Nanoscience in Food and Agriculture

Sustainable Agriculture Reviews 20
Shivendu Ranjan
Nandita Dasgupta
Eric Lichtfouse Editors
Nanoscience
in Food and
Agriculture
1
Sustainable Agriculture Reviews
Volume 20
Series editor
Eric Lichtfouse
Other Publications by Dr. Eric Lichtfouse
Books
Scientific Writing for Impact Factor Journals
Nova Publishers 2013
Sustainable Agriculture
Springer 2009
Sustainable Agriculture Volume 2
Springer 2011
Environmental Chemistry. Green Chemistry and Pollutants in Ecosystems
Springer 2005
Rédiger pour être publié ! Conseils pratiques pour les scientifiques
Springer 2012, 2e édition.
Journals and Series
Agronomy for Sustainable Development
www.springer.com/journal/13593
www.springer.com/series/8380
Environmental Chemistry Letters
Environmental Chemistry for a Sustainable World
Blog
Agronomy blog
http://www1.montpellier.inra.fr/agronomy-blog
Magazine
Publier La Science
https://listes.inra.fr/sympa/d_read/veillecaps/
Sustainable agriculture is a rapidly growing field aiming at producing food and energy in a sustainable
way for humans and their children. Sustainable agriculture is a discipline that addresses current issues
such as climate change, increasing food and fuel prices, poor-nation starvation, rich-nation obesity, water
pollution, soil erosion, fertility loss, pest control, and biodiversity depletion.
Novel, environmentally-friendly solutions are proposed based on integrated knowledge from sci-
ences as diverse as agronomy, soil science, molecular biology, chemistry, toxicology, ecology, economy,
and social sciences. Indeed, sustainable agriculture decipher mechanisms of processes that occur from
the molecular level to the farming system to the global level at time scales ranging from seconds to cen-
turies. For that, scientists use the system approach that involves studying components and interactions of
a whole system to address scientific, economic and social issues. In that respect, sustainable agriculture
is not a classical, narrow science. Instead of solving problems using the classical painkiller approach that
treats only negative impacts, sustainable agriculture treats problem sources.
Because most actual society issues are now intertwined, global, and fast-developing, sustainable
agriculture will bring solutions to build a safer world. This book series gathers review articles that ana-
lyze current agricultural issues and knowledge, then propose alternative solutions. It will therefore help
all scientists, decision-makers, professors, farmers and politicians who wish to build a safe agriculture,
energy and food system for future generations.
More information about this series at http://www.springer.com/series/8380

Shivendu Ranjan • Nandita Dasgupta
Eric Lichtfouse
Editors
Nanoscience in Food
and Agriculture 1
Editors
Shivendu Ranjan Nandita Dasgupta
Nano-food Research Group, Instrumental Nano-food Research Group, Instrumental
and Food Analysis Laboratory, Industrial and Food Analysis Laboratory,
Biotechnology Division, School of Industrial Biotechnology Division,
BioSciences and Technology School of BioSciences and Technology
Vellore Institute of Technology Vellore Institute of Technology
Vellore, Tamil Nadu, India Vellore, Tamil Nadu, India
Eric Lichtfouse
INRA
Dijon, France
ISSN 2210-4410 ISSN 2210-4429 (electronic)

ISBN 978-3-319-39302-5 ISBN 978-3-319-39303-2 (eBook)
DOI 10.1007/978-3-319-39303-2
Library of Congress Control Number: 2016947716
© Springer International Publishing Switzerland 2016

This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of
the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation,
broadcasting, reproduction on microfilms or in any other physical way, and transmission or information
storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology
now known or hereafter developed.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication
does not imply, even in the absence of a specific statement, that such names are exempt from the relevant
protective laws and regulations and therefore free for general use.
The publisher, the authors and the editors are safe to assume that the advice and information in this book
are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the
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or omissions that may have been made.
Printed on acid-free paper
This Springer imprint is published by Springer Nature

The registered company is Springer International Publishing AG Switzerland
We dedicate this book to our parents
–The Editors
There is plenty of room at the bottom
–Richard Feynman
Preface
This book is the first of several volumes on Nanoscience and Food in Agriculture,
which will be published in series Sustainable Agriculture Reviews. Nanotechnology
is a fast-evolving discipline that already produces outstanding basic knowledge and
industrial applications for the benefit of society. Whereas the first applications of
nanotechnology have been developed mainly in material sciences, applications in
agriculture and food sectors are still emerging. Due to a rapid population growth,
there is a need to produce food and beverages in a more efficient, safe and sustain-
able way. Here nanotechnology is a promising way to improve crop production,
water quality, nutrition, packaging, and food security. There are actually a few com-
prehensive reviews and clear textbooks on nanotechnology in agriculture, water,
and food. Therefore in this book we present ten chapters describing the synthesis
and application of nanomaterials for health, food and agriculture. Applications to
agriculture, food and water quality are symbolized in Fig. 1.
Definitions and an overall view of nanotechnology applications in agriculture,
food, water and environment are described in the two first chapters by Dasgupta
Fig. 1 Nanotechnology will allow to improve the quality of water and food. Left: Roselette lake
and Mont Blanc mountains, France (Copyright: G. Balvay/INRA 2015). Right: Ebly wheat rhu-
barb salad (Copyright: P. Libert/INRA 2015)
vii
viii Preface
Fig. 2 Major applications of nanotechnology in agriculture. Dasgupta et al. Chap. 1
et al. and Singh (Fig. 2). Health and environmental applications of nanotechnology
are presented in Chaps. 3, 4, and 5. Shukla and Iravani review green methods to
synthesize metal nanoparticles and give applications to water purification in Chap.
3. The removal of up to 95 % of contaminants by nanoparticles, nanotubes and
nanostructured membranes is described by Naghdi et al. in Chap. 4. Yoti et al. then
review nanosensors for the detection of pathogenic bacteria in Chap. 5. Those nano-
sensors can be used as biodiagnostics to control food and water quality. Food appli-
cations of nanoscience are presented in Chaps. 6 and 7 by Kuswandi and Sarkar
et al. Kuswandi explain in Chap. 6 that nanomaterials can improve packaging qual-
ity and that nanosensors can detect freshness and contaminants. The use of
nanoparticles to protect ingredients such as vitamins, flavours and antimicrobials is
reviewed by Sarkar et al. in Chap. 7.
Agricultural applications of nanotechnology are given in the last three chapters
by Pulimi and Subramanian, Chhipa and Joshi, and Shalaby and El-Ramady. Pulimi
and Subramanian explain in Chap. 8 that nanoclays, nanozeolites and nanominerals
can be used as plant nutrient carriers, and to improve water retention in soils. They
also describe the used of nanoparticles to improve classical methods of pollutant
Preface ix
remediation such as phytoremediation and electrokinetic degradation. Chhipa and

Joshi review the use of nanofertilisers, nanopesticides and nanosensors in agricul-
ture in Chap. 9. Nanosensors are particularly useful in precision agriculture because
they detect pests locally in real-time, which allow to treat them fast with minimal
side-effects. In Chap. 10, Shalaby and El-Ramady reveal the benefits of zinc oxide
and silicon nanofertilisers for plant growth.
Thanks for reading
Vellore, TN, India Shivendu Ranjan

Nandita Dasgupta
Dijon, France Eric Lichtfouse
Contents
1 Nanoagriculture and Water Quality Management . . . . . . . . . . . . . . . . . 1

Nandita Dasgupta, Shivendu Ranjan, Arkadyuti Roy Chakraborty,
Chidambaram Ramalingam, Rishi Shanker, and Ashutosh Kumar
2 Nanotechnology Definitions, Research, Industry
and Property Rights . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
Namita Ashish Singh
3 Green Synthesis and Spectroscopic Characterization
of Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
Ashutosh Kumar Shukla and Siavash Iravani
4 Nanotechnology to Remove Contaminants . . . . . . . . . . . . . . . . . . . . . . 101
Mitra Naghdi, Mehrdad Taheran, Saurabh Jyoti Sarma,
Satinder Kaur Brar, Antonio A. Ramirez, and Mausam Verma
5 Nanosensors for the Detection of Pathogenic Bacteria . . . . . . . . . . . . 129
Anurag Jyoti, Rajesh Singh Tomar, and Rishi Shanker
6 Nanotechnology in Food Packaging . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
Bambang Kuswandi
7 Nanotechnology in Food Processing and Packaging . . . . . . . . . . . . . . 185
Preetam Sarkar, Syed Irshaan, S. Sivapratha, and Ruplal Choudhary
8 Nanomaterials for Soil Fertilisation and Contaminant Removal . . . . 229
Mrudula Pulimi and Sangeetha Subramanian
9 Nanofertilisers, Nanopesticides and Nanosensors in Agriculture . . . 247
Hemraj Chhipa and Piyush Joshi
xi
xii Contents
10 Nanoparticles, Soils, Plants and Sustainable Agriculture . . . . . . . . . . 283

Tarek A. Shalaby, Yousry Bayoumi, Neama Abdalla,
Hussein Taha, Tarek Alshaal, Said Shehata, Megahed Amer,
Éva Domokos-Szabolcsy and Hassan El-Ramady
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
Contributors
Neama Abdalla Plant Biotechnology Department, Genetic Engineering Division,

