additive compounds have been incorporated in the star/linear-PLA
blends and their diffusion kinetics from films have been studied by Fourier transform infrared (FTIR)
spectroscopy, in order to tailor their releasing during time for biomedical and active packaging
purposes. Furthermore, mechanical, thermal as well as antibacterial properties of the final materials
have been characterized. Finally, the biodegradability of the obtained free-standing films in presence
of increasing amounts of star-PDLLA has been studied, revealing the effect of star-shaped atactic
poly(lactic acid) on the degradation rate, as well as the potential of these blended renewable materials
for the production of injected active packaging products.
[1]. Burke, J.; Donno, R.; D’Arcy, R.; Cartmell, S.; Tirelli, N. Biomacromolecules 2017, 18 (3), 728–
739.
178
BIOTECH-OR33

Live quantitative monitoring of mineral deposition in human stem

cells using an antibiotic molecule

1, 2 1 2 2 3
Laura MACRI-PELLIZZERI , Nigel DE MELO , Ifty AHMED , David GRANT , Brigitte SCAMMELL ,
1
Virginie SOTTILE *

1
Wolfson STEM Centre, School of Medicine, The University of Nottingham, UK
2
Advanced Materials Group, Faculty of Engineering, The University of Nottingham, UK
3
Orthopaedics and Trauma Group, School of Medicine, The University of Nottingham, UK
Keywords: Live & quantitative monitoring of stem cell mineralization.
The final stage of osteogenic differentiation is characterized by the production of mineral deposits
containing calcium cations and inorganic phosphates, which populate the extracellular matrix
surrounding the cells. Conventional histological techniques for the assessment of mineralization in
vitro, such as Von Kossa and Alizarin Red S staining, are end-point techniques requiring cell fixation.
Moreover, in both cases staining quantitation requires dye extraction which irreversibly alters the ECM
conformation and structure, therefore preventing the use of the sample for further analysis.
In this study, we used the known antibiotic molecule Tetracycline hydrochloride (TC) to develop a new
procedure for the non-destructive staining, quantitation and imaging of mineralizing bone-like nodules
in live cultures of human stem cells cultured under osteogenic conditions. Overnight administration of
TC to living cells was shown not to alter the metabolic activity or the progression of cell differentiation.
When applied to differentiating cultures, cell exposure to serial doses of TC was found to produce
quantifiable fluorescence emission specifically in osteogenic cultures. Incubation with TC enabled
fluorescence imaging of mineralised areas in live cultures and the combination with other fluorophores
using appropriate filters. These results demonstrate a new qualitative and quantitative detection
technique for the monitoring and evaluation of the differentiation process in live cells which provide an
additional real time assay for cell and tissue engineering.
Fig. 1: Quantification of fluorescence signal in MSCs cultures at day 21 after exposure to TC.
179
BIOTECH-OR34

In vitro anti-diabetic activity of Philippine Mulberry leaves (Morus

alba Linn.) extract

1 1 1 1
Josh Ramilo RAFOLS, Wayne Janzen BAUTISTA, Kristine Nicole DACLILI, Elwin Angelo HALILI,
1 1,2
Marcy Lance SE, Kathrina Lois TAACA*,

1
Far Eastern University-Diliman, Quezon City, Philippines;
2
Mapua University,Manila,Philippines;

Keywords: diabetes, mulberry, spectroscopy, glucose, phytochemical analysis
Abstract:
Diabetes is a major cause of premature illness and death worldwide. Although several medications
have already been commercialized, herbal medicines are still being used for treating diabetes. In the
Philippines, medicinal plants are still traditionally used as medication for this ailment aside from
commercial drugs. Regardless of the benefits, there are only few studies assessing on the effectivity
of these herbs. This study aims to find an organic treatment for diabetes. Specifically, this study
focused on determining the anti-diabetic effect of Mulberry leaves (Morus alba Linn.) using in vitro
analysis. The physical extraction of Mulberry leaves yielded 86.96% juice. Phytochemical analysis
revealed that the leaves contain an abundant amount of amino acids and flavonoids. The pH and the
in vitro anti-diabetic activity of the Mulberry extract were compared with Metformin, a commercially
available drug. The pH levels the Mulberry extract and Metformin were measured to be 5.8 and 7.7,
respectively. The in vitro anti-diabetic activities of the samples were assessed via α-amylase inhibition.
UV-Vis spectrum of the Mulberry extract and Metformin is shown in Fig. 1. Starch hydrolysis is
observed at 368 nm. High absorbance at this peak indicates a high amylase activity, responsible for
the conversion of starch to glucose. Metformin, the control drug, displayed no peak at 368 nm,
implying that the activity of amylase is well controlled. On the other hand, the Mulberry extract
depicted about 45% absorbance at the corresponding peak. Based from these preliminary results,
extraction of Mulberry is easy and cost-efficient. The low pH of Mulberry may have caused the
presence of amylase activity on the extract. However, further investigation will still be conducted to
evaluate other in vitro anti-diabetic activities of the extract. Yet, this study suggests Mulberry extract as
possible alternative treatment to diabetes.
Fig. 1 UV-Vis Spectrum of the Mulberry extract and Metformin
[1]. A. Abirami, G. Nagarani, P. Siddhuraju, Food Sci. and Hum. Well. 2014, 3, 16-25.
180
BIOTECH-OR35

Bio-based poly(Schiff-base) comprising bifurfural

1,2 1 1 1,2
Yuya TACHIBANA, Senri HAYASHI, Tatsuya WASANO, Ken-ichi KASUYA,

1
Division of Molecular Science, Faculty of Science and Technology, Gunma University, 1-5-1 Tenjin,
Kiryu, Gunma, 376-8515, Japan
2
Gunma University Center for Food Science and Wellness, 4-2 Aramaki, Maebashi, Gunma, 371-
8510, Japan

Keywords: Furfural, Bio-based polymer, Poly(Schiff base)
Furfural has been paid attention as an inedible bio-based chemical that is second generation
biomass. We have previously synthesized a range of bio-based chemicals as a monomer of general
purpose polymers and functional polymers, i.e. terephthalic acid [1] and oxabicyclic anhydride [2, 3, 4],
from furfural alone. On the other hands, these products are devoid of furan rings, while the chemicals
containing furan rings, such as furfural, furfuryl alcohol, 5-(hydroxymethyl)furfural, 2,5-dimethyl furan,
and 2,5-furandicarboxylic acid (FDCA) are produced industrially only from biomass and never from
fossil resources due to the high costs involved. As the furan ring is able to be produced from biomass,
the use of furan ring can endow polymers with an unique advantage derived only from biomass. We
have focused on the bifuryl group, which consists of two furan rings connected directly. Bifurfural
composing one bifuryl group and two formyl groups can be prepared from furfural.
In this study, we synthesized bifurfural from furfural, analyzed the structure of bifuryl group
analyzed by single crystal X-ray structure analysis and density functional theory (DFT) calculation
1
method, and then polymerized it with several diamines to poly(Schiff base)s.[5] H NMR, IR and
MALDI-TOF-MS spectra indicate that poly(Schiff base)s were a mixture of linear and cyclic structures.
UV-vis spectra and molecular orbital theory showed the expansion of π-conjugated poly(Schiff base)
comprising bifurfural and p-phenylenediamine. Poly(Schiff base)s comprising bifurfural and 1,3-
propanediamine, 1,4-butandiamine, 1,5-pentanediamine and 1,6-hexanediamine were moulded at 120
°C to films that were tough to bend and had good strength. These results indicate that the poly(Schiff
base) comprising bifurfural is a promising bio-based material.

Ethylene glycol 1) Pd(OAc)2, DMSO-AcOH, O
H cat. p-TsOH O H O
50 ºC, 24 h
O O O H
Toluene 2) 1M HClaq., THF
O reflux, 12 h
O r.t., 1 min
O
Bifurfural
Furfural 2-(2-furyl)-1,3-dioxolane
R = (CH2)2: PSE
Diamine O (CH2)3: PSPr
N R N (CH2)4: PSB
O
n (CH2)5: PSPe
(CH2)6: PSH
Poly(Schiff base)
p-phenylene: PSPh
Fig. 1: Schmatic illustration for the synthesis of poly(Schiff base)
[1]. Y. Tachibana, S. Kimura, K. Kasuya, Sci. Rep. 2015, 5, 8249.

[2]. Y. Tachibana, M. Yamahata, K. Kasuya, Green Chem. 2013, 15, 1318-1325.
[3]. Y. Tachibana, M. Yamahata, H. Ichihara, K. Kasuya, Polym. Degrad. Stab. 2017, 146, 121–125.
[4]. Y. Tachibana, J. Torii, K. Kasuya, M. Funabashi, M. Kunioka, RSC Adv. 2014, 4, 55723-55731.
[5]. Y. Tachibana, S. Hayashi, K. Kasuya, ACS Omega, in press.
181
BIOTECH-OR36

Bioinspired sodium alginate-tomato peel composites with enhanced
hydrodynamic properties
,1,2 3 4 5, 6
Giacomo TEDESCHI * , José Jesùs BENÍTEZ , Luca CESERACCIU , Antonio HEREDIA ,
,1 ,1
Athanassia ATHANASSIOU * , José A. HEREDIA-GUERRERO *

1 2
Smart Materials, Istituto Italiano di Tecnologia, Genoa, Italy; DIBRIS, Università di Genova, Genoa,
3 4
Italy; Instituto de Ciencia de Materiales de Sevilla (ICMSE), Seville, Spain; Materials
5
Characterization Facility, Istituto Italiano di Tecnologia, Genoa, Italy; Instituto de Hortofruticultura
Subtropical y Mediterránea (IHSM) La Mayora, Universidad de Málaga-CSIC, Malaga, Spain;
6
Departamento de Biología Molecular y Bioquímica, Universidad de Málaga, Málaga, Spain
Keywords: tomato peel monomers, tomato cutin, sodium alginate, biocomposites, plant-mimic
material, sustainable process.
Plant cuticles are the outermost membranes that cover and protect the aerial organs of plants such as
leaves, fruits, stems, and flowers, being one of the most important plant barriers [1]. Cuticles are
mainly composed by polysaccharides, different kind of waxes, and cutin. In particular, cutin is the main
component of plant cuticles, which acts as the polymer matrix that supports the rest of the cuticle
components [2]. Cutin of tomato fruits is mainly composed by hydroxylated fatty acids. In this work,
tomato ‘peel’ monomers (T) were dissolved in a mix of water/ethanol (1/1, v/v) through a sonication
process and blended with an aqueous solution of sodium alginate (A). Different alginate/tomato
monomers (AT) weight ratios (100/0, 75/25 and 50/50) were prepared. Free-standing films were
obtained and characterized in order to study morphological, mechanical, thermal, hydrodynamic and
barrier properties. In addition, to induce an esterification process in tomato cutin monomers, all the
materials were thermally treated at 150°C for 8 hours. AT-50 sample, after the thermal treatment in
oven, resulted the best composite material with an interesting morphology and hydrophobic behaviour.
Nevertheless, to enhance the mechanical and barrier properties, three different percentages (5, 15, 30
wt.%) of beeswax (BW) were added. The addition of beeswax led to a significative increase of both
mechanical and water barrier properties. These green alginate-cutin-beeswax composite materials
can be potentially used in food packaging.
Fig. 1: SEM top-view and cross-section images of AT-50p sample after polymerization in oven
and after addition of 5 wt.% beeswax (AT-50p B-5).
Fig. 2: Water vapor transmission rate (WTR, black) and water vapor permeability (WVP, red) of
alginate/tomato peel polyester after heating treatment (AT-0p, AT-25p and AT-50p) and after
addition of beeswax (B-5, B-15 and B-30).
[1]. E. Dominguez, J. A. Heredia-Guerrero, A. Heredia, New Phytologist. 2011, 189, 938-949.

[2]. J. A. Heredia-Guerrero, A. Heredia, E. Dominguez, R. Cingolani, I. S. Bayer, A. Athanassiou, J. J.
Benítez, Journal of Experimental Botany, 2017, 19, 5401-541
182
BIOTECH-OR37

Synthesis of fully bio-based polybenzoxazine resins by solvent-free

method
1 1 1
Acerina TREJO-MACHIN, Laura PUCHOT , Pierre VERGE *
1
Luxembourg Institute of Science and Technology, Luxembourg, Luxembourg
Keywords: Benzoxazine, bio-phenol, phloretic acid, thermosets, solventless
Benzoxazine resins – namely polybenzoxazines (PBz) – have been developed by academia and
industry as a promising substitute of phenolic and epoxy resins due to their outstanding properties
such as near-zero shrinkage upon polymerization, high glass transition temperatures, high char yield
and excellent electrical and mechanical properties.[1, 2] PBz are benefiting from the versatility of the
design of their chemical structure, with the growing trend to employ renewable resources for the
synthesis of their monomers. Furthermore, the incorporation of benzoxazine functionalities onto
polymer chains is gaining attention as it is offering the asset to combine the properties from the
polymer and benzoxazine. Among the different approaches, one common is relying on the
phenolation, or the Friedel-Craft alkylation of phenols, which in both cases wreak havoc on human
health. In this communication, a sustainable approach based on the use of renewable resources, and
leading to fully bio-based polybenzoxazine resins will be exposed.[3] In this approach, phloretic acid, a
naturally occurring phenol, was used as a renewable building block to functionalize polyethylene
glycols by Fischer esterification, leading to phenol-terminated molecules. These phenolic groups were
further reacted with a bio-based amine, furfurylamine, to form 100% bio-based benzoxazine end-
capped molecules (Fig. 1). It is noteworthy that the two-step synthesis did not require solvent or
purification. Finally, the newly prepared monomers were polymerized to obtain materials exhibiting a
wide range of properties depending on the molecular weight of the polyethylene glycols.
Fig. 1: Fully bio-based end-chain benzoxazine
[1]. Ning, X. & Ishida, H. J. Polym. Sci. Part Polym. Chem. 1994, 32, 1121–1129
[2]. Ishida, H. & Allen, D. J. J. Polym. Sci. Part B Polym. Phys. 1996, 34, 1019–1030
[3]. Trejo-Machin, A., Verge, P., Puchot, L. & Quintana, R. Green Chem. 2017, 19, 5065–5073
183
BIOTECH-OR38

Bioinspired extracellular matrices for tissue engineering

1 1 1 2
Franck CLEYMAND*, Charles ROUX-PERTUS, Solenne FLEUTOT, João MANO,

1
Institut Jean Lamour UMR 7198 CNRS/Université de Lorraine, Nancy, France;
2
Department of Chemistry, CICECO, University of Aveiro, Aveiro, Portugal

Keywords: bioinspired scaffolds, electrospinning, bioinspired, beetle, chitosan, lecithin, cicada wings
In the context of Tissue Engineering and Regenerative Medicine [1;2], we developed bio-inspired
scaffold from renewable resources with controlled external shape and internal architecture. Different
homemade fabrication apparatuses have been developed to produce controlled systems inspired by
the nature. Mechanical, physico-chemical and biological characterizations assess the therapeutic
potential.
This presentation will report our recent advances on bioinspired scaffolds such as:
1) Electrospun fibers of chitosan and crosslinked chitosan which has been inspired by the hierarchical
structure of Dynastes hercules elytra [3] and can be seen as new architecture to TE.
2) Free standing membranes functionalized in volume by incorporating nanoliposomes based on
marin origin lecithin [4].
3) Cicada wings Bioinspired Membranes for Tissue Engineering
[1]. Tissue Engineering, Cell Therapy and Transplantation: Products, Technologies & Market
Opportunities, Worldwide, 2009-2018.” Report #S520; Med Market Diligence, LLC.
[2]. R. Langer, D.A. Tirrell, Nature 2004, 428, 487-492.
[3]. C. Roux-Pertus, E. oliviero, V. Viguier, F. fernandez, F. Maillot, O. Ferry, S. Fleutot, J.F. Mano, F.
Cleymand Micron 2017, 101, 16-24.
[4]. F. Cleymand, H. Zhang, G. Dostert, P. Menu, E. Arab-Tehrany, E. Velot, João F. Mano, RCS
Advances 2016, 6, 83626-83637
184
BIOTECH-OR40

3D bioprinting of stimuli-responsive cell-laden cellulosic hydrogel

1 1 1 1
Naresh D. Sanandiya , Jyothsna Vasudevan , Rupambika Das , & Javier G. Fernandez *
1
Singapore University of Technology & Design, 8 Somapah Road, Singapore 487372
*Correspondence to: [email protected]

Keywords: Injectable hydrogel, cell therapy, cellulose hydrogel, Thixotropy
Polymeric hydrogels are the forefront of cell delivery technologies. They are highly hydrated molecular
networks with similar characteristics as that of the extracellular matrix and enable fluent diffusion of
biomolecules. Based on their functions, there are two main types of hydrogels currently in use in
tissue engineering; those forming cell-laden mechanically robust structures in vitro that later are
implanted, and those hydrogels with fluid characteristics that can be sprayed or injected. These
mutually exclusive characteristics seriously limit the general utility of most hydrogels for various tissue-
engineering applications. Solid hydrogels provide a good protective environment and encapsulation for
the new cells but can result in trauma from surgical implantation. Additionally, solid hydrogels lack the
ability to adapt to the geometry and mechanical properties of the host tissue required to establish an
optimal host-implant interaction. On the other hand, most injectable hydrogels fail to retain structural
integrity after injection, providing a limited ability to retain the encapsulated cells. Hence there is an
imperative need in tissue engineering to develop hydrogels that simultaneously provide protection to
the cells during injection, become mechanically robust and maintain high cell viability.
We present the biomedical application of a cellulosic thixotropic gel with stimuli responsiveness for
cell-delivery and 3D bioprinting. This biocompatible hydrogel acts as a reversible shear thinning
hydrogel, enabling the shield of cells to external forces during delivery, and conforming a stable and
protecting environment for cells after injection. The tri-stimuli responsiveness enables the use of this
hydrogel in an unprecedented number of delivery and conformation strategies, based in both chemical
and mechanical triggers, ranging from injectable cell delivery to three-dimensional (3D) bio-printing.
The bioprinting ability of the cellulose was explored in a cell culture media, unlike the reported
bioprinting studies where additionally curing or crosslinking agents are used. The CNF hydrogel is
highly compatible to the human breast cancer cells (MCF-7) and mouse embryonic stem cells (MCF-7)
with homogeneous distribution in the gel matrix, signifying applicability as cell delivery carrier for
sustained release of paracrine factors and for tissue regeneration with unique versatility for injection,
scaffolding, and 3D bioprinting.
185
BIOTECH-OR41

Surface Coating of Polymer Membranes for Water Treatment:
a New Approach to Mitigate Biofouling
1 1 2
Viktor KOCHKODAN , Muataz HUSSEIN , Olga KOCHKODAN
1
Qatar Energy and Environment Research Institute (QEERI),
Hamad bin Khalifa University (HBKU), Qatar Foundation, Doha, Qatar
2
National University of Life and Environmental Science of Ukraine, Kyiv, Ukraine
Keywords: membrane biofouling, surface coating, layer by layer deposition, polyelectrolytes
The main problem arising upon water treatment and desalination with pressure driven membrane
processes is membrane fouling that seriously hampers the application of the membrane technologies [1].
The surface coating of the membranes via nature inspired layer-by-layer (LbL) deposition of
polyelectrolytes seems to be a simple and flexible technique to improve the membrane fouling
resistance [2]. In this method, polycationic and polyanionic polyelectrolytes are alternately deposited
on a membrane surface mainly due to electrostatic interactions. Advantages of LbL modification are
that hydrophilicity and thickness of a deposited layer can be controlled at the nanometer scale to allow
high water flux and the membrane's properties can be optimized by varying of the polyelectrolyte type
[3]. [It should be also highlighted that LbL assembly might be used for membrane modification directly
“in situ” in commercial membrane elements
In this study composite polyamide membranes NF-90, NF-270 and BW-30 were modified via LbL
approach using electrostatic deposition of polyelectrolyte multilayers made from various polycationic
and polyanionic polymers of different molecular weights. Four anionic polyelectrolytes such as:
poly(sodium 4-styrene sulfonate), poly(vinylsulfonic acid, sodium salt), poly(4-styrene sulfonic acid-co-
maleic acid) sodium salt, poly(acrylic acid) sodium salt and three cationic polyelectrolytes such as
poly(diallyldimethylammonium chloride), poly(ethylenimine) and poly(hexamethylene biguanide were
used for modification.
The surface morphology of the prepared composite membranes were studied using atomic force
microscopy. FTIR technique was used to confirm that LbL deposition of the polyelectrolyte layers on
the membrane surface had taken place. An effect of deposition time, a number of polyelectrolyte
layers, chemical nature and molecular weight of used polyelectrolytes on degree of membrane
modification (DM) has been evaluated. It was found that DM values of the membranes grows with
modification time, with an increase in the number of LbL layers on the membrane surface and with
molecular weight of polyelectrolytes used for modification. Measurement of contact angles on the
membrane surface has proved that modification of the membrane surface via LbL polymer deposition
leads to hydrophilization of the membrane surface. It was shown that the surface charge of LBL
modified membrane can be switched between positive and negative after coating with a cationic or an
anionic polyelectrolyte.
The antimicrobial properties of the modified membranes towards Pseudomonas aeruginosa (P.
aeruginosa) bacteria have been studied. Confocal imaging of the growth of P. aeruginosa bacteria on
the membrane surface has shown a clear difference in the number of live and dead cells on the
membrane surfaces of neat and modified samples due to the bactericidal properties of deposited
polycationic layers on the membrane surface A possible mechanism of the bactericidal action of the
modified membranes has been discussed. An enhanced performance of the modified membrane
samples was shown during treatment of Arabian Gulf sea water in the non-continuous regime.
[1]. I.C. Escobar, E.M. Hoek, C.J. Gabelich and F.A. DiGiano, J. Am. Water Works Assoc.,
2005, 97, 79-89.
[2]. V. Kochkodan and N. Hilal, Desalination, 2015, 356, 187-207.
[3]. L.Y. Ng, A.W. Mohammad and C.Y. Ng, Adv. Colloid Interf., 2013, 197-198, 85-107.
186
NANOTECH-OR01

Microstructural surface properties of drifting seeds – a model for
non-toxic antifouling agents
1 2
Antje CLASEN , Antonia B. KESEL
1
Institute of Environmental and Biotechnology, City University of Applied Sciences, Bremen, Germany
2
Biomimetics-Innovation-Center, City University of Applied Sciences, Bremen, Germany
Keywords: biofouling, drifting seeds, surface structure, biomimetic, replication technique, curvature
A significant problem in the shipping and marine industry is biofouling on surfaces. The formation of
biofilm is a hierarchical and active process [1], based on the adhesion of microorganisms. Its strength
influenced by various factors including the surface topography. Therefore, in the last few years,
research activities have been focused on the potential of microstructured surfaces for non-toxic
antifouling strategies for substituting biocides. Studies on the skin of pilot whales and sharks as well
as on shells of mussels and crabs have shown promising results [2].
In the current doctoral project, the physical surface properties of eight selected terrestrial plant species
(A. wrightii, C. borhidiana, C. boschiana, E. berteroana, I. alba, L. spinosa, S. saponaria, T. peruviana
yellow) are analyzed with regard to their antifouling effect. The surface structures of the seeds were
identified and compared with each other, using a scanning electron microscope (SEM). In the second
step, selected surface structure properties are transferred to artificial materials, applying a two-step
replication process technique used by Koch et al. 2008 [3] and Prüm et al. 2013 [4]. After comparing
the original surface structures of the drifting seeds with their replicas using the SEM, the plant seeds
and their replicas were exposed to the cold water area of the North Sea for several time periods.
After the scanning microscopic analysis verified that replication is a suitable method for replicating
surfaces of drifting seeds, the surface of the exposed seeds and replicas were examined. Results of
the fouling analyses showed that drifting seeds with honeycomb-shaped surface structures (e.g.
Acoelorrhaphe wrightii and Licuala spinosa) exhibited less fouling than seeds with a smooth surface
(e.g. Erythrina berteroana and Sapindus saponaria). Furthermore, data prove a correlation between
increasing curvature and decreasing fouling. Is the curvature less than 0.27 mm , the growth of
-1
biofouling organisms decreases to almost zero.

These findings serve as a starting point for further steps in the development of non-toxic antifouling
agents that will build on the interaction of microstructures and geometric shapes. However, in addition
to the physical properties, the chemical constituents of the propellants or even a combination of
different mechanisms of action may also play a role in the defense against fouling. Further research is
needed for determining the degree of the interaction of physical and chemical factors.
[1] A. Rosenhahn, S. Schilp, H.J. Kreuzer M. Grunze, Physical chemistry chemical physics, 2010, 12:
4275-4286.
[2] M. Salta, J.A. Whartin, P. Stoodley, S.P. Dennington, L.R. Goodes, S. Werwinski, U. Mart, R.J.K.
Wood, K.R. Stokes, Philosophical Transactions of the Royal Society A, 2010, 368: 4729-4754.
[3] K. Koch, A.J. Schulte, A. Fischer, S.N. Gorb, W. Barthlott, Bioinspir Biomim, 2008, 3:046002.
[4] B. Prüm, H.F. Bohn, R. Seidel, S. Rubach, T. Speck, Acta Biomaterialia, 2013, 9:63606368.
187
NANOTECH-OR02

Towards the Fabrication of a Bioinspired Fluid for Biotriblogical

Applications
1,2 1 1 2
Jimmy FAIVRE, , Guillaume SUDRE, Alexandra MONTEMBAULT, Buddha R. SHRESTHA,
3 4 5 1
Florina MOLDOVAN, Stéphane BENAYOUN, Krzysztof MATYJASZEWSKI, Thierry DELAIR,
2 1
Xavier BANQUY, Laurent DAVID *,
1
Laboratoire Ingénierie des Matériaux Polymères, Université Claude Bernard Lyon1, Lyon, France;
2
Biomaterials and Structured Interfaces Laboratory, Université de Montréal, Montréal, Canada;
3
Centre Hospitalier Sainte-Justine, Montréal, Québec, Canada;
4
Laboratoire de Tribologie et de dynamique des Systèmes, Centrale Lyon, Lyon, France;
5
Center for Macromolecular Engineering, Department of Chemistry, Carnegie Mellon University,
Pittsburgh, PA, USA
Keywords: Lubrication, Wear, Bottlebrush polymer, Bioinspiration, Tribo-supplementation
Synovial joints exhibit excellent lubrication and wear protection throughout individual lifetime due to
the prominent role of lubricine, aggrecan, phospholipids and hyaluronic acid (HA) from bathing
synovial fluid. We hypothesized that by mimicking the lubricine architecture, we could synthesize a
polymer substitute able to provide excellent tribological properties in various biomedical applications.
The aim of this project is to develop a polymer solution able to provide a long-term protection of
tissues or biomaterials used in vivo as well as excellent lubrication properties to sustain intense body
coercions such as what is found in synovial joints.
We synthesized a library of bottlebrush (BB) polymer mimicking the structure of the lubricine using
ATRP technique [1, 2]. These polymers own a central polyzwitterionic lubricating domain, inspired
from joint phospholipids, and none to two lateral and non-specific anchoring groups (Fig. 1). The
tribological properties of BB polymer along with HA and the ability to protect various kind of model
surfaces were characterized using a home-made tribometer, the surface forces apparatus and
interferometry. Model surfaces were selected to anticipate the use of our fluid in different potential
applications such as intra-articular injection for osteoarthritis treatment, enhancement of contact
lenses, or treatment of dry eyes. BB polymers with HA exhibited physiological friction coefficients (µ ~
0.02) [1-3] both on mica and hydrogels substrates under boundary lubrication. The number of
attachment groups of the polymer played a crucial role on the range of applied pressures the polymer
coatings can sustain. With no anchoring groups, the polymer could only sustain an applied pressure of
15 atm whereas with two anchoring groups, BB polymer sustained more than 140 atm, typically in the
range of physiological values found in joints. Furthermore, no surface damage of the BB polymers
coated substrates were noticed up to these pressure values.
We developed a potential biocompatible fluid for biotribological in vivo applications able to reduce
friction to physiological values and protect the coated surfaces up to several atmospheres of
pressures. The polymer can be formulated in aqueous solution for direct administration without any
surface modifications.

100 nm

Figure 1. Schematics of the BB polymers structures with (A) none, (B) one, and (C) two
anchoring groups
[1]. X. Banquy, et al., J. Am. Chem. Soc. 2014, 136, 6199-6202.

[2]. J. Faivre, et al., ACS Nano. 2017, 11, 1762-1769
[3]. J. Faivre, et al., Biomacromolecules. 2017, 18, 4002-4010
188
NANOTECH-OR03

Making superhydrophobic surfaces with magnetic elastomer:

towards controlled droplet movement

1,2,3 3 2 1
Blandine Bolteau, Jérémie Teisseire, Etienne Barthel, Jérôme Fresnais,*,

1
Sorbonne Université, CNRS, Laboratoire de Physico-chimie des Electrolytes et Nanosystèmes
Interfaciaux, PHENIX - UMR 8234, F-75252 Paris cedex 05, France.
2
CNRS/UPMC/ESPCI ParisTech-PSL Research University, UMR 7615, Laboratoire SIMM, 10 Rue
Vauquelin, 75231 Paris, FranceAffiliation 2, City, Country
3
Surface du Verre et Interfaces, UMR 125 CNRS/Saint-Gobain, 39 Quai Lucien Lefranc, F-93303
Aubervilliers, Cedex, France
Keywords: superhydrophobic surfaces, magnetic elastomer, controlled droplet movement
In the field of superhydrophobic surfaces, natural surfaces exhibiting non-wetting filament networks
remain a challenge to understand. Indeed, if classical superhydrophobic surfaces developed
roughness at different scales, superhydrophobicity on hairy surfaces shows elastic behavior that is
more difficult to model. Our approach was to elaborate model surfaces with high aspect ratio
elastomeric pillars. By changing the geometry of the structures, we controlled stiffness and surface
density to elucidate the role of elasticity upon wetting properties in the Cassie state. Using compliant
pillars, we were able to measure the forces exerted by the contact line on the pillars. Unexpectedly,
despite the deformations incurred by the pillars, the contact angle (either advancing or receding ones)
and the dropsliding angle did not change significantly with the Young modulus of the pillars, in the
range of 60 kPa to 2400 kPa.
Finally, we demonstrated that it is possible to induce the step by step motion of a droplet on a tilted
surface by the application of a magnet above magnetically functionalized elastomeric pillars array (fig.
1). The microscopic origin of this displacement is the tilt of the pillar tops which affects the pinning
condition of the triple line.
Time (
s )
Fig. 1: Step by step motion of a droplet on a tilted surface and corresponding snapshots. Each
step is obtained by an individual magnet scan.
189
NANOTECH-OR04

Rapid Access to Functional Oil-Filled poly(vinyl alcohol)-based

Glyconanocapsules through Nanoprecipitation
1 1 1
Luxiao CHAI, Etienne Fleury, Julien Bernard *,
1
INSA-Lyon, CNRS UMR 5223, Ingénierie des Matériaux Polymères, 69621 Villeurbanne, France
Keywords: Nanoprecipitation, Phase diagrams, PVA, Glyconanocapsules
Herein, we report on the preparation of PVA-based nanocapsules (NCs) through nanoprecipitation.

Based on PVA and hexadecane/water/acetone phase diagrams, we first demonstrate that well-defined
NCs can be reproducibly produced through solvent shifting procedures in the Ouzo domain (see
1
Figure 1). The resulting NCs can be conveniently loaded with hydrophobic actives (fluorescence tags,
drugs…) and peripherally decorated with PEG grafts for stealth purposes. To broaden the functionality
of PVA-based NCs, we further show that poly(vinyl ester) random copolymers of vinyl chloroacetate
2
and 6-O-vinyladipoyl-D-glucopyranose can be selectively hydrolyzed under mild conditions and
engaged in the construction of PVA-based glycoNCs through nanoprecipitation.

Fig. 1: TEM image of PVA nanocapsules obtained through nanoprecipitation (left) and
functional nanocapsules (right)
[1]. X. Yan, M. Delgado, A. Fu, P. Alcouffe, S. G. Gouin, E. Fleury, J. L. Katz, F. Ganachaud, J.

Bernard, Angew.Chem.Int.Ed. 2014, 53, 6910-6913.
[2]. M. H. Repollet-Pedrosa, R. L. Weber, A. L. Schmitt, M. K. Mahanthappa, Macromolecules.
2010, 43, 7900-7902.
190
NANOTECH-OR05

Wettability assisted selective deposition of nanoparticles on

patterned glass fibers

Seethalakshmi CHANDRAMOULI*, Larissa GORBATIKH, David SEVENO

Department of Materials Engineering, KU Leuven, Leuven, 3001, Belgium

Keywords: Glass fibers, UV Patterning, dynamic contact angles, dip coating, polystyrene nanoparticles
The idea of evenly introducing particles on fibers has been long standing for several advanced
applications ranging from sensors and solid-state devices [1], functional textiles to high-performance
composites [2]. Gao et al. [3] added colloidal silica particles to glass fibers and observed an increase
in the energy dissipation and overall strength of the glass fiber-epoxy composite system. It is well
known that by engineering the fiber-matrix interface, one can tune the overall mechanical properties of
the composite system [4, 5]. While a strong interface ensures sufficient stress transfer between the
fiber and the matrix, weakness in the interface region is beneficial for energy dissipation and
redistribution of stresses. However, traditional engineering materials suffer the trade-off in
simultaneous improvement of strength and toughness.
In this work, we explore possibilities to create ‘intermittent’ coating on glass fibers. Intermittent
fiber/matrix interface bonding controlled by spasmodically coating the fiber to contain regions of high
and low adhesion has shown significant improvements in toughness while largely retaining the
composite strength [6]. Individual E-glass fibers are patterned using optical (UV) lithography to contain
alternating micrometer to millimeter size regions of varying chemical functionalities and fiber surface
wettabilities. Dynamic contact angle measurements using the wilhelmy technique exhibits marked
changes in the wetting behavior (figure 1, left), confirming the presence of hydrophilic, non-silane
treated and hydrophobic, silane treated regions along the length of the modified glass fibers.
Subsequently, these patterned glass fibers are used as substrates to selectively deposit polystyrene
(PS) nanoparticles from an aqueous dispersion at the air-water interface via a dip-coating method.
Low contact angles and faster de-wetting allows the particles to predominantly confine onto the
hydrophilic regions of the modified glass fibers. Thus, this approach demonstrates the possibility of
creating fibers with intermittent surface properties for potential applications in composite systems.
Fig. 1: (left) Representative Dynamic Contact Angle plot of a patterned glass fibre and (right)
SEM images of the hydrophilic and hydrophobic segments of the glass fibre, with and without
PS nanoparticles.
[1] B.G. Jung, S.-H. Min, C.-W. Kwon, S.-H. Park, K.-B. Kim, T.-S. Yoon, Journal of The
Electrochemical Society, 156, 2009, K86.
[2] L. Tzounis, C. Gravalidis, S. Vassiliadou, S. Logothetidis, Materials Today: Proceedings, 4, 2017,
7070-7075.
[3] X. Gao, R.E. Jensen, S.H. McKnight, J.W. Gillespie, Composites Part A: Applied
Science and Manufacturing, 42 (2011) 1738-1747.
[4] J. Karger-Kocsis, H. Mahmood, A. Pegoretti, Progress in Materials Science, 73 (2015) 1-43.
[5] Israel Greenfeld, Wenyong Zhang, Xiao MengSui, H. DanielWagner, Composites Science and
Technology, Volume 160, 26 May 2018, Pages 21-31.
[6] A.G. Atkins, Journal of Materials Science, 10 (1975) 819-832.
191
NANOTECH-OR06

Effect of Air Contamination on The Wettability of Mono and Few-

layered InSe Films

1 ,1
Xuan CHEN, Zuankai WANG *
1
Department of Mechanical and Biomedical Engineering, City University of Hong Kong, Hong Kong,
China;
* Address correspondence to [email protected]

Keywords: Indium selenide, Wetting, Aging, Hydrophobic
Understanding and controlling the two-dimensional(2D) materials are of significant importance for
1-2
basic fundamental research and diverse practical industrial devices . Recently, the single phase 2D
Indium selenide (InSe) nanosheet has been the subject of intense research due to its splendid
electrical transport characteristics, outstanding quantum property and superior photo-response
3-4
capacity . To date, there is very limited research in understanding the wetting behavior of mono and
few-layer 2D InSe nanosheet. The water wetting ability, which interprets the interaction between InSe
nanosheet and its surrounding environment, exerts strong influences on many of the material
properties such as uniformity, crystallinity and thermal stability. Therefore, it is dramatically critical to
understand how water wets the InSe surface.
Typically, the 2D semiconducting materials including transition metal dichalcogenides (TMDs) and
compound from group IIIA (Ga and In) and chalcogenide group VIA (S, Se and Te) have attracted
tremendous interest for their wide variety of applications among 2D van der Waal semiconductors,
THz generation source, memory device, and photo sensor. In recent years, many studies have
characterized the wetting property of two-dimensional (2D) transition metal dichalcogenides (TMDs)
such as crystalline sheets of molybdenum disulfide (MoS2) and tungsten disulfide (WS2) on substrates.
However, there is no clear understanding on the wettability of III-VI material of InSe and no study
investigates the aging effect, which has been regarded as one of most important effects for other 2D
5
materials such as graphene, MoS2 and WS2 . Recently, ultrathin layered InSe films synthesized using
typical physical bottom-up method--pulse laser deposition(PLD) could be exploited into the
6
fundamental study of wettability of InSe films . The present work involve growth of wafer-scale layered
InSe film onto different substrates with large lateral size.
Herein, we systematically investigate the wetting measurement and explore how the airborne
contamination impacts wettability of supported InSe nanosheet. After being exposed to ambient air,
the water wettability of PLD-grown single layer and multilayered InSe nanosheet on a SiO2/Si
substrate. The WCA of fresh InSe/SiO2/Si sample is ~55 °, suggesting the surface is hydrophilic.
When exposed to air, the WCA increased gradually to around 75 ° within 20 min and stabilized at ~90
° after about 1 hour. The results show that fresh-prepared InSe films possess intrinsic hydrophilic
nature, which would be correspondingly concealed by aging effect over time.
[1]. Marks, T. J.; Hersam, M. C. Materials Science: Semiconductors Grown Large and Thin. Nature
2015, 520, 631−632.
[2]. Franklin, A. D. Nanomaterials in Transistors: From High-Performance to Thin-Film Applications.
Science 2015, 349, aab2750.
[3]. Chhowalla, M.; Shin, H. S.; Eda, G.; Li, L.-J.; Loh, K. P.; Zhang,H. The Chemistry of Two-
Dimensional Layered Transition Metal Dichalcogenide Nanosheets. Nat. Chem. 2013, 5, 263−275.
[4]. Wu, W.; Wang, L.; Li, Y.; Zhang, F.; Lin, L.; Niu, S.; Chenet, D.;Zhang, X.; Hao, Y.; Heinz, T. F.; et
al. Piezoelectricity of Single-Atomic-Layer MoS2 for Energy Conversion and Piezotronics. Nature
2014, 514, 470−474.
[5]. Chow P K, Singh E, Viana B C, et al. Wetting of mono and few-layered WS2 and MoS2 films
supported on Si/SiO2 substrates[J]. Acs Nano, 2015, 9(3): 3023-3031.
[6]. Yang Z, Jie W, Mak C H, et al. Wafer-scale synthesis of high-quality semiconducting two-
dimensional layered InSe with broadband photoresponse[J]. ACS nano, 2017, 11(4): 4225-4236.
192
NANOTECH-OR08

Density of Nanometrically Thin Amorphous Films Varies by
Thickness
Yael ETINGER-GELLER, Alexander KATSMAN, Boaz POKROY*
Department of Materials Science and Engineering, Technion – Israel Institute of Technology, Haifa,
Israel
Keywords: Bioinspired, Amorphous, ALD
Amorphous materials, in contrast to crystalline ones, lack long-range order. Its order decays rapidly
with the distance and while the local environment for a particular type of atom is quite similar, it is not
identical; these fine changes in the atomistic structure of the materials lead to new and very
interesting phenomena which are unique for amorphous materials. Although many aspects of
science and technology rely on amorphous materials, much less research is conducted about their
structure than on their crystalline counterparts.
In nature there are many organisms that use crystallization via an amorphous phase in order to
achieve controlled mineralization. One of the main advantages of this method is that it enables the
organism to exert control over the resulting polymorph, which is not necessarily the
thermodynamically-stable one, by first controlling the short-range order in the amorphous phase.
In this research we draw inspiration from nature and study the ability to control various structural
aspects of amorphous materials via nanometer size effects. We chose atomic layer deposition (ALD)
as our material deposition method, since it is a technique that can provide extremely precise, sub-
nanometric, thickness control and can deposit conformal and pinhole-free amorphous films of
various materials.
Amorphous thin films of aluminum oxide deposited by atomic layer deposition method were found to
vary structurally as a function of size; thinner films, as predicted and also confirmed by atomistic
simulations, exhibited more 4-coordinated Al sites. These atomistic alterations were expected to
change the amorphous thin film’s average density, and indeed it was found to vary with the alumina
layer thickness. This effect is explained in terms of the deposition process, where each newly
deposited layer is a new surface layer that ‘remembers’ its structure, resulting in thin films of
substantially lower density. This further encouraged us to study the effect of size on different density-
dependent properties; we believe that the ability to tune one property or another solely by size,
according to a specific requirement, can open new possibilities for materials selections and
applications, in science and technology.
[1]. Y. Etinger-Geller, A. Katsman, B. Pokroy, Chem. Mater. 2017, 29, 4912-4919.

[2]. L. Bloch, Y. Kauffmann, B. Pokroy, Cryst. Growth Des. 2014, 14, 3983-3989.
193
NANOTECH-OR09

Engineering the properties of self-assembled bio-inspired
nanocomposite materials

1 1 1 1 1,2
Olivier FELIX *, Rémi MERINDOL, Rebecca BLELL, Xiaofeng LIN, Matthias PAULY, Thierry
1,2 1,2 1,2
ROLAND, Christian GAUTHIER, Gero DECHER

1
Institut Charles Sadron UPR22-CNRS, 23 rue du Loess, 67034 Strasbourg Cedex 2, France;
2
Université de Strasbourg, Faculté de Chimie, 1 rue Blaise Pascal, 67008 Strasbourg, France

Keywords: LbL assembly, grazing incidence spraying, thin films, nanocomposite materials,
anisotropic properties, bio-inspired complex superstructures
Through evolution, nature has developed composite materials (e.g. bone, wood, nacre or crustacean
exoskeleton) with complex and hierarchical organization from the nano- to the macro-scale via
molecular assembly. Such materials possess fascinating combinations of properties such as
lightweight, strength or shock resistance by assembling hard and soft elements. The remarkable
mechanical performance of such natural hybrid materials has prompted the fabrication of bio-inspired
composites.
The development of nanocomposite materials of high compositional and structural complexity is
generally thought to be very important but not much explored due to the lack of appropriate methods
for their preparation. With respect to the preparation of multimaterial thin films with a high level of
control over the spatial positioning of their constituents, Layer-by-Layer (LbL) assembly [1,2] has
gained its merits as a simple and highly versatile nanofabrication method. While the sequence of
components in layered multimaterial films can be very well controlled by LbL-assembly, tuning of the
in-plane anisotropy has not yet been achieved. Recently, we have introduced a novel method called
“Grazing Incidence Spraying” for the in-plane alignment of anisotropic nanoparticles (cellulose
nanofibrils, metallic nanowires and nanorods, …) on large areas [3,5]. Its combination with the LbL-
approach permits to extend it toward the preparation of complex (e.g. helical) multilayer films in which
the composition and orientation can be controlled independently in each layer.
The talk will illustrate some of our recent results on the design of bio-inspired nanostructured materials
combining hard anisotropic elements like nanofibrillated cellulose and silver nanowires with soft
polymer building blocks. The preparation of such thin films will be presented and their optical and
mechanical properties as function of the film composition and geometry will be discussed.
Fig. 1: (a) In-plane alignment of anisotropic nano-objects (1D (left) and crisscross (right)). (b)
Optical photograph of a cellulose based-LbL film. (c) Tensile properties of random (red) and
oriented nano-composites (along (blue) and across (red) the direction of orientation).
[1]. G. Decher, Science 1997, 277, 1232-1237.

[2]. Multilayer Thin Films: Sequential Assembly of Nanocomposite Materials, 2nd Edition (Eds:
Decher, G. and Schlenoff, J. B.), Wiley-VCH: Weinheim, 2012.
[3]. S. Sekar, V. Lemaire, H. Hu, G. Decher, M. Pauly, Faraday Discuss. 2016, 191, 373-389.
[4]. H. Hu, M. Pauly, O. Felix, G. Decher, Nanoscale 2017, 9, 1307-1314.
[5]. R. Blell, X. Lin, T. Lindström, M. Ankerfors, M. Pauly, O. Felix, G. Decher, ACS Nano 2017,
11, 84-9
194
NANOTECH-OR10

Versatile capped superparamagnetic iron oxide nanoparticles

1 1 2 3 3
Solenne FLEUTOT*, Pierre VENTURINI, Jean-Luc SIX, Jean-Charles.DUPIN, Hervé MARTINEZ,
1
Franck CLEYMAND
1
IJL - UMR CNRS 7198, Université de Lorraine, Nancy, France;
2
EEIGM, Université de Lorraine, Nancy, France;
3
IPREM - UMR CNRS 5254, Université de Pau et des Pays de l'Adour, Pau, France
[email protected]
Capped SuperParamagnetic Iron Oxide Nanoparticles (NPs) can be used for several applications
(environmental, biomedical applications …) [1]. In this context, numerous synthesis and
functionalization methods have been reported [2] to control composition, size, and surface state of
NPs and capped NPs to perform and control their magnetic properties [3].
In this study, capped NPs (NPs@Cit) have been synthesized in a controlled range size of 5-15 nm by
a method derivate from the co-precipitation synthesis [4] to which we add an “in-situ” functionalization
of the nanoparticles by citrate ions (Cit). The influence of citrate addition during the synthesis on each
physicochemical parameter of the nanoparticles was studied. A comparison with the standard
synthesis results will be presented. Indeed, if this method provides nanoparticles dispersed in
aqueous medium, essential point for biomedical applications, it usually leads to samples tending to
aggregate. The nanoparticles aggregation should be avoided by the electrostatic repulsions caused by
citrates bounded to the SPIONs surfaces. In addition, free hydroxyl and carboxylate functional groups
of the citrate can be used as anchor functional groups for further functionalization. A special attention
has been given to the reproducibility of samples and to their colloidal stability over time in aqueous
suspension.
Beside the influence of the in situ functionalization, several synthesis parameters such as the ratio
ligand (citrate) / precursor (iron species) and the citrate addition time compared to the nanoparticles
precipitation have been studied especially for their effects on NPs’ size, composition, colloidal stability
and magnetic properties. The influence of these parameters was considered in relation to the
nucleation and growth of nanoparticles.
To evaluate the influence of monitored parameters on the size, composition and colloidal stability, a
physico-chemical and magnetic characterization was conducted systematically by classical methods:
Transmission Electron Microscopy (TEM), X-Ray diffraction (XRD) and Dynamic Light Scattering
(DLS). Magnetic measurements were performed using a SQUID VSM. Iron oxidation degree was
determined by Mössbauer spectroscopy and X-ray photoelectron spectroscopy (XPS). XPS was
allowed to characterize the nature of the interactions between iron oxide core and citrate shell.
The chemical modification of the citrate shell is finally considered for versatility of developed
nanoparticles. In order to add new functionalities (thermo-responsive shell, UV-responsive shell, etc.)
to citrates grafted onto the surface of NPs@Cit, a study has been undertaken to directly modify these
molecules by an alkyne group and form NPs@Cit-Alkyne usable for "click chemistry" reactions.
[1] M. Colombo, S. Carregal-Romero,M. F. Casula, Chem. Soc. Rev. 41, 4306-4334 (2012)
[2] A-H. Lu, E. L. Salabas, F. Schütz, Angewandte Chemie. 46, 1222-1244 (2007)
[3] A. K. Gupta, S. Wells, IEEE Trans. Nanobio. 3, 66-73 (2004)
[4] A. Bee, R. Massart, S. Neveu, J. Magn. Magn. Mater. 149, 6 (1995)
[5] K. N. Jayaprabha, A. Joy, RSC Advances. 5, 22117 (2015)
195
NANOTECH-OR11

Facile synthesis of polyoxazoline

coated iron oxide nanoparticles
1 1 2 1
Pierre VENTURINI, Solenne FLEUTOT*, Jean-Charles DUPIN, Jaafar GHANBAJA, Hervé
2 3 1 3
MARTINEZ, Jean-Jacques ROBIN, Franck CLEYMAND, Vincent LAPINTE
1
IJL - UMR CNRS 7198, Université de Lorraine, Nancy, France;
2
IPREM - UMR CNRS 5254, Université de Pau et des Pays de l'Adour, Pau, France;
3
ICGM – UMR 5253 – CNRS-UM-ENSCM, Montpellier, France.
[email protected]
Keywords: iron oxide ; nanoparticles ; magnetic properties ; polyoxazoline ; synthesis
Polyoxazoline coated superparamagnetic iron oxide nanoparticles (SIONs@POx) have been

synthesized according to a simple process. Stable water-dispersible with a well-crystalized spinel
structure are produced. The functionnalization efficiency is demonstrated using several
complementary techniques including direct HR-TEM observations of the polyoxazoline layer.
Magnetic measurements indicate the superparamagnetic behavior of SIONs@POx nanoparticles with
high saturation magnetization. The properties of stable water-dispersible SIONs combined with the
potential for use and modification of POx make these hybrid systems, developed in one-step in water,
prime candidates for future applications in the green chemistry field. We think that this work show a
new way for further development of new nanomaterials for healthcare and environmental applications.

Fig. 1: A) TEM micrograph and B) HR-TEM micrograph of SIONs@POx nanoparticles.
196
NANOTECH-OR12

Hydrophobin-polymer bioconjugate for antifouling and low non-
specific binding surfaces
1 1 1 2,5 2
Yingying Liu , Tarja Nevanen , Arja Paananen , Kristian Kempe , Paul Wilson , Leena-Sisko
3 1 4 2 ,1
Johansson , Jussi J. Joensuu , Markus B. Linder , David M. Haddleton , and Roberto Milani*
1
VTT Technical Research Centre of Finland Ltd, P.O. Box 1000, FI-02044, Espoo, Finland
2
Department of Chemistry, University of Warwick CV4 7AL , Coventry , United Kingdom
3
Department of Forest Products Technology, Aalto University, P.O. Box 11000, FI-00076 Aalto,
Finland
4
Department of Bioproducts and Biosystems, Aalto University, P.O. Box 16100, FI-00076 Aalto,
Finland
5
ARC Centre of Excellence in Convergent Bio-Nano Science and Technology, Monash Institute of
Pharmaceutical Sciences, Monash University, Parkville, VIC 3052, Australia.
Keywords: antifouling surfaces, non-specific binding, biosensors, surface initiated living radical
polymerization, hydrophobin
Poorly reactive surfaces modification often requires previous activation through environmentally
aggressive or energy-intensive methods. Instead, we utilized hydrophobins [1], small Janus-like
amphiphilic proteins produced by filamentous fungi, as intermediates for surface modification. Due to
their unique structure, they can self-assemble as a film on hydrophobic surfaces and expose a
reactive hydrophilic surface within minutes from substrate immersion. In this study, we demonstrated a
new method for preparing antifouling and low nonspecific adsorption surfaces by using hydrophobins
to activate the poorly reactive surfaces. Hydrophobins were first covalently modified with a controlled
radical polymerization initiator, and then the modified hydrophobins spontaneously formed a
monolayer on the hydrophobic surface. Following this, poly(ethylene glycol) methyl ether acrylate
(PEGA) was polymerized in situ by Cu(0) mediated living radical polymerization [2] for preparing
antifouling surfaces. Furthermore, the same method was applied to prepare low nonspecific
adsorption surfaces with protein A for IgG1 binding [3]. The success of surface modification was
evaluated by contact angle, XPS and AFM. The antifouling performance with a reduction of BSA
protein adsorption by more than 90% and the reduction of non-specific binding were investigated by
QCM-D.
[1] M. B. Linder, Curr. Opin. Colloid In. 2009, 14, 356-363

[2] A. Anastasaki, V. Nikolaou, G. Nurumbetov, P. Wilson, K. Kempe, J. F. Quinn, T. P. Davis, M. R.
Whittaker, D. M.Haddleton, Chem. Rev. 2016, 116, 835–877
[3] M. Soikkeli, K. Kurppa, M. Kainlauri, S. Arpiainen, A. Paananen, D. Gunnarsson, J. J. Joensuu, P.
Laaksonen, M. Prunnila, M. B. Linder, J. Ahopelto, ACS Appl. Mater. Interfaces 2016, 8, 8257.
197
NANOTECH-OR13

Coatings-free Desalination Membranes from Bio-inspiration
Himanshu Mishra*, Ratul Das, Sankara Arunachalam, Edelberto Manalastas, Ahad Syed
King Abdullah University of Science and Technology (KAUST), Water Desalination and Reuse Center
(WDRC), and Biological and Environmental Science and Engineering (BESE) Division,
Thuwal 23955-6900, Saudi Arabia
Keywords: bio-inspiration; omniphobicity; doubly reentrant; coatings-free membranes; desalination;

membrane distillation
Membrane distillation (MD) refers to thermally driven desalination processes exploiting hydrophobic
membranes to extract pure water vapor from salty seawaters. In comparison to other desalination
platforms, including reverse osmosis and multi-stage flash, MD processes present lower carbon
footprint because of their ability to exploit low-grade waste heat and renewables, such as
geothermal[1]. So far, perfluorinated membranes have been the sine qua non for MD processes
because of their intrinsic hydrophobicity[2]. Unfortunately, those coatings could be vulnerable to the
mildly hot conditions of MD processes[3], and also pose economic and environmental concerns[4]. In
response, we will unveil a bio-inspired approach to realize omniphobic membranes from intrinsically
wetting materials that could enable MD processes without depending on perfluorinated coatings. The
pores in those membranes have mushroom-shaped inlets that prevent liquid water from penetrating
inside[5], leaving only water vapor to transport from the hot side to the cold side. This strategy could
broaden the scope of MD processes employing membranes composed of common materials.
[1] E. Drioli, A. Ali, F. Macedonio, Desalination 2015, 356, 56; N. Ghaffour, S. Lattemann, T.
Missimer, K. C. Ng, S. Sinha, G. Amy, Applied Energy 2014, 136, 1155.
[2] S. Feng, Z. Zhong, Y. Wang, W. Xing, E. Drioli, Journal of Membrane Science 2018, 549, 332.
[3] Z. D. Hendren, J. Brant, M. R. Wiesner, Journal of Membrane Science 2009, 331, 1.
[4] A. B. Lindstrom, M. J. Strynar, E. L. Libelo, Environmental Science & Technology 2011, 45,
7954.
[5] E. M. Domingues, S. Arunachalam, H. Mishra, ACS Applied Materials & Interfaces 2017, 9,
21532.
198
NANOTECH-OR14

Microbial concrete provides resistance to concrete structures
exposed to severe sulfate attacks
1* 1 2
M. Sudhakara Reddy , Sumit Joshi , Shweta Goyal
1
Department of Biotechnology, Thapar Institute of Engineering & Technology, Patiala, India.
2
Department of Civil Engineering, Thapar Institute of Engineering & Technology, Patiala, India.
*
[email protected]
Keywords: Concrete, Mortar, Biomineralization, Sulfate attack, Expansion, Deterioration.
Concrete is the most widely used and the most important element of infrastructure development
across the globe. Strength and durability are regarded as the most important criteria in concrete
structure design. Long-term performance of concrete is often suffered from chemical attack, which
affects the lifecycle performance of concrete. Sulfate attack is one of the phenomena which cause
gradual but severe damage to concrete structure. Application of microbial induced calcium carbonate
precipitation via biomineralization process in improving compressive strength, durability and self-
healing of building materials is widely used recently. In the present investigation, effect of sulfate salt
attack on the durability properties of concrete structures treated with bacteria Bacillus sp. CT5 was
studied. The concrete cubes of dimension 100 x 100 x 100 mm were exposed to 10% sulfate solution
(5% Na2SO4 and 5% MgSO4) to study the change in compressive strength, mass change and micro-
structural properties (SEM and XRD). Changes in mechanical and micro-structural properties of
specimens submerged in sulfate solution were monitored on the monthly basis. To accelerate the
sulfate attack, wetting-drying cycle was done in which concrete samples were exposed to sulfate salt
solution for 5 days (Wet cycle) and air dried for 2 days (Dry cycle) regularly. To examine the length
expansion on sulfate exposure, mortar prism specimens (285 x 25 x 25 mm) were also submerged in
sulfate solution. To investigate the salt efflorescence effect, prismatic specimens were partially
immersed in the sulfate solution. Results of this study showed that sulfate attack was more damaging
in untreated concrete specimen causing ultimate failure due to expansion. However, biocementation
ability of alkaliphilic bacteria Bacillus sp.CT-5 improved the treated concrete towards sulfate
resistance. An experimental result indicates the reduced salt efflorescence effect, expansion rate and
concrete surface degradation in bacteria treated concrete in sulfate environments. The outcome of
current study supports the potential of this technology for applications in improving resistance of
concrete against sulfate environment.
199
NANOTECH-OR15

Bio-inspired Strategies for Design of Ice-Resistant Materials
based on Polymeric Janus Colloids

Alla Synytska
Leibniz-Institut für Polymerforschung Dresden e.V., Functional Particles and Interfaces Group,
Dresden, Germany
E-mail: [email protected] (A.S.)
Keywords: Ice-resistant materials, Janus colloids, bio-inspired design
The development of surfaces with reduced icing or easy de-icing is of paramount importance for the
wind turbine technology as well as automotive and aircraft industries [1]. Combining of the both anti-
icing and de-icing properties in one material is very challenging task and requires the controlling of
several parameters such as ice nucleation, growth and ice adhesion [2].
Herein, we propose new approaches for the design of heterogeneous surfaces with anti-icing and de-
icing capabilities based on polymer-modified core-shell particles. First, we use a mixture of different
types of particles with controlled and tunable chemical composition and size in various ratios to form
heterogeneous surfaces and to fundamentally investigate their wettability, ice nucleation and grow as
well as ice adhesion [2-3]. We will discuss the impact of chemical and topographical heterogeneities
on the mentioned above phenomena.
Second, we compare these results with the findings obtained on a heterogeneous surfaces made of
hybrid polymeric modified Janus particles. The heterogeneous surfaces formed by Janus particles
exhibit special surface “edge” morphologies and show a synergism of two main effects, the area is
free of ice and they form large unstable dendrites at the edges of heterogeneities. This leads to an
extremely low ice adhesion [3].
[1] J. Chanda, L. Ionov, A. Kirillova, and A. Synytska, Soft Matter, 2015, 11, 9126 – 9134.
[2] A. Krillova, L. Ionov, I. V. Roisman, and A. Synytska, Chem. Mater. 2016, 28, 19, 6995 – 7005.
[3] M. Schwarzer, T. Otto, C. Marschelke, M. Schremb, I.V. Roisman, and A. Synytska, submitted.
200
NANOTECH-OR16

Liquid-repellent coatings for friction and drag reduction in
industrial applications

1 1 1
Federico VERONESI* , Mariarosa RAIMONDO , Giulio BOVERI

1
Institute of Science and Technology for Ceramics CNR-ISTEC, Faenza, Italy

Keywords: nanostructured surfaces, superhydrophobic, oleophobic, liquid-infused, friction, drag
Friction and drag are phenomena that cause energy dissipation and a resulting negative economic
effect in many application fields, ranging from mechanics to waterborne transportation. Therefore,
design and fabrication of surface coatings with anti-friction and anti-drag properties would represent a
huge innovation with many potential positive fallouts.
Biomimetic, liquid-repellent coatings have been extensively investigated for their supposed anti-
friction[1] and drag reduction[2] properties. However, a vast majority of the studies reported in the
literature test these coated surfaces in small, lab-scale facilities in conditions far from those they would
face in potential applications. Thus, we focused on the fabrication of liquid-repellent coatings as per
different biomimetic approaches followed by the characterization of their anti-friction and anti-drag
properties in real operative conditions.
The anti-friction properties of a hybrid amphiphobic coating (superhydrophobic + oleophobic) based on
nanostructured boehmite AlOOH and fluorolalkylsilanes were first assessed[3]. We deposited the
coating on a brass slippers used in axial piston pumps for earth-moving applications, and observed
that their wetting properties were effectively modified (from oleophilic to oleophobic with respect to a
commonly used lubricant oil). Then, we measured their friction coefficient when rubbing against a
swashplate in conditions of hydrodynamic lift. We observed a remarkable reduction in friction
coefficient (up to 27% compared to that of uncoated slippers) at pressures up to 100 bars, typical of
the starting phases of pump operation. In addition, friction coefficient was still remarkably reduced
even after 20 hours of endurance test at constant pressure of 50 bars.
On the other hand, the frictional drag reduction properties of different liquid-repellent surfaces were
investigated in a high speed water channel. We fabricated water-repellent surfaces on large aluminum
2
plates (48x28 cm ) following two well-known biomimetic approaches, namely the SuperHydrophobic
Surface (SHS) approach and the Liquid-Infused Surface (LIS) one. In the experimental setup, water
6
flow in turbulent regime (Re≈10 ) exerted drag on the floating aluminum surfaces and a flexural load
cell measured the frictional force. While SHSs showed quick air plastron depletion during the tests and
similar drag compared to a reference uncoated panel, LISs showed remarkable drag reduction (up to
16%) in the 1.0÷3.5 m/s velocity range.
These first evidences of exceptional anti-friction and drag reduction properties of liquid-repellent
coatings foster the need for deeper studies on these subjects and hint at relevant future applications in
fields like mechanics and waterborne transportation.
[1]. M. Björling, R. Larsson, P. Marklund, Tribol. Lett. 2014, 55, 353-362.

[2]. K. B. Golovin, J. W. Gose, M. Perlin, S. L. Ceccio, A. Tuteja, Phil. Trans. R. Soc. A. 2016, 374,
20160189.
[3]. G. Rizzo, G.P. Massarotti, A. Bonanno, R. Paoluzzi, M. Raimondo, M. Blosi, F. Veronesi, A.
Caldarelli, G. Guarini, International Journal of Fluid Power 2015, 16:1, 1-10.
201
NANOTECH-OR18

Studying CaCu3Ti4O12 behavior after adding the boron nitride
nanosheets
a,b b a c a
Sara Kawrani , Madona Boulos , Sophie Tingry , Olivier Fontaine , David Cornu , Mikhael
a
Bechelany
a
France
b
Laboratoire de chimie physique des matériaux (LCPM), Plateforme de recherches et de
nanotechnologies, Faculté Des Sciences II, Fanar, Université Libanaise, Liban
c
Institut Charles Gerhardt de Montpellier, ICGM – UMR 5253, ENSCM, CNRS, Univ Montpellier,
Montpellier, France
CaCu3Ti4O12 (CCTO) ceramics showed good dielectric properties among the perovskite structures.
4 5
Several studies demonstrated that its high dielectric constant (10 -10 ) is stable for temperature
ranging from 100 K-600 K, without any phase transition. The mechanism responsible of this behavior
is not fully understand, it can be related to different reason due to a non-stoichiometric report of the
ceramic content or models based on oxygen loss(1). On the other hand the impedance spectroscopy
studies showed that the CCTO ceramics are electrically heterogeneous consisting at semiconducting
grains and insulating grain boundaries, these measurement suggesting an internal barrier layer (IBLC)
effect that could be a main reason to achieve a high dielectric constant for CCTO ceramics (2).
Despite the high permittivity, the problem is its high values of loss tangent (tanδ) so that many
investigations focused on doping CCTO ceramics with different ions (3-5) to adjust the electrical
properties on grains and grain boundaries. In this work a new strategy was used to improve the
dielectric properties by adding boron nitride nanosheets (BNN) into the CCTO ceramics to modify the
electrical response of grains and grains boundaries. BNNs have a similar structure of graphene in
which C atoms was alternatively substituted by B and N atoms. The properties of BNNs are due to its
high surface area, high thermal and chemical stabilities, large band gap, low dielectric constant, and
large thermal conductivity (6). We will present our first results concerning the preparation and
characterization CCTO@BNNs nanocomposites.
Figure 1: CCTO with Boron Nitride
[1]: A.Felix, V.Bezzon, M.Orlandi, D.Vengust, M.Spreitzer, E.Longo, D.Suvorov, J.Varela,

J.Eur.Ceram.Soc.2016
[2]: Ming Li, Derek C. Sinclair, Anthony R. West, J. Appl. Phys. 2011
[3]: J.Jumpatam, B.Putasaeng, N.Chanlek, P.Kidkhunthod,P.Thongbai, S.Maensiri, P.Chindaprasirt,
RSC Adv, 2017
[4]: N.Barman, P.Singh, C.Narayana, K. B. R. Varma, AIP.Adv, 2017
[5]: P. Thongbai, J.Jumpatam, B. Putasaeng, T.Yamwong, S.Maensiri, J. Appl. Phys. 2012
[6]: J. Biscarat, M. Bechelany, C. Pochat-Bohatier ,P. Miele, Nanoscale. 2015
202
NANOTECH-OR22

Correlation studies of nanoscale adhesion and friction using
mushroom-shaped and cylindrical pillar patterns of varying
physico-chemical characteristics

1 1, 2 1 1, 2 1, 3
Prashant PENDYALA, Hong Nam KIM, Sung-Wook YANG, Il-Joo CHO, Eui-Sung YOON *,

1
Center for BioMicrosystems, Korea Institute of Science and Technology (KIST), Seoul 02792,
Republic of Korea;
2
Division of Bio-Medical Science and Technology, KIST School, University of Science and
Technology, Seoul 02792, Republic of Korea,
3
Division of Nano & Information Technology, KIST School, University of Science and Technology,
Seoul 02792, Republic of Korea

Keywords: mushroom-shaped, adhesion, friction
Development of bio-inspired nanoscale anti-adhesive surfaces was difficult primarily due to the
limitations in fabrication techniques. Further, the correlation between adhesion and friction of such
surfaces required precise fabrication of structures with varying physico-chemical cues. In this work, we
used capillary-force lithography along with nano-drawing procedures to generate mushroom-shaped
and cylindrical nanoscale patterns with varying curvature, surface energy, hierarchy and pitch.
Adhesion and friction measurements were performed using a borosilicate ball tip of 5 um radius in
Bruker DI atomic force microscopy. Adhesion (pull-off) force was dependent on the curvature, surface
energy and density of patterns whereas friction force was predominantly controlled by the effective
lateral stiffness determined by the geometry and capillary forces. Interestingly, in contrast to the
previous studies, cylindrical and mushroom-shaped pillars exhibited similar adhesive characteristics
but very different friction characteristics. Importantly, a master curve that correlates the adhesion and
friction was observed in plot of adhesion vs. friction for two orders of magnitude of adhesion. The
slope of the master curve was related to the effective lateral stiffness and was independent of
curvature, material, surface energy, and pattern density. The results will help in understanding the
relation between adhesion and friction at nanoscale topographical interactions.