National Research Center, Dokki, Cairo, Egypt
Tarek Alshaal Soil and Water Department, Faculty of Agriculture, Kafrelsheikh
University, Kafr El-Sheikh, Egypt
Megahed Amer Soil, Water and Environment Research Institute (SWERI),
Agricultural Research Center (ARC), Egypt
Satinder Kaur Brar INRS-ETE, Université du Québec, Québec, Canada
Yousry Bayoumi Horticulture Department, Faculty of Agriculture, Kafrelsheikh
Arkadyuti Roy Chakraborty Nano-food Research Group, Instrumental and Food
Analysis Laboratory, Industrial Biotechnology Division, School of BioSciences and
Technology, Vellore Institute of Technology, Vellore, Tamil Nadu, India
Hemraj Chhipa The Energy and Resources Institute, IHC, New Delhi, India
Ruplal Choudhary Department of Plant Soil and Agricultural Systems, Southern
Illinois University Carbondale, Carbondale, IL, USA
Nandita Dasgupta Nano-food Research Group, Instrumental and Food Analysis
Laboratory, Industrial Biotechnology Division, School of BioSciences and
Éva Domokos-Szabolcsy Plant Biotechnology Department, Debrecen University,
Böszörményi Útca, Debrecen, Hungary
Hassan El-Ramady Soil and Water Department, Faculty of Agriculture,
Kafrelsheikh University, Kafr El-Sheikh, Egypt
Siavash Iravani Faculty of Pharmacy and Pharmaceutical Sciences, Isfahan
University of Medical Sciences, Isfahan, Iran
xiii
xiv Contributors
Syed Irshaan Department of Food Process Engineering, National Institute of

Technology Rourkela, Rourkela, Odisha, India
Piyush Joshi The Energy and Resources Institute, IHC, New Delhi, India
Anurag Jyoti Amity Institute of Biotechnology, Amity University Madhya
Pradesh, Gwalior, MP, India
Ashutosh Kumar Institute of Life Sciences, School of Science and Technology,
Ahmedabad University, Ahmedabad, Gujarat, India
Bambang Kuswandi Chemo and Biosensors Group, Faculty of Pharmacy,
University of Jember, East Java, Indonesia
Mitra Naghdi INRS-ETE, Université du Québec, Québec, Canada
Mrudula Pulimi Centre for Nanobiotechnology, VIT University, Vellore,
Tamilnadu, India
Chidambaram Ramalingam Nano-food Research Group, Instrumental and Food
Analysis Laboratory, Industrial Biotechnology Division, School of BioSciences and
Antonio A. Ramirez Centre National en Électrochimie et en Technologie
Environnementales Inc., Québec, Canada
Shivendu Ranjan Nano-food Research Group, Instrumental and Food Analysis
Laboratory, Industrial Biotechnology Division, School of BioSciences and
Research Wing, Veer Kunwar Singh Memorial Trust, Chapra, India
Xpert Arena Technological Services Pvt. Ltd, Chapra, India
Preetam Sarkar Department of Food Process Engineering, National Institute of
Saurabh Jyoti Sarma INRS-ETE, Université du Québec, Québec, Canada
Tarek A. Shalaby Horticulture Department, Faculty of Agriculture, Kafrelsheikh
College of Agricultural and Food Sciences, King Faisal University, Al-Hassa, Saudi
Arabia
Rishi Shanker Institute of Life Sciences, School of Science and Technology,
Said Shehata Vegetable crops Department, Faculty of Agriculture, Cairo
University, Giza, Egypt
Ashutosh Kumar Shukla Physics Department, Ewing Christian College,
Allahabad, UP, India
Contributors xv
Namita Ashish Singh Department of Life Sciences, Institute of applied medicine

and research, Ghaziabad, UP, India
S. Sivapratha Department of Food Process Engineering, National Institute of
Sangeetha Subramanian School of Bio Sciences and Technology, VIT University,
Vellore, Tamilnadu, India
Hussein Taha Plant Biotechnology Department, Genetic Engineering Division,
National Research Center, Dokki, Cairo, Egypt
Mehrdad Taheran INRS-ETE, Université du Québec, Québec, Canada
Rajesh Singh Tomar Amity Institute of Biotechnology, Amity University Madhya
Pradesh, Gwalior, MP, India
Mausam Verma CO2 Solutions Inc., Québec, Canada
About the Editors
Shivendu Ranjan is currently working as DBT-

Research Fellow, Department of Biotechnology,
Ministry of Science and Technology, Govt of India at
VIT University, Vellore, Tamil Nadu, India. He is also
serving for a non-government organization as an
Honorary-Director, Research Wing, Veer Kunwar
Singh Memorial Trust, Chapra, Bihar, India. He is the
Founder-Director at Xpert Arena Technological
Services Pvt. Ltd., India (www.xpertarena.com); this
company is dedicated to serve in online and offline
sectors with a vision to simplify the education. He has
also founded and drafted the concept for first edition of
VIT Bio Summit in 2012, and the same has been continued till date by the
university.
His area of research is multidisciplinary whichare as but not limited to: Nano-
food technology, Nano-agri technology, Nanobiotechnology, Nano-toxicology,
Natural products technology, Natural products chemistry, Bio-business, Food
chemistry and Food Engineering. He has published many scientific articles in inter-
national peer reviewed journals and also serving as editorial board member and
referee for reputed international peer reviewed journals. He has bagged several
awards from different organizations,e.g. Best poster award, achiever award, research
award, young researcher award,etc.
xvii
xviii About the Editors
Nandita Dasgupta is currently serving as Research

Associate at VIT University, Vellore, Tamil Nadu,
India. She has exposure of research institutes and
industries including CSIR-Central Food Technological
Research Institute, Mysore, India, and Uttar Pradesh
Drugs and Pharmaceutical Co. Ltd., Lucknow, India.
Her areas of interest include toxicological analysis,
natural products technology, nanobiotechnology and
agri-food technology.
She has published many scientific articles in inter-
national peer reviewed journals and also serving as
editorial board member and referee for reputed international peer reviewed journals.
She has received Elsevier Certificate for “Outstanding Contribution” in reviewing
from Elsevier, The Netherlands. She has also been nominated for Elsevier advisory
panel for Elsevier, The Netherlands. She was the Guest Editor in Journal of
Chemistry for the special issue entitled “Food Nanotechnology Opportunities and
Challenges”. She has received several awards from different organizations e.g. Best
poster award, young researcher award, special achiever award, research award, etc.
Eric Lichtfouse, 56, is a soil scientist at the French

National Institute for Agricultural Research (INRA).
He has invented the 13C-dating method1 allowing to
measure the dynamics of soil organic molecules, thus
opening the field of molecular-level investigations of
soil carbon sequestration. Chief Editor of the awarded
journal Agronomy for Sustainable Development,2,3 he
has raised the journal rank from 29/53 in 2003, with an
impact factor of 0.56, to 2/81 in 2014, with an impact
factor of 3.99, in the Agronomy category. He is also
Chief Editor and founder of the journal Environmental
Chemistry Letters4 and the book series Sustainable
5
Agriculture Reviews. He is lecturing scientific writing and communication in uni-
versities worldwide.6 His publication assistance service at the INRA has founded
1
http://dx.doi.org/10.1007/s10311-011-0334-2
2
http://archive.sciencewatch.com/inter/jou/2010/10novAgrSusDev
3
http://www.springer.com/journal/13593
4
http://www.springer.com/journal/10311
5
http://www.springer.com/series/8380
6
http://fr.slideshare.net/lichtfouse/scientific-writing-and-communication, https://www.youtube.
com/playlist?list=PLKEz5Pbi4p3By53Q0gclKPeSBTK2HJGK_
About the Editors xix
the french-english newsletter Publier La Science.7 He has published the book

Scientific Writing for Impact Factor Journal.8 This textbook describes in particular
the micro-article,9 a new tool to identify the novelty of experimental results. Further
details are available on Slideshare,10 LinkedIn,11 ResearchGate,12 ResearcherID13
and Orcid.14
7
http://www6.inra.fr/caps-publierlascience
8
https://www.novapublishers.com/catalog/product_info.php?products_id=42211
9
http://fr.slideshare.net/lichtfouse/micro-arten
10
http://fr.slideshare.net/lichtfouse
11
https://fr.linkedin.com/in/ericlichtfouse
12
https://www.researchgate.net/profile/Eric_Lichtfouse
13
http://www.researcherid.com/rid/F-4759-2011
14
http://orcid.org/0000-0002-8535-8073
Chapter 1
Nanoagriculture and Water Quality
Management
Nandita Dasgupta, Shivendu Ranjan, Arkadyuti Roy Chakraborty,