[1]. P. Pendyala, H.S. Grewal, H.N. Kim, I.J. Cho, E.S. Yoon. ACS Appl Mater Inter. 2016;
8(44):30590-600.
203
NANOTECH-OR25

Stable New Polymorph Gold and Silver Nanowires Fabricated in
Nanoscale Confinement

Seonhee Lee, Changdeuck bae, and Hyunjung Shin*

Department of Energy Science, Sungkyunkwan University, Suwon, Korea

Keywords: Au Nanowire, Ag Nanowire, nanoscale confinement, polymorph, photoelectrochemical
reduction, transmission electron microscopy
Polymorphism is a phenomenon that materials adopt more than two crystal structures without
compositional changes. The significance of polymorphism in material science is that the change of
crystal structure incudes the intrinsic material properties. Here we have synthesized high aspect-ratio
single crystalline Au and Ag nanowires having unusual polymorph, which have not been reported
before, by photoelectrochemical reduction method by using TiO2 nanotubes. The crystal structure of
Au and Ag polymorphs were identified as hexagonal non-close-packed (ncp-2H) structure and the
lattice parameters were calculated by XRD and TEM tilting experiment. Ncp-2H structure shows quite
large interplanar spacing between close-packed planes, (0001), like a graphite. The formation of ncp-
2H structure was closely related with the volume which the nucleation process occurs. It is considered
that the nanoscale confinement provides the comparable saddle points in their fee-energy minima.
Ncp-2H Au and Ag nanowires showed exceptional stability under ambient. Especially ncp-2H Au
nanowires were stable under intense electron beam irradiation, and also showed the thermal stability
up to 400 °C. Moreover, the resulting physical properties as a result of the corresponding electronic
structures change were investigated by comparing the optical properties of fcc and ncp-2H Au NWs.
[1]. S. Lee, C. Bae, J. Lee, S. Lee, S. H. Oh, J. Kim, G.-S. Park, H. S. Jung, H. Shin, Adv. Mater.
2018, (DOI: 10.1002/adma.201706261).
[2]. S. Lee, C. Bae, H. Shin, ACS Appl. Mater. Interfaces (under revision).
204
NANOTECH-OR29

Identification of the molecular bases of arthropod natural glues

1 1,2 1,2
Andrey ZAYTSEV, Mathilde ARQUE, Oliver BECERRA-GONZALEZ, Marianne
2 2 1 1 1
WEIDENHAUPT, Franz BRUCKERT, Rémy AGNIEL, Olivier GALLET, Cédric R. PICOT,
,1,2
Charlotte VENDRELY * .
1
ERRMECe, I-MAT FD4122, Université de Cergy-Pontoise, MIR, rue Descartes, 95031 Neuville sur
Oise Cedex, France.
2
Université Grenoble Alpes, CNRS, Grenoble INP, LMGP, F-38000 Grenoble, France

Keywords: protein self-assembly, adhesion, surfaces, biomaterial.
In our daily lives, all conventional man-made adhesives are petrochemical products, with major
drawbacks for biomaterials because of their toxicity and limited efficiency in wet conditions. The goal
of this project is to understand the chemical processes of arthropods natural glues effective in air
and/or in wet conditions. For these animals, the adhesive proteins have been identified and the
adhesion mechanism seems to be related to protein self-assembly on the surfaces. However, the
precise mechanism as well as the molecular basis of this process remain to be elucidated. The
adhesive proteins show particular sequences with repetitive architectures. Peptides have been used to
mimic the primary structure elements of the natural proteins. Their self-assembly and adsorption
processes have been investigated using various techniques including fluorescence spectroscopy,
atomic force microscopy and surface plasmon resonance. Different types of primary structure
elements could be discriminated within the natural protein sequences: some are important for the self-
assembly and the interactions to different material surfaces; whereas others seem not to be involved
in these mechanisms. The putative roles of these different types of primary structure elements are
discussed, in the context of the function of the proteins in the natural glue, as well as for future
applications in the biomedical domain.
205
NANOTECH-OR31

Development of an injectable cement allowing multiple drug

delivery for the treatment of breast cancer bone metastasis
a,b b a b a
Habib Belaid , Catherine Teyssier , David Cornu , Vincent Cavailles , Mikhael Bechelany
a
France
b
IRCM, Institut de Recherche en Cancérologie de Montpellier, INSERM U1194, Université
Montpellier, Montpellier F-34298, France
[email protected], https://ircm.fr/, www.iemm.univ-montp2.fr
Keywords: Injectable cement; Microspheres; Bone metastasis; Breast cancer; Drug delivery
Cancer is a tremendous health problem, and tens of millions of people are diagnosed with this disease
around the world every year. In breast cancer, bone metastasis cause considerable pain and high
patient morbidity. The treatment of bone is challenging due to bone repair, and patients are often
treated with implants such as passive artificial junctions. Calcium phosphate based cements (CPCs)
are often applied as bone substitute materials in orthopedics, due to their optimal bone defect filling
and their ability to allow natural bone growth. However, their use is still hindered because of their slow
in-vivo resorption rate.
A novel route presented in this work is based on a bio-inspired 3D material "scaffold" which mimics the
multi-scale structure of the bone and allows the controlled local release of anticancer drugs for the
optimal treatment of patients presenting bone metastasis. This innovative route is based on the
incorporation of degradable poly(lactic-co-glycolic acid)(PLGA) microspheres into the CPC. PLGA is
ideally suited, as this material is biocompatible and biodegradable, exhibits a wide range of erosion
times, and is FDA approved. The controlled porosity created by these microspheres allows a
modulation of the cement degradation time. Furthermore, PLGA microspheres are also used as
carriers for two drugs including raloxifene hydrochloride (RH) and alendronate (AL). Raloxifene
hydrochloride (RH) is a selective estrogen receptor modulator (SERM) indicated for the treatment and
the prevention of osteoporosis and breast cancer. Alendronate (AL) is a class of drugs similar to
natural pyrophosphate compounds, inhibiting bone resorption with a direct effect on osteoclast activity,
and increasing osteoblast proliferation and maturation. RH shows extremely poor bioavailability due to
its limited water solubility and extensive intestinal/hepatic first-pass metabolism, and only AL low
concentration can be actually incorporated in the bone via oral administration. The ultimate goal of this
work is therefore to develop a biomimetic and biodegradable injectable cement, allowing for both bone
regeneration and inhibition of breast cancer cell proliferation through the local release of osteogenic
and anticancer drugs.
We first achieved the loading of RH and AL within PLGA microspheres, which were then incorporated
into an injectable CPC. The physicochemical properties of the CPC scaffolds have been determined
using scanning electron microscopy, dynamic light scattering, granulometry, mercury porosimetry and
UV-spectrometry. The results showed that the microspheres were elongated and slightly less smooth
after the loading of RH and AL, depicting the successful encapsulation of the drugs. Encapsulation
efficiencies of 14% and 54% have been obtained for RH and AL respectively. Furthermore, SEM
analysis showed that the loaded microspheres were well incorporated in the CPC scaffold. Finally,
initial biological testing has been carried out in order to define the properties of the scaffolds. A cell
viability test using MG63 cells has also been conducted to determine the scaffold biocompatibility and
its effects on cell proliferation. The successful cell adhesion has been revealed by fluorescent
microscopy, and MG63 bone differentiation has been obtained as well, as determined by Alizarin red
staining and semi-quantitative RT-PCR.
These first results are therefore very promising and open prospects for bone metastasis treatment in
breast cancers.
206
NANOTECH-OR32

Characterisation of functional layers and biomolecular interactions

using Multi-Parametric Surface Plasmon Resonance (MP-SPR)
Radek Bombera, Annika Järvinen, Johana Kuncova-Kallio

BioNavis Ltd, Tampere, Finland, Corresponding author: [email protected]
Surface Plasmon Resonance is a biophysical surface technique that has been established for more than
20 years in Life Sciences research. This label-free and real-time analysis technique has been widely used in
measurements of biomolecular interactions and successfully applied in drug discovery processes. BioNavis Ltd.
has further developed and optimized the SPR technology to extend its application towards materials research.
While, traditional SPR set-up is limited to studies within a layer of around 150nm, our approach of Multi-
Parametric SPR (MP-SPR) overcomes such limitation. Indeed, MP-SPR technique combines wide angular
scanning and multiple wavelengths thus providing a unique possibility to assess functional layers from Ångströms
up to tens of microns. Therefore, MP-SPR enables characterization of a large variety of materials ranging from
thin films (such as graphene monolayer) and metal layers up to thicker coatings (nanocellulose, hydroxyapatite),
responsive polymers, nanoparticle assemblies and even live cells. The technology gives insight into the
properties of layers (thickness and refractive index) along with affinity and kinetic data on interactions with small
compounds, proteins and nanoparticles.
The unique optical configuration of MP-SPR enables direct measurement of kinetic parameters (kon, koff)
of the interactions and additionally provides calculation of layer refractive index (RI) and its thickness (d) without
prior knowledge of either parameter. Apart from applicability to a large variety of materials, our technology is
capable of detecting and separating bulk effect without reference channel. This feature is especially useful in
context of biomaterials, where coating varies across the surface and a proper reference is not available or for
studies of biological crude samples such as 100% serum. The performances of MP-SPR technique are
demonstrated in different measurements of biointerfaces such as: adsorption of polymers [1,2], antifouling
efficacy against serum [3], ionic liquids, virus-peptide interaction [4], conformation changes of electroswitchable
surfaces [5], cell adhesion on hydroxyapatite [6] and drug/nanoparticle uptake studies on living cells [7,8].
The MP-SPR method evidences good correlation with reference methods such as QCM, fluorescence
microscopy, AFM and Raman spectroscopy. The MP-SPR based characterization method for a wide variety of
biomaterials appears to be accurate and sensitive, especially for applications requiring both measurement of the
film properties and interactions with molecules or particles.
[1]. Niegelhell et al. Langmuir 2016, 32
[2]. Emilsson et al. ACS Applied Materials & Interfaces 2015, 7
[3]. Vuoriluoto et al. Journal of Physical Chemistry B, 2015, 119
[4]. Capasso et al. OncoImmunology, 2015
[5]. Malmström et al. Macromolecules, 2013, 46 (12)
[6]. Vilardell et al. Journal of Functional Biomaterials, 2016, 7 (23)
[7]. Viitala et.al., PLOS One, 2013, 8 (8)
[8]. Baghirov et al. PLOS One, 2016
Fig.1: Poly (acrylic acid) PAA polymer brushes swelling and Fig.2: Assessment of protein corona formation when loading
collapse caused by pH and electric potential change are serum onto liposomes.
measured in situ.
207
SMARTTECH-OR01

Development of a 3D printed scaffold allowing multiple drug

delivery for the treatment of bone metastasis in breast cancers
a,b b a b a
Habib Belaid , Catherine Teyssier , David Cornu , Vincent Cavailles , Mikhael Bechelany
a
France
b
[email protected], https://ircm.fr/, www.iemm.univ-montp2.fr
Keywords: 3D printing; Scaffolds; Bone metastasis; Breast cancer; Drug delivery
Breast cancer is the most common invasive cancer in women, and the second main cause of cancer
death in women. In metastatic breast cancer, cancer cells spread to the bones through the blood and
lymphatic system causing considerable pain and high patient morbidity. The treatment of bone is
challenging due to bone repair, and patients are often treated by implanting a passive artificial junction
in addition to a systemic chemotherapy treatment.
3D printing is emerging as a powerful tool for bone repair. Long-term bone regeneration of normal
anatomic structure, shape, and function is clinically important subsequent to fracture due to bone
trauma and tumor. 3D printing is providing the ability to print bone substitute materials or “scaffolds”
designed to mimic the extracellular matrix. The scaffolds need to be biocompatible and bioresorbable
with a highly porous and interconnected pore network to control the degradation and resorption rate.
They have a controlled shape and a suitable chemist surface for cell attachment, proliferation, and
differentiation. Finally, the mechanical properties have to match those of the tissues at the site of
implantation. For patients with bone metastasis, the scaffold may also allow the controlled and local
release of anticancer drugs. One of the strategies to deliver these drugs by the scaffolds is to
encapsulate them in microspheres such as Poly (lactic-co-glycolide) or PLGA microspheres which are
one of the acknowledged vehicles for drug release approved by FDA.
The aim of this work is the development and characterization of novel biomimetic biodegradable 3D
printing scaffolds allowing both bone regeneration and inhibition of breast cancer cell proliferation. To
this aim, PLGA microspheres have been loaded with Raloxifene hydrochloride (RH) which is a
selective estrogen receptor modulator (SERM) and Alendronate (AL) which is a bisphosphonate drug
used for the treatment of bone metastasis. These drugs show an extremely poor bioavailability via oral
administration thus justifying a local release. These microspheres have been incorporated into a 3D
scaffold fabricated using a Stereolithography 3D printer system with a Poly (propylene fumarate)
(PPF) photopolymer. PPF is an ultraviolet curable and biodegradable polymer with potential
applications for bone regeneration and excellent mechanical properties. The physicochemical
properties of the 3D printed scaffold have been determined using scanning electron microscopy,
dynamic light scattering, granulometry and UV-spectrometry. The results showed that the
microspheres were elongated and slightly less smooth after the loading of RH and AL, depicting the
successful encapsulation of the drugs. Encapsulation efficiencies of 14% and 54% were obtained for
RH and AL respectively. Furthermore, SEM analysis showed that the loaded microspheres were well
incorporated in the PPF scaffold. Finally, initial biological testing has been carried out in order to
confirm the effects of RH and AL on MCF7 cells proliferation. A cell viability test using MG63 cells has
been conducted to determine the scaffold biocompatibility and its effects on cell proliferation. The
successful cell adhesion was revealed by fluorescent microscopy, and MG63 bone differentiation was
monitored by Alizarin red staining and semi-quantitative RT-PCR.
These first results appear very promising and open prospects for bone metastasis treatment in breast
cancers.
208
SMARTTECH-OR03

Porous Silicon Optical Biosensors for Rapid Environmental

Monitoring of Trace Heavy Metals

1 2
Mike Bismuth, Giorgi Shtenberg,

1 Life Sciences and Nanotechnology, Bar Ilan University, Ramat-Gan, Israel;
2
Institute of Agricultural Engineering, ARO, The Volcani Center, Bet Dagan, Israel

Keywords: Heavy Metals, Optical Biosensors, Porous Si, Enzyme, Laccase, Horseradish Peroxidase
The proposed research is designed as a response to the important challenge of monitoring heavy
metal pollutants in the environment by developing a generic integrated biosensing platform for on-site
monitoring applications. Heavy metals are one of the most serious environmental pollution problems of
our time, specifically in developing countries, owing to its widespread in nature and threatening health
risk impacts to any living organisms. Long-term exposure causes serious physiological implications
requiring frequent determination in water, soil, agricultural and food samples. Environmental
authorities are constantly monitoring water quality by a range of chemical and biological methods to
ensure safe and secure water composition. Traditional methods of detection, based on laboratory
techniques, possess major on-site limitation (e.g., bulky equipment, tedious and complex preparation
protocols, off-line monitoring, low frequency data sampling and delay upon results availability)
revealing their inadequacy for real-time analysis. Thus, an early and rapid detection of heavy metals
followed by corrective and/or prevention actions can lead to reduction of the overall polluting impact to
safeguard public health. Herein, we have designed and fabricated a simple optical biosensing
platform, based on porous Silicon (PSi) nanostructures, a Fabry-Pérot thin film, for the detection and
quantification of metallic pollutants in aqueous media by enzymatic activity inhibition. First, we show a
general detection assay by immobilizing horseradish peroxidase (HRP) within the oxidized PSi
nanostructure and monitor its catalytic activity in real-time by reflective interferometric Fourier
transform spectroscopy. Optical studies reveal high specificity and sensitivity of the HRP-immobilized
+ 2+ 2+
PSi towards three metal ions (Ag >Pb >Cu ), with a detection limit range of 56-104 parts per billion
2+
(ppb). Next, we demonstrate this concept for specific detection of Cu ions (used as a model heavy
metal) by immobilizing Laccase, a multi-copper oxidase, within the oxidized PSi. The resulting
biosensor allows for specific detection and quantification of copper ions in real surface and ground
water samples (used for irrigation) by monitoring the Laccase relative activity. The optical biosensing
results are found to be in excellent agreement with those obtained by the gold standard analytical
technique (ICP-AES) for all water samples. Thus, the main advantage of the presented biosensing
concept is the ability to detect heavy metal ions, at environmentally relevant concentrations, using a
simple and portable experimental setup, while the specific biosensor design can be tailored by varying
the enzyme type.
Fig. 1: A schematic illustration of the enzymatic inhibition caused by heavy metals, revealing
the selectivity of enzyme binding site toward heavy metal ions.
209
SMARTTECH-OR04

Antibiotic Releasing Multilayers of Poly(2-isopropyl 2-oxazoline)

and Tannic Acid
1 1 1,2
Eda CAGLI, Esma UGUR, and Irem EREL-GOKTEPE, *
1
Department of Chemistry, Middle East Technical University, Ankara, TURKEY
2
Center of Excellence in Biomaterials and Tissue Engineering, Middle East Technical University,
Ankara, TURKEY
Keywords: Stimuli-responsive polymer, polyoxazoline, layer-by-layer films, antibiotic release
Polymer platforms releasing therapeutics via stimuli trigger is great of interest in treatment of infectious
diseases. Poly(2-alkyl-2-oxazoline)s, also called as pseudo-peptides due to their structural similarity to
polypeptides, display significant biological properties such as biocompatibility, nontoxicity, anti-fouling
behavior [1][2]. In this study, we prepared poly(2-isopropyl-2-oxazoline) (PIPOX) based multilayer
films and examined their potential for stimuli-triggered release of a broad range spectrum antibiotic,
Ciprofloxacin (CIP) from multilayer surface. PIPOX and Tannic Acid (TA) layer-by-layer films were
constructed at strongly acidic media (pH 2.5) and 25°C via hydrogen bonding interactions. CIP was
loaded into the multilayers at neutral conditions (pH 7.4) mainly through interactions within protonated
piperazinyl group of CIP and free phenolate groups of TA. CIP loaded PIPOX/TA films were found to
be stable in PBS up to 24 hours. CIP release from the surface was slightly greater at pH 6 than that at
pH 7.4 due to disruption of electrostatic interactions among CIP and TA as TA got protonated when
pH was decreased. In addition, CIP release from the surface was greater at 37°C than that at 25°C
due to lower critical solution temperature of PIPOX near body temperature resulting in possibly a
conformational rearrangement within the multilayers (Figure 1). Such multilayers, capable of releasing
antibiotic at slightly acidic conditions within a physiologically related temperature range are promising
due to local pH drops caused by infection in the body. Antibacterial activity of the multilayers against
Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus are currently under
investigation.
CIP
PIPOX
TA
˚
constructed at pH 2.5 25 C / pH 6 / 25 ˚C
postloaded with CIP at pH
7.4
pH 6 / 37 ˚C
Figure 1. CIP release from PIPOX/TA multilayers at 25 ֯◌ C and 37 ֯◌ C.
[1] Viegas TX, Bentley MD, Harris JM, Fang Z, Yoon K, Dizman B et al., Bioconjug Chem. 2011, 22,
976–986.
[2] De La Rosa VR, J Mater Sci Mater Med. 2014, 25, 1211–1225.
Acknowledgement: E.C. acknowledges the financial support of Center of Excellence in Biomaterials

and Tissue Engineering, Middle East Technical University for the conference.
210
SMARTTECH-OR05

The role of interface functionalization on self-healing and relaxation

properties of vitrimer nanocomposites

1 1 1 1
Isis CASTRO-CABRERA, Armand FAHS , Sophie BERLIOZ , Pascal CARRIERE*

1
Laboratoire MAPIEM (MAtériaux, Polymères, Interfaces et Environnement Marin), Université de
Toulon, Toulon, France.

Keywords : nanofibrilles cellulose, vitrimers composites
Vitrimers are a new kind of materials pioneered by Leibler [1]. The viscoelasticity of vitrimers is
characterized by two transition temperatures: glass transition temperature (Tg) and the topological
freezing transition temperature (Tv). In the case of vitrimers, while the exchangeable covalent bonds in
the network as i.e. reversible Diels-Alder bonds, are rearranged by different triggers (thermal, pH,
UV,…), the network integrity is maintained into the network. This integrity is not maintained for
reversible Diels-Alder bonds, which cannot be classified as a vitrimer material. Usually, Arrhenius law
assesses the viscosity behavior of vitrimer like chemical reactions where the reaction rate is controlled
by temperature. Vitrimers ongoing topic concerns mainly soft and non-structural materials because of
the focus on the self-healing properties with some exceptions [2].
Industrials developments of high-performance vitrimer materials with self-healing impose the study
relaxation properties of vitrimer composites. However, the influence of reinforcement particles on the
mechanical properties and relaxation of vitrimers has rarely been investigated. In the interphase
region, typically around hundreds of nanometers, the restricted mobility and the conformation
confinement induce an increase of the mechanical properties of nanocomposite materials. This
modifies the topological properties of dynamic networks. Legrand et al. suggested that the vitrimer
composites could fully relax stress by functionalization of fillers with the same exchangeable bonds as
the matrix. Nevertheless, relaxation rate is greatly retarded and the self-healing efficiency has not
been considered [3].
The objective of this pioneering study is to investigate this assertion by controlling the functionalization
of nanoparticles with or without dynamic covalent bonds. The vitrimer system studied is a disulfide
exchange bonds in a network made from epoxy resin and a dynamic diamine bringing the exchange
bonds as hardener.
Nano fibrillated cellulose was used as the reinforcement fibers whereby epoxy silane or amino silane
coupling agent in order to control respectively the interactions or the covalent coupling of the fiber with
the functional hardener. The mechanical and thermal properties of materials with different levels of
grafting were investigated by using both, dynamic mechanical analysis and differential scanning
calorimetry. The discussion will focus on the relationships between the reinforcement level and the
relaxation and self-healing properties of these vitrimers nanocomposites.

[1]. D. MONTARNAL, M. CAPELOT, F. TOURNILHAC, L. LEIBLER, Science, 2011, 334, 965-968
[2]. A. RUYZ DE LUZURIAGA, R. MARTIN, N. MARKAIDE, A. REKONDO, G. CABANERO, J.
RODRIGUEZ, I ; ODRIOZOLA, Mater Horiz., 2016, 3, 241-247
[3]. A. LEGRAND, C. SOULIE-ZIKOVIC, Macromolecules, 2016, 49, 5893-5902

211
SMARTTECH-OR06

Polymeric supramolecular transporters for nucleic acids delivery

1
Lilia CLIMA*,

1
“Petru Poni” Institute of Macromolecular Chemistry, Iasi, Romania
Keywords: drug delivery, supramolecular chemistry, self-assembly
Nucleic acids (gene therapy) have the unique potential to provide therapies for many targets that are
currently undruggable and to do so with higher success rates in clinical trials. Yet, it is still a difficult
problem to address in the gene therapy how the transfection efficiency of gene can be improved, so
that target gene could be delivered to the target sites of the organism efficiently and showing no toxic
and side effects. Some of the reasons are the inefficient transporter molecule (vector) used for
delivering nucleic acids, poor unloading into target cells, low activity, immune response, regulatory
issues and ethical concerns and commercialization [1, 2]. Our main strategy is the easy building and
self-generation of multifunctional nanostructures from commercially available or “easy to prepare”
units, which will further self-assemble in a complex, tuneable and multifunctional materials, suitable for
specific targeted gene delivery and by this to overcome some existing issues. On the other hand,
nucleic acids and target cells are highly variable and therefore, rational design is limited to a relatively
small number of components and a high number of synthetic steps, thus exploring dynamic chemistry
and combinatorial approach for building nucleic acid vectors will provide an facile method to build
large libraries of various compounds [3, 4]. In this communication, the preparation of llibraries of
polymeric micellar supramolecular assemblies based on pegylated squalene derivative linked with
linear polyethylene glycol and branched polyethyleneimine of various lengths through a multifunctional
core connector and testing as non-viral vectors for plasmid DNA delivery are reported. The correlation
of linear polyethylene glycol, in terms of length and ratio in the composition of vectors with the size
and stability of vectors and their nucleic acid binding affinity as well as transfection efficiency and
cytotoxicity was established.
This work was supported by Horizon 2020 WIDESPREAD 2-2014: ERA Chairs Project no 667387 and
a grant of the Romanian National Authority for Scientific Research and Innovation, CNCS/CCCDI –
UEFISCDI, project number PN-III-P3-3.6-H2020- 2016-0011, within PNCDI III.
[1]. C. E. Dunbar, K. A. High, J. K. Joung, D. B. Kohn, K. Ozawa, and M. Sadelain, Science, 2018,
359.
[2]. H. Yin, R. L. Kanasty, A. A. Eltoukhy, A. J. Vegas, J. R. Dorkin, and D. G. Anderson, Nat. Rev.
Genet., 2014, 15, 541-555.
[3]. Y. Zhang and M. Barboiu, ACS Omega, 2018, 3, 329-333.
[4]. R. Catana, M. Barboiu, I. Moleavin, L. Clima, A. Rotaru, E. L. Ursu, et al, Chem. Commun.,
2015, 51, 2021-2024.
212
SMARTTECH-OR07

Redox triggered peel-off of antifouling polymer layers for on

demand activation of surface patterns.

1 1 1 1
Julien DUPRÉ DE BAUBIGNY, Louise HESPEL, Emmanuel MARIE, Christophe TRIBET*,

1
Ecole Normale Supérieure - PSL Research University, Département de Chimie, CNRS UMR 8640
PASTEUR, Paris, France
*[email protected]

Keywords: stimuli-responsive materials, polymer brushes, redox-sensitive, adhesion.
Controlling surface interactions by adjustment of the redox potential is a convenient approach for
engineering specific layers on electrochemical devices, biosensors, and in general to achieve mild
chemical switch onto thin polymer films. On demand detachment of chains from the surface enables
1,2
the design of a diversity of functions including triggered catalysis, wetting, adhesion, etc. To achieve
robust functionalities, in particular in complex matrices such as biological fluids, these responsive
layers combine antifouling chains with redox-sensitive moieties. For instance, responsive SAM have
been implemented on metal-coated surfaces with poly(ethylene oxide) (biorepellent) strands mixed
with polymer-coupled peptides or enzymes introduced in adjusted amount as the bioactive
component. On non-metal surfaces, however, a demanding chemistry is needed to prepare similar
mixed layers, which precludes optimization of their properties by non-chemists.
We develop a straightforward method to functionalize most anionic surfaces (e.g. glass, plasma-
treated polystyrene or PDMS, ceramics, etc) with no need for expert surface chemistry. The method is
based on spontaneous adsorption of poly(lysine) (PLL) comb-like copolymers. Deposition of controlled
3
densities of active moieties is tunable by mixing functionalized and non-functionalized copolymers.
Our recent, yet unpublished, systems use redox-cleavable PLL-g-PEG copolymers to achieve on
demand detachment of surface strands, and to trigger either adhesion/wetting or deadhesion.
Cleavable disulfide bridges were introduced between the PEG, antifouling, lateral chains and the PLL
backbone (Figure 1). Functionalities, e.g. fluorophores or peptides, can be clicked on the top of the
PEG layer and then are released on demand upon exposure to mild reducing agents in water (Figure
1). Quantitative studies of the layer density (fluorescence, QCM-D measurements), kinetics of redox
release of polymers and control of zeta-potential will be presented. Application to triggered wetting and
to manage specific adhesion (e.g. mammal cells) are developed. This strategy is promising for coating
a surface in a simple way with various functionalities, and with a smart and local response with a
redox-stimulus.
Fig. 1: Redox-responsive coating based on cleavable PLL-g-PEG.
[1]. N. Abbott, C Gorman, G. Whitesides, Langmuir 1995, 11, 16-18 & J. Collman, N. Devaraj, T.
Eberspacher, C. Chidsey, Langmuir, 2006, 22, 2457-2464.
[2]. R. Inaba, A. Khademhosseini, H. Suzuki, J. Fukuda, Biomaterials, 2009, 30, 3573-3579
[3]. S.F.M. Dongen, J. Janvore, S.S. van Berkel, E. Marie, M. Piel, C. Tribet, Chemical Science,
2012, 3 (10), 3000-3006 & S.F.M. Dongen, P. Maiuri, E. Marie, C. Tribet, M. Piel, Advanced
Materials, 2013, 25 (12), 1687-1691
213
SMARTTECH-OR09

Compartments and cascades: a model reaction for complex
nanoscale systems
1 1 1 1
Andrea Belluati, Ioana Craciun, Juan Liu, Cornelia G. Palivan
Department of Chemistry, University of Basel, Mattenstrasse 24a 4058, Basel
Keywords: Compartments, uric acid, in vitro, cascade reaction.
Compartimentalization at the nanoscale is fundamental in nature, where the spatial segregation of

biochemical reactions within cells ensures optimal conditions for regulating metabolic pathways.
Here, we present a nature inspired approach to engineer enzymatic cascade reactions taking
place between separate vesicular nanocompartments, each containing one enzyme type. We
propose by the selected combination of enzymes, an efficient solution to detoxify the harmful
effect of uric acid and H2O2, associated with various pathologic conditions (e.g. gout and oxidative
stress). The two-step enzymatic cascade involves the fungal uricase (UOX) and horseradish
peroxidase (HRP) that are separately encapsulated within nanocompartments, equipped with a
channel porin to allow passage of substrates and products of each step of the reaction. We
established the molecular factors affecting the efficiency of the overall reaction, and the protective
role of the compartments. Interestingly, the cascade reaction between two separate
nanocompartments was as efficient as for free enzymes in complex media, such as human serum.
Addition of the tandem catalytic nanocompartments to cells exposed to uric acid provided
simultaneous detoxification of uric acid and H2O2 whilst the nanocompartments were non toxic for
cells. Such catalytic nanocompartments can be used as a platform for understanding fundamental
factors affecting intracellular communication and introduce non-native metabolic reactions to
living systems for therapeutic applications.
Fig. 1: the concerted action of UOX- and HRP-loaded polymersomes transforms uric acid
and produces the fluorescent resorufin
[1].Palivan, C. G.; Goers, R.; Najer, A.; Zhang, X.; Car, A.; Meier, W., Chem. Soc. Rev. 2016, 45,
377-411.
[2]. P. Tanner, O. Onaca, V. Balasubramanian, W. Meier, C. G. Palivan Chem. Eur. J, 2011, 17,
4552-4560.
214
SMARTTECH-OR10

Metallo-Supramolecular Polymer: Stimuli-Responsive Properties
and Smart Window Device Application

Masayoshi HIGUCHI*

National Institute for Materials Science, 1-1 Namiki, Tsukuba 305-0044, Japan

Keywords: metallo-supramolecular polymer, stimuli-responsive, electrochromism, smart window
Metallo-supramolecular polymers are synthesized by the complexation of metal ions and multitopic
organic ligands (Fig. 1). The polymers are expected to show unique electronic and optical properties
based on the electronic interaction between the metal and ligand. We investigate the stimuli-
responsive properties of polymers [1]. In this presentation we report the electrochromic properties and
smart window device application.
Metal ion
Inorganic
Organic ligand Metallo-supramolecular polymer

Fig. 1: Synthesis of metallo-supramolecular polymer
Fe(II)-based metallo-supramolecular polymer (polyFe) was prepared by 1:1 complexation of Fe(II)

acetate and bis(terpyridyl)benzene in acetic acid. The obtained polymer has blue color due to the
metal-to-ligand charge transfer (MLCT) absorption. During electrochemical measurement, we found
reversible color change of the polymer film (Fig. 2). The blue color disappeared upon applying an
+
oxidative potential higher than the redox potential (0.77 V vs Ag/Ag ) of iron between Fe(II) and Fe(III).
This result indicates that the oxidation of Fe(II) to Fe(III) causes disappearance of the MLCT
absorption in the polymer. The electrochromism is very stable and we confirmed cycle stability more
than 100,000 time.
0 V 1 V
Fig. 2: Electrochromism of polyFe
We successfully fabricated solid-state devices using the metallo-supramolecular polymer. We

prepared the polymer film on an ITO glass electrode and pasted a gel electrolyte on it, then cover with
another ITO glass electrode. This device is applicable for sunlight adjustable glass (smart window),
which will contribute reducing energy consumption of air-conditioning in our rooms.
Acknowledgement: this research is financially supported by JST-CREST (grand No. ).
[1]. M. Higuchi, J. Mater. Chem. C 2014, 2, 9331-9341 (Feature article).
215
SMARTTECH-OR11

Supported lipid monolayer with unprecedented mechanical and

dielectric properties: Application to ISFET sensors
(1) (4) (1) (1) (2)
Volkan Kilinc , Tin Nguy , Sebastien Lamant , Frédéric Brunel , Catherine Henry-de-Villeneuve ,
(3) (1) (4) (1) (1)
Guillaume Monier , Matthieu Petit , Yutaka Wakayama , Jean-Manuel Raimundo , Anne Charrier*
(1)
CINaM, Aix Marseille Université, CNRS, Campus de Luminy, 13009 Marseille, France
(2)
PMC, Ecole Polytechnique,91128 Palaiseau, France.
(3)
Institut Pascal, 4 Avenue Blaise Pascal, 63178 Aubière, France
(4)
NIMS, Tsukuba, Japan
Keywords: Lipid layers, Mechanical and dielectric properties, Transistors, Detection of ions
The development of sensors with low limit of detection and a specificity that can be easily tuned is still
a challenge in the field of sensors.
We present an original platform constituted of an engineered lipid monolayer which is used as the
active sensitive layer and as ultra-thin gate dielectric in field effect transistor sensors. Supported lipid
layers, with thicknesses of a few nanometers indeed constitute good candidates. In living cells lipid
membranes are known to constitute natural insulators which play an efficient role as barrier to both
ionic and electronic transport across the membrane, associated with an electrical resistance of the
order of several giga-Ohms in magnitude. However, despite excellent insulating properties, lipid
bilayers and even more lipid monolayers have been poorly exploited in devices due to their inherent
instability under application of an electric field, leading to damages caused mainly by an
electroporation process occurring at low electric field. Furthermore a lack of mechanical stability is
often observed.
We show that the mechanical and chemical stability of lipid layers as well as their dielectric
performances can be improved by changing the molecular structure of the lipids and by achieving
intra-chain reticulations within the layer, and that surprisingly both these properties are correlated. In
fact such reticulated layers with a thickness of 2.5 nm only have a direct dielectric breakdown
occurring at ~30 MV/cm, i.e. much higher than for a silicon oxide layer of similar thickness.
We show that ones the lipid monolayer on the
transistor channel the specificity of the sensor
given by the grafting of probes to the lipids can
be tuned using simple procedure making our
sensor extremely versatile.
As a proof of concept, we present here different
sensors that were developed for the detection of
3+, 2+ +
Fe Cu and Cs ions using different materials,
inorganic transistors with silicon channel and
organic transistors with a Poly(3-hethyl)thiophen
as channel, and different types of probes:
derivatives of γ-pyrone, Di-picolylamine, and
calixarene.
Our sensors present good specificities with
exceptional low limit of detection down to the
Figure 1: Transistor using a lipid sub-femtomolar range, sensitivity up to 90
monolayer as gate dielectric and a tunable mV/decade and a linear response over more
probe for the specificity. than 8 decades.
[1] Langmuir 26, 2538-2543 (2010). Patent: FR2983637/WO2013083490A1. Langmuir 27, 13643-13647 (2011).
J. Phys. Chem. B 116, 7190-7195 (2012). J. Mat. Chem. B 1, 443-446 (2013). Biosens. Bioelect. 54, 571-577
(2014). Anal. Chem.(88) 3804-3809 (2016). Patent: PCT/EP2016/074569. Adv. Func. Mat. (2018, under revision)
Funding: ANR-16-JTIC-0003-01 and SATT-Sud Est under contract N°147680.
216
SMARTTECH-OR12

pH-Responsive Mesoporous Silica Nanoparticles for Combination

Cancer Therapy

1,2 1 2 1
Albane BIRAULT*, Carole CARCEL, John BARTLETT, Michel WONG CHI MAN

1
Institut Charles Gerhardt Montpellier UMR 5253, CNRS-ENSCM-UM, AM2N, 8 rue de l’Ecole
Normale 34296, Montpellier, France (* email: [email protected])
2
Faculty of Science, Health, Education and Engineering, University of the Sunshine Coast, Sunshine
Coast, Australia

Keywords: Mesoporous Silica Nanoparticles, Sol-Gel process, Advanced Functionnalized Materials,
Autonomous Drug Delivery System, Cancer Therapy.
In the past decades, several smart nanomaterials have been developed particularly as drug
delivery systems for application in medical fields. Appropriately designed drug carriers with controlled
delivery triggered by stimuli, without premature release, to the targeted cells can overcome some
issues of conventional therapy and enhance the therapeutic performance of a given drug. Among
several strategies, mesoporous silica nanoparticles (MSN) appear as one of the most promising drug
carrier.
[1]
Following our recent reports , we describe here the preparation of new hybrid silica
nanoparticles as pH-operating nanomachines, and for the first time, with a cytotoxic stopper derived
from the anticancer drug 5-fluorouracil (5-FU). The novelty and the main strengths of these SNP are
that (1) the stopper is itself a drug-effective molecule, (2) other drugs can be introduced and blocked
by the stopper inside the mesopores and (3) due to the acidic pH-sensitivity of these MSN, a
completely autonomous drug delivery is achieved directly in the targeted cancer cells. Indeed, due to
EPR effect, these MSN are endocytosed in the infected cells to the acidic lysosome compartment to
deliver, without premature leakage, drugs from the pores (in this work, camptothecin) and from the
caps (5-FU) allowing a multi-therapy process. The highly significant multi-drug delivery performance of
these new MSN, investigated in vitro,
will be presented.
Fig. 1: MSN as autonomous drug delivery system with pH-sensitive and cytotoxic cap
[1]. L. Fertier, C. Théron, C. Carcel, P. Trens, M. Wong Chi Man, Chem. Mater., 2011, 23, 2100-2106.
b) S. Giret, C. Théron, A. Gallud, M. Maynadier, M. Gary-Bobo, M. Garcia, M. Wong Chi Man, C.
Carcel, Chem. Eur. J., 2013, 19, 12806-12814.

217
SMARTTECH-OR13

Novel Surfactant made of plants from the United Arab Emirates to

remove zinc from wastewater
Omar CHALAAL, Hameed Muhamad, Zainab AKHTER, Archana THOMAS, Maha AJMAL
Abu Dhabi University,AbuDhabi, United Arab Emirates
The use of readily available natural materials as adsorbents of heavy metals from
industrial wastewaters is investigated. Metallic ions like Zn are some of the most difficult
contaminants to remove from the aqueous streams in the environment. This research
proposes a novel process for removal of this element from wastewater using natural
surfactant extracted from plants collected from the United Arab Emirates environment.
The proposed technique could be used at low cost and with great efficiency in the
purification of contaminated water. The method used in this research was developed in
order to develop a comprehensive technique that reduces the heavy metal concentration
to an acceptable level. The surfactant will be tested in a bubble column. The foam will be
collected and analyzed using ICP. Furthermore, the stability of the foam will be
investigated.
218
SMARTTECH-OR15

Enzymatic transformation of biopolymers to produce
nanohydrogels as surface modifiers and slow release devices for
bioactive substances

1
Annie Chimphango,
Process Engineering Department, Stellenbosch University , Stellenbosch 7600, South Africa;

Keywords: Biopolymers, arabinoxylan, glucuronoxylan, nano-hydrogels, enzymes, encapsulation,
surface modification, slow release device
Biopolymers from biomass have potential for production of biobased hydrogels with diversified
applications including encapsulation matrices and surface modifications depending on mode of
transformation. The aforementioned applications are based on the alteration of the degree and pattern
of substitution on the hemicelluloses backbone and the Inherent interaction between hemicelluloses
and cellulose in plant cell wall matrix, respectively. Biobased nano-hydrogels formed by modification of
structural properties of hemicelluloses using enzymatic and chemical methods were evaluated for their
application as encapsulation matrices for slow release delivery devices of gallic acid and as surface
modifiers for cellulosic materials. The hemicelluloses, in particular, glucuronoxylan from beechwood
and arabinoxylans from wheat bran were modified through enzymatic removal of 4-O-methyl-
glucuronic acid and arabinose substituents using α-D-glucuronidase and recombinant α-L-
arabinofuranosidase (AbfB), respectively. The performances of the enzymatically modified
hemicelluloses as slow release devices and as surface modifiers were compared with chemically
modified hemicelluloses (based on coacervation effect using NaOH and CH3COOH) . Gallic acid
(GA) that requires encapsulation in a hydrogel because of low-bioavailability and unpleasant taste
was used as a model bioactive substance. Nano-hydrogel particle size distribution, surface charge,
GA encapsulation capacity, GA antioxidant capacity retention and release pattern determined the
functionality of the hydrogels as slow release device. In-situ enzymatically produced nano-hydrogels
exhibited narrow particle size distribution and higher ability preserve anti-oxidant capacity (91%)
during encapsulation and release of the gallic acid over 48 h. The enzymatically formed
nanohydrogels outperformance over the chemically formed hydrogels as slow release devices for GA
was attributed to customised modification, in non-toxic conditions, of the wheat arabinoxylans by the
recombinant α-L-arabinofuranosidase (AbfB). The combined use of wheat-arabinoxylans and
enzymatic modification method provides an effective green method for producing biobased slow
release devices for sensitive bioactive substances. Similarly, in cellulosic surface modification, in-situ
enzyme aided glucuronoxylan adsorption method exhibited highest adsorption capacity. However, the
highest adsorption was evident on bleached pulp followed by filter paper and pure cellulose.
Therefore, enzymatic aided modification and adsorption is a potential non-toxic way of diversifying
surface and functional properties of the cellulosic materials. The use of the enzymes demonstrated in
the two applications would allow a one-stop process where combined nano-hemicellulose nano-
hydrogel production, cellulose surface modification and encapsulation of bioactive substances would
occur, thus, broadening the application of biopolymers.

219
SMARTTECH-OR16

Mussel-bioinspired polydopamine coated coccoliths as novel

therapeutic carriers

1 2 1
Mihai Lomora, David Shumate, Abhay Pandit*,

1
Centre for Research in Medical Devices (CÚRAM), National University of Ireland, Galway, Ireland
2
Georgia Institute of Technology, Atlanta, Georgia

Keywords: coccoliths, polydopamine, therapeutic carriers
Novel therapeutic carriers are continuously sought to overcome the limitations of current conventional
drug delivery therapies, such as poor entrapment efficiency or stability, toxicity, harmful degradation
1,2
products or high costs. The exploitation of coccoliths as therapeutic carriers offers essential
3
advantages, such as higher surface area and a readily available intricate mineralized morphology. As
compared to other similar composition-based particulate drug delivery systems (e.g. porous CaCO3
microparticles), Emiliana Huxleyi extracted coccoliths provides almost five times higher surface area,
4
and thus increased enzyme immobilisation (i.e. glucose oxidase and uricase) with preserved activity.
Therefore, coccoliths – elementary organisms to grow and support in artificial culture – can be easily
functionalized: i) in vitro, by their simple immersion in a solution containing biomacromolecules (e.g.
polydopamine, enzymes, flavonoids), or ii) during their in vivo culturing, by the addition of
ions/molecules of interest to their growth media. Moreover, material deposition, such as
polydopamine, onto their surface leads to the design of coccolith replicas. Polydopamine was chosen
as a bioinspired material with an excellent ability for post-functionalization, in addition to its
5
antibacterial, photo-thermal, and antioxidant properties. Our strategy is for the first time establishing a
novel platform based on polydopamine coated coccoliths as an ideal scaffold for the development of
novel and efficient therapeutic carriers.
Fig. 1: Transmission electron micrographs of coccoliths, polydopamine coated coccoliths, and

coccolith replica
[1]. J. F. Coelho, P. C. Ferreira, P. Alves, R. Cordeiro, A. C. Fonseca, J. R. Góis and M. H. Gil, EPMA
journal, 2010, 1, 164-209.
[2]. K. Kita, C. Dittrich, Expert Opin. Drug Deliv, 2011, 8, 329-342.
[3]. A. V. Skeffington, A. Scheffel, Current Opinion in Biotechnology, 2018, 49, 57-63.
[4]. H. Takano, E. Manabe, M. Hirano, M. Okazaki, J. G. Burgess, N. Nakamura and T.
Matsunaga, Applied Biochemistry and Biotechnology, 1993, 39, 239-247.
[5]. J. H. Ryu, P. B. Messersmith, H. Lee, ACS Appl. Mater. Interfaces, 2018, 10, 7523-7540.
Acknowledgment: This publication has emanated from research supported in part by a Swiss
National Science Foundation (SNSF) Early Postdoc Mobility Fellowship and by a research grant from
Science Foundation Ireland (SFI) and is co-funded under the European Regional Development Fund
under Grant Number 13/RC/2073.
220
SMARTTECH-OR17

Mixed AD Layers of Poly(lysine)-based Copolymers to Dynamically

Control Cell Adhesion/Migration

1, * 1 1 1 1
E. Marie , L. Hespel , F. Dalier , D. Zanchi , C. Tribet

1
PASTEUR, Département de chimie, École normale supérieure, PSL Research University, Sorbonne
Universités, UPMC Univ. Paris 06, CNRS, 75005 Paris, France;

Keywords: Polymer brush, responsive polymers, cell adhesion/migration, PLL copolymer
Current challenges in tissue engineering and cell biology often require control over when and where
cells can attach, migrate, or proliferate. In addition, it’s highly desirable to allow a dynamic control of
the cell-substrate interactions; to this aim, surface properties of the substrate should be switchable by
localized non toxic stimuli. In this context, stimuli responsive polymer brushes are exiting tools
although highly demanding surface chemistry is often required.
We explore here a straightforward method to functionalize anionic surfaces with controlled densities of
diverse polymer grafts and applied it to modulate specific and non-specific adhesion/deadhesion
patterns of mammalian cells via stimuli-triggered properties. It relies on tight spontaneous adsorption
of comb-like polycationic derivatives of poly(Lysine) (PLL). We studied PLL grafted with either
polyethylene oxide (PEO) reactive strands [1], or temperature-responsive ones (poly(N-
isopropylacrylamide strands, PNIPAM)[2-5]. Surface properties have been carefully analyzed by AFM,
quartz crystal microbalance, and particle capture experiments. Both nonspecific and specific
interactions have been considered. Examples of applications on the thermal control of capture of
particles [2, 5], dynamic modulation of cell adhesion/migration [3], and kinetics of coagulation [4] will
be discussed.
Fig.1: Examples of mixed brush based on PLL-PEG and thermo-responsive PLL-NIPAM
[1]. S. F. M. van Dongen, P. Maiuri, E. Marie, C. Tribet, M. Piel, Advanced Materials, 2013, 25(12),
1687–16911
[2]. F. Dalier, F. Eghiaian, S. Scheuring, E. Marie, C. Tribet, Biomacromolecules, 2016, 17(5), 1727-
1736.
[3]. F. Dalier, G. V. Dubacheva, M. Coniel, D. Zanchi, , A. Galtayries, M. Piel, E. Marie, C. Tribet, ACS
Applied Materials &Interfaces, 2018, 10 (3), 2253–2258.
[4]. J. Malinge, F. Mousseau, D. Zanchi, G. Brun, C. Tribet, E.; Marie, Journal of Colloid and Interface
Science, 2016, 461(1), 50-55.
[5]. G. Boniello, C. Tribet, E. Marie, V. Croquette, D. Zanchi Physical Review E, 2018, E 97, 012609.
221
SMARTTECH-OR18

New delivery system for crop protection based on biosourced
molecularly imprinted polymers

1 1 1 1 1
Nicolas LE GOFF, Isabelle FOMBA, Elise PROST, Franck MERLIER, Karsten HAUPT , Antoine
2 1
FAYEULLE, Aude FALCIMAIGNE-CORDIN*,
1
Sorbonne University, Université de technologie de Compiègne, Enzymatic and Cellular Engineering,
Centre de recherche Royallieu - CS 60 319, 60 203 Compiègne cedex
2
Sorbonne University, Université de technologie de Compiègne, ESCOM, EA 4297 TIMR, Centre de
recherche Royallieu - CS 60 319, 60 203 Compiègne cedex
Keywords: molecularly imprinted polymers, biosourced monomers, delivery systems
The extensive use of chemical pesticides has become a major environmental and health concern,
contaminating environmental compartments with high reminiscent period and showing toxicity for
mammalians. However, pest management remains a major concern of modern agricultural industry.
Biopesticides have attracted great interest to compensate the use of chemical phytosanitary products.
Resveratrol is a natural polyphenol of the stilbene family that matches all the biopesticides criteria. It is
implicated in plant defense mechanisms against several stresses (UV-light, physical damages,
phytopathogen attacks). It has also been widely described for its interesting antioxidant properties, as
an anti-aging, anti-cancer, anti-inflammatory and cardioprotective agent [1, 2]. Thus, resveratrol is a
high-value compound for cosmetic, nutraceutic and pharmaceutics industries [3]. However, this
molecule is sensitive to light, extreme pH, high temperatures, resulting in loss of biological activities
[4]. The aim of our work is to design a smart polymeric delivery system based on molecular imprinting
technology to improve the environmental stability and efficiency of biopesticides [5]. We focus here on
the synthesis of biosourced Molecularly Imprinted Polymers (MIPs) as delivery systems for resveratrol
as a biopesticide to fight against common fungal phytopathogens of crops [6]. This study presents the
screening of functional monomers for the MIPs design, the effect of the substitution of ethylene glycol
dimethacrylate EGDMA, a petro chemistry derivative cross-linker commonly used in imprinting
technology, by a biosourced and sustainable monomer and the MIPs application as biopesticide
delivery system to inhibit phytopathogen development.
[1] S. S. Kulkarni, C. Cantó, BBA-Mol. Basis Dis. 2015, 1852, 1114-1123

[2] A. Amri, J.C. Chaumeil, S. Sfar, C. Charrueau, J. Control. Release. 2012, 158, 182-193
[3] G. Davidov-Pardo, D. J. McClements, Trends Food Sci. Tech. 2014, 38, 88-103
[4] Š. Zupancic, Z. Lavric, J. Kristl, Eur. J. Pharm. Biopharm. 2015, 93, 196-204
[5] L. J. Schwarz, B. Danylec, S. J. Harris, R. I. Boysen, M. T.W. Hearn, J. Chromatog. A. 2011, 1218,
2189–2195
[6] P. Luliński, Mat. Sci. Eng. C. 2017, 76, 1344–1353
222
SMARTTECH-OR19

PVA-based polymer micelles for ice recrystallization inhibition

1,2 1,3 1,3
Christian C. M. SPRONCKEN, Romà SURÍS-VALLS, Hande E. CINGIL, Christophe
4 1,3,
DETREMBLEUR, Ilja K. VOETS *

1
Laboratory of Self-Organizing Soft Matter and Institute for Complex Molecular Systems, Eindhoven
University of Technology, The Netherlands;
2
Laboratory of Physical Chemistry, Eindhoven University of Technology, The Netherlands
3
Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, The
Netherlands
4
Center for Education and Research on Macromolecules, University of Liège, Belgium
Keywords: bio-inspired functional materials, polyelectrolytes, ice recrystallization inhibition, polymer

assembly, micelles
Various complications arise due to ice crystal formation and growth on different types of surfaces.
Current solutions to remove ice from car windshields and airplane exteriors consist of toxic and
flammable de-icing fluids. The need to reduce the amounts of harmful glycols and alcohols in anti-icing
formulations for health and environmental concerns motivated us to study alternatives that can slow
the growth of ice crystals at very low concentration. We are inspired by nature’s way of tackling ice
growth: antifreeze proteins that inhibit ice recrystallization (IRI) at nM concentrations and thereby help
organisms to survive subzero temperatures. Production of synthetic mimics is complicated and
expensive. However, poly(vinyl alcohol) (PVA), which can be produced in high amounts at low cost,
shows remarkable IRI activity. Recently, it was shown that block copolymerization of PVA had no
adverse effect on IRI activity [1], while random copolymerization led to a decrease of activity [2]. With
this in mind, we use a block copolymer of poly(vinyl alcohol) and anionic poly(acrylic acid) (PVA273-b-
PAA353), mixed in aqueous solution with the cationic homopolymer poly(N-methyl-4-vinylpyridinium
iodide) (P4VMP233), to produce complex coacervate core micelles (C3Ms, Fig. 1). We first confirm the
formation of C3Ms by static (SLS) and dynamic light scattering (DLS) and optimize the conditions
(concentration, salt, mixing ratio). Then, we quantify the IRI activity of these PVA-C3Ms. To this end,
we conduct sucrose sandwich assays to accurately determine the ice growth rate constants as a
function of PVA concentration. We find an IRI efficacy of 0.33 mM of PVA monomer, comparable to
that of linear PVA homopolymer and grafted bottlebrushes of PVA, as studied previously in the group
[3]. These results shed new light on the design of polymeric anti-icing materials.
Fig. 1: Complex coacervate core micelles are prepared by mixing poly(vinyl alcohol)-block-
poly(acrylic acid) and poly(N-methyl-4-vinylpyridinium iodide) in aqueous solution at pH 10.5.
-3
From 10 M monomeric concentration and up, the poly(vinyl alcohol) blocks the growth of ice
crystals in the solution.
[1] Congdon, T. R., Notman, R. & Gibson, M. I. Biomacromolecules 2016, 17, 3033–3039
[2] Congdon, T., Notman, R. & Gibson, M. I. Biomacromolecules 2013, 14, 1578–1586
[3] Olijve, L. L. C., Hendrix, M. M. R. M. & Voets, I. K. Macromol. Chem. Phys. 2016, 217, 951–
958
223
SMARTTECH-OR20

Stretching of biosourced polyethylene 2,5-furandicarboxylate above
its glass transition and associated microstructural development

1,2* 1 1 2 2 3 3 3
E.Forestier , C.Combeaud , N.Billon , N.Guigo , N.Sbirrazzuoli , M. Derrien , M.Sandrini , H.Port ,
4
H.A Visser
1
Mines-Paristech, PSL-Research University, CEMEF, CNRS UMR 7635, Sophia-Antipolis (France)
2
University of Nice Sophia Antipolis, ICN, CNRS UMR 7336, Nice (France)
3
Sidel, Octeville-sur-Mer (France)
4
Avantium Chemicals B.V., Zekeringstraat 29, 1014 BV, Amsterdam (The Netherlands)
Keywords: polyethylene(2,5-furandicarboxylate), PEF, stretching, strain induced crystallization (SIC),

bottles blowing

Poly(ethylene 2,5-furandicarboxylate), called “PEF”, is a new biosourced polymer, a bio-based
polyester, issuing from esterification reaction of bio ethylene glycol (EG) and 2,5-furandicarboxylic acid
(FDCA). It has gained interest the last few years, because it is now considered as the potential
successor of poly(ethylene terephthalate) or “PET”. Currently, the behaviour of PET during industrial
stretching and its microstructural development has been investigated [1,2]. On the contrary, thermo-
mechanical behaviour of PEF has not been much explored as well as its microstructural development
during uniaxial and biaxial stretching [3,4]. The purpose of this communication is to draw a parallel
between PET and PEF mechanical behaviours and the way the two polyesters develops an organized
microstructure
PET comes from the petrochemistry and is widely used in packaging applications and especially in
bottles packaging. In industry, bottles are formed according to ISBM process (Injection Stretch Blow
Molding). During this process, the material is first stretched above its glass transition and then blown
against a cooled mold. At the laboratory scale, this process is reproduced by combining uniaxial and
biaxial stretching in the material rubbery-like state (Tg=75°C for PET). Then, it can be easily stretched
until stretching ratios in the order of magnitude of 2 to 4 (or 2x2 to 4x4 in bi-axial conditions). PEF
also presents a glass transition at 85°C and has the ability to be stretched to higher draw ratio than
PET [4].
For both PET and PEF taken from their amorphous state, the material will become textured and its
microstructure is going to change. From a mechanical point of view, strain hardening can be clearly
observed. It results from the formation of a periodic order (or mesophase) which can lead to a
crystalline structure. The formation of the microstructure is closely related to two main factors: the
temperature (or strain rate if time/temperature equivalence is verified) and the way the material is
cooled down after stretching. These two parameters are key points regarding the final microstructure
organization and also its stability in time. The microstructural stability will induce a dimensional stability
of the deformed material which is crucial for thermoforming or blowing applications.
As a result, thanks to stretching, the new material owns improved thermo-mechanical and barrier
properties. All the final properties of a bottle result from the way the microstructure is locally organized.
Along the bottle, microstructure may present different organizations because of different solicitations
modes induced by the process itself. A focus will be made on these new properties relative to both
PET and PEF.
This work is supported by ADEME, in collaboration with two laboratories: CEMEF (Center of Material
Forming) and ICN (Institute of Chemistry of Nice). Two companies are also involved : Sidel (France)
and Synvina (the Netherlands).
[1] E. Gorlier, Agassant J-F., Haudin J-M., Billon N., “Experimental and theoretical study of uniaxial
deformation of amorphous poly(ethylene terephthalate) above glass transition temperature”, Plastics,
Rubber and Composites, Vol 30, no. 2, pp 48-55, 2001
[2] E. Gorlier, J-M. Haudin, and N. Billon, “Strain-induced crystallisation in bulk amorphous PET under
uni-axial loading,” Polymer, vol. 42, no. 23, pp. 9541–9549, 2001.
[3] G. Stoclet, J.M. Lefebvre, B. Yeniad, G. Gobius du Sart, S. de Vos, On the strain-induced structural
evolution of Poly(ethylene-2,5-furanoate) upon uniaxial stretching: An in-situ SAXS-WAXS study,
Polymer. (n.d.). doi:10.1016/j.polymer.2017.11.071.
[4] J.G. van Berkel, N. Guigo, J.J. Kolstad, N. Sbirrazzuoli, Bi-axial Orientation of Poly(ethylene 2,5-
furandicarboxylate): An Explorative Study, Macromol. Mater. Eng. (2018) 1700507.
224
SMARTTECH-OR22

Pectin aerogels: structure-properties correlations and use for drug
controlled-release
1 2 2 2
Sophie GROULT, Gabriela PRICOPE, Dragos PEPTANARIU, Diana CIOLACU, Tatiana
1
BUDTOVA*,
1
Center for Materials Forming - CEMEF, MINES ParisTech, PSL Research University, UMR CNRS
7635, CS 10207, 06904 Sophia Antipolis, France
2
“Petru Poni” Institute of Macromolecular Chemistry, 41A, Grigore Ghica Voda Alley, 700487 Iasi,
Romania
Keywords: Aerogel, Pectin, Structural properties, Drug controlled-release
Aerogels are lightweight materials with outstanding structural properties as pores’ high surface area
and open porosity, suitable for loading active compounds. Using polysaccharides like pectin to
produce bio-based aerogels is especially attractive due to their biodegradability and biocompatibility,
essential for food and biomedical applications.
The goal of our work was to understand the influence of preparation conditions on pectin aerogels’
morphology and properties. Their potential as drug delivery systems was evaluated using theophylline
as the drug model. Aerogels were prepared by polymer dissolution followed by coagulation in ethanol
and drying with supercritical CO2. Polymer concentration, solution pH and presence of divalent ions
were varied to tune pectin gelation mechanism and the state of matter (solution or gel). Drug was
loaded in a wet pectin matrix via impregnation in ethanol and their in vitro release in liquid media was
studied by spectrophotometric measurements (Figure 1). The influence of preparation conditions on
pectin aerogels’ density, specific surface area, morphology and drug release kinetics will be presented
and discussed.
We also demonstrated that pectin aerogels are non-cytotoxic materials, using MTS assays to
determine relative cell viability of normal human dermal fibroblasts cultures. Pectin aerogels are
promising biocompatible and degradable carriers for drug delivery systems.

Fig. 1: Use of pectin-aerogel for drug controlled-release in gastric / intestinal media

Acknowledgements:
The work was performed within “BIOGELS” project in the frame of Programme Hubert Curien-
Brancusi cooperation grant sponsored by Campus France and CNCS - UEFISCDI, Romania (PN-III-
P3-3.1-PM-RO). Authors are grateful to Cargill for providing pectin. We thank Pierre Ilbizian (PERSEE,
Mines ParisTech) for supercritical drying.
225
SMARTTECH-OR23

The structural and morphological controlling of Polycaprolactone

microspheres via electrospraying and selecting green solvent

1, 2 1, 2 1, 2
Shengchang ZHANG, Christine CAMPAGNE, Fabien SALAUN*,

1
Université de Lille Nord de France, F-59000 Lille, France;
2
GEMTEX, ENSAIT, F-59100 Roubaix, France;

Keywords: Polycaprolactone microspheres, electrospraying, structure and morphology, green solvent,
process parameters
Due to its biocompatibility, biodegradation and non-toxicity, polycaprolactone (PCL) can be widely
used in medical tissue engineering, drug delivery, controlled release systems and the food packaging
industry [1]. Electrospraying has recently emerged as a new microencapsulation technique [2]. PCL
particles obtained from this process have a higher specific surface area, lower mass density, higher
cell fixation and porous structure, and would provide new applications and orientations of interest in
these areas. At the same time, this technique, as a new micro-nanotechnology, allows better control of
particle size distribution, average diameter and morphology. During the process, many interrelated
parameters, such as the physico-chemical properties of the solution, process parameters and
environmental conditions, influence stability and final results. Among these interdependent variables,
the choice of a desirable solvent or solvent system to support the PCL is one of the key criteria for
optimizing the electrospraying and controlling the morphology and structure of the final PCL
microspheres.
On the one hand, the formation of Taylor cone during electrospraying is closely related with the
physico-chemical properties of electrospraying solution which is mainly determined by the used
solvent system [3]. Meanwhile, the process parameters for achieving Taylor cone would be also
influenced by these solution properties. On the other hand, related properties and parameters also
influence the breaking and solidification of the droplets after the cone jet. Finally, all these factors
determine the obtained morphology and structure of the PCL microspheres from electrospraying. In
order to study in detail the effects of different solvent systems on the electrospray process and the
final microspheres, four solvents (anisole, ethyl acetate, acetic acid and acetone) were selected in this
study to prepare the PCL microspheres by electrospraying. More importantly, these solvents have
been classified in class 3 as defined by the European Pharmacopoeia which aims to reduce toxicity
and pollution during PCL electrospray and further achieving the greening and non-toxic of biomedical
polymer materials [4]. In addition, the way to obtain a jet cone and to control the morphology and
structure of the PCL microspheres during electrospray via the handling of solution components and
working parameters were also analyzed.
Fig. 1: Optical images of PCL (concentration: 5%) microspheres obtained from different
solvent.
References
[1]. N. Bock, T. R. Dargraville, M. A. Woodruff, Progress in Polymer Science. 2012, 37, 1510-1551.
[2]. S. Chakraborty, I. Liao, A. Adler, K. W. Leong, Advanced Drug Delivery Reviews. 2009, 61 1043–
1054.
[3]. D. P. H. Smith, IEEE Transactions on Industry Applications. 1986, 3, IA-22, 527-535.
[4]. C. Bordes, V. Fréville, E. Ruffin et al, International Journal of Pharmaceutics. 2010, 383, 236-243.
226
SMARTTECH-OR24

Tailored Assembly of Biomimetic Nacre-like Catalytic Multilayers

for Artificial Photosynthesis

Dasom Jeon, Nayeong Kim, Sanghyun Bae, and Jungki Ryu*
1
Department of Energy Engineering, School of Energy and Chemical Engineering
Ulsan National Institute of Science and Technology (UNIST)
Ulsan 44919, Republic of Korea
*E-mail: [email protected]

Keywords: artificial nacre, artificial photosynthesis, solar water oxidation, polyoxometalate, graphene
oxide
Artificial photosynthesis has been considered a promising solution to global energy and environmental
issues as it allows sustainable production and the use of valuable chemicals (e.g., formate, synthesis
gas, and methanol) from abundant carbon dioxide and water through a series of photoelectrochemical
processes. For the successful development of efficient and stable photosynthetic devices, it is critically
required to precisely assemble various functional materials for efficient exciton generation, exciton
dissociation, charge transport, and electrocatalytic charge transfer reactions. Here, we report the
development of an efficient and stable hematite-based photoanode for solar water oxidation using
biomimetic nacre-like catalytic multilayers (CMs), which was fabricated using the layer-by-layer
assembly of cationic graphene oxide (GO) nanosheets and anionic molecular metal oxide catalysts.
The nacre-like CMs not only resemble the mesoscale organization of thylakoid organelles of plants but
also significantly improve the photocatalytic performance of the underlying hematite photoanode with a
huge cathodic shift of onset potential for water oxidation and remarkable increase of photocurrent.
Unexpectedly, it was also found that deposition of alternating layers of cationic and anionic polymers
prior to the artificial nacre film allowed fine-tuning of the work-function of the hematite electrode by the
surface dipole effect. We believe that our biomimetic approaches can provide a general and simple
method to fabricate an efficient photosynthetic device, as well as an insight to scientists and engineers
for designing a novel electrochemical/photoelectrochemical device.
Figure 4. Design and fabrication of nacre-like hybrid films are studied for efficient and solar
water oxidation. Through tailored assembly of organic and inorganic functional components
into a nacre-like architecture, combined with precise tuning of work function using
polyelectrolytes base layers, the performance of the underlying hematite photoanode is
significantly improved in terms of catalytic efficiency and stability.
[1]. D. Jeon, H. Kim, C. Lee, Y. Han, M. Gu, B.-S. Kim, J. Ryu, ACS Appl. Mater. & Interfaces 2017,
9, 40151-40161.
[2]. Y. Choi, D. Jeon, Y. Choi, T. Lee, N. Kim, M. Gu, H.-W. Lee, B.-S. Kim, J. Ryu, Submitted.
227
SMARTTECH-OR25

Self-rolled polymeric thin film: Toward fully functionalized

microsystems

1 1 2 1
Florent Malloggi*, Rémy Brossard, Valeriy Luchnikov, Patrick Guenoun,

1
LIONS-NIMBE, CEA, CNRS, Université Paris-Saclay, CEA Saclay, Gif sur Yvette, France;
2
Institut de Science des Matériaux de Mulhouse, UMR 7361 CNRS-UHA, 15 rue Jean Starcky,
Mulhouse, France

Keywords: microfabrication, 3D microfluidics, self-rolling, functionalization, microtube, lab in the tube
We present a new route for the fabrication of highly specialized micro-capillaries, based on the
phenomenon of thin polymer films self-rolling. Before rolling, the surface can be patterned (chemically,
topographically), permitting the fabrication of inexpensive fully functionalized capillaries.
Fig. 1. Schematic of the rolling process. Pictures of 3D functionalized microtubes
Spontaneous curvature is a well-known instability [1] which occurs in films with gradients of stress
along the normal axis. We focus on the application of those self-rolled microsystems to lab-on-chip
technology [2]. We propose methods to induce the spontaneous rolling of polymeric films, more
precisely polydimethylsiloxane (PDMS). The advantage of such system is three-fold: i - Those
systems are inexpensive to design. ii - The inner surface of the capillary is accessible before rolling
and can be properly functionalized and characterized. iii - The formation of the channel itself is not a
lithographic process. The fabrication of patterned channel are done with only one lithographic step,
which implies a great economy in terms of means and efforts.
Thin films of PDMS are either coated by a layer of hard material or have their surface hardened by
plasma oxidation [3]. They are then driven out of equilibrium by selective solvent swelling resulting in a
tubular rolled-up system (figure 1).
We demonstrate topographical and chemical patterning, respectively by embossing and microcontact
printing. In both cases, the pattern covers the whole surface of the tube, which typically cannot be
obtained with standard techniques [4].
Spontaneous curvature effect can be used for the inexpensive auto-assembly of micro-capillaries. The
inner surface of those is fully accessible before the rolling occurs and can be easily functionalized. The
main remaining challenge of this technique is the integration of the rolled-up system in a larger
microfluidic systems. Methods are developed to obtain soft lithographic / self-rolled hybrid systems in
order to make use of the advantages of both processes. We believe in the potential of this method for
the design of cutting edge microfluidic technology.
[1] Timoshenko, S. et al. J. Opt. Soc. Am 11(3), 233–255 (1925).

[2] Smith, E. J., Xi, W., Makarov, D., Mönch, I., Harazim, S., Quiñones, V. A. B., Schmidt, C. K., Mei,
Y., Sanchez, S., and Schmidt, O. G. Lab on a Chip 12(11), 1917–1931 (2012).
[3] Sarrazin, B., Brossard, R., Guenoun, P., and Malloggi, F. Soft Matter, 12, 2200-2207 (2016).
[4]Brossard, R., Luchnikov, V., Guenoun, P., and Malloggi, F. Polymer Physics Polymer Physics 55,
721-728 (2017)
228
SMARTTECH-OR27

Combining DNA phase transition and hybridization to form all-DNA

colloids and superstructures.
1 2 2 2
Rémi Merindol, Sebastian Loescher, Avik Samanta, Andreas Walther*,
1
Centre de Recherche Paul Pascal, University of Bordeaux, Pessac, 33600, France
2
Institute for Macromolecular Chemistry, Albert-Ludwigs-University of Freiburg, Freiburg, 79104,
Germany
Keywords: Self-assembly, pathway-control, structured hydrogel, core-shell, capsule, DNA, gold

nanoparticle.
Inspired by biological soft-tissues, the fabrication of addressable, biocompatible and hierarchically

structured materials is a key challenge for material science, nanotechnology and medicine.[1] DNA
provides synthetics materials with the highest level of molecular structural control and nanoscale
complexity (DNA origami…). Yet processes to create micro and macro-structured DNA architectures
are scarce.
Here we present a new method at the interface of biochemistry and macromolecular physics to
prepare various all DNA microstructures. We use long “multiblock” single stranded DNA synthesized
by rolling circle amplification as primary elements. The key for fast and efficient structuration rely on
two antagonistic processes. A new sequence dependent LCST-type phase-transition that promotes
self-assembly at high temperature; and canonical DNA hybridization which prevails at low temperature
(Fig. 1A). We developed multiple strategies to navigate these complex self-assembly landscapes and
freeze the assembly upon cooling to obtain homogeneous (Fig. 1B) or core-shell particles (Fig. 1C)
(with a solid or liquid core), and capsules (Fig. 1D). Since the particles consist mostly of single
stranded DNA they can be addressed for functionalization, self-assembly and hierarchical
superstructure formation. As examples we prepared multiparticle assemblies (Fig. 1E), continuous
cellular hydrogels (Fig. 1F), and light responsive hybrid DNA/gold-nanoparticles structures (Fig. 1G).
Fig. 1: (A) Schematic representation of the two temperature dependent processes driving the
formation of all-DNA colloids. (B-F) Confocal microscopy imaging of various colloids and
superstructures. The primary structures consist of (B) homogeneous particles, (C) core-shell
particles and (D) capsules. DNA driven assembly and controlled heating allow the formation of
(E) core-satellites aggregates and (F) continuous cellular hydrogels. (G) Transmission electron
microscopy of light responsive DNA colloids decorated with gold nanoparticles. Scale bars:
(B-F) 10 µm, (G) 500 nm.
[1]. R. Merindol and A. Walther, Chem. Soc. Rev. 2017, 46, 5588-5619.
229
SMARTTECH-OR28

Macroscopic DNA hydrogels that sense mechanical strain.
1 2 2 3
Rémi Merindol, Giovanne Delechiave, Luiz Henrique Catalani, Andreas Walther*,

1
Centre de Recherche Paul Pascal, University of Bordeaux, Pessac, 33600, France
2
Institute of chemistry, University on São-Paulo, São-Paulo, 05508-900, Brazil
3
Institute for Macromolecular Chemistry, Albert-Ludwigs-University of Freiburg, Freiburg, 79104,
Germany
Keywords: DNA hydrogel, FRET, soft-mechanochemistry, mechanochromic, mechanosensitive.
Mechanosensitive materials can sense and respond to mechanical actuation. Such materials
are ubiquitous in nature and control many biological processes from cell spreading and differentiation
to senses of hear and touch.[1] These concepts inspired the design of artificial mechanochromic
materials which respond optically to mechanical actuation. Current approaches generally based on
covalent bond rupture or chromophore aggregation are irreversible and require large actuation
forces.[2,3] These systems are incompatibles with hydrogels and soft materials. Weak and reversible
force sensing require new mechanisms inspired from biological design and based on dynamic
supramolecular changes.[4,5]
Here we present a new concept for the modular design of fluorescent mechanochromic
hydrogels based on DNA self-assembly. We prepared macroscopic all-DNA hydrogels using partially
complementary multiblock single stranded DNA synthesized via enzymatic rolling circle amplification.
These hydrogels are thermoplastic which allows for shaping and recycling by heating them above their
melting temperature. We also designed these hydrogels to present large amounts of single stranded
domains that we later use to anchor our fluorescent force sensors. The mechanochromic modules
consist in a weak DNA duplex functionalized on one side with a fluorophore and one the other side
with a quencher. As long as the duplex holds both in proximity non-radiative Förster energy transfer
(FRET) prevents fluorescence. Mechanical stretching triggers the opening of the duplex which induces
a decrease of FRET and an increase of fluoresce (Fig. 1A). We show quantitative strain-fluorescence
measurements in homogeneous hydrogels (Fig. 1B, C) and control over the reversibility depending on
the sequence and architecture of the module. We also present proof of concept applications for
multiscale strain monitoring in composite materials (Fig. 1D), and visualization of freezing induced
stress patterns (Fig. 1E).
Fig. 1: (A) Molecular mechanism of the DNA based mechanochromic module. (B) Widefield
fluorescence imaging of the DNA hydrogel before and after stretching. (C) Quantitative strain-
fluorescence curve (Fluo488/510)/(Fluo530/580) for module 1 and a control module without force
sensing duplex. (D) Confocal fluorescence imaging of an inhomogeneous strain field in a
composite. (E) Widefield fluorescence imaging reveals freezing induced stress patterns.
[1]. A. W. Orr, B. P. Helmke, B. R. Blackman and M. A Schwartz, Cell, 2006, 10, 11

[2]. C. Löwe, and C. Weder, Adv. Mater., 2002, 14, 1625-1629,
[3]. D.A. Davis, et al. , Nature, 2009, 459, 68-72.
[4]. P. Lavalle, F. Boulmedais, P. Schaaf and L. Jierry, Langmuir, 2016, 32, 7265-7276.
[5]. R. Merindol and A. Walther, Chem. Soc. Rev., 2017, 46, 5588-5619.
230
SMARTTECH-OR29

Application of Molecularly Imprinted Polymers in Cosmetics: A New
Deodorant Principle

1 1 2 1
Alejandra MIER, Sofia NESTORA, Andrew GREAVES, Karsten HAUPT, Bernadette TSE SUM
1
BUI*,

1
Sorbonne Universités, Université de Technologie de Compiègne, CNRS Enzyme and Cell
Engineering Laboratory, Rue Roger Couttolenc, Compiègne Cedex, France
2
L’Oréal Research and Innovation, 1 avenue Eugène Schueller, 93600 Aulnay sous Bois, France

Keywords: body odors, cosmetics, human sweat, molecularly imprinted polymer, stoichiometric
monomer
Axillary (armpit) malodors are mainly caused by volatile medium chain branched fatty acids, produced
from their non-odorant glutamine conjugate precursors by the action of bacteria, commensal to the
skin. In order to combat malodors, we have synthesized a molecularly imprinted polymer (MIP) that
can capture the glutamine conjugate precursors in human sweat, hence preventing their
transformation into malodorous acids [1] (Figure 1). The MIP, blended in a dermo-cosmetic deodorant
formulation, can selectively capture the undesirable molecules in human sweat, despite the presence
of a multitude of other molecules contained in this complex medium [2]. The diameter of the MIP
particles was around 600 nm and therefore they cannot penetrate into the skin. The biological effects
of the MIP in terms of epidermal cell viability and irritation (cytotoxicity and release of proinflammatory
cytokines) were assessed in vitro on human keratinocytes (HaCaT cells). Furthermore, the MIP does
not affect the growth of skin bacteria (Staphylococcus epidermidis, Corynebacterium Striatum and
Micrococcus luteus) isolated from human sweat, indicating that the MIP will not perturb the fragile
microbial equilibrium of the skin. This innovative application of MIPs meets the needs of cosmetic
industries in the development of mild deodorant active ingredients as alternatives to the currently-used
unspecific antimicrobial agents [3], hence preserving the integrity of the skin microbiota.