Chidambaram Ramalingam, Rishi Shanker, and Ashutosh Kumar
Abstract Nanomaterials have rapidly gained importance in many fields of science

and technology due to their unique properties. Nanomaterials are used in the agri-
food sector notably for preservation and packaging, for agriculture and for water
quality management. Future applications will improve shelf life, food quality,
safety, and fortification. Nanosensors will be used to analyse contaminated food and
water. Here we review the application of nanotechnology in agriculture and subdis-
ciplines. The major points are the following. We explain the classification and syn-
thesis of nanomaterials used for agriculture and water management. Then we
present major applications such as nanoscale carriers, fabricated xylem vessels,
nanolignocellulosic materials, clay nanotubes, photocatalysis, bioremediation of
resistant pesticides, disinfectants, agricultural wastewater treatment, nanobarcode
technology, quantum dots for staining bacteria, and nano-biosensors. Applications
to water quality management include nanolignodynamic metallic particles, photo-
catalysis, desalination, removal of heavy metals, and wireless nanosensors.
Keywords Nanotechnology • Nanomaterials • Agriculture • Water quality manage-

ment • Environment
N. Dasgupta • A.R. Chakraborty • C. Ramalingam

Nano-food Research Group, Instrumental and Food Analysis Laboratory,
Industrial Biotechnology Division, School of BioSciences and Technology,
Vellore Institute of Technology, Vellore, Tamil Nadu, India
e-mail: [email protected]; [email protected]; [email protected]
S. Ranjan (*)
Nano-food Research Group, Instrumental and Food Analysis Laboratory,
Industrial Biotechnology Division, School of BioSciences and Technology,
Vellore Institute of Technology, Vellore, Tamil Nadu, India
Research Wing, Veer Kunwar Singh Memorial Trust, Chapra, India
Xpert Arena Technological Services Pvt. Ltd., Chapra, India
e-mail: [email protected]
R. Shanker • A. Kumar
Institute of Life Sciences, School of Science and Technology,
e-mail: [email protected]; [email protected]
© Springer International Publishing Switzerland 2016 1

S. Ranjan et al. (eds.), Nanoscience in Food and Agriculture 1,
Sustainable Agriculture Reviews 20, DOI 10.1007/978-3-319-39303-2_1
2 N. Dasgupta et al.
1.1 Introduction
The term ‘nano’ is coined from the Greek word for dwarf. A nanometre (nm) is
1-billionth of a metre, or approximately 100,000th of the width of a human hair.
Nanotechnology has many applications in biotechnology and its allied field e.g. tis-
sue engineering, drug delivery, biomedical engineering, food science and technol-
ogy among others (Danie et al. 2013; Ranjan et al. 2014; Dasgupta et al. 2014).
The applied nanotechnology has been shown in Fig. 1.1 using solar system model.
A wide range of applications of nanotechnology is also emerged into the “agri-food
sector” which includes the nanosensors, tracking devices, targeted delivery of
required components, food safety, new product developments, precision processing,
smart packaging and others, shown in Fig. 1.2 (Huang et al. 2010; McClements
et al. 2009; Ranjan et al. 2014; Dasgupta et al. 2014). Nanotechnology can also
improve the water solubility, thermal stability and bioavailability of the functional
compounds of food (McClements et al. 2007, 2009; Miguel et al. 2014). Figures 1.3
and 1.4 represent the major applications of nanotechnology in food processing and
packaging, the same has already been discussed in many review articles earlier, by
Ranjan et al. (2014) and Dasgupta et al. (2014).
Fig. 1.1 Solar system model showing applications of nanotechnology in different allied sectors
including industrial, electronics, environment, renewable energy, textiles, biomedical, healthcare,
foods, agriculture and agro-foods. The red-circled part has been covered in this chapter (Courtesy:
www.lurasia.com/nano and www.xpertarena.com)
- Nutraceutical & nutrient
delivery
- Nanoencapsulation of
- Mineral and vitamin
flavours
fortification
- Gelation &
- Water purification
thickening agent
- Sensory for supplement
- Nanoemulsion
characteristics
- Anticaking
Processing
Nutrition Product
- Novel pesticides Agriculture

- Targeted genetic - UV protections
engineering - Antimicrobials
- Agrochemical delivery - High barrier plastic
- Sensor to monitor soil - Contaminant sensors
condition
Fig. 1.2 A mind-map showing the linkage of nano-foods with agriculture, nutritional, process
development and product development. Pictorial representation for some of the major applications
of nanotechnology in different sectors of food and agriculture (Courtesy: Ranjan et al. 2014)
Nano-food Processing
Nano-food products containing nanostructures have been
commercialized or are being currently developed for different
purposes
Nano emulsification
Nano encapsulation
Nano filtration
Nano-particle based
delivery
Fig. 1.3 Major types of nano-structures or processes which are being used to develop nano-foods
to be launched in market
Food Packaging
Nanotechnology
Nacomposite smart
Nanoreinforcement packaging
packaging Nanocomposite
Active packaging
Time-Temp
Integrator
Nanoclays
Nanoreinforcement Antimicrobial System
Gas Detectors
Cellulose
Reinforcement O2 Scavengers System
Enzyme Nanosensors
Other Immobilization System
Nanoreinforcement
Fig. 1.4 Pictorial representation to sumamrize the different types and sub-types of nano-food-
packaging being used along with their different applications (Courtesy: Ranjan et al. 2014)
Agricultural products influence most aspects of life, including everyday materials,

such as fuels, textiles, furniture, feedstock for bio-based products including food
and feed. Technology advancement is needed to achieve the future global needs
from agriculture. Nanoscience and nanotechnology has shown great potential in
improving food safety, quality, product traceability, nutrient delivery, enhancing
packaging performance, and improving agricultural and food processing. In the
present review an attempt has been made to summarize the classification and the
synthesis method for the nanomaterials used in agricultural practices and water
quality management. Also, the application of nanomaterials in the agriculture such
as nanoscale carriers, fabricated xylem vessels, nanolignocellulosic materials, clay
nanotubes, photo-catalysis, bioremediation of resistant pesticides, disinfectants,
agricultural wastewater treatment, nanobarcode technology, quantum dots for stain-
ing bacteria, different types of nano-biosensors along with the current research
trends, future directions, opportunities and research gaps in this field has been dis-
cussed in detail. The goal of this article is to provide the perspectives of researchers
working with nanotechnology to address agricultural and water quality manage-
ment problems.
1 Nanoagriculture and Water Quality Management 5
1.2 Classification of Nanomaterials
Nanomaterials can be classified as (i) nanoparticles (ii) nanoclays and (iii) nano-
emulsions, which can be synthesized by a number of methods and have many
applications in agri-food sector.
1.2.1 Nanoparticles
Nanoparticles can be categorized into different types based on their ability to carry
different reactions with different ingredients and environmental conditions.
Depending on the chemical characteristics, Nanoparticles can also be divided into
two broad categories- organic and inorganic.
Organic Nanoparticle-sometimes referred to as nanocapsules, when used to
enhance the bioavailability of nutrient and their delivery. However, seen from a
general level, they can be defined as nano-vesicular systems that exhibit a typical
core-shell structure in which the drug is confined to a reservoir or within a cavity
surrounded by a polymer membrane or coating (Anton et al. 2008). There are six
classical methods for the preparation of nanocapsules: nanoprecipitation, emulsion-
diffusion, double emulsification, emulsion-coacervation, polymer-coating and layer
by-layer (Mora-Huertas et al. 2010) as mentioned in Table 1.1. Recently a new class
of water-soluble red fluorescent organic nanoparticles have been prepared for an
application in cell imaging which further can be used in the development of nano-
sensors (Xiqi et al. 2014). Also, a fluorescent organic nanoparticle has been devel-
oped by Zhang et al. (2014) with dye removal (remediation) from soil as well as and
water. This facilely incorporated polymeric nanoparticle showed high water
dispersibility, uniform size, strong red fluorescence and excellent biocompatibility,
which makes them promising in water purification, nano-sensor development for
water as well as agricultural products (Zhang et al. 2014).
1.2.1.1 Inorganic Nanoparticles
Inorganic ingredients manufactured at the nanoscale with variations of compounds

and approved for use in food, e.g. titanium dioxide, a food colorant, can be used as
a UV protection barrier in food packaging when used as a nanoparticle. New storage
containers/utensils (food contact materials) based on embedded inorganic nanopar-
ticle have been designed for preservation of prepared agricultural products. Grain
storage bins are being produced with silver nanoparticle embedded in the plastic for
killing bacteria from any food that was previously stored in the bins and minimizing
health risks (Food Safety Authority of Ireland 2008). A cellulose-based bactericidal
nanocomposites containing silver nanoparticle have been developed, which
Table 1.1 Upstream and downstream procedures for the preparation of nanocapsules
(Mora-Huertas et al. 2010)
S. No. Upstream process for nanocapsule formation Downstream process for
nanocapsule concentration,
purification and stabilization
1 Nanoprecipitation Method Solvent Elimination
Organic phase is slowly injected (dropwise and Moderate magnetic
moderate stirring) to the aqueous phase agitation
2 Emulsification-diffusion Method Evaporation by vacuum
Organic and aqueous phase are emulsified (high Tangential ultrafiltration
shear mixture)
Diffused (moderate stirring) to dilution phase Purification
3 Emulsification-coacervation Method Water washing
Organic and aqueous phase are emulsified Diafiltration
(mechanical stirring or sonication) Filtration through
Coacervation (moderate stirring) in the presence 0.45µm
of crosslinking agents or dehydratant agent Gel filtration
4 Double emulsification Method (Water-Oil-Water)
Organic phase and first Aqueous phase are Recuperation
emulsified in water-oil system (sonication) Ultrasonication
Second aqueous phase and previous solution are
emulsified in oil water system (high shear
mixture) Stabilization
5 Polymer coating Method (Water-Oil-Water) Spray drying
Organic and aqueous phase are emulsified in Lyophilization/freeze
water-oil system (sonication) drying
Second phase i.e. coating agent and previous
solution are emulsified in oil water system
(sonication or high shear mixture)
6 Layer by layer
Template will be encapsulated with several
layers of mixture of anionic/cationic polymers
and coat charged polymer
exhibited an improved bactericidal and nanocomposite properties. Further it has