Fig. 1: Formation of volatile malodorous acids from their non-odorant glutamine conjugates by
skin bacteria in axillary sweat (left); capture of the odorless precursors by MIP, preventing the
bacteria to convert them to malodorous acids (right).
[1]. A. Greaves, F. Manfre, K. Haupt, B. Tse Sum Bui, 2014, Molecularly imprinted polymer for
trapping odorous molecules. Patent WO 2014102077 A1
[2]. S. Nestora, F. Merlier, S. Beyazit, E. Prost, L. Duma, B. Baril, A. Greaves, K. Haupt, B. Tse Sum
Bui, Angew. Chem. Int. Ed. 2016, 55, 6252-6256
[3]. C. Callewaert, P. Hutapea, T. Van de Wiele, N. Boon, Arch. Dermatol. Res. 2014, 306, 701-
710
231
SMARTTECH-OR30

Selective Photooxidation of Lignin Model Compound- Benzyl

Alcohol in a ZnO Coated Microfluidic Reactor
1 1 1
Vaishakh NAIR*, Tomasz DAŃKO, Juan Carlos COLMENARES *,
1
Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224, Warsaw,
Poland
*[email protected], [email protected]
Keywords: Photocatalysis, lignin, semiconductor oxides, microreactors, high-value aromatics,

ultrasounds.
Selective oxidation of lignin-based model aromatics to other value added chemicals mostly aromatic
compounds containing aldehyde and carboxylic groups is a promising field for developing new
pathways for generation of chemicals from lignin, a major by-product generated from biorefineries and
paper industries. The high value chemical compounds are stated to be replacement to expensive
chemicals used in various products e.g. in food and pharma industries.[1,2] Photocatalytic oxidation of
lignin in a microfluidic reactor system may be particularly beneficial in comparison with conventional
batch processes due to the increase of contact surface area between the reagents and the catalyst,
shorter molecular diffusion distance, improved heat and mass transfers, no requirement for separation
steps and a facile control of reaction parameters, all this together leading to high selectivity for the
desired products (e.g. aromatic aldehydes/ acids).[3,4]
Encouraged by the benefits of microfluidic based photoreactor system, the current work focusses
on studies on photocatalytic oxidation of the simplest model aromatic compound of lignin- benzyl
alcohol in a fluoropolymer based microfluidic photoreactor. For this study, nanostructured ZnO were
synthesized by ultrasound-promoted sol-gel process and deposited on the internal walls of
Polyfluoroethylenepropylene (FEP) microtubes. During the ultrasonication process, changes in the
polymer surface were observed and characterized using Attenuated Total Reflectance spectroscopy,
Scanning Electron Microscopy and Confocal Microscopy. The rough patches form sites for catalyst
deposition resulting in the formation of thin layer of photocatalyst nanoparticles in the inner walls of the
microtube. The photocatalytic activity of the semiconductor coated fluoropolymer based microcapillary
was evaluated for selective conversion of benzyl alcohol to benzylaldehyde.
Acknowledgements: This work was supported by the National Science Centre (NCN) in Poland
within research project Sonata Bis Nr. 2015/18/E/ST5/00306. More information on this project at
http://photo-catalysis.org
Fig. 1: Photocatalysis of lignin based model compounds in photomicroreactors
[1] S.H. Li, S. Liu, J.C. Colmenares, Y.J. Xu, Green Chem. 2016, 18, 594-607.
[2] R.Rinaldi, R.Jastrzebski, M.T.Clough, J.Ralph, M.Kennema, P.C.Bruijnincx, B.M. Weckhuysen,
Angew. Chem. Int. Ed. 2016, 55, 8164-8215.
[3] J.C. Colmenares, R.S. Varma, V. Nair, Chem. Soc. Rev. 2017, 46, 6675-6686.
[4] J.C. Colmenares, V. Nair, E. Kuna, D. Lomot, Ultrason. Sonochem. 2018, 41, 297-302.
232
SMARTTECH-OR31

Effect of the Space Dimension upon the Spin Magnetic Ordering

in the Electron Fermi-Gas

1 2
Elena ORLENKO, Fedor ORLENKO *,
1
Theoretical Physics Department, Peter the Great St.Petersburg Polytechnic University,
Saint-Petersburg, Russia;
2,
Physics Department, St.Petersburg Pharmacological Academy,
Saint-Petersburg, Russia
Keywords: Low dimensional systems, Degenerated Fermi-gas, Magnetic properties, Spin ordering,
Exchange interaction effects.
The main goal of the present investigations is general effect of dimension upon the
spontaneous polarization in the electron Fermi-gas. The possibility of spontaneous magnetism was
discussed theoretically using the Hartree–Fock method, the Landau Fermi-liquid formalism,
Heisenberg variation model [1,2] . We consider low dimension sizes ν=1,2 and quasi-low dimensions
ν*=0,1,2 corresponding to the intermediate size ν=6,5,4. Thermodynamic properties of the electron
Fermi-gas of an arbitrary dimension will be discussed in general consideration. We have developed
the general criteria for appearing the spontaneous polarization in the electron Fermi-gas of arbitrary
dimension .
We calculated the total energy of the arbitrary dimension system, as well as the exchange
contribution per particle using the Hartree–Fock method. The dependence of the energy per particle
on the polarization degree of the system has been determined. It is shown that spontaneous
polarization exits in the system when a universal parameter related to the density of the particles
satisfies the inequality rs ≥rs*. We has analytically calculated this parameter for each type of
dimension size. A comparative analysis of one-, two- to six-dimensional systems is performed.
We have obtained a general expression for the total energy per particle as a function of the
polarization and dimension of the system. According to this expression, the possibility of spontaneous
polarization in the system is dependent of the dimension of the system.
[1]. F. E. Orlenko, G. G. Zegrya, and E. V. Orlenko, Tech. Phys. 2008, 53, 978-983.
[2]. F.E. Orlenko, S.I. Chelkak, E.V. Orlenko, G.G. Zegrya, JETP, 2010,110 ( 5), 805–810.
233
SMARTTECH-OR32

Porous Silicon Optical Biosensors for Detection of Subclinical

Mastitis Biomarkers in Bovine Milk

1 2
Nofar Pinker , Giorgi Shtenberg

1
Department of Biotechnology, Faculty of Agriculture, Food and Environment, the Hebrew University,
Rehovot, Israel
2
Institute of Agricultural Engineering, ARO, The Volcani Center, Bet Dagan, Israel

Keywords: Haptoglobin, Bovine Mastitis, Optical Biosensors, Porous Si, Dairy Cow, Hemoglobin
The proposed research is specifically addresses the most prevalent health problem in dairy cows and
major problem for the dairy industry worldwide, by developing a generic integrated biosensing platform
for on-site monitoring applications. Bovine mastitis (BM) is one of the most frequent diseases in dairy
cattle, having a large adverse effect on farm economics, including increased treatment costs,
decreased milk yield, escalation of somatic cell counts (SCC), and increased risk of removal from the
herd or even death. The mammary gland inflammation is usually classified upon its severity into
chronic, clinical and subclinical forms. The latter form is difficult to detect due to the absence of any
visible indications in milk or udder, as the overall milk production decreases, the composition is altered
and microbiologically infected. Consequently, many of these cases remain undetected, leading not
only to the spread of BM-causing pathogens in the herd, but also to long-term reduction in milk yield.
Thus, before BM becomes chronic, it is highly important to rapidly identify the new clinical cases in
order to prevent deterioration and/or control infection in the herd. Haptoglobin (Hp) is one of the most
sensitive acute phase proteins in milk during udder inflammation and is used as a biomarker of
mastitis. Traditionally, the detection of BM depends on the efficiency and reliability of the methods
designed to estimate SCC, indicate inflammation, measure the biomarkers associated with the onset
of the disease and to identify the causative microorganisms. However, all these methods have their
limitations: traditional microbiology culturing techniques require several days to obtain the results,
making “real-time” assessment unfeasible. The advanced rapid techniques although very accurate,
lack the ability to detect analytes in “real-time” or outside the laboratory boundaries. Even, the "on-site"
California Mastitis Test (CMT) or electrical conductivity (EC) has low sensitivity and difficulties in
results interpretation. Thus, an early and rapid detection of mastitis followed by corrective and/or
prevention actions can positively affect animal’s health and overall economy of dairy farms. Herein, we
have designed and fabricated a simple optical biosensing platform, based on porous Silicon (PSi)
nanostructures, a Fabry-Pérot thin film, for the detection and quantification of Hp as an indicator of
mastitis by affinity binding. First, we show a general detection assay by immobilizing Hemoglobin (Hb)
within the oxidized PSi nanostructure and monitor its affinity to Hp in real-time by reflective
interferometric Fourier transform spectroscopy. Our studies reveal that the optical nanostructure
capable of multitasking i.e., immobilization, size-exclusion separation, rapid and sensitive detection of
specific biological targets (i.e., BM predicting biomarkers) in “real” samples (i.e., bovine milk), offering
simultaneous real-time detection based on physical characteristics. Thus, the main advantage of the
presented biosensing concept is the ability to detect Hp in milk as an indicator for mastitis, using a
simple and portable experimental setup.
Fig. 1: A schematic illustration of the PSi-based optical biosensor for detection of mastitis. A
miniaturized “lab-on-chip” optically monitors milk samples from different cattle.
234
SMARTTECH-OR33

A Biological Strategy for Presstressing Crystalline Calcite Lenses

1 1 1*
Iryna Polishchuk , Alex Katsman and Boaz Pokroy
1
Department of Materials Science and Engineering and the Russel Berrie Nanotechnology Institute,
Haifa, Israel
Keywords: bio-strategy, prestressed matrix, bio-inspired ceramics
In contrast to synthetic materials, materials produced by organisms are formed in ambient

conditions and with a limited selection of elements. Nevertheless, living organisms reveal elegant
strategies for achieving specific functions, ranging from skeletal support to mastication, from sensors
and defensive tools to optical function. Very recently our discovery of a novel biostrategy for
strengthening and toughening brittle crystals of calcite was published in Science (1). Our studies on the
atomic- and nano-structure of the mineralized lenses of the brittlestar Ophiocoma wendtii revealed the
presence of metastable coherent nanoprecipitates that induce compressive stress on a single crystal
(Fig. 1A-B). Although structurally akin to the Guinier–Preston zones well known in classical metallurgy
(2) the brittlestar’s nanostructure is achieved via a completely novel mechanism, in which single
crystals being formed at ambient conditions from a supersaturated amorphous precursor contain
coherently aligned nanoprecipitates. These nanoprecipitates are rich in magnesium which substitutes
calcium in the lattice and leads to a lattice parameters shrinkage which is the source of compressive
stresses on the matrix. This is the best manner to strengthen and toughen ceramic materials similar to
tempered glass and prestressed concrete.
In addition, the magnesium-rich nanoprecipitates are found to be present in layers with alternating
density which can be clearly seen by diffraction as well as by nanoCT imaging (Fig 1C). The effect of
these layers on the mechanical properties will be discussed. We will also discuss the lessons we can
learn from the brittlestar in toughening and strengthening man-made engineering materials in a
bioinspired manner.
Fig. 1: (A) SEM image showing an entire dorsal arm plate and a higher-magnification inset. (B)
HRTEM image from a single lens revealing coherent nanodomains. (C) SAXS intensity map of
the same lens.
References
[1]. Polishchuk, I and Pokroy, B et al. Science 2017, 358, 1294.
[2]. Duparc, O. B. M. H. Metall. Mater. Trans. A 2010, 41A, 1873.
235
SMARTTECH-OR34

Nanocapsules with functional (T-switchable) polymer corona

produced by microbial cell factories

1 2 3 3 1
Jorges ROYES MIR , Galina DUBACHEVA , Oana ILIOAIA , Bruno MIROUX , Christophe TRIBET

1
PASTEUR, Ecole Normale Supérieure, Dépt Chimie. 24 rue Lhomond, Paris, France;
2
PPSM CNRS UMR 8531, ENS Cachan, Univ. Paris-Saclay, 61 Av. du Pdt Wilson, Cachan, France;
3
UMR CNRS 7099, IBPC, Univ Paris Diderot, Sorbonne Paris Cité, PSL research Univ.

Keywords: bacterial synthesis, nanocapsules, temperature-responsive, polypeptides
Advances in metabolic engineering and synthetic biology in the last 20 years have markedly
facilitated the use of microorganisms as "cell factories"[1] inspiring eco-friendly alternatives to
chemical synthesis. Nowadays, "Microbial synthesis" becomes a promising tool in material and
polymer science, mostly to produce biopoly(esters),[2] or functional peptides such as temperature-
responsive elastin-like polymers (ELP [3]). To go beyond the present bio-engineering of molecules, we
propose to use cell machineries to formulate and assemble functional objects at supra-molecular
levels inside bacteria. Here we will show how to replace "in glassware" nanocapsules assemblies for
“in bacteria” ones. We will illustrate the design of genetically-encoded, polymer-coated capsules,
similar to polymer-decorated liposomes, imparted with temperature responsiveness.
We used inner membrane proliferation induced by overexpression of a membrane protein
(subunit of ATP synthase) in C43(DE3) E.coli [4] to produce lipidic capsules (scheme 1). They can be
spontaneously decorated with artificial fusion polypeptides, in particular T-responsive ones.
Optimization of extraction procedures (aqueous enzymolysis, low mechanical shear) yields
homogenous population of capsules (size distribution and composition were characterized by particle
tracking, DLS, fluorescence). We assessed the response to temperature of vesicles coated by elastin-
like peptides fused with diverse polypeptide sequences. We believe that biointegrated encapsulation
will enable straightforward protection of fragile biomolecules, while displaying capacities to achieve
targeting and on-demand delivery.
Fluo or
His tag
ATP-b cytosolic
domain
Overexpressed membrane Extractions
compartments in E. coli ELP
biofunctionalized
liposomes
Scheme 1 : E.Coli expressing cytosolic membranes and schematic drawing of

biofunctionalized lipid capsules.
[1]. Clomburg, J.M., Crumbley, A.M., Gonzalez, R., Science, 2017, 355, aag0804.
[2]. Thomson, N., Summers D., Sivaniah, E., Soft Matter, 2010, 6, 4045
[3]. Yousefpour P., Chikolti A., Biotechnol. and Bioeng. 2014, 111 (9), 1699, & Bataille L., Dieryck W,
Hocquellet A., Cabanne C., Bathany K., Lecommandoux S., Garbay B.; Garanger E., Prot.
Expression & Purif. 2016, 121, 81.
[4]. Arechaga I., Miroux, B., Karrasch S., Huijbregts R., Kruijff B., Runswick, M.J., Waker, J.E. FEBS
letters, 2000,482, 215.
236
SMARTTECH-OR35

Specific functionalization of the surface –key for molecular

recognition approach

1* 1,2 1
Gulaim A SEISENBAEVA, Ievgen PYLYPCHUK, Vadim G. KESSLER
1
Department of Molecular Sciences, Swedish University of Agricultural Sciences, 75007 Uppsala,
Sweden;
2
Chuiko Institute of Surface Chemistry, National Academy of Sciences of Ukraine, 17, General
Naumov Street, Kyiv 03164, Ukraine
Sol-gel technology is a versatile approach for preparation of complex materials with multipurpose
functions for different use, in particular, as adsorbent materials and drug delivery substrates. The
insight into the molecular aspects of ligand grafting and potential maximal capacity of hybrid organic–
inorganic adsorbents bearing ligand monolayers as active functions, allowed to produce adsorbents
with high specific affinity towards target cations or specific molecules. Materials with bi- or
multifunctional surface layers possess, undoubtedly, certain advantages over the materials with
monofunctional coatings. Combining hydrophobic and hydrophilic groups, reveals opportunities for
creating, for example, the patchy surface with hydrophobic walls and a hydrophilic center, influencing
their sorption capacity [1] or catalytic properties. Introducing aminophosphonic [2] or aminocarboxylic
[3] functions on the surface allows to create adsorption materials specific for certain metal cations. The
principles for design of functional ligand monolayers have been developed using insight into
coordination geometry of relevant molecular compounds [2, 3]. Tailoring of functional ligand layer
facilitates further attachment of larger bio-catalyst molecules. Grafting of specific enzymes, hydrolases
and oxidases, along with ligands capable to efficiently adsorb metal cations open for creation of
multifunctional adsorbents, combining removal of hazardous metal cations with bio-catalytic action,
destroying organic pollutants [4, 5].
Fig. 1: Simultaneous grafting of molecular recognition function and immobilization of a

biocatalyst [5].
[1]. Tomina V.V., Seisenbaeva G.A., et al., Beilstein J. Nanotechnol. 2017, 8, 334–347.
[2]. Seisenbaeva G.A., Melnyk I.V., et al., RSC Adv., 2015, 5, 24575–24585.
[3]. Polido Legaria E., Seisenbaeva G.A., et al., ACS Inorg. Chem., 2017, 56, 13938−13948.
[4]. Pogorilyi R.P., Seisenbaeva G.A., et al., Colloids&Surfaces B: Biointerfaces, 2016, 144, 135-142.
[5]. Pylypchuk I., Seisenbaeva G.A., et al., Nanomaterials, 2017, 7, 298, 1-17.
237
SMARTTECH-OR36

Biomimetic Assemblies based on Subcompartmentalized Giant

Polymersomes
1 2 1 1
Sagana THAMBOO , Adrian NAJER , Claudio VON PLANTA , Cornelia PALIVAN , Wolfgang
1
MEIER*
1
Department Physical Chemistry, University of Basel, Basel, Switzerland;
2
Imperial College Network of Excellence in Malaria, Imperial College London, London, UK
Keywords: multicompartment systems, self-assembly, giant polymersomes, bioinspiration, stimuli-

responsiveness
Compartmentalization plays a pivotal role in the highly complex functions of eukaryotic cells.
Incompatible materials are stored separately and specific metabolic activities happen in individual
steps in isolated compartments which is a prerequisite of many cellular regulatory mechanisms. To
attain a better understanding of the complexity of cellular multistep processes, the creation of
multicompartmentalized assembly is aimed. Vesicular systems provide the simplicity which is required
for the creation of a controllable model and they resemble the architecture of a biological cell and its
organelles. The outer membrane of such a multicompartment is required to be semipermeable to allow
passive diffusion of small molecules while the designated compartments and bigger biological
elements remain inside the microenvironment. [1, 2] Due to the lack of stability of liposomes, the use
of synthetic membranes based on block copolymers with properties as biocompatibility,
biodegradability and tunability provides a better solution for various biomedical application. [3] In this
perspective, we have studied a subcompartmentalized giant polymersome built-up from a fully
synthetic membrane based on poly(2–methyloxazoline)–block–poly(dimethylsiloxane)–block–poly(2–
methyloxazoline (PMOXA-b-PDMS-b-PMOXA). Additionally, the outer membrane of this synthetic
carriers contains another block copolymer caled PDMS–block–heparin which functions as a receptor-
like molecule. [4] In an effort to form a multicompartment structure, we have encapsulated desired
smaller nanostructures, such as nanoparticles, vesicles or micelles, within a larger micron-sized giant
polymersome using a gentle film rehydration method, whose combination has not been reported
before to our knowledge. Such a controllable approach has given us the opportunity to incorporate
and characterize nanosized inner compartments with different physicochemical properties such as
stimuli-response into the main cavity. More importantly, this favors controlled on-demand release of
multiple desired components while avoiding cross-contamination. Confocal microscopy was used to
access the morphology of these multicompartments. The existence of inner compartments inside the
giant synthetic containers have been studied using fluorescence correlation spectroscopy. Important
parameters like the number of particles in the confocal volume, count rate and hydrodynamic diameter
were determined using this characterization method. As well, the passage of reducing agents through
the outer polymer membrane was shown which lead to the formation of the active fluorescence dye
resorufin inside the cavity of the giant vesicles. As a proof of concept, we subsequently demonstrated
the burst of the inner reduction sensitive nanoparticles triggered by the presence of reducing agents.
Such stimuli-responsive multicompartment system can be tailored to potentially suit for the
applications in theranostics and development of biosensors. The ultimate goal is to provide a smart
cell-like material that can substitute missing or lost activities in the cells. Such a biomimetic platform
can lead to the achievement of a man-made cell self-assembly with the ability to function and adapt as
that found in nature. [5]
[1] R. J. R. W. Peters, M. Marguet, S. Marais, M. W. Fraaije, J.C.M. van Hest, S. Lecommandoux,

Angew. Chem. 2014, 126, 150-154.
[2] M.J. York-Duran, M. Godoy-Gallardo, C. Labay, A.J. Urquhart, T.L. Andresen, L. Hosta-Rigau, Col.
Surf. B. 2017, 152, 199-213.
[3] C. G. Palivan, R. Goers, A. Najer , Xi. Zhang , A. Car, W. Meier, Chem. Soc. Rev. 2016, 45, 377-
411.
[4] A. Najer, D. Wu, A. Bieri, F. Brand, C. G. Palivan, H. Beck, and W. Meier, ACS Nano 2014, 8,
12560-12571.
[5] A. H. Gröschel, F. H. Schacher, H. Schmalz, O. V. Borisov, E. B. Zhulina, A. Walther, A. H.E.
Müller, Nat. Commun. 2012, 3, 710.
238
SMARTTECH-OR37

Atomic layer deposition for biosensing applications

1 1 1 1 1
Octavio GRANIEL, Jean-Marc JANOT, Sebastien BALME, Matthieu WEBER, Philippe MIELE, and
1
Mikhael BECHELANY

1
Institut Européen des Membranes, IEM-UMR 5635 ENSCM, UM, CNRS, Université de Montpellier,
Place Eugène Bataillon, 34095 Montpellier Cedex 5, France

Keywords: ALD, Biosensor, ZnO, Photoluminescence, Nanowires
ZnO is one of the most used transducer materials due to its optical properties and biocompatibility.
Silicon nanowires (Si NWs) have attracted much attention for applications in photovoltaics, lithium-ion
batteries, electronics and biosensors due to their mechanical, electrical and optical properties.
The high aspect ratio of SiNWs and the optical properties of ZnO are exploited to build the substrate of
an optical biosensor. In this work Si NWs were obtained by combining metal assisted chemical etching
(MACE) and nanosphere lithography (NSL). The resulting structures were later covered with a 50 nm
thick ZnO layer and characterized by SEM and photoluminescence. As a first approach, the
photoluminescence response to H2O2 was investigated.
Figure 1: Cross Section SEM image of SiNWs covered with 50nm thick ZnO by ALD
239
HUGS-OR01

Flame retardant behavior of PLA containing phosphorus

and nitrogen chemically modified lignin
1 2 2 1 1
Lucie Costes , Mario Aguedo , Aurore Richel , Christian delvosalle , Fouad Laoutid* ,
1 1
Philippe Dubois , Sylvain Brohez
1
University of Mons, Mons, Belgium
2
University of Liège, Gembloux Belgium
Keywords: PLA, Lignin, flame retardant, biobased materials
Polymer materials play a significant role in our daily life thanks to their wide range of advantages such
as versatile mechanical properties, ease of processing and possibility of recycling. Bioplastics issued
from renewable resources represent an interesting alternative to reduce carbon footprint instead of
using polymers made of fossil carbon. However, to extend the development of technical and durable
applications for bioplastics, some properties like impact resistance and tensile strength, service
temperature, long-term stability, fire behavior need to be improved.
Flame retardancy is an active research subject developing numerous and efficient strategies to endow
polymers with good fire-resistant properties. This study focuses on the use of lignin, which is the
second most abundant constituent of the biomass, as sustainable flame retardant additive for
polylactide (PLA). Indeed, thanks to its aromatic structure, lignin could be advantageously used, in
polymeric matrices, as a char promotor agent that can allow some reduction of the combustion rate [1-
3]. An original and simple approach, based on a two-step phosphorus / nitrogen chemical modification,
is proposed to enhance the flame retardant effect of lignin in PLA. The effect of the chemical
modification on both structure and properties of lignin was deeply investigated by using several
characterization techniques. Fire properties and thermal behavior of PLA composites containing 20
wt% of both untreated and treated lignins were characterized by using cone calorimeter, UL-94 test
and thermogravimetric analysis. Results showed that the incorporation of untreated lignins led to
significant deterioration of both thermal and fire properties of PLA, i.e. significant reduction of the
thermal stability during TGA experiment, important decrease of the time to ignition while only
organosolv lignin allowed a significant reduction of the peak of heat release rate. In contrast, both
phosphorus / nitrogen chemically treated lignins have been found to limit PLA thermal degradation
during melt processing as well as during TGA experiments and also to significantly improve fire
properties allowing to reach V-0 classification at UL-94 test. The nature of the gases evolved during
thermal decomposition of treated and untreated lignins by using TGA-Mass spectrometer and cone
calorimeter – FTIR couplings is also investigated.
Acknowledgments
This work was supported by the European Commission and Région Wallonne FEDER program
(Materia Nova), by the Interuniversity Attraction Pole program of the Belgian Federal Science Policy
Office (PAI 7/05) and by FNRS-FRFC.
[1]. A. De Chirico, M. Armanini, P. Chini, G. Cioccolo, F. Provasoli, G. Audisio, Polymer Degradation

and Stability, 2003, 79, 1, 139–145.
[2]. L. Costes, F. Laoutid, M. Aguedo, A. Richel, S. Brohez, C. Delvosalle, Ph. Dubois, European
Polymer Journal, 2016, 84, 652–667
[3]. L. Ferry,G. Dorez, A. Taguet, B. Otazaghine, J.M. Lopez-Cuesta, Polymer Degradation and
Stability, 2015, 113, 135-143.
240
HUGS-OR03

From Cellulose Fibers Dissolution and Swelling toward

Manufacturing All Cellulose Composites

1 1 1 1, 2
Feng CHEN, Michael HUMMEL, Herbert SIXTA, Tatiana BUDTOVA,

1
Aalto University, School of Chemical Engineering, Department of Bioproducts and Biosystems,
Helsinki, Finland;
2
MINES ParisTech, PSL Research University, Center for Materials Forming- CEMEF, Sophia
Antipolis, France
Keywords: all cellulose composites, dissolution, swelling and ionic liquids
There has been an insistent demand for ‘green’ materials in the last decades leading to the
development of all-cellulose composites (ACCs). ACCs are composed of a cellulose matrix reinforced
with partially dissolved cellulose fibers. In terms of building the strategy for making strong ACCs, it is
of importance to guarantee partial dissolution rather than dismantling or complete dissolution of the
reinforcing fiber. The evolution of fibers’ behaviour in cellulose solvents is thus a very important step to
be studied so as to control ACC properties.
In this work we used dissolving wood pulp to make cellulose matrix and different types of reinforcing
fibers, man-made and natural. Two ionic liquids were used as solvents. The relationships between the
type and properties of reinforcing fibers and their dissolution and/or swelling kinetics in the solvent
were investigated. Different from general “selective dissolution” ACCs manufacturing approach, a new
strategy toward ACCs manufacturing via “selective swelling” was firstly proposed inspired by the
results of kinetics study. In addition, the mechanical properties and morphological structures of ACCs
produced by “selective dissolution” and “selective swelling” strategies were compared.
[1]. T. Nishino, I. Matsuda, K. Hirao, Macromolecules 2004 37, 7683-7687.

[2]. T Huber et al., J. Mater. Sci. 2012, 47, 1171.
Acknowledgements: The financial support from Business Finland (former TEKES, Finnish Funding
Agency for Innovation), Stora Enso Oyj and UPM-Kymmene Oyj is gratefully acknowledged.
Additionally, authors wish to thank Separation Research Oy Ab and Fibertus Oy for collaboration.
241
HUGS-OR06

Caprolactam precursors from biomass-derived levulinic acid
Fatima El Ouahabi, Annemarie Marckwordt, Hadis Amani, Narayana V. Kalevaru, Sebastian Wohlrab,
Sergey Tin, Paul Kamer, and Johannes G. de Vries,
Leibniz Institute for Catalysis, Rostock, Germany
The production of Nylon has been exponentially increased since its discovery by DuPont and co-
[1]
workers in 1930, who reported the synthesis of caprolactam from benzene . In the 1990's DSM,
BASF and DuPont have worked on synthetic strategies towards caprolactam precursors such as
[2]
Methyl 3-pentenoate (M3P), starting from the less expensive butadiene .
Intending to reduce the dependence on the oil fossil fuels, biomass has become an important
feedstock for valuable chemicals over the last decade. For example, levulinic acid (LA) is a platform
chemical that can be obtained from lignocellulosic biomass by treatment with dilute acids at high
temperatures.
The well-known catalytic hydrogenation of LA affords full conversion towards gamma-valerolactone
[3]
(GVL) which follows the ring-opening in a gas phase type reaction in the presence of methanol and
forms an isomeric mixture of methyl-pentenoates enriched with Methyl 4-pentenoate (M4P).
In this work, we intend to report the formation Methyl 5-formylvalerate (M5FV) from the selective
biphasic hydroformylation reaction of M4P in the presence of CO/H2 and Rh(CO)2(acac)/TPPS
rd
catalyst system as shown in the 3 step in Scheme 1. After purification by distillation, the remaining
isomers are subjected to a palladium-catalysed isomerising methoxycarbonylation to afford dimethyl
adipate which later will be converted into adipic acid.
Scheme 1. Reaction steps from LA to caprolactam and dimethyl adipate.
[1] European Chemical News, 18 (October 1999, 25–31). L.F.Hatch, S. Matar, Hydrocarbon
Processing, (April 1980, 211).
[2] WO 97/23454.
[3] W. Luo, P.C.A. Bruijnincx, B. M. Weckhuysen, ChemSusChem, 2013, 6, 600–603.
242
HUGS-OR07

Catalytic approaches for biorefinery’s waste valorization:
The humins challenge

1 1 2 1
Layla FILICIOTTO *, Alina M. BALU, Jan C. van der Waal , Rafael Luque

1
Departamento de Química Orgánica, Universidad de Córdoba, Edificio Marie Curie (C-3), Ctra Nnal
IV-A, Km 396,E14014 Córdoba, España;
2
Avantium Chemicals B.V., Zekeringstraat 29, 1014 BV Amsterdam, The Netherlands.

Keywords: Biomass valorization; catalysis; catalytic materials; humin by-products
The conversion of biomass is nowadays one of the leading renewable technologies in the production
of both (platform) chemicals and materials. Yet, the technological advancement of biomass conversion
into valuable compounds (e.g. furanics, levulinics) presents a challenge: the random condensation of
starting materials and products to a caramel-like material known as humins by-products [1].
Depending on the process conditions of the acid-catalyzed conversion of biomass, remarkably high
yield of humins (up to 50 wt% [2]) can be achieved, being the thermodynamically favored product. This
carbon loss impacts heavily the economics of biomass conversion strategies, thus requiring the
valorization of these by-products.
Only a few valorization strategies have been carried out on humins, such as steam reforming to
syngas [3], polymeric composites [4], (catalytic) liquefaction to aromatics [5], and foam materials [6].
Traditional research is focused on the minimization of humins by-products, by addition of organic co-
solvents [7,8] to the aqueous biomass conversion media and/or using ionic liquids [9]. These means,
however, further increase process economics. In order to make biomass processing cost-competitive,
thus, a circular economy must be envisioned (i.e. take, make, recycle), and valorization of wastes is a
must.
As part of the European ITN HUGS project [10], the aim of this communication is to show that catalytic
approaches can give a mean of valorization of humin by-products. Different catalytic routes have been
taken into considerations, such as the catalytic decomposition of humin by-products, as well as their
use as carbon support for catalytically active nanocomposites. Consistent decomposition trends were
found independently from the methodology employed (e.g. hydrogenation/oxidation; continuous
flow/batch), giving important structural information. On the other hand, the use of humins as carbon
supports brought upon enhanced activity of metal oxide species, showing a synergistic effect of the
carbon residues in challenging selective oxidations [11].
[1]. L. Filiciotto, A. M. Balu, J. C. van der Waal, R. Luque, Catal. Today 2018, 302, 2-15.
[2]. I. V. Sumerskii, S. M. Krutov, M. Y. Zarubin, Russ. J. Appl. Chem. 2010, 83, 320-327.
[3]. T. M. C. Hoang, E. R. H. van Eck, W. P. Bula, J. G. E. Gardeniers, L. Lefferts, K. Seshan, Green
Chem. 2015, 17, 959-972.
[4]. J.-M. Pin, N. Guigo, A. Mija, L. Vincent, N. Sbirrazzuoli, J. C. van der Waal, E. de Jong, ACS
Sustain. Chem. Eng. 2014, 2, 2182-2190.
[5]. Y. Wang, S. Agarwal, A. Kloekhorst, H. J. Heeres, ChemSusChem 2016, 9, 951-961.
[6]. A. Mija, E. de Jong, J.C. van der Waal, G.P.M. van Klink, Humins-containing foam, 2017,
WO2017074183 A8.
[7]. X. Tang, Y. Sun, X. Zeng, W. Hao, L. Lin, S. Liu, Energy Fuels 2014, 28, 4251-4255.
[8]. K. L. von Hebel, J.-P. Lange, Process for liquefying a cellulosic material and its products, 2011,
WO/20110277378.
[9]. M. Chidambaram, A.T Bell, Green Chem. 2010, 7, 1253-1262.
[10]. MSCA-ITN-EID-675323-HUGS website, http://www.uco.es/hugs/ (Accessed on 25 March
2018).
[11]. L. Filiciotto, A.M. Balu, A.A. Romero, E. Rodriguez-Castellon, J.C. van der Waal, R. Luque.
Green Chem. 2017, 19, 4423-4434.

243
HUGS-OR08

Biobased Building-Blocks for Thermosets Epoxy Resins

1 ,1 2 2 3
Samuel MALBURET, Alain GRAILLOT,* Aratz GENUA, Sarah MONTES, Alice MIJA, Chiara Di
3 1
MAURO, Cédric LOUBAT

1
SPECIFIC POLYMERS, ZAC Via Domitia, 150 Avenue des Cocardières, 34160 Castries, France.
2
CIDETEC, Paseo de Miramón, 196, 20014 Donostia-San Sebastián (Gipuzkoa), Spain;
3
Université Côte d’Azur, Université Nice-Sophia Antipolis, Institut de Chimie de Nice, UMR CNRS
7272, 06108 Nice Cedex 02, France.

Keywords: Biobased Epoxy Resins, DGEVA, Phloroglucinol, Vegetable Oils, Composite Materials.
SPECIFIC POLYMERS (SP - www.specificpolymers.fr) is a SME with 14 employees acting as R&D

service provider and scale up producer in the field of functional building-blocks, polymers and
materials with high specificity. The main goal of the innovative product developed by SPECIFIC
POLYMERS is to validate proof of concepts and develop tomorrow’s materials. In this context, green
material chemistry and biomass valorization is a fundamental aspect of SP research and development
activities. Many industrial and collaborative projects are ongoing to find biobased breakthrough
alternatives to fossil resources having an industrial viability. In this scope, SP research effort is mainly
dedicated to (i) biobased alternative building-blocks to substitute toxic and petrobased precursors
(Bisphenol-A, Formophenolic, Isocyanates, etc.) in thermoset resins and composites and (ii) the end-
of-life phase of corresponding thermoset materials that suffer from a lack of reprocessability,
reparability and recyclability.
SP-9S-5-003 O O
O O
O O O
n
OH
Wood Dust Lignin Vanillin DGEVA (Vanillin Diglycidyl Ether)

O
OH O
OH
O O SP-9S-5-005
O
O O
O
HO OH
O Phloroglucinol
Triglycidyl Ether
Algae Phloroglucinol O
O
OH O
O O O
O
O O
O
OH O O
O O O O
O
O
O
O
Inedible oils OH
O O Epoxy-Castor Oil
Castor Oil, Tung Oil, Tall Oil, …
Fig. 1: Biobased Building-Blocks for Thermoset Epoxy resins
ECOXY H2020 project (www.ecoxy.eu) is an integral part of this innovation work. Indeed, in this
project, innovative biobased epoxy resins are synthesized in order to produce new sustainable
thermoset composites exhibiting reparability, reprocessability and recyclability properties (3R). The 3R
functionalities are achieved by combining SP biobased epoxy building-blocks with suitable dynamic
hardeners. A key challenge of the project is to reach targeted 3R properties while meeting end-users
specifications in terms of processability and final mechanical properties. To do so, SP developed the
synthesis of biobased epoxy precursor exhibiting a set of properties that can be adjusted depending
on the application. A significant part of the work was dedicated to (i) the synthesis of Vanillin
DiGlycidyl Ether (DGEVA) prepared from vanillyl alcohol that can be extracted from lignin and to (ii)
Phloroglucinol TriGlycidyl Ether (Phloroglucinol-TGE) that can be extracted from algae. Both epoxy
resins are aromatic multifunctional glycidyl ethers that can be combined to reach a range of
thermomechanical properties. On the other hand, epoxidation of various vegetable oils was also
studied. The degree of unsaturation and the chemical nature of vegetable oils have a great influence
on reachable epoxidation degree and thus final epoxy resin properties. Overall, particular attention
was given to the influence of the epoxy index, the molecular weight and the epoxy reactivity of
synthesized precursors on resins processability and thermomechanical properties. Indeed, the
ultimate goal of the project is to produce 50 to 100 kilograms of the most suitable resins for their
evaluation in both automotive and construction sectors.
244
HUGS-OR09

Preventing the deactivation of Sn-containing zeolites during

continuous biomass processing
1 1 1
Ceri HAMMOND, Daniele PADOVAN and Luca BOTTI
1
Cardiff Catalysis Institute, Cardiff University, Cardiff, CF10 3AT; E-mail: [email protected]
The production of chemicals from biomass represents a focal point of contemporary chemical
research. Unlike petroleum, the highly oxygenated nature of sugar-based feedstock necessitates
processing in the liquid phase. Unfortunately, the addition of a solvent, along with the chelating nature
of the substrates in solution, can dramatically impact the stability of solid catalysts, particularly when
elevated pressures and temperatures are required. As such, despite the surge of interest in catalytic
sugar upgrading, the development of robust catalytic materials capable of continuous operation has
not yet been achieved. Consequently, study and optimization of the stability of various catalysts under
true operational conditions is an essential challenge [1].
During this presentation, we will highlight some of our team’s recent research focused upon
overcoming the deactivation of zeolite Sn-β during the continuous conversion of hexoses. Specifically,
the conversion of glucose to fructose, and the conversion of hexoses to alkyl lactates, will be
discussed [2,3]. In addition to highlighting the various mechanisms of deactivation present in each of
these systems, strategies to overcome these processes – including novel material design and process
optimisation – will be highlighted [4]. Along with demonstrating improved levels of catalyst stability, we
also show how the combination of catalyst design and reaction engineering results in space-time-yield
improvements of over 2 orders of magnitude in each of these systems. The consequences of these
findings, particularly with respect potential intensification of these systems, are also considered.
Figure 1: Representation of our approach to continuous biomass processing, combining

detailed kinetic studies and in situ spectroscopic insights.
[1] C. Hammond, Green Chem. 2017, 19, 2711.

[2] D. Padovan, C. Parsons, M. Simplicio-Grasina, C. Hammond, Green Chem. 2016, 18, 5041.
[3] D. Padovan, S. Tolborg, L. Botti, E. Taarning, I. Sadaba, C. Hammond, React. Chem. Eng. 2018,
Accepted article.
[4] A. Al-Nayili, K. Yakabi, C. Hammond, J. Mat. Chem. A. 2016, 4, 1373.
245
HUGS-OR10

Catalytic glycosylation of glucose with alkyl alcohols over
sulfonated mesoporous carbons

1 1 1 2
Wahiba Ghezali Ramdani, Ayman Karam, Karine De Oliveira Vigier, Sébastien Rio, Anne
2 1
Ponchel, François Jérôme*,

1
Institut de Chimie des Milieux et Matériaux de Poitiers, CNRS/Université de Poitiers, 1 rue Marcel
Doré, ENSIP Bat B1, 86073 Poitiers, France;
2 Unité de Catalyse et de Chimie du Solide (UCCS), Université Artois, CNRS, Centrale Lille, ENSCL,
Université Lille, F-62300 Lens, France

Keywords: Mesoporous carbons • Glycosylation • Catalysis • Carbohydrates • Biomass
Over the course of several decades, chemistry has developed very efficient and economically
competitive catalytic technologies to convert fossil feedstocks to a wide range of fuels, chemicals and
materials. With the transition of our society to a more sustainable development mode, chemistry is
now facing important scientific hurdles, in particular in the production of renewably-sourced chemicals
and fuels from sugars.[1] Despite a plethora of articles daily reported on the catalytic conversion of
sugars, these reactions are often difficult to implement at an industrial scale due to (1) high dilution,
typically employed to avoid degradation reactions (e.g. reversion reactions, formation of humins or tar-
like materials, etc.) and (ii) deactivation of catalysts, often caused by the presence of water used as a
solvent or released as a co-product.[2]
In this communication, we will present the synthesis of various sulfonated mesoporous carbons
through the nanocasting method using a mesoporous SBA-15 as a mold and sugar as a carbon
source. After complete characterization, the catalytic performances of the as-obtained sulfonated
mesoporous carbons were assessed in the Fisher glycosylation of carbohydrates with alkyl alcohols,
in particular with fatty alcohols to produce safe and non-ionic surfactants. Under optimized conditions,
the targeted amphiphilic alkyl glycosides were obtained in 89% yield, together with a turn over
frequency and a space time yield even higher than those of the best heterogeneous catalysts reported
so far in such reaction. Catalytic recycling experiments and comparison with non-porous sulfonated
carbons showed the importance of mesopores, not only to facilitate the accessibility of the catalytic
sites but also to limit the deactivation of the catalyst, often caused in such reaction by the deposition of
tar-like materials.
Thermo-polymerization
Pyrrolysis
Sulfonation
SO3-, H3O+
BIOSURFACTANTS
ü Yield up to 89%
ü Space time Yield up to 48 kg/m3/h
ü Recyclable
Sulfonated mesoporous
carbons
Fig. 1: general overview of the work
[1]. A. Corma, S. Iborra, A. Velty, Chem. Rev., 2007, 107, 2411-2502.

[2]. a) J.-P. Lange, Angew. Chem .Int. Ed., 2015, 54, 13186-13197; b) J.-P. Lange, Catal. Sci.
Technol., 2016, 6, 4759-4767.
246
HUGS-OR11

Selective conversion of concentrated feeds of furfuryl alcohol to
alkyl levulinates catalyzed by metal triflates

1 2 1 2 1
Alban Chappaz, Jonathan Lai, Karine De Oliveira Vigier, Raphael Wischert, François Jérôme*,

1
2 Eco-Efficient Products and Processes Laboratory, UMI 3464 CNRS/Solvay, 3966 Jin Du Road,
Shanghai 201108, CHINA

Keywords: Acid catalysis, furfuryl alcohol, alkyl levulinate, metal triflates, concentrated feed of biomass
The catalytic conversion of renewable feedstocks to fuels, fine or specialty chemicals is now the
subject of intense research efforts. Although a myriad of reports published daily on this topic, the
emergence of bio-based fuels and chemicals in our society is unfortunately facing important hurdles
such as catalyst deactivation and high dilution (often required to better control the selectivity of
reactions), thus leading to unacceptable space time yields for industrial implementation.[1] The acid-
catalyzed ring opening of furfuryl alcohol (FA) in alcoholic media is a perfect example. This reaction
yields alkyl levulinates (AL) that are promising bio-based fuel additives and also industrially relevant
solvents or intermediates for the manufacture of pesticides, plasticizers or polymers. Several recent
studies have highlighted the possible production of ALs from FA in high yields (> 80%) using either
heterogeneous or homogeneous acid catalysts. To inhibit the unwanted acid-catalyzed polymerization
of FA, reactions are unfortunately conducted under diluted conditions, at FA concentrations in a typical
range of 0.2-3 wt% (vs. 30–40 wt. % in the current industrial process).
In this communication, we will show that bismuth triflate was capable of selectively converting
concentrated feeds of FA to ALs.[2] Under optimized conditions, butyl levulinate were obtained in up to
91% yield at a concentration of FA as high as 30 wt. %, which corresponds to an unprecedented
3
space time yield of 182 kg/m /h. This catalytic system is also compatible with other alkyl alcohols such
as methanol, ethanol, or isopropanol. Importantly, a catalytic amount of water in the alcoholic solution
of FA plays an important role on the activity and selectivity of Bi(OTf)3. Since no triflic acid was
detected in our experiments, alcoholysis of Bi(OTf)3 by n-butanol or furfuryl alcohol was excluded.
Instead, it was proposed a proton transfer between water molecules of the inner sphere of hydrated
+ -
Bi(OTf)3, forming a (OTf)3Bi-(H3O )( OH) complex (so-called Lewis-assisted Brønsted mechanism).
According to the amount of water, the exact composition of this complex will vary, and thus its catalytic
performances. A comparison with the commercialized SFOS process, operated by a subsidiary of the
former Rhône-Poulenc group and running until the beginning of the 90’s, shows that this novel
catalytic route is compatible with industrial requirements in terms of yield, productivity and capacity. An
extrapolation of these results to the dimension of the batch reactor used in the SFOS process
indicated that the annual production capacity could be theoretically improved to 14.5 kT in the
presence of the Bi(OTf)3/H2O catalytic system (vs. 5.6 kT for the SFOS process) while the E Factor
could be reduced to 0.06.
Synergistic effect with a
catalytic amount of H2O
+ CnH2n+1OH

H2O
High concentration + TOF = 500 h-1
M(OTf)x
feed (up to 40 wt%) Yield > 91%
Prod.> 200 kg/m3/h

[1]. a) J.-P. Lange, Angew. Chem .Int. Ed., 2015, 54, 13186-13197; b) J.-P. Lange, Catal. Sci.
Technol., 2016, 6, 4759-4767.
[2]. A. Chappaz, J. Lai, K. De Oliveira Vigier, D. Morvan, R. Wischert, M. Corbet, B. Doumert, X.
Trivelli, A. Liebens, F. Jérôme*, ACS Sust. Chem. Eng., 2018, 6 (3), 4405-4411.
247
HUGS-OR12

Unveiling the role of choline chloride
on furfural synthesis from a highly concentrated xylose

1 2 3
Shi Jiang, Charlie Verrier, Changru Ma,
2 3 1 1
Yves Queneau, Marc Pera-Titus, François Jérôme, Karine De Oliveira Vigier *,
1
IC2MP UMR CNRS_Université de Poitiers 7285, ENSIP 1 rue Marcel Doré, TSA 41195, 86073
Poitiers Cedex 9, France;
2
Université de Lyon, UCBL, CNRS, INSA Lyon, CPE Lyon, UMR 5246, ICBMS, Bat. Lederer, F-69622
Villeurbanne Cedex, France;
3
Eco-Efficient Products and Processes Laboratory (E2P2L), UMI 3464 CNRS-Solvay, 3966 Jin Du
Road, Xin Zhuang Ind. Zone, 201108 Shanghai, China
Keywords: Xylose, Choline chloride, Choline-xyloside, Furfural, High concentration
Furfural has recently been emphasized as a versatile platform chemical for the production of top
[1-2]
value-added chemicals such as fuel additives , being identified as one of the key chemicals
[3]
produced from biomass . The conversion of xylose to furfural occurs in an acidic media trough a
dehydration reaction. Many research are devoted to this reaction, but starting from a low concentrated
solution of xylose (up to 20 wt%). Indeed, the conversion of highly concentrated solution of xylose to
furfural is scarcely reported in the literature due to polymerization reactions leading to a low selectivity
to furfural. The main challenge of this reaction is to control the selectivity of this reaction by preventing
the formation of humins.
We have studied the conversion of a highly concentrated solution of xylose (up to 50 wt%) to furfural
in the presence of choline chloride, a cheap ammonium salt in the presence of HCl. We were pleased
to see that 70% yield of furfural was obtained and that the initial production rate was enhanced due to
the formation of choline-xyloside intermediate exhibiting higher reactivity than xylose(Scheme 1). A
mechanism describing the action of choline chloride during xylose hydrolysis is proposed based on the
kinetic and computational studies and will be presented.
Scheme 1 : Synthesis of furfural from a high concentrated feed of xylose in the presence of
choline chloride and HCl : formation of a high reactive choline-xyloside.
[1]. D. M. Alonso, S. G. Wettstein, M. A. Mellmer, E. I. Gurbuz, J. A. Dumesic, Energy Environ. Sci.,

2013, 6, 76-80
[2]. M. J. Climent, A. Corma, S. Iborra, Green Chem., 2014, 16, 516-547
[3]. J. J. Bozell, G. R. Petersen, Green Chem., 2010, 12, 539-554
248
HUGS-OR13

Biomass-derived electrodes for flexible supercapacitors

1 2 2 2 2
Jinjun CAI, Maria Magdalena TITIRICI, Philipp SCHLEE, Servan HEROU, Linh TRAN, Dina
3 3 3 2
IBRAHIM ABOUELAMAIEM, Daniel J. L. BRETT, Paul S. SHEARING, Ana Belen JORGE*,

1
School of Chemical Engineering, Xiangtan University, Xiangtan, China;
2
Materials Research Institute, School of Engineering and Materials Science, Queen Mary University of
London, London, United Kingdom;
3
Electrochemical Innovation Lab, Department of Chemical Engineering, University College London,
London, United Kingdom;

Keywords: biomass, supercapacitor, algae, cellulose, low-cost, sustainable, hydrothermal
carbonisation, chemical activation
At present, supercapacitors constitute, along with batteries, one of the most promising electrochemical
energy storage technology. The recent emerging generation of bendable portable electronic devices
has boosted the research of new materials, new processing techniques and new designs that can
meet the demands in terms of mechanical stability upon bending or stretching, without compromising
their electrochemical performance, at an acceptable cost. Among all the electrode materials currently
explored, biomass-derived carbons hold a great potential, due to their low-cost, easy processing
techniques, stability and versatility. Here we introduce the range of renewable precursors available
and current state-of-the-art performances, and explore the challenges regarding flexibility and
sustainability. I will also present latest results in our group on biomass-derived electrodes for
supercapacitor applications.
Fig. 1: Micro and nanostructured carbon materials from biomass and bio-inspired nano-
structure [1].
[1]. S. Herou, P. Schlee, A. Belen Jorge, M. Titirici, Current Opinion in Green and Sustainable
Chemistry. 2017, 9, 18.24.
[2]. D. Ibrahim Abouelamaiem, G. He, I. P Parkin, T. Neville, A Belen Jorge, S. Ji, R. Wang, M. Titirici,
P. Shearing, D. Brett, Sustainable Energy & Fuels, 2018, DOI: 10.1039/C7SE00519A.
249
HUGS-OR14

Solid State Assembly of Cellulose Nanocrystals in the Template of a
Fiber Cell Wall

1 1 2 3 4
Eero KONTTURI*, Iina SOLALA, Paavo A. PENTTILÄ, Jani SEITSONEN, Andreas MAUTNER,
2 5
Ralf SCHWEINS, Carlos DRIEMEIER

1
Department of Bioproducts and Biosystems, School of Chemical Engineering, Aalto University,
Espoo, Finland;
2
Institut Max von Laue - Paul Langevin (ILL) 71, Grenoble, France;
3
Nanomicroscopy Center, Aalto University, Espoo, Finland;
4
Polymer and Composite Engineering (PaCE) Group, Institute of Materials Chemistry and Research,
Faculty of Chemistry, University of Vienna, Austria;
5
Brazilian Bioethanol Science and Technology Laboratory (CTBE), São Paulo, Brazil
Keywords: renewable nanoparticles; solid state assembly
Assembly of nanoparticles is a much researched phenomenon in modern nanotechnology. While most

accounts have focused on metal nanoparticles, assembly of nanoparticles from biologically derived
materials has recently gained ground. Cellulose nanocrystals (CNCs), rigid nanorods isolated from
native plant cells, have been of particular interest, owing to their chirality, tunable aspect ratio, strong
mechanical properties, and renewable origin. Here, we present how CNCs can undergo directed
assembly before their isolation from their native template of a fiber cell wall.
CNCs are typically prepared by acid hydrolysis that selectively cleaves the disordered segments in
cellulose microfibrils, the supramolecular building blocks in the fiber cell wall. Generally, the isolation
of CNCs, i.e., the disintegration of the fibers, and the hydrolysis occurs simultaneously in a liquid/solid
medium. However, we recently showed that when HCl vapor or gas is used instead of liquid acid, the
1
fiber morphology remains intact although the hydrolysis into CNCs is completed. In this study, we
demonstrate that CNCs re-assemble during the hydrolysis inside the cotton linter fiber cell wall in solid
state due to the van der Waals attraction between the neighboring CNCs. The assembly was followed
by electron microscopy, small angle x-ray scattering, and inverse ion chromatography. It has tangible
ramifications which are demonstrated by their greatly decreased water uptake of the hydrolyzed fibers.
Assembly guided by the template of the fiber cell wall is a new concept in constructing nanoparticle
complexes and may prove important in utilizing the native origin of biological nanomaterials for
sustainable applications that do not even exist at this stage.
[1]. E. Kontturi, A. Meriluoto, P. A. Penttilä, N. Baccile, J.-M. Malho, A. Potthast, T. Rosenau, J.

Ruokolainen, R. Serimaa, J. Laine, H. Sixta, Angew. Chem. Int. Ed. 2016, 55, 14455-14458.

250
HUGS-OR15

On the oat husks modified polypropylene composite for injection
molding applications

1 1 1 2
Janis ZICANS,* Remo MERIJS MERI, Tatjana IVANOVA, Ivans BOCHKOVS, Piotr
2 3
FRANCISZCZAK, Andrzej K. BLEDZKI

1
Institute of Polymer Materials, FMSAC, RTU, Riga, Latvia;
2
Institute of Materials Science, ZUT, Szczecin, Poland

Keywords: polypropylene, biobased, composite, injection moulding, husks
Biobased polymer composites (BPC) become increasingly significant in the light of climate change
and depleting fossil resources. Consciousness of these global environmental problems has underlined
the importance of the development of biobased composites, which is now promoted by global and EU
level initiatives like EU Bioeconomy Strategy and OECDs “The Bioeconomy to 2030” project.
One of the most challenging issues in the development of natural sources derived composites is
increment of biobased content by keeping possibly high functionality of the multi-phase system. Since
decades wood flour (WF) is broadly used as technically comparatively effective and economically
viable reinforcement [1]. The effectiveness of WF, however, is limited to some extent due to
comparatively low aspect ratio of the reinforcement. Flax, hemp, jute, ramie, kenaf, sisal, harakeke
and many other natural fibers [2] with considerably higher aspect ratios have been used as an
alternative to WF to increase reinforcing efficiency of BPCs. In later years increasing attention is
devoted also to the fibers derived from other forms of lignocellulose sources, including agricultural
waste [3].
Consequently, the current research is devoted to the development of BPC with lignocellulosic
reinforcement, derived from husks, thus contributing to the world-wide circular economy initiative.
Reinforcement for BPC has been derived from oat husks (OH) due to it abundance in the region. The
content of OH has been fixed to 40wt.% to ensure suitability of the manufactured BPC for injection
molding applications. BPC, based on polypropylene (PP) matrix, has been obtained by using twin
screw extrusion and maleic anhydride grafted PP has been used to increase compatibility within the
multiphase system. Apart from structural investigations, particular attention has been devoted to
characterization of elastic, flexural, impact, thermal and moisture sorption properties of the developed
BPC to ensure its potential applications for manufacturing of injection molded articles for specific
building and automotive sectors.
Results of the investigation show that compatibilized PP/OH composite possess considerably
improved modulus of elasticity, flexural strength and impact strength in comparison to the neat
polymer matrix. In the meantime, ultimate deformation of OH reinforced PP composite is considerably
higher than that of the PP composite with WF. Improvement in the aforementioned mechanical
properties of PP/OH composite is generally due to the increased interaction between the polymer
matrix and the lignocellulosic reinforcement as confirmed by structural investigations.
[1]. M. Schwarzkopf, M. D. Burnard. Plastic Composites—Performance and Environmental Impacts.

In: Environmental Impacts of Traditional and Innovative Forest-based Bioproducts. Ch. 1. Ed. A.
Kutnar, S.S. Muthu, Springer, 2016, pp. 19-43.
[2]. K. L. Pickering, M. G. Aruan, Efendy, T. M. Le, Composites Part A 2016, 83, 98-112.
[3]. A. K. Bledzki, A. A. Mamuna, J. Volk, Composites Part A 2010, 41, 480-488.
251
HUGS-OR17

Importance of safety considerations of furanics compounds and

their side streams in advanced biorefineries

1,2,3 1 1 2
Anitha MURALIDHARA, Pascal PANDARD, Anne BADO-NILLES, Christophe LEN, Gerard VAN
3 1
KLINK and Guy MARLAIR *

1
Institut national de l'environnement industriel et des risques (INERIS), Verneuil-en-Halatte, France
2
Sorbonne Universités, Université de Technologie de Compiègne, Compiègne ,France
3
Avantium Chemicals B.V., Amsterdam, the Netherlands
Keywords: Humins, furanics, thermal hazard, fire and accidental risk, toxicity
One of the biggest challenges in today’s biorefinery operations is to handle the side stream residues
generated during their process. Humins are side stream residues generated during the acid catalyzed
dehydration of C6 and C5 sugars during the production of furanic intermediates such as HMF and
derivatives,[1] eventually leading to FDCA [2] and other platform chemicals of potential industrial
applications.[3] With the concept of circular economy, biorefinery operations are envisaging the
valorization of humins,[4] while transforming them into valuable byproducts worth some applications.
To achieve a reasonable market value, one of the preliminary requirements is to understand the safety
attributes of the material when subjected to various process conditions or applications. Considering
the large diversity of furanic compounds, we may anticipate varying risk profiles for each of them. So
far, very limited members of furanic family are thoroughly characterized so as to establish their
conventional hazards according to mandatory applicable haz-mat classification systems (such as GHS
or UN model regulations for transport of dangerous goods etc). Concerning industrial humins, there
are fairly good amount of characterizations done so far to understand their chemical nature.[5]
However, there are no dedicated studies done in terms of safety assessment either on furanics or
humins to understand their behavior at various conditions as well as foreseeable risks during
applications.[6]
Worth realizing that, safety is an important aspect in achieving sustainable products and processes,
which shall not be bound just to the extent of official haz-mat classification systems. There are several
aspects such as thermal stability, speed of combustion, chemical incompatibilities, ease of ignition,
hotspot ignition and other environmental attributes which can clearly influence chemical accidents, if
not correctly taken care of.
Therefore, this study specifically aims at identifying various patterns of safety characteristics and
defining trends to understand the family of furanic compounds and humins for their sustainable
applications. Fire and explosion risks, physico-chemical and eco-toxicological safety studies are
performed for humins and other furanics appearing in the value chain of humins production process
via experimentation. Additional insights on safety behavior of other furanic compounds will also be
done with the use of dedicated predictive models and tools.
[1] I. Van Zandvoort, Y. Wang, C.B. Rasrendra, E.R.H. Van Eck, P.C.A. Bruijnincx, H.J. Heeres,
B.M. Weckhuysen, ChemSusChem. 6 (2013) 1745–1758.
[2] E. De Jong, M.A. Dam, L. Sipos, G.-J.M. Gruter, ACS Symp. Ser. (2012). doi:10.1021/bk-2012-
1105.ch001.
[3] E. De Jong, G.-J. Gruter, SAE 2009 Powertrains Fuels Lubr. Meet. FFL 2009. 4970 (2009) 1–
7.
[4] J.M. Pin, N. Guigo, A. Mija, L. Vincent, N. Sbirrazzuoli, J.C. Van Der Waal, E. De Jong, ACS
Sustain. Chem. Eng. 2 (2014) 2182–2190.
[5] I. van Zandvoort, E.J. Koers, M. Weingarth, P.C.A. Bruijnincx, M. Baldus, B.M. Weckhuysen,
Green Chem. 17 (2015) 4383–4392.
[6] Avantium Chemicals BV, humins sds_2.pdf, (2014).
252
HUGS-OR20

Fully biobased composites by humins valorization

1,2 2 1 2
Anna Sangregorio , Nathanael GUIGO , Jan C. van der Waal , Nicolas Sbirrazzuoli

1
Avantium Chemicals B.V., Zekeringstraat 29, 1014 BV Amsterdam, the Netherlands;
2
Universitée cote d’azur, Institut de chimie de Nice, CNRS, UMR 7272, 2, France

Keywords: Biomass valorization, humins co-product, natural fibers composites
Humins, heterogeneous and polydisperse macromolecules, are a co-product derived from sugar
dehydration processes. Humins are mainly constituted of furanic rings (interconnected and/or bonded
by alkylene moieties) and functional groups such as aldehydes, ketones and hydroxyls. So far, the
scientific community has been targeting ways to avoid humins formation during biorefinery processes.
Nonetheless, humins formation appears to be almost inevitable. Therefore, the attention is focusing on
ways to make high-value products out of humins. Despite many potential applications have been
envisioned, humins are predominately used for energy and heat applications such as burning and
gasification. This is due not only to the lack of knowledge concerning the humins structure but their
reactive behavior as well. Increasing this knowledge is fundamental to increment the humins
valorization value and look for potential applications of this biobased macromolecule.
Applications involving humins as biobased thermoset material were studied. The ability of this material
to crosslink under different conditions was demonstrated. It is possible to obtain a thermoset polymer
with different properties, based on the treatment used. Humins were tested as matrix with flax fibers,
to make 100% biobased thermoset materials. Mechanical properties showed promising results and a
good interface was observed by SEM. These results indicate that humins can be a very promising
material for the preparation of the next generation of biobased thermoset composites.
Fig. 1: SEM image of a flax fiber embedded with cross-linked humins
253
HUGS-OR21

Synthesis of HHD and HHD-derived chemicals from HMF

1 1 1 2 1
Bartosz Wozniak, Sergey Tin, Anke Spannenberg, Yuehui Li, Sandra Hinze, Johannes G. de
1
Vries *,

1
Leibniz-Institut für Katalyse, Rostock, Germany
2
Lanzou Institute of Chemical Physics, Lanzou, China

Keywords: biomass, 5-(hydroxymethyl)furfural (5-HMF), 1-hydroxyhexane-2,5-dione (HHD), 3-
methylcyclopent-2-enone (MCP), pyrrole
In view of the dwindling supply of fossil resources new scenarios need to be developed for the
manufacture of the chemicals our lives depend upon, such as pharmaceuticals or plastics, which are
currently derived from crude oil. We are interested in the catalytic conversion of platform chemicals
derived from renewable resources to existing or new chemicals [1]. 5-(Hydroxymethyl)furfural (HMF, 1,
Scheme 1) is obtained by the dehydration of fructose, and has become a well-known platform
chemical for the production of numerous valuable chemicals (such as 2,5-furan-dicarboxylic acid) [2].
Recently, we became interested in the further development of the synthesis of 1-hydroxyhexane-2,5-
dione (HHD, 2, Scheme 1), a product of the hydrogenation/hydrolytic ring opening of HMF [3].
HHD is a promising precursor for the production of valuable biomass-based fine chemicals. Apart from
its synthesis, we are also going to describe the synthesis of HHD-derived compounds, such as 3-
methylcyclopent-2-enone (MCP) and its derivatives [4], pyrroles [5] and others.
Scheme 1: Synthesis of HHD and HHD-derived products from HMF
[1]. (a) Top Value-Added Chemicals from Biomass Vol. I—Results of Screening for Potential
Candidates from Sugars and Synthesis Gas (eds. T. Werpy, G. Petersen), U. S. Department of
Energy (DOE) by the National Renewable Energy Laboratory, a DOE national Laboratory, 2004;
(b) P. J. Deuss, K. Barta, J. G. de Vries, Catal. Sci. Technol. 2014, 4, 1174-1196; (c) J. G. de
Vries, Chem. Rec. 2016, 16, 2787-2800.
[2]. (a) R. Karinen, K. Vilonen, M. Niemela, ChemSusChem 2011, 4, 1002-1016; (b) T. Ståhlberg, W.
Fu, J. M. Woodley, A. Riisager, ChemSusChem 2011, 4, 451-458; (c) R. J. van Putten, J. C. van
der Waal, E. de Jong, C. B. Rasrendra, H. J. Heeres, J. G. de Vries, Chem. Rev. 2013, 113, 1499-
1597; (d) J.G. de Vries in Heterocyclic Chemistry in the 21st Century: A Tribute to Alan Katritzky,
Advances in Heterocyclic Chemistry Volume 121, ed. E.F.V. Scriven, C.A. Ramsden, Academic
Press (Elsevier), Cambridge, MA, 2017, pp 247–293.
[3]. (a) Z. Xu, P. Yan, W. Xu, X. Liu, Z. Xia, B. Chung, S. Jia, Z.C. Zhang, ACS Catal. 2015, 5, 788-
792; b) Z. Xu, P. Yan, H. Li, K. Liu, X. Liu, S. Jia, Z.C. Zhang, ACS Catal. 2016, 6, 3784-3788; c)
W.P. Wu, Y.J. Xu, R. Zhu, M.S. Cui, X.L. Li, J. Deng, Y. Fu, ChemSusChem, 2016, 9, 1209-1215.
[4]. (a) J. Ohyama, R. Kanao, A. Esaki, A. Satsuma, Chem. Commun. 2014, 50, 5633-5336; (b) J.
Ohyama, R. Kanao, Y. Ohira, A. Satsuma, Green Chem. 2016, 18, 676-680; (c) B. Wozniak, A.
Spannenberg, Y. Li, S. Hinze, J. G. de Vries, ChemSusChem, 2017, 10, 1.
[5]. B. Wozniak, Y. Li, S. Hinze, S. Tin, J. G. de Vries, Eur. J. Org. Chem., 2018, article accepted.

254
HUGS-OR22

New rigid foams based on industrial humins

1 2 1
Pierluigi Tosi, Gerard P. M. van Klink, Alice Mija *

1
Université Côte d’Azur, Institut de Chimie de Nice UMR 7272, 06108 Nice, France;
2
Avantium Chemicals B.V., Zekeringstraat 29, 1014 BV, Amsterdam, the Netherlands

Keywords: humins, porous materials, carbon foams, lignocellulosic biomass, by-product valorization
Novel carbonaceous polymeric porous materials have been recently produced by a straightforward
[1]
auto-crosslinking reaction of industrial humins using a simple thermal process.
Humins are the principal side-products of the production of levulinic acid, 5-hydroxymethylfurfural and
[2]
derivatives during the acid catalyzed dehydration of C6-sugars in biorefinery. During this process, a
random incontrollable polymerization occurs between several intermediates in the acid media, leading
[3,4]
to a black viscous mixture of oligomers with a C/O/H average ratio of 60/32/5 wt%. The humins
chemical structure is made by a network of furanic rings and aliphatic chains bearing reactive moieties
[5]
(hydroxyls, esters, ketons and aldehydes), while several monomers are trapped in the matrix. These
groups and species allowed humins to be able to auto-crosslink in a thermoset material if sufficient
[6]
thermal energy is furnished. Noteworthy, we found that this behavior is accompanied by a self-
foaming capacity, leading to macroporosity in the final material (Fig. 1). The mechanism of foaming
has been studied, revealing to be a combination of phenomena occurring simultaneously, such as a
6
decreasing of viscosity of 10 Pa·s up to 120°C, volatiles releasing from 140°C, polymerization
reactions from 170°C.
These humins based foams can be produced from the crude industrial humins as received, without
any purification or modification step, without the use of any harsh reagent and with a simple
straightforward thermal step, which is a clear advantage for biorefinery. Several parameters, such as
C%, density, surface polarity, pores dimension and morphology of the final material, as well as the
yield of open/closed cells, can be controlled by selecting the thermal program used during the foaming
step. The C% can be increased up to 95% with a thermal treatment at 900°C, enhancing property
such surface neutrality and electrical conductivity, which could be useful in application as
supercapacitor or electrode.
In this presentation several aspects of humins foams production, applications and modifications will be
discussed.
[1] P. Tosi, G. P. van Klink, A. Celzard, V. Fierro, L. Vincent, E. de Jong, A. Mija, ChemSusChem
2018.
[2] R. Van Putten, J. C. Van Der Waal, E. De Jong, C. B. Rasrendra, H. J. Heeres, J. G. De Vries,
R.-J. van Putten, J. C. van der Waal, E. de Jong, C. B. Rasrendra, et al., Chem. Rev. 2013,
113, 1499–1597.
[3] B. Girisuta, B. Danon, R. Manurung, L. P. B. M. Janssen, H. J. Heeres, Bioresour. Technol.
2008, 99, 8367–8375.
[4] A. Mija, J. C. van der Waal, J. M. Pin, N. Guigo, E. de Jong, Constr. Build. Mater. 2017, 139,
594–601.
[5] I. van Zandvoort, E. J. Koers, M. Weingarth, P. C. A. Bruijnincx, M. Baldus, B. M. Weckhuysen,
Green Chem. 2015, 17, 4383–4392.
[6] A. Mija, E. de Jong, J. C. van der Waal, G. van Klink, Humins Containing Foam, 2017, WO
2017074183 A1 20170504.

255
HUGS-OR23

Nanomaterials and biorefineries: inspiring some safety thoughts

1
Alexis Vignes
1
INERIS, Parc Technologique ALATA, BP2, 60550 Verneuil-en-Halatte, France;
Keywords: nanosafety, bio-based chemicals, biorefineries, accident risks
This presentation aims essentially at examining and discussing the potential nanosafety issues
pertaining to the production of advanced bio-based chemicals that might impact their development.
Nanomaterials are now used for energy storage and conversion, the production of various added-
value chemicals from biomass including biochemicals, biomaterials and biofuels. Several
nanomaterials are also synthetized from renewable and highly abundant feedstocks like carbonaceous
nanomaterials (fullerene, carbon nanotubes) or nanocellulose. The use of nanomaterials has paved
the road of multiple sustainable innovations and is perceived as rather safe because "green", i.e.
avoiding the use and generation of toxic and polluting substances [1]. Safety concerns about these
materials were raised by the bio-community only recently [2]. It is however important to have a closer
look at their potential environmental and occupational risks. Concerning hazards related to
nanomaterials, their potential toxicity is the first thing that comes to mind. However, toxicity of these
materials is not the only potential hazard. Thermal stability, flammability and dust explosivity also have
to be assessed as several types of nanomaterials are combustible powdered materials that
may accidentally turn into explosible atmospheres. Historically, literature studies concerning the
evaluation of explosion and flammability hazards of powders were essentially but several
investigations are being carried out also on nanomaterials and several questions are raised through
EU research projects as well as in the European Standardization Committees, CEN TC 352. Testing
strategies that may be used for screening purposes at pre-commercial stages should also be
discussed as they require dedicated facilities such as the S-NANO Platform at INERIS. The hazard
characterization of the nanomaterials issued from bio-engineering is essential to ensure that their
market deployment is not delayed by uncertainties related to their safety. This presentation gives a
brief overview of the current challenges and knowledge on the topic as well as some considerations
about the concepts related to the inherent safety design of these materials.
[1]. Rafael Luque, Alina Mariana Balu, Producing fuels and fine chemicals from biomass using
nanomaterials, 2014, CRC Press, Taylor and Francis, 328 pp.
[2]. Julia Catalán Hannu Norppa, Safety Aspects of Bio-Based Nanomaterials, Bioengineering
2017, 4, 94; doi:10.3390/bioengineering4040094
256
HUGS-OR24

Is Doping Performance Enhancing? Hydrothermal Carbons in
Catalyst Development.

1, 1
Robin J. White, * Monika Bosilj,
1
Sustainable Catalytic Materials Group, Division Hydrogen Technologies, Fraunhofer Institute for
Solar Energy Systems ISE, Heidenhofstr. 2, 79110 Freiburg, Germany
Keywords: Catalysis, Hydrothermal Carbon, Functional Materials, Sustainability, Green Chemistry
Catalysts are key to the establishment of sustainable circular energy/chemical economies based on
1
renewable energy, CO2 and biomass. In this context, carbon supported catalysts have an important
role provided there their properties can be tailored at various length scales to address the catalytic
demands of these economies (e.g. challenging aqueous phase chemistry of the Biorefinery). In this
presentation, the development of efficient synthesis methods to meet this need - i.e. to produce
tuneable functional materials with suitable porosity – will be introduced. Carbon material
nanostructuration assists good diffusion and mass transport, whilst bulk and surface chemistry
optimisation may lead to application benefits (e.g. metal-support interactions, retention behaviour etc.).
This “tailoring” should be conducted through scalable and sustainable technologies whilst also being
market competitive (e.g. vs. Activated Carbons). The use of hydrothermal carbonisation (HTC)
2
approach will be introduced, with a particular focus on produce nitrogen-doped carbons,
3 4
demonstrating direction of functionality, and porosity (e.g. micro- vs. mesoporosity). One particular
approach of interest is the HTC of model (amino) sugars and globular proteins or amino acids to
porous, functional, nitrogen-doped carbonaceous materials, which allows scope to tailor nitrogen
incorporation (e.g. pyrrolic vs. pyridinic content) – e.g. important regarding sorption properties. This
synthesis is inspired by Maillard-type chemistry and the reaction between reducing sugars and amino
groups (as the nitrogen source), and lays the basis for the development of a flexible, controllable
synthesis platform, to materials suitable for a wide range of applications (e.g. as catalysts supports,
electrodes, etc.). As an example of the potential application benefit, the demanding direct oxidation of
5
CH4 (e.g. as sourced from biogas) to CH3OH is presented. Likewise, the use of N-doped carbons as
templates in the synthesis of meso-structured single crystal zeolites (e.g. H-ZSM-5 for CH3OH
6
upgrading), will also be discussed, highlighting further the remit of these synthetic approaches.
Fig. 1: Examples of different porous functional carbons produced via HTC.
[1]. R. J. White, “The Sustainable Synthesis of Methanol - Renewable Energy, Carbon Dioxide and an
Anthropogenic Carbon Cycle”, in “Chemical Processes for a Sustainable Future”, 2015, Ch. 8, p.
195, Ed.: T. M. Letcher, J. L. Scott, D. Patterson, Royal Society of Chemistry, Cambridge, UK.
[2]. M. M. Titirici, R. J. White, N. Brun, V. L. Budarin, D. S. Su, F. del Monte, J. H. Clark, M. J.
MacLachlan, Chem. Soc. Rev., 2015, 44, 1, 250.
[3]. R. J. White, N. Yoshizawa, M. Antonietti, M. M. Titirici, Green Chem., 2011, 13, 9, 2428.
[4]. R. J. White, N. Brun, V. L. Budarin, J. H. Clark, M. M. Titirici, ChemSusChem, 2014, 7, 3, 670.
[5]. M. Soorholtz, R. J. White, T. Zimmermann, M. M. Titirici, M. Antonietti, R. Palkovits, F. Schüth,
Chem. Commun., 2013, 49, 240.
[6]. R. J. White, A. Fischer, C. Goebel, A. Thomas, J. Am. Chem. Soc., 2014, 136, 7, 2715.
257
HUGS-OR25

Fluorescent/Transparent Wood based Composite Materials

Zhihao Bi, Lifeng Yan *

Hefei National Laboratory for Physical Sciences at the Microscale, Department of Chemical Physics,
iCHEM, University of Science and Technology of China. Hefei, 230026, P.R.China

Keywords: Wood, composites, fluorescence, transparent
Woods or substrates made of cellulose fibers are ubiquitously used in solar cell and building.
However, transparent and/or fluorescent wood is scare for its complex structure of cellulose,
hemicellulose and lignin. Here, lignin was first removed from wood using a green solvent of ionic
liquid, and porous cellulose based wood was obtained, and then acrylic acid solution was immerged
and polymerized therein to form a new composite of wood/PAA, where PAA owns similar refractive
index to cellulose, making the composite a high transparent and flexible composite with mechanical
tensile strength of 60.92 MPa when Balsa wood was used as the feedstock. Interestingly, when the
acrylic acid monomer was polymerized in the presence of carbon nanodots (CDots),
fluorescent/transparent wood composite can be prepared, which emitted fluorescence in a wide range
of wavelength from ultraviolet to visible region, makes potential materials for various application in a
wide range of fields, such as smart windows, electronic devices, etc.
Fig. 1: Photographs of the CDots/transparent wood composite with different kinds of CDots (a-
c) and fluorescent images of relative composite under light irradiation (d-f)
[1]. F. Jiang, T. Li, Y. J. Li, Y. Zhang, A. Gong, J. Q. Dai, E. Hitz, W. Luo, L. B. Hu Adv Mater. 2018,
30, 1703453.
[2]. A. W. Lang,Y. Li, M. D. Keersmaecker, D. E. Shen, A. M. Osterholm, L. Berglund, J. R. Reynolds.
ChemSusChem 2018, 11, 854-863.
258
HUGS-OR26

Platform Technology for a Guayule Biorefinery
Gianni Girotti
Green Chemistry R&D Manager - Piazza M. Boldrini, San Donato Milanese, (MI), Italy
[email protected]
Guayule is a desert shrub native to Mexico and southwestern U.S, known as alternative source of
Natural Rubber (NR, the most important bio-polimer) whose worldwide production is about 10.6 Ml T/y
(1.2 million fully imported every year in Europe) nowadays only obtained from Hevea Brasiliensis
cultivated mainly in Asia (93 %) and in Africa.
Alternative sources of NR like Guayule (and also Russian Dandelion indigenous to Uzbekistan &
Kazakhstan) are of great and increasing interest for main end users due to several reasons like
threats to Hevea trees (SALB and WRD), its competition with Palm Oil plantation as well as many
social problems connected to the large use of women and children workers in the plantations (where
manpower is predominant), all projecting for the next 5-10 years a NR shortage/price increase.
Versalis started in 2014 the R&D project on Guayule with two main targets : developing (i) an
agricultural protocol viable for south Europe and (ii) a technology platform supporting a Guayule
biorefinery where every part of the biomass is valorized to obtain a pattern of products. From Guayule
can be obtained two kind of primary NR such as the latex – having unique anallergenic properties
particularly suitable for medical devices and performance suits manufacturing – and the dry one,
suitable for less value but larger amount uses such as tyre and general purpose goods manufacturing,
both obtained by means of proper water/solvent extraction technologies.
Furthermore and greatly contributing to guayule’s biorefinery economic sustainability, the Guayule
plant also produces a complex and valuable mixture of terpene-based resins and essential oils again
extracted by water/solvent technology, finally leaving a residual lignocellulosic biomass (bagasse)
further used to produce second generation sugars (by means of proper saccharification technology) to
be used in bio-based chemicals or bio-fuels production thorough specific fermentation technologies as
well as in power generation (this latter limited to lignin fraction residual from saccharification process).
In 2017 Versalis & Bridgestone, who had started independently its own Guayule project taking also
advantage of previous and large experience and know-how developed by Firestone Corp. during the
2° World War within the Emergency Rubber Program (ERP), decided to join their efforts and
backgrounds to develop a joint platform technology specifically targeting a Guayule biorefinery
exploiting the entire biomass value, including Agro development for improved and customized seeds
to be used in both desert/semi arid (like in south U.S.) and continental (like in south EU) pedo-climatic
conditions as well as improved harvesting machineries and plant management techniques before
extraction.
Currently Versalis has demo fields of Guayule in the south of Italy (Sicily and Basilicata regions)
managed in cooperation with Bridgestone Agro-Operation team (Arizona) in order to take advantage
from the availability of different soil and climate condition allowing faster testing of selected germplasm
resources and planting techniques, which have already lead to comparable yields in terms of Tons of
NR per hectar per year (obtained in both Italy and Arizona locations and based on a completely
mechanized guayule cultivation/harvesting/extraction processes) over the completely manual Hevea
Brasiliensis.
259
ENERGY-OR02

Mussel-inspired hydrophilic polymer binder for cathode in seawater

batteries

1 1 1 1 1
Myeongjin Baek, Jieun Choi, Jintae Park, Chanoong Lim, Dong Woog Lee *,
1
School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology
(UNIST), UNIST-gil 50, Ulsan 689-798, Republic of Korea;
Keywords: Mussel-inspired, Catechol, DOPA, Hydrophilic binder, Seawater battery
Seawater batteries have advantages of being low-cost, eco-friendly and low toxicity due to lack of
toxic chemical compounds such as nickel and cobalt [1]. In general, the most used polymer binders
are hydrophobic (e.g., PvdF, Nafion) [2], but these binders have low wettability toward seawater which
can cause various problems such as unstable charge-discharge reaction and low performance. Thus,
development of a hydrophilic polymer binder which can enhance the wettability between the current
collector and seawater is necessary. Herein, hydrophilic polymer binders are synthesized by
copolymerization of two moeities: (i) Poly(ethylene glycol), a hydrophilic polymer, and (ii) 3.4-
Dihydroxyphenylalanine (DOPA), which plays an important role in mussel adhesive proteins [3]. In
order to prevent dissolution of polymer binders, 2 wt% of Poly(ethylene glycol) diacrylate (PEGDA)
was used as crosslinking agent. Synthesized DOPA-hydrophilic binder exhibited enhanced wettability
toward seawater which resulted in higher power, charge-discharge cycle stability compared to
conventional hydrophobic binders. The adhesion forces of polymer binders (containing catechol,
phenol, and benzene) against carbon felt are measured by using a surface force apparatus (SFA),
resulting in the highest adhesion force with catechol group containing polymer(Fad ~ 7.2 mN),
compared to the phenol (Fad ~ 4.2 mN) and benzene (Fad ~ 2.6 mN) containing polymers.
Furthermore, when using the synthesized polymer, a power output of 16.0 mW was measured, which
is 88% higher than the power output (8.5 mW) using PvdF. These results indicate that DOPA-
hydrophilic binder plays a key role improving the performance and stability of the seawater batteries.

Fig. 1. The synthesized hydrophilic binder in a seawater battery.

The catechol group in synthesized polymer hold Pt/C catalyst in a well-distribute state and
makes catalyst tightly tightly with carbon felt.
[1]. Y. Kim, J. Kim, C. Vaalma, G. Bae, G. Kim, S. Passerini, Y. Kim, Carbon. 2018, 129, 564-571.
[2]. S. Park, B. SenthilKymar, K. Kim, S. M. Hwang, Y. K, J. Mater. Chem. A. 2016, 4, 7207-7213.
[3]. J. Waite, X. Qin, Biochemistry. 2001, 40, 2887-2893.
260
ENERGY-OR05

Self-assembly of Amino Acidic Bolaamphiphiles for Building

Enzyme-mimetic Catalysts

1 1 1
Changjoon Keum, Min-Chul Kim, Sang-Yup Lee*,

1
Department of Chemical & Biomolecular Engineering,Yonsei University, Seoul, South Korea

Keywords: self-assembly; bolaamphiphile; catalyst; histidine
Bolaamphiphile is a kind of amphiphilic molecules which has two hydrophilic moieties linked to
ends of the central hydrophobic segment. The bolaamphipihles self-assemble to build stable complex
structures because of the symmetric structure [1]. Recently, amino acids are adopted as hydrophilic
segments to build amino acidic bolaamphiphiles. The amino acidic bolaamphiphiles are advantageous
to construct a protein-mimetic structure where the functional groups of the amino acids interplay to
exhibit biochemical activities [2]. In this study, the assembled structure of histidyl bolaamphiphiles was
used as a host matrix to build metalloenzyme-mimetic catalysts. The histidyl bolaamphiphiles that
adopt histidines as amino acid self-assembled to form solid particulate structures with exposure of
histidine imidazoles on the surface. The histidine imidazoles are densely packed on the surface of
assembled structure such that they can be functioned as multiple imidazole ligands to coordinate with
transition metal ions. Zn and Mn ions were coordinated to the histidyl self-assembled structures and
displayed catalytic activities for the hydration of carbon dioxide and oxidation of organic compounds,
respectively [3-5]. Spectroscopic observation confirmed coordination of those transition metal ions to
the histidine imidazoles displaying metalloenzyme-like catalytic activities. The assembly of amino
acidic bolaamphiphiles is advantageous for the construction of protein-like structures and for
mimicking the metalloenzymes.

Fig. 1. Construction of the enzyme-mimetic catalyst via bolaamphiphile self-assembly
[1] J. H. Fuhrhop, T. Wang, Chem. Rev. 2004, 104, 2901-2937.

[2] J. Kwak, S. S. Nam, J. Cho, E. Sim, S.-Y. Lee, Phys. Chem. Chem. Phys. 2017, 19, 10274-
10281.
[3] M.-C. Kim, S.-Y. Lee, Chem. Eur. J. 2014, 17019-17024.
[4] M.-C. Kim, S.-Y. Lee, Nanoscale, 2015, 7, 17063-17070.
[5] C. Keum, M.-C. Kim, S.-Y. Lee, J. Mol. Catal. A, 2015, 408, 69-74.
261
ENERGY-OR07

Enabling Solar-Fuel Production with Biomimetic Architectures

Dasom Jeon, Hyunwoo Kim, Sanghyun Bae, Cheolmin Lee, and Jungki Ryu*
1
Ulsan 44919, Republic of Korea
*E-mail: [email protected]

Keywords: biomimetics, artificial photosynthesis, solar water oxidation,
Solar water oxidation has been considered a holy grail of scientists and engineers as it allows
production and the use of valuable chemical compounds in a sustainable and carbon-neutral manner.
In principle, virtually any kinds of chemical compounds can be produced by developing a proper
electrocatalyst for synthesis of a target compound and coupling it with photocatalytic water oxidation,
so-called artificial photosynthesis. Despite huge efforts made for decades, its practical application
remains questionable due to its low efficiency and stability. Considering that it is enabled by a series of
photoelectrochemical processes with multiple functional components, their tailored assembly into an
integrated device with a nanoscale precision is critically required as well as development of individual
components with high performance. Indeed, the Mother Nature has crafted a unique method to
precisely assembly various functional components by self-assembly to effectively facilitate and couple
individual processes/components. To date, however, the importance of the precise assembly has
been often ignored, losing an opportunity to improve the performance of the photosynthetic devices
even further.
To address such a problem, we report herein the fabrication of biomimetic architectures,
especially nacre-like layered structure and its application in efficient solar-fuel (e.g., H2) production.
Briefly, we could readily deposit various functional components such as light-harvesting, charge
transporting, and catalytic components using the layer-by-layer assembly in a desired order and
dimension, resulting in the formation of precisely assembled nacre-like film with a significantly
improved photocatalytic performances. This was because of efficient charge transport enabled by
precise assembly of individual functional components, which is reminiscent of mesoscale organization
of thylakoid organelles of plants. Our detailed analysis also revealed that the deposition of the nacre-
like film allows engineering of the work-function of underlying electrodes, improving the performance
of devices even further. Based on these findings, we could successfully build a bias-free
photoelectrochemical cell for solar fuel production through the overall water splitting. We believe that
our results demonstrate the versatility of biomimetic approaches for the design and fabrication of
efficient photosynthetic devices.
Fig 1. Graphical illustration showing the fabrication and principles of photosynthetic devices with
nacre-like nanoarchitectures for solar fuel production.
[1] Ryu, D. H. Nam, S. H. Lee, C. B. Park, Chem. Eur. J. 2014, 20, 12020-12025.
[2] D. Jeon, H. Kim, C. Lee, Y. Han, M. Gu, B.-S. Kim, J. Ryu, ACS Appl. Mater. Interfaces 2017,
9, 40151-40161.
[3] D. Jeon, N. Kim, S. Bae, Y. Han, J. Ryu, ACS Appl. Mater. Interfaces 2018, 10, 8036-8044.
[4] Y. Choi, D. Jeon, Y. Choi, J. Ryu, B-S. Kim, ACS Appl. Mater. Interfaces 2018, 10, 13434-
13441.
262
ENERGY-OR08

Photocatalytic O2 Reduction at a Laccase

Yasmina Mekmouche, Pierre Rousselot-Pailley, Simeng Zhou, Vincent Seyahi, Bruno Faure, Julien
Massin, A. Jalila Simaan and Thierry Tron*
iSM2, UMR7313, Aix Marseille University, Marseille, France
Keywords: photo-catalysis; chemo-enzymatic system; laccase; renewable electron acceptor
We have recently reported on the photo-catalytic four-electron, four-proton reduction of O2 in a multi

copper oxidase (MCO) using porphyrin and ruthenium polypyridine chromophores in the presence of
[1, 2] [3]
an electron donor. In this system, the enzyme’s unique set of copper centres - a mononuclear
type 1 and tri-nuclear cluster (TNC) – couples photo-oxidation reactions to dioxygen reduction. This
makes the enzyme laccase a substitute for sacrificial electron scavengers in driving photocatalytic
multielectronic oxidative processes (Fig. 1). From our initial bi-molecular systems we will present our
[4]
latest architectures introducing electron relays and an oriented grafting of the enzyme’s surface.
Efficiency of photo-enzymatic catalysts for olefin oxidation will be discussed.
Fig. 1. Photo-oxidation of olefins coupled to the light-driven reduction of O2 by a Ru–

polypyridyl complex–laccase. The paths depicted in grey do not lead to product formation in
the absence of enzyme. Ribbon model of laccase: Cu ions are depicted as grey spheres.
[1]. T. Lazarides et al., J. Am. Chem. Soc. 2013, 135, 3095

[2]. L. Schneider et al., Chem. Sus. Chem., 2015, 8, 3048
[3]. E. Solomon, U. Sundaram, T. Machonkin, Chem. Rev., 1996, 96, 2563
[4]. V. Robert, et al., Chem Plus Chem, 2017, 82, 607
263
ENERGY-OR09

From biophenols to fully biobased thermosets: focus on
benzoxazine resins

1 1 1
Acerina TREJO-MACHIN, Laura PUCHOT , Pierre VERGE *

1
Luxembourg Institute of Science and Technology, Luxembourg, Luxembourg

Keywords: Benzoxazine, biophenols, cardanol, phloretic acid, thermoset resins
Thermoset polymers are mainly represented by phenolic and epoxy resins, known for their high
performance applications due to notable thermal and mechanical properties, good chemical resistance
and flame retardation. However, these high performance multicomponent thermosets are mainly
derived from petroleum resources and composed of chemicals that wreak havoc on human health.
Benzoxazine resins – namely polybenzoxazines (PBz) – are a new class of thermoset polymers
emerging since several decades and are considered as a promising substitution of phenolic or epoxy
resins [1, 2]. Indeed, benzoxazine monomers are synthesized through a Mannich-like condensation of
a phenolic derivative, a primary amine (aliphatic or aromatic) and formaldehyde, followed by a ring-
closure process. With the growing trend to produce environmentally-friendly and high performance
materials derived from renewable resources, the use of bio-based phenolic derivatives for the
synthesis of Bz monomers is considered as a viable alternative. A broad screening of various mono-
or di-functional Bz monomers from naturally occurring phenolic compounds and their resulting
materials have been reported during the last years, attesting the clear trend of promoting the use of
renewable bio-resourced reagents for the development of competitive bio-based thermosets.
During this lecture will be given an overview of the biophenols used for the design of polybenzoxazine
resins. In particular, the most recent advances reached in our Institute will be detailed. Concrete
examples of 100% biobased benzoxazine resins (Fig. 1) with specific properties, currently in
development in our laboratories, will be presented [3, 4].
Fig. 1: Example of the chemical structures of 100% biobased benzoxazine resins
[5]. Ning, X. & Ishida, H. J. Polym. Sci. Part Polym. Chem. 1994, 32, 1121–1129
[6]. Ishida, H. & Allen, D. J. J. Polym. Sci. Part B Polym. Phys. 1996, 34, 1019–1030
[7]. Puchot, L., Verge, P., Vancaeyzeele, C., Vidal, F., Habibi, Y., Green Chem. 2016, 18, 3346–
3353.
[8]. Trejo-Machin, A., Verge, P., Puchot, L. & Quintana, R. Green Chem. 2017, 19, 5065–5073
264
ENERGY-OR10

Cross-Species Inspired Patterned Slippery Surfaces
for Fog Harvesting

1,3 2,3 2,3
Lin WANG, Jing WANG, Tak-Sing WONG *,
1
Department of Material Science and Engineering;
2
Department of Mechanical and Nuclear Engineering;
3
Material Research Institute;
The Pennsylvania State University, University Park, Pennsylvania, USA

Keywords: Bio-Inspired, Slippery Surface, Pattern, Wettability, Fog Harvesting,
Developing a technology that could efficiently harvest fresh water from fog is essential to alleviate
the global water crisis, especially in the coastal and arid regions. In nature, Namib Desert beetles have
developed hydrophobic/hydrophilic patterned surfaces to capture fog efficiently as drinking water to
thrive in the desert [1]. A variety of methods have been proposed to fabricate such wettability
patterned materials [2-5]. However, these surfaces are still plagued with problems in rapidly shedding
off the collected water. Nepenthes pitcher plant, on the other hand, has evolved micro-structured
surface which becomes super-slippery when infused with a liquid lubricant within their porous
structures [6]. Recent studies have shown that synthetic slippery surfaces are advantages over other
conventional surfaces in droplet shedding [7, 8]. In this study, we present a cross-species inspired
design approach by incorporating both of the tactics used by desert beetle and pitcher plant to
fabricate a hybrid patterned slippery surface. We have shown that the cross-species inspired surface
outperforms the conventional fog harvesting surfaces significantly.
Fig. 1: Cross-Species Bio-Inspired Patterned Slippery Surfaces for Fog Harvesting
[1] Parker, C. Lawrence, Nature. 2001, 414, 33-34.

[2] L. Zhai, M. C. Berg, F. C. Cebeci, Y. Kim, J. M. Milwid, M. F. Rubner, and R. E. Cohen, Nano
Lett. 2006, 6, 1213-1217.
[3] R. P. Garrod, L. G. Harris, W. C. E. Schofield, J. McGettrick, L. J. Ward, D. O. H. Teare, and
J. P. S. Badyal, Langmuir. 2007, 23, 689-693.
[4] Dorrer, J. Rühe, Langmuir. 2008, 24, 6154-6158.
[5] H. Bai, L. Wang, J. Ju, R. Sun, Y. Zheng, and L. Jiang, Adv. Mater. 2014, 26, 5025-5030.
[6] T.-S. Wong, S. H. Kang, S. K. Tang, E. J. Smythe, B. D. Hatton, A. Grinthal, and J. Aizenberg,
Nature, 2011, 477,443-447.
[7] K. C. Park, P. Kim, A. Grinthal, N. He, D. Fox, J. C. Weaver and J. Aizenberg, Nature. 2016,
531, 78-82.
[8] X. Dai, N. Sun, S.O. Nielsen, B. B. Stogin, J. Wang, S. Yang, T.-S. Wong, Sci. Adv. 2018, 4,
eaaq0919.
265
ENERGY-OR11

Design, synthesis, and properties of several new bio-based

elastomers

1 1 1 1 1
Zhao Wang, Liqun Zhang*, Runguo Wang, Yong He, Shuai Tang

1
State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology,
Beijing 100029, P. R. China;

Keywords: bio-based elastomer, soybean oil, non-isocynate polyurethane, polyamide, limonene
Elastomer plays a very important role in our daily life. However, most synthetic elastomers are
petroleum-based. To meet the growing demand for sustainable development, it is imperative to
explore renewable raw materials to synthesize bio-based elastomers as next-generation rubbers. We
have designed and synthesized a few bio-based elastomers by different stratagems with various
monomers. As a result, soybean-oil-based elastomer,[1] non-isocyanate polyurethane,[2] polyamide
elastomer [3] and limonene-based elastomer [4] were developed via ring-opening polymerization or
polycondensation method. (a) Soybean-oil-based elastomer was synthesized from epoxidized
soybean oil and diamine by combining the ring-opening reaction with ammonolysis, in which ring-
opening reaction contributes to chain growth and ammonolysis is expected to break the glycerol
centre. The reaction sketch was shown below. It is the first time that processable elastomer was
synthesized from soybean oil, and then the soybean-oil-based elastomer was processed by traditional
rubber processing method. The tensile strength of the bioelastomer cross-linked with 11 phr succinic
anhydride was found to reach 8.5 MPa and the elongation at break was about 200% without nano-filler
reinforcement. (b) Non-isocyanate polyurethanes (PBDAs) were not dependent on isocynate and
synthesized via an eco-friendly route from ethylene carbonate, decamethylene diamine, and various
bio-based diacids. The Mn values of these PBDAs were in the range of 13900-28700 g/mol; their
mechanical properties varied from brittle to soft/flexible, and their degrees of crystallinity were different
as well. (c) Bio-based aliphatic polyamides (BDIS) were synthesized from sebacic aci, itaconic acid, 1,
10-decanediamine, and 1, 4- butanediamine. The use of four monomers and the introduction of IA
aimed to decrease the crystallization. With different amount of IA, some new polyamides with tunable
properties were obtained, such as semi-crystalline polyamide with relatively low melting point, glassy
polyamide with excellent toughness, and even rubbery polyamide after hydration. (d) Limonene is
found in many essential oil and represents an adaptable chemical feedstock. A diol monomer was
synthesized first from thiol and limonene via click reaction. Then the limonene-based elastomer was
synthesized from the diol monomer and various bio-based diacid. All the limonene-based elastomers
were amorphous with low glass transition temperatures from -48 to -17 °C. These new bio-based
elastomers could extend the variety of bio-based elastomers, and some of them are promising
materials for the replacement of the existed elastomers or provide new applications.
[1] Z. Wang, X. Zhang, R. Wang, H. Kang, J. Ma, L. Zhang, H. Wang. Macromolecules 2012, 45(22),
9010−9019.
[2] Z. Wang, X. Zhang, L. Zhang, T. Tan, H. Fong. ACS Sustainable. Chem. Eng. 2016, 4(5), 2762–
2770.
[3] Z. Wang, T. Wei, X. Xue, M. He, J. Xue, M. Song, S. Wu, H. Kang, L. Zhang, Q. Jia. Polymer
2014, 55, 4846–4856.
[4] S. Khan, Z. Wang, R. Wang, L. Zhang. Mater. Sci. Eng. C-Materials for Biological Applications,
2016, 67, 554–560.
266
2D3D-OR01

Controlling the Stiffness and Porosity of Polyacrylamide Hydrogel

Matrices and Evaluating their Effect on Podocyte-Behavior
1,2 *,1 *,2 3 1
Maya ABDALLAH , Maria BASSIL , Sebastien BALME ,Wissam H. FAOUR , Mario EL TAHCHI ,
*,2
Michael BECHELANY
1. LBMI, Department of Physics, Lebanese University - Faculty of Sciences II, Jdeidet, Lebanon.
2. Institut Européen des Membranes, UMR 5635, CNRS, Université Montpellier, ENSCM, Place
Eugène Bataillon, F-34095 Montpellier Cedex5, France
3. Gilbert and Rose-Marie Chaghoury School of Medicine, Lebanese American University, Byblos,
Lebanon
Keywords: Podocyte, Extracellular matrix, Hydrogel.
Chronic kidney disease (CKD) is characterized by reduced kidney function that progresses to end-
stage renal disease (ESRD). Podocytes are highly specialized glomerular epithelial cells which form
with the glomerular basement membrane (GBM) and capillary endothelium the glomerular filtration
barrier (GFB). Extracellular matrix (ECM) acts as a scaffold support and provides both mechanical and
biophysical signals in order to control podocytes molecular behavior, essential for normal kidney
filtration. Many materials have been used as ECM like Polyethylene Glycol (PEG) [1] and Gelatin [2].
The modulus of elasticity E or stiffness is an essential characteristic of the ECM that controls the cell
function. Among these materials, hydrolyzed polyacrylamide (PAAm) hydrogel is a non-toxic cross-
linked polymer, which is characterized by its high water content, non-biodegradability and
biocompatibility. The hydrogel properties provide a resemblance to in vivo setting for tissues opening
great opportunities for biomedical applications. Therefore, hydrolyzed PAAm hydrogel is investigated
for its potential use as a new construct to engineer a functional in vitro glomerular-like filtration barrier
and to regulate podocyte cell functions by controlling the physical properties (stiffness, swelling and
porosity) of PAAm membrane acting as an ECM.
In the present work, several PAAm hydrogels layers were prepared by changing the crosslinker
concentration. The macromolecular microstructure and stiffness are evaluated by Scanning Electron
Microscopy (SEM) and Atomic Force Microscopy (AFM) techniques respectively. The physicochemical
properties of PAAm hydrogels were tailored over a wide range of crosslinker amount (0.5 to 30µl). We
showed that by controlling the crosslinker concentration, the swelling degree, the mechanical
properties and the polymeric network porosity can also be controlled. Swelling test indicated that an
increase in crosslinker concentration contributed to a significant decrease in the swelling ratio, and this
variation is due to network rigidity that diminishes the network chain movement. In addition, PAAm
Hydrogel with the highest amount of crosslinker (30µl) is a very connected network with pore size of
29 µm and represents a high rigidity with a young modulus of 46 KPa. We are currently in the process
of optimizing podocytes culture on PAAm membranes with the aim of understanding the molecular
mechanisms by which podocytes respond and react to the mechanical properties of the substrate.
a b

100µm
100µm 100µm
Figure 1. SEM images of PAAm Hydrogels (a) M1 and (b) M6 samples with 0.5µl and 30µl of
crosslinker amount respectively
[1] Chiu, Y.-C., et al., Evaluation of Physical and Mechanical Properties of Porous Poly (Ethylene
Glycol)-co-(L-Lactic Acid) Hydrogels during Degradation. PLoS ONE, 2013. 8(4): p. e60728.
[2] Hu, M., et al., A biomimetic gelatin-based platform elicits a pro-differentiation effect on
podocytes through mechanotransduction. Scientific Reports, 2017. 7: p. 43934.
267
2D3D-OR02

Electrostatic protein-phthalocyanine assemblies towards biohybrid

photoactive materials
1 1 1
Eduardo ANAYA-PLAZA, Joona MIKKILÄ, Mauri A. KOSTIAINEN*,
1
Biohybrid Materials, Department of Bioproducts and Biosystems, Aalto University, Espoo, Finland
Keywords: Protein cage, Biohybrids, Phthalocyanine, Singlet Oxygen
Proteins represent one of the most versatile biomacromolecules employed by Nature to address
structural, recognition, transport, and catalytic functions. Taking advantage of this, we have
investigated the electrostatic assembly of several protein architectures with different relevant
nanomaterials, such as NPs, micelles, polymers and dyes. Among the latest, phthalocyanines (Pcs)
hold a privileged position due to their outstanding optical, electronical and physicochemical properties.
Pcs broad application scope relies on their strong absorption at the near-infrared region, long-lived
fluorescence and high singlet oxygen quantum yields, among other properties. However, formulation
of these hydrophobic chromophores in aqueous media without losing their properties due to self-
aggregation, represent a milestone to achieve towards their applicability. With this objective, we
reported the hierarchical organization of a Pc-based supramolecular assembly and apoferritin (aFt)
protein cage into photoactive crystals by means of electrostatic recognition. The obtained ternary
cocrystals retain the optical properties of the pristine dye molecules, such as fluorescence and
efficient light-induced singlet oxygen production, which is widely utilized in important technologies
such as photodynamic therapy, water treatments, diagnostic arrays, and as an oxidant in organic
synthesis [1]. Furthermore, cocrystallization of Pcs with toroidal proteins like tobacco mosaic virus
(TVM) coat protein disks into columnar stacks has allowed us to explore exciting properties arising
from the precise distribution of Pcs within the anisotropic crystals. These materials, with improved
features constitute a new approach towards biohybrid semiconductors, and light-harvesting antennas.
Figure 1: Schematic representation of electrostatic assembly of cationic Pcs with aFt (top) and
TMV disks (bottom).
[1]. J. Mikkilä, E. Anaya-Plaza, V. Liljeström, J.R. Cason, T. Torres, A. de la Escosura, and M.A.
Kostiainen, ACS Nano 2016, 10, 1565-1571.
268
2D3D-OR03

Identification of amyloid motifs in the protein TasA of Bacillus

subtilis

Thomas COUSSEAU, Charlotte VENDRELY, Damien SEYER, Patrick DI MARTINO *

Laboratoire ERRMECe-EA1391 Université de Cergy-Pontoise, Cergy-Pontoise, France;

Keywords: amyloid, Bacillus subtilis, TasA, peptides
The purpose of this study was to better understand the self-assembly mechanism of TasA, a 31 kDa
amyloid protein that is the main proteinaceous component of Bacillus subtilis biofilms. We first mapped
aggregation hotspots in the TasA sequence with a computational approach. AGGRESCAN, TANGO
and PASTA software identified four common hot spots of aggregation in TasA. We selected two
predicted aggregation hot spots and designed the corresponding synthetic peptides SY13 (77-89),
KL7 (81-87), LK13 (106-118) and VG7 (111-117). The additional peptides LL13 and LT13
corresponding to scrambled amino acid sequences of SY13 and LK13 respectively were also
synthetized. We characterized the self-assembly properties of the six synthetic peptides derived from
the TasA sequence by different methods. In the presence of any of the 13-residues peptides SY13,
LK13, LL13 or LT13, an increase in the fluorescence intensity of the amyloid marker thioflavin T was
observed. The fluorescence intensity increase was higher with the two peptides SY13 and LK13
corresponding to the wild-type sequences. No fluorescence emission was observed with the two 7-
residues peptides KL7 and VG7. Spontaneous formation of amyloid fibres was observed with the six
peptides by polarized light imaging in the presence of Congo red and by atomic force microscopy.
Isolated and/or fagot fibres were observed, depending on the peptide. The presence of intermolecular
β-sheets in all the peptide preparations was confirmed by infrared spectroscopy analysis. In
conclusion, the amyloid motifs that might be involved in/explain the self-assembly of the protein have
been identified in the TasA sequence.
269
2D3D-OR04

Nanostructures of diatom silica: how biominerals adapt to high-

performance lightweight geometries

1 1 1, 2
Christian HAMM, Lars FRIEDRICHS , Corinna DUBISCHAR Sasa BAJT
1
Alfred Wegener Institute Helmholtz Center for Polar and Marine Research
2
DESY, Photon Science, Notkestr. 85, 22607 Hamburg
Diatoms are unicellular algae, which possess intricte silica shells – the frustules. These structures are
an efficient mechanical defense against predation, occur in a very high diversity and are often
extremely complex. It has been shown that their intricate geometries have evolved to make the
frustules extremely resilient and at the same time very light. In addition, the diatom silica has an
2
exceptionally high strength (>3000 N/mm ). Nanostructure analyses of the silica have revealed that
the silica is not amorphous and isotropic, but consists, like nacre, of different components such as
layers and particles. Based on the hypothesis that the prime function of the frustules is mechanical
defence, it can be expected that the lightweight geometries and material nanostructure have been co-
optimized. We have investigated diatom silica and other biominerals using x-rays from a synchrotron
combined with Multilayer Laue Lenses (MLL), (Bajt et al. 2018) TEM and FIB – technologies. Here we
show results on the nanostructures of diatom silica and discuss how the complex lightweight
geometries and the material nanostructure may have co-evolved.

[1]. Bajt et al. 2018: Light: Science & Applications 7, 17162.
270
2D3D-OR05

Janus-type nanorods by surface-initiated polymer grafting from the

reducing end-groups of cellulose nanocrystals
1, 2 1 2
Katja HEISE, Mauri KOSTIAINEN *, Eero KONTTURI *,
1
Biohybrid Materials, Department of Bioproducts and Biosystems, Aalto University, Espoo, Finland;
2
Materials Chemistry of Cellulose, Department of Bioproducts and Biosystems, Aalto University,
Espoo, Finland
Keywords: biohybrid, anisotropic, nanocellulose
Owing to their anisotropic nature and the outstanding ability to self-assemble in complex 3D
structures, Janus particles have attracted increasing interest as molecular building blocks in various
fields, ranging from fundamental science to material applications. In this study, rod-like cellulose
nanocrystals (CNCs) isolated top-down from the plant cell wall were used as an experimental template
for the synthesis of non-spherical Janus-type nanohybrids. The synthetic path takes advantage of the
inherent directionality of CNCs which feature reactive aldehyde groups exclusively on one end
(reducing end, Fig. 1) albeit in equilibrium with cyclic hemiacetals. Starting from the reducing end,
tailor-made polymer building blocks were tethered via surface-initiated atom-transfer polymerization
(SI-ATRP). In order to facilitate endwise monomer grafting, CNCs were first modified with 4-
hydrazinobenzoic acid in aqueous borate buffer (pH 9.0). The formation of hydrazone linkages ((i),
Fig. 1) thereby enabled simple monitoring of the topochemical cellulose functionalization via UV-VIS
spectroscopy. In the subsequent reaction, ATRP initiation sites were introduced by attaching
bromoisobutyryl bromide via an ethylenediamine bridge ((ii), Fig. 1) to the benzoic acid residue
forming CNC macroinitiator complexes. Monomer selection – covering, e.g., N-isopropylacrylamide
and di(ethylene glycol) methylether methacrylate – and precise polymerization control in the final step
created a library of hybrid architectures. Transmission electron microscopy was used to monitor the
successful one-sided polymer attachment. Moreover, non-uniform zeta potentials of the Janus-type
hybrids demonstrate the asymmetric distribution of charges on the particle surfaces due to the
“patchy” modification of CNCs with neutral polymers chains. Moving forward to the interplay between
hybrid architecture and properties, we foresee miscellaneous effects of polymer tethered CNCs in
terms of colloidal self-assembly.
Fig. 2: Path for the synthesis of Janus-type nanohybrids using CNCs as experimental template
271
2D3D-OR06

Robust Superhydrophobic Surfaces via Concave pillar

1 2 1
Kwang Hui Jung, Jeong Jun Lee, Dong Woog Lee *,
1
(UNIST), UNIST-gil 50, Ulsan 689-798, Republic of Korea
2
School of Life Sciences, Ulsan National Institute of Science and Technology (UNIST), UNIST-gil 50,
Ulsan 689-798, Republic of Korea
Keywords: hydrophobic, concave pillar, Cassie-Baxter, Wenzel, micropatterning, anisotropic etching
Hydrophobic surfaces are widely used in many applications which is generally fabricated by
roughening or patterning the surfaces, but fabrication of a robust surface which sustains Cassie-
Baxter state (without transitioning to Wenzel state) for a prolonged period is still a challenging task.
Arolia of flies and leaf beetles have a hydrophobic concave hairy structure and the structure exhibits
self-cleaning ability to prevent contamination [1]. Herein, inspired by the structure of arolia we
fabricated a concave pillar structure by using photolithography (anisotropic etching of a silicon and the
Bosch process). Anisotropic etching of silicon and a mixture of nitric acid (HNO3) and hydrofluoric acid
(HF) make circular shape hole [2] and by controlling the etching time and the pattern size of the photo
mask, we made a vast of concave pillar (hole depth, diameter, spacing). These concave pillars
represent admirable superhydrophobicity and self-cleaning ability. Moreover, it was able to maintain
the Cassie-Baxter state underwater even when exposed to air jet, while rapid Cassie Baxter to Wenzel
transition has been observed with normal cylindrical structures. The bioinspired concave pillar
structures not only help to develop robust and stable superhydrophobic surfaces but also advance the
understanding behind the Cassie Baxter to Wenzel transition phenomena.
Fig. 1: (a) SEM images of the concave pillar structure. Inset is magnification of the concave
pillar. (b) Measured contact angle on the concave pillar structure. (c) Underwater air injection
test for (c) the normal pillar, (d) the concave pillar. Cassie-Baxter state is maintained for the
concave pillar.
[1]. C.J. Clemente, J.M.R. Bullock, A. Beale, W. Federle, The Journal of Experimental Biology, 20
10, 213 , 635-642.
[2]. Y. Jiang, G. Liu, J. Zhou, Journal of Micromechanics and Microengineering, 2009, 19, 01550
5.
272
2D3D-OR07

Artificial repeat protein as in-situ capping agents of 2D gold

nanocrystals for a single particle sensing platform
1,2 1 3 4 4
Laureen Moreaud , Janak Prasad , Sirin Celiksoy , Sébastien Viollet , Agathe Urvoas , Cécile
1 4 4 3 1
Marcelot , Marie Valerio-Lepiniec , Philippe Minard, Carsten Soennichsen and Erik Dujardin*
1
CEMES, CNRS UPR 8011, 29 rue Jeanne Marvig, F-31055 Toulouse, France
2
University of Toulouse III, UPS, 118 route de Narbonne, F-31062 Toulouse, France
3
Institute of Physical Chemistry, University of Mainz, Duesbergweg 10-14, 55128 Mainz, Germany
4
I2BC, Univ Paris Sud, CNRS, CEA UMR 9198, Bât. 430, F-91405 Orsay, France
Keywords: morphosynthesis, biosensors, plasmonic
Customized shape control of metal nanocrystals by structure-directing natural and engineered amino
acid sequences [1] has a tremendous potential for integrated plasmonics,[2] biosensing [3] and
catalysis.[4] Here, we use a family of thermo-stable artificial proteins (a-Repins) and select, by the
phage display technique, some individual proteins with specific Au(111) binding affinity.[5] Next, we
use them as inhibitors during gold nanocrystal growth in order to control the shape and
crystallographic facet expression. Structural characterization by electron and atomic force microscopy
reveals the exclusive formation of {111}-terminated gold nanocrystals - icosahedrons, decahedrons
and 2D nanoplates - in high yield. Furthermore, the protein adsorption onto the gold facets is strong
enough to allow direct functionalization without resorting to ligand exchange. As a proof-of-concept we
use the well-known biotin/streptavidin pair as model system. Biotin-modified a-Rep proteins are used
as capping agents during gold nanoplate synthesis. Single nanoplate sensing experiments
Streptavidin show a 140 nm/RIU sensitivity. A significant 10 nm redshift in nanoplate suspension
spectra is observed upon addition of streptavidin, which is highly significant for nanostructures
exhibiting a lower sensitivity than gold nanorods.[6] With a large surface available per particle and a
ready-to-modify protein coating, these nanocrystals offer a promising alternative to standard CTAB-
coated nanorods for single particle sensing and detection.
Fig. 1: (a) Crystallographic structure of a 4-repeat α-Rep protein. In orange the hypervariable
region used for phage display selection. (b) Schematic of a-Rep mediated (111) facetted gold
nanocrystal growth. (c) Streptavidin sensing scheme on gold nanoplates coated with
biotinylated modified proteins. (d, e) Absorbance spectra before (black) and after (green, red)
exposure of biotinylated gold nanoplate suspensions to streptavidin. In (e) the first derivative
signal around the resonance peak position (dotted box in (d)) shows a 7 nm redshift.
[1]. Chiu, C.Y. et al, Nat. Chem. 3, 393 (2011).

[2]. Viarbitskaya, S. et al, Nat. Mater. 12, 426 (2013). Jain. P. et al, J. Phys. Chem. C, 118, 14502
(2014)
[3]. Anker J.N. et al., Nature Mater., 8, 442 (2009). Beeram, S.R. et al, ACS Nano, 4, 3633 (2010)
[4]. Corma Aet al. Chem. Soc. Rev., 37, 2096 (2008). Sun, Y., et al, Angew. Chem., 48, 6824 (2009).
[5]. Urvoas, A. et al, J. Mol. Biol. 404, 307 (2010). J. Prasad et al., submitted for publication (2018)
[6]. C. Rosman et al., Nano Lett., 13, 3243 (2013). Qin, F. et al, Adv. Optical Mat., 4, 76 (2016).
Corresponding author: [email protected]
273
2D3D-OR08

2D nanosheets; novel candidate to improve the mechanical
property of polymer fiber for tissue engineering application

1,2 1,3 1 3
Sakthivel Nagarajan , Habib Belaid , Céline Pochat-Bohatier , Catherine Teyssier , Sébastien
1 1 2 3 1
Balme , Philippe Miele , S Narayana Kalkura, Vincent Cavaillès and Mikhael Bechelany *
1
Institut Européen des Membranes, UMR 5635 Université Montpellier, CNRS, ENSCM, Place Eugene
Bataillon, F-34095 Montpellier cedex 5, France
2
Crystal Growth Centre, Anna University, Chennai, India, 600025.
3
* Corresponding author: [email protected], Phone: +33467149167, Fax:
+33467149119
Biopolymers are advantageous material for biomedical applications. It is due to their

properties such as biocompatibility and biodegradability [1]. However, poor mechanical properties,
change in hierarchical structure during the extraction and solubility limit their application for biomedical
field. Hence, designing biopolymers with improved mechanical properties and biocompatibility is
essential. Nanofibers mimicking the extra cellular matrix (ECM) architecture are suitable for cell
attachment and differentiation [2]. Various methods such as electrospinning, fiber self-assembly etc.
were employed for the fabrication of 3D hierarchical fibrous structure [3]. Here, electrospinning
technique was employed for the fabrication of 3D scaffolds which mimics the ECM. Gelatin was
employed for nanofibers fabrication. Gelatin is a biopolymer obtained from the partial hydrolysis of
collagen. Gelatin displays poor mechanical properties which can be improved using 2D nanosheets
such as graphene oxide (GO) and boron nitride (BN). Graphene and BN were reported as materials
which possesses mechanical properties similar to diamond [4]. Hence, gelatin nanofibers were
reinforced by 2D nanosheets such as BN and GO [5, 6]. Tensile strength of the BN and GO reinforced
electrospun fibers evidenced that reinforcement improved young’s modulus (3 fold increase) of the
composite in comparison to pristine gelatin. Indeed, crosslinking and treatment with aqueous solution
maintained the fibrous morphology of BN and GO reinforced electrospun fibers. Electrospun fibers
biocompatibility were analyzed using human osteosarcoma cells. Electrospun fibers allow cell
attachment and proliferation which clearly evidenced that reinforcement with 2D nanosheets and
crosslinking treatment does not affect the biocompatibility. Hence, 2D nanosheets are promising
material to improve the mechanical properties of gelatin fibers.
[1]. Vieira, M. G. A., da Silva, M. A., dos Santos, L. O., and Beppu, M. M. (2011). European Polymer
Journal 47, 254-263
[2]. Nagarajan, S., Pochat-Bohatier, C., Balme, S., et al. (2017). Pure and Applied Chemistry, 89(12),
pp. 1799-1808. Retrieved 29 Mar. 2018
[3]. Huang, Z.-M., Zhang, Y. Z., Kotaki, M., and Ramakrishna, S. (2003) Composites Science and
Technology 63, 2223-2253
[4]. Falin, A., Cai, Q., Santos, E. J. G., Scullion, D., Qian, D., Zhang, R., Yang, Z., Huang, S.,
Watanabe, K., Taniguchi, T., Barnett, M. R., Chen, Y., Ruoff, R. S., and Li, L. H. (2017) Nature
Communications 8, 15815
[5]. Nagarajan, S.; Belaid, H.; Pochat-Bohatier, C.; Teyssier, C.; Iatsunskyi, I.; Coy, E.; Balme, S.;
Cornu, D.; Miele, P.; Kalkura, N. S.; Cavaillès, V.; Bechelany, M., (2017). ACS Applied Materials &
Interfaces 9 (39), 33695-33706.
[6]. Nagarajan, S.; Pochat-Bohatier, C.; Teyssier, C.; Balme, S.; Miele, P.; Kalkura, N.; Cavailles, V.;
Bechelany, M., (2016) RSC Advances, 6 (110), 109150-109156.
Acknowledgement: The authors would like to thank the financial support from Indo-France
collaborative project CEFIPRA (Project 5608-1).
274
2D3D-OR09

Biomimetic Proteoglycans Enhance Type I Collagen Fibrillogenesis
1 1 1
Katsiaryna PRUDNIKOVA, Carli MOOREHEAD, Michele MARCOLONGO *
1
Department of Materials Science and Engineering, Drexel University, Philadelphia, USA
Keywords: chondroitin sulfate, proteoglycans, collagen, extracellular matrix, fibrillogenesis
Introduction. Regulation of collagen fibrillogenesis and degradation is important in the treatment of a

number of diseases from orthopedic injuries to genetic deficiencies. In the body, this process is
1
generally regulated by proteoglycans (PGs) that contain both protein and sugar components.
Recently, novel, biocompatible, semi-synthetic biomimetic proteoglycans (BPGs) were developed,
which consist of an enzymatically resistant polymer core and natural chondroitin sulfate (CS)
2,3
bristles. It was demonstrated that BPGs can delay the kinetic formation of collagen gels in vitro
4
similar to native PGs. This indicates that the morphology of collagen scaffolds as well as endogenous
ECM could also be modulated by proteoglycan mimics. However, confocal microscopy used
previously did not yield the resolution necessary to spatially localize BPGs within the collagen network
and elucidate the effect of BPGs on the quality of collagen fibrils. To address this challenge, a
histological technique, electron tomography, was adapted and utilized to 2D and 3D image nano-scale
structures within this simplified tissue model.
Materials and Methods. Collagen gels (1.5 mg/mL) were prepared by neutralizing acid soluble type I
collagen precursors (Corning) in vitro, and fibrillization was performed for 2 hrs at 37°C. Gels were
augmented prior to fibrillogenesis with various concentrations (0.1,1.0, and 10 mg/mL) of three
lengths of BPGs. Gels were quenched into cold DI H2O and vortexed to create a 10-fold dilution of
collagen fibrils. Solutions were deposited onto 200-square mesh carbon coated copper TEM grids
(Electron Microscopy Science) and allowed to adhere for 60 min before staining twice with 3% Uranyl
Acetate. 10 nm colloidal gold nanoparticles (MP Biomedicals, LLC) were added in addition to the stain
for samples to be 3D imaged. Samples were imaged in 2D and 3D under TEM at 80 kV (JEOL 2100,
JEOL USA). 2D imaging was performed in triplicate collecting ~20 images of each sample and fibril
primary and bundle diameters were measured using ImageJ (NIH). Fibril banding spacing was
calculated from the fast Fourier transform of the images. Finally, representative tilt-series (-60° to 60°)
of each condition were captured using Serial EM tomography control software and reconstructed using
IMOD.
Results. BPGs were found to aid in lateral growth (Fig. 1A) and enhance fibril banding periodicity (Fig.
1B) resulting in structures more closely resembling those in tissue, in addition to attaching to the
collagen surface despite the lack of a protein core (Fig.1C).
Conclusion. Despite the lack of protein activity, BPGs still interacted with and enhanced type I
collagen fibrillogenesis. This interaction was mediated by the CS bristle indicating that simplified
synthetic alternatives may be a viable pathway towards augmenting healing in remodeling tissues on a
molecular scale.
Figure 1. A) Fibril primary and bundle diameters. B) Fibril band spacing increases with CS
content. C) BPGs wrap around collagen fibrils.
[1]. S. Kalamajski, A. Oldberg, Matrix Biol. 2010, 29, 248-253.

[2]. S. Sarkar et al., Carbohyd. Polym. 2012, 90, 431-440.
[3]. K. Prudnikova et al., Biomacromolecules. 2017, 18, 1713-1723.
[4]. K. Prudnikova et al., N.I.C.E. 2016, Nice, France, Oct 16-19, 2016.
275
PLASMAT-OR01

Synthesis of Transparent, Omniphobic, Self-cleaning Surfaces by

Silanization and Atmospheric Plasma-assisted Metal-oxide
Coatings Inspired from Lotus Leaves

1 1 1
Po-Yu CHEN,* Ching-Yu Yang, Jenq-Gong DUH

1
Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu, Taiwan

Effective self-cleaning coatings with liquid repellency are crucial for eliminating surface contamination
and reducing drag force, which enables wide industrial applications. However, most coatings are
fabricated through complicated and expensive processes that limit mass production capability. To
overcome this limitation, we designed a simple methodology based on atmospheric-pressure-plasma-
assisted fabrication. Hierarchically-structured, stalagmite-like tungsten oxide coatings were
synthesized within a few seconds. After silanization, the coatings not only acquired cost-effective
superhydrophobic surfaces with high static contact angles toward water (160±2°, surface tension 72.8
dyn/cm), but also showed oleophobicity toward liquids with lower surface tension, ranging from 64 to
27.5 dyn/cm. In addition, their two-tier topography decorated with fluoroalkylsilane traps air cushions
within the textures, contributing to low sliding angle (<2°) and low contact angle hysteresis toward both
water and glycerol. Their robust Cassie state can even sustain the high impact velocity of a liquid drop
exceeding 2m/s. Moreover, the coatings exhibited superior self-cleaning abilities and multi-
functionality, including high transparency, flexibility, and mechanical and thermal stability. The growth
mechanism of hierarchical WO3x and the dynamic behavior of liquid droplets on the coatings were
also investigated in this study. These micro- and nano-structures synthesized at room temperature
enable seamless integration on various substrates, such as plastic films, glasses and fibrous papers,
and have the potential to scale-up, leading to wide and more realistic applications.
Fig. 1: (a) High speed camera images reveal a water drop bouncing on the SCWO-coated paper.
(b) Image of the anti-wettability comparison for the SCWO-coated and uncoated papers.
SEM images of (c) SCWO-coated and (d) uncoated papers.
[1]. C.-Y. Yang, S.-I. Chuang, Y.-H. Lo, H.-M. Cheng, J.-G. Duh, P.-Y. Chen*. J. Mater. Chem. A
2016, 4, 3406-3414.
276
PLASMAT-OR02

Low Voltage-SEM insights into Nanoscale Surface Modification of

Ramie Plant Fibers by Plasma Treatment

Sameer F. Hamad *, C. Rodenburg
Department of Materials Science and Engineering, The University of Sheffield, UK

Keywords: Ramie fiber, Low Voltage-SEM, Plasma treatment, Nanoscale surface roughness.
The surface characteristics of natural plant fibers have important implications for the interfacial
bonding in fiber polymer composites [1]. Knowledge of, and the ability to control, the surface
morphology and surface composition are thus important in developing natural fiber reinforced
composites. Scanning Electron Microscopy (SEM) is traditionally used to study the surface
morphology of various materials. However conventional SEM techniques are hard to realize for
organic polymers due to the surface sensitivity and limited material contrast between organic species
as well as require coating of the samples to avoid build-up of negative charge and beam damage
limitations [2]. Therefore, significant advances in the surface morphology of non-conductive materials
can be achieved with use of Low Voltage-SEM technique (LV-SEM) [3].
In this work, LV-SEM is used to investigate the effects of plasma treatment on the surface morphology
of the ramie plant fibers. The high resolution LV-SEM imaging of uncoated plasma treated fibers
reveals rough surface with bright nanoscale structures after only 1 min of plasma treatment (see Fig
1b), when compared to the untreated fiber surface (Fig. 1a). It has been reported in the literature that
amorphous polymer phases can be etched by plasma more easily than crystalline phases [4].
Therefore we attribute these nanoscale features to the crystalline cellulose microfibrils (see the inset in
Fig. 1b) which remain after selective etching of the amorphous portions by plasma treatment. It can
also be seen from Figure 1b that most of the impurities have been removed from the fiber surface
when compared to the untreated surface (arrows in Figure 1a). Such changes on the fiber surface
characteristics are expected to improve the fiber surface wettability, surface energy, and surface
adhesion properties. Hence, the use of plasma-surface modification could have immense benefits in
the production of fiber polymer composites with good interface integrity and could pose a big step
forward in replacing fossil-fuel based fibers. In addition, the use of LV-SEM is powerful technique for
the understanding of the surface characteristics of plant fibers.
Fig. 1: LV-SEM images of (a) untreated and plasma treated ramie fibers (b) 1 min. The inset in
(b) shows the microfibrils structure.
[1] G.R. Arpitha, B. Yogesha, Materials Today: Proceedings. 2017, 4, 2755-2760.

[2] R.W. Truss, B. Wood, R. Rasch, J. APPL. POLYM. SCI. 2016, 1-9.
[3] Q. Wan, et al., Ultramicroscopy. 2016, 126–138.
[4] E. Wohlfart, et al., Macromolecules. 2010, 43, 9908–9917.
277
3D-OR01

3D hydrogel neuronal microenvironments fabricated by two-photon
lithography
1, 2 1 1
Angelo ACCARDO, * Isabelle LOUBINOUX, Christophe VIEU, Laurent MALAQUIN
1
LAAS-CNRS, Université de Toulouse, CNRS, F-31400, Toulouse, France
2
ToNIC, Toulouse NeuroImaging Center, Université de Toulouse, Inserm, 31024, UPS, France
Keywords: direct laser writing, cell scaffold, 3D fabrication, PEGDA hydrogel, neuro2A cell
Cells in our bodies are arranged in three dimensions (3D) according to complex architectures, which
play a fundamental role in the functionality of the living tissue. There is therefore an urgent need to
develop 3D architectures featuring biomaterials that provide the biocompatibility and the physico-
chemical properties necessary for the proliferation, differentiation and functionality of living cells. At the
same time, such materials must be ‘compatible’ with thorough immunofluorescence imaging protocols
able to unveil cellular functional features also in the most hidden regions of the scaffold. Here, we
report the realization of Poly(ethylene glycol)diacrylate (PEGDA) biocompatible hydrogel scaffolds for
supporting neuronal cell growth [1,2]. The 3D hydrogel cross porous woodpile architecture has been
realized using two-photon direct laser writing (2P-DLW) that exploits the two-photon absorption (TPA)
of near-infrared (NIR) femtosecond laser pulses focused onto the photosensitive material [3]. Thanks
to the porous nature of the proposed scaffold geometry, we observed the efficient growth of a ramified
neuronal network throughout the 3D architecture highlighting the formation of multiple neuritic
extensions per cell with a length between 10 and 60 µm. Conventional morphological characterization
(based on scanning electron microscopy) has been associated to advanced 3D fluorescence imaging
techniques (based on two-photon confocal imaging) in order to “shed light” on the localization and the
morphology of the cells not only around the 3D scaffold but also within its most inaccessible core
regions. In such context, PEGDA hydrogel showed very low intrinsic fluorescent emission (≈100 times
lower than conventional polymeric materials employed in 2P-DLW), thus enabling a multi-staining
immunofluorescence evaluation of the functional features of neuro2A cells in three dimensions. These
unique “quasi-transparency” optical properties allowed a full 3D immunofluorescence reconstruction of
the cell colonization of the scaffold as well as the detection of F-Actin microfilaments and β-tubulin
neuronal marker even “through” the PEGDA structures.
Fig. 1. A: PEGDA solution preparation and 2P-DLW fabrication; B: SEM micrograph of the
scaffold colonized by neuro2A cells; C: histogram highlighting the number of neuritic
extensions per cell; D, E: two-photon confocal 3D reconstructions of the neuronal scaffold.
[2]. A. Accardo, M.-C. Blatché, R. Courson, I. Loubinoux, C. Vieu, L. Malaquin, Mater. Today 2018, in
press, doi.org/10.1016/j.mattod.2018.02.004.
[3]. A. Accardo, M.-C. Blatché, R. Courson, I. Loubinoux, C. Vieu, L. Malaquin, Biomed. Phys. Eng.
Express 2018, 4, 027009.
[4]. A. Accardo, M.-C. Blatché, R. Courson, I. Loubinoux, C. Thibault, L. Malaquin, C. Vieu, Small
2017, 13 (27), 1700621.
278
3D-OR02

4D Biofabrication by Shape-Morphing Polymers
1
Leonid Ionov *
1
University of Bayreuth, Universitätsstr. 30, 95440 Bayreuth, Germany
Keywords: biofabrication, 3D printing
Most powerful technique for biofabrication – 3D printing still has certain limitations, which substantially
restrict its broader use. These disadvantages are inability to achieve sufficient resolution and high-
density cell printing, difficulty of fabrication of multicomponent and hollow structures, difficulty of
orienting of cells and limited oxygen diffusion. We advanced design of biomaterials by developing 4D
biofabrication approach using special polymers, which are able to change their shape – shape-
morphing polymers. In particular, we developed a number of approaches for design of biocompatible
shape-morphing polymeric objects using solid polymers and hydrogels, which are able to change their
shape in response to such “biocompatible” stimuli as temperature and presence of calcium ions. We
developed approaches for deposition of cells on and inside of shape-morphing polymeric objects. We
have also demonstrated application of 4D biofabrication approach for controlled encapsulation of cells,
design of porous scaffolds with controlled porosity and pore orientation, complex 3D cell patterning as
well as fabrication of hydrogel-cell hollow structures.
Fig. 1: Scheme of the fabrication of self-folding hydrogel-based (cell-laden) tubes via 4D

bioprinting: a) printing of mathacrylated alginate or hyaluronic acid solutions without/with
living cells onto different substrates; b) crosslinking of the printed films with green light (530
nm) and mild drying; c) instant folding into tubes upon immersion of the crosslinked films in
water, PBS, or cell culture media; d) examples of the fabricated self-folding tubes (from right to
left): schematic illustrations and representative microscope images of single tubes
with/without printed cells formed through the described 4D printing process; photograph of a
glass vial containing a large number of self-folded tubes, indicating on the possibility of their
large-scale fabrication.
[1]. Kirillova, A.; Maxson, J.; Gomillion, C.T.; Ionov, L Advanced Materials 2017 29, 170344.
Stroganov, V.; Pant, K.; Stoychev, G.; Janke, A.; Jehnichen, D.; Fery, A.; Handa, H.; Ionov, L.
Advanced Functional Materials 2018, 28 1706248
279
3D-OR03

Dynamic polymerization photolithography yields 3D biomimetic
models of small intestine in a simple fabrication process

1,2,3 1 1 1 1
Elena Martínez* , Albert G. Castaño , María García-Díaz , Gizem Altay , Núria Torras
1
Institute for Bioengineering of Catalonia (IBEC), The Barcelona Institute of Science and Technology
(BIST), Barcelona, Spain
2
Centro de Investigación Biomédica en Red (CIBER), Madrid, Spain
3
Department of Electronics and Biomedical engineering, University of Barcelona (UB), Barcelona,
Spain
Keywords: microengineered 3D tissue models, poly(ethylene glycol) hydrogel, photopolymerization,

microstructure, biomimetic environment, intestinal epithelium
Epithelial tissues contain three-dimensional microstructures that guide cell self-organization at the
tissue level. In the small intestine, crypts and finger-like villi microstructures improve its absorbance
function, provides specific microenvironments for the microbiota and compartmentalize cell types [1–
3]. Despite its physiological relevance, this architecture is neglected in the standard in vitro models of
the small intestine, questioning the predictive capacity of current drug development preclinical tests
[4].
We in here have engineered a simple, single-step fabrication strategy to produce biomimetic scaffolds
faithfully replicating the 3D complex architecture of the small intestinal epithelium in soft synthetic
hydrogels. By using a set-up that combines photolithography with dynamic reaction-diffusion
polymerization processes, anatomically correct villi-like scaffolds can be easily produced directly on
Transwell® filter inserts. In addition, we copolymerize poly(ethylene glycol) diacrylate polymer with
acrylic acid, which we show provides the scaffold material with tunable ligand densities while
maintaining soft mechanical properties, therefore further extending the potential of this fabrication
technique. Previous studies reported about combining sequential polymerization steps to produce
complex 3D structures [5]. However, to our best knowledge, our method is the first work that provides
experimental evidence that such structures can be obtained in a single polymerization step by
controlling the dynamics of the reaction-diffusion polymerization process. Improving the prediction
capabilities of cell-based assays is a growing strategy to lead to more efficient drug development
processes. As 2D-based systems are showing their limits, new 3D strategies are gaining acceptance
among the scientific community. The methodology described in our work aims to further accelerate
this trend by providing a feasible strategy to routinely incorporate 3D structures mimicking
microtopographies at the tissue level in cell culture systems.
[1]. G.J. Tortora, B.H. Derrickson, Principles of Anatomy and Physiology, 14th Editi, Wiley Global
Education, 2014.
[2]. M.N. Marsh, J.A. Swift, Gut 1969, 10 940–949.
[3]. P. Kelly, I. Menzies, R. Crane, I. Zulu, C. Nickols, R. Feakins, J. Mwansa, V. Mudenda, M.
Katubulushi, S. Greenwald, M. Farthing, Am. J. Trop. Med. Hyg. 2004, 70, 412–419.
[4]. A. Abbott, Nature 2003, 424, 870–872.
[5]. T.S. Shim, S.-M. Yang, S.-H. Kim, Nat. Commun. 2015, 6, 6584.
280
3D-OR04

3D-bioprinting of peptide based hybrid organic-inorganic
hydrogels: Encapsulation of mesenchymal stem cells for cartilage
repair
1,2 1,2 3 3 1
Laurine VALOT, Cécile ECHALIER, Marie MAUMUS, Danièle NOEL, Jean MARTINEZ, Ahmad
2 1
MEHDI*, Gilles SUBRA*,
1
Institute of Biomolecules Max Mousseron, Montpellier, France;
2
Institute Charles Gerhardt, Montpellier, France
3
Institute of Regenerative Medicine and Biotherapy, Montpellier, France
Keywords: 3D-bioprinting, hybrid, hydrogel, bioink, cartilage repair, synthetic extracellular matrix
Extracellular matrix (ECM) is a complex environment giving to cells a suitable support for their
growth but also programming their differentiation, migration and fate. Mimicking the complexity of ECM
with synthetic biomaterials remain a challenge. In this context, we developed a versatile and bottom-
up strategy to synthesize ‘à la carte’ multifunctional biomimetic hydrogels. At the same time, with
settlement and aging of population, more and more people suffer from cartilage or bone damage. 3D-
[1]
printing techniques may be used to prepare scaffolds and prosthesis to treat articulation defects .
One of the main challenge is to develop bioinks, suitable for cells encapsulation and whose
composition can be adapted to each type of tissue before being degraded and replaced by native
extracellular matrix. In this context, we choose to use our biomimetic inorganic/bioorganic hydrogels to
3D-print biomimetic and containing cells prosthesis to repair articulation damages.
This approach relies on novel hybrid bioorganic-inorganic blocks (peptide, biopolymers, dyes,
[2]
drugs…) , bearing at least one silyl group. These blocks are mixed in chosen ratio and engaged in a
sol-gel inorganic polymerization yielding, in a single step, cross-linked hydrogel networks. Noteworthy,
the sol-gel process proceeds in water at 37°C, thus being fully biocompatible with fragile biomolecules
and cell encapsulation. After optimization using bisilylated -polyethylene glycol, peptide integrin
[3]
ligands or antibacterial peptides , this approach is now applied to cartilage repair using bisilylated -
[4]
peptides mimicking the sequence of collagen and silylated -hyaluronic acid to reach the composition
of naturel ECM.
Thanks to good viability and proliferation of encapsulated cells, our hydrogel seems to be a
useful platform for any 3D printing with biological application or even just for more biomimetic cell and
tissue culture.
O
O
hybrid silylated 3D network
HO H
N O O N
N H O NH 2 HO
H
N
O
O N O O O OH
NH N N hydrolysis and Si
N N O
O Si
OH
NH condensation
O O
OH O NH O
n HO Si O
O Si
HN H
N
O Si O
O Si O
O O
O Si
O O
O O Si
= O
(EtO)3 Si Si(OEt) 3 O Si O
Si O
O
O
Fig. 1: Sol gel process giving hydrogel
[1] M. Gomes, et Al. Tissue Engineering Part B. 2017, 23, 3.