been concluded that these properties may have the future applications in active
packaging of food and agricultural products (Márcia et al. 2012). Also, silver
nanoparticle incorporated into carboxymethylcellulose films have been studied for
its antimicrobial studies for food and agricultural products packaging and found
suitable for the same (Siqueira et al. 2014). The detailed view on packaging of agri-
cultural and food product is provided by Ranjan et al. (2014) and Dasgupta et al.
(2014).
Similar to organic, inorganic nanoparticles are also having several methods of
production e.g. gas and liquid phase synthesis method, which are further classified
into different methods. Gas phase synthesis methods have mainly three types for
synthesis (a) flamed spray synthesis (b) laser induced gas evaporation method
synthesis (c) plasma based synthesis. However, liquid phase inorganic nanoparticles
synthesis methods may further categorized into (a) co-precipitation method and
(b) sol-gel approach (Food Safety Authority of Ireland 2008). The properties of
nanoparticles have shown to be dependent on the size and other surface properties,
which ultimately depend on the synthesis procedure. Hence, it is necessary to
understand the synthesis procedures of nanoparticles for their specific application.
The detailed overview of inorganic nanoparticles synthesis has been given in the
book of Jesus et al. (2012), which has been summarized below for better
understanding.
1.2.1.2 Flame Spray Synthesis
Three large scale commodities have been around for half a century which are pig-
mentary titania (white pigment), aerosol-made silica and carbon black (tire soot) are
made by flame processes at several megatons per year (Layman 1995; Ulrich 1984).
Production of these materials started in the 1940s. In principle, it would appear
attractive to extend this apparently useful flame processes to other materials (Stark
et al. 2002). Flame-made oxides have been explored for applications as sensors
which further can be used in agricultural field (Athanassiou et al. 2006). As a result,
a number of products have become available in the form of nanoparticles, such as
nano-gypsum (Osterwalder et al. 2007), nano-salt (Grass and Stark 2005) and nano-
tricalcium phosphate (Maciejewski et al. 2008). Further adaptations within the
flame spray synthesis technology gives access to the production of metal nanopar-
ticles (Athanassiou et al. 2006; Grass and Stark 2006). This is achieved by a modi-
fication of the flame reactor operating under reducing (oxygen starved) conditions
(Grass and Stark 2006). Very recently, one further step was taken and the controlled
deposition of carbon on the metal surface of nanoparticle also became accessible
(Athanassiou et al. 2006, 2007). For example, the suitability of carbon coated cop-
per nanoparticles in water based dispersions or inks of such have been shown to
offer a simple production method to highly sensitive humidity sensor coatings
(Luechinger et al. 2007). In summary, flame spray synthesis allows the scalable
fabrication of most accurate mixed oxide compositions, salt, metal and carbon-
coated metal or silica-coated metal oxide nanoparticle (Teleki et al. 2008) based on
metal loaded liquid precursors.
1.2.1.3 Laser Induced Gas Evaporation Method
Instead of combustion of a liquid precursor giving access to oxidic nanoparticles,

Kato (1976) produce a range of different ultrafine refractory oxides (SiO2, MgO,
Al2O3, Fe3O4, Mg2SiO4, CaTiO3 and MgAl2O4) by the use of a CO2 laser. The laser
was used to vaporize starting material in form of powder or sintered or fused blocks.
The vaporized material condensed in an environment of inactive gases and resulted in
nanoparticles of around 10 nm particle diameter at a production rate of 10 mg/min

(0.6 g/h). Ullmann et al. (2002) studied the systematic influence of the operating
parameters on laser ablation for the aerosol generation and concluded that laser
ablation is a convenient method for laboratory scale nanoparticles generation.
1.2.1.4 Plasma Based Nanoparticles Production
A similar method to laser induced gas evaporation are plasma reactors. In this case
plasma delivers the energy necessary to evaporate the starting materials of various
types including gases, liquids and solids. At temperatures of around 10,000 °C the
plasma generates reactive ions and radicals. During the pull-out from the plasma
region the temperature of the gas drops and nanoparticles are formed (Young and
Pfender 1985). Plasma based methods have been used to synthesize nanoparticles in
form of metal oxides (Suzuki et al. 2001), metals (Jiang and Yatsui 1998) or metal
nitrides (Kinemuchi et al. 2003).
1.2.1.5 Co-precipitation Method
In a first step of a typical co-precipitation reaction, the conditions are adjusted to

maximize the simultaneous generation of sparingly soluble particles. The key prop-
erties of the final product (above all particle size and morphology) are subsequently
determined in secondary processes such as aggregation or Ostwald ripening. In the
final step, the as-formed particles are usually thermally decomposed to oxides. An
advantage of the co-precipitation method is that particle sizes can be well controlled
for the fabrication of monodisperse inorganic nanoparticles possible. A major dis-
advantage though is the involvement of vast amounts of solvents and surfactants
(Cushing et al. 2004).
1.2.1.6 Sol-Gel Method for Inorganic Nanoparticles Synthesis
Another inorganic nanoparticles synthesis method based on liquid precursors is the

processing of materials by the sol-gel method. This process dates back to the mid
1800s where scientists found that they were able to synthesize ceramic or glassy
material from a viscous gel. Typically, metal alkoxides or metal chlorides are used
as starting materials forming the solvated metal precursor (the sol). This precursor
undergoes hydrolysis and polycondensation reactions to form a gelated colloid (the
gel). The reactions of this oxide- or alcohol-bridged network continue until the gel
transforms into a solid mass under expulsion of the solvent from the pores.
Subsequently, the monolith is calcined at temperatures up to 800 °C. In the firing
step when the temperature rises above 800 °C densification and decomposition of
the gel occurs under collapse of the gel network. The sol-gel process is ideally
suited for the fabrication of synthetic zeolites, where a porous “open” structure is
desired for the accommodation of a wide variety of cations (Hench and West 1990).
1.2.2 Nanoclays
They are naturally occurring aluminium silicate, primarily composed of fine-grained

minerals having sheet-like geometry. The sheet-structured hydrous silicates are gen-
erally referred to as phyllosilicates. They are inexpensive and eco-friendly materials
and have been found for multifarious application. These clay minerals have been
widely studied in practical applications such as in geology, agriculture, construc-
tion, engineering, process industries, and environmental applications. They provide
an attractive alternative for the decontamination of soils, underground waters, sedi-
ments and industrial effluents i.e. in the field of water purification and recently
nanoclays have been found to have application in sensor development (Garrido-
Ramirez et al. 2010; Grasielli et al. 2012). The most studied nanoclayis montmoril-
lonite (MMT), whose chemical general formula is Mx(Al4-xMgx) Si8O20(OH)4.
montmorillonite is a representative of 2:1 layered phyllosilicates, whose platelets
have two layers of tetrahedral silica sheets filled with a central octahedral alumina
sheet (Weiss et al. 2006). This kind of clay has a moderate negative surface charge
that is important to define the interlayer spacing (Xin-Juan et al. 2015). The imbalance
of the surface negative charges is compensated by exchangeable cations (typically
Na+ and Ca2+). The parallel layers are linked together by weak electrostatic forces
(Tan et al. 2008). Montmorillonite is excellent reinforcing filler, due to its high sur-
face area and large aspect ratio, which ranges from 50 to 1000 (Uyama et al. 2003).
The improved barrier properties of polymer-clay nanocomposites seem to be due to
an increased tortuosity of the diffusive path for permeants, forcing them to travel a
longer path to diffuse through the film. The increase in path length is a function of
the aspect ratio of the clay and the volume fraction of the filler in the composite.
This theory was developed by (Nielsen 1967) and was further corroborated by other
authors (Mirzadeh and Kokabi 2007; Adame and Beall 2009). Clays have also been
reported to improve the mechanical strength of biopolymers (Cyras et al. 2008),
although they may decrease polymerelongation (Petersson and Oksman 2006).
Recently many applications have been found using montmorillonite and/or
incorporating/modifying montmorillonite using several techniques. Gholam et al.
(2013) have been found the increased adsorption rate and more nanocomposite
strength when modified montmorillonite based nanoclay – further the application of
which was found for water purification by removal of crystal violet dye. Hydrogel
nanocomposites were synthesized from grafting of acrylamide onto hydroxypropyl
methylcellulose using methylenebisacrylamide cross linker and sodium montmoril-
lonite (Na-MMT) nanoclay. The investigation of the dye adsorption capacity and
rate of nanocomposite hydrogels as a function of Na-MMT content revealed that the
both adsorption capacity and rate is enhanced as the nanoclay content is increased
in nanocomposite composition (Gholam et al. 2013). Soy protein hydrogels with
intercalated montmorillonite nanoclay bound with transglutaminase cross-linking
shows enhanced elastic properties. This intercalated soy proteins with montmorillonite
can be used to manufacture biodegradable nanocomposite materials with improved
functional performances further application of which is food and agricultural
products packaging (Jin and Zhong 2013). A nanofilm have been developed by
novel dispersion method using gum exudates from Brea tree and nanoclayparticles
(montmorillonite) and characterized – the main properties of this biofilm are
improved water barrier capacity, reduced film permeability and reduced permselec-
tivity for gases. These properties of this (montmorillonite nanoclay based biofilm)
gives ample scope for its application for packaging as well as preservation of agri-
cultural products (Aníbal et al. 2014). Montmorillonite nanoclay has been found
application in biosensor development as well. Grasielli et al. (2012) have developed
a novel atemoya biosensor for glyphosate determination which was based on the
inhibitor effect of the pesticide on enzymatic activity. The peroxidase enzyme was
immobilised on nanoclay based on montmorillonite modified (Grasielli et al. 2012).
Other than montmorillonite a novel polyvinylidene fluoride (PVDF)/NC hollow
fibre membranes were fabricated by non-solvent induced phase separation (NIPS)
to study the improvement of membrane physical endurance. PVDF membranes con-
taining commercial nanoparticles are therefore promising for improved abrasion
resistance in water treatment applications (Yan et al. 2014).
1.2.3 Nanoemulsions
Nanoemulsion consists of a lipid phase dispersed in an aqueous continuous phase,