[2] G. Subra, et al. WO2013190148 A1.
[3] C. Echalier, et Al. RSC Adv. 2017, 7, 12231.
[4] C. Echalier, et Al. Materials Today 2017, 20, 2.
281
BIOADH-OR01

Metal Ion Interactions in Protein- and Protein-Inspired Materials

1 1
Amanda Andersen, Henrik Birkedal *,

1
iNANO and Department of Chemistry Aarhus University, Aarhus, Denmark;

Keywords: Hofmeister effects, Metal-Protein interaction, Gelatin hardening, Mussel foot protein, DOPA
The function of many soft biological tissues relies on the dynamic abilities of their constituent
molecules. This has inspired the development of a wide variety of synthetic materials, particularly
1
materials inspired by the dynamic and highly functionalized chemistry of proteins . The higher order
2
structures and functions of many proteins are defined by interactions with metal ions . Understanding
these interactions in both native proteins and synthetic model systems is important when seeking to
utilize protein properties for material design. Such interactions can be either a direct design principle
or act through specific ion (Hofmeister) effects.
Consider for example hydrogels that form through network formation either through covalent
3,4 3,4 5
bonding , physical interactions or coordination bonds . Metal ions can directly participate in the
5 6
cross-linking of hydrogels or act as agents to salt in or -out the polymer backbone of the hydrogel ; in
3,4,5,6
all cases the presence of metal ions effect the physical properties of the material .
Herein we explore both these effects.
First, we discuss the use of coordination chemistry in mussel-inspired hydrogel design. Mussel foot
proteins are rich in the modified amino acid 3,4-dihydroxyphenylalanine (DOPA), which is an excellent
metal chelator. Using this ability afford robust and self-healing hydrogels based on covalent and
coordination bonds both mediate by DOPA through, respectively oxidative covalent bond formation
5,7,8
and coordination chemistry . We show how the chelating group can be chemically modified to
9
obtain direct control of redox- and mechanical properties in the hydrogels .
Second, we explore Hofmeister effects of cations on hydrogel rheological properties. Ion specific
effects for salting-in or –out hydrogels have been widely explored for anions but much less so for
6
cations . We study the impact of metal cations on the physical interactions that supports the network
of gelatin hydrogels. Addition of mono- and divalent ions causes destabilization of the network with
6,10
relative effects consistent with the chaotropic Hofmeister series . However, the trivalent Cr(III) and
11
Al(III) are known to harden of collagen material by is known from the tanning of leather and old
12
school photographic fixing baths . For the hydrogels, we find a complicated temperature and
concentration dependent behavior of strengthening and weakning.
The results show that using the ability of metal ions to modulate the properties of bioinspired materials
provides a wide palette of possible control over materials properties.
[1]. B. D. Olsen, AIChE Journal, 2013, 59, 3558-3568.

[2]. M. M. Harding, Crystallography Reviews. 2010, 16, 247-302.
[3]. W. E. Hennink, C. F. van Nostrum, Adv Drug Deliver Rev 2012, 64, 223-236.
[4]. A. S. Hoffman, Adv Drug Deliver Rev 2012, 64, 18-23.
[5]. M. Krogsgaard, V. Nue, H. Birkedal, Chem. Eur. J. 2016, 22, 844–857.
[6]. Y. Zhang, P. S. Cremer, Curr. Opin. Chem. Biol. 2006, 10, 658-663.
[7]. M. Krogsgaard, A. Andersen, H. Birkedal, Chem. Commun. 2014, 50, 13278-13281.
[8]. S. Azevedo, A. M. S. Costa, A. Andersen, I. S. Choi, H.Birkedal, J. F. Mano, Advanced Materials,
2017, 29, 1700759.
[9]. A. Andersen, M. Krogsgaard, H. Birkedal, Biomacromolecules, 2018, in press, DOI:
10.1021/acs.biomac.7b01249
[10]. A. Andersen, C. J. S. Ibsen, H. Birkedal, submitted.
[11]. A. D. Covington,1997, Chemical Society Reviews, 26, 111-126.
[12]. L. H. Baumbach, H. E. Gausman, Journal of the Society of Motion Picture Engineers, 1946,
47, 22-54.
282
BIOADH-OR02

Adhesive and elastic fusion proteins toward nanocomposites
materials: a single molecule study

1 1 1 1
Alessandra GRIFFO, Bart ROOIJAKKERS, Markus B. LINDER ,Päivi LAAKSONEN*,

1
Department of Bioproducts and Biosystems, Aalto University, Espoo, Finland

Keywords: biomimetics, single molecule force spectroscopy, bio-adhesion, fusion proteins
In Nature, it is common that particles and components with mismatched properties exist in close
contact, leading to unusual combinations of properties that differ from the bulk materials, and having
excellent mechanical response. The most frequent example is nacre, a strong and resilient material
composed by a mix of inorganic sheet alternating to elastic biopolymers that firmly adhere to the
organic layers. An area of large attraction over the last few decades includes also bioinspired protein-
based adhesives as mussels and gecko-like structures that employ strong adhesion to a variety of
surfaces, and a control of the cohesive properties of the materials [1].
In the current study we aim to investigate how a new class of genetically engineered elastic
biomolecules, can adhere on surfaces having different properties and chemical composition.
In detail the attention is here directed to fusion proteins having cellulose binding domains (CBMs)
found in carbohydrate active enzymes as cellulases, which are developed by certain organism as
fungi, bacteria and algae [2]. Such constructs, for their binding affinity toward heterogeneous
materials, are candidates to be engaged as building block in hybrids structures of high mechanical
performance.
The study is employed at molecular lever using the powerful technique of Single Molecule Force
Spectroscopy, where a functionalized tip is brought in contact with a wide range of surfaces from
cellulose in its amorphous and crystalline form to graphene sheets deposited on different sub
surfaces. The proposed study will create understanding from the molecule level events to the
properties of materials.
Fig. 1: Cartoon of the fusion protein studied a) Sketch of the interaction between the fusion
protein and the surface studied with the corresponding Fd curves b),c),d)
[1]. A. H. Hofman, I. A. van Hees, J. Yang, and M. Kamperman, Adv. Mater. 2018, 1704640.
[2] M. Linder and T. T. Teeri, Proceedings of the National Academy of Sciences 1996, 93, 12251-
12255
283
BIOADH-OR03

Bio-inspired adhesives triggered by polyelectrolyte complexation

and surface priming

Dong Woog LEE


Keywords: Catechol, Polyelectrolyte complexation, Surface priming
Sandcastle worm cement protein inspired strong wet-contact adhesive was developed which
enables both a triggered complexation of polyelectrolytes, and formation of a porous architecture. A
catechol-functionalized weak poly-anion was premixed with a poly-cation in DMSO. When applied
underwater to substrates, electrostatic complexation, phase inversion, and rapid setting were actuated
by water-DMSO solvent exchange, which offers enhanced spatial and temporal control of
complexation, fostering rapid and robust underwater adhesion [1].
Marine mussel inspired catecholic primers were also developed which increases the adhesion
strength of crosslinked PMA resin on mineral surfaces by up to an order of magnitude when compared
with conventional primers such as silane- and phosphate- based grafts. Moreover, the strong and
energy-dissipative interfacial bonding on to mineral surfaces provided significant reinforcement in
ultimate strength and toughness of a highly rigid mineral-PMMA composite [2].
Fig. 1: Using cement proteins, sandcastle worms (Phragmatopoma californica) glue sand
grains together to make tubes shaped habitat
[1]. Q. Zhao, D. W. Lee, et al., Nat. Mater. 2016, 15, 407-413.

[2]. S. Seo, D. W. Lee, et al., Adv. Mater. 2017, 29, 1703026.
284
BIOADH-OR04

Development and evaluation on the surface properties of
polyaniline-chitosan bio-inspired adhesive: Experimental study and
Numerical/Molecular Dynamics simulation

1 1 1 2
Kathrina Lois TAACA*, Doebner Von TUMACDER, Maria Teresa PULIDO, Rhenish SIMON, Ma.
3 3 4 5
Roxan ABIQUIBIL, Haidee MANA-AY, Rhys MONTECILLO, and Joseph Vermont BANDOY

1
Mapua University Manila,Philippines;
2
University of the Philippines-Manila,Manila,Philippines;
3
Silliman University, Negros Oriental, Philippines;
4
Negros Oriental State University, Negros Oriental, Philippines
5
Gwangju Institute of Science and Technology, Korea

Keywords: polyaniline, chitosan, surface properties, adhesion
The development of various biological-driven glues and adhesive materials have revolutionized the
biomaterial science field since these materials can be used in a variety of applications including wound
healing patches, tissue sealants and hemostatic materials [1,2]. Most of the studies aimed at
addressing the adhesion of biomaterials as most of them exhibit poor adhesion to tissue and related
surfaces [2]. The surface of a biomaterial is the first to come in contact when implanted. This, in turn,
creates an interaction with biological components where the response is dependent on the surface
properties [3]. In this study, polyaniline-chitosan (Pani-Cs) bio-inspired adhesive, synthesized via
copolymerization and crosslinking, will be prepared in a solution casting approach. Various amounts of
Pani (0.01 M, 0.1 M, and 1 M) will be added to 0.1 M chitosan mixture. The fabricated film will be
analyzed using Fourier transform infrared spectroscopy (FTIR), contact angle (CA), surface free
energy (SFE), and two-probe test. Preliminary investigation showed that Cs has a degree of
deacetylation (DD) of 87.94, calculated using the equation of Brugnerotto et al [4]. Moreover, IR
-1
spectrum (Fig. 1) revealed that Cs has the following functional groups: hydroxyl (3290cm ), primary
-1 -1 -1
amino (1589cm ), primary amide (1641cm ) and secondary amide (1410cm ) groups. CA
measurements revealed that chitosan is highly wettable to diiodomethane, nonpolar test liquid, than
water with corresponding values of 38.63°±9.34 and 99.7°±5.43, respectively. This is due to the
calculated SFE of Cs, 40.13±4.76 dynes/cm, where it was determined that the adhesion was
predominantly due to its dispersive components. Based from these, it is expected that with the
presence of Pani, hydrophobicity of Cs will increase since the change in the amount of polar group,
amino and amide, will not also significantly affect the DD of Cs. In addition, electrical conductivity of
the Pani-Cs composites will improve due to the presence of Pani. Numerical simulations will be
conducted to determine the wetting curve as well as to study the electrical properties of the
composites. From these, it may be observed that Pani-Cs composite may be an essential bio-inspired
adhesive to be possibly used for tissue engineering and bio-sensing applications.
Fig. 3 IR Spectrum of chitosan
[1]. M. Mehdizadeh, J. Yang, Macromol Biosci 2013, 13 (3), 271-288.

[2]. J. H. Ryu, S. Hong, H. L, Acta Biomater 2015, 27, 101-115.
[3]. R. Dey, A. Ray, Biomaterials 2003, 24(18), 2985-2993.
[4]. J. Brugnerotto, J. Lizardi, et. al., Polymer 2001, 42, 3569-358.
285

POSTER ABSTRACTS
286
BIOTECH-P01

Application of Rare Aquatic Plants (Salvinia Natans) for Wastewater

Treatment under Algerian Semi-Arid Climate
1 2 3, 4
Ayache LAABASSI *, Daoud HARZALLAH , Asma BOUDEHANE Azzedine FERCHA
1
Department of Biological Sciences, Faculty of Sciences, University of Batna 2, 05000 Algeria.
2
Laboratory of applied microbiology. Faculty of Natural and Life Sciences, University Sétif 1, 19000
Algeria.
3
Department of Biological Sciences, Faculty of Sciences, University of Batna 2, 05000 Algeria.
4
Department of Agronomy, Faculty of Natural and Life Sciences, University Abbas Laghrour
Khenchela Algeria.
Keywords: Nutrient removal, Salvinia natans, semi-arid climate, Wastewater treatment
Macrophyte pond has developed strongly in the field of wastewater treatment for irrigation in rural
areas and small communities. Their association allows, in some cases, to increase the hydraulic
capacity while maintaining the highest level of quality.
The present work is devoted to the treatment of domestic wastewater under climatic conditions of
Algeria (semi-arid) through a system using two tanks planted with Salvinia natans.
The performance study and treatment efficiency of the system overall shows that the latter
provides a significant removal of nitrogen pollution: total Kjeldahl nitrogen NTK (85.2%),
+ -
Ammonium NH 4 -N (79%), Nitrite NO 2 -N (40%) also, a major meaningful reduction of biochemical
oxygen demand BOD 5 was observed at the output of the system (96.9 %). As BOD 5, the chemical
oxygen demand (COD) removal was higher than 95 % at the exit of the two tanks. A moderately
3
low yield of phosphate-phosphorus (PO 4 -P) was achieved with values not exceeding 37 %. In
general, the quality of treated effluent meets the Algerian standard of discharge and which allows
us to select a suitable species in constructed wetland treatment systems under semi-arid climate.
287
BIOTECH-P02

Petroselinum crispum as biosorbent for the removal of metallic

trace elements
1,2 2 3 3 1 1
Ahmed BAHLOUL*, H. ZOUAOUI, A. MIRIBAI, , A. DIAFAT, Y. NOUFEL, M. DERRARDJA,
1
Département de Génie de l’environnement, Faculté des science et de la technologie, Université
Mohamed El Bachir El Ibrahimi Bordj Bou Arréridj, Algeria
2
Laboratoire d’Energétique et d’Electrochimie du Solide, Université Ferhat Abbas Sétif-1, Sétif, Algeria
3
Département des Sciences Agronomiques-Faculté Sciences de la Nature et de la Vie, Université
Mohamed El Bachir El Ibrahimi, Bordj Bou Arréridj, Algeria
Keywords: Metallic trace elements, biosorbent, Petroselinum crispum, biotechnology, environment
The metallic trace elements are characterized by their persistence, toxicity and accumulation in
the natural environment. Consequently their presence in the environment can be detrimental to
several varieties of living species [1]. For this purpose, several scientific researchers have been
developed in order to minimize their concentrations. The removal of metallic trace elements from our
environment especially in wastewater is now shifting from the use of conventional adsorbents to the
use of biosorbents. It can be considered as an alternative green technology which has been proved as
more efficient and economical for metallic trace elements [2].
In this work, we propose to test the ability of Petroselinum crispum (Parsley) seeds in the
2+ 2+ 2+
elimination of trace metals (Pb , Cd and Cu ) in aqueous solution. This study was carried out by
electrochemical and spectroscopic characterization (FTIR). The Petroselinum crispum seeds are
2+ 2+
powdered and added with different mass (0.1, 0.2, 0.4, 1 and 2g) to the solutions of Pb , Cd and
2+
Cu (20 ppm), after filtration all solutions were analyzed by differential pulse polarography by technic.
2+
The obtained results had shown an important removal of the toxic elements, 98.99% for Pb , 99.55%
2+ 2+
for Cd and 93.2% for Cu . The Petroselinum crispum is a good support for elimination of toxic
2+ 2+ 2+
metals. The metallic trace elements ions Pb , Cd and Cu are mainly interacted with the
Petroselinum crispum particles by chelation between metallic ions and the carboxylate anion.
[5]. V. P. Singh, Toxic metals and environmental issues, Ed. Sarup & Sons, 2005
[6]. X. Liu, G. R. Chen, D. J. Lee,T. Kawamoto, H. Tanaka M. L. Chen,Y. K. Luo, Bioresource
Technology, 2014, 160, 142-149
288
BIOTECH-P03

Synthesis and characterization of new analogues of Azomethin-β-D-

Glucosamines
1 1 2
Hocine BOULEGHLEM, Amira HAMRIT, Salima ZIDANE,
1
with Organic chemistry laboratory Applied (LCOA), Group of Chemistry Bioorganique Faculty of
Science, Department of Chemistry. University Badji-Mokhtar 23000 Annaba, ALGERIA;
2
Laboratory of Electrochemistry, Molecular Engineering and Catalysis Redox LEIMCR University F.
ABBAS - 19000 Setif, ALGERIA.
Keywords: Aldehyde, azomethine, β-D-Glucosamine, regioselective deprotection, Glucosamine

hydrochloride, selective protection, condensation reaction.
In this study, we synthesized a new series of tetra-O-acetylazomethin-β-D-Glucosamine. The

synthesis of the azomethine [1] protecting group (HC=N) is carried out by the condensation reaction of
Ac-GlucNH2.HCl [2] with three aldehyde derivatives which are benzaldehyde, acetaldehyde and
formaldehyde.
The synthesis is carried out in three steps starting from the selective protection of the amine function
of β-D-Glucosamine hydrochloride by tert-butoxycarbonyl, followed by acylation of the hydroxyl
functional groups (H-1, H-3, H-4 and H-6) by acetic anhydride, protection is followed by regioselective
deprotection of the amine function by irradiation via microwave[3], and finally condensation with the
aldehydes.
The two diastereoisomers (Z/E) of products condensed via benzaldehyde were characterized by
visible UV. The structures of the synthesized compounds have been elucidated by the usual
spectroscopic methods IR, NMR (1H, 13C) and MS. The diastereoisomers resulting from the
condensation via benzeldehyde (Va) were separated by crystallization to give (E) and (Z), the UV-
Visible characterization and the melting point measurement determined the difference between them.
[1] H. Schiff, J. Liebigs., Ann. Chem. . 1866, 140, 92-137.

[2] T. Towheed , L. Maxwell , T-P. Anastassiades, B. Shea, J-B. Houpt, V.Welch, M-C Hochberg, G-A
Wells. Cochrane Database Syst. Rev. 2005,18, 8 -17.
[3] S. Tehranchian, T. Akbarzadeh, M. R. Fazeli, H. Jamalifar, Bioorg. Med. Chem. Lett. 2005, 15, 23-
26.
289
BIOTECH-P04

Textos: Improvement of the interface between tissues and scaffolds

1 1 1 2 2
Xavier Carette , Rosica Mincheva , Jean-Marie Raquez , Morgane Herbin , Thomas Godfroid ,
1
Laetitia Mespouille
1
Laboratory of Polymeric and Composite Materials (LPCM), University of Mons, Place du Parc, 23, B-
7000, Mons, Belgium
2
Laboratory of chemistry of plasma-surface interaction (ChIPS), University of Mons, 23 Place du Parc,
B-7000 Mons, Belgium
The goal of this cross-border project is to develop an innovative 3-D matrix for tissue engineering (TE)
allowing the reconstruction, regeneration or the replacement of living tissues or organs. This matrix will
act as a suitable scaffold for the proliferation of cell directly implantable in the body and will be made
of biosourced polymers/ceramic fillers (nano)composites [1], [2]. The originality lies in the 3D structure
of the device. The composites made of polyester, chitosan and hydroxyapatite will be made into fibers
and then knitting to form a sterilized porous scaffold, easy to handle.
A critical point for TE is the interface between the polymer scaffold and the newly growth implant [3].
First process is the adhesion of cells on the scaffold. This step requires the scaffold to be able to
interact with the cells. The polyester mainly hydrophobic present a poor adhesion due to the
hydrophilicity of the cells. Many ways to improve the interface can be found in the literature[4]–[7]. The
main technique is the grafting of molecules or functions on the surface of the polyester. This technique
allows us to tune the properties of the surface and then to reach the optimal contact angle (between
55 and 70°). The molecules need to be biocompatible and biodegradable to be used in TE.
Atmospheric plasma can be used to effectively graft molecules on a surface [7]. The plasma is used to
activate the surface and create new functionalities capable of interact with the molecule. In this work, a
microwave atmospheric plasma torch was used to improve the grafting of chitosan on a polyester
surface. The presence of chitosan was investigated by infra-red spectroscopy (IR) and X-ray photon
spectroscopy (XPS). The hydrophilicity of the surface was also investigated by contact angle.
Figure 5 TEXTOS project
[1] S.-S. Kim et al, Biomaterials, 2006, 27, 1399–409.

[2] I. Armentano, et al , Polym. Degrad. Stab.,2010, 95, 11, 2126–2146.
[3] R. Morent et al , Plasma Process. Polym.,2011, 8, 171–190.
[4] J. Yang et al, Biomaterials, 2002, 23, 2607–2614.
[5] N. Saranya et al , J. Biom. Nanotech., 2011,7, 238-244.
[6] Y. Tamada and Y. Ikada, Polymer, 1993, 34, 2208–2212.
[7] M. Nakagawa et al , J. of Biom. Mat. research. Part A, 2006, 84, 1110-1116.
290
BIOTECH-P05

Edible colloidal colorants from water insoluble proteins

1 1 1 1,2,3
Frankje DE BOER *, Rutger KOK, Arnout IMHOF, Krassimir VELIKOV,

1
Utrecht University, Utrecht, The Netherlands;
2
Unilever, Vlaardingen, The Netherlands;
3
University of Amsterdam, Amsterdam, The Netherlands
Keywords: colloidal synthesis, light scattering, color determination, protein
In this work, colloidal colorants were synthesized from the water insoluble protein zein, which is a
protein from corn. Zein has advantageous properties which make this protein interesting for possible
future applications in food and cosmetics: it is edible, renewable and biodegradable. In addition, zein
is soluble in food-safe solvents such as water-ethanol mixtures and it is capable of film formation with
good barrier properties.
This project is divided into two main parts. The first part of this project is to design a colloidal
dispersion that has a white appearance. The motivation to synthesize white particles is to develop a
bio-based and renewable alternative for the inorganic titanium dioxide (E171) which can be used as a
white colorant in wet food products [1-3]. To synthesize these white colorants, zein is purified and
converted into stable colloidal particles via anti-solvent precipitation (figure1a and b) [4]. The second is
to encapsulate colorants by using co-precipitation of the colorants together with zein (figure 1c and d).
Both types of particles, white and colored, are then characterized on the single particle level and in
concentrated suspensions. On the single particle level characterization is done by UV-Vis
spectroscopy and dynamic light scattering. In concentrated suspensions, characterization is done by
total reflection and total transmission measurements. And finally the experimentally found scattering
properties of the particles are compared to light scattering theory.

Fig. 1: white zein colloids after synthesis a) and corresponding SEM image b), and blue zein
colloids after synthesis c) and corresponding SEM image d).
[1]. A. Weir et al. Environ. Sci. Technol. 2012, 46, 2242–2250.

[2]. M. Lomer et al. Analyst. 2000, 125, 2339–2343.
[3]. R. J. B. Peters et al. J. Agric. Food Chem. 2014, 62, 6285–6293.
[4]. F. Y. De Boer et al. Soft Matter. Submitted
291
BIOTECH-P06

Production of Halomonas Levan and Polymethylsilsesquioxane
Nanofibres With Co-Axial Electrospinning For Wound Healing
Applications
1 2 1
Tugce DOGRUEL , Oguzhan GUNDUZ , Ebru TOKSOY ONER

1
IBSB, Department of Bioengineering, Marmara University, Istanbul, Turkey
2
Advanced Nanomaterials Research Laboratory, Marmara University, Istanbul, Turkey
Keywords: Halomonas Levan, PMSQ, Electrospinning, Wound Healing
Levan is an uncharged natural polymer comprised of β (2→6)-linked fructose rings. It is produced by a

wide range of microorganisms and plants. Halomonas levan (HL) is unbranched levan polysaccharide
produced by Halomonas smyrnensis cultures [1]. HL is soluble in water, highly adhesive,
biocompatible, biodegradable, anti-inflammatory, anti-bacterial and film-forming biopolymer [2,3].
Polymethylsilsesquioxane (PMSQ) is classified as a polysiloxane (silicone resin) and consists of
methylsilsesquioxane units which are trifunctional organosilicon units [4]. Due to its properties such as
biocompatibility, non-toxicity, non-polarity and chemical stability, PMSQ is a promising material in
tissue engineering [5, 6]. Electrospun nanofibers have important properties such as mimicking the
natural structure of extracellular matrix and high wound healing ability [7]. This study aimed to
complement the distinctive features of levan and PMSQ to obtain novel adhesive nanofiber matrices
for wound healing applications. For this purpose, levan and PMSQ were co-axially spun under
different conditions and the obtained matrices were characterized for their mechanical, physical,
morphological and biological properties.
The financial support provided by TÜBİTAK through project 116M838 is gratefully acknowledged.
[1]. Poli, Annarita, et al., Carbohydrate Polymers 2009, 78, 651-657.

[2]. Erginer, M., et al., Carbohydrate polymers 2016, 149, 289-296.
[3]. Toksoy Oner, E., et al., Biotechnology advances 2016, 34, 827-844.
[4]. Chae, H. S., et al., Molecular Crystals and Liquid Crystals 2008, 492, 28/[392]-338/[402].
[5]. Luo, C., et al., Polymer 2010, 51, 1654-1662.
[6]. Luo, C., et al., Polymer International 2015, 64, 183-187.
[7]. Agarwal, S., et al., Polymer 2008, 49, 5603-5621.
292
BIOTECH-P07

Halomonas Levan as a Bioactive Cosmetic Ingredient

1 1
Merve ERGİNER HASKÖYLÜ and Ebru TOKSOY ÖNER

1
IBSB, Marmara University Department of Bioengineering, Istanbul,Turkey

Keywords: Halomonas Levan, Fructan, Exopolysaccharide, Cosmeceuticals
Ageing is a common biological and genetic process and cumulative environmental damages occur in
all living organisms [1]. Age related skin changes are major concerns worldwide for both cosmetic and
pharmaceutical industries. There is an increased consumer demand on natural cosmetic ingredients to
maintain longevity and anti-ageing which made researchers to seek new formulations with natural
active ingredients like plant, marine and bacterial polysaccharides that mimic natural growth factors
and cytokines for biological metabolisms [2,3]. Ageing in skin can be characterized by anatomical,
biological, and physiological changes like skin barrier function, trans epidermal water loss, elastin,
hyaluronic acid and collagen synthesis. Skin care products are used to moisturize skin via restoration
of water loss in stratum corneum, increasing repairing function of skin and normalizing cellular
turnover. Hyaluronic acid and bacterial cellulose are widely used as active ingredients in cosmetics [4].
Levan is a β (2→6)- linked fructan exopolysaccharide. This biocompatible, film former, nontoxic,
strongly adhesive, water soluble polymer is one of the most common fructan polymers in nature and
has many application areas from food, feed, chemical industries and pharmacy to medicine [5].
Halomonas levan is a biopolymer produced by halophilic bacterial cultures and it has various features
like antioxidant, anticoagulant, anticancer, biocompatible and immunostimulatory effects [6] and could
be a strong candidate for cosmetic applications. This study investigates the potential uses of levan
based formulations in cosmetics and hence effects of Halomonas levan on human dermal fibroblast
and keratinocyte cells are investigated in detail in vitro. In the light of this study possible application
areas of this polymer like wound healing, skin repair and antiaging will be understood to develop new
biomaterials and cosmetic formulations.
Acknowledgement : Special thanks to 2211C TUBITAK scholarship and FEN-C-DRP-170118-0014

project for financial support.
[1]. C. Wiegand, C. Raschke, P. Elsner. Textbook of Aging Skin. 2017, 55-65.

[2]. Z. I. Gazitaeva, A.O. Drobintseva, Y. Chung, V.O. Polyakova, I.M. Clin. Cosmet. Investig.
Dermatol. 2017, 10, 11-16.
[3]. A. Adrien, A. Bonnet, D. Dufour, S. Baudouin, T. Maugard, N. Bridiau, N. Carbohydr. Polym. 2017,
157, 1306-1314.
[4]. F. Freitas, V.D. Alves, M. A. Reis. Polysachharides: Bioactivity and Biotechnology. 2015, 2017-
2043.
[5]. E.T. Öner, L. Hernández, J. Combie. Biotechnol. Adv. 2016, 34, 827-844.
[6]. M. Erginer, B. Coskunkan, T. Morova, D. Rende, S. Bucak, N. Baysal, R. Ozisik, M.S. Eroglu, M.
Agirbasli, E.T. Öner. Carbohyd. Polym. 2016, 149, 289-296.

293
BIOTECH-P08

Catalytic Olefin Metathesis for Preparation of Macrocyclic Musks
and Fine Chemicals from Biomass

Karol Grela*

Biological and Chemical Research Centre
Faculty of Chemistry, University of Warsaw
Żwirki i Wigury Street 101, 02-089 Warsaw, Poland

Keywords: Olefin metathesis, catalysis, organic synthesis, musk, natural products, terpenes,
renewable materials
Ruthenium-catalyzed olefin metathesis reaction represent an attractive and powerful transformation

for the formation of carbon-carbon double bonds [1]. Herein we report successful utilization of
sequential ethenolysis and ring-closing metathesis of dec-9-enoic acid based dienes in synthesis of
macrocyclic lactones that possess a strong scent of musk. Alternatively, oleic ester can be utilized in
musk production, using tailored catalysts and techniques developed in our group [2,3]. In addition,
application of metathesis in self-CM of α-olefins and valorization of biomass, will be presented.
O O [Ru] 17
13 16
O 17
O O O
[Ru]
O
CO2Et CO2Et
50 ppm CO2Et
C2H4 (20 bar) 9DAEE CO2Et
70 °C, 5 h +
Ethyl oleat e neat
9DE
expected product s unw ant ed products
N N N
Cl Cl
Ru Ru
Cl Cat. Conversion Select ivit y
Cl N N
O O [Ru]-1 89% 76%
[Ru]-2 67% 97% Cl
[Ru]-1 [Ru]-2 Ru
Cl
O
[Ru] Cat. Conversion
500 ppm
Hov-II 4% [Ru]-3
C2H4 (10 bar) 20%
H H [Ru]-1
DCM, 0.1 M H H [Ru]-3 99% (68% f or 250 ppm)
40 °C, 1 h
(- )- b- caryophyllene
Fig. 1: Application of olefin metathesis in musks and fine chemicals production from biomass
[1]. Olefin Metathesis: Theory and Practice, Grela, K. (Ed.), John Wiley & Sons, 2014.
[2]. M. Dąbrowski, K. L. Grela, Patent P419637 (2016), PCT/IB2017/05751 (2017).
[3]. K. Grela, M. Smoleń, Patent EP158237701 (2017).
294
BIOTECH-P09

Phage Display Derived Short Peptides for the Recovery of Valuable
Metal Ions from Water Streams
1 2 1 1 3
Sabine MATYS, Nora SCHÖNBERGER, Robert BRAUN, Falk LEHMANN, Katrin FLEMMING,
1 1
Franziska LEDERER, Katrin POLLMANN*,
1
Helmholtz-Zentrum Dresden-Rossendorf, Helmholtz Institute Freiberg for Resource Technology,
Freiberg, Germany,
2
Technische Universität Bergakademie Freiberg, Institute of Non-Metallurgy and Pure Substances,
Freiberg, Germany,
3
Helmholtz-Zentrum Dresden-Rossendorf, Institute of Resource Ecology, Dresden, Germany
Keywords: phage surface display, biopanning, metal recovery
Since several years, the phage surface display technique (PSD) has been successfully applied for the
development of new receptor-ligand pairs for medical purposes, new pharmaceuticals or the
elucidation of protein-protein interactions [1,2]. A comparatively new methodological approach is the
use of this technique for bioremediation [3,4]. We established the PSD as novel biotechnological
platform for the selective recovery of industrial relevant elements either in ionic form or as small
particles. The commercially available bacteriophage libraries Ph.D.C7C and Ph.D.12 (New England
Biolabs, Inc.) were used for isolation and identification of specific nickel, cobalt and gallium ion binding
peptides.
Fig. 1: Schematic drawing of M13 phage with genetically modified coat proteins as
representatives for commercially available phage libraries with introduced short peptide
motifs.
9
From a pool of 1,2 x 10 different peptide motifs, 24 phage clones for nickel, 20 for cobalt and 108 for
gallium were isolated in the iterative bio-panning process. The binding strength of these phages
clones was compared with the one of unmodified wild type phages by performing adsorption tests onto
metal loaded agarose beads. Cross binding tests revealed for most of the nickel binding phages also
binding capacities for cobalt and vice versa.
[1]. H.M.E. Azzazy, W.E. Highsmith Jr., Clinical Biochemistry. 2002, 35, 425-45:
[2] J. Pande, M.M. Szewczyk, A.K. Grover, Biotechnology Advances. 2010, 28, 849-58:
[3] S.B. Curtis, J. Hewitt, R.T.A. MacGillivray, W.S. Dunbar, Biotech. Bioeng. 2009, 102, 644-650:
[4] T. Hatanaka, A. Matsugami, T. Nonaka, H. Takagi, F. Hayashi, T. Tani, N. Ishida, Nature
Comm. 2017, 8, 15670:
295
BIOTECH-P10

Coherent-synchronized oxidation reaction of
3-picolin by nitrous oxide
1,2 1 2 1
Tofik NAGIEV, Nahmad ALI-ZADEH, Inara NAGIEVA, Eynulla BAHRAMOV
1
Nagiev Institute of Catalysis and Inorganic Chemistry, Baku, Azerbaijan
2
Baku State University, Baku, Azerbaijan
E-mail: [email protected]
Keywords: coherent-synchronized, green oxidant, 3-picolin
Studied mechanism of purposed products production based on known mechanisms of coherent-

synchronized oxidation of hydrocarbons by hydrogen peroxide (green oxidant) according to the
ordinary technology [1]. From this point of view, oxidation of 3-picolin by nitrous oxide (green oxidant)
has a great practical and theoretical interest.
As a result of corresponding investigations there have been established spheres of running
coherent-synchronized oxidation of 3-picolin with the reaction of decomposition nitrous oxide. The
reaction system elaborated by us makes possible, according to the ordinary technology, to obtain a
number of valuable monomers, which are used in many fields of industry and it has a number of
advantages compared to heterogeneous catalytic processes. In the present work, we report the
results of the experiments of 3-picolin gas-phase oxidation to pyridine 4,4-(1,2-ethanedil)bis and 2,2-
bipyridine 4,4-dimethyl. The reaction was performed in the flow quartz reactor, construction of which
ensured the entry of 3-picolin into reaction zone by a quartz tube, separately from nitrous oxide. By
other quartz tube preliminarily heated nitrous oxide in a gaseous state is fed. The volume of reaction
3
zone made up 5.5cm . The reaction products were analyzed chromatographically. The qualitative
determination of the reaction products composition was carried out by chromatomass-spectroscopic
method: (Agilent technologies 7820A, GERMANY).
The investigations were carried out under following conditions: temperature 560-5800C, feeding
rate of 3-picolin to reaction zone – 0,8-1,6ml/h, feeding rate of nitrous oxide – 100-250ml/h.
Experimental investigations allow us to study kinetics of reaction and showed that this process is
coherent-synchronized oxidation reaction. For the preliminary results, yields of Pyridine, 4,4'-(1,2-
ethanediyl) bis and 4,4'-dimethyl-2,2'-bipyridine accounted for 11-12% and 8-10%, respectively.
[1]. Nagiev T.M. Coherent Synchronized Oxidadtion by Hydrogen Peroxide, Elsevier. Amsterdam.
2007. p. 325.
296
BIOTECH-P11

Synthesis and Characterization of Functional Polyamides from
Tulipalin A

1 1
Falko PIPPIG*, Jaroslav MOSNACEK,

1
Polymer Institute of the Slovak Academy of Sciences, Bratislava, Slovak Republic

Keywords: Polyamide, Tulipalin A, Polyaddition, renewable
α-Methylene-β-butyrolactone (MBL), also known as Tulipalin A, is a monomer, which can be identified

in tulips [1]. Therefore, it is potentially renewable. It can be also synthesized via organic synthesis.
MBL can be polymerized via radical co-polymerization [2]. Recently, Kollár et. al. presented a
copolymer based on hydrolyzed MBL and acrylamide showing properties of a superabsorbent
hydrogel [3]. With this contribution we would like to present a novel potentially fully renewable and
functional polyamide, which can be produced based on this monomer. Here we show that MBL reacts
with various diamines and forms a polyamide bearing pendant OH groups as it can be seen in the
figure 1.
O
O
O NH
+ H2N
x
NH 2 H 3C NH
x
CH 3
CH 2
OH
n
x = 0, 1, 2, 3, 4, 5
Fig. 1: scheme of the synthesis of the polyamide from Tulipalin A
It is possible to synthesize polymers with various diamines like 1.2-diaminoethane, 1.3-diaminoethane,

1.4-diaminopropane, 1.5-diaminopentane (cadaverine), 1.6-dioaminohexane and 1.7-diaminoheptane
-1
up to molar masses (Mw) of 70 000 g mol . The polymerization can be made without solvent and at
different temperatures. The reaction is very fast compared to the published examples for the
polymerization of polyamides. It is possible to synthesize polymers with a molar mass (Mw) up to 20
-1
000 g mol in less than 30 min. The polydispersity (PDI) of the polymers is in the range of 2 to 6. All of
the polymers are hard and transparent. They form strings in melted state. Additional, it is possible to
create transparent films. The commercially available polyamides are usually produced via
polycondensation. Here the mechanism is based on polyaddition. The presented polymers were
1 13
investigated with H and C NMR, GPC, MALDI-MS, DSC and TG. We are convinced that our new
polymer has a huge a potential in the field of production of new polymeric materials from biobased and
renewable monomers.
Acknowledgement: Authors thank for financial support to APVV grant agency through grant no. APVV-
15-0545 and grant agency VEGA through grant no. VEGA 2/0158/17.
[1]. W. P. C. M. van Rossum, M. Alberda, L. H. W. van der Plas, Phytochemistry 1998, 49 (3), 723-
729.
[2]. A. R. Cockburn, F. L. T. McKenna, R. A. Hutchinson, Macromolecular Chemistry and Physics
2010, 211, 501-509.
[3]. J. Kollár, M. Mrlík, D. Moravčíková, Z. Kroneková, T. Liptaj, I. Lacík, J. Mosnáček, Macromolecules
2016, 49(11), 4047-4056.
297
BIOTECH-P12

The characterization and testing of dermal scales of Scophthalmus

rhombus for application in antifouling technology

1 1 1
Chloe Richards, Ivan Maguire, Fiona Regan

1
School of Chemical Sciences, DCU Water Institute, Dublin City University, Dublin, Ireland

Keywords: biofouling, marine benthic diatoms, brill fish, 3D printing, antifouling, scophthalmus
rhombus

In recent years, there has become a growing need for the development of antifouling technology.
Fouling from ships, sensors and buoys leads to the production of large amounts of biomass resulting
in substantial economic losses for the marine industry. Biofilm build-up or slime films have a
remarkable impact on the hydrodynamic performance of a surface. [1] In a paper by Lewthwaite et al,
it was discovered that a slime layer of 1mm in thickness that had developed on a 23m vessel caused a
15% loss in the speed of the ship in comparison to the values achieved for the clean hull. [1]
Current technologies to combat fouling include the use of commercial paints. However, new
regulations insist upon a change from self-polishing copolymer organotin systems to silicone and
copper-consisting antifouling technologies. The growth of microfouling communities that contribute to
this fouling now require in-depth understanding to provide ship owners with the best antifouling
alternatives. [1]
Marine organisms such as Scophthalmus rhombus (Fig. 1) have evolved to present physical,
behavioral and chemical mechanisms that exhibit antifouling properties. [2] In that respect, the
mechanisms used by marine organisms to prevent fouling on external surfaces are of huge interest to
researchers of antifouling technology. The ability to transfer these properties observed in nature to
artificial surfaces is highly sought after by those in the marine industry combatting fouling. This
research study focusses on the topic of biologically inspired designs. In this study, dermal scales of
Scophthalmus rhombus will be characterized for antifouling properties. Synthetic Scophthalmus
rhombus scales can then be reproduced using natural dermal scales as a template and tested in field
conditions for differences in attachment of marine biofouling organisms, benthic diatoms. [2]
Fig. 1: This figure shows the scale of Scophthalmus rhombus under SEM magnification,
20.0kV. Fouling organisms find it hard to settle on these detailed surfaces comprising of
concentric ridges and spoke-like rays.
[1] F. Casse, G. W. Swain, International Biodeterioration & Biodegradation. 2006, 57, 179-185
[2] T. Sullivan, F. Regan, Bioinspir. Biomim. 2011, 6 046001
298
BIOTECH-P13

Spherical Zinc Oxide Materials with Antimicrobial Activity

1* 1 2
Greta Socoteanu, Jose Maria CALDERÓN-MORENO, Carmen Mariana CHIFIRIUC,
2 3 *
Crina SAVIUC, Ruxandra BIRJEGA, Oana CARP
1
"Ilie Murgulescu" Institute of Physical Chemistry, Romanian Academy, Spl. Independentei 202,
060021 Bucharest, Romania
2
Department of Microbiology, Faculty of Biology, University of Bucharest, Research Institute of
University of Bucharest, Ale. Portocalilor 1-3, 60101 Bucharest, Romania
3
National Institute for Lasers, Plasma and Radiation Physics, Atomistilor 409, PO-Box MG-36, 077125
Magurele, Romania
Keywords: Green chemistry, Carbohydrates, ZnO, Antibacterial activity
The increase receptiveness towards the environment, forced a reinventing of the

nanotechnology in a green context and also has opened an avenue for the use of carbohydrates
(saccharides) in the synthesis of various materials [1]. Their availability (from renewable natural
resources) and versatility (stabilizing, templating, functionalizing, coordination abilities, etc.) are crucial
to their use in the control of materials synthesis in terms of size, shape, and porosity [2].
Zinc oxide, a bio-safe and bio-compatible semiconductor, is a valuable key functional material
for applications in different fields, due to their attractive and unique characteristics, together with its
huge variety of morphologies.
A simple and totally green one-pot hydrothermal route which involve starch biopolymer,
followed by an adequate thermal processing, leads to distinct spherical ZnO morphologies - hollow,
compartmented, core-shell and full solid ZnO spheres, dispersed or interconnected [3]. The variation
of the raw materials concentration dictates the type of ZnO spheres morphology. The carbonaceous
precursors were characterized by infrared spectroscopy, thermal analysis and scanning electron
microscopy, while the ZnO spheres, obtained after the calcination, were investigated by X-ray
diffraction, Raman spectroscopy, scanning electron microscopy, UV-VIS spectroscopy,
photoluminescence measurements, antimicrobial, anti-biofilm (Fig.1) and flow cytometry tests. The
formation mechanism of the ZnO spheres was also proposed. The materials exhibit high antibacterial
and anti-biofilm activity against Gram-positive and Gram-negative bacteria, demonstrating great
potential for new ZnO anti-biofilm formulations.
Fig. 1: Dose dependent anti-biofilm effect of interconnected solid ZnO spheres
[1]. O. Carp, A. Tirsoaga, B. Jurca, R. Ene, S. Somacescu, A. Ianculescu, Carboh. Polym. 2015, 115,
285-293.
[2]. D. Visinescu, G. Patrinoiu, A. Tirsoaga, O. Carp, in Environmental Chemistry for a Sustainable
World, Vol. 1 (Eds: E. Lichtfouse, J. Schwarbauer, D. Roberts), Springer, 2012, pp. 119-172.
[3]. G. Patrinoiu, J.M. Calderón-Moreno, C.M. Chifiriuc, C. Saviuc, R. Birjega, O. Carp, J. Colloid
Interf. Science 2016, 462, 64-74.
Acknowledgements: This work was supported by a research project number 234PED/2017.
299
BIOTECH-P16

Green polymer chemistry : Approach to artificial “urushi” via

oxidative polymerization of cardanol in w/o emulsion

Hideki YAMANE,* Takumi OTSUKA, and Shiro KOBAYASHI

Kyoto Institute of Technology, Kyoto, Japan;

Keywords: Urushi lacquer, urushiol, cardanol, biomimetic reaction, W/O emulsion
1. Introduction:
Urushi is sap of Japanese lacquer tree and has
been utilized as a typical Japanese traditional
coating showing an excellent toughness and
brilliance for a long period. Urushiol, a main
ingredient of urushi, is a catechol derivative with
unsaturated hydrocarbon chains, and can be crosslinked with laccase catalysis and subsequent
aerobic oxidation in water-in-oil (w/o) emulsion system. Cardanol, a main ingredient of cashew nut
shell liquid (CNSL), is a phenol derivative with hydrocarbon chains similar to those of urushiol and is
expected to be an alternative of the natural urushi liquid. This study explored a new cardanol
polymerization carried out in w/o emulsion system for synthetic approach to artificial urushi. This study
provides with a novel biomimetic reaction of natural urushi system and a green reaction system using
a renewable biomass of cardanol as monomer without using any organic solvents. It also brings about
the formation of a stable prepolymer emulsion, to lead to smoother film formation as well as to the
cured hard film formation.
2. Results and discussion:
Since it is known that natural urushi sap is polymerized in water-in-urushiol (w/o) emulsion system,
we have mimicked the system for cardanol. In order to obtain ‘artificial urushi’ starting from cardanol, a
biomimetic reaction was developed for the first time to find the polymerization conditions for a water-
in-oil (w/o) emulsion formation. Combination of an oligo- or polyamine and acetic acid (AA) was found
to be a good emulsifier. The prepolymer emulsion could be stored stably for longer than one month
when air is shut off and then could be used to form a coated film. Then, the polymerization of cardanol
is carried out in water-in-cardanol (w/o) emulsion to give prepolymer emulsion and further cured by
crosslinking, which is a new biomimetic polymerization of cardanol. Fe-salen catalyzed polymerization
of cardanol in the emulsion proceeded smoothly to produce a prepolymer emulsion, which gave good
films for curing. Films were prepared from the prepolymer emulsion and their curing was achieved by
thermal-annealing or by cobalt naphthenate-catalyzed crosslinking in air to give ‘artificial urushi’.
Rheological properties of cardanol monomer and prepolymer emulsions revealed an excellent film
formability on the substrate. The cured film showed a strong hardness evaluated by the hardness test
as well as by the thermo-mechanical analysis, and looked smooth and brilliant like natural urushi.
Thus, the present emulsion system provides with a new coating material for potentially practical
applications in commodity-use. Further, this study employs a renewable biobased cardanol without
using an organic solvent, and thus, provides with a good example of green polymer chemistry.
300
BIOTECH-P16

Silica fumed as a carrier for synthetic metalloporphyrins emulating

ligninolytic peroxidases: the effect of ligands

1 1 1 1
Paolo ZUCCA, Enrico SANJUST *, Andrea COCCO , Gianmarco COCCO

1
Dipartimento di Scienze Biomediche, Università di Cagliari, Italy

Keywords: Biomimetic, Metalloporphyrins, Metalloporphines, Peroxidase, Thionine, Imidazole,
Pyridine.
Synthetic metalloporphyrins have been widely used as effective catalysts for the emulation of
ligninolytic peroxidases [1]. However, to accomplish a real emulation of enzymatic active site, thus
increasing the redox potential of the metalloporphyrin, immobilization should be achieved through
coordination with imidazole or other nitrogen base [2]. Here, we describe the immobilization of
5,10,15,20-tetrakis(2,6-dichlorophenyl)porphine (FeTDCPP) onto imidazole- and pyridine-grafted
fumed silica (respectively, FSI and FSP, Figure 1). Imidazole- or pyridine-functionalized silane was
synthesized through reaction between imidazole-4(5)carboxyaldehyde or 4-pyridinecarboxyaldeyde in
the presence of sodium cyanoborohydride. The resulting silane was used to silanize FS surface, and
subsequent FeTDCPP immobilization.
Figure 6: Scheme of the tested catalyst, using pyridine as the ligand.
The two catalysts were tested about their ability to oxidize thionine textile dyes. Both FSI/FeTDCPP
and FSP/FeTDCPP were able to completely oxidize both thionine and methylene blue in about 5 h, in
the presence of hydrogen peroxide as the oxidant. But the former gave, for instance, only 23%
bleaching of thionine in 10’, whereas in the same time FSP/FeTDCPP gave 61%. The higher electron
deficiency of pyridine could explain such difference. This, in fact, could increase CpdI analogue
reactivity, and thus the overall catalytic performances of the pyridine-functionalized catalyst.
Accordingly, FSP/FeTDCPP was chosen for the rest of the study.
Scanning electron microscopy (SEM) and Fourier Transform - Infra Red (FT-IR) spectrometry were
used to check surface chemical changes of the FS along the modification reactions. Minimal changes
were detected and nanostructures were still within the nanoscale range (⩽100 nm). Mean particle size
only increased from 61 nm (FS) to 123 nm (FSP), being compatible to metalloporphyrin
immobilization. Functionalization reaction was also confirmed by FT-IR, as already reported for similar
-1 -1
supports. New bands arose around 1550 cm and 2900 cm in FSP, possibly suggesting the
presence of heteroaromatic rings or secondary amines.
Catalytic activity has been characterized showing an optimum at pH 3, using hydrogen peroxide as the
oxidant. On the contrary, the use of monopersulfate instead increased activity also at neutrality. Some
preliminary test have been also performed using lignosulfonate as the substrate. UV-vis spectra
showed an arising additional peak at 255 nm, suggesting an effective catalytic activity of
FSP/FeTDCPP with both oxidants. Even in this case, hydrogen peroxide was more active at pH 3,
whereas monopersulfate also at neutrality.
[1]. P. Zucca, A. Rescigno, A.C. Rinaldi, E. Sanjust, J. Molec. Catal. A: Chem. 2014, 388, 2-34.
[2]. G. Cocco, A. Cocco, F. Sollai, E. Sanjust, P. Zucca, Int. J. Molec. Sci. 2017, 18, 2553.
301
BIOTECH-P17

Synthesis of Some Glycosteroidal Bolaphiles
(1.2)
Fahima ALI-RACHEDI
1
Univ Souk Ahras, Faculty of Science and Technology, PB 1553, 41000 Souk Ahras, Algeria
2 Laboratory of Applied Organic Chemistry, University of Annaba, 23000 Annaba, Algeria
Keywords: Glycosteroides, carbohydrates, metathesis,
This work describe the synthesis of bolaphile biomimics composed based on sacharids head groups
and steroidal units, the two entities are linked together by a methylene chain of varying length. Many
compounds in this family are natural products, which possess important biological properties[1] This
family of compounds has been prepared by the CMGL-synthon strategy[2] and reporting our
preliminary results on the thermotropic behaviour of acyl steroid glycosides (ASG), namely cholesteryl
6-O-acyl-β-gluco- and -galacto-pyranosides. These systems can exhibit several types of structures
depending on their polarity pattern based on the number of polar and non-polar moieties and their
resulting formed by self-organization of the products as a function of temperature were characterized
by differential scanning calorimetry and thermal polarized light microscopy. The diagram below can
explain the protocol followed
R1 OAc
R1 OAc R1
R2 O OAc
AcO O R2 O 1)-1 ou 1a R2 O
NH2
O AcO O AcO
HO O HO O NH
O NH 2)- 5% G-H II, O
CH2Cl2, rt., 24h O (Z et E)
: cholestérol ou cholestanol
HO
Scheme 1: Diagram explained the protocol followed for the synthesis of bolaphils componds
[1] Goodby, J. W.; Görtz, V.; Cowling, S. J.; MacKenzie, G.; Martin, P.; Plusquellec, D.; Benvegnu, T.;
Boullanger, P.; Lafont, D.; Queneau, Y.; Chambert, S.; Fitremann, J. Chem.Soc. Rev. 2007, 36, 1971-
2032
[2] S. Trombotto, M. Danel, J. Fitremann, A. Bouchu, Y. Queneau, J. Org. Chem.; 2003; 68; 6672-
6678.
302
BIOTECH-P18

Characterization of oat and spelt husks for development of
polypropylene based composites

1 1 1 2
Remo MERIJS-MERI,* Janis ZICANS, Madara VARKALE, Janis GRAVITIS, Paulius Pavelas
3 4
DANILOVAS, Andrzej K. BLEDZKI

1
Institute of Polymer Materials, FMSAC, RTU, Riga, Latvia;
2
Latvian State Institute of Wood Chemistry, Riga, Latvia;
3
Department of Polymer Chemistry and Technology, KTU, Kaunas, Lithuania
4
Institute of Materials Science, ZUT, Szczecin, Poland

Keywords: oat, spelt, husks, steam-explosion, characterization
Resource efficiency plays an important role in implementation of the Europe 2020 Strategy, being a
roadmap for sustainable development. Because of limited fossil resources, sustainable development is
not achievable without the use of renewable resources whenever possible. Renewable natural
resources offer a vast source for development of effective solutions in energetics, building, automotive
and other sectors of national economy. Of particular interest to the international community is
purposeful use of natural waste products.
In this context, the current research is focused on the evaluation of the suitability of agricultural waste
products, such as oat and spelt husks (OH and SH, respectively), for reinforcing of polypropylene,
thus trying to find economically and technologically viable alternatives to wood flour (WF) containing
polymer composites. By considering that aspect ratio plays an important role in determining
reinforcement efficiency of the filler, especial attention has been paid to elaboration of mechanical pre-
treatment procedures of OH and SH, by considering technological parameters such as grinding speed
and time. Beyond mechanical milling/sieving protocols, suitability of the lab-scale steam explosion
processing has been also evaluated. Steam explosion treatment of natural fibers is known to ensure
increased cellulose content [1-3], as well as higher surface area [3], being important indicators for
increased reinforcing efficiency of the lignocellulosic filler in the polymer matrix.
Taking into account the previously mentioned, in the current research OH and SH before and after
pre-treatment (either mechanical milling with grinding speeds in the interval 700-3000 rpm or steam
o
explosion at 235 C and 3.2 MPa for 1, 3 or 5 min.) have been characterized in comparison to
commercial WF. Microscopy image analysis, bulk density, chemical structure analysis (FTIR),
thermogravimetric analysis, as well as moisture sorption characteristics of OH, SH and WF, as
reference, have been determined.
Results of the investigations reveal that aspect ratio of the steam exploded fibres is considerably
greater in comparison to mechanically milled microfibers, bulk density increases along with increasing
grinding speed, while chemical composition of husks and WF is similar. However, the amount of
distinct chemical constituents in husks and WF is not the same; the most remarkable difference
probably being in the amount of the extractives, in particular, waxes, as characterized by the
-1
differences in the spectral region between 2850 and 2920cm . In respect of thermal decomposition
profiles of OH, SH and WF, certain differences have been also observed; particularly, steam exploded
husks seem to show greater remaining masses at the end of the thermogravimetric experiment.
In general, grain husks, prepared according to the elaborated pre-treatment procedures, possess the
structure and properties, allowing their successful application for the development of polypropylene
matrix biocomposites.
[1]. R. Biswas, H. Uellendahl, B. K. Ahring, Bioenerg. Res. 2015, 3(8), 1101–1116.

[2]. L. Cui, Z. Liu, C. Si, L. Hui, N. Kang, T. Zhao, BioResources 2012, 7(3), 4202-4213.
[3]. A. Kaushik, M. Singh, G. Verma, Carbohydr. Polym. 2010, 82 337–345.
303
BIOTECH-P19

Bionanocomposites based on gelatin and cellulose nanocrystals
obtained by continuous casting

1 1 1
Liliane Samara Ferreira LEITE,* Caio Moreira FERREIRA, Francys Kley Veira MOREIRA, Luiz
2
Henrique Capparelli MATTOSO,

1
Federal University of São Carlos, São Carlos, Brazil;
2
Embrapa Instrumentation, São Carlos, Brazil
[email protected]
Keywords: Gelatin; Cellulose nanocrystals, Continuous casting, Edible films, Mechanical properties
Increasing environmental concern regarding the plastic pollution worldwide has stimulated the
development of low-cost biodegradable materials. Renewable sources for bio-plastics, which include
proteins such as gelatin, can be an alternative. Gelatin is a soluble protein obtained by extraction from
connective tissues, bones, and skin of animals by mild heat treatments under acidic or alkaline
conditions. Gelatin can be used in food packaging applications, biomedical applications including
wound dressing, adhesives, adsorbent materials, and drug delivery as hard or soft capsule, due to its
1
high film-forming properties, low cost, environmentally friendly, biodegradability, and biocompatibility .
However, using only proteins is not enough for producing films with satisfactory mechanical and
barrier properties for food packaging use. A way to increase the properties of these films is the use of
cellulose nanocrystals (CNC) as reinforcement. CNC are favorable not only in terms of
biodegradability, renewability, non-toxicity, and abundance, but they also have well-defined
2
dimensions, a high elastic modulus (~150 ± 50 GPa), and high tensile strength (~7.5 GPa) . The aim
of this study was to produce and characterize films based on gelatin and CNC obtained by the
continuous casting method. To produce bionanocomposites of gelatin plastic, gelatin was first
solubilized in ultra pure water at 80 °C for 20 min. Glycerol and CNC were added as a plasticizer and
reinforcement, respectively. Gelatin solutions were then turned into plastics by continuous casting on a
KTF-B labcoater unit (Mathis, Switzerland). Solutions were spread to a wet layer of thickness 1.0 mm
over a polyester sheet conveyor which was transported through hot air convective ovens (two in a
row) for drying. The Thermo-mechanical properties of processed bionanocomposites were studied by
dynamical mechanical analyses (DMA) and tensile tests. The effect of the CNC on mechanical
properties of the films was evaluated using the Tukey test, with a significance level of 95%. The
gelatin films produced by continuous casting displayed handle ability, homogeneity, and continuity,
whereas fractures and insoluble particles on their surface were absent. The glass transition (Tg) of the
nanocomposite matrix seems to be slightly affected by the presence of nanofillers. DMA showed that
this thermal transition occurred in gelatin plastic at 39 °C. and for gelatin plastic reinforced with 0.5
wt.% CNC at 69 °C. This result showed that CNC affect the onset of translational and rotational
backbone motions in the composite matrix, which contributes to increase of thermal properties.
Tensile tests showed that the addition of 0.5 wt% CNC improved significantly (P>0.05) tensile strength
(77%) and Young's modulus (48%) and decreased the elongation at break (24%) when compared with
gelatin plastics without CNC. These results showed the promising use of gelatin plastics reinforced
with CNC for applications such as packaging. The authors thanks the Fapesp (process
n° 2016/03080-3 and 2018/00278-2) for support.
[1]. J. S. Alvez, K. C dos Reis, E.G.T. Menezes, F.V. Pereira, J. Pereira, Carbohyd. Polym. 2015, 115,
215-222.
[2]. E. Gicquel, C. Martin, J. G. Yanez, J. Bras, J. Mater. Sci. 2017, 3048-3061
304
BIOTECH-P20

Phytochemical and analysis of hydromethanolic extracts and their

fractions from three lamiaceae species

1 1
Soumeya KRIMAT* , Aicha KSOURI

1
Laboratory of bioactive products and biomass valorization research. Ecole Normale Supérieure-
kouba, Algeria

Abstract: This work concerns the study of phytochemical of medicinal plants belonging to the
Lamiaceae family: Salvia chudaei Batt. et Trab., Lavandula antineae Maire and Origanum
glandulosum Desf. The aim of the phytochemical analysis was the characterization of different classes
of secondary metabolites, the quantification of total phenolic and total flavonoid contents and the
chemical analysis of phenolic compounds [1, 2]. The phytochemical screening of the extracts of aerial
parts of three plants reavealed a remarkable presence of flavonoids, tanins, sterols, terpens,
saponins, anthraquinons with total absence of alkaloids. The colorimetric assay showed that the
contents of total phenolic and flavonoid of hydromethanolic extracts and their fractions differ from one
plant to another and that diethyl ether and ethyl acetate fractions showed the highest polyphenols
content which ranged between 537.58±16.92 and 54.49±6.76 mg EAG/g ES. The chromatographic
characterization of hydromethanolic extracts by HPLC-DAD revealed the presence of phenolic acids,
flavanols, flavanons, flavonols and flavons.
Keywords: phytochemical analysis, HPLC-DAD analysis, phenolic compounds, flavonoid contents.
References:
[1]. J. Lamairson, A. Carnet, Pharmaceutica Acta Helvetia. 1990, 65,315−320.
[2]. A. Braca, C. Sortino, M. Politi, I, Morelli, J. Mendez, J. Ethnopharmacol. 2002, 79, 379-381.
305
BIOTECH-P21

Fully bio-based epoxy resins from fractionated BCD lignin

1,2 1,2 1,2
Pablo ORTIZ *, Marten Wiekamp, Richard Vendamme.

1
Flemish Institute for Technological Research – VITO, Separation & Conversion Technology,
Boeretang 200, 2400 Mol, Belgium.
2
Biorizon, Green Chemistry Campus, Auvergnedijk 2, 4612 PZ Bergen op Zoom, The Netherlands

Keywords: Lignin, bio-based, epoxy, green chemistry
Most epoxy thermosets are currently derived from non-renewable resources. Moreover, Bisphenol A (BPA),
an endocrine disruptor, is present in more than 90% of the epoxy polymers. Hence there is a health and
environmental urge to develop bio-based epoxy resins. [1] Among the possible natural substitutes of BPA,
the most promising candidate is lignin. Despite being the largest aromatic biopolymer and second most
abundant biopolymer is currently almost only used as a fuel. However, during the last years, the interest in
lignin valorisation has increased.[2]
Typically, lignin (native or modified) is reacted with epichlorohydrin, then blended in different ratios with the
diglycidyl ether of BPA (BADGE) and finally cured it with a polyamine.[3] Although following this method
resins with satisfactory properties have been obtained, BPA is not completely avoided, and the bio-based
content of the resins is still low. Our ambitious goal is to make fully bio-based epoxy resins within the
biorefinery frame. More specifically, we aim at valorising two major biorefinery by-products, namely Kraft
lignin (from pulp and paper industry) and glycerol (from biodiesel production).
Fig. 1: Epoxy monomers and representative lignin oligomer structure
The membrane separation technology developed at Vito [4] has been used to separate base catalysed
depolymerized (BCD) lignin into low and high molecular weight lignin fractions. The latter has been used as
a polyol source and reacted with the diglycidyl ether of glycerol (GDE) to obtain epoxy resins. [5] The
stiffness of the resin can be modulated varying the proportion of the two reactants. The incorporation of other
bio-based molecules in the resins has also been studied. Tannic acid has been incorporated as a second
polyol source and a dimmer diamine has been used as a curing agent. All the resins were prepared in water,
further contributing to the sustainability and the “greenness” of the procedure.
[1] R. Auvergne, S. Caillol, G. David, B. Boutevin, J.-P. Pascault, Chem. Rev. 2014, 114, 1082–1115.
[2] R. Rinaldi, R. Jastrzebski, M. T. Clough, J. Ralph,M. Kennema, P. C. A. Bruijnincx, B. M.
Weckhuysen, Angew. Chem. Int. Ed. 2016, 55, 8164–8215.
[3] B. M. Upton, A. M. Kasko, Chem. Rev. 2016, 116, 2275–2306.
[4] M.F.S. Dubreuil, K. Servaes, D. Ormerod, D. Van Houtven, W. Porto-Carrero, P. Vandezande, G.
Vanermen, A. Buekenhoudt, Separation and Purification Technology, 2017, 178, 56–65.
[5] P. Ortiz, M. Wiekamp, R. Vendamme, Manuscript in preparation.

306
BIOTECH-P22

Mixotrophic cultivation of Chlorella sorokiniana and Chlorella
vulgaris using cheese whey as carbon source

1 2 2 2
Amanda S. RESENDE , Guilherme P. CASTRO , Paulo H. de PAULA Junior , Ana M. OLIVEIRA ,
2
Enio N. OLIVEIRA JUNIOR*

1
Federal University of São João del Rei– UFSJ/CAP, Graduate Program in Technologies for
Sustainable Development, Ouro Branco, Brazil;
2
Federal University of São João del Rei – UFSJ/CAP, Department of Chemistry, Biotechnology and
Bioprocesses Engineering - DQBIO, Ouro Branco, Brazil
*e-mail: [email protected]

Keywords: Microalgae, Biomass, Cheese Whey, Chemical Oxygen Demand, Lactose.
Microalgae have been widely used as raw material in many processes due to a range of products
resultants from its metabolism and the need to find substitutes to the usual biomass sources. The
microalgae growth has advantages which make it a potential solution to energy and environmental
problems [1]. The applicatin of these microorganisms in effluent treatment process has been used
once is possible to associate the production of microalgae biomass to effluent contaminants removal
[1]. Many species of microalgae are able to grow in wastewater because they can be cultivated under
mixotrophic conditions. Mixotrophy is a trophic culture method in which microalgae can grow in both
photoautotrophy and heterotrophy conditions utilizing both inorganic and organic carbon sources that
provide higher biomass and lipid productivities than cultivation under photoautotrophic conditions [2].
The aim of this study was to investigate the effect of organic carbon source, the cheese whey,
industrial dairy waste, on the growth of Chlorella Sorokiniana and Chlorella Vulgaris. Futhermore, the
removal of organic matter and lactose are also investigated. The rotational central composite design
(RCCD) 2² experimental design was used to evaluate the influence of concentrations (% v/v) of
variables cheese whey and basal medium in the production of microalgae biomass. The cultures were
conducted on economic photobioreactors using transparent PET bottles at a luminosity of 130 ± 5
klux, and aeration of 1L/min at temperature of 25ºC. The biomass production responses (g/100ml)
were statistically evaluated using model and response surface for significant interactions between the
study variables in order to define optimal process conditions. The results showed that the higher
production of biomass was obtained from medium composed of 20% (v/v) cheese whey and 30% (v/v)
basal medium (0,57 g/100 mL in Chlorella Sorokiniana culture and 0,72 g/100mL in Chlorella vulgaris
culture), and according to the statistical analysis, only the cheese whey has a significant influence on
the results obtained. Futhermore, the removal of Chemical oxygen demand (COD) in this medium was
more than 80% to C. sorokiniana culture and more than 70% to C. vulgaris culture, and the removal of
lactose was 98,3% and 95,9%, respectively. Therefore, it was possible to conclude that a high
production of microalgae biomass and high removal of COD and lactose of the medium with cheese
whey were obtained. It is known that despite the enormous potential of microalgae, there are still
technological limitations that increase the cost of large-scale production of algal biomass, making
these products and processes uncompetitive in the market. The cheese whey, industrial dairy waste,
is a low-cost alternative culture medium, besides that the culture of microalgae in industrial dairy
waste improves the final quality of effluent, then, its use in microalgae growth is economic and the
environmental advantageous.
[1]. SILVA, N. F. P. Crescimento de Microalgas em águas residuais: Produção de Biomassa e

Remoção de Nutrientes. Porto: Mestrado integrado em Engenharia do Ambiente, 2014.
[2]. SALATI, S.; D’IMPORZANO, G.; MENIN, B.; VERONESI, D.; SCAGLIA, B.; ABBRUSCATO, P.;
MARIANI, P.; ADANI, F. Mixotrophic cultivation of Chlorella for local protein production using
agro-food by-products. Bioresource.Technology, n. 230, p.82-89, 2017.
307
BIOTECH-P23

Bio-Inspired Hybrid Systems: A Route to Self-Healing Materials
1 2 1
Nicolette MOREAU, Xuejian ZHOU, Paul RACE *
1
Department of Biochemistry, University of Bristol, UK
2
Bristol Centre for Functional Nanomaterials, University of Bristol, UK
Keywords: bio-inspired, bio-mimetic, hybrid, self-healing, smart materials
The ability for materials to heal in response to damage, wherever and whenever it occurs, is a highly
desirable property in manufacturing [1], [2]. A capability here to intrinsically recover functionality
without human intervention would increase product lifetimes, minimise repair costs and decrease the
requirement for people to deal with damaged equipment in hazardous or difficult environments.
In contrast to currently available manufacturing materials, self-healing in living systems is

commonplace and essential for survival [1]. This can occur at the nanoscale, exemplified by DNA
repair at the single nucleotide level, through to centimetre scale regeneration, as seen in skin repair
after bleeding and the regeneration of lost body parts in flatworms or newts [1], [3], [4]. These
processes are carefully mediated through a pre-programmed, highly co-ordinated sequence of events
allowing autonomous repair. A range of biomimetic approaches to self-healing are now being
developed for use in novel materials [5]–[9] with intrinsic systems of particular interest due to their
latent self-healing functionality [1], [10]–[12]. However, bioinspired solutions are often difficult to
implement due to the complexity of the highly evolved biological systems that are imitated, or a lack of
understanding as to how these components can be incorporated into traditional manufacturing.
Additionally, material production is constrained by the narrow range of conditions within which a
biological component is functional.
Here, we show that bio-inspired hybrid systems with a biological component combine the benefits of
both approaches. We focus on the rational design and development of modular hybrid materials,
demonstrating an intrinsic capability to self-heal that can be enhanced with other functionalities in a
predictable manner to produce a new generation of smart materials.
[1] S. R. White, B. J. Blaiszik, S. L. B. Kramer, S. C. Olugebefola, J. S. Moore, and N. R. Sottos,

“Self-healing polymers and composites,” Am. Sci., vol. 99, no. 5, pp. 392–399, 2011.
[2] S. R. Diesendruck, Charles E.; Sottos, Nancy R.; Moore, Jeffrey S.;White, “Biomimetic Self-
Healing,” Angew. Chemie Int. Ed., vol. 54, no. 36, 2015.
[3] “A Biological P r o g r a m m i n g Model for Self-Healing Selvin George David Evans
StevenMarche ~ e Department of Computer Science University of Virginia [ selvin , evans ,
sam7p ]@ cs . virginia . edu Nature ’ s Programs,” 2003.
[4] B. Bhushan, “Biomimetics: Lessons from Nature - an overview,” Philos. Trans. R. Soc. A Math.
Phys. Eng. Sci., vol. 367, no. 1893, pp. 1445–1486, 2009.
[5] S. M. Bleay, C. B. Loader, V. J. Hawyes, L. Humberstone, and P. T. Curtis, “A smart repair
system for polymer matrix composites - 2001.PDF,” vol. 32, 2001.
[6] M. R. Kessler, N. R. Sottos, and S. R. White, “Self-healing structural composite materials,”
Compos. Part A Appl. Sci. Manuf., vol. 34, no. 8, pp. 743–753, 2003.
[7] M. R. Kessler and S. R. White, “Self-activated healing of delamination damage in woven
composites,” Compos. Part A Appl. Sci. Manuf., vol. 32, no. 5, pp. 683–699, 2001.
[8] S. A. Hayes, W. Zhang, M. Branthwaite, and F. R. Jones, “Self-healing of damage in fibre-
reinforced polymer-matrix composites,” J. R. Soc. Interface, vol. 4, no. 13, pp. 381–387, 2007.
[9] X. Chen, F. Wudl, A. K. Mal, H. Shen, and S. R. Nutt, “New thermally remendable highly cross-
linked polymeric materials,” Macromolecules, vol. 36, no. 6, pp. 1802–1807, 2003.
[10] J. Chen, Q. Dong, X. Ma, T. H. Fan, and Y. Lei, “Repetitive biomimetic self-healing of Ca2+-
induced nanocomposite protein hydrogels,” Sci. Rep., vol. 6, no. July, pp. 1–9, 2016.
[11] J. Lan, X. Ni, C. Zhao, Q. Liu, and C. Chen, “Multiamine-induced self-healing poly (Acrylic Acid)
hydrogels with shape memory behavior,” Polym. J., pp. 1–9, 2018.
[12] M. Krogsgaard, M. A. Behrens, J. S. Pedersen, and H. Birkedal, “Self-healing mussel-inspired
multi-pH-responsive hydrogels,” Biomacromolecules, vol. 14, no. 2, pp. 297–301, 2013.
308
BIOTECH-P24

Plasmonic Fluorescent Assay for molecular lipid membrane
binging, Permeation and dynamics of permeation.