with each oil droplet being surrounded by a thin interfacial layer consisting of
emulsifier molecules (Acosta 2009; McClements et al. 2007; Nicolas et al. 2014).
Usually, nanoemulsions are highly stable to gravitational separation because the
relatively small particle size means that Brownian motion effects dominate gravita-
tional forces. They also have good stability against droplet aggregation because the
range of attractive forces acting between the droplets decreases with decreasing
particle size, while the range of steric repulsion is less dependent on particle size
(Tadros et al. 2004; Siti et al. 2013).
Other than increasing bioavailability (Hira et al. 2014) and antioxidant (Dasgupta
et al. 2015) the bactericidal (Vijayalakshmi et al. 2013), antimicrobial (Karthikeyan
et al. 2012; Dasgupta et al. 2015), antihelminthc (Karthikeyan et al. 2011), insecti-
cidal (Megha et al. 2014) properties of nanoemulsion gave it importance to be used
in agriculture – mainly to increase the shelf life of agricultural products and water
quality management (Ranjan et al. 2014; Dasgupta et al. 2014). Chaw et al. (2013)
have formulated a nanoemulsion with the insecticidal and pesticidal activity.
The green nanoemulsion – laden glyphosate isopropylamine – formulated were able
to suppress creeping foxglove (A. gangetica), slender button weed (D. ocimifolia)
and buffalo grass (P. conjugatum). This initial discovery could be the platform for
developing better penetration of agrochemical formulations in the future (Chaw
et al. 2013). Similarly they have again used the same nanoemulsion with slight
modification as a herbicide and have concluded that it is having controlling ability
for Eleusine indica (Chaw et al. 2012). Recently many authors have given hypoth-
esis that the microbial products can be used as natural emulsifier to have safer
nanoemulsion to be used in the field of agro-food products (Shivendu et al. 2014;
Vanaja et al. 2014). Also many have hypothesized that the plant extracts or natural
products could be more efficient for its activity when the same can be used in the
form of nanoemulsions (Nandita et al. 2014, 2015b, c). To understand the activity of
nanoemulsion, it is mandatory to understand the synthesis procedures. Also, to get
better bioactivity, the understanding of the bioactive components retention with
nanoemulsion should also be understood.
1.2.3.1 Production of Nanoemulsion
Nanoemulsion can be produced using a variety of methods, which are classified as

either high-energy or low energy approaches (Acosta 2009; Leong et al. 2009;
Tadros et al. 2004; Koroleva and Evgenii 2012; Silva et al. 2012).
High-energy approaches revolve around the use of mechanical force to generate
intense disruptive forces that breakup the oil and water phases thereby forming oil
droplets. For example, high-pressure valve homogenisers, micro-fluidizers, and
sonication methods (Leong et al. 2009; Wooster et al. 2008). The production of
nanoemulsions via this method is primarily governed by composition i.e. mainly
surfactants, functional compounds and secondarily by the quantity of energy
applied. Hence these emulsions depict a tendency towards preserving their forma-
tion against formulation modification like addition of monomer, surfactant, co-
surfactant etc. (Anton et al. 2008). High energy approach for production of
nanoemulsionis further classified into high pressure homogenization, Ultrasound
approach (Quintanilla-Carvajal et al. 2010) and high speed devices approach (Anton
et al. 2008).
1.2.3.2 High-Pressure Homogenization
The mixture is exposed to very high pressures and is pumped through a restrictive
valve. The very high shear stress causes the formation of very fine emulsion droplets
(Quintanilla-Carvajal et al. 2010). Further the impact of homogenization on design
and structure of nanoemulsion have been described by Finke et al. (2014).
Nanoemulsions with antimicrobial/microbial inactivation property have been
developed by high-pressure homogenization method. This formulation can be further
applied for increasing shelf life of agricultural products and also can be used in
water quality management by decreasing microbial load of the water (Francesco
et al. 2013).
1.2.3.3 Ultrasound
When two immiscible liquids are submitted to high-frequency sound waves in the
presence of a surfactant, emulsion droplets are formed by cavitation. This causes
intense shock waves in the surrounding liquid and the formation of liquid jets at
high speed is responsible for the formation of emulsion droplets. However, this
technology has not yet been efficiently used for industrial-scale applications (Maa
and Hsu 1999; Quintanilla-Carvajal et al. 2010; Sanguansri and Augustin 2006).
The scaled up process fornanoemulsion formulation at industrial level by ultrasound
method have been described by using continuous-flow production method – which
can be further applied for formulating nanoemulsion for agricultural applications
(Alexey and Simon 2014). Shams and Ahi (2013) have developed 5A zeolite nano-
crystals using kaolin via nanoemulsion by ultrasonic technique with a increased
sorption properties which can further be used in water quality management for
remediating the sludge (Shams and Ahi 2013).
1.2.3.4 High-Speed Devices
Rotor/stator devices (such as Ultra-Turrax) when compared with the other high
energy approaches do not provide a good dispersion in terms of droplet sizes. With
the energy provided mostly being dissipated as generating heat. Stable nanoemul-
sions are difficult to obtain (Anton et al. 2008; Walstra 1993). Francesco et al.
(2012) have increased the antimicrobial delivery system of nanoemulsion when
designed by high-speed devices (Ultra-Turrax) and proper emulsifier. Same method
can be used to develop nanoemulsions with improved activities which can be applied
in the field of agriculture and water quality management.
Low energy approaches rest upon the impromptu formation of oil droplets within
mixed oil-water-emulsifier systems as and when solution conditions are altered,
e.g., phase inversion and solvent demixing methods (Anton et al. 2008; Yin et al.
2009). Nanoemulsions are obtained in response to phase transitions during emulsi-
fication at constant temperature and altered composition (Usón et al. 2004) or vice
versa (Morales et al. 2003). Low energy approaches are further classified into mem-
brane emulsification (Sanguansri and Augustin 2006), spontaneous emulsification
(Anton et al. 2008), solvent displacement (Yin et al. 2009), emulsion inversion point
(Sadtler et al. 2010) and phase inversion point (Sadurní et al. 2005).
1.2.3.5 Membrane Emulsification
It is a low-energy process that requires less surfactant (when compared with high
energy methods) and produces emulsions with a narrow size distribution range. This
method involves formation of a dispersed phase (droplets) through a membrane into
a continuous phase. Nevertheless, this method has as limitation the ‘low flux’ of the
dispersed phase through the membrane, this being an issue during scale-up
(Sanguansri and Augustin 2006). Membrane emulsification mainly used to increase
the bioavailability of the nutrients e.g. vitamine E (Abdallah et al. 2012; Dasgupta
et al. 2015). Many nanoemulsions have been formulated (by membrane emulsifica-
tion) to increase the shelf life of post harvested products (Ghosh et al. 2014). Some
nanoemulsions have been formulated by this method with improved bioactivity
(Joseph and Heike 2014) and also which acts as a carrier to deliver some bioactive
compound and/or compounds (Keun et al. 2012). In the same way some nanoemul-
sion should be discovered/identified which can be used as a carrier either in plant
tissues or at soil/water/plant interface; also some nanoemulsion conjugated with the
compounds needed for plant growth and can increase the bioavailability of it should
be researched.
1.2.3.6 Spontaneous Emulsification
This mechanism occurs when an organic phase and an aqueous phase are mixed,
with the organic phase being a homogeneous solution of oil, lipophilic surfactant
and water-miscible solvent, and the aqueous phase consisting of water and hydro-
philic surfactant (Bouchemal et al. 2004). Spontaneous emulsification is produced
by different mechanisms (e.g. diffusion of solutes between two phases, interfacial
turbulence, surface tension gradient, dispersion mechanism, condensation mecha-
nism) which seem to be affected by the systems’ compositions and their physico-
chemical characteristics like the physical properties of the oily phase and nature of
the surfactants (Bouchemal et al. 2004). This process itself increases entropy and
thus decreases the Gibbs free energy of the system (Anton et al. 2008).
1.2.3.7 Solvent Displacement
This method consists of mixing a water-miscible organic solvent containing lipo-

philic functional compounds in an aqueous phase containing an emulsifier. The
rapid diffusion of the organic solvent in the aqueous phase promotes the formation
of nanoemulsions enabling their preparation in one step at low-energy input with
high yield of encapsulation. Finally, the organic solvent is removed from the nano-
dispersion under reduced pressure. Nevertheless the use of this technique is limited
to water-miscible solvents (Yin et al. 2009). The non soluble compounds can be
made available by using this method of nanoemulsion fabrication (Regina et al.
2007; Kyle et al. 2014; Gabriel and David 2015) – thus solvent displacement method
can be used in those agricultural soils in which some of the compounds are unavail-
able because of its poor solubility.
1.2.3.8 Emulsion Inversion and Phase Inversion Point
It involves variation of system composition at a constant temperature. The structures

are formed through a progressive dilution with water or oil in order to create kineti-
cally stable nanoemulsions (Anton et al. 2008; Sadtler et al. 2010). Phase inversion
point method uses the specific ability of surfactants (non-ionic) to alter their affini-
ties to water and oil in function of temperature at a fixed composition. It consists in
suddenly breaking-up the micro-emulsions maintained at the phase inversion point
by a rapid cooling (Izquierdo et al. 2004; Sadurní et al. 2005) or by a dilution in
water or oil (Anton et al. 2008). Nanoemulsions immediately formed are kinetically
stable and can be considered as irreversible. This process is relatively simple, pre-
vents the encapsulated drug being degraded during processing, consumes low
amounts of energy and allows an easy industrial scale-up (Anton et al. 2008).
Emulsion inversion and phase inversion methods are used to control the droplet size
and stability of nanoemulsion (Felix et al. 2012). For nanoemulsion research for
agricultural applications these two methods should also be analyzed.
1.3 Nanotechnology and Research Trends in Agriculture
Currently, the major challenges faced by world agriculture include changing cli-
mate, urbanization, sustainable use of natural resources and environmental issues
like runoff and accumulation of pesticides and fertilizers. These problems are fur-
ther intensified by an alarming increase in food demand that will be needed to feed
an estimated population of six to nine billion by 2050 (Chen and Yada 2011). This
above-mentioned scenario of a rapidly developing and complex agricultural system
exists and greater challenges will be posed to the developing countries as, in the
developing countries, agriculture is the backbone of the national economy.
Nanotechnology, this vast field of the twenty-first century, is making a very
significant impact on the world’s economy, industry and people’s lives (Gruere et al.
2011; Scott and Chen 2003). Applications of nanotechnology in materials science
and biomass conversion technologies applied in agriculture are the basis of provid-
ing food, feed, fibre, fire and fuels. Through advancement in nanotechnology, a
number of state-of-the-art techniques are available for the improvement of precision
farming practices that will allow precise control at nanometer scale (Fig. 1.5).
Nanotechnology can also be an alternative source of fertilizer. In an experiment, it
was observed that SiO2 Nanoparticles enhanced germination in tomato (Lycopersicum
esculentum) seeds (Manzer and Mohamed 2014).
1.3.1 Nanoscale Carriers
Nanoscale carriers can be utilized for the efficient delivery of fertilizers, pesticides,
herbicides, plant growth regulators etc. The mechanisms involved in the efficient
delivery, better storage and controlled release include: encapsulation and entrap-
ment, polymers and dendrimers, surface ionic and weak bond attachments among
others. These mechanisms help improve stability against degradation in the environ-
ment and ultimately reduce the mass/amount to be applied, which reduces chemical
runoff and alleviates environmental problems. These carriers can be designed in
such a way that they can anchor the plant roots to the surrounding soil structure and
organic matter. This can only be possible through the molecular and conformational
mechanisms between the delivery nanoscale structure and targeted structures and
Fig. 1.5 Schematic representation for the application of nanotechnology in modern agriculture
(Courtesy: Dasgupta et al. 2014)
matter in soil (Johnston 2010). These advances will help in increasing the bioavail-
ability of active ingredients, thereby reducing the amount of inputs to be used and
also the waste produced. Cai et al. (2014) developed nanoclays which can be added
to traditional fertilizer to improve the retention capacity of nitrogen. Thus, nitrogen
loss is reduced and sufficient nutrition is provided to crops. Many nanoemulsions
have also been formulated to increase the bioavailability of herbicide and pesticide
(Chaw et al. 2012, 2013; Megha et al. 2014).
1.3.2 Fabricated Xylem Vessels
Recent advancement in nanofabrication and characterization tools has enabled the

study of physico-chemical and biological interactions of plant cell bodies and vari-
ous disease-causing organisms. These tools are useful in understanding the mecha-
nisms of pathogenesis and ultimately improved the strategies for the treatment of
these diseases (Cursino et al. 2009; Chen and Yada 2011). To study xylem-inhabiting
bacteria, changes in bacterial populations were monitored through destructive

sampling techniques at different distances from inoculation sites but this does not
provide information about colonization, film development, and subsequent move-
ment and re-colonization at new areas because the same sample site cannot be fol-
lowed temporarily. It has only been through the discovery of micro-fabricated xylem
vessels with nano-sized features that we are able to study the above mechanisms
which otherwise was not possible through traditional methods (Zaini et al. 2009;
Allah 2012). A probe is used which can be inserted into the xylem vessel at the root
base which can monitor xylem pressure, the radial electrical gradients in the root
and activity of particular ions (Wegner 2012). A detailed description of nanotech-
nology in fabricated xylem vessels have been described by Bandyopadhyay et al.
(2013) and fabricated xylem system in the form of nanoliter/picoliter scale fluidic
systems have been summarized (Morgan et al. 2013). Biomimicking of micro/nano-
fabricated xylem vessels system by using microbes e.g. researchers have looked at
the attachment behaviour of Xylella fastidiosa (Leonardo et al. 2007) and Escherichia
coli (Bunpot et al. 2011) in microfluidic flow chambers mimicking plant xylem.
Biomimicking of capillary action has been developed by using micro/nanofabrica-
tion – which may have future application in fabricated xylem vessel development
(Qian et al. 2014; Bharat 2011). To control the photoluminescent emission Carlos
et al. (2013) have used ZnO and Al2O3 nanoparticles in Calamus rotang plant in
natura xylem samples.
1.3.3 Nanolignocellulosic Materials
Recently, nanosized lignocellulosic materials have been obtained from crops and
trees which had opened a new market for innovative and value-added nano-sized
materials and products, e.g. nano-sized cellulosic crystals have been used as light-
weight reinforcement in polymeric matrix (Laborie 2009). These can be applied in
food and other packaging, construction, and transportation vehicle body structures.
Cellulosic nano-whisker production technology from wheat straw has been devel-
oped by Michigan Biotechnology Incorporate (MBI) International, and is expected
to make biocomposites that could substitute for fibre glass and plastics in many
applications, including automotive parts. North Dakota State University (NDSU) is
currently engaged in a project for the commercialization of this technology (Leistritz
et al. 2007). With the applications of food and other packaging, construction, and
transportation vehicle body structures production of nanolignocellulosic materials
is the best way for agricultural waste management – since we can derive nanoligno-
cellulosic materials from lignin and cellulose based agricultural waste (Brinchia
et al. 2013; Ming-xiong et al. 2014).
1.3.4 Clay Nanotubes
Clay nanotubes (Halloysite) have been developed as carriers of pesticides for low
cost, extended release and better contact with plants, and they will reduce the
amount of pesticides by 70–80 %, hence reducing the cost of pesticide and also the
impact on water streams (Murphy 2008). The sorptive and electrical behaviour of
nanocomposites (polylactide and carbon nanotubes/smectite-clay nanocomposites)
was studied and found that polylactide nanocomposites are endowed with increased
sorption and outstandingly enhanced conductivity (up to six or even nine orders of
magnitude) with respect to the pristine polymer (Conductivity = 1 * 10−10 S/m)
(Saveria et al. 2011). This increased sorptive and increased conductivity properties
of nanocomposites may have the future application as selective purification of water
and also this property can be applicable in plant-soil-water interface to increase the
ion transport and sorption of nutrients. Hsu and Jheng (2009) have synthesized and
characterized carbon nanotubes on clay minerals with the application of biosensor
for glucose and hydrogen peroxide detection (Hsu and Jheng 2009) – which may
has major applications in pre as well as post harvested agricultural products and
their quality control. Suprakas (2013) has highlighted the tensile strength of clay/
carbon nanotubes which may further be used in agricultural fields to provide
strength to the crops and protect them from strong wind.
1.3.5 Photocatalysis
One of the processes using nanoparticles is photocatalysis. It involves the reaction

of catalyst with chemical compounds in the presence of light. The mechanism of
this reaction is that when nanoparticles of specific compounds are subjected to UV
light, the electrons in the outermost shell (valence electrons) are excited resulting in
the formation of electron hole pairs, i.e. negative electrons and positive holes
(Zhaoxia et al. 2011). These are excellent oxidizing agents and include metal oxides
like TiO2 (Bhatkande et al. 2001; Khataee et al. 2013), Silver (Zhaoxia et al. 2011),
gold (Vongani et al. 2011) ZnO (Li and Haneda 2003; Mohammad et al. 2011),
SnO2 (Ko et al. 2009), platinum (Zhi and Wenfeng 2014), Ag-α-Fe2O3 nanocompos-
ites (Shaofeng et al. 2014), lanthanum ferrite Nanoparticles (Abazari et al. 2014),
etc., as well as sulfides like ZnS (Feigl et al. 2010) and CdS (Xingyuan et al. 2014).
As the size of particles decrease, surface atoms are increased, which results in tre-
mendous increase in chemical reactivity and other physico-chemical properties
related to some specific conditions such as photocatalysis, photoluminescence, etc.
So this process can be used for the decomposition of many toxic compounds such
as pesticides, which take a long time to degrade under normal conditions (Malato
et al. 2002), e.g. pathogens. Ankita and Vidya (2014) have remediated reactive blue
220 dye with solar light induced photocatalytic degradation by using Ag core–TiO2
shell (Ag@TiO2) nanoparticles. They found higher rate of photocatalysis under
solar light as compared to UV light and also Ag@TiO2 is a better photocatalyst