Agata Steplewska, Kiang Wei Kho, Aurelian Gimenez, Tia Keyes

Keywords: Microcavities, Metal enhanced fluorescence, Lipid Bilayers. Microfluidic chip, permeability
assay

ABSTRACT: Membrane permeability is a key property of any prospective drug and the interaction of a
drug with the cellular membrane influences its pharmokinetics as many drug targets are intracellular,
Herein we describe a new concept based on plasmonics for gaining new insights into the
determination as to whether a molecule is membrane permeable, mechanic insights into membrane
interactions and the kinetics of permeability. This is achieved using metal cavity supported lipid
bilayers. In this approach lipid bilayers spanned over gold microcavities are exploited as surface
enhanced fluorescence (SEF) substrates. Through the use of Raman and Fluorescence spectroscopy,
we can detect if and how a drug interacts with the lipid membrane, while also obtaining an insight of
the dynamics of the interaction and the rate of permeation through the bilayer and arrival into the
plasmonic field of the gold cavity. It was found that gold microcavity substrates gave a significant
increase in fluorescence intensity over planar gold substrates, regardless of modifications or bilayer
presence. Through Electrochemical Impedance spectroscopy (EIS), DOPC symmetric bilayers are
shown to be stable for an average of 7 hours, which increases with membrane complexity, where our
ternary bilayer composition (DOPC/SM/CH) (40/40/20) shown an average stability for 8 hours.
Through SEF measurements, the bilayer residential time and diffusion time were found for the drugs
Doxorubicin and Daunorubicin over a range of concentrations and membrane compositions.
Interestingly, the method could easily distinguish aggregation of drug above certain concentrations
that lead to a reduction in permeation rate. This work demonstrates a new versatile and useful
paradigm for drug- membrane permeability assay.
Drug
Lipid Bilayer
Site of plasmonic
enhancement.
Gold
microca
vities
Fig. 1: Schematic diagram showing the introduction of a fluorescent drug to our membrane
platform. As the drug reaches the bilayer, fluorescence is observed, which is then drastically
increased once the drug diffuses into the cavity region of plasmonic enhancement.
309
BIOTECH-P25

Catalytic glycosylation of glucose with alkyl alcohols over
sulfonated mesoporous carbons

1 1 1 2
Wahiba Ghezali Ramdani, Ayman Karam, Karine De Oliveira Vigier, Sébastien Rio, Anne
2 1
Ponchel, François Jérôme*,

1
2 Unité de Catalyse et de Chimie du Solide (UCCS), Université Artois, CNRS, Centrale Lille, ENSCL,
Université Lille, F-62300 Lens, France

Keywords: Mesoporous carbons • Glycosylation • Catalysis • Carbohydrates • Biomass
Over the course of several decades, chemistry has developed very efficient and economically
competitive catalytic technologies to convert fossil feedstocks to a wide range of fuels, chemicals and
materials. With the transition of our society to a more sustainable development mode, chemistry is
now facing important scientific hurdles, in particular in the production of renewably-sourced chemicals
and fuels from sugars.[1] Despite a plethora of articles daily reported on the catalytic conversion of
sugars, these reactions are often difficult to implement at an industrial scale due to (1) high dilution,
typically employed to avoid degradation reactions (e.g. reversion reactions, formation of humins or tar-
like materials, etc.) and (ii) deactivation of catalysts, often caused by the presence of water used as a
solvent or released as a co-product.[2]
In this communication, we will present the synthesis of various sulfonated mesoporous carbons
through the nanocasting method using a mesoporous SBA-15 as a mold and sugar as a carbon
source. After complete characterization, the catalytic performances of the as-obtained sulfonated
mesoporous carbons were assessed in the Fisher glycosylation of carbohydrates with alkyl alcohols,
in particular with fatty alcohols to produce safe and non-ionic surfactants. Under optimized conditions,
the targeted amphiphilic alkyl glycosides were obtained in 89% yield, together with a turn over
frequency and a space time yield even higher than those of the best heterogeneous catalysts reported
so far in such reaction. Catalytic recycling experiments and comparison with non-porous sulfonated
carbons showed the importance of mesopores, not only to facilitate the accessibility of the catalytic
sites but also to limit the deactivation of the catalyst, often caused in such reaction by the deposition of
tar-like materials.
Thermo-polymerization
Pyrrolysis
Sulfonation
SO3-, H3O+
BIOSURFACTANTS
ü Yield up to 89%
ü Space time Yield up to 48 kg/m3/h
Sulfonated mesoporous ü Recyclable
carbons

[1]. A. Corma, S. Iborra, A. Velty, Chem. Rev., 2007, 107, 2411-2502.

[2]. J.-P. Lange, Angew. Chem .Int. Ed., 2015, 54, 13186-13197; b) J.-P. Lange, Catal. Sci. Technol.,
2016, 6, 4759-4767.
310
BIOTECH-P26

Sustainable hydrothermal Carbons for Biorefinery-related Catalysis

1,2 1 1 1 2
Monika BOSILJ , Nagendar NUTHALAPATI , Mustafa BOZOGLU , Robin WHITE , Anna FISCHER

1
Fraunhofer Institute for Solar Energy Systems ISE, Freiburg, Germany;
2
Institute of Inorganic and Analytical Chemistry, Freiburg, Germany

Keywords: Hydrothermal carbonization, heterogeneous catalysis, biomass conversion
Catalysed chemical transformations in the liquid phase are a critical component of the continuing
elaboration of Power-to-X and Biorefinery concepts. Due to a variety of challenges regarding
homogeneous catalysts use and recycling, and with regards to the principles of Green Chemistry, it
would be desirable to substitute homogeneous with heterogeneous catalysts. Sustainable techniques
that have potential to synthesize tailorable and functional nanomaterials in this context are required to
address the challenges of conducting new catalysis in such “circular economies” is required (e.g.
aqueous phase). One manner to produce nanostructured porous functional carbons is so-called
[1]
“Hydrothermal Carbonisation” (HTC) process. This process is based on the conversion of natural
[2]
precursors (e.g. biomass-derived sugars), in H2O under relatively low temperatures (e.g. 180 °C) and
[3]
autogenous pressures (< 10 bar). HTC materials can be prepared in the presence of identified
[4] [5]
additives such as sodium borate and albumin known to generate promisingly structured porous
carbons and opening the possibility of structural heteroatom (e.g. nitrogen) doping. Carbonaceous
2 -1
gels can be synthesized in this manner, typically presenting high surface areas (SBET > 250 m g and
3 -1
pore volumes (Vmeso > 0.4 cm g ), the nanostructures of which are very attractive with regard to
layered porosity in tandem with functional surfaces (Figure 1a). Furthermore, a secondary processing
step (e.g. surface modification, a post-thermal carbonisation step, etc.) can be used to direct catalyst
support functionality. In this context, our work focuses on the production of porous HTC carbon
materials and the introduction of catalytic entities (e.g. metal nanoparticles). As an example of our
investigations, N-doped carbon supports (NDC) were prepared via HTC and then thermally carbonized
at different temperatures (i.e. to direct surface chemistry/nitrogen-containing surface motifs). The
prepared supports were then subsequently impregnated with Pd nanoparticles (Figure 1b). These
Pd/NDC catalysts were compared against commercial catalyst for the hydrogenation of phenol to
cyclohexanone (e.g. as basis for lignin-to-nylon production). Post-carbonisation at elevated
temperature alters the support chemistry and nitrogen bonding motif(s) which controls the size
distribution and electronic structures of the loaded Pd nanoparticles. Consequently, this affects
catalyst selectivity, activity and stability for the hydrogenation of phenol to cyclohexanone.
a) b)
Fig. 1: SEM images of a) NDC supports and b) impregnated NDC supports with Pd
nanoparticles.
[1] M.-M. Titirici, R. J. White, N. Brun, V. L. Budarin, D. S. Su, F. del Monte, J. H. Clark, M. J.
MacLachlan, Chemical Society reviews 2015, 44, 250–290.
[2] C. Falco, M. Sevilla, R. J. White, R. Rothe, M.-M. Titirici, ChemSusChem 2012, 5, 1834–1840.
[3] Robin J White, Porous Carbon Materials from Sustainable Precursors, 2015.
[4] T.-P. Fellinger, R. J. White, M.-M. Titirici, M. Antonietti, Adv. Funct. Mater. 2012, 22, 3254–3260.
[5] R. J. White, N. Yoshizawa, M. Antonietti, M.-M. Titirici, Green Chem. 2011, 13, 2428.
311
NANOTECH-P01

Supramolecular engineering of 1-D nanomaterials by self-assembly

of artificial amyloid proteins

1 1 1 1
Luca ALBERTIN, * Nicolas DURAFFOURG, Olivier HAMELIN, Olivier SENEQUE, Stéphane
1 1
TORELLI, Vincent FORGE
1
Laboratoire de Chimie et Biologie des Métaux, UMR 5249 – Université Grenoble Alpes, CEA, CNRS,
17 rue des Martyrs, 38054 Grenoble, France.

Keywords: 1-D nanomaterials, self-assembly, supramolecular polymerization, hybrid proteins, artificial
amyloid nanomaterials.
One-dimensional (1-D) nanomaterials are ideally suited for exploring a number of physical phenomena
at the nanoscale and for investigating the dependence of physical properties on size and
dimensionality. They also hold much promise as interconnects and as key elements for the fabrication
1
of electronic, optoelectronic and electrochemical energy devices with nanoscale dimensions. The
lack of facile, simple, high-yield methods for the production of 1-D nanomaterials in large quantities is
nonetheless a major obstacle to their widespread use and study, and development of bottom-up
manufacturing processes based on self-assembly at room temperature in environmentally benign
solvents remains a major challenge in nanoscience.
Living systems provide numerous examples of self-organization in aqueous environment in the form of
protein structures amyloid fibrils. The latter are self-assembled one-dimensional protein arrays with β-
2
strands perpendicular to the growth axis (Figure 1).

600 nm
Fig. 1: Structure of viologen functionalized protein nanowire (left), TEM image and cyclic
voltammogram (right) of a redox biofilm deposited on an electrode of vitreous carbon.
We now report a few examples of biohybrid protein nanofilaments obtained by conjugation of an

artificial prosthetic group to HETPFD – the prion forming domain of the HET protein from the fungus P.
anserina – followed by self-assembly of the resulting artificial protein in aqueous solution. The
obtained nanofilaments show a high degree structural and morphological homogeneity and, if properly
functinalized, can exchange electrons with an electrode in a reversible manner.
[1]. Tiwari, J. N.; Tiwari, R. N.; Kim, K. S., Zero-dimensional, one-dimensional, two-dimensional
and three-dimensional nanostructured materials for advanced electrochemical energy devices.
Progress in Materials Science 2012, 57 (4), 724-803.
[2]. Chiti, F.; Dobson, C. M., Protein Misfolding, Functional Amyloid, and Human Disease. Annual
Review of Biochemistry 2006, 75 (1), 333-366.
312
NANOTECH-P02

Preparation of a new material composite film (polybithiopene-MnO2
nanoparticles) and their photocurrent properties.

1,2 2 2
Ahmed BAHLOUL*, H. ZOUAOUI, D. ABDI,

1
Département de Génie de l’environnement, Faculté des science et de la technologie, Université
Mohamed El Bachir El Ibrahimi Bordj Bou Arréridj, Algeria
2
Laboratoire d’Energétique et d’Electrochimie du Solide, Université Ferhat Abbas Sétif-1, Sétif, Algeria

Keywords: MnO2 nanoparticles, conjugated polymers, AFM, polybithiophene, Photovoltaic cells
Polythiophenes constitute a particularly important class of conjugated polymers, which has been
extensively studied for the relation between the geometrical structure and the optic and electronic
properties. They are, furthermore, chemically and thermally stable materials, and are very attractive
for exploitation of their physical properties [1]. In photo-electrochemical reactions the observation of
photocurrents from polythiophene-modified metal electrodes has been reported by several groups of
investigators [2, 3].
In this work, a composite thin film containing polybithophene (PBTh) and manganese dioxide
(MnO2) on indium tin oxide (ITO) glass substrates was prepared by electro-polymerization of
bithiophene in the presence MnO2 nanoparticles dispersed in the electrolytic solution. The films
ITO/PBTh–MnO2 are characterized by AFM and SEM, the analyses show an increase in roughness
and the incorporated MnO2 particles are of size in the range of 50 nm.
As a result, the electrochemical gap and the optical gap is shifted by the incorporation of MnO 2
nanoparticles from 2.23 eV for ITO/PBTh to 2.03 eV for ITO/PBTh–MnO2. The photocurrent
measurements indicate that the ITO/PBTh–MnO2 films show a value that is three times higher than
that of polymer substrate, so that such a composite can be used as a new active material in solar
cells.
[1]. T.A. Skotheim, R.L. Elsenbaumer, J.R. Reynolds, Handbook of Conducting Polymers, second
ed., Marcel Dekker Inc., 1998.
[3]. M. Toshiko, T. Nobutaka, M. Tetsuhiko, S. Yousei, K. Tomoyuki, Journal of Nanoscience and
Nanotechnology 2018, 18, 2702-2710.
[4]. N. Maity, R. Ghosh, A. K. Nandi, Langmuir , 2018, XX, xxxx–xxxx.
313
NANOTECH-P03

Characterization of CuGaxIn1-xSe2 Nanoparticles synthesized by
one-step green hydrothermal route

1 1
Abdesselam BOULOUFA*, Meryem LASLADJ,

1
Laboratoire d’Electrochimie et Matériaux, Université Ferhat Abbas de Sétif-1, Sétif, Algérie

Keywords: CuGaxIn1-xSe2, Solvothermal, Nanoparticles,Cathodoluminescence, Raman spectra.
Nanoparticles of CuGaxIn1-xSe2 (CIGS) for x=0, 0.3 and 1 have been synthesized by a simple one-step
hydrothermal route without annealing [1-4]. Metal chlorides and sodium sulfide precursors were
dissolved in green solvent (water) and maintained at 230 °C for 24 h in a laboratory scale autoclave.
Structural, morphological and optical characterization of synthesized CIGS nanoparticles has been
performed by Energy Dispersive Spectrometry (EDS), X-Ray Diffraction (XRD), Raman Spectroscopy,
Field Emission Scanning Electron Microscopy (FESEM), Transmission Electron Microscopy (TEM)
and UV-Visible-NIR Spectroscopy. Quasi-stoichiometric cubic CTS nanoparticles were obtained and
no secondary phases have been detected. This result is confirmed by Raman analysis. The average
size of the synthesized nanoparticles was estimated to be 25 nm. From the optical measurements, the
optical band gap energy is in the range of 1 to 1.65 eV (1). This is very close to the optimal value
required for an absorber material in photovoltaic (PV) solar energy conversion.
[1] Chang-Ting Yang, Hsing-I. Hsiang, Mater. Res. Bulletin, 2018, 97, 30-36.
[2] Sekou Mariama Camara, Lingling Wang and Xintong Zhang, Nanotechnology, 2013, 24, 495401.
[3] John Bincy, Genifer Silvena G., Leo Rajesh A., Mater. Res. Bulletin, 2017, 95, 267-276.
[4] Y T Castellanos Báez, D A Fuquen Peña, J A Gómez-Cuaspud, E Vera-López and Y Pineda-
Triana, J. Phys.: Conf. Ser., 2017, 935, 012004.
(1)
X-ray cartography: individual mapping of Cu, In, Ga and Se.

314
NANOTECH-P04

Synthesis and study of the repellent properties of fluorine-

containing diblock copolymer films
1 1 1
Kirill E. Chekurov, Anna I. BARABANOVA, Alexei R. KHOKHLOV,
1
A.N.Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow,
Russia
Keywords: RAFT-copolymerization, self-assembly, block copolymers
Reversible addition-fragmentation chain-transfer (RAFT) polymerization of 2,3,4,5,6-

pentaflurostyrene (PFS), and two methacrylic monomers - 2-hydroxypropyl methacrylate (HPMA) and
2-hydroxyethyl methacrylate (HEMA), in the presence of three chain transfer agents: 2-
(dodecylthiocarbonothioylthio)-2-methylpropionic acid (CTA1), 4-сyano-4-
(phenylcarbonothioylthio)pentanoic acid (CTA2) and 2-cyano-2-propyl-dithiobenzoate (CTA3) was
studied. To find the optimal conditions of synthesis of macroCTAs with different molar weights (chain
lengths) we have varied the type of CTA, the [CTA]/[AIBN] molar ratio and reaction time. The living
radical polymerization resulted in controlled molecular weights Mn and narrow polydispersity indices
Mw/Mn of 1.1-1.3. The activity of CTAs was changed in order CTA2>CTA3>CTA1.
The method of synthesis of fluorine-containing diblock-copolymers (DC) by RAFT
polymerization of PFS in the presence of PHPMA and PHEMA as macroCTAs, and AIBN as initiator
was developed. The narrow and broad molecular weight distributions DC with different composition
and molecular weight were obtained.
The morphology of the films prepared with slow evaporation of 5 wt % solutions of the
copolymers in toluene, followed by annealing under vacuum was studied by transmission electron
microscopy. It was shown that DC containing 44 mol % of PPFS adopt spherical morphology. We
have observed 40 nm spherical nanodomains dispersed in the PHEMA matrix. At increasing of PPFS
content to 57 mol % the elongated spherical nanodomains (L = 70 nm, ∅ 40 nm) were obtained. The
observed microphase separation with the formation of spherical nanodomains is not typical for DC a
composition close to equimolecular one and is probably associated with the formation of hydrogen
bonds between the hydroxyl and carbonyl groups (OH ··· OH and C = O ··· HO) in poly-2-hydroxyethyl
methacrylate blocks.
Repellent properties of polymers films surface were studied by the wetting method. Installed
repellent properties of DC of different composition are determined by the morphology of the films. It
was found that films having spherical morphology possess the best repelling properties.

315
NANOTECH-P05

Using Internal Light Sources for Localized Photopolymerization of
MIP Shells Around Carbon Dots: Plastic Antibodies for Targeted
Bioimaging

Bilal Demir, Maria Panagiotopoulou, Bernadette Tse Sum Bui, Karsten Haupt*

Sorbonne Universités, Université de Technologie de Compiègne, CNRS Enzyme and Cell Engineering
Laboratory, Rue Roger Couttolenc, CS 60319, 60203, Compiègne Cedex, France

Keywords: Molecularly imprinted polymers (MIPs), nanocomposites, cell targeting, bioimaging
We report a facile and generic strategy to synthesize core-shell molecularly imprinted polymer (MIP)
nanocomposites. The method uses the UV or visible light emitted from carbon dots (CDs), upon
excitation by near infrared or UV radiation respectively, to photopolymerize a MIP shell on their
1-3
surface. Since the emission from the core NPs is weak as compared to direct light, polymerization is
3
confined to the cores’ surface and thus produces core-shell particles (Figure 1). CD-MIP were applied
for cell labeling and imaging of cancer biomarkers: hyaluronic acid (HA) on keratinocytes and human
cervix adenocarcinoma (HeLa) cells. Glucuronic acid (GlcA), a substructure of HA was used as the
template. The CDs have two main functionalities: (i) as an internal light source to trigger
photopolymerization and (ii) as a fluorescent probe for bioimaging of cells specifically targeted by the
MIP shell. The application of non-cytotoxic MIP-coated CDs as artificial receptors and imaging agents
for glycosylation sites paves the way for new applications in diagnostics, theranostics, and
therapeutics.
Fig. 1: Schematical illustration of MIP-coated nanocomposites synthesized by internal light of

fluorescent NPs for bioimaging.
[1]. S. Beyazit, S. Ambrosini, N. Marchyk, E. Palo, V. Kale, T. Soukka, B. Tse Sum Bui, K. Haupt,
Angew. Chem. Int. Ed. 2014, 53, 8919-8923.
[2]. M. Panagiotopoulou, Y. Salinas, S. Beyazit, S. Kunath, L. Duma, E. Prost, A. G. Mayes, M.
Resmini, B. Tse Sum Bui, K. Haupt, Angew. Chem. Int. Ed. 2016, 55, 1-6.
[3]. B. Demir, M. M. Lemberger, M. Panagiotopoulou, P. X. Medina Rangel, S. Timur, T. Hirsch, B.
Tse Sum Bui, J. Wegener, K. Haupt, ACS Appl. Mater. Interfaces 10, 3305-3313.
316
NANOTECH-P06

Structural properties and catalytic activity of bulk and supported iron
cobaltite spinel oxide FeCo2O4
1 1 1,2* 1
Yasmina Hammiche-Bellal , Amel Benadda , Amar Djadoun , Laaldja Meddour-Boukhobza
1
Laboratoire des Matériaux Catalytiques et Catalyse en Chimie Organique, Faculté de Chimie, USTHB, BP32
El Alia, Bab Ezzouar, 16111, Alger, Algeria.
2
Laboratoire de Geophysique, FSTGAT, USTHB, BP32 El Alia, Bab Ezzouar, 16111, Alger, Algeria.
*Corresponding author: [email protected]
Keywords: Spinel oxide- co-precipitation- impregnation- ethanol combustion.
Catalytic combustion is one of the most important and attractive technologie for reducing volatile organic
compounds (VOCs) [1]. The main sources of VOCs are vehicles and ethanol is a renewable fuel that can be
used as an additive to gasoline or its substitute as it can reduced carbon monoxide exhaust emissions [2].
Recently, catalytic properties of ferrite oxides in the VOCs combustion were evidenced [3-4]. In this work, we
propose a comparative study between bulk and supported iron cobaltite spinel oxide FeCo2O4 used as catalyst
in the total oxidation of ethanol. The effect of the preparation method and the nature of the support on the
catalytic properties were investigated.
489 CP-600
(a) (a) HT-2h-150
100 (a)
Hydrogen consumption
523 Acetaldehyde yield

80 1.0
Acetic acid yield
Conversion (%)
0.8
Intensity
CP-600
60
0.6
Yield (%)
0.4
228 264 444 0.2
40
CP-500
0.0
200 220 240 260 280 300
Temperature (°C)
HT-2h-500 398 20 CP-500

CP-600
Precursor 0
HT-2h-150
20 40 60 80
200 400 600 800 200 250 300 350 400
2 theta (°) Temperature (°C) Temperature (°C)
501
364
606
326
SiO2 Al2O3 (b) (b) 100

(b)
Consommation d'hydrogène
IMP-SiO2 IMP-Al2O3
385
Acetaldehyde yield
80 Acetic acid yield
Conversion (%)
0.30
450
Acetaldehyde yield (IMP-Co1-500)

Intensity
0.25
60 0.20
822
623
0.15
40 0.10
0.05
20
812
0.00
200 220 240 260 280 300
Temperature (°C)
IMP-SiO2 IMP-SiO2
0
IMP-Al2O3 IMP-Al2O3
20 40 60 80
100 200 300 400 500 600 700 800 900 200 250 300 350
2 theta Température (°C) Temperature (°C)
Figure1. XRD diffractogram reaction Figure 2. TPR profiles Figure 3. Conversion plots versus
(a) bulk catalysts (b) supported catalysts (a) bulk catalysts (b) supported catalysts (a) bulk catalysts (b) supported catalysts time
FeCo2O4 spinel oxide materials were synthesized as bulk and supported catalysts using co-precipitation and
impregnation methods respectively. The obtained powders were used as catalysts in the ethanol combustion
reaction. The reactivity of a supported catalyst is clearly better than the bulk oxide. The catalytic activity was
2+
attributed to the Co ions; the more easily they are reduced, the more active is the solid in the ethanol
combustion.
References
[1] T. Takeguchi, S. Aoyama, J. Ueda, R. Kikuchi, K. Eguchi, Top. Catal. 23. 2003, 159.
[2] F.N. Aguero, A. Scian, B.P. Barbero, L.E. Cadus, Catal. Today. 2008, 493, 133–135.
[3] N. Rezlescu, E. Rezlescu, P.D. Popa, E. Popovici, C. Doroftei, M. Ignat, Mater.Chem. Phys. 2013, 137
922.
[4] Y. Hammiche-Bellal et al. Mater. Chem. Phys. 2016, 177, 384.
317
NANOTECH-P07

Bioinspired Blue Coloration Approach Based on Alcedo Atthis
Feather’s Structural Color
1, 2 2 3 3 1, 2,
Deok-Jin Jeon , Seungmuk Ji , Eunok Lee , Yung Kun Kim , and Jong-Souk Yeo *
1
School of Integrated Technology, Yonsei University, Incheon, Republic of Korea
2
Yonsei Institute of Convergence Technology, Yonsei University, Incheon, Republic of Korea
3
Division of Convergence Research, Bureau of Ecological Research, National Institute of Ecology,
Seocheon-gun, Choongnam, Republic of Korea
Keywords: Bioinspired, Biopolymer, Photonic Crystal, Bird, Structural Color
Coloration in nature has evolved for a long time to become biologically diversified for camouflage,
predation, signal communication, and mate choice. Nature’s coloration methods are mainly divided
1, 2
into three: pigments, structural colors, and bioluminescence. Especially, the structural coloration has
considerable value as it provides the extraordinary coloration methods from 2D and 3D architectures
made of micro- and/or nano-structures. The most common structural coloration mechanisms include
film interference, diffraction grating, scattering, and photonic crystal, however, color is not only
3
produced by a single mechanism but also caused by their combinations.
Colors in avian feathers are generated by additional coloration mechanisms such as pigments and
light scattering through micro- and nanostructures. Here, we report coloration mechanism of the
common kingfisher, Alcedo Atthis, which has blue and cyan feathers at the back and tail. The blue and
cyan barbs contain spongy-like nano-structures composed with keratin and melanin, which cause their
unique reflectance spectra. The optical properties of the feathers are characterized by ultraviolet and
visible (UV-Vis) spectrophotometer and modeled using finite difference time domain (FDTD) method.
The microscopic top and cross-sectional images of the feathers’ barbs are obtained through scanning
electron microscopy (SEM) and transmission electron microscopy (TEM). TEM samples are prepared
by using focused ion beam (FIB) to show how nano-structures are formed. We also use X-ray
photoelectron spectroscopy (XPS) to verify the elemental composition and chemical state of the
elements present in the feather. By close investigation of the feather, underlying design rule for its
brilliant color is proposed for the fabrication of bioinspired non-iridescent color film. This enhanced
understanding on the biomimetic mechanism from Alcedo Atthis’ blue coloration has a potential for the
industrial application for reflective colors such as digital signage and color reflective display.
This research was supported by the MIST (Ministry of Science and ICT), Korea, under the “ICT
Consilience Creative Program” (IITP-2018-2017-0-01015) supervised by the IITP (Institute for
Information & Communications Technology Promotion).
[1] Booth, C.L., 1990. Evolutionary significance of ontogenetic colour change in animals. Biological
Journal of the Linnean Society, 40(2), pp.125-163.
[2] Parker, A.R., 2000. 515 million years of structural colour. Journal of Optics A: Pure and Applied
Optics, 2(6), p.R15.
[3] Sun, J., Bhushan, B. and Tong, J., 2013. Structural coloration in nature. Rsc Advances, 3(35),
pp.14862-14889.
318
NANOTECH-P08

Simple and Facile Approach To Create Charge Reversible Pores via
Hydrophobic Anchoring of Ionic Amphiphiles

1 1 2 1
K.P. Sonu, Pavan Kumar B. V. V. S., Subi J. GEORGE *, Muthusamy ESWARAMOORTHY *,

1
Nanomaterials and Catalysis Lab, Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre
for Advanced Scientific Research, Jakkur P.O., Bangalore 560064, India;
2
Supramolecular Chemistry Laboratory, New Chemistry Unit, Jawaharlal Nehru Centre for Advanced
Scientific Research, Jakkur P.O., Bangalore 560064, India

Keywords: charge reversal, hydrophobic interaction, mesoporous materials, supramolecular
chemistry, dye adsorption, recyclable scaffold
Mesoporous silica-based charge reversal systems have gained significant attention in recent years
due to a variety of applications such as drug delivery, dye adsorption, catalysis, chromatography, etc.
Such systems often use covalent strategies to immobilize charge-bearing functional groups on the
mesoporous silica scaffold. However, lack of dynamism, modularity, and post-synthetic flexibility
associated with covalent routes limit their wider applicability. In this context, supramolecular
noncovalent approaches towards functionalization are receiving increased attention in recent years
due to their ability to lend reversibility and flexible modularity to these rigid porous solid matrixes.
These supramolecularly switchable hybrid materials combine the advantages of dynamic nature and
flexibility of non-covalent moieties with the rigidity and periodicity of mesoporous materials. Here, we
introduce a simple and facile noncovalent design for a highly reversible assembly of charged
amphiphiles within mesopores. Hexyl pendant groups were covalently attached to the surface to
provide hydrophobic anchoring for charged amphiphiles to enable facile switching of surface charge of
the mesoporous silica (Fig. 1). The modularity of this approach was utilized for engineering highly
recyclable materials for charge-based adsorption and selective separation of dye molecules.
Fig. 1: Fabrication of charge reversal surface: Charged amphiphiles are noncovalently

assembled within hydrophobic mesoporous channels. Reversible manipulation of surface
charges is achieved by breaking the assembly in appropriate solvent, which allows the pore a
new assembly. Conversion from one charge state to other is also possible through competitive
amphiphile replacement.
[1]. Sonu K. P., Kumar, B. V. V. S. P., George, S. J., Eswaramoorthy, M., ACS Appl. Mater.
Interfaces, 2017, 9 (10), pp 9136–9142.
319
NANOTECH-P09

Poly styrene Nanocomposites: Preparation, Characterization and

Investigation of Mechanical Properties
1 2 2
Mrah Lahouari, Rachid MEGHABAR , Mohammed BELBACHIR *,
1
Laboratory of Polymer Chemical, Department of Chemistry, Faculty of Exact and Applied Sciences,
University of Oran1 Ahmed Benbella, 31100 Oran, Algeria.
Keywords: nanocomposites , Montmorillonite, Organophilic , polystyrene, in situ polymerization.
A reactive cationic surfactant cetyltrimethylammonium bromide (CTAB) was synthesized for

intercalation of montmorillonite Mmt. a Maghnite type of clay. The pristine montmorillonite (Mmt) was
obtained from Algerian plant with a cation exchange Organophilic Mmt was prepared by ion
+
exchange between Na ions in the clay. CTAB-intercalated Mmt particles were easily dispersed and
swollen in styrene monomer, polystyrene / Mmt-CTAB nanocomposites were synthesized via in situ
polymerization, in-situ polymerization, this method is based on the swelling of the silicate layers with
the liquid polymer. The polymer composites were characterized using different techniques such as X-
ray diffraction (XRD), The results were showed that, the basal space of the silicate layer increased, as
determined by XRD, from 12.79 to 32.603 Å and transmission electron microscopy TEM revealed that
the modified montmorillonite layers were uniformly dispersed and exfoliated in the styrene matrix for
low levels of clay .In our current research,we continue this research and study infrared
spectrophotometery (IR), differentialscanning calorimetery (DSC), and balayage electron microscope
(MEB) thermal gravimetric analysis (TGA), force atomic microscopy (AFM) and tensile measurements.
320
NANOTECH-P10

Towards the fabrication of nanocomposite films with bio-inspired
complex reinforcing architectures.

1,2 1,3 2 1,2
Randy MUJICA *, Vincent LE HOUEROU, Olivier FELIX, Gero DECHER.

1
Université de Strasbourg, Strasbourg, France;
2
CNRS – Institut Charles Sadron, Strasbourg, France;
3
CNRS – ICube, Université de Strasbourg, Strasbourg, France
Keywords: Nanocomposite materials, cellulose nanofibers (CNF), layer-by-layer (LbL) assembly,

polyelectrolyte multilayers, bio-inspired complex superstructures.
The development of the next generation of high-performance composite materials currently

encompasses two fields of increasing interest among material scientists, namely bio-inspiration and
nanotechnology. On one hand, some natural materials exhibit an attractive combination of properties
that commonly restrain one another, such as the lightweight yet stiff bone or the hard but tough nacre.
The remarkable performance of such materials has boosted the scientific interest for mimicking their
hierarchical architectures. On the other hand, nanosized objects have emerged as promising
reinforcing agents owing to their large surface-to-volume ratio and their superior strength and stiffness
compared to their micro- and macro-size counterparts. In the last two decades, many research groups
have reported the fabrication of various types of polymer nanocomposites with improved mechanical
properties; however, the high potential of nano-reinforced materials remains underexploited mainly
due to the inherent difficulty of dispersing large volume fractions of the reinforcing phase and the
insufficient control over the nanostructuring. A versatile and widely used bottom-up approach that has
demonstrated potentiality to overcome these two limitations in the fabrication of 2D composite thin
films is the so-called layer-by-layer (LbL) assembly [1]. This technique has been used, for instance, for
the fabrication of nacre-like nanocomposite film using clay platelets and poly(diallyldimethylammonium
chloride) [2].
Here we demonstrate the LbL assembly of complex nanoreinforced architectures, which are inspired
by the helicoidal staking of aligned layers of chitinous fibers present in the tough exoskeleton of some
crustaceans. We use cellulose nanofibers (CNF) as a bio-based reinforcing phase, whose diluted
suspension is sprayed at small angles to impart a preferential in-plane orientation of the fibrils, as
previously reported by our group [3]. This approach allows us to control the alignment direction of
each layer independently of that of the adjacent layers. The resulting mechanical properties of the
nanocomposites are explored by tensile and nanoindentation tests and are correlated to the different
compositions and structural characteristics of the films.
a b
c
Fig. 1: (a) Schematic of the sprayed-assisted LbL methodology (modified from [1]); (b) AFM
image of the anisotropic alignment of the CNF. The arrow indicates the spraying direction,
scale bar equals 600 nm; (c) Helicoidal structure of oriented fibers. Taken from [4].
[1]. G. Decher, Science. 1997, 277, 1232–1237.

[2]. Z. Tang, N. A. Kotov, S. Magonov, and B. Ozturk, Nat. Mater. 2003, 2, 413–418.
[3]. R. Blell, X. Lin, T. Lindström, M. Ankerfors, M. Pauly, O. Felix, and G. Decher, ACS Nano,
2016, 11, 84-94.
[4]. D. Ginzburg, F. Pinto, O. Iervolino, and M. Meo, Compos. Struct., 2017, 161, 187-203.
321
NANOTECH-P11

Development of nanostrutured coatings of chitosan for postharvest
preservation of guavas 'Pedro Sato'
1 1 2 2
Camila S. Oliveira ,Thamara C. Coutinho , Igor J. B. Santos , Ana M. Oliveira , Enio N. Oliveira
2
Junior*

1
Universidade Federal de São João Del Rei – UFSJ/CAP, Programa de Pós-Graduação em
Tecnologias para o Desenvolvimento Sustentável, Ouro Branco, Brazil;
2
Universidade Federal de São João Del Rei – UFSJ/CAP, Departamento de Química, Biotecnologia e
Eng. de Bioprocessos - DQBIO, Ouro Branco, Brazil.
Keywords: Films, Nanostructures, Shelf life, Packaging.
Brazil is one of the largest producers of guava in the world [1], but exports a tiny amount of this fruit,
since guava is highly perishable and susceptible to fungal diseases [2]. To overcome this problem, it is
possible to use coatings, which can increase the shelf life of the product. Thus, the objective of this
work was to produce and characterize chitosan citrate and chitosan acetate films with the addition of
calcium carbonate and chitosan nanostructures, to apply them in guavas and to perform post-harvest
analysis of the fruit to evaluate ripening. The films were characterized in terms of thickness, weight,
solubility, moisture content, water vapor permeability, contact angle, tensile strength and elongation. In
addition, the antimicrobial activity of the films was analyzed. The chitosan acetate film with addition of
nanocarbonate appeared to be whitish and brittle. The other films were transparent, homogeneous
and flexible. In this way, the solutions of these films were used to cover guavas Pedro Sato. The
chitosan citrate coatings with nanochitosan addition were not homogeneous on the surface of the fruit,
preventing it from efficiently protecting the guavas. Chitosan acetate films showed good adhesion to
the fruits. The guavas were analyzed from day 0 to day 10, monitoring the coloration, loss of mass,
firmness, soluble solids, titratable acidity, pH, sugars and pectic substances, to observe the speed of
ripening. It was observed that soluble solids, titratable acidity and pH did not change during ripening in
all treatments. In the analysis of sugars and pectic substances, there was no significant difference
between treatments. It was possible to observe differences between the groups of guavas when
analyzing the color, firmness and loss of mass, where the guavas coated with chitosan acetate
(control and with nanochitosan addition) remained more in relation to the others. The addition of
nanostructures in guavas proved to be effective in the antimicrobial effect, since it prevented the
appearance of the anthracnose, but in the other analyzes, its addition did not provide a significant
difference in relation to the control treatment. However, it was possible to observe that chitosan
acetate coatings are indeed able to extend the shelf life of the Pedro Sato guavas.

[1]. SEBRAE. O cultivo e o mercado da goiaba. 2016. Disponível em:
https://www.sebrae.com.br/sites/PortalSebrae/artigos/o-cultivo-e-o-mercado-da-
goiaba,d3aa9e665b182410VgnVCM100000b272010aRCRD. Acesso em: 12 de novembro de 2016.
[2]. FERRAZ, D. M. M. Controle da antracnose (Colletotrichum gloeosporioides) em pós-colheita
de goiaba (Psidium guajava), produzida em sistema de cultivo convencional orgânico, pela aplicação
de fosfitos, hidrotermia e cloreto de cálcio. 2010. 119 f. Dissertação (Mestrado em Fitopatologia) –
Universidade de Brasília, Brasília, 2010.
322
NANOTECH-P12

Morphology and thermal properties of poly (alkyl
methacrylates)/bentonite nanocomposites prepared via in situ
polymerization initiated by Ni (II) α-Benzoinoxime (NBO) complex.
1, 2 1 3
Kamal Ouaad , Saïd Djadoun and Nicolas Sbirrazzuoli .
1
Université des Sciences et de la Technologie Houari Boumediene, Laboratoire des Matériaux
Polymères, Faculté de Chimie, BP 32 El-Alia, Bab-Ezzouar 16111, Algiers, Algeria.
2
Université M’Hamed Bougara, Département de Chimie, Faculté des Sciences, Avenue de
l’Indépendance, 35000, Boumerdès, Algeria.
3
Université de Nice Sophia Antipolis, Laboratoire de Physique de la Matière Condensée, CNRS UMR
7336, Parc Valrose, 06108 Nice Cedex-2, France.
In the present contribution, a novel initiator, Ni(II)α-Benzoinoxime (NBO) complex, was successfully
used in the preparation via in situ polymerization of poly(ethyl methacrylate) (PEMA), poly (n-butyl
methacrylate) (PBMA) and their corresponding nanocomposites at room temperature in presence of
an organically modified bentonite (OBT) [1].
The morphology and thermal properties of these materials were investigated by FTIR spectroscopy, X-
Ray Diffraction (XRD), Transmission Electronic Microscopy (TEM), Differential Scanning Calorimetry
(DSC) and Thermogravimetry (TGA).
FTIR spectroscopy confirmed the presence of polymer/clay from the broadening and slight shift,
observed with the hybrids in the carbonyl region
Depending on the clay loading, hybrids of intercalated or partially exfoliated structures were evidenced
by X-Ray diffraction (XRD) and Transmission Electron Microscopy (TEM).
The nano-scale dispersion of the clay was also evidenced by a moderate increase of the Tg and a
significant enhanced thermal stability of these nanocomposites, compared to their virgin polymers.
An analysis of the apparent activation energies Eα of thermal decomposition of these polymers and
their corresponding hybrid materials, estimated using Tang’s method, confirmed the change in the
degradation mechanism with the clay loading and the intercalated/exfoliated structures.
[1] K. Ouaad; S. Djadoun; N. Sbirrazzuoli and L. Vincent. Thermochim. Acta. 2013, 555, 30-36
323
NANOTECH-P13

Elaboration and thermal analysis of blends and nanoblends based
on poly (methyl methacrylate–co-4-vinylpyridine)/cellulose acetate
butyrate and Maghnia bentonite.
1,2 4 3 1
Kamal OUAAD , Amar DJADOUN , Luc VINCENT, Nicolas SBIRRAZZUOLI and Saïd DJADOUN .
1
Université des Sciences et de la Technologie Houari Boumediene, Laboratoire des Matériaux
Polymères, Faculté de Chimie, BP 32 El-Alia, Bab-Ezzouar 16111, Algiers, Algeria.
2
Université M’Hamed Bougara, Département de Chimie, Faculté des Sciences, Avenue de
l’Indépendance, 35000, Boumerdès, Algeria.
3
Université de Nice Sophia Antipolis, Laboratoire de Physique de la Matière Condensée, CNRS UMR
7336, Parc Valrose, 06108 Nice Cedex-2, France.
4
Université des Sciences et de la Technologie Houari Boumediene, Faculté des Sciences de la terre
et de l’aménagement du territoire, BP 32, El-Alia, Bab-Ezzouar 16111, Algiers, Algeria.
Keywords: Thermal analysis, phase behavior, specific interactions, miscibility, Cellulose acetate
butyrate, poly (methyl methacrylate-co-4-vinyl pyridine).
Blends and naoblends based on an organically modified bentonite, from Maghnia Algeria (OBT) and a
copolymer of methyl methacrylate with 4-vinylpyridine (PMM4VP32) synthesized in dioxan at room
temperature using a neutral Ni (II)α-benzoinoxime complex (NBO) as a single component initiator [1]
and different ratios of Cellulose Acetate Butyrate (CAB), were elaborated via solution intercalation
method and characterized by several techniques.
Depending on the blend composition, favorable specific interactions occurred within these blends and
were evidenced by Fourier transform infrared spectroscopy (FTIR).
X-Ray Diffraction (XRD) and Transmission Electron Microscopy (TEM) investigations indicate that
mainly exfoliated and intercalated PMM4VP32/CAB/OBT nanoblends were elaborated and that the
degree of exfoliation decreases with an increase of the OBT loading.
Phase behavior and thermal properties of these blends were investigated by Differential Scanning
Calorimetry (DSC) and Thermogravimetry Analysis (TGA).
[1] K. Ouaad; S. Djadoun, J. Appl. Polym. Sci. 2013, 129 (4), 2029-2035
324
NANOTECH-P14

Poly(ethylene terephthalate)/poly(ɛ-caprolactone) blend nanocomposites : A
‘green’ route compatibilization using a reduced graphene properly
functionalized
1,2 2 2 1 2
Dalila. Saaoui , Samira. Benali , Rosica. Mincheva , Aberrahmane. Habi , Philippe. Dubois , Jean-
2
Marie. Raquez
email: [email protected]
1
Laboratoire des Matériaux Organiques, Faculté de Technologie, Université Abderrahmane Mira,
Route de Targa Ouzemour, 06000 Bejaia, Algeria
2
Center of Innovation and Research in Materials and Polymers (CIRMAP), Research Institute for
Materials Science and Engineering, University of Mons- UMONS Place du Parc 20, B-7000 Mons,
Belgium
Keywords: Graphene, ionic liquid, nanocomposite.
Poly(ethylene terephthalate) (PET) is one of the most widely used low-cost polymers,
especially for food and beverage applications, and its recycling is of great importance[1]. The
presence of small amounts of the biodegradable, and potentially biosourced, poly(ɛ-caprolactone)
(PCL) in the PET waste can significantly affect the post-consumer recycling process. However, the
incompatibility between the PET and PCL doesn’t be able to obtain performant materials because of
the problems at the interface.
Among the strategies to improve the adhesion between the phases, recently, graphene, a
“rising-star” carbon spurred intensive interest in developing high-performance in many fields such as
nanocomposites [2]. The stabilization and modification of graphene have attracted extensive research
interest [3]. In this regard, several recent reports have realized on the functionalization of graphene by
both covalent and non-covalent approaches. Ionic liquids (ILs) have been proposed as “green”
alternatives to conventional solvents because of their unique properties like negligible vapor pressure
and thermal stabilities [4]. The marriage between ILs and graphene generating exfoliated graphene
sheets directly from graphene oxide, to prepare a long-term stable graphene sheets that can be
readily dispersed in the PET/PCL to improve a compatibility of the blend.
-
In this work, the IL 1-Butyl-3-methylimidazol bis(trifluoromethylsulfonyl)imide [BIMIm][TF2N ]
has been used to functionalize the GO through electrostatic interactions in aqueous suspensions and
then was reduced with hydrazine monohydrate. The main objective is to study the effect of
imidazolium in the dispersion and localization of CRGO in the blend PET/PCL. Subsequently the
-
nanocomposites PET/PCL/CRGO-[BIMIm][TF2N ] were obtained by extrusion processing (PET/PCL
-
70/30 (wt/wt) with 2.5wt% of CRGO). The localization of CRGO-[BIMIm][TF2N ] in the blend of the
different systems were determined by (TEM) analysis and approved by theoretical predictions using
the wetting parameter. The dispersion and the morphology of the nanofillers in the PET/PCL
nanocomposite blend were evaluated by XRD analysis, TEM and SEM.
[1] Colbeaux, A., Fenouillot, F., Gerard, J. F., Taha, M., Wautier, H. J. Appl. Polym. Sci., 2004, 93,
2237–2244.
[2] Li, F.; Chai, J.; Yang, H.; Han, D.; Niu, L. Talanta 2010, 81 (3), 1063–1068.
[3]Lonkar, S. P.; Bobenrieth, A.; Winter, J. De; Gerbaux, P.; Raquez, J.-M.; Dubois, P. A .J. Mater.
Chem. 2012, 22 (35), 18124..
[4]Lu, J.; Yang, J.; Wang, J.; Lim, A.; Wang, S.; Loh, K. P. ACS Nano 2009, 3 (8), 2367–2375.
325
NANOTECH-P15

Comprehensive evaluation of biomimetic nanocomposite scaffolds
for bone surgery

1,2 1 3 4 4
Tomáš SUCHÝ *, Monika ŠUPOVÁ, Martin BARTOŠ, Marco PIOLA, Monica SONCINI,
4 2 5,6
Gianfranco Beniamino FIORE, Radek SEDLÁČEK, Pavla SAUEROVÁ, Marie HUBÁLEK
5,6
KALBÁČOVÁ,

1
Department of Composites and Carbon Materials, Institute of Rock Structure and Mechanics,
Academy of Sciences of the Czech Republic, Prague, Czech Republic;
2
Laboratory of Biomechanics, Department of Mechanics, Biomechanics and Mechatronics, Faculty of
Mechanical Engineering, Czech Technical University in Prague, Prague, Czech Republic;
3
Department of Stomatology, First Faculty of Medicine, Charles University and General University
Hospital in Prague, Prague, Czech Republic;
4
Dipartimento di Elettronica, Informazione e Bioingegneria, Politecnico di Milano, Milano, Italy;
5
Institute of Pathological Physiology, 1st Faculty of Medicine, Charles University, Prague,
Czech Republic;
6
Biomedical Centre, Faculty of Medicine in Pilsen, Charles University, Pilsen, Czech Republic

Keywords: collagen, calcium phosphates, nanocomposite scaffolds, mesenchymal stem cells
One of the main aims of bone tissue engineering and regenerative medicine is to develop an optimal
artificial environment (scaffold) that can trigger a favorable response within the host tissue and its
resident cells and which can be applied as a cell therapy tool. This study involved the fabrication of
eight types of scaffold differing in terms of composition (higher content of collagen type I or higher
content of natural calcium phosphate nanoparticles) and, subsequently, the testing of their physical,
chemical and structural properties in dry and hydrated states (Fig. 1). Mesenchymal stem cells
(MSCs) were used for the verification of scaffold cellularization ability due to their differentiation
capacity and native trophic effects within organisms. The study further focused on the most effective
ways to ensure MSCs scaffold colonization based on the mechanical and structural characterization
thereof employing i) dynamic seeding using a perfusion bioreactor followed by static cultivation and ii)
static cultivation only for the whole period. Subsequently, one type of scaffolds was selected for
biological evaluation under the in vivo conditions and its regenerative potential was evaluated by
standard histological techniques and micro-CT analyses. Scaffolds were seeded by autologous MSCs
and implanted for 3, 6 and 12 months using experimental pig model. New bone tissue formation was
compared with implanted scaffolds without MSCs, empty defect and defect filled with autologous bone
graft.
Fig. 1: Mechanical and structural properties of nanocomposite scaffolds were characterized in

dry and hydrated states prior to their biological evaluation.
Acknowledgements: This study was supported by a grant project awarded by the Ministry of Health of
the Czech Republic (15-25813A).
326
NANOTECH-P16

Peptide Self-Assembly-Directed Gold Nanocrystal Synthesis

,1 2
Kin-ya Tomizaki,* Masahiro Asano,

1
Department of Materials Chemistry, Ryukoku University, Otsu, Japan
2
Department of Environmental Solutions Technology, Ryukoku University, Otsu, Japan

Keywords: peptide, self-assembly, gold nanocrystal
Gold nanocrystals have been gathering attractions in the use as catalysts, photonic/plasmonic
devices, sensing/imaging systems, and therapeutic materials. Significant efforts have been devoted to
control the size, shape, and structure of gold nanocrystals with various organic templates. Recently,
the synthesis of gold nanorods that are potential for photothermal therapy requires a cytotoxic
cetyltrimethyammonium bromide (CTAB) to control their morphologies. Thus, alternative synthetic
methodology using biocompatible template to control the shape of anisotropic gold nanocrystal
including gold nanorods is strongly required. So far, we have demonstrated the use of a de novo
designed beta-sheet-forming nonapeptide (RU006: Ac-AIAKAXKIA-NH2, X = L-2-naphthylalanine,
Nal(2)) and its analogs to synthesize anisotropic gold nanocrystals by just mixing peptides and HAuCl4
in water [1,2,3]. We found the reaction afforded ultrathin gold nanoribbons with 50–100 nm wide and
several nanometers high, and microns long. Here, we report the results of anisotropic gold nanocrystal
synthesis towards gold nanorod formation with biocompatible peptide templates.
Fig. 1: Amino acid sequence of RU006.
[1]. K.-Y. Tomizaki, S. Wakizaka, Y. Yamaguchi, A. Kobayashi, T. Imai, Langmuir, 2014, 30, 846-
856.
[2]. K.-Y. Tomizaki, K. Kishioka, H. Kobayashi, A. Kobayashi, N. Yamada, S. Kataoka, T. Imai,
Bioorg. Med. Chem. 2015, 23, 7282-7291.
[3]. K.-Y. Tomizaki, R. Nanbu, M. Kasuga, T. Imai, Protein Peptide Lett., 2018, 25(1), 48-55.
327
NANOTECH-P17

Composite materials and coatings based on polytetrafluoroethylene
nanofilms of different temperature fractions
,
Aleksandr Tsvetnikov, Matveenko L.A., Kuryaviy V.G., Puz A.V., Egorkin V.S.,
Mashtalyar D.V., Golub A.V., Pavlov A.D., Gnedenkov S.V
Institute for Chemistry of Far Eastern Branch of Russian Academy of Science,

Stoletiya Vladivostoka prospect 159, Vladivostok, 690022, Russia

Keywords: polytetrafluoroethylene, nanofilms, composite, coating.
The thermo-gas-dynamic (TGD) method is based on the principle of the thermal-gradient synthesis of
a polymer in the flow of cooled gas [1]. In the course of the polytetrafluoroethylene (PTFE) thermal
destruction under conditions of the TGD process, the oligomers with different molecular weights
appear together with gaseous monomers [2]. As a result of homophase nucleation of the PTFE
molecules, the nanofilms of PTFE (NPTFE) emerge. Depending on the process realization conditions
these nanofilms condense in the form of films, micro-tubes and micro-onion particles with diameter of
about 1 µ. PTFE molecules were separated according their molecular weights [3] using the method of
chromatomass-spectrometry. As the result, it was discovered that is case of temperature growth up to
о
400 C, molecules with weights from 338 Da to 3000 Da are sublimated. NPTFE molecules condense
in the form of 5-10 nm thick nano-films and, depending on condensation conditions, congregate in gas
phase into bundles of different shapes (micro-films, micro-pipes, micro-spheres) and sizes (0,2-15
µm). Films are weakly linked with each other and are easily released during mechanical action applied
on a particle, which allows creating stable coatings on any surface due to the nano-effect. Method of
extracting different temperature fractions from NPTF was developed, and their physic-chemical
properties were analyzed. Low-molecular fraction NPTFE was successfully used as the ski lubricants,
and high-molecular fraction NPTFE was used to protect metal surfaces against sludging and scale
formation. Methods of creating multifunctional composite layers on titanium, aluminum, magnesium
alloys and steel, including structural and functional materials – which are widely used in aviation,
shipbuilding, ship repair and marine engineering – by means of plasma electrolytic oxidation with
subsequent application of NPTFE, were developed [4]. Created composite coatings protect metals
and alloys against various types of corrosive damage in the air and in the seawater (coatings increase
the resistance against charge transfer by 5-6 orders of magnitude, as compared to unprotected
metal/alloy without coating), as well as against physical deterioration and bio fouling. They greatly
decrease the surface wettability and the friction coefficient. The properties of metals coatings based
on NPTFE in pure form as well as in the form of a component of composite polymer compositions
о
were investigated [5]. It was shown that coatings’ wetting angle increases up to 130 , friction
coefficient decreases in 3-5 times, deposit decreases in 5-7 times, chemical durability along with the
anti-icing and anti-fouling characteristics increase in several times [6]. Researches of NPTFE oil-
compositions influence to an internal-combustion engine and different types of mechanisms have
proved the decrease in vibration, rubbing parts wear-out and fuel consumption as well as increase of
engine oil lifetime.
[1]. A.K. Tsvetnikov, Vestnik FEB RAS, 2, 18-22, 2009.

[2]. A.K. Tsvetnikov, R.F. patent 2035308, 1995.
[3]. A.D. Pavlov, S.V Suhoverhov., A.K. Tsvetnikov, Vestnik FEB RAS, 5, 51-55, 2011.
[4]. S.V. Gnedenkov, S.L Sinebryukhov., D.V. Mashtalyar, V.S. Egorkin, A.K. Tsvetnikov, A.N.
Minaev, Protection of Metals, , 44(7), 704–709, 2008.
[5]. A.K. Tsvetnikov., L.A. Matveenko, A .V. Puz, V.S Egorkin, A.V. Golub, S.I. Maslennikov, A.D.
Pavlov, S.V Gnedenkov, Russian Coatings Journal,1-2, 63-67, 2016.
[6] A.K. Tsvetnikov., L.A. Matveenko, A .V. Puz, V.S Egorkin, S.V Gnedenkov, A.R. Garifullin.
R.F. Patent 2619687, 2017.
328
NANOTECH-P18

Experimental and modelling studies on wetting of nanoscale bio-
inspired pattern shapes and contours

1 2 1 1, 3
Prashant PENDYALA, Harpreet Singh GREWAL, Sung Yeun YANG, Il-Joo CHO, Eui-Sung
1, 4
YOON *,

1
Center for BioMicrosystems, Korea Institute of Science and Technology (KIST), Seoul 02792,
Republic of Korea;
2
Department of Mechanical Engineering, Shiv Nadar University, Noida, India
3
Division of Bio-Medical Science and Technology, KIST School, University of Science and
Technology, Seoul 02792, Republic of Korea,
4
Division of Nano & Information Technology, KIST School, University of Science and Technology,
Seoul 02792, Republic of Korea
Affiliation 2, City, Country

Keywords: Mushroom-shaped, Wetting, re-entrant angle
Wetting related dynamic phenomenon are sub-micron scale in nature. How the small changes in
physico-chemical characteristics of the surfaces at those scales affect the wetting was not explored.
One of the reason was the difficulty in fabricating well-defined nanoscale patterns of varying physico-
chemical cues and the high acquisition testing procedures. In this work, the influence of nanoscale
pattern shapes, contours, and surface chemistry on wetting were investigated using well-defined
nanoscale patterns of mushroom-shaped and cylindrical pillars. The patterns were fabricated using a
combination of capillary force lithography and nano-drawing procedures. The viscous effects wetting
were explored using high speed imaging techniques and corresponding simulations. We showed that
topographies with smaller intrinsic angles were better able to support the liquid droplet. Re-entrant
topography of the mushroom-shaped pillar patterns showed superior restraining capability of liquid-air
interface in accordance with Gibbs criteria. Based on the observations, two criteria in the design of
superhydrophobic patterns were proposed. It was observed that, viscous effects were dominant in the
initial stage of drop deposition and for the surfaces exhibiting Cassie-Baxter state, the viscous forces
were small. Further, topographies with smooth geometries and high slop lengths also exhibited
smaller viscous effects.
[1]. H.S. Grewal, I.J. Cho, J.E. Oh, E.S. Yoon. Nanoscale. 2014; 6(24):15321-32.
329
NANOTECH-P19

Optical Proprieties of CdxZn1-xS Thin Films Deposed by Chemical
Bath Deposition

1, 2 1 2 3 2*
Rahima Zellagui , Heider Dehdouh , Toufik Sahraoui , Denis Chaumont , Mohamed Adnane

1 Research Center in Industrial Technologies CRTI, P.O.Box 64, Cheraga 16014, Algiers, Algeria,
2 Laboratory of Electron Microscopy and Materials Sciences, Université des Science et des
Technologies d’Oran, P.O. Box 1505 El-M’naouer, 31000 Oran, Algéria
3 Laboratoire Interdisciplinaire Carnot de Bourgogne, University of Bourgogne France Comté, Dijon,
France.

Keywords: CdZnS, chemical bath, thin films, solar cells.
Thin films of CdxZn1-xS were deposed on glass substrates by chemical bath deposition for
photovoltaic applications. The thin films CdZnS were synthesize by chemical bath (CBD) with different
deposition protocols for optimized the parameter of deposition as the temperature, time of deposition,
concentrations of ion and pH. Surface morphology, optical and chemical composition properties of
thins films CdZnS were investigating by SEM, EDS, XRD, AFM and spectrophotometer. The
transmittance is 80% in visible region 300 nm – 1000 nm; it has been observe the grain size is
between 90 nm and 150 nm. It is observe that the transmittance and the shape are change with the
concentration of Zinc in the solution. This result favors of application these films in solar cells; the
chemical analysis with EDAX gives information about the presence of Cd, Zn and S elements. This
result favors of application these films in solar cells.
Fig. 1: AFM image of CdZnS thin films.
330
NANOTECH-P20

In vivo Two-photon Imaging of Tumor with Porous Silicon
Nanoparticles

1 1, 2, 3
Yuna Jung, Dokyong Kim*

1
Department of Biomedical Science, Graduate School, Kyung Hee University, 26 KyungheedaeRo,
Dongdaemun-Gu, Seoul 02447, Republic of Korea;
2
Department of Anatomy and Neurobiology, College of Medicine, Kyung Hee University, 26
Kyungheedae-Ro, Dongdaemun-Gu, Seoul 02447, Republic of Korea;
3
Center for Converging Humanities, Kyung Hee University, 26 Kyungheedae-Ro, Dongdaemun-Gu,
Seoul 02447, Republic of Korea.

Keywords: Porous Silicon, Nanoparticles, Bio-imaging, Nanomedicine, Two-photon Microscopy
Monitoring of biological systems is important to understand the life. Among various monitoring tools,
fluorescence-based method has attracted much attention because of their many advantageous
features. In particular, photoluminescence-based bio-imaging has a lot of merits such as non-
invasive, simply operative, sensitive, cost-effective, and rapidly visualizing only targeted regions with
high resolution at a specific substrate. For the fluorescence imaging, confocal laser scanning
microscopy (CLSM) has been conventionally used as an effective tool, however, it also has been
shown drawbacks for the tissue imaging. The biggest limitations of the tissue imaging with CLSM is a
limited imaging depth (a few tens of micrometers) because of light scattering and auto-fluorescence
interference from intrinsic biomolecules. To overcome this issue, two-photon microscopy(TPM) was
recently developed that can be operated at excitation wavelength 650-1000 nm. TPM can provide the
improved penetration depths and enhanced spatial resolution against the tissue auto-fluorescence and
light scattering issue.
In this study, two-photon excitable and near-infrared fluorescence emittable porous silicon
nanoparticles (pSiNPs) were synthesized.[1] A high quantum yield and two-photon absorption cross-
section(TPACS) have been observed for the new pSiNPs formulation. The functionalization of the
pSiNPs surface with a tumor-targeting moiety, iRGD, shows efficient tumor homing properties in the
tumor xenograft mouse model. This study represents that pSiNPs can be applied to the tumor-specific
drug delivery system with monitoring of the distribution of pSiNPs in vivo by TPM. In conclusion, the
pSiNPs functionalized with the disease target moiety are selectively able to be accumulated on the
disease site and applied in vivo bio-imaging.
Fig. 1: (a) The illustration and TEM image of porous silicon nanoparticle formulation. (b) In vivo
two-photon imaging of tumor xenograft mouse model.
[1]. D. Kim, et al., Adv. Mater., 2017, 29, 1703309.
331
NANOTECH-P21

Development of a Molecular Photoacoustic Imaging Agent
Encapsulated Porous Silicon Nanoparticle Formulation

1 1, 2, 3
NaHee Kim, Dokyoung Kim*

1
Department of Biomedical Science, Graduate School, Kyung Hee University, 26 KyungheedaeRo,
Dongdaemun-Gu, Seoul 02447, Republic of Korea;
2
Department of Anatomy and Neurobiology, College of Medicine, Kyung Hee University, 26
Kyungheedae-Ro, Dongdaemun-Gu, Seoul 02447, Republic of Korea;
3
Center for Converging Humanities, Kyung Hee University, 26 Kyungheedae-Ro, Dongdaemun-Gu,
Seoul 02447, Republic of Korea.

Keywords: Photoacoustic Imaging, Porous Silicon, Indocyanine Green, Biomedical Imaging
Photoacoustic imaging combines the advantages of optical imaging and ultrasound imaging such as
advantage of distinguishing different colors with high resolution and deep tissue penetration. The
principle of photoacoustic imaging is that when a short pulse laser enters a living tissue, a part of the
energy is absorbed into tissue, converted into heat, and thermally expanded, resulting in the
generation of sound waves.
In this study, we have developed a new porous silicon nanoparticle (pSiNPs) formulation that
photoacoustic imaging agent, indocyanine green (ICG), encapsulated.[1] ICG is a representative FDA-
approved photoacoustic imaging contrast agent, which is used to measure heart and liver function and
blood flow. The results prove that ICG can be encapsulated in porous silicon nanoparticles and show
17-fold enhanced photoacoustic imaging response. Since pSiNPs has shown low cytotoxicity and
superior biocompatibility relative to metallic nanoparticles, the new pSiNPs-ICG formulation in this
study is considered as an advanced agent for photoacoustic imaging in the translational research. The
photoacoustic imaging efficiency of pSiNPs-ICG formulation is tested in the in vitro assay and ex vivo
mouse tissue samples, the results prove that higher signals are generated in the pSiNPs-ICG
formulation than bared ICG or PBS control. In conclusion, we demonstrated that pSiNPs can
overcome the drawbacks of known photoacoustic imaging agents such as photothermical unstability
and maintain the large light-induced heat, which greatly improves the performance.
Fig. 1: a) The schematic illustration for ICG loaded porous silicon nanoparticles (pSiNPs). b)
Photoacoustic images of mouse brain tissues with PBS, ICG, and pSiNPs formulation.
[1]. D. Kim et al., Adv. Mater., 2018, 1800512
332
NANOTECH-P22

Nanofibrous surfaces with high hydrophobicity from
electrodeposited poly(3,4-ethylenedioxypyrrole) and poly(3,4-
propylenedioxypyrrole) films substituted by alkyl chains

1 1 1 2 ,2
Omar Sané, Alioune Diouf, Samba Yandé Dieng, Frédéric Guittard, Thierry Darmanin*

1
Université Cheikh Anta Diop, Dakar, Sénégal;
2
Université Cote d’Azur, NICE Lab, IMREDD, Nice, France

Keywords: Hydrophobic, Adhesion, Nanostructures, Electropolymerization, Conducting Polymers
The control of surface wettability is very important for applications in antibioadhesion, separation
membrane, for example [1]. Both the surface structure and the surface energy play a fundamental role
on hydrophobic. Nanofibrous surface were found to be extremely interesting in the control of
hydrophobicity surface and surface adhesion [2-4]. In this poster, we report nanofibrous surfaces
through the electropolymerisation of 3,4-ethylenedioxypyrrole (EDOP) and 3,4-propylenedioxypyrrole
(ProDOP) with various alkyls chain grafted on the 3,4-alkylenedioxy bridge. Best results are obtained
with nonyl (C9), undecyl (C11) (intermediate hydrophobicity) using ProDOP as polymerization core.
More precisely, two different wetting were observed. PProDOP-C9 is parahydrophobic (high water
adhesion), as in rose petals while PProDOP-C11 is close to superhydrophobic properties such as lotus
leaves. This work could find many potential applications such as in water harvesting, oil/water
separation membrane.

-2 -2
Fig. 1: SEM images PProDOP-C9 (200mC cm ) and PProDOP-C11 (400 mCcm )

[1]. B. Su, Y. Tian, L. Jiang, J. Am. Chem. Soc. 2016, 138, 1727–1748.
[2]. C. Mortier, T. Darmanin, F. Guittard, Mater. Today Chem. 2018, 7, 65–75.
[3]. Z. Chu, S. Olveira, S. Seeger, ChemistrySelect 2017, 2, 5463–5468.
[4] D. Diouf, A. Diouf, C. Mortier, T. Darmanin, S. Y. Dieng, F. Guittard, ChemistrySelect 2017, 2,
9490–9494.
333
NANOTECH-P23

Synthesis of a novel 3,4-ethylenedioxypyrrole (EDOP) and 3,4-
propylenedioxypyrrole (ProDOP) monomers for special wetting
properties
1 2 1
Djibril Diouf , Thierry Darmanin* , Alioune Diouf , Samba Yandé Dieng, Frédéric Guittard
1
Université Cheikh Anta Diop, Faculté des Sciences et Techniques, Département de Chimie,
B.P. 5005 Dakar, Sénégal
2
Université Côte d’Azur, NICE Lab, IMREDD, 61-63 Av. Simon Veil, 06200 Nice, France
*[email protected]
Keywords: Surfaces, Hydrophobicity, Conducting polymers, Electropolymerization, Nanostructures.
Inspired by natural surfaces, the surface hydrophobicity is depending on both the surface energy and
the surface roughness/morphology [1,2]. The processes to create structured surfaces are numerous
and imply different treatments (chemical, physical, mechanical...) such as etching, plasma, laser,
lithography, templating [3]. A novel 3,4-ethylenedioxypyrrole (EDOP) and 3,4-propylenedioxypyrrole
(ProDOP) monomers with branched aromatic rings on the 3-position are prepared by
electropolymerization. Reynolds and al. were the first to report their substitution not only on the
nitrogen and also on the bridge leading to a huge synthesis possibility [4]. Differents natures of
branched aromatic rings are studied (phenyl, biphenyl, diphenyl, naphthalenyl, fluorenyl and pyrenyl)
as well as the polymerizable core (EDOP or ProDOP) and we show that the surface properties can be
tuned by the nature of these rings and the monomer structure.
Fig. 1: Original monomers studied: Ar = Phenyl, Biphenyl, Di-Phenyl, Naphthalenyl, Fluorenyl,

Pyrenyl.
Previously, it was found a way to obtain EDOP and ProDOP derivatives with hydroxyl groups on the
bridge using epibromohydrin [5]. These monomers could be easily functionalized by simple
esterification reaction. The monomers are exceptional for their ultra-low exceptional potential and
leading to polymers with unique opto-electronic properties [6, 7]. Thanks to the presence of NH
groups, nanostructured and nanoporous films were obtained with aromatic rings.
The best results are obtained with both EDOP and diphenyl, with which extremely high hydrophobic
properties (up to 116°) and nanoporous films are obtained. Indeed, due the presence of surface
nanoporosity, air is trapped between the surface and the water droplet and the Cassie-Baxter can
explain these results indicating of the presence of air between the surface and the water droplet [8].
The synthesis strategy is extremely interesting and many other molecules will be envisaged in the
future.