than Degussa-P25, TiO2NP and Ag doped TiO2 nanoparticle. It can be noted that
Degussa-P25 is a existing product with these properties manufactured by Evonik
Degussa India Pvt. Ltd. Their basic research may turn up with a development of
WQM instruments and/or other agricultural engineering devices (Ankita and Vidya
2014). Using nano-titania Pigeot-Rémy et al. (2011) have used TiO2 nanoparticle
for photocatalysis and disinfection of water and also to decrease target bacterial
load and a rectangular photoreactor has been designed and optimized (Fathinia and
Khataee 2013). Recent research trend is shifting towards finding doped-nanoparticles
with better efficiency for photocatalysis (Saraschandra et al. 2015; Tahir and Amin
2015; Sankar and Vijayanand 2015; Khataee et al. 2015).
1.3.6 Nanobioremediation
Nanoparticles can be used for the bioremediation of resistant or slowly degradable

compounds like pesticides. These harmful compounds tend to join the positive
holes, are degraded and converted into non-toxic compounds. Otherwise these
harmful compounds enter the food chain and result in serious problems for the
body, hence nanoparticles can be used for environmental safety (Lhomme et al.
2008). The main applications of nanotechnology in bioremediation (nanobioreme-
diation) are as uranium remediation, hydrocarbon remediation, groundwater and
wastewater remediation, solid waste remediation, heavy metal remediation. Some
main nanomaterials involved in nanobioremediation are as: nanoiron and its deriva-
tives, nano-sized dendrimers, carbon nanotubes, single enzyme nanoparticles,
engineered nanoparticles etc. (Rizwan et al. 2014; Avinash et al. 2014). Engineered
polymeric nanoparticles have been used in bioremediation of hydrophobic contami-
nants (Tungittiplakorn et al. 2005) and soil remediation (Tungittiplakorn et al.
2004). Biogenic uranite nanoparticles have been used for uranium bioremediation
(Bargar et al. 2008). Biologically synthesized nanomaterials from organisms
Gundelia tournefortii, Centaurea virgata,Reseda lutea, Scariola orientalis,
Eleagnum angustifolia, Bacillus sp. andNoaea Mucronata accumulated heavy
metals – mainly Cu, Zn, Pb, and Ni (Arvind et al. 2011; Avinash et al. 2014; Rizwan
et al. 2014).
1.3.7 Disinfectants
The electron hole pair, especially the negative electrons resulting from the excitation
of nanoparticles, can also be used as a disinfectant of bacteria, as when bacteria make
contact with nanoparticles, the excited electrons are injected into their bodies, which
results in the bacterial removal from the object concerned, as in fruit packaging and
food engineering (Melemeni et al. 2009). Comparatively nanoparticles are better
disinfectants than chemical disinfectants e.g. sodium hypochlorite (NaClO) and
phenol (C6H5OH) etc. (Karthik et al. 2011).Wei et al. (2012) have concluded that
the porous Ca-Si based nanospheres may be developed into a new intra-canal disin-
fectant-carrier for infected canal treatment. Nano-disinfectant in the form of biofilm
has shown improved antimicrobial activity for salmonella and staphylococcus Sp.
(Carla et al. 2012; Hans et al. 2012; Kumar and Ting 2013; Nithila et al. 2014).
1.3.8 Wastewater Treatment
In modern environmental science, the removal of wastewater is an emerging issue

due to its effects on living organisms (Babula et al. 2008; Mulligan et al. 2001).
Many strategies have been applied for wastewater treatment including nanotechnol-
ogy. Photocatalysis can be used for purification, decontamination and deodorization
of air. It has been found that semiconductor sensitized photosynthetic and
photocatalytic processes can be used for the removal of organics, destruction of
cancer cells, bacteria and viruses. Application of photocatalytic degradation has
gained popularity in the area of wastewater treatment (Melemeni et al. 2009).
The detailed mechanism of action (Fig. 1.6) for bactericidal/antimicrobial activity
of nanomaterials has been described (Fahim et al. 2014). There will be differences
Fig. 1.6 Mechanism of bacteria cell damage by the induction of reactive oxygen species
between the mechanism of action for bactericidal activity of metal and metal oxide
Nanoparticles (Solmaz et al. 2014). Understanding the differences in inactivation
mechanisms helps to identify rate-limiting steps involved in the inactivation process
as well as to develop more effective disinfection strategies. Detailed discussion on
wastewater treatment is given in later section of this article.
1.3.9 Nanobarcode Technology
In our daily life, identification tags have been applied in wholesale agriculture and
livestock products. Due to their small size, nanoparticles have been applied in many
fields ranging from advanced biotechnology to agricultural encoding. Nanobarcodes
(>1 million) have been applied in multiplexed bioassays and general encoding
because of their possibility of formation of a large number of combinations that
make them attractive for this purpose. The UV lamp and optical microscope are
used for the identification of micrometer-sized glass barcodes which are formed by
doping with rare earth containing a specific type of pattern of different fluorescent
materials. The particles to be utilized in nanobarcodes should be easily encodeable,
machine-readable, durable, sub-micronsized taggant particles. For the manufacture
of these nanobarcode particles, the process is semi-automated and highly scalable,
involving the electroplating of inert metals (gold, silver) into templates defining
particle diameter, and then the resulting striped nanorods from the templates are
released. These nanobarcodes have the biological as well as non-biological applica-
tions (Mathew et al. 2009). Cost effective nanobarcode technology development is
a major challenge for the researchers – this can be concluded based on the fact that
total of 18 documents found on Scopus indexed article database (SIAD). Out of 18
articles notes (1 in number), conference paper (6 in number) review article (2 in
number) and only 9 research articles were available in last 10 years by the keyword
of “nanobarcode” (SIAD 2014). Similarly, only 32 articles are present in SciFinder®
database with the same keyword. After refining it with year wise none of the article
were found for 2014; only one article in duplicate were found of Han et al. (2013)
which have been discussed earlier; similarly, only three articles have been found for
the year 2012 but none of them have described the application of nanobarcode in
agricultural field (SciFinder 2014). This shows that development of nanobarcode
technology for agricultural application is one of the thrust areas.
1.3.9.1 Biological Applications of Nanobarcodes
Nanobarcodes have been used as ID tags for multiplexed analysis of gene expres-
sion and intracellular histopathology. Improvement in the plant resistance against
various environmental stresses such as drought, salinity, diseases and others have
only been possible through advancement in the field of biotechnology at the
nanoscale. In the near future, more effective identification and utilization of plant
gene trait resources is expected to introduce rapid and cost effective capability
through advances in nanotechnology-based gene sequencing (Branton et al. 2008).

Nanobarcodes can also be used for cost- effective detection of pathogens from food
products (Han et al. 2013).
1.3.9.2 Non-Biological Applications of Nanobarcodes
Nanobarcodes serve as uniquely identifiable nanoscale tags and have been applied
for non-biological applications such as for authentication or tracking in agricultural
food and husbandry products. This nanobarcode technology will enable us to
develop new auto-ID technologies for the tagging of items previously not practical
to tag with conventional barcodes (Branton et al. 2008).
1.3.9.3 Quantum Dots for Staining Bacteria
There are numerous bacteria which are responsible for many diseases in humans
like tetanus, typhoid fever, diphtheria, syphilis, cholera, food-borne illness, leprosy
and tuberculosis caused by different species. As a remedial process, we need to
detect bacteria and for this, dye staining method is used. To stain bacteria, the most
commonly used biolabels are organic dyes, but these are expensive and their
fluorescence degrades with time. So the need of the hour is to find durable and
economical alternatives. Fluorescent labelling by quantum dots with bio-recognition
molecules has been discovered through the recent developments in the field of
luminescent nanocrystals. Quantum dots are better than conventional organic
fluorophores (dyes) due to their more efficient luminescence compared to the organic
dyes, narrow emission spectra, excellent photostability, symmetry and tunability
according to the particle sizes and material composition. By a single excitation light
source, they can be excited to all colors of the Quantum dots due to their broad
absorption spectra (Warad et al. 2004). Bio-labeled bacillus bacteria with
Nanoparticles consisting of ZnS and Mn2+ capped with bio compatible ‘chitosan’
gave an orange glow when viewed under a fluorescence microscope. For the detec-
tion of E. coli O157:H7, Quantum dots were used as a fluorescence marker coupled
with immune magnetic separation (Su and Li 2004). For this purpose, magnetic
beads were coated with anti-E. Coli O157 antibodies to selectively attach target
bacteria, and biotin-conjugated anti – E. coli antibodies to form sandwich immune
complexes. Quantum dots were labelled with the immune complexes via biotin
streptavidin conjugation after magnetic separation.
1.3.10 Biosensors
A variety of characteristic volatile compounds are produced by microorganisms