[1] T. Darmanin, F. Guittard, Mater. Today 2015, 18, 273–285.
[2] G. S. Watson, B. W. Cribb, J. A. Watson, ACS Nano 2010, 4, 129–136.
[3] J. Yong, F. Chen, Q. Yang, Z. Jiang, X. Hou, Adv. Mater. Interfaces 2018, 5, 1701370.
[4] R. M. Walczak, J.R. Reynolds, Adv. Mater. 2006, 18, 1121–1131.
[5] C. Mortier, T. Darmanin, F. Guittard, ChemNanoMat 2017, 3, 885–894.
[6] T. Darmanin, F. Guittard, J. Phys. Chem. C 2014, 118, 26912–26920.
[7] C. Mortier, T. Darmanin, F. Guittard, Mater Today Chem. 2018, 7, 65–75.
[8] A.B.D. Cassie, S. Baxter, Trans. Faraday Soc. 1944, 5, 546–551.
334
NANOTECH-P24

Electrodeposition Mechanism and Morphological Analysis of A
Highly Ordered Structure Polyaniline (PAni)

1 1 1 1
Doebner von TUMACDER*, Kathrina Lois TAACA, Maria Teresa PULIDO, Rhenish Simon

1
Mapua University, Manila, Philippines;
2
University of the Philippines-Manila, Manila, Philippines
Keywords: Polyaniline, electrochemical polymerization, chemical polymerization, FTIR, SEM
Abstract:
Various processes have been explored on the production of PAni that includes chemical and
electrochemical polymerization of aniline. The usual process of PAni growth is chemical
polymerization but this process is simultaneously carried out in the whole volume which could lead to
the formation of PAni with different properties from the surface and into the volume of PAni [1,2]. In the
electrochemical process, inert electrodes are used that act as oxidant in an electrolytic solution of
aniline [1]. As a result, oxidation only occurs in the electrode material and the properties of the
produced PAni are easy to control by just changing the electrode potential used during synthesis.
There has been no report on well-structured growth of PAni using two-electrode process which is the
focus of this study. In this report, PAni was synthesized electrochemically using platinum and stainless
steel electrodes at 0.70, 0.80, 0.90, 2.0, and 3.0 V applied potentials in 0.1 M aniline and 1.0 M HCl
solution. Morphological and PAni growth on the electrode surface is elucidated using scanning
electron microscopy (SEM) and Fourier Transform Infrared (FTIR) spectroscopy, respectively. FTIR
analyses indicated formation of PAni in the emeraldine-salt oxidation state represented by the almost
-1 -1
equal occurrence of the quinoid and benzenoid unit stretching vibrations at 1563 cm and 1480 cm ,
-1
respectively (Figure 1). The synthesized PAni has weak absorption at 3500-3600 cm which indicates
that the samples has less amount of absorbed water where it is considered ideal for applications
requiring fast-charge transport. FTIR analyses further indicate that PAni produced electrochemically
-1
has a highly organized chain due to the occurrence of “H-“peaks around 2800-3400 cm . These
properties have not been observed for chemically produced PAni. SEM images showed that PAni
produced in the present process contains more uniform structures of PAni which further indicates
highly organized fibrillar morphology compared to the reported non-uniform agglomerated morphology
of PAni obtained using chemical polymerization. With the formation of interconnected fibers,
electrochemically-produced PAni may have conductivity property suitable for biosensing applications.

Fig. 1: FTIR pattern of PAni
[1]. G. Umadevi, V. Ponnusamy, M. Paramsivam, S. Palaniswamy Rasayan J. Chem. 2010, 3, 194-

200
[2] S. Bhadra, D. Khastgir, N. Singha, J.H. Lee Progress in Polymer Science 2009, 34, 783-810,
335
NANOTECH-P25

Bentonite Activated by Copper and Nickel: Cytotoxicity Testing
and Antimicrobial Activity Studies
1, 2 1 3 4
Kathrina Lois M. TAACA , Luigi A. DAHONOG , Vina B. ARGAYOSA , Raquel O. RUBIO
1
and Eleanor M. OLEGARIO*
1
Department of Mining, Metallurgical and Materials Engineering, University of the Philippines, Diliman,
Quezon City 1101, Philippines
2
Department of Physics, Mapua University, 658 Muralla Street, Intramuros, Manila 1002, Philippines
3
Microbiological Research and Services Laboratory, Natural Sciences Research Institute, University of
the Philippines, Diliman, Quezon City 1101, Philippines
4
Biological Research and Services Laboratory, Natural Sciences Research Institute, University of the
Philippines, Diliman, Quezon City 1101, Philippines

Keywords: Bentonite, Cu, Ni, MMT, cytotoxicity testing, antimicrobial activity, potential biomedical
application

Bentonite (B) clay from SAILE Industries, Inc. in Mangatarem, Pangasinan, Philippines was
characterized and fabricated as Cu-bentonite (Cu-B) and Ni-bentonite (Ni-B) modified materials to
determine their potential for biomedical applications. This B sample used in this study is composed of
montmorillonite smectite and mordenite zeolite groups [1]. The two (2) sets of B clay powders were
mixed with 0.2 M CuCl2 and 0.2 M Ni(NO3)2 solutions via ion-exchange process. The synthesized
powders were filtered using centrifugation for 5 min, washed with deionized water to remove any
2+ 2+
excess Cu and Ni ions, and dried at 60°C. The Cu-B and Ni-B samples were not subjected to post-
treatment such as calcination and were pelletized with a constant diameter of 8 mm prior to
characterization.
Bentonite with Cu and Ni were tested for cytotoxicity and antimicrobial properties to assess their
potential for biological applications. Antibacterial activity of Cu-B and Ni-B samples were evaluated
using the aerobic plate count method with Staphylococcus aureus ATCC 6538 as test organism at
room temperature (RT). Results revealed that Cu-B and Ni-B samples, both at 0.025 g/ml, showed
>99.9% kill of S. aureus ATCC 6538 after 24 hours contact time. These samples provided antibacterial
effect against the S. aureus ATCC 6538 test organism compared to the as-received B clay samples
with no antibacterial effect against the test organism at RT. The cytotoxicity test of both samples (Cu-B
and Ni-B) was conducted using trypan blue assay and with lymphocytes from normal blood as test
culture. Results (Fig 1) showed 88.2 ± 1.97% and 86.9 ± 4.58% live cells of the lymphocyte culture
after the 24 h incubation, respectively. These values indicate the low cytotoxicity of the samples, as
compared to the positive control, 0.1% Triton X-100. These % live cell values of the lymphocytes,
moreover, implied that the solvent and the concentration of metals used do not induce harmful effect
to the cell culture.

Fig. 1: Cytotoxicity test of CuB and NiB samples
[1]. E. Olegario-Sanchez, J.C. Felizco, Key Engineering Materials. 2017, 737, 401-406.

336
NANOTECH-P26

Study of the wettability and morphology of parahydrophobic
surfaces made of polymers with hyperbranched alkyl chains
1 1 1 2 ,2
Omar Thiam, Alioune Diouf, Samba Yandé Dieng, Frédéric Guittard, Thierry Darmanin*
1
Université Cheikh Anta Diop, Dakar, Sénégal;
2
Université Cote d’Azur, NICE Lab, IMREDD, Nice, France
Keywords: Hydrophobic, Adhesion, Nanostructures, Electropolymerization, Conducting Polymers.
The need to control the surface wettability is very important for various applications at interfaces such
as oil/water separation membranes, water harvesting systems, non-stick pans, anti-icing windows or
antifouling paints [1]. There are numerous examples in Nature where species have special wettability
such as superhydrophobicity (both high hydrophobicity and low water adhesion) and
parahydrophobicity (both high hydrophobicity and high water adhesion) [2,3]. The natural species
show the interest to control both the surface energy and surface structuration.
Particularly, the nanofibers are very interesting structures to control the surface hydrophobicity and
water adhesion because these properties are dependent on their length, diameter, orientation to the
substrates as well as their spacing, for example. Conducting polymers are often used to obtain
nanofibers not only in solution but also on substrates [4]. Among them, the electropolymerization was
demonstrated as a technique for a fine tuning of the surface nanostructures by playing with both
electropolymerization parameters and the monomer chemical structures. Thanks to NH groups, the
use of aniline or 3,4-alkylenedioxypyrrole (XDOP) non-substituted on the nitrogen are excellent
candidates for the formation of conducting polymer nanofibers with special wetting properties [5].
Here, I will present example of results obtained with 3,4-ethylenedioxypyrrole (EDOP) and 3,4-
propylenedioxypyrrole (ProDOP), in the aim to favor the formation of nanofibrous parahydrophobic
surfaces (Fig. 1).

Fig. 1: Example of results obtained with this process.
[1]. B. Su, Y. Tian, L. Jiang, J. Am. Chem. Soc. 2016, 138, 1727–1748.
[2]. T. Darmanin, F. Guittard, Mater. Today 2015, 18, 273–285.
[3]. A. Marmur, Soft Matter 2012, 8, 6867–6870.
[4] Y. Zhao, J. Stejskal, J. Wang, Nanoscale 2013, 5, 2620–2626.
[5] D. Diouf, A. Diouf, C. Mortier, T. Darmanin, S. Y. Dieng, F. Guittard, ChemistrySelect 2017, 2,
9490–9494.
337
NANOTECH-P27

Electrodeposition Mechanism and Morphological Analysis of A
Highly Ordered Structure Polyaniline (PAni)

1 1 1 1
Doebner von TUMACDER*, Kathrina Lois TAACA, Maria Teresa PULIDO, Rhenish Simon

1
Mapua University, Manila, Philippines;
2
University of the Philippines-Manila, Manila, Philippines

Keywords: Polyaniline, electrochemical polymerization, chemical polymerization, FTIR, SEM
Abstract:
Various processes have been explored on the production of PAni that includes chemical and
electrochemical polymerization of aniline. The usual process of PAni growth is chemical
polymerization but this process is simultaneously carried out in the whole volume which could lead to
the formation of PAni with different properties from the surface and into the volume of PAni [1,2]. In the
electrochemical process, inert electrodes are used that act as oxidant in an electrolytic solution of
aniline [1]. As a result, oxidation only occurs in the electrode material and the properties of the
produced PAni are easy to control by just changing the electrode potential used during synthesis.
There has been no report on well-structured growth of PAni using two-electrode process which is the
focus of this study. In this report, PAni was synthesized electrochemically using platinum and stainless
steel electrodes at 0.70, 0.80, 0.90, 2.0, and 3.0 V applied potentials in 0.1 M aniline and 1.0 M HCl
solution. Morphological and PAni growth on the electrode surface is elucidated using scanning
electron microscopy (SEM) and Fourier Transform Infrared (FTIR) spectroscopy, respectively. FTIR
analyses indicated formation of PAni in the emeraldine-salt oxidation state represented by the almost
-1 -1
equal occurrence of the quinoid and benzenoid unit stretching vibrations at 1563 cm and 1480 cm ,
-1
respectively (Figure 1). The synthesized PAni has weak absorption at 3500-3600 cm which indicates
that the samples has less amount of absorbed water where it is considered ideal for applications
requiring fast-charge transport. FTIR analyses further indicate that PAni produced electrochemically
-1
has a highly organized chain due to the occurrence of “H-“peaks around 2800-3400 cm . These
properties have not been observed for chemically produced PAni. SEM images showed that PAni
produced in the present process contains more uniform structures of PAni which further indicates
highly organized fibrillar morphology compared to the reported non-uniform agglomerated morphology
of PAni obtained using chemical polymerization. With the formation of interconnected fibers,
electrochemically-produced PAni may have conductivity property suitable for biosensing applications.

Fig. 1: FTIR pattern of PAni
[1]. G. Umadevi, V. Ponnusamy, M. Paramsivam, S. Palaniswamy Rasayan J. Chem. 2010, 3, 194-

200
[2] S. Bhadra, D. Khastgir, N. Singha, J.H. Lee Progress in Polymer Science 2009, 34, 783-810,
338
NANOTECH-P29

Synthesis and characterisation of nanomaterials Dawson type
Ouahiba Bechiri
Department of Process Engineering, Faculty of Engineering

University of Annaba P.O. Box 12, 23000 Annaba, Algeria
Keywords: polyoxometalates, Dawson type, nanomaterials, synthesis, caracterization
Polyoxometalates (POMs) constitute a diverse class of inorganic oxo-metal clusters composed of

early transition metals in their highest oxidation state. They have a great deal of structural diversity
and various applications in different areas, including catalysis, material sciences, medicine, and
biology. Several types have been characterized, and each of them is defined by the M/X ratio used in
the polycondensation under acidic conditions. The two best known heteropolyanions are the Keggin-
n+ (8-n)- n+ (16-2n)-
type [X M12O40] [1], the latter ones called the Wells-Dawson type [(X ) 2M18O62] [2] (Fig1).
However, these compounds remained only laboratory curiosities during many years. It is only at the
end of the nineteen seventies that extensive studies by many groups around the world put them in the
spotlight and nowadays their applications have exploded, in catalysis as well as in various other
domains, such as analytical chemistry biochemistry/medicinal chemistry or development of new
31
materials with optical [3] or magnetic properties. In this work, the synthesis, IR , P NMR and cyclic
voltammetry characterizations of a new Wells- Dawson-type heteropolyanions which contains the
cobalt [HP2W18NiO61]and [HP2W15Mo3NiO61] are reported.
Fig. 1: Polyhedral representation of the Dawson structure of polyanion
References:
1. A. Müller, F. Peters, MT. Pope, D. Gatteschi. Chem Rev. 1998.
2. M. Mizano, M. Mizano, Chem.Rev. 1998.
3. JT. Rule, CL. Hill, D.A. Judd, R.F. Schinazi. Chem. Rev. 1998.
4. B. Dawson, Acta. Cristallogr, 1953.

339
NANOTECH-P30

Synthesis and characterization of new superhydrophobic polymers
1 2, 2 1
El Hadji Yade THIAM , Thierry Darmanin *, Frederic Guittard , Abdoulaye Dramé ,
1 1 1
Aboubacary Séne , Samba Yande Dieng , Salif Sow

1
Université Cheikh Anta DIOP, Lab. Chimie Organique, Dakar, Sénégal
2
Université Côte d’Azur, NICE Lab, IMREDD, Nice, France

Keywords: Superhydrophobic, wettability, morphology.
In recent years, the development of new materials for the control of surface wettability
(superhydrophobic and superoleophobic) has attracted a great deal of interest, due to their remarkable
properties in several fields such as battery coverings, adhesion antibacterial, waterproof textiles, self-
cleaning windows for the automotive and aerospace industry and fuel transportation [1-3]. The theory
of superhydrophobicity comes from observations made on animal and plant species. Indeedn these
natural sources inspired the researchers to reproduce these properties which depend mainly on the
surface chemistry but also morphology. These two parameters must therefore be taken into account
when developing superhydrophobic surfaces.
Here, new superhydrophobic, biodegradable polymers have been made from monoacids having two
mixed chains (hydrocarbon and fluorocarbon) and polymerizable nuclei. The polymer surfaces were
obtained by electropolymerization. The characterization of all these compounds was carried out by
mass spectroscopy, NMR, potentiostat and Kruss DSA30 goniometer and SEM (scanning electron
microscope).
Here, both compounds have interesting surface properties and could be used in the future for various
industrial applications. The electrochemical parameters such as the deposition charge, the substrate,
the electrolyte salt or the chemical structure of the monomer made it possible to control the wetting
properties very easily.
Fig. 1: Example of results.
[1]. S. H Nguyen, H. K. Webb, P. J. Mahon, R. J. Crawford, E. P. Ivanova, Molecules, 2014, 19,

13614-13630.
[2]. H. K. Webb, Russell J. Crawford, Elena P. Ivanova, Adv. Colloid Interface Sci., 2014, 210, 58-
64.
[3]. T. Darmanin, F. Guittard, Mater. Today, 2015, 18, 273–285.
340
NANOTECH-P31

Design and development of bionanocomposites for food packaging
applications

1 1 1 2
Salima SAIDI-BESBES*, Khadidja TALEB, Amel MECHKEN, Yves GROHENS,

1
University Oran1 Ahmed Benbella, Applied organic Synthesis laboratory (LSOA), Chemistry
department, FSEA, BP 1524 EL Mnaouer, 31000 Oran – Algeria.
2
IRDL-FRE CNRS 3744, University of Bretagne Sud, Lorient 56100, France
*Email : [email protected],
Keywords: Biocomposite, Gemini surfactants, organoclay, WVP, mechanical properties
Polylactic acid (PLA) is a sustainable alternative to petrochemical-derived products since it is

biodegradable, biocompatible and obtained from renewable resources. Although these features make
PLA an appropriate candidate for biomedical and food packaging applications, some drawbacks which
often limit its end uses still to be overcome such as poor thermal and mechanical properties, low flame
retardant and limited barrier properties for small molecules (water and oxygen). Nowadays, research
efforts are devoted to the development of PLA with better performances mainly by means of blending
with other biopolymers, additives or nanofillers [1-2].
We present in this work, PLA nanocomposites prepared with clays organomodified with gemini-
quaternary ammonium surfactants and their characterization in terms of composition, morphology,
thermal, mechanical and barrier properties. We show that substantial improvement of crystallinity
index, mechanical, rheological and morphological properties can be targeted through appropriate
structural adjustments of surfactant molecules. Incorporating of 1-3 wt. % of nanoclays into the PLA
matrix led to a significant reduction in water vapor permeability (38-50% in comparison to pristine PLA)
and an increase of the mechanical properties such as tensile modulus, strain at break and toughness
of PLA nanocomposites. The hydrolytic degradation of nanocomposites showed an increase of water
absorption which is in favor of improvement of the degradation rate of these materials [3-4]
[1]. P. Bordes, E. Pollet, Prog. Polym. Sci. 2009, 33, 125–155.

[2]. S-L. Bee, M. A. A. Abdullah, S-T. Bee, L. T. Sin, A. R. Rahmat, Prog. Polym. Sci. 2018, 85, 57-82.
[3]. K. Taleb, M. Mohamed-Benkada, N. Benhamed, S. Saidi-Besbes, Y. Grohens, A. Derdour, J. Mol.
Liq. 2017, 241, 81-90.
[4]. K. Taleb, I. Pillin, Y. Grohens S. Saidi-Besbes, Appl. Clays. Sci. 2018, 161, 48-56
341
NANOTECH-P32

Iron oxide based magnetic nanomaterials for water remediation

1 1 1 1
Salima SAIDI-BESBES*, Zakaria MOKADEM, Nadia CHEKALIL, Hadjira LAHMAR, Abdelhamid
2
ELAISSARI,
1
University Oran1 Ahmed Benbella, Applied organic Synthesis laboratory (LSOA), Chemistry
department, FSEA, BP 1524 EL Mnaouer, 31000 Oran – Algeria.
2
University Lyon-1, Villeurbanne; CNRS, UMR-5007, LAGEP- CPE; 43 bd 11 Novembre 1918,
F-69622 Villeurbanne, France.
*Email : [email protected],
Keywords: magnetic nanoparticles, pollutant, adsorption, environment
Water pollution has become a critical environmental issue since it continues to threaten both quality of
life and public health around the world. The contamination is usually associated with intensive industry
activities, mining smelting, agriculture, factory farms, roadways and automobiles and others activities
like fracking [1-2]. Great efforts have been made in last decades to develop suitable technologies and
processes that are easy to use, sustainable and economically feasible for remedying polluted water
effluents.
We report in this presentation some of our results on the design of efficient, easily accessible,
sensitive and reusable magnetic nanoadsorbents [3-5]. These adsorbents have the advantage to be
superparamagnetic and could be easily recovered or manipulated with an external magnetic field after
metal remediation without the degradation of the active sites. Several materials have been
investigated: functionalized iron oxide nanoparticles with chelating units, magnetic polyHIPE monolith
adsorbents and low cost magnetic tea composites. Their adsorption and regeneration behaviors were
investigated for several heavy metal ions, dyes and organic pollutants.
[1]. Q. Wang, Z. Yang, Env. Pol. 2016, 218, 358-365.

[2]. A. S. Adeleye, J. R. Conway, K. Garner, Y. Huang, Y. Su, A. A. Keller, Chem. Eng. J. 2016, 286,
640-662.
[3]. Z. Mokadem, S. Mekki, S. Saïdi-Besbes, G. Agusti, A. Elaissari, A. Derdour, Arab. J. Chem. 2017,
10, 1039-1051.
[4]. Z. Mokadem, S. Saïdi-Besbes, G. Agusti, A. Elaissari, A. Derdour, J. Colloid Sci. Biotech. 2016, 5,
111-133.
[5]. H. Lahmar, S. Saïdi-Besbes, A. Elaissari, A. Derdour A, J. Colloid Sci. Biotech. 2016, 4, 64-70.
342
NANOTECH-P33

Connecting structural, optical, and electronic properties and
photocatalytic activity of Ag3PO4:Mo complemented by DFT
calculations
1 1 1 1
Aline Barrios Trench , Thales Rafael Machado , Amanda Fernandes Gouveia , Marcelo Assis ,
2 1 3 3
Letícia Guerreiro da Trindade , Clayane Santos , Andre Perrin , Christiane Perrin ,
4 4 1
Mónica Oliva , Juan Andrés , Elson Longo
1
CDMF, Universidade Federal de São Carlos, P.O. Box 676, São Carlos, SP, 13565-905, Brazil
2
Institute of Chemistry, UFRGS, P.O. Box 15003, Porto Alegre, RS, 91501-970, Brazil
3
University of Rennes 1, Campus de Beaulieu, av. Général Leclerc, F-35042, Rennes-Cedex, France
4
Department of Analytical and Physical Chemistry, University Jaume I, Castellón, 12071, Spain
Keywords: Ag3PO4:Mo microcrystals; Photocatalytic activity; DFT calculations
The photodegradation process of organic compounds has been considered as an effective method for
waste treatment due to its high efficiency. Herewith, several researches have been made related to
modifications and development of materials for improvement of its photocatalytic properties.
Therefore, since silver phosphate (Ag3PO4) is one of the most photoactive material under visible light,
1
it is essential the understanding of its properties as well the improvement of its photocatalytic activity .
The present join experimental and theoretical work provides in-depth understanding on the
relationship among structural, optical, and electronic properties and photocatalytic activity of
Ag3PO4:Mo microcrystals. We prepared Ag3PO4 and (Mo-doped) Ag3PO4:Mo microcrystals using
the chemical precipitation method. The as-synthetized samples have been characterized by X-ray
diffraction (XRD), X-ray photoelectron spectroscopy, transmission electron microscopy, high angle
annular dark field scanning transmission electron microscopy (HAADFSTEM), energy-dispersive X-ray
spectroscopy (EDS) techniques, and photoluminescence (PL) emission. Density functional theory
calculations have been performed to complement the experimental results and understand the
physical phenomena taking place in the structure, electronic and optical properties involved in the Mo
doping process on the Ag3PO4, and consequently the photocatalytic performances of these new
materials. XRD analysis showed that at a doping level below 2% the samples did not present any
secondary phases, demonstrating that the Mo cations have been actually incorporated in the Ag3PO4
structure. Moreover, HAADF-STEM and EDS mapping showed that the samples were homogeneous,
especially with respect to the Mo cations, and showed no signs of segregation. The Egap value and
PL measurements indicated that the doping process caused structural defects in the Ag3PO4
structure. The photocatalytic activity of both the pure and Mo-doped materials was tested for the
degradation of Rhodamine B under visible light irradiation. The results demonstrated that the sample
of Ag3PO4:Mo with 0.5% Mo had a faster degradation rate, approximately 92% after 5 min of
irradiation, while the degradation rate of the pure sample was only 46% during the same time.
(1) X.J. Chen, Y.Z. Dai, X.Y. Wang, J. Alloys Compd. 2015, 649, 910–932.
(2) Trench, A. B. et al. Applied Catalysis B: Environmental, 2018, 238, 198-211.
343
NANOTECH-P34

Microsphere lithography in diamond technology

1 1 1 1
Mária DOMONKOS,* Marián VARGA, Lukáš ONDIČ, Alexander KROMKA
1
Institute of Physics of the Czech Academy of Sciences, Prague, Czech Republic
Keywords: microsphere lithography; reactive ion etching; polycrystalline diamond film; photonic crystal
Polycrystalline diamond thin films have received a considerable attention due to their unique
properties [1]. Modifications of their surface morphology (i.e. creation of holes, nanowires,
nanoneedles, porous structures, etc.) expand their possible applications by enlarging the surface area.
However, the controlled fabrication of diamond nanostructures on large areas in a time and cost-
effective way is still a challenging task.
We focus on the fabrication of nanostructures without using conventional lithographic techniques.
We chose an alternative route, by combining diamond technology with microsphere lithography (MSL).
The presented approaches are based on a multi-step procedure, which uses relatively simple and
widespread techniques (e.g. spin-coating, plasma etching, metal evaporation, annealing, lift-off, etc.).
The steps are optimised individually, and then combined for sculpting various diamond
nanostructures. The major challenge of MSL is making a high-quality mask (i.e. uniform and compact
monolayer of monodisperse microspheres in a hexagonal lattice with low defect density) over large
areas [2]. First, a series of experiments are done to achieve a monolayer of submicron sized (200–
1500 nm) polystyrene (PS) spheres on silicon substrates using the Langmuir-Blodgett method or spin-
coating. Then, the spin-coating is also applied to rough diamond film and the main fabrication
challenges (e.g. critical process parameters, substrate properties) are discussed, especially focusing
on the relation between the diamond film surface roughness and microsphere diameter. The sphere
diameter is tailored to the surface roughness of the diamond film, e.g. films with relatively low peak-to-
valley roughness (up to ~ 300 nm) are smooth enough to be coated by a monolayer of PS spheres
with diameter up to 1 µm. After the monolayer deposition, the desired geometrical patterns (e.g.
spherical, pyramidal, ball-and-stick) and size scales are achieved by reactive ion etching the PS
spheres using different etching recipes. Such modified masks serve as a template for the subsequent
diamond deposition (bottom-up approach, i.e. pre-growth structuring) or etching (top-down approach,
i.e. structuring after the diamond growth process). The deposition of polycrystalline diamond thin films
is carried out in a focused microwave plasma chemical vapour deposition system. Reactive ion
etching is performed in a capacitively coupled radiofrequency reactor using different process
conditions (e.g. gas mixture).
Applicability of the MSL to diamond technology is demonstrated by the fabrication of periodically
ordered nanostructures with tailored morphology and properties (size, geometry and lattice constant).
Hillock-like structures are created using a four-step top-down fabrication process (deposition of
diamond film, mask preparation from PS spheres with an initial diameter of 1.5 µm, mask modification
and diamond etching). An air-hole type photonic crystal with hexagonal lattice symmetry is simulated,
fabricated and characterised. The dimensions (a = 1080 nm, d = 750 nm, h = wh = 150 nm) of the
structure are tuned to have a leaky mode at 1.31 µm. The measured transmission spectra are shown
to be in good agreement with the simulations [3]. Selective area deposition of periodically ordered
diamond columns (with a periodicity of 0.25 - 1 µm) is realised using a bottom-up approach (masks
from PS spheres are used for plasma etching the seeding layer) [4].
The presented fabrication approaches are not as flexible and precise as the standard lithographic
techniques (e.g. electron beam lithography) because the final MSL based structure always includes a
variety of defects due to spheres size variations and the self-assembly process. The MSL approaches
win out however in simplicity, cost and speed, especially on larger areas. The realised diamond
nanostructures have promising morphology for various applications in photonics, plasmonics,
sensorics, biomedicine, etc.
This work was supported by the research GACR project P108/12/G108.
[1]. T. Izak et al., Phys. status solidi b 2012, 249, 2600–2603

[2]. P. Colson et al., J Nanomater 2013, 2013, 1-19
[3]. M. Domonkos et al., Mater. Des 2018, 139, 363–371
[4]. M. Domonkos et al., Phys. status solidi b 2014, 251, 2587–2592
344
NANOTECH-P35

Synthesis and Properties of Activated Nano
Carbon/Collagen/Cellulose Acetate Nanofiber by Electrospinning

1 1 1
Muhamad NASIR,* Wahyuni SAPRI, Rana Ida SUGATRI,

1
Research Unit for Clean Technology, Indonesian Institute of Sciences (LIPI),Bandung, Indonesia
*[email protected]
Keywords: carbon/collagen cellulose acetate nanofiber, nanofiber, electrospinning, dip coating
Activated nanocarbon/collagen/cellulose acetate nanofiber has been synthesis by combination of

electrospinning and coating process. Cellulose acetate nanofiber was synthesis by electrospinning
process and after that nanofiber was coated with a mixed solution of activated nano carbon/collagen.
Smooth nanofiber morphology with average fiber diameter 477 nm was confirmed and calculated after
characterized by scanning electron microscopy (SEM). There was no changed in chemical functional
group of nanofiber after confirmed by FTIR. Water surface property of nanofiber was identified by
water contact angle measurement. Water contact angle and water spreading time of nanofiber were
o
75 and 1 second, respectively. This nanofiber research has potential application for biotechnology
1
and medical fields

30
25
20
F re que nc y
15

10
0
0-99 100-199 200-299 300-399400-499 500-599 600-699700-799 800-899 900-9991000-1099
D ia m e te r (nm )
Fig. 1: Morphology and diameter distribution of activated nanocarbon/collagen/cellulose

acetate nanofiber
[1] M.Nasir, D. Apriani, IOP Conference Series: Materials Science and Engineering, 2017, 293(1),
012004.
345
NANOTECH-P36

Biomass-derived Carbon Dots (C-Dots) for multi-color imaging

1,2 1 2 3
Raja SEBASTIAN, Luiz H. C. Mattoso , Zenke MARTIN, Eva Miriam BHUL, Stephen
4 2
DRESCHERS, Sechi ANTONIO*,

1
Laboratório Nacional de Nanotecnologia Aplicada ao Agronegócio (LNNA), Embrapa Instrumentaçao,
São Carlos – SP, Brasil;
2
Institute for Biomedical Engineering, Department of Cell Biology, Uniklinik, RWTH Aachen, Germany;
3
Institute for Pathology, Uniklinik, RWTH Aachen, Germany;
4
Neonatology, Uniklinik, RWTH Aachen, Germany

Keywords: Biomass, curaua, C-dots, multi-color imaging, cytotoxicity
Development of novel materials from the natural resources that meet our daily needs and are at the
same time environmental-friendly in nature is highly desirable [1]. Carbon dots (C-dots) are a novel
class of carbon nanoparticles (CNPs) that encompass discrete, quasi-spheroidal morphology with
sizes below 10 nm. Generally, C-dots can be synthesized either from “top-down” or “bottom-up”
approaches from various chemical and natural precursors [2, 3]. They are considered as superior
materials than organic dyes and semiconductor quantum dots on the account of their excellent
photostability, outstanding water-solubility, robust chemical inertness, high resistance to
photobleaching, tunable fluorescence emission and excitation and facile surface modification.
Moreover, the remarkable biological properties such as biocompatibility, excellent selectivity, and low
toxicity endow C-dots as promising candidates for drug delivery, bioimaging, and biosensors
applications [4, 5]. In addition, one exciting feature i.e., excitation-dependent emission commonly
observed in most C-dots, suggest their potential use as probes for multi-color imaging application.
Herein, we present novel highly fluorescent biomass-derived (curaua, a Brazilian pineapple leaves) C-
dots along with their multicolor imaging studies including photostabilty and cytotoxicity analyses.

Curaua - fibers C-dots

In vitro multicolor imaging
Fig. 1: Curaua-derived C-dots for multicolor imaging
[1]. V. Sharma, P. Tiwari, SM. Mobin, J. Mater. Chem. B. 2017, 5, 8904 - 8924.
[2]. Z. Peng, S. Li, AO. Al-Youbi, AS. Bashammakh, MS. El-Shahawi, RM. Leblanc, Coord. Chem.
Rev. 2017, 343, 256 - 277.
[3]. J. Gao, M. Zhu, H. Huang, Y. Liu, Z. Kang, Inorg. Chem. Front. 2017, 4, 1963 - 1986.
[4]. J. Zhang, S. Yu, Materials Today 2016, 9, 382 - 393.
[5]. PG. Luo, S. Yang, SK. Sonkar, L. Yang, JJ. Broglie, Y. Liu, Y. Sun, RSC Adv. 2014, 4, 10791 -
10807.
Acknowledgement: The authors thank EMBRAPA, Uniklinik RWTH and FAPESP (Proc. No.
2015/00094-0 and Proc. No. 2017/22017-3) for financial support.
346
NANOTECH-P37

Inulin-based nanosensors for enhanced detection of tumorigenic
ioxynil residues in garlic
,1 2 2
Grzegorz BAZYLAK* , Raluca-Ioana STEFAN-VAN-STADEN , Jacobus F. VAN-STADEN ,
2 2
Grigorina MITROFAN , Ionela R. COMNEA-STANCU ,
3 4
Constantina P. KAPNISSI-CHRISTODOULOU , Hassan Y. ABOUL-ENEIN
1
Department of Pharmaco-Bromatology & Molecular Nutrition , Faculty of Pharmacy,
Collegium Medicum, Nicolaus Copernicus University, Bydgoszcz, Poland;
2
PATLAB, National Institute of Research for Electrochemistry & Condensed Matter,
Bucharest, Romania;
3
Department of Chemistry, University of Cyprus, Nicosia, Cyprus;
4
Pharmaceutical Chemistry Department, National Research Centre, Dokki-Giza, Egypt
Keywords: Nanosensors, Polyfructans, Ioxynil, Bioconjugates, Electrophoresis, Garlic
Ioxynil (IO) is iodocyanophenolic type herbicide used in raw crop protection of garlic (Allium sativum
L.) and linked with suppression of thyroid hormones and induction of various tumors in mammals by
inhibiting of intercellular communications related with connexin43 assembled gap junction channels
[1]. Residual amounts of IO as commonly consumed with garlic should be continuously monitored to
enable elimination of this xenobiotic. Ability of plant derived inulin chains for highly specific recognition,
binding and transport of iodine containing thyroid hormones [2,3,4] and urea [5,6] was observed in the
previous electrochemical study. On these results the formation of intermolecular bioconjugates
between iodine containing IO and model inulins, as structurally similar to originated in garlic native
inulins (GNIs), could be postulated and used to predict tendency for IO storage by garlic treated as
source of probiotic dietary fiber. Thus, content of IO and its bioconjugates was determined by SPE-
CE-MS/MS and SPE-CE-hyphenated with potentiometric detection using originally developed series of
liquid-membrane microsensors containing nanodiamond particles functionalized with four structurally
different types of commercial inulins as IQ (oligofructans), HD (short polyfructans), TEX (long
polyfructans) and IN (dodecylated polyfructans). GNIs was isolated by ultrafiltration, ion-exchage and
1 13
gel-chromatographic procedures and analyzed by H and C NMR. Superior limit of detection for
assay of free IO (20 ng/g d.m.) was obtained using constructed microsensors based on TEX. Mean
content of IO in garlic samples was 55 ng/g (range 36÷178 ng/g) and was accompanied by increased
ratio of polyfructans fraction in mixture of oligo and polyfructans forming the GNIs. Polyfructan fraction
of garlic inulins is possible potential nanocarrier of traceable amounts of stable ioxynil bioconjugates
which could easy penetrate into lower section of human intestine.

References:
[1] E. Leithe, A. Kjenseth, J. Bruun, S. Simes, E. Rivedal, Toxicol. Appl. Pharmacol. 2010, 247, 10-17.
[2] R.-I. Stefan-van-Staden, S.-C. Balasoiu, G. Bazylak, J.F. van Staden, H.Y. Aboul-Enein, G.L.
Radu, J. Electrochem. Soc. 2013, 160(10), B192-B195.
[3] G. Mitrofan, R.I. Stefan-van-Staden, I.R. Comnea-Stancu, I.F. van Staden, G. Bazylak, C.P.
Kapnissi-Christodoulou, H.Y. Aboul-Enein, Chirality 2015, 27(12), 973-978.
[4] R.-I. Stefan-van-Staden, G. Mitrofan, RSC Advances 2017, 69, 43567-43573.
[5] G. Jayanthi Kalaivani, S.K. Suja, Carbohydrate Res. 2016, 143, 51-60.
[6] G. Jayanthi Kalaivani, S.K. Suja, Appl. Surface Sci. 2018, 449, 266-276.

347
NANOTECH-P38

Microstructure Evolution and Magnetic Properties of
Nanocrystalline Ni75Fe25 Thin Films: Effects of Substrate and
Thickness.
1 2 3 3 3 4 1
Amel Kaibi* , A. Guittoum , R. M. Öksüzoğlu , C.Yavru , S. Özgün , M. Boudissa , M. Kechouane
1
Physics of Materials laboratory (PML), Faculty of physics, Algiers, USTHB, BP 32 El Alia, Algeria.
2
Nuclear Research Centre of Algiers, Algiers, 02 Bd Frantz Fanon, BP 399, Algeria.
3
University of Anadolu, Faculty of Engineering, Department of Materials Sciences and Engineering,
Eskişehir İki Eylül Campus, 26555, Turkey.
4
ENMC Laboratory, Physics Department, University of Sétif, 19000, Algeria.
* Corresponding author: [email protected]
Keywords: Ni75Fe25 films, magnetic thin films, thickness, substrate, X-ray diffraction, SEM, AFM,
magnetic measurements.
Permalloy (Py) thin films were evaporated from nanocrystalline soft Ni75Fe25 powder onto glass and
Al2O3 substrates [1]. The thicknesses of these films range from 16 nm to 250 nm. The as deposited
films were characterized by Grazing incidence X-ray diffraction (GIXRD), Scanning Electron
Microscopy (SEM), Atomic Force Microscopy (AFM) and vibrating sample magnetometry (VSM). From
GIXRD spectra, we have shown that the films are amorphous for the thinner films. However, for the
thicker films, a polycrystalline fcc structure is present. For the intermediate thicknesses, the nature of
substrate determines the texture of the films. The SEM micrographs indicate that the nature of
substrate influences on the morphology and grains size of Py films. From AFM observations, the
nanocrystalline nature of the grains is evidenced. Hysteresis loops reveals the ferromagnetic character
of Py films. We have shown that the values of coercive field, Hc, generally, decrease with increasing
thickness. Moreover, the Hc values are higher for films deposited onto Al2O3 substrate than those on
glass one. The nature of substrate and thickness seems to influence the magnetic properties of Py
films. A correlation between these physical properties will be established and discussed.
[1] A. KAIBI, A. GUITTOUM, N. FENINECHE, N. SOUAMI and M. KECHOUANE, Sens. Lett. Vol.11
(2013) p.1–7.

348
NANOTECH-P39

Crack pattern formation in plasma-treated TiO2 thin films

,1 2 1,2 2
Hernando S. SALAPARE III* , Raphaël HATTAB , Ananya SATHANIKAN , Manon FLORENT ,
2 2 1 1
Mayeul FLAMMIN , Anthony CARREIRA , Arnaud ZENERINO , Sonia AMIGONI , Frédéric
1
GUITTARD

1
Université Nice Côte d’Azur, NICE Lab, IMREDD, Nice 06200, France;
2
Université Nice – Sophia Antipolis, NICE Learning, IMREDD, Nice 06200, France
*[email protected]

Keywords: plasma processing, titanium dioxide, thin film, crack pattern formation,
Plants contain chlorophyll that is known to be a natural photocatalyst since it transforms water and
carbon dioxide into oxygen and glucose with the help of sunlight. Taking inspiration from natural
photocatalysts, we deposited titanium dioxide (TiO2) thin films on glass substrates using sol-gel and
dip coating methods, that acts as a photocatalytic material intended for air treatment applications,
particularly on the absorption and degradation of air pollutants and greenhouse gases like NOx, O3,
and CO using photocatalysis. The TiO2 thin films were post-treated with low power nitrogen plasma
produced from a P300 plasma device (Alliance Concept, France) to provide further structuration on
the surface of the thin film. The samples were characterized by contact angle measurements,
scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), Fourier transform
infrared spectroscopy (FTIR), and optical profilometry to determine that changes in the surface of the
material before and after the plasma treatment. FTIR and EDS characterizations confirmed that TiO 2
thin films were deposited on the glass substrates. The thin films were found be to hydrophilic and
oleophilic with average and r.m.s surface roughness that is higher than that of the glass substrate.
These properties are useful in terms of possible applications of the material as an antimicrobial and an
antibiofouling surface. Crack pattern formations were seen from the SEM micrographs and these
crack patterns negatively affected the adhesion performance of the TiO2 thin films on the glass
substrates. However, the crack pattern formations can increase the photocatalytic activity of the
material due the increase in the exposed surface area and the size and structure of the photocatalyst.
Fig. 1: SEM image of the plasma-treated TiO2 thin film showing crack pattern formations.
[1]. A. Kumar, G. Pandey, Mater. Sci. Eng. Inter. J. 2017, 1, 00018.

[2]. L. Matejovà, et al., J. Nanosci. Nanotechnol. 2016, 16, 504-514.
[3]. E. Boonen, A. Beeldens, Coating. 2014, 4, 553-573.
[4]. J.A.P. Nuñez, H.S. Salapare III, M.M.S. Villamayor, L.D.S. Valladares, H.J. Ramos, Protect. Metal.
Phys. Chem. Surface. 2017, 53, 1022-1027.
349
NANOTECH-P40

Cupric oxide (CuO) nanoparticle formation from plasma surface
modification of copper

,1 2 2 2
Hernando S. SALAPARE III* , Léo CLERC , Pierre BASSOLEIL , Mickaël GALERNE , Valentin
2 2 1 1 1
CARLAC , Quentin OLLAGNIER , Arnaud ZENERINO , Sonia AMIGONI , Frédéric GUITTARD

1
Université Nice Côte d’Azur, NICE Lab, IMREDD, Nice 06200, France;
2
Université Nice – Sophia Antipolis, NICE Learning, IMREDD, Nice 06200, France
*[email protected]

Keywords: plasma processing, copper, cupric oxide, nanoparticles, surface modification
Taking inspiration from the hydrophilic and superhydrophilic properties observed from the
nanostructures present on the leaves of plants such as Alocasia odora, Calathea zebrina, and Ruelia
devosiana, we were able to synthesized cupric oxide (CuO) nanoparticles from direct plasma surface
modification of copper that exhibits hydrophilic properties. The copper sheets were exposed to oxygen
plasma produced from the P300 plasma device (Alliance Concept, France) at varying power (100W to
300 W) and constant irradiation time of 5-min. The untreated and plasma-treated copper sheets were
characterized by contact angle measurements, scanning electron microscopy (SEM), energy
dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR), and optical
profilometry to determine that changes in the surface of the material before and after plasma
treatment. Results showed the treated copper sheets exhibited enhanced hydrophilic properties as
compared to the untreated samples. The decrease in the measured water contact angles after plasma
treatment can be attributed to the formation of CuO nanoparticles on the surface of the material, as
confirmed by the EDS and FTIR results, and the increase in the average and r.m.s. surface
roughness. The presence of CuO nanoparticles on the surface is very useful in terms of the material’s
possible applications such as (1) in antimicrobial and anti-biofouling tubings; (2) to improve heat
dissipation devices such as microfluidic cooling systems and heat pipes; and (3) an additional
protection to the copper substrate from further corrosion.
(a) (b)
Fig. 1: SEM image of (a) untreated copper and (b) plasma-treated copper showing cupric oxide
(CuO) nanoparticles on the surface.
[1]. K. Koch, W. Barthlott, Phil. Trans. R. Soc. A 2009, 367, 1487-1509.

[2]. S.B. Adeloju, Y.Y. Duan, Br. Corros. J. 1994, 29, 315.
[3]. H.S. Salapare III, B.A.T. Suarez, H.S.O. Cosiñero, M.Y. Bacaoco, H.J. Ramos, Mater. Sci. Eng. C
2015, 46, 270-275.
[4]. U. Nerle, M.K. Rabinal, IOSR J. Appl. Phys. 2013, 5, 01-07.
[5]. B.T. McDonald, T. Cui, J. Colloid Inter. Sci. 2011, 354, 1-6.
350
SMARTTECH-P01

Lignin/polypyrrole biocomposites and their carbonized analogues
as materials for supercapacitors

Patrycja Bober,* Ivana Šeděnková, Udit Acharya, Jiří Pfleger, Sergey K. Filippov, Jaroslav Stejskal

Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6,
Czech Republic

Keywords: polypyrrole, lignin, composites, carbonization, double-carbon, electrochemical properties
Lignin/polypyrrole composites were prepared by a single-step coating of water-insoluble Kraft lignin

with polypyrrole. The polymerization of pyrrole was performed with and without the presence of methyl
orange, leading to the formation of polypyrrole films of two different morphologies, globular and
nanotubular, respectively, on the Kraft lignin surface. Such composites were converted to double-
carbon composites enriched in nitrogen atoms by pyrolysis in inert atmosphere at 650 ºC. The
carbonization process was followed by thermogravimetric analysis and confirmed by Raman
spectroscopy. The properties of all composites were investigated by FTIR spectroscopy, XPS, EPR,
SEM, specific surface area and electrical conductivity measurements. Electrochemical properties were
analyzed in terms of their capacitive behavior mainly in acidic solutions (Fig. 1), but also in neutral and
alkaline media.
0.10
3
0.05
2
0.00 1
I / mA
-0.05
-0.10
1 - Kraft lignin
2 - Lignin/PPy globular/carbonized
-0.15 3 - Lignin/PPy nanotubular/carbonized
-0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
E vs. SCE
Fig. 1: Cyclic voltammograms of Kraft lignin and of composites after carbonization

–1
in 0.5 M H2SO4 at sweep rate of 20 mV s
Acknowledgment
The authors wish to thank the Czech Science Foundation (17-05095S) for the financial support. The
coordination within the Programme for Funding Multilateral Scientific and Technological Cooperation
Projects in the Danube Region 2017–2018 (DS-2016-0027) was financially supported by the Ministry
of Education, Youth and Sports of the Czech Republic (8X17027); the assistance of the project
participants is also gratefully acknowledged.
351
SMARTTECH-P02

Local scale characterizations of smart interface in thin coatings

1 1
Moslem ALAAEDDINE, Pascal CARRIERE*,
1
Laboratoire MAPIEM (MAtériaux, Polymères, Interfaces et Environnement Marin), Université de
Toulon, Toulon, France;
Keywords: thermosets thin films, interfacial functionalization, smart coating, microthermal analysis
Healable polymers and composites materials offer the ability to prolong the functional lifetime of their
resulting structures and coatings. Those materials undergo a thermomechanical healing to an applied
strimulis. In order to achieve the mechanical strength required for many structural applications or
protective coatings, highly cross-linked polymeric materials are necessary. These resulting materials
tend to be brittle and more prone to develop cracks through normal usage, ultimately failing, especially
in the interphase region. In this study, smart interface should be able to achieve healing, via reversible
bonds present at the interface of the substrate and the coating.
Diels-Alder reactions have been used to self-healing network and composite panels. It has been
shown that 60% or fracture toughness is recovered. In the case of composite, Diels-Alder monomers
between fiber reinforcements and resin including Diels-Alders reversible bonds, delamination was
thermally remended and strain energy recovery up to 90% [1].
This study focus on the ability to quantify the evolution of thermomechanical properties (Young
Modulus, glass transition temperature) of reversible chemical bonds according to Diels-Alder and
retro-Diels-Alder bonds. Here, we strictly modify the substrate surface using furan and maleimide
molecules and deposit on top an epoxy-amine resin [2]. Nanothermal analysis and Peakforce
Quantitative NanoMechanical using AFM allow us to obtain thermomechanical properties [3] of this
smart interphase. Correlation with Dynamical Mechanical Analysis afford us to evaluate the coating
self-healing properties.
[1]. J. S. Park, T. Darlington, A. F. Starr, K. Takahashi,J. Riendeau and H. T. Hahn, Compos. Sci.
Technol. 2010, 70, 2154–2159.
[2]. P. Carriere, S. Onard, S. Mallarino Surface and Interface Analysis, 2009, 41, 858–864
[3]. S. Onard, I. Martin, A. Crespy, JF Chailan, P. Carriere, Macromolecules, 2011, 44, 3485–3493
352
SMARTTECH-P04

Novel 1’,3,3’,4-Tetrahydrospiro[chromene-2,2’-indole] Based Azo
Dyes for Naked Eye Detection of Cyanide Ion

1 2 2 2
Miglė DAGILIENĖ, Giedrė MARKUCKAITĖ, Sonata KRIKŠTOLAITYTĖ, Vytas MARTYNAITIS,
,1,2
Algirdas ŠAČKUS*

1
Institute of Synthetic Chemistry, Kaunas University of Technology, Kaunas, Lithuania;
2
Department of Organic Chemistry, Kaunas University of Technology, Kaunas, Lithuania

Keywords: chemosensor, cyanide, spiro[chromene-2,2’-indole], azo dyes
-
The cyanide ion (CN ) is a highly toxic chemical even at low concentrations. In order to control the
presence of cyanide in food, feedstock, drinking water, and the environment, numerous studies have
focused on the development of methods for its detection, including the use of chemosensors in which
a change in color is monitored [1]. We have recently developed a new class of chemosensors based
on the 6-nitro-1',3,3',4-tetrahydrospiro[chromene-2,2 '-indole] ring system, which detects cyanide with
high specificity [2,3]. In the present work new derivatives of 1',3,3',4-tetrahydrospiro[chromene-2,2'-
indole] 1a-f that possess a nitrophenyldiazenyl substituent on the chromene part of the molecule, were
synthesized and their potential application for the detection of cyanide ion was evaluated. These
chemosensors show a distinct color change when treated with cyanide in acetonitrile solution buffered
with sodium phosphate, and this procedure is not affected by the presence of other common anions.
The novel chemosensors exhibit high sensitivity to low concentrations of cyanide. The mechanism for
detection is rationalized by the nucleophilic substitution of the phenolic oxygen atom at the indoline C-
2 atom of 1a-f by the cyanide anion to form a stable indolylnitrile adducts 2a-f and generate the
colored 4-(4-nitrophenyldiazenyl)phenolate chromophore (Fig. 1)
Fig. 1: Detection of cyanide ion by 1’,3,3’,4-tetrahydrospiro[chromene-2,2’-indole] based azo

dyes.
Structures of the newly synthesized compounds were assigned using standard NMR spectroscopy
techniques and HRMS.
[1]. D. Udhayakumari, Sens. Actuators, B 2018, 259, 20122-20157.

[2]. M. Dagilienė, V. Martynaitis, V. Kriščiūnienė, S. Krikštolaitytė, A. Šačkus, ChemistryOpen 2015, 4,
363-369.
[3]. G. Ragaitė, M. Dagilienė, S. Krikštolaitytė, V. Martynaitis, A. Šačkus, J. Fluorine Chem. 2016, 182,
34-40.
353
SMARTTECH-P05

Hybrid Material of Bacterial Cellulose Nanocrystals
Based Surface-Loaded Silver Nanoparticles and
Alginate-Molybdenum Trioxide Nanoparticles Film with
Hydrogen Sulfide Gas Sensor Ability

1 1
Pongpat SUKHAVATTANAKUL and Hathaikarn MANUSPIYA*,

1
The Petroleum and Petrochemical College,
Chulalongkorn University, Bangkok, Thailand
Keywords: Bacterial cellulose nanocrystals; hydrogen sulfide gas sensor; molybdenum trioxide
nanoparticles; silver nanoparticles; sodium alginate
Nanocrystalline materials prepared from bacterial cellulose (BC) are considered as “fascinating green
nanomaterials” characterized by their renewable nature, environmentally friendly biological materials,
moldability, and remarkable mechanical properties. BC obtained from Komagataeibacter xylinus
(Gluconacetobacter xylinus) in the form of pellicle with long fibers were acid hydrolyzed (hydrochloric
(HCl) acid and sulfuric (H2SO4) acid) under controlled conditions to obtain bacterial cellulose
nanocrystals (BCNCs), and the resulting H2SO4 acid-hydrolyzed BCNCs were evaluated for their
highest surface area for interaction with metallic nanoparticles with the smallest crystallite size and
nanoparticles size distribution. The hybrid material of BCNCs based surface-loaded silver
nanoparticles (AgNPs) and alginate-molybdenum trioxide nanoparticles (MoO3NPs) film was
developed for hydrogen sulfide (H2S) gas sensor. The MoO3NPs was used as the metal oxide source
that are readily reduced to a colored sub-oxide by atomic hydrogen that produced and received from
the reaction of H2S gas, when activated by a partial loading of a H2S reactive metal. The AgNPs was
used as the H2S reactive metal. The alginate polysaccharide was used as the film matrix characterized
by its anionic polysaccharide, colorless, transparent and BCNCs compatibility. The H2S gas was
produced by a reaction solid ZnS and HCl acid solution, collected in septum-capped glass bottle. The
film samples (20 mm ×20 mm × 0.09 mm) were placed in septum-capped glass bottle under different
H2S gas volume and exposure time-varying. The sensor characteristics were studied as well as its
response with H2S. For demonstration of the hybrid material of BCNCs-AgNPs and alginate-MoO3NPs
film. The H2SO4 acid-hydrolyzed BCNCs-AgNPs were developed via physical adsorption of the AgNPs
on the surface of BCNCs by reducing agent solution and then the freeze-dried H2SO4 acid-hydrolyzed
BCNCs-AgNPs was immersed in the alginate-MoO3NPs solution. Metal part were bonded to the
surface of BCNCs by both in attractive or repulsive electrostatic interactions (ion-dipole) and ionic
bonding by reason of the BCNCs has many hydroxyl and ether bonds, forming the effective reactive
sites to anchor metallic ions on the surface of the BCNCs. The change of oxidation state number and
the reduction mechanism by atomic hydrogen intercalating of MoO3NPs on the hybrid BCNCs-
4+ 5+ 6+
AgNPs/alginate-MoO3NPs film can be Mo(IV)O3(Mo ), Mo(V)O3(Mo ), and Mo(VI)O3 (Mo )
characterized by x-ray photoelectron spectroscopy (XPS) technique.
Schematic Illustration of BCNCs prepared by acid hydrolysis of BC and the hybrid material of
BCNCs-AgNPs/alginate-MoO3NPs prepared by physical adsorption techniques.
354
SMARTTECH-P06

Bioinspired tyrosine photo-crosslinked gels for the enhanced
properties of supramolecular systems

1 2 1
Josipa MATIĆ, Marijana VINKOVIĆ, Zoran DŽOLIĆ*,

1
Laboratory for supramolecular chemistry, Division of Organic Chemistry and Biochemistry, Ruđer
Bošković Institute, Zagreb, Croatia;
2
NMR Centre, Ruđer Bošković Institute, Zagreb, Croatia
Keywords: Tyrosine, Dityrosine, Photo-crosslinking, Ruthenium catalyst, Supramolecular gels
Peptide-based materials employed in supramolecular systems hold the potential for a development of
diverse functional materials, with the application in medicine, cosmetics, bioengineering and many
other.[1] Hydrogels offer significant advantageous features in this regard, such as biocompatibility and
low toxicity, yet their application is often limited due to the poor mechanical properties. Introduction of
covalent bonds in these systems can yield robust and stable structures. This principle is often
employed in biological crosslinking systems. Being a prominent example, dityrosine crosslinking draws
a great deal of attention while it provides outstanding elasticity of the material and intrinsic blue
fluorescence.[2] Dityrosine bonds in nature are found in structural proteins such as elastin and silk,
and in some of very firm biological materials, like elastic protein resilin, found in the cuticle of insects
and arthropods.[3]
In this study, tyrosine-based supramolecular gels have been explored. Gelators are subsequently
2+
transformed into dityrosine analogues by a well-known fast protocol utilizing Ru(bpy)3 -catalyzed
photo-cross-linking, which generates dityrosine adducts within few minutes upon exposure to white
light.[4] The gels are characterized by electron microscopy, CD, UV and NMR spectroscopy. In
addition, dityrosine moiety as a reducing agent has been utilized for the in situ synthesis of gold
nanoparticles.
OH
O O
H H
N N O
O HN n N
H
O n=0-4 O O
Fig. 1: Schematic representation of tyrosine-based gelators
[1]. F. Baneyx, D.T. Schwartz., Curr. Opin. Biotechnol. 2007, 18, 312–317.
[2]. K.-I. Min, D.-H. Kim, H.-J. Lee, L.i Lin, D.-P. Kim, Angew. Chem. Int. Ed., 2017, DOI:
10.1002/anie.201713261.
[3]. K.-I. Min, G. Yun, Y. Jang, K.-R. Kim, Y. H. Ko, H.-S. Jang, Y.-S. Lee, K. Kim, D.-P. Kim, Angew.
Chem. Int. Ed., 2016, 55, 6925–6928.
[4]. Y. Ding, Y. Li, M. Qin, Y. Cao, W. Wang, Langmuir 2013, 29, 13299–13306.
[5]. M. Cametti, Z. Džolić, Chem. Commun., 2014, 50, 8273–8286.
This work has been fully supported by Croatian Science Foundation under the project number IP-
2016-06-5983.
355
SMARTTECH-P07

Halomonas Levan Based Hydrogels

1 1*
Sinem Selvin SELVI, Ebru TOKSOY ONER,

1
Department of Bioengineering, Marmara University, İstanbul, Turkey

Keywords: Hydrogels; levan, Halomonas, polysaccharide
Hydrogels are extremely hydrophilic polymeric networks which can be crosslinked chemically or
physically. Their unique properties such as, soft tissue-like structures, flexibility, high water contents
and high sensitivity make hydrogel a focus of scientific interests for biomedical applications like drug
carrier systems or wound healing materials. Hydrogels show high environmental response with
temperature, pH and can swell and shrink in reversible ways. Different hydrogels with several
polymers are being developed and our research group mainly focused on levan polysaccharide. Levan
is an unusual fructan type-homopolysaccharide that is composed of beta-(2-6)-fructofuranosyl
residues and it is produced by various microorganisms and plants. Levan is biocompatible and film
forming biopolymer and has high adhesive properties with low intrinsic viscosity. Recent studies
focused on unique properties and valuable applications of this underdiscovered polysaccharide in
scientific and industrial areas. Halomonas levan (HL) is produced by halophilic Halomonas smyrnensis
with high yields from sucrose as a substrate. Among microbial levan producers, this extremophilic
production system brings advantages like enabling unsterile and low-cost production. In recent years,
heparin-mimetic material, nano and micro drug carrier systems, adhesive multilayer and blend films,
temperature responsive hydrogels and micro-fibers of HL were studied. Currently, HL and its
chemically modified forms are being synthesized to develop adhesive hydrogels. Unmodified,
hydrolyzed, sulphated and phosphonated derivatives are used to form hydrogels for adhesive wound
healing patches. Natural and chemically modified HL could open new areas in biomaterial studies.
Acknowledgements: This study supported by 116M838 TUBITAK and FEN-C-YLP-120917-0549 BAP

projects.
[1]. J. Ho, C. Walsh, D. Yue, A. Dardik & U. Cheema, Adv. Wound Care 2017, 6, 191-209.
[2]. E. Toksoy Öner, L. Hernández, J. Combie, Biotechnol Adv. 2016, 34, 827-844.
356
SMARTTECH-P08

Layer-by-Layer Modification of Surfaces Using Zwitterionic Block
Copolymer Micelles for Preparation of Anti-adhesive Coatings
a b c a,d,*
Sinem ULUSAN , Vural BUTUN , Sreeparna BANERJEE and Irem EREL-GOKTEPE
a
Department of Chemistry, Middle East Technical University, 06800, Cankaya, Ankara, Turkey
b
Department of Chemistry, Eskisehir Osmangazi University, 26480 Eskisehir, Turkey
c
Department of Biological Sciences, Middle East Technical University, 06800, Cankaya, Ankara,
Turkey
d
Center of Excellence in Biomaterials and Tissue Engineering, Middle East Technical University,
06800, Ankara, TURKEY
Keywords: anti-adhesiveness, layer-by-layer coating, zwitterionic micelles
Polymers that can respond to a certain stimuli are called as stimuli responsive polymers and they are
widely used in many areas such as, targeting and controlled drug release studies for treatment of
cancer, infectious diseases as well as for coating implants. Polyzwitterions are important class of
polymers because they show anti-adhesive behaviour against adsorption of proteins, platelet and
bacteria. In this study, poly[3-dimethyl (methacryloyloxyethyl) ammonium propane sulfonate-b-2-
(diisopropylamino)ethyl methacrylate] (bPDMA-b-PDPA) was used to obtain block copolymer micelles
with zwitterionic corona and pH-responsive cores through pH-induced self-assembly in aqueous
solution. These zwitterionic micelles were then used for modification of surfaces through layer-by-layer
(LbL) deposition method using different polyanions such as hyaluronic acid (HA), poly(sodium 4-
styrenesulfonate) (PSS) and Tannic acid (TA). Anti-adhesive behaviour of these three different
multilayer coated surfaces against protein adsorption and bacteria, i.e. E.coli and S.aureus were
assessed and contrasted. Moreover, we showed that by taking advantage of the hydrophobic micellar
cores, an anti-inflammatory drug, Curcumin could be loaded into the micellar cores and released at
slightly acidic pH. Anti-adhesive behaviour of the surfaces against protein and bacteria, together with
the pH-dependent release of curcumin from the surface make such LbL coatings promising for coating
implants.
Acknowledgement: S.U. acknowledges the financial support of Center of Excellence in Biomaterials

and Tissue Engineering, Middle East Technical University for the conference.
[1] P. Yusan, I. Tuncel, V. Bütün, A.L. Demirel, I. Erel-Goktepe, PH-responsive layer-by-layer films of
zwitterionic block copolymer micelles, Polym. Chem. 5 ,2014, 3777–3787.
[2] B. Onat, V. Bütün, S. Banerjee, I. Erel-Goktepe, Bacterial anti-adhesive and pH-induced
antibacterial agent releasing ultra-thin films of zwitterionic copolymer micelles, Acta Biomaterialia, 40
,2016, 293–309.
357
SMARTTECH-P09

Removal of directs dyes from textile wastewater
by coton fiber waste
1 2*
Mohamed –zine MESSAOUD-BOUREGHDA ,Nacera. OUSLIMANI
1:
Laboratory of food technology², M’hamed Bougara University ,Boumerdes 35000. Algeria,
[email protected] Tel: 0540346828 (corresponding author)
2
Laboratory of polymer materials, M’hamed Bougara University ,Boumerdes 35000. Algeria,
[email protected],Tel:0559770137
Keywords: Cotton directs dyes, adsorption reuse wastewater, textile, kinetics equilibrium, kinetics
thermodynamic
Environnent protection is a précondition for sustained growth and a better quality of life for all peoples
on earth. Aqueous industrial effluents are the main sources of pollution. Among the compounds of
these effluents, dyes are particularly resistant to discoloration by conventional methods, and
discharges present many problems that must be supported
Synthetic dyes are used in industrials sectors; especially in the textile, industry. there is a certain
selectivity of raw cotton fibers for the different types of dyes, depending on the chemical structure of
the dyes. We note that this affinity is very high for direct dyes and decreases for reactive dyes and
pigment dyes
This study focuses on the elimination of direct dyes wastewater from the textile industry, by their
adsorption on waste very adsorbent cotton fibers,the removal rate greater than 75% for the three
types of direct dyes used, a mathematical of the adsorption isotherms of and their kinetics of
adsorption was made and shows the mathematical models of adsorption curves, it shows that the
direct dye red216 adsorbs very easily and the saturation is obtained after 30 mn and the direct
yellow4 dye s' adsorbs regularly and reaches the saturation 100 mm, which shows that the adsorption
is done according to the spatial structure of the dye and the porosity of the cotton this technique is
interesting, it allows to recover adsorbate cotton as raw material for several uses and at very low cost
358
SMARTTECH-P10

Amphiphilic covalent hybrid hydrogels from PEG/PLA-based
thermoreversible networks.
1 1,2 2 1
Nathalie MIGNARD , Sirine MHIRI , Majdi ABID , Mohamed TAHA
1
Univ Lyon, UJM-Saint Etienne, CNRS, IMP UMR 5223, R-42023, Saint Etienne, France
2
Laboratoire de Chimie Appliquée HCGP, Faculté des Sciences, Université de Sfax, 3000 Sfax,
Tunisie
Polylactic acid (PLA) is an FDA approved polyester with a wide range of applications primarily in the
biomedical field attributed to its unique properties from being hydrophobic, biobased, biocompatible
and bioassimilable material [1]. In addition, the hydrophilic Polyethylene glycol (PEG) is also an FDA
approved material and used in the biomedical field. However, being a non-biodegradable polymer, the
biomedical applications of PEG were significantly reduced. To enhance its utilization in regenerative
medicine and tissue engineering, a combined polymeric blend of PLA/PEG can be formulated to
design a scaffold hydrogel with a hydrophilic/hydrophobic balance [2]. In this study we have
developed a green technology for the syntheses of thermosensitive hydrogels from PEG/PLA by
means of reactive extrusion (REX).
In this research, the Diels-Alder reaction was used as a well-enriched thermoreversible chemistry [3].
It is a chemical reaction between the conjugate diene and dienophile. Herein, the PLA was grafted
with the dienophile, whereas the PEG was grafted by the diene. The designed polymers were allowed
then to react with each other via Diels-Alder chemistry in a solvent free process (REX) and gave with
success the expected hybrid networks. The hydrogels were formed by immersion in water. Dried
networks were studied by their mechanical and thermal properties whereas hydrogels were
characterized by their swelling by water diffusion, their hydrolytic degradation and biodegradation by
aerobic microorganisms. Results revealed that the designed gels present biodegradability and
elasticity according to their composition and that lyophilisation gives porous structures (Fig.1).
30µm

(a) (b)
Fig. 1: PEG/PLA hydrogels (a) non lyophilized (b) lyophilized
[1]. J. K. Oh. Soft. Matter. 2011, 7, 5096-5108.

[2]. Z. Li, B. H. Tan, T. Lin, C. He. Prog. Polym. Sci. 2016, 72, 22-72.
[3]. S.MHIRI, N.MIGNARD, M.ABID, F.PROCHAZKA, JC.MAJESTE, M.TAHA, Eur.Polym.J., 2017,
88, 292-310.
359
SMARTTECH-P11

DNA Supercoiling Inspired Fiber Conductors

Wonkyeong SON, and Changsoon CHOI*

Smart Textile Convergence Research Group, DGIST, Daegu, Korea

Keywords: DNA, Supercoil, Superelastic, Fiber, Conductor
Fiber shaped, wearable, and highly stretchable conductors with stretch-invariant electrical property are
needed for diverse applications. Here we report the DNA supercoil structure (coiling of a coil) inspired,
conducting fibers fabricated by inserting giant twists into the carbon nanotube sheath wrapped
spandex core fibers. Resulting fibers show macroscopically ordered and compact structure along fiber
direction, providing reversible structural strain up to 1000%. On the microscopic scale, buckled CNTs
formed on the fiber surface effectively absorb the tensile strain generated during deformations,
providing an essentially constant electrical conductance. Moreover, present DNA inspired,
macroscopically supercoiled, and microscopically buckled fibers show superelastic performance that
less than 5% resistance increase is observed for a 1000% stretch when over-coated by passivation
layer.

Fig. 1: (A) Schematic illustration of DNA structure inspired CNT/spandex fiber (inset shows
supercoil structured DNA). SEM images for (B) microscopic scaled buckles formed on the
surface of relaxed CNT@spandex fiber after pre-strain relaxation (scale bar = 15 µm), and (C)
its magnification (scale bar = 5 µm). SEM images for (D) noncoiled, (E) first coiled, and (F)
supercoiled CNT@spandex fibers (scale bars for D, E, and F are 200 µm). (G) Stress-strain
curve for supercoiled CNT@spandex fiber (inset shows SS curve comparison before and after
1000% strain-relaxation cycle). (H) Normalized resistance change versus strain change. Inset
shows ΔR/R0 versus number of cyclically applied 1000% strain.
360
SMARTTECH-P12

Design and Synthesis of Novel pH-sensitive Fluorescence Polymer
Structures For Biomedical Applications

1 1 1 1
Selen ISMAIL*, Rayna BRYASKOVA, Nikolay GEORGIEV, Vladimir BOJINOV
* corresponding author: [email protected]

1
University of Chemical Technology and Metallurgy ,1756 Sofia, Bulgaria;

Keywords: pH-sensitive block copolymer, nanoparticles carriers, controlled radical polymerization.
Abstract: pH-sensitive polymers can be defined as polyelectrolytes that include in their structure weak
acidic or basic groups that either accept or release protons in response to a change in the
environmental pH [1]. This work summarizes the design, synthesis and potential applications of pH-
responsive fluorescent copolymers in the biomedical field. This was achieved using atom transfer
radical polymerization (ATRP) of tert-butyl acrylate using a CuBr/N,N,N’,N”N”-
pentamethyldiethylenetriamine catalyst system in conjunction with an alkyl bromide as the initiator.
Well-defined macroinitiators based on poly (tert.butyl acrylate) with narrow molecular weight
distributions were obtained by the addition of an appropriate solvent system in order to create a
homogeneous catalytic system. The addition of second monomer in order to create well-defined block
copolymers, followed by chemical modification of the block copolymers and functionalization with an
appropriate fluorescent compound determined the potential applications of these systems in the field
of biomedicine as biosensors, controlled drug delivery systems and so on.[1-2]
[1]. F. REYES-ORTEGA, Smart Polymers and their Applications Soc. 2014,

DOI:10.1533/9780857097026.1.45.
[2]. Sheng Dai, Palaniswamy Ravi and Kam Chiu Tam, The Royal Society of Chemistry Soc. 2008, 4,
435–449.
361
SMARTTECH-P13

Double-oriented micrometric surface texturing: a way to antifogging
through filmwise condensation

1* 1 2 1
Stéphane VALETTE, Nicolas PIONNIER, Solmaz BORROMANDI-BARATI, Elise CONTRAIRES,
1
Stéphane BENAYOUN,

1
Univ. de Lyon, Ecole Centrale de Lyon, Laboratoire de Tribologie et Dynamique des Systèmes,
LTDS, UMR CNRS 5513, 36 avenue Guy de Collongue, 69134 Ecully cedex, France;
2
Ecole des Mines de Saint-Etienne, 156 Cours Fauriel, 42000 Saint-Etienne, France

Keywords: Surface texturing, multiscale topography, condensation, filmwise, droplets, wettability,
polycarbonate, numerical modeling
Formation of dew on surfaces is of first interest in many applications. For example, dropwise
condensation may be attended for heat transfer application to enhance the thermal exchanges
between droplets and the substrate of condensation [1]. In addition, filmwise condensation may be
researched in antifogging applications to avoid optical modifications of transparent surfaces (sport
applications, automotive and aeronautics windshields) [2]. Both approaches need to understand the
mechanisms of the formation of water condensation on surfaces.
A recently developed dew tracking setup allowing the monitoring of breath figures of water
droplets onto transparent surfaces is used [3]. The evolution of the number of droplets and the droplet
growth rate are studied according to the relative humidity. By applying low relative humidity levels and
sub-cooling, it was possible to observe the droplets appearance and the different step transitions
during the condensation process. The impact of a microscale surface texturing on the breath figures
dynamics is studied (Figure 1). It is shown that micrometric dimples textured on the surface of
transparent polycarbonate may modify the condensation process from dropwise to filmwise
condensation. A double-oriented micrometric pattern is proposed to obtain a quasi-filmwise
condensation on textured surfaces.
In parallel to experimental results, a numerical approach is developed. This approach allows
modeling water condensation on sub-cooled surfaces and a specifically numerical treatment is
developed to take into account the pattern figures in the image analysis.

Fig. 1: Smooth (a) and textured (b) water condensation on polycarbonate surface
2
(Image size: 2,7x3,3 mm )

[1] J.W. Rose, E.J. Le Fevre, A theory of heat transfer by dropwise condensation, Proceedings of 3rd
International Heat Transfer, 1966, pp. 362–375.
[2] D. Beysens, Dew nucleation and growth, C. R. Phys., 7, 2006, pp. 1082-1100.
[3] N. Pionnier, S. Boroomandi Barati, E. Contraires, R. Berger, M. Guibert, S. Benayoun and S.
Valette, Design of an environment controlled dew tracking setup to emphasize the role of the relative
humidity on breath figure dynamics, EPJ Techniques and Instrumentation, 5:2 (2018)
[4] S. Boroomandi Barati, N. Pionnier, J.-C. Pinoli, S. Valette and Y. Gavet, Investigation spatial
distribution of droplets and the percentage of surface coverage during dropwise condensation, Int.
Jour. of Th. Sc. 124 356-365 (2018)
362
SMARTTECH-P14

Surface Modification of 3D-Printed PBAT by Ultraviolet Radiation

* 1 1 1 2
Guilherme K. BELMONTE , Felipe C. MENEZES, Andressa PEYROT, Douglas A. SIMON,
3 1
Gabriela R. CHAGAS, Daniel E. WEIBEL,

1
Universidade Federal do Rio Grande do Sul, Porto Alegre, Brazil;
2
Instituto Federal de Educação, Ciência e Tecnologia do Rio Grande do Sul, Farroupilha, Brazil
3
Université de Toulon, Toulon, France
* [email protected]
Keywords: 3D printing, PBAT, UV radiation, XPS.
Biocompatibility still represents a major challenge in the development of new biomaterials. The
uses of different materials in medical devices, such as polymers, ceramics, composites and metals, in
special titanium and stainless steel, are well known. Polymeric devices are widely applied as scaffold
in the biomedical field. Natural polymers are usually biocompatible and biodegradable, however,
because they are derived from natural sources they can contain impurities that could impact
negatively on cell growth. In addition, natural polymers have poor mechanical and thermal properties.
On the contrary, synthetic polymers show good mechanical and thermal stability that confers excellent
processability. Some synthetic, such as polyesters are biodegradable, characteristic that provide their
use as temporary scaffolds. However, most of the synthetic polymers show hydrophobic properties on
the surface that difficult the adsorption process and spread of the cells. The surface modification of
synthetic polymers appears as an alternative to induce cellular adhesion and proliferation without
compromise the bulk structure. The use of electromagnetic radiation in the surface of polymers is
advantageous, since it is possible to work according to the wavelength selected, in addition to lower
operating costs when compared to other techniques, such as plasma, ion bean, high-energy electrons,
ions and neutrons. The surface chemistry properties in three-dimensional polymeric scaffolds
produced by 3D printing technology has been a focus of research in the last years. Although the 3D
printing technology had initiated in the early 1980s by Charles Hull to improve methods in prototyping,
nowadays 3D printing has many potential industrial applications. For example, automotive, aerospace,
medical, consumer goods, military, food industry, in fashion and those applications are considered by
many as a new industrial revolution [1], [2]. This technology when applied to develop biomedical
devices shows versatility and applicability, high customization and a high degree of control of the final
product. However 3D printing is still a slow process for some applications. In the present work, the
photo-oxidation of 3D printed devices of polybutylene adipate-co-terephthalate (PBAT) by ultraviolet
radiation in the presence of oxygen was studied. The prototypes were characterized by X-Ray
photoelectron spectroscopy (XPS), FTIR-ATR, Water Contact Angle (WCA) and Scanning Electron
Microscopy (SEM). The PBAT is a synthetic biodegradable polyester and has good mechanical and
thermal properties. The pellets of PBAT were
extruded to produce filaments of appropriated
diameter (1.5 mm) to use in a commercial 3D printer
Cliever CL1 Black Edition. The prototypes were
irradiated in different times under a flux of oxidative
atmosphere. The results show that the hydrophilicity
is controlled by the UV exposure time and its
increases with the increase of irradiation time. Also it
was observed an anisotropic behavior of the
wettability, in which the drop of water spread through
the patters lines formed in the 3D printing process.
Surface chemical information obtained from FTIR-
ATR and XPS (Fig. 1) showed an increase of polar
groups (COO and C-OH) and a new typical signal of
C=O appears. Cytotoxicity tests are underway. Figure 1. C 1s HR-XPS spectra of the
3D printed PBAT in different UV
[1] B. Berman. Bus. Horiz. 2012 vol. 55, 2, 155–162. irradiations times.
[2] B. C. Gross, J. L. Erkal, S. Y. Lockwood, C.
Chen, and D. M. Spence. Anal. Chem. 2014 vol.
86, 7, 3240–3253.
363
SMARTTECH-P15

Bioinspired hairy surfaces

Stefan MÜLLERS, Jürgen RÜHE,
IMTEK, Albert-Ludwigs Universität Freiburg, Germany

E-mail: [email protected]
Everywhere in our natural environment, we can find various types of hairy surfaces. Some make
surfaces water repellent as on plant surfaces [1], others ensure the strong adhesion of gecko feet on
surfaces [2] or act as insulation layer against the cold as animal fur [3].
The fabrication of nano-/micro- polymer hairs can be conducted by using conventional methods such
as lithography [4] or microreplication [1]. These techniques are often limited to rather small sample
areas and low aspect ratios.
We developed a template assisted method (Figure 1) which represents a simple and fast way to
produce high aspect ratio polymer hairs (up to >100) with less sample size limitations. In our process
we use different microporous templates for either microreplication and/or nanodrawing. The aspect
ratio of the microstructure depends on fabrication parameters such as molding- / demolding-
temperature, molding time, pressure or pore size. Our current work concentrates on the conditions
needed to accomplish nanodrawing and high aspect ratio structures. This process requires the
delicate balance between the frictional force inside the pores of the template during the demolding
step and the yield force of the polymer material. A theoretical model considering these two parameters
will be presented. The calculations fit well with our experimental results using HDPE (high density
polyethylene) as substrate with a PC (polycarbonate) template (pore diameter 0.2 µm – 10 µm).
Furthermore, our research shows that there are drastic changes in the wetting properties of the used
polyethylene surface. The microstructured surface can be rendered super hydrophobic by this
approach.
Figure 1: Membrane assisted method for generating artificial bioinspired hairy surfaces.
References
[1] S. Hsu, K. Woan, W. Sigmund, Materials Science & Engineering R, 2011, 72(10), 189–201.
[2] D. Y. Lee, D. H. Lee, S. G. Lee, K. Cho, Soft Matter, 2012 8, 4905.
[3] A. Nasto, M. Regli, P. Brun, C. Clanet, A. E. Hosoi, Phys. Rev. Fluids, 2016, 1, 33905.
[4] F. Chen, ACS Appl. Mater. Interfaces, 2013, 5, 6777−6792.

364
SMARTTECH-P16

Synthesis and characterization of molecularly imprinted polymers
for solid phase extraction of quercetin

1 1 2 3
Pinar Cakir Hatir , Batuhan Balta , Elif Cepni Yuzbasioglu , Nazende Gunday Tureli

1
Istanbul Arel University, İstanbul, Turkey
2
Ebittek Biyoteknoloji Ar-Ge Tic. Ltd. Şti., İstanbul, Turkey
3
MJR PharmJet GmbH, Überherrn, Germany

Keywords: Molecularly imprinted polymers, solid phase extraction, quercetin, caper.

Molecularly imprinted polymers (MIPs) are tailor-made materials with specific and selective
molecular recognition properties, that at the same time have a higher stability, lower cost and better
availability compared to biomacromolecules [1,2]. Due to the specific recognition characteristics, MIP
based biomimetic systems can be successfully employed for the applications in sensing, catalysis,
chromatography, solid phase extraction and drug delivery. Quercetin, one of the bioactive flavonoids,
has pharmaceutical activities like antioxidant, anti-inflammatory, anticancer actions and it is found in
many fruits, vegetables, leaves and grains such as caper, apple, strawberry, tea, and hazelnut [3]. The
caper (Capparis spinosa), which has been used since ancient times, is found in Mediterranean
especially in Turkey. The goal of the study is to isolate quercetin from the caper. To achieve this goal,
MIPs were synthesized for solid phase extraction of quercetin. Before the synthesis, intermolecular
interactions between the functional monomers and quercetin were investigated using FTIR and UV/Vis
spectroscopy. Additionally, to optimize the synthesis procedure, the design of experiments was
applied [4]. MIPs were synthesized with various synthesis conditions determined by the design of
experiments, and their recognition characteristics were investigated.
Fig. 1: Schematic representation of quercetin extraction.
[1]. K. Haupt, K. Mosbach, Chem. Rev. 2000, 100 (7), 2495- 2504.
[2]. P. Çakir, A. Cutivet, M. Resmini, B.T.S Bui, K. Haupt, Adv. Mater. 2013, 25(7), 1048- 1051.
[3]. M. Curcio, G. Cirillo, O.I. Parisi, F. Iemma, N. Picci, F. Puoci, J. Funct. Biomater. 2012, 3 (2),
269-282.
[4]. C. Rossi, K. Haupt, Anal. Bioanal. Chem. 2007, 389 (2), 455- 460.
365
SMARTTECH-P17

Polypyrene films and their potential applications:
superhydrophobic, fluorescent, anti-bacterial and pH-sensitive
coatings

1,2 1 1
Gabriela RAMOS CHAGAS, Thierry DARMANIN, Frédéric GUITTARD *

1
Université Côte d’Azur, NICE Lab, IMREDD, 06200 Nice, France
2
Université de Toulon, MAPIEM, CS 60584 -83041 Toulon, France
*[email protected]
Bionspired materials with superhydrophobic properties are highly desirable for many potential
applications including anti-bacterial or anti-corrosion coatings, oil/water separation membranes, water
transport and harvesting or for optical sensors. Electropolymerization is a very versatile method that
can be used to control the surface hydrophobicity and water adhesion and to produce tunable
nanostructured materials. Here, we show that by differing the chemical structure of the pyrene
monomer, varied surface morphologies are produced by a direct electropolymerization process.
Indeed, various potential applications were studied (Fig. 1). This work uses an innovative strategy to
show a combination of superhydrophobic and fluorescent properties on polypyrenes surfaces.
Superhydrophobic surfaces with controlled water adhesion (θwater = 159º, hysteresis = 1º) and highly
oleophobic properties (θhexadecane = 98º) were obtained using fluorinated substituents on the pyrene
1
monomer due to the presence of dual-scale particles. Indeed, the polypyrene films presented a
fluorescent properties in the green region. It was showed that the fluorinated polypyrenes present a
great stability concerning about the electrodeposition parameters, showing surfaces with similar
2
wettability and morphologies. Copolymers of pyrenes were also been polymerized giving surfaces
with switchable wettability. The fluorinated polypyrene was combined with a pyrene monomer with a
pH-sensitive group leading to superhydrophobic and superhydrophilic surfaces depending on the acid-
3
base medium to which they are subjected. Such materials are excellent candidates for separation
membranes. Indeed, a new proposal to measure the water adhesion of sticky and non-sticky surfaces
4
was evaluate using copolymers of pyrenes by the ejection test method. The polypyrenes also have a
potential application to serve as coatings towards to reduce the bacterial adhesion (30-90%) and to
5
the prevention of biofilm formation (90-99%). This study opens new doors to explore this domain
since the control of surface wettability and water adhesion is extremely important for various
applications.

Fig. 1: (a) Superhydrophobic and fluorescent properties, (b) anti-bacterial properties (Staphylococcus
aureus and Pseudomonas aeruginosa as strains), (c) pH-sensitive properties (NaOH and H2SO4 treatment)
and water adhesion control by the ejection test method on the polypyrene surfaces.

(1) Ramos Chagas, G.; Xie, X.; Darmanin, T.; Steenkeste, K.; Gaucher, A.; Prim, D.; Méallet-Renault, R.; Godeau, G.;
Amigoni, S.; Guittard, F. J. Phys. Chem. C 2016, 120, 7077–7087.
(2) Ramos Chagas, G.; Darmanin, T.; Godeau, G.; Amigoni, S.; Guittard, F. J. Fluor. Chem. 2017, 193, 73–81.
(3) Ramos Chagas, G.; Kiryanenko, D.; Godeau, G.; Guittard, F.; Darmanin, T. ChemPhysChem 2017, 18, 3429–3436.
(4) Raufaste, C.; Ramos Chagas, G.; Darmanin, T.; Claudet, C.; Guittard, F.; Celestini, F. Phys. Rev. Lett. 2017, 119,
108001.
(5) Ramos Chagas, G.; Morán Cruz, G.; Giraudon-Colas, G.; Savina, F.; Méallet-Renault, R.; Amigoni, S.; Guittard, F.;
Darmanin, T. Appl. Surf. Sci. 2018, 452, 352–363.
366
ENERGY-P01

The influence of the heating on the nanostructure of the ZnO and

the characterization by spectroscopy (AES, XPS, UPS)
detecting a gas

1 1
Kadda Benmokhtar BENSASSI, Amar CHEBLI

1
University of Science and Technology of Oran (USTO) 1, Oran, Algeria;

Keywords: ZNO; PL; XPS; AES; EELS; UPS; AFM; Spectroscopy; gas detection
Zinc oxide (ZnO) grown on the silicon (Si) substrates by spray pyrolysis, shown Herein; a comparative
study We used several experimental methods that are compatible with each other in order to
ascertain the result in studying the physical characteristics of the surface by the photoluminescence
PL and we use both characterized by XPS (X Rays Photoelectron Spectroscopy); and AES (Auger
Electron Spectroscopy), In addition to UPS (Ultraviolet photoelectron spectroscopy) EELS (Electron
energy loss spectroscopy) and AFM (Atomic force microscopy) Illustration of the picture and We have
also made a comparison between several operations at the same time During each study to several
processors.
We also experimented with detecting some types of gases that interact with ZnO.
367
ENERGY-P02
Electrochemical Oxidation of Biomass for Solar Fuel Production

1 1 1*
Hyeonmyeong OH, Yujin Han, Jungki Ryu

1
, Ulsan, Republic of Korea

Keywords: biomass, electrochemical oxidation, solar fuel, artificial photosynthesis
Solar-to-chemical energy conversion, so-called artificial photosynthesis has received great attentions
to address modern energy and environmental problems as it allows carbon-neutral production and the
use of various chemical compounds, such as hydrogen, CO, and formate. Despite huge efforts made
for decades, it still remains promising but premature for practical implementation due to low efficiency
and stability of photosynthetic devices/materials. This is because of the slow and harsh water
oxidation process, which can act as a rate-determining step for the overall reactions and lower the
stability of photosynthetic devices. To address such problems, here, we report the coupling of
photocatalytic reduction reactions for the synthesis of target chemicals with the electrochemical
oxidation of biomass. By utilizing catalytic redox mediators, electrons were readily extracted from
electrocatalytic oxidation and depolymerization of biomasses for electrochemical and
photoelectrochemical hydrogen production. As a result, we could significantly reduce the oxidation
potential for the extraction of electrons by several hundreds of mV and improve the performance of the
devices in terms of kinetics and stability by employing biomass as a source of electrons instead of
water. The catalytic redox mediators exhibited excellent stability in repeated biomass oxidation. We
believe that the present study can provide insights for design and fabrication of artificial photosynthetic
devices for practical application.
[1]. G. Wang, Y. Deng, J. Yu, L. Zheng, L. Du, H. Song and S. Liao, ACS Appl. Mater. Interfaces
2017, 9, 32168−32178.
[2]. W. Liu, W. Mu, M. Liu, X. Zhang, H. Cai and Y. Deng, Nat. Commun. 2014, 5, 3208.
368
ENERGY-P03
Cathode materials for high-energy lithium electrochemical systems

based on fluorinated wood and lignin
Aleksandr Tsvetnikov, Ludmila Matveenko, Alexander Ustinov, Valeriy Kuriaviy, Denis Opra, Sergey
Sinebryukhov, Sergey Gnedenkov, Valentin Sergienko
Institute of Chemistry Far-East Branch of the Russian Academy of Science, 159, Prospect Stoletiya
*
Vladivostoka, Vladivostok, 690022, Russia
Keywords: cathodic material, wood, hydrolyzed lignin, fluorine, fluoridation of biopolymers.
The creation of compact and powerfull electrical current sources, preferably based on the renewable
raw materials (biopolymers), is an important challenge of modern time. One of the solutions of this
problem is to use the hydrolyzed lignin of wood [1,2] as the cathodes in lithium chemical current
sources (LCCS). This report describes the possibility of using the fluorinated wood and the fluorinated
lignins of different origins as a cathode material for primary lithium chemical current sources. We have
developed the methods of producing fluorinated wood (FW) and fluorinated lignin hydrolysis (FLH) for
cathodes of lithium electrochemical current sources, which allows to increase their energy intensity in
several times and thereby extend the service life of autonomous devices. Fluoridating the hydrolyzed
lignin (HL) with the gaseous fluoride of high purity, diluted in nitrogen, allows increasing the degree of
fluorination up to 40-45 atomic %. The maximum number of fluorine atoms in the composition of lignin
is achieved by gas-phase fluorination of HL using the fluorine generator Generation-80®. One of the
possible ways of interaction between lithium and fluorinated hydrolyzed lignin of buckwheat husk can
be presented as follows:
19nLi + (C9O4F11)n=4nLi2O+ 11nLiF + 9nC
where n is the number of polymer links. The theoretical energy intensity of the cathode material based
on fluorinated lignin of buckwheat husks is 1370 A*h/kg.
According to the data of XPS, carbon atoms in the molecule of fluorinated lignin are bonded with
oxygen and fluorine. The bonding energy of 1s electrons in fluorine, oxygen and carbon atoms allows
to suggest that the fluorination of lignin leads to replacement of hydroxyl groups, hydrogen and partial
rupture of double bonds-C=C-, as a result, the functional groups are formed: >CF2, ≡СF, -OF, >CO, -
CF2-CF2-, >CF-CF<, ≡C-CF. Besides lignin, polysaccharides are present in the wood ; the spectrum
of x-ray photo-electronic spectrometer shows the different ratio of functional groups after fluorination,
as well as the appearance of –CF3 group.
FLH and HL were investigated using the impedance spectroscopy of electrical conductivity, scanning
electron microscopy (SEM) and energy dispersion spectroscopy. According to the SEM data, the sizes
of the particles forming FLH and HL vary in the range from 5 to 30 microns, and the particles
themselves have an extensive network of micro-and macropores on their surfaces. Such porosity and
mesh morphological structure of FHL and HL can greatly contribute to the diffusion of lithium cations in
the cathode volume during the operation of lithium power source. The basic parameters and behavior
of the lithium electrochemical power sources, based on FLH and HL, have been investigated using
two electrolyte systems, namely: 1 М LiBF4 in γ-butyrolacton and 1 М LiClO4 in propylene carbonate
[3].
[1]. Tsvetnikov A.K., Matveenko L.A., Opra D.P., Sinebryukhov S.L., Gnedenkov S.V., Sergienko
V.I. R.F. Patent 2482571, 2013.
[2]. Opra D.P. Gnedenkov S.V., Sinebryukhov S.L., Tsvetnikov A.K., Sergienko V.I. Solid State
Phenomena 2014, 213, 154-159.
[3]. Tsvetnikov A.K., Sokolov A.A., Opra D.P., Matveenko L.A., Sinebryukhov S.L., Gnedenkov
S.V., Sergienko V.I. R.F. Patent № 2597607, 2016.
369
ENERGY-P04
Discounted Cash Flow (DCF) valuation for an assessment of

strategic investments in a hydrogen production and distribution
center
1 2 2
Jonni Guiller Ferreira Madeira* , Angel Ramon Sanchez Delgado , Eluã Ramos Coutinho ,
1 1 1
Elizabeth Mendes de Oliveira , Vanessa de Almeida Guimarães , Marcus Val Springer
1
Group of Nanoscience and environment, Mechanical Engineering Department,Federal Center of
Technological Education of Rio de Janeiro-CEFET/RJ, Areal Street, 522 - Mambucaba Park, Angra
dos Reis - RJ, 23953-030
2
Federal Rural University of Rio de Janeiro-UFRRJ, Road BR 465 - Km 7 - Campus Universitário -
Zona Rural, Seropédica - RJ, 23851-970
Keywords: biohydrogen; discounted cash flow; cassava wastewater; net present value; internal rate of
return.
In Brazil, the use of bioenergy has increased during the last years, due to problems originating from
fossil fuels. Biohydrogen, produced from Cassava processing appears as an alternative fuel to fossil
fuels and also becomes economically competitive, due to the low cost of production and the low
utilization of this residue. A theoretical study using biogas, from cassava wastewater, to hydrogen
production by simulation of steam reforming of methane (SRM) using Hysys. This study approached
from the economic point of view the production and storage of hydrogen, forming a central of
production and distribution of hydrogen. For this analysis, Discounted Cash Flow (DCF) analysis was
used to simulate 18 different scenarios of economic projection, considering the following conditions:
Number of hours of production per day during the year (12, 16 and 24 hours); Investment in initial
working capital (no initial working capital, 6 months and 1 year); Investment in machinery, equipment
and facilities (CAPEX) in year 0 or amortized, every scenarios using a biogas with 97,14%
concentration of CH4. Finally, the most viable scenario were the production systems with 6 months of
initial working capital, with an Internal Rate of Return (IRR) of 22.67% per year (CAPEX in year 0) and
33.16% per year (Amortized CAPEX) both above the IIR (16.75% per year). In relation to Net Present
Value (NPV), using CAPEX in year 0 or amortized, for theses production scenarios are respectively:
US $3.645.204,05 and US $ 3.671.178,23.
Table 1: Investment indicators of projected discounted cash flow simulations
CAPEX carried out in year 0 CAPEX amortized
24h 16h 12h 24h 16h 12h
Payback (years) 3,66 4,61 5,49 2,82 4,74 9,1
Discountedpayback (years) 4,81 6,99 9,44 3,3 6,99 > 10 anos
capital(1 year)
Initial working
IRR(10 years) 25,54% 18,80% 14,31% 36,53% 18,77% 9,56%

MIRR (10 years) 20,46% 17,67% 15,60% 24,93% 17,68% 11,33%
Net Present Value - NPV (10 years) 9.627.521,70 6.648.336,56 5.160.015,79 5.304.598,88 1.943.779,26 837.092,98
NPV–Investiment(CAPEX + Inicial
working capital) 2.584.401,07 503.810,98 -535.595,88 2.610.375,26 148.150,67 -509.621,69
Profitability Index - PI 1,6 1,26 1,06 2,3 1,26 0,73
Payback (years) 2,96 3,94 4,84 1,42 2,48 6,66
capital(6 months)
Discountedpayback (years) 3,58 5,39 7,69 1,49 2,84 9,43

Initial working
IRR (10 years)

MIRR (10 years) 32,21% 22,60% 16,72% 71,70% 41,80% 17,29%
Net Present Value - NPV (10 years) 22,67% 19,20% 16,74% 33,16% 26,13% 17,10%
NPV–Investiment (CAPEX + Inicial
working capital) 9.341.212,86 6.457.519,32 5.016.903,58 5.018.290,05 1.943.779,26 693.980,76
Profitability Index - PI 1,91 1,44 1,17 4,35 2,53 1,2
Payback (years) 2,26 3,26 4,19 ND ND ND
No initialworking
Discountedpayback (years) 2,55 4,08 5,95 ND ND ND

IRR (10 years) 43,05% 28,07% 19,98% Infinite Infinite Infinite
capital
MIRR (10 years) 25,63% 21,09% 18,09% Infinite Infinite Infinite

Net Present Value - NPV (10 years) 9.054.904,02 6.266.702,07 4.873.791,36 4.731.981,21 1.943.779,26 550.868,55
NPV–Investiment(CAPEX + Inicial
working capital) 4.706.007,02 1.917.805,07 524.894,36 4.731.981,21 1.943.779,26 550.868,55
370
ENERGY-P05
Natural thermal-insulation materials composed of renewable

resources: characterization of local date palm fibers (LDPF)
1 1
Said SABIR , N.NADI
1
Research Laboratory of Physical Chemistry of Materials applied Sciences Faculty Ben M'sik,
Morocco
[email protected]
Keywords: Date palm waste; physical and mechanical properties; microstructures; thermal insulation.
This research work is focused on analyzing the potential application of local date palm waste (LDPW)
as an alternative sources of plant-based energy-conserving materials for uses either singly or as a
composite material to prevent heat conduction through walls into or out of interior spaces in the vessel
of refrigerator, cooler and food flask. First, physical and mechanical properties of seven varieties of
local date palm waste from Errachidia oasis in Morocco namely Khalt, Boufeggous, Bu-Slikhen,
Mejhoul, Admou, Khalt Zhar and Tazaout were measured and analyzed. The result showed that
Boufeggous varieties were found to have the most important physico-chemical and mechanical
properties compared with other varieties. Hence scanning electron microscopy (SEM) and energy
dispersive spectroscopy (EDS) analysis of the date palm fibers of Boufeggous varieties were
investigated to characterize the microstructure and the chemical composition of the sample. It was
found that carbon and oxygen were the only consistent compounds in these palm fibers varieties. It
can be also noted that the surface of fibers is irregular and rough with many impurities, cells and
pores. A simultaneous determination of the thermal conductivity was achieved using a periodic
method. The thermal conductivity measured in atmospheric pressure showed that the material
remains with good properties compared with other natural and synthetic insulating materials with a
thermal conductivity value of 0.041 W/m.K, which suggest that the date palm wood of the Boufeggous
varieties is useful for further development and design of natural efficient and safe thermal insulating
materials for people’s daily life.
371
ENERGY-P06
Effect of pH and Oxidant on the First Steps of Polydopamine

Formation: A Thermodynamic Approach

1,2 1,3 1,3 1,2 1,3
Lauri MARTTILA, Mikko SALOMÄKI, Henri KIVELÄ, Tuomo OUVINEN, Jukka LUKKARI *,

1
Department of Chemistry, University of Turku, Turku, Finland;
2
Doctoral Programme in Physical and Chemical Sciences, University of Turku Graduate School
(UTUGS), Turku, Finland;
3
Turku University Centre for Surfaces and Materials (MatSurf), Turku, Finland

Keywords: melanin, polydopamine, effect of pH, effect of oxidant

Polydopamine is a bioinspired material that resembles the biological pigment eumelanin.
Polydopamine is easily synthesized by oxidation of dopamine. Dissolved oxygen oxidizes dopamine to
a suspension of polydopamine particles in basic aqueous solutions and transition metal ions, like
Ce(IV)[1,2] and Fe(III)[1,3], can be used as an oxidant even in anaerobic and mildly acidic conditions.
The first critical step in the dopamine oxidation process is the oxidation of dopamine (DA) to
dopaminesemiquinone (DSQ) and further to dopaminequinone (DQ). It is followed by the second
critical step: the intramolecular cyclization of dopaminequinone to leucodopaminechrome (DAL). We
studied the pH dependence of these critical steps using dissolved oxygen as an oxidant (autoxidation)
and also in the presence of Ce(IV), Fe(III) and Cu(II) ions, both in aerobic and anaerobic conditions.[1]
In acidic conditions, Ce(IV) and Fe(III) ions have good oxidizing power but it decreases with pH.
However, the rate constant of dopaminequinone cyclization increases with pH, and at low pH, the
cyclization of dopaminequinone is the rate-determining step in the dopamine oxidation process. In
spite of this, in mildly acidic conditions, one-electron oxidation of dopamine to dopaminesemiquinone
by Ce(IV) or Fe(III) occurs at reasonable rate also in anaerobic conditions, and the enhancement of
this step explains the overall rate enhancement of the whole oxidation process.
Cu(II) alone cannot oxidize dopamine to polydopamine at reasonable rate in similar acidic
conditions than Ce(IV) and Fe(III) but chloride ions stabilize Cu(I) ions which increases the oxidizing
power of the Cu(II)/Cu(I) redox pair.[1,4]
Scheme 1: Initial steps in autoxidation of dopamine[1]
[1]. M. Salomäki, L. Marttila, H. Kivelä, T. Ouvinen, J. Lukkari, J. Phys. Chem. B 2018, 122, 6314-
6327.
[2]. M. Salomäki, M. Tupala, T. Parviainen, J. Leiro, M. Karonen, J. Lukkari, Langmuir 2016, 32, 4103-
4112.
[3]. W. Linert, E. Herlinger, R. F. Jameson, E. Kienzl, K. Jellinger, M. B. H. Youdim, Biochim. Biophys.
Acta, Mol. Basis Dis. 1996, 1316, 160-168.
[4]. A. N. Pham, T. D. Waite, J. Inorg. Biochem. 2014, 137, 74-84.
372
ENERGY-P07
Techno-economic evaluation of solar fuels production system

using CO2 hydrogenation with a fibrous Cu/Zn/Al/Zr catalyst
1 1 2
Chanhee You , Do Thai Ngan and Jiyong Kim
1
Department of Energy and Chemical Engineering, Incheon National University, Incheon 406-772,
Republic of Korea
2
Innovation center for chemical engineering, Incheon National University, Incheon 406-772, Republic
of Korea
Keywords: Solar fuels, CO2 hydrogenation, methanol production, process design, economic evaluation
One of the promising solutions as a substitute for the conventional energy system is ‘Sunshine to
Petrol’ (S2P) technology framework, which uses solar-thermal energy to convert CO2 and water to
liquid hydrocarbons. In this study, we proposed new advanced S2P systems using the CO2
hydrogenation technology for methanol production, which is coupled with appropriate CO2 capture and
storage (CCS) technology for recycling carbon and sustainably storing solar energy. By developing
rigorous process models using a commercial simulator, we comparatively analyzed the technical and
economic performance of the proposed systems with conventional methanol production routes.
Especially, we involved the CO2 hydrogenation with a fibrous Cu/Zn/Al/Zr catalyst to enhance the
energy efficiency of the systems, thereby reducing the utility consumption compared to the
conventional methanol production route via synthesis gas (syngas). As a result, the proposed systems
shows the improved primary and process energy efficiencies, while the unit production cost (USD/kg
of methanol) got dramatically improved against the conventional route. Furthermore, we discussed
practical strategies to demonstrate the proposed system through examining alternative scenarios to
find the most optimistic conditions.
373
ENERGY-P08
Study of custom-made ceramic membranes for microbial fuel cells

1 1 1,2 1
Jiseon YOU, Lauren WALLIS, John GREENMAN, Ioannis IEROPOULOS*,

1
Bristol BioEnergy Centre, BRL, University of the West of England, Bristol, UK
2
Centre for Research in Biosciences, University of the West of England, Bristol, UK
Keywords: microbial fuel cell (MFC), electricity output, ceramic membrane, combined ceramics
For the practical implementation of microbial fuel cells, reducing system building/maintenance cost as
well as improving the performance such as power generation, wastewater treatment, resource
recovery or sensing, are essential. Use of ceramic membranes in MFCs has been widely reported as
a suitable material with comparable performance to that of selective ion exchange membranes but
with much less cost [1].
In this study, eight different types of ceramic membranes made of three ceramic materials, namely
brown – “engineering brick”, red – terracotta base and white - earthenware and labelled as “B”, “R”
and “W”, respectively, were tested in two different geometries; cylindrical: inner diameter 18 mm,
height 55 mm, thickness 3 mm, and flat sheet: width 50 mm, length 60 mm, thickness 3 mm. As part of
the study, the different ceramic parts were prepared with single ceramic materials (i.e. all brown, red
or white) but also with combinations of materials, whereby two ceramics were integrated together (but
not mixed); this was in order to investigate the MFC performance when ions would be diffusing at
possibly different rates, through the two different materials. The material properties were analysed to
better understand their performance as MFC membranes. Plain carbon fibre veil of 300 mm x 90 mm
for both cylindrical membrane MFC (C-MFC) and flat plate membrane MFC (F-MFC) was used as the
anode electrode. Open-to-air cathodes (50 mm x 40 mm for a C-MFC and 60 mm x 40 mm for an F-
MFC) were prepared by adding hot-pressed activated carbon onto the plain carbon veil. All MFCs
were fed with fresh human urine on a daily basis, collected from healthy donors.
For single component membrane types, white ceramic outperformed the rest by producing ca. 560 µW
(for F-MFC) and 712 µW (for C-MFC). These results were corroborated with water absorption tests,
showing the white ceramic being the most porous of the three, with a water absorption amount (by
weight) of 14.4 % (SD 0.1) followed by 14.1 % (SD 0.0) for red and 12.8 % (SD 0.3) for brown
ceramics. The combined/integrated ceramics, with red terracotta as the main component both with
white and brown added “spots”, produced higher power outputs than the plain red terracotta-based
MFCs, suggesting that this could be a way of improving the functionality of the ceramic ion-exchange
separator. In some cases, especially with the flat sheet white ceramic base with brown “spots (WB),
relatively big gaps were observed, where the two materials met, due to the different degree of
shrinkage during the firing process. This resulted in high rates of anolyte crossover to the cathode,
which made any comparison difficult or invalid.
1000
900
800
700
PMAX (µW)
600
500
F-MFC
400
300 C-MFC
200
100
0
B BW BR R RW RB W WB
Membrane type
Fig. 1: maximum power output of each test
[1] J. Winfield, I. Gajda, J. Greenman, I. Ieropoulos, Bioresour. Technol. 2016, 215, 296-303.
374
2D3D-P01
Towards a better understanding of nature inspired Aquaporin

biomimetic membrane

1, 2 1,3 1,3 1, 2
Hui Xian GAN, Hu ZHOU, Qinsong LIN, Yen Wah TONG*,

1
National University of Singapore, NUS Environmental Research Institute (NERI), Singapore, 117411,
Singapore, [email protected], [email protected]
2
National University of Singapore, Chemical and Biomolecular Engineering, Singapore, 117576,
Singapore, [email protected]
3
National University of Singapore, Department of Biological Sciences, Singapore, 117543, Singapore,
[email protected]

Keywords: Aquaporin, membrane, biomimetic
Since the discovery of Aquaporin protein water channel, numerous works have been done to
demonstrate the application of Aquaporin for developing the next generation membrane. Nonetheless,
the membrane performance achieved to date is still far from the capabilities of Aquaporin in nature. In
this work, method will be presented to accurately quantify the amount of vesicles that are immobilized
on membrane and correlate them with membrane performance. This would provide great insights into
the role of biomimetic Aquaporin vesicles on membrane.
Results and discussion

Validation of inductively coupled plasma mass spectrometry (ICP-MS) quantification method
Various known amount of E.coli lipid was spiked into membrane samples and the phosphorus content
in each sample was measured with ICP-MS to validate it as a viable quantification method. As
expected, the results show that the phosphorus reading vary linearly with the amount of E.coli lipid
spiked.
Correlation between vesicles immobilized and membrane performance
The biomimetic membranes were prepared via interfacial polymerization between m-
phenylenediamine (MPD) and trimesoyl chloride (TMC) according to a previously reported method [1].
Assuming that all vesicles loaded are successfully immobilized onto the membrane, the amount of
lipid vesicles required to fully cover a fixed membrane unit area with a single layer of E.coli vesicles is
2
calculated to be 0.2 ng/cm . In Fig. 1 (a), the amount of vesicles loaded according to calculation and
the amount of vesicles successfully immobilized on the membrane according to ICP-MS
measurements, are presented. The membrane performance of membrane with different amount of
lipid vesicles loaded is shown in Fig. 1 (b).
Fig. 1: 1(a) Vesicles loaded and vesicles successfully immobilized onto membrane. 1(b)
Membrane performance of membranes with different amount of vesicles loaded.
Conclusion
In this work, ICP-MS is demonstrated as a viable method to determine the amount of vesicles
successfully immobilized onto biomimetic membrane. This quantification method can be used to gain
an accurate correlation between the amount of immobilized vesicles and membrane performance. We
anticipate that this would bring about better evaluate the current state of the art and development of
strategies to improve the existing technology.
[1]. Zhao, Y., et al., Synthesis of robust and high-performance aquaporin-based biomimetic
membranes by interfacial polymerization-membrane preparation and RO performance
characterization. Journal of Membrane Science, 2012. 423: p. 422-428.
375
2D3D-P02
Heat-induced reversible stiffening and liquid crystallinity in

cellulose composite hydrogels

1 3 4 5 1,2
Ville HYNNINEN, Sami HIETALA, Jason R McKEE , Lasse MURTOMÄKI , Orlando J ROJAS , Olli
1,2 1,2
IKKALA *, Nonappa *

1
Department of Applied Physics, School of Science, Aalto University, Espoo, Finland
2
Department of Bioproducts and Biosystems, School of Chemical Engineering, Aalto University,
Espoo, Finland
3
Department of Chemistry, University of Helsinki, Helsinki, Finland
4
Betulium Ltd, Espoo, Finland
5
Departments of Chemical & Metallurgical Engineering and Chemistry & Materials Science, School of
Chemical Engineering, Aalto University, Espoo, Finland
Keywords: cellulose nanocrystal, methylcellulose, thermoreversible hydrogel, liquid crystallinity
Composite hydrogels comprising methyl cellulose (MC) polymers and cellulose nanocrystal (CNC)
colloidal rods display upon heating reversible and enhanced mechanical properties and optical
birefringence, indicating thermoreversibly enhanced liquid crystallinity. This is unlike commonly
observed, where materials tend to become softer and the liquid crystalline order becomes reduced
upon heating. The CNC concentration of the hybrid gels was kept below the critical liquid crystallinity
concentration of pure CNC (0 - 3.5 wt %) [1], while fixing the MC concentration at 1.0 wt %. At room
o
temperature (20 C), the storage modulus (G’) of the hybrid gels was enhanced upon increasing CNC
concentration up to 1.5 wt %, where the G’ reached a plateau and the birefringence underwent a
stepwise increase, thus, suggesting a percolative phenomenon. At 60 °C, G´ became an order of
magnitude higher, while the birefringence also appeared systematically more intense. (Figure 1a, b)
o
Isothermal titration calorimetry (ITC) suggests that at 60 C, the CNC rods are entropically driven to
assemble as tactoid-like aggregates on the MC chains known to collapse into colloidal-scale persistent
fibrils with hollow cross-section at that temperature [2,3]. (Figure 1c) At room temperature, ITC shows
enthalpic binding between CNCs and MC with the latter behaving as randomly dispersed polymer
chains, therefore, leading to less efficient confinement. Thus, the thermoreversible assembly of CNC
within the dynamic MC gel meshes can be used to tune the rheological properties and to access liquid
crystalline properties at exceptionally low concentrations of CNC.
Fig. 1: Thermally induced properties of MC/CNC gels. (a) G’ and (b) birefringence intensity as a
function of CNC concentration at 20 °C and at 60 °C reveal broadly adjustable mechanical and
optical properties. Schematics depicting the structure of MC/CNC gels at the two different
temperatures are shown in (c). MC polymer: blue lines; CNC: green rods.
[1]. C. Honorato-Rios, A. Kuhnhold, J. R. Bruckner, R. Dannert, T. Schilling, J. P. F. Lagerwall, Front.

Mater. 2016, 3, 21.
[2]. R. Bodvik, A. Dedinaite, L. Karlson, M. Bergström, P. Bäverbäck, J. S. Pedersen, K. Edwards, G.
Karlsson, I. Varga, P. M. Claesson, Colloids Surf. A Physicochem. Eng. Asp. 2010, 354, 162-171.
[3]. V. V. Ginzburg, R. L. Sammler, W. Huang, R. G. Larson, J. Polym. Sci. Part B Polym. Phys. 2016,
54, 1624-1636.
376
2D3D-P03
Ruthenium complex-DNA conjugates and their linear and 2D-

nanoassemblies

1 1
Joris IRVOAS, Valérie SARTOR *,

1
Laboratoire des IMRCP, Université de Toulouse, CNRS UMR 5623, Toulouse, France
Keywords: Ruthenium complex, DNA, Ru-DNA conjugate, self-assembly
Polypyridyl ruthenium complexes are very interesting and powerful 3D building blocks to the
construction of a large variety of original nanoarchitectures. Their chemistry, their photochemistry and
their photophysic are well known and various applications were developed from them. Moreover, the
number and the position of function introduced in the ruthenium complex can be modulated.
We developed two synthetic pathways for the synthesis of Ruthenium complex-oligonucleotide
conjugates. We first used the very useful and powerful copper-catalyzed Azide Alkyne cycloaddition
(CuAAC) reaction, commonly called click chemistry, with tris bipyridine ruthenium complexes bearing
one to six azide functions and alkyne functionalized oligonucleotides. It allowed us to synthesize a
variety of DNA-Ruthenium conjugates with different oligonucleotide lengths, with complementary
sequences, with symmetrical or unsymmetrical DNA arms and with a number of DNA single strands
linked from one to six.[1] The second synthetic pathway was based on a solid support amidation
reaction. DNA-ruthenium hybrids containing one and two oligonucleotides with different sequences
length were synthesized. They were assembled to give well-defined multimetallic DNA-based linear
nanostructures and three-way junction assemblies.[2,3]
Fig. 1: Multimetallic three-way junction assemblies based on DNA-ruthenium conjugates
[1]. V. Sartor, J. Irvoas, G. Bordeau, N. Chouini-Lalanne, Eur. J. Inorg. Chem. 2017, 20, 2661-2700.
[2]. J. Irvoas, A. Noirot, N. Chouini-Lalanne, O. Reynes, V. Sartor, New J. Chem. 2013, 37, 2324-
2329.
[3]. J. Irvoas, A. Noirot, N. Chouini-Lalanne, O. Reynes, J.-C. Garrigues, V. Sartor. RCS Adv. 2012, 2,
9538-9542.
377
2D3D-P04
Capillary nanostamping with spongy mesoporous silica stamps

1 1
Mercedes SCHMIDT, Martin STEINHART*,

1
Institute of Chemistry of New Materials, Universität Osnabrück, 49069 Osnabrück, Germany

Keywords: Sol-gel chemistry, stamping, fullerenes, nanodiamonds
We report patterning of surfaces by capillary nanostamping using silica stamps containing continuous
[1]
a mesopore system. Spongy mesoporous silica stamps with contact surfaces topographically
structured with contact elements ~400 nm in diameter and ~500 nm in height (Figure 1a) were
synthesized via a sol-gel process. We obtained mechanically stable stamps consisting of silica
networks with mesopore sizes of ~30 nm by using methyltrimethoxy silane (MTMS) as trifunctional
[2]
silica precursor according to Kanamori et al. The continuous mesopore system can be used as
internal ink reservoir and allows continuous ink supply during stamp operation. Thus, multiple
stamping cycles can be carried out under ambient conditions without interruptions to reload the
stamps with ink and without deterioration of the quality of the stamped patterns. Capillary
nanostamping can be carried out manually without expensive instrumentation (Figure 1c).
a b c
Fig. 1: SEM images of a) a mesoporous silica stamp and b) magnification of a single contact
element. c) Stamp mounted on a stamp holder.
C60 fullerenes are of great interest for organic solar-cell design and as a model for endohedral
fullerenes. Diamonds in the nanometer size range containing NV centers are used for the design of
sensors and research on quantum information. Solutions of C60 in toluene and of nanodiamonds in
isopropanol were stamped onto hydrophobically modified or on unmodified glass slides (Figure 2
shows exemplary arrays of C60 generated by capillary nanostamping). Thus, regular large-area arrays
of C60 nanocrystals and nanodiamonds with sizes of ~150 nm were obtained.
a b
Fig. 2: SEM images of a) arrays and b) magnification of C60 particles generated by capillary
nanostamping.
[1] M. Schmidt, M. Philippi, M. Münzner, J. M. Stangl, R. Wieczorek, W. Harneit, K. Müller-

Buschbaum, D. Enke, M. Steinhart, Adv. Func. Mat. 2018 (accepted) [2] K. Kanamori, M. Aizawa, K.
Nakanishi, T. Hanada, Adv. Mater. 2007, 19, 1589-1593.
378
2D3D-P05
3D Polymer Gels as Matrices of Solid-phase Sensors

for the Determination of Neuromediators: Catecholamines
and Their Metabolites
1* 1 1 1
Tatiana SHEKHOVTSOVA , Irina VESELOVA , Maria MAKEDONSKAYA , Anastasia MIKHAILOVA ,
2
Junji FUKUDA
1
Chemistry Department, M.V. Lomonosov Moscow State University, Moscow, Russian Federation
2
Graduate School of Engineering, Yokohama National University, Japan
Keywords: 3D structures, native polymer gels, solid-phase indicator systems, fluorometric

determination, catecholamines and their metabolites
One of topical problems of modern bioanalytical research is the development of solid-phase sensor
nanocomposite materials of directly matched design of microporous surface that provides visualization
and determination of the markers of various diseases, particularly neuromediators, directly in live
vascular and neuronic structures. In this connection, the main goal of our research consists in the
development of 3D gel structures based on native polymers and proteins (chitosan, collagen, alginate,
gelatin, etc.), which could simultaneously comprise biocompatible matrices for the growth of cellular
cultures and the base for solid-phase indicator systems for multiplex determination of catecholamines
and their metabolites in vivo using methods of optical visualization, and specifically solid-phase
fluorometry.
To establish the methods for catecholamines and their metabolites determination, we used two
promising approaches. One of them includes the formation of the intensely fluorescent complexes of
the analytes with lanthanoid ions; another one consists in obtaining the strongly fluorescent derivatives
of catecholamines and their metabolites with aromatic amines in the presence of the enzyme –
horseradish peroxidase. In the first case we used the system based on the intensively fluorescent
ternary complex of analytes with europium and oxytetracycline. Such system provides the
enhancement of fluorescence of catecholamines up to 200-400-fold in comparison with their intrinsic
fluorescence and moves the maximum of emission batochromically.
In the second system, multiplex determination of catecholamines and their metabolites simultaneously
in one sample was achieved due to directed regulation of wavelengths of excitation and emission (in
the ranges 300 – 356 and 425 – 480 nm, respectively) and application of two derivatization agents -
meso-1,2-diphenylethylenediamine and benzylamine. Besides, first-order derivative fluorescence
spectroscopy was applied for the resolution of their spectra.
The conditions for the impregnation of the components of the indicator reactions of both above-
mentioned systems to the polymer structures of chitosan and collagen gels in 96-well microplates
were optimized.
With the application of the developed sensor matrix the solid-phase indicator systems were
established for highly sensitive, selective, and reproducible determination of individual markers of
neuromediator exchange (dopamine, noradrenaline, normetanephrine, serotonin, homovanillic, and
vanillylmandelic acids). The proposed procedures provide rapid registration of the analytical signal of a
large number of samples at low concentrations of analytes: 1 fM – 1 nM). For instance, it is possible to
determine dopamine in the concentration range 0.5 – 1.0 pМ with the detection limit 0.2 pМ (RSD, % =
4.3).
We are grateful to the Russian Foundation for Basic Research for the financial support of this research
(grant no. 17-53-50025)
379
2D3D-P06
DFT studies on vibrational spectra, HOMO-LUMO and NBO of

Tetrodoxine

1 1
Amel BOUTASTA*, Abdelhakim BENOSMAN,
1
Département de Physique, Faculté de Science, Université de Tlemcen .
;
Keywords: Tetrodoxine, HUMO, LUMO, Hartree Fock, DFT and FT-IR.
In the present study, the FT-IR spectra of tetrodotoxine have been recorded in the region 4000–
450 cm−1. The fundamental modes of vibrational frequencies of tetrodotoxine are assigned.
Theoretical information on the optimized geometry, harmonic vibrational frequencies, infrared and
Raman intensities were obtained by means of ab initio Hartree–Fock (HF) and density functional
theory (DFT) gradient calculations with complete relaxation in the potential energy surface using 6-
31G(d,p) basis set. The vibrational frequencies which were determined experimentally from the
spectral data are compared with those obtained theoretically from ab initio and DFT calculations. A
close agreement was achieved between the observed and calculated frequencies by refinement of the
scale factors. The infrared and Raman spectra were also predicted from the calculated intensities. The
calculated HOMO–LUMO energy gap reveals that charge transfer occurs within the molecule. Stability
of the molecule arising from hyper conjugative interactions, charge delocalization have been analyzed
using natural bond orbitals (NBO) analysis. Unambiguous vibrational assignment of all the
fundamentals was made using the total energy distribution (TED).

380
2D3D-P07
Structural coloration of Alpine Black Swallowtail via nanostructures

1 1, 2 3 3 3 1, 2
Seungmuk Ji , Deok-Jin Jeon , Eunok Lee , Yung Kun Kim , Gil-sang Jeong , Jong-Souk Yeo*

1
School of Integrated Technology, Yonsei University, Incheon, Korea,
2
Yonsei Institute of Convergence Technology, Yonsei University, Incheon, Korea,
3
Bureau of Ecological Research, National Institute of Ecology, Seocheon-gun, Korea
Keywords: Structural color, butterfly wing, thin film interference, light absorption
Creatures in nature have developed structural colors as part of their survival strategies over a long period of
evolution. The color expressed by a creature has the advantage of being energetically efficient from an
engineering standpoint, in particular, in that it utilizes 2D or 3D photonic nanostructures.
In this work, we investigate the nanostructures on the wing scales of Alpine Black Swallowtail butterfly
(Papilio maackii) that reveal specific colors. We observe the nanostructures by sectioning technique
using focused ion beam (FIB) system. The nanostructures of the butterfly scales have two main types
of structure depending on whether it produces an iridescent color or not. The nanostructures exhibiting
the iridescent color have a multilayered structure with several tens of nanometer spacing under
aligned line-ridges, and the inner space between line-ridges are comparted by wavy structures. Unlike
iridescent scales, non-iridescent scales have porous nanostructures filling between the line-ridges.
These observations imply that the iridescent color is produced by the multilayer thin film interference
and that the non-iridescent color is due to the light absorption mechanism.
Numerical simulations based on finite difference time domain method are performed to verify the role
of each element of the wing nanostructures on the coloration including line-ridges, the underneath
multi-layers, and porous structures. Based on these investigations, we suggest a feasible model in
engineering aspects to realize biomimetic coloration that mimics the way of the butterfly.
This research was supported by the Basic Science Research Program of the National Research
Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2017R1D1A1B04033182) and
also supported by Research Program through the National Institute of Ecology (NIE-basic research-
2018-18).
381
PLASMAT-P01
Structural, electronic, optical, elastic, mechanical and

thermodynamic properties of zincblende III-X ( X= As, Sb): ab-initio
calculations
1,* 2 1 1
Moufdi HADJAB , Gazi Yalcin BATTAL , Fayçal BOUZID , Abderrahim HADJ LARBI , Samah
1 1 3
BOUDOUR , Nezzari HASSENE , Smail BERRAH .
1
Research Center in Industrial Technologies CRTI, B. O. Box 64, Cheraga 16014, Algiers, Algeria.
2
Department of Physics, Sakarya University, Esentepe Campus, 54187 Sakarya, Turkey.
3
Mastery Renewable Energies Laboratory LMER, University of A. Mira, Bejaia 6000, Algeria

Keywords: DFT, FP-LAPW, Zincblende materials, III-As, III-Sb, Physical properties
In this research work, the ab-initio calculations have been carry out to study the structural, electronic,
optical elestic, mechanical and thermodynamic properties of zincblende III-As and III-Sb binary
compounds, within the Full Potential Linearized Augmented Plane Wave (FP-LAPW) method based
on Density Functional Theory (DFT) [1] as implemented in WIEN2k [2] computational code. The Local
Density Approximation (LDA) [3] and Wu–Cohen Generalized Gradient Approximation (WC–GGA) [4]
were employed as the exchange–correlation term to calculate the structural and electronic properties.
Moreover, the Engel–Vosko GGA (EV-GGA) [5] and the recently modified semi–local Becke–Johnson
(mBJ) [6] functional were also used to calculate the electronic and optical properties in order to get
some better degree of precision. The real and the imaginary parts of the dielectric function, refractive
index, extinction coefficient, reflectivity, absorption coefficient and optical conductivity were calculated
to discuss the linear optical properties of AlAs, GaAs, InAs, AlSb, GaSb and InSb. The elastic
constants, tetragonal shear constant, Kleinman’s internal-strain parameter, shear modulus anisotropy,
the average shear modulus, Young’s modulus, Poisson’s ratio of studied materials, also has been
investigated in details. Otherwise, the microhardness parameter, Cauchy pressure, first and second
Lame constants, wave velocities, Debye temperature, melting point and the minimum thermal
conductivity of the considerate compounds have been predicted. The achieved results show a great
potential utilization in optoelectronic, mechanic and thermodynamic applications especially in infrared
devices.

Fig. 1: Crystal structure of III-As and III-Sb (primitive cell)
[1] W. Kohn, L. J. Sham, Phys. Rev. A 1965, 140, 1133–1138.

[2] P. Blaha, K. Schwarz, G. K. H. Madsen, D. Kvasnicka, J. Luitz, WIEN2k, An Augmented Plane
Wave plus Local Orbital Program for Calculating Crystal Properties, Vienna University of
Technology, Vienna, Austria, 2001.
[3] J. P. Perdew, Y. Wang, Phys. Rev. B 1992, 45, 13244.
[4] Z. Wu, R.E. Cohen, Phys. Rev. B 2006, 73, 235116.
[5] E. Engel, S.H. Vosko, Phys. Rev. B 1993, 47, 13164.
[6] F. Tran, P. Blaha, Phys. Rev. Lett. 2009, 102, 226401.
382
PLASMAT-P02
Laser-structured Janus wire mesh for efficient oil-water separation

1
Yu-Qing Liu, Yong-Lai Zhang, *

1
State Key Laboratory of Integrated Optoelectronics, College of Electronic Science and Engineering,
Jilin University, Changchun, China
Keywords: Laser processing, Janus mesh, oil/water separation, superhydrophobic, underwater

superoleophobic
Efficient oil–water separation has long been considered an important issue, since the frequently
occurring oil spillage events and the industrial wastewater discharge continuously threaten the
aqueous environment, even affecting human health. Inspired by nature creatures that demonstrate
unique wettability, such as lotus leaves and fish scales. Both superhydrophobic surfaces and under
water superoleophobic surfaces have been developed for efficient oil-water separation. However, both
of these kinds of oil–water separation mesh/membranes are not universally applicable. Each kind of
mesh is only suitable for a certain case, and it further depends on the density of the oils. Moreover,
both of them are incapable of unidirectional transport of oils or water.
We report here the fabrication of a Janus wire mesh by a combined process of laser structuring and
fluorosilane/graphene oxide (GO) modification of the two sides of the mesh, respectively, toward its
applications in efficient oil/water separation. Femtosecond laser processing has been employed to
make different laser-induced periodic surface structures (LIPSS) on each side of the mesh. Surface
modification with fluorosilane on one side and GO on the other side endows the two sides of the Janus
mesh with distinct wettability. Thus, one side is superhydrophobic and superoleophilic in air, and the
other side is superhydrophilic in air and superoleophobic under water. As a proof of concept, we
demonstrated the separation of light/heavy oil and water mixtures using this Janus mesh. To realize
an efficient separation, the intrusion pressure that is dominated by the wire mesh framework and the
wettability should be taken into account. Our strategy may open up a new way to design and fabricate
Janus structures with distinct wettability; and the resultant Janus mesh may find broad applications in
the separation of oil contaminants from water.
Fig. 1: left scheme is the fabrication procedure, right, wettability of the Janus mesh
[1]. Y. Liu, D. Han, Z. Jiao, Y. Liu, H. Jiang, X. Wu, H. Ding, Y. Zhang, H. Sun, Nanoscale, 2017, 9,
17933–17938.
[2]. Y. Liu, X. Fu, Y. Zhang, H. Sun, ACS Appl. Mater. Interf, 2015, 7, 20930–20936.
383
PLASMAT-P03
Plasma activated water - a new and effective alternative for

duodenoscope reprocessing

1 2 1 1
Irina ROȘCA *, Gheorghe G. BĂLAN, Elena-Laura URSU, Florica DOROFTEI, Andra-Cristina
3 4 3 5 1
BOSTANARU, Eugen HNATIUC, Valentin NĂSTASĂ, Vasile ȘANDRU, Gabriela ȘTEFĂNESCU,
2 3
Anca TRIFAN, Mihai MAREȘ,

1
“Petru Poni” Institute of Macromolecular Chemistry, Iași, Romania;
2
“Grigore T. Popa” University of Medicine and Pharmacy, Iași, Romania;
3
“Ion Ionescu de la Brad” University, Iași, Romania;
4
”Gheorghe Asachi” Technical University, Iași, Romania;
5
Clinical Emergency Hospital of Bucharest, Bucharest, Romania
Corresponding author address: [email protected]

Keywords: PAW, antibacterial activity, duodenoscope, disinfection.
Duodenoscopes have been widely used for both diagnostic and therapeutic endoscopic
retrograde cholangiopancreatography procedures. Numerous outbreaks of duodenoscope-associated
infections involving multidrug resistant bacteria have recently been reported [1-3].
Plasma activated water (PAW) has been widely considered an effective method for surface
decontamination and is increasingly used for disinfection of medical equipment [4]. The aim of this
study was to evaluate whether the duodenoscopes currently on market are suited for the repeated use
of PAW and to test the efficacy of PAW for their disinfection. In order to evaluate the disinfection
efficacy and the required time of contact, the duodenoscope samples were contaminated by -
immersion in fasted-state simulated intestine fluid containing Escherichia coli, Klebsiella pneumoniae,
Acinetobacter baumannii and Pseudomonas aeruginosa, prior to PAW exposure. Significant
reductions in bacterial populations were achieved after 30 minutes of PAW treatment indicating a high
level disinfection.
In order to test the duodenoscope polymer compatibility with PAW, a challenge test was done by
immersing the samples in PAW for 30 minutes daily, 45 days consecutively. Using atomic force
microscopy and scanning electron microscopy, it was demonstrated that repeated PAW treatment of
duodenoscope coating polymer samples doesn’t result in significant morphological surface differences
between the treated and untreated samples. Energy-dispersive X-ray spectroscopy analysis also
showed no significant differences between the elemental composition of the duodenoscope coating
polymer samples before and after repeated PAW treatment.
Considering these preliminary results, PAW could be considered as a new alternative for
duodenoscope reprocessing.
Acknowledgements: This project has received funding from the European Union’s Horizon 2020
research and innovation programme under grant agreement No 667387 WIDESPREAD 2-2014
SupraChem Lab.
[3]. J. Kovaleva, F.T. Peters, H.C. van der Mei, Clin. Microbiol. Rev. 2013, 26(2), 231-254.
[4]. L.F. Muscarella, World J. Gastrointest. Endosc. 2014, 6(10), 457-474.
[5]. R.M. Humphries, G. McDonnell, J. Clin. Microbiol. 2015, 53, 3118-3125.
[6]. G. Farin, K.E. Grund, Endosc. Surg. Allied Technol. 1994, 2, 71–77.
384
PLASMAT-P04
Carbon dimers enrichment in excimer laser generated graphite

plasma
1 1 2 1
Elena-Laura URSU, Lilia CLIMA, Petru-Edward NICA, Bogdan CRACIUN, Ana Lacramioara
1 1
LUNGOCI, Cristian URSU *,
1
“Petru Poni” Institute of Macromolecular Chemistry, Iasi, Romania
2
Department of Physics, “Gheorghe Asachi” Technical University of Iasi, Iasi, Romania
Corresponding author address: [email protected]
Keywords: excimer laser generated plasma, carbon dimers, nanostructured materials.
Development of ultrashort pulse lasers in the last decades has raised an increased interest in
laser processing and deposition of high quality materials with bio-inspired functionalities. However, the
advance of applications involving nanosecond lasers remains in a continuous progress. Among them,
the excimer lasers have already proved an extended applicability, from industrial, to medical and
laboratory research in developing new or improved materials properties.
In this work a KrF laser is used for the ablation of a graphite target in vacuum and argon ambient
2
gas. For certain beam focusing conditions, in a moderate fluence regime (1.2 - 2.1 J/cm ) it leads to a
V-like plasma shape [1,2]. Having in view that carbon dimers (C2) play a significant role in nano-
structured material deposition (carbon nanotubes, nanowires, graphene, diamond-like carbon films)
[3], we investigate the formation mechanism of these molecules by means of complementary
techniques: ICCD fast imaging, time- and space-resolved optical emission spectroscopy, and angular
ion distribution by Faraday cup measurements. Space-resolved spectral measurements show the
presence of carbon dimers in an extended region in the axial expansion direction, up to a distance of
12.5 mm from the target while, radially, their distribution is more pronounced in two plasma arms
defining the V-like plasma structure. Conversely, the results on angular distribution of positively
charged species obtained by Faraday cup measurements show an unexpected maximum on the
normal direction to the target surface (Figure 1). Moreover, in the assumption of local thermodynamic
equilibrium, different plasma parameters (such as, excitation temperature and vibrational temperature,
etc.) are evaluated as function of delay after the laser pulse, along longitudinal and radial directions.
Fig. 1: Radial and angular distribution of optically and electrically investigated plasma species.
This enrichment of carbon dimers over a wider area compared to other literature results is an
encouraging premise in the development of a dedicated plasma source for obtaining improved carbon
nanomaterials.
Acknowledgements: The present work was supported by the Romanian Space Agency (ROSA)
within Space Technology and Advanced Research (STAR) Program (Project no.: 169/20.07.2017).
[1]. P.-E. Nica, G.B. Rusu, O.-G. Dragos, C. Ursu, IEEE Trans. Plasma Sci. 2014, 42, 2694–2695.
[2]. C. Ursu, P.-E. Nica, J. Optoelectron. Adv. Mater. 2013, 15, 42–45.
[3]. K.F. Al-Shboul, S.S. Harilal, A. Hassanein, J. Appl. Phys. 2013, 113, 163305.
385
3D-P01

3D Printed Levan Scaffolds for Cardiac Regeneration
1 2 1
Edina EMINAGIC , Oguzhan GUNDUZ , Ebru TOKSOY ONER
1
IBSB, Department of Bioengineering, Marmara University, Istanbul, Turkey
2
Advanced Nanomaterials Research Laboratory, Faculty of Technology, Department of Metallurgical
and Materials Marmara University, Istanbul, Turkey
Keywords: Halomonas levan, glycan, 3D bioprinting, scaffold, cardiac tissue engineering
There is a clear need for novel scaffolds in cardiac tissue engineering due to the current problems
such as deficit of donor tissues, immune rejection, anticoagulation therapy, and limited durability of
vascular implants. Recent advances in this field have applied 3D bioprinting as an advanced
fabrication technique to produce biocompatible materials, cells and supporting components with great
promise for artificial organ printing and regenerative medicine applications [1, 2]. Glycans like alginate
and cellulose are commonly used for cardiac tissue engineering applications. As such, levan
polysaccharide has been gaining escalating attention due to its distinguishing properties like high
biocompatibility, strong adhesively and amphiphilic nature [3]. Levan is a fructose based
homopolysaccharide, a fructan, and the sulfated derivative of levan produced by Halomonas
smyrnensis cultures, Halomonas levan, has been shown to be a very promising biomaterial for cardiac
tissue engineering applications [4, 5]. This study aims to elucidate the potential of Halomonas levan
sulfate as a biomaterial in 3D bioprinting technique for cardiac tissue engineering purposes. For this,
glycan-based scaffolds were produced with levan and other glycans and the scaffolds were
characterized comprehensively for their morphological, mechanical, surface and biological properties.
[1] B. Duan, Ann Biomed Eng, 2016, 45, 195-209.

[2] X. Li, R. Cui, L. Sun, K. Aifantis, Y. Fan, Q. Feng, Int J Polym Sci, 2014, 829145, 1-13.
[3] Öner E., L. Hernández, J. Combie, Biotechnol. Adv, 2016, 34, 827-844.
[4] M. Erginer, A. Akcay, B. Coskunkan,T. Morova, D. Rende, S. Bucak, Carbohydr Polym., 2016, 149,
289-296.
[5] T. Gomes, S. Caridade, M. Sousa, S. Azevedo, M. Kandur, E. Öner, N. Alves, J. Mano, Acta
Biomater., 2018, 69,183-195.
386

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What is the conference about?

What is the conference about?

What are some examples of bioinspired inventions mentioned?

What are some examples of bioinspired inventions mentioned?

th

Nice, France ©2018 H.S. Salapare III

Today, we are facing the consequences of the over-exploitation of

Welcome to N.I.C.E. Conference 2018!

International Scientific Committee p. iii

Organizing Scientific Committee p. v

Partners and Endorsers p. ix

Main Conference Themes p. xi

Special Thematic Sessions p. xii

Keynote speakers p. xvii

Oral Abstracts p. 152

Poster Abstracts p. 286

Matthias BALLAUFF (Humboldt University Berlin)

Georges BELFORT (Rensselaer Polytechnic Institute)

Gabriele CENTI (University of Messina, Chair - Editorial Board - ChemSusChem)

Xiaodong CHEN (Nanyang Technological University, Advisory board of Advanced

Tao DENG (Shangai Jiao Tong University)

John DUTCHER (University of Guelph)

Julian EASTOE (University of Bristol, Co-editor Journal of Colloid and Interface

Catarina ESTEVES (Technische Universiteit Eindhoven)

Michele FERRARI (Consiglio Nazionale delle Ricerche)

Justin GOODING (University of New South Wales)

Nicholas KOTOV (University of Michigan)

Chao-Jun LI (McGill University, Associate editor of Green Chemistry)

Feng-Huei LIN (National Taiwan University)

Federica LO VERSO (University of Southern Denmark)

Cefe LOPEZ (Instituto de Ciencia de Materiales de Madrid, Advisory board –

Avi MARMUR (Technion Israel Institute of Technology)

Elena MARTÍNEZ (Institute of Bioengineering of Catalonia)

Christopher K. OBER (Cornell University)

Roshan PAUL (University of Beira Interior)

Frank QUINA (University of São Paulo)

Anupama SHARMA (Panjab University)

Alina SIONKOWSKA (Nicolaus Copernicus University)

Richard SPONTAK (North Carolina State University)

Nicolas VOELCKER (Monash University)

Silvia VIGNOLINI (Cambridge University)

Valentine VULLEV (University of California, Riverside)

Kristina WANIECK (Deggendorf Institute of Technology)

Françoise WINNIK (University of Montreal, Editor-in-chief - Langmuir)

Bai YANG (Jilin University)

Peidong YANG (University of California, Berkeley, Associate Editor - JACS)

Bioinspired Chemistry and Materials for Sustainable Energy

Biomass Valorization: Catalysis, New Materials and Applications (HUGS)

Bioinspired 2D and 3D Molecular and Hybrid Architectures

3D Printing of Bioinspired Materials

Hernando S. SALAPARE III

Biomass Valorization: Catalysis, New Materials, and

Bioinspired 2D and 3D Molecular and Hybrid Architecture

SYMPOSIUM CHAIR/S AND CONTACT PERSON/S

3D Printing of Bioinspired Materials

JOSEP SAMITIER, Barcelona Institute of Science and Technology,

Background in Physics (M.S. Degree in Physics, University of Barcelona

STEPHEN WEINER, Weizmann Institute of Science,

Maria Abrahamsson Igor Alabugin Florent Allais