that are useful as well as harmful to human beings, e.g. fermentation makes use of
yeasts while alcohol is produced as a by-product when bacteria eat sugar. The most
common causal organisms of food rotting are bacteria. Foul odour is a clear indication
of food degradation which may be detected by visual and nasal sensation, but some-
times it may be impractical and a further cause for poisoning. Therefore, it is more
sensible to use an instrument like rapid detection biosensors for the detection of
these odours (Compagnone et al. 1995). The future application of nano-biosensors
recently developed by Xiqi et al. (2014) and Zhang et al. (2014). Nanobiosensors
are hot area of interest in the fields other than food and agriculture but recently
many sensors have been developed after considering its importance. A detailed
review on this has been done by Teresa (2013). ZigBee™ is a wireless mesh net-
working standard with low-cost and utilizes low-power. It has given the concept of
‘Smart Fields’ and ‘SoilNet’. It consists of one or more sensors for environmental
data (temperature, humidity, etc.), a signal conditioning block, a microprocessor/
microcontroller with an external memory chip and a radio module for wireless
communication between the sensor nodes and/or a base station. It can be used for
the identification and monitoring of pests, drought or increased moisture levels in
order to counterbalance their adverse effects on crop production (Kalra et al. 2010).
Through this wireless sensor technology with nanoscale sensitivity, we can control
plant viruses and level of soil nutrients, as the plant surfaces can be changed at
nanoscale with specific proteins. This technology is important in realizing the vision
of smart fields in particular. Wireless network sensor technology can also be used
for monitoring the optimal conditions for mobile plants biotechnology.
1.3.10.1 Rapid Detection Biosensors
These instruments are able to reduce the time required for lengthy microbial testing
and immunoassays. Applications of these instruments include detection of contami-
nants in different bodies such as water supplies, raw food materials and food prod-
ucts (Compagnone et al. 1995). Recently, nano biosensors are developed for rapid
detection of IgG and metabolites (Labroo and Cui 2014; Türkoğlu et al. 2013).
1.3.10.2 Enzymatic Biosensors
Enzymes can act as a sensing element as these are very specific in attachment to
certain biomolecules. According to Patel (2002), enzymatic biosensors on the basis
of immobilization surface are classified into four groups (i) controlled-pore glass
beads with optical transducer element, (ii) polyurethane foam with photo-thermal
transducer element, (iii) ion-selective membrane with either potentiometric or
amperometric transducer element and (iv) screen-printed electrode with ampero-
metric transducer element. Considering microbial contamination a device
(Electrogenerated chemiluminescence immunosensor) has been found by using
Fe3O4@Au to detect Bacillus thuringiensis (Jianping et al. 2013). By keeping food
and agricultural safety into consideration a biosensor using chemiluminescence and
electro-chemiluminescence immunoassay have been found to detect botulinum
neurotoxin serotypes A and B (Cheng and Stanker 2013). While considering

aquaculture – to measure volatile amines levels in fishan optical fiber-based micro-
analyzer was designed – this has future aspect as to develop such nano-biosensor
instead of micro (Silva et al. 2010).
1.3.11 Electronic Nose
It is a device based on the operation of the human nose and is used to identify
different types of odours; it uses a pattern of response across an array of gas sensors.
It can identify the odorant, estimate the concentration of the odorant and find
characteristic properties of the odour in the same way as might be perceived by the
human nose. It mainly consists of gas sensors which are composed of nanoparticles
e.g. ZnO nanowires (Hossain et al. 2005; Sugunan et al. 2005). ZnO nanorods are
used to develop electronic nose which can detect impurities from vapour mixture
(Ko et al. 2013). Their resistance changes with the passage of a certain gas and
generates a change in electrical signal that forms the fingerprint pattern for gas
detection. This pattern is used to determine the type, quality and quantity of the
odour being detected. There is also an improved surface area which helps in better
absorption of the gas.
1.3.12 Gold Nanoparticles
Gold nanoparticles, commercially used as rapid testing arrays for pregnancy tests
and biomolecule detectors, are based on the fact that the colour of these colloids
depends on the particle size, shape, refractive index of the surrounding media and
separation between the nanoparticles. A quantifiable shift in the surface plasmon
response (SPR) absorption peak results due to a small change in any of these param-
eters. We can make these nanoparticles attach to specific molecules by carefully
choosing the capping agent for stabilizing gold nanoparticles. These specific mole-
cules get adsorbed on the surface of these nanoparticles and change the effective
refractive index of the immediate surroundings of the nanoparticles (Nath and
Chilkoti 2004; Yuanyuang et al. 2010). A few nanoparticles will be adsorbed if the
detecting molecules (bio-macromolecules) are larger than the gold nanoparticles
and result in the formation of lumps after agglomeration. Ultimately, colour of gold
nanoparticles is changed due to shift in SPR that result from the reduction of parti-
cle spacing. These properties provide a great opportunity to use gold nanoparticles
for biosensor development. In the field of pharmaceutical science and other
biomedical fields many Gold-nanoparticles-based biosensors have been already
developed for detection of enzyme activity – the same should be researched in the
field of food, agriculture and water quality management (Eliza and Dusica 2013).
1.4 Nanotechnology and Research Trends in Water Quality

Management
Currently, provision of clean and abundant fresh water is one of the most important
challenges faced by the world for human use and industrial applications such as
agriculture (Vörösmarty et al. 2010; Allah 2012). According to a survey, more than
one billion people in the world are deprived of clean water and the situation is get-
ting worse. In the near future, it has been estimated that average water supply per
person will drop by a factor of one third, which will result in the avoidable prema-
ture death of millions of people. Meanwhile non contaminated water is also not
available for proper agricultural practices (Cross et al. 2009). A large amount of
fresh water is required in agriculture, but in turn, it contributes to groundwater pol-
lution through the use of pesticides, fertilizers and other agricultural chemicals. To
combat this problem, novel, sustainable and cost effective technologies will be
required for the treatment of this large amount of waste water produced. During the
treatment of wastewater, critical issues like water quality and quantity, treatment
and reuse, safety due to chemical and biological hazards, monitoring and sensors
should be considered (Schoumans et al. 2014; Thorburn et al. 2013). Research and
development in nanotechnology has enabled us to find novel and economically fea-
sible solutions for remediation and purification of this wastewater. Accessible water
resources are mostly contaminated with water-borne pathogenic microorganisms
like cryptosporidium, coliform bacteria, virus, etc., various salts and metals (Cu, Pb,
As), runoff agricultural chemicals, tens of thousands of compounds considered as
pharmaceuticals and personal care products (PPCP), and endocrine disrupting com-
pounds (EDC) and radioactive contaminants, either naturally occurring or as the
result of oil and gas production as well as mining activities due to natural leaching
and anthropogenic activities (Speed et al. 1987; Jasra et al. 1999). Nano-scale zero-
valent iron can be used for the treatment of distillery wastewater (Homhoul et al.
2011). For improving water quality, nanotechnology has provided novel solutions
(Fig. 1.7).
1.4.1 Nano-oligodynamic Metallic Particles
Physico-chemical microbial disinfection systems like chlorine dioxide, ozone and

ultraviolet are being commonly used in developed countries, but most of the devel-
oping countries are lacking these systems due to the requirement of large infra-
structure which make them costly. The need of the hour is to search and develop
alternative cost-effective technologies. Nanotechnology based oligodynamic
metallic particles have the ability to serve this function. Among these nanomaterials,
silver is the most promising one as it is both bactericidal and viricidal due to the
production of reactive oxygen species that cleaves DNA and can be utilized for a wide
range of applications. Other properties include low toxicity, ease of use, its charge
Fig. 1.7 Diagrammatic representation of nanotechnological aspects in water quality management

which includes heavy metal removal, desalination, photocatalysis, nnao-oligodynamic metals and
nano-sensors
capacity, high surface-to-volume ratios, crystallographic structure and adaptability

to various substrates (Nangmenyi and Economy 2009; Chen and Yada 2011; Faunce
et al. 2014; Jain et al. 2016). Recently researches have been done to vary the size of
silver and gold nanoparticles with simple approaches i.e. changing the concentra-
tion of reactants. The improved activity of antimicrobial and anticancerous activity
was observed for them (Nandita et al. 2015a; Maddineni et al. 2015; Shivendu et al.
2016; Janardan et al. 2016). It also can be noted that, recently trends are changing
toward in silico and computational approach towards toxicity evaluation of inor-
ganic nanoparticles (Ranjan et al. 2015, 2016).
1.4.2 Photocatalysis
Visible light photocatalysis of transition metal oxides, another nanoscale techno-

logical development, produces nanoparticles, nanoporous fibers and nanoporous
foams that can be used for microbial disinfection (Li et al. 2009) and for the removal
of organic contaminants like personal care products (PPCP) and endocrine disrupt-
ing compounds (EDC). Moreover, tubular nanostructures, embedded into microbial
cell wall, can disrupt its cell structure resulting in the leakage of intracellular com-
pounds, and ultimately cell death. A detailed research trends in the field of photoca-
talysis has been discussed above in detail. As discussed above – the recent research
trends for photocatalysis using nanomaterials has been shifted from single
nanoparticles to hybrid nanocomposite e.g. Ag/AgVO3 one-dimensional hybrid

nanoribbons with enhanced performance of plasmonic visible-light photocatalysis
(Zhao et al. 2015); fabrication of plasmonic Pt nanoparticles on Ga-doped ZnO
nanopagodas array with enhanced photocatalytic activity (Hsien-Ming et al. 2015);
PbS quantum dots in ZnO@PbS/graphene oxide has been synthesized for enhanced
photocatalytic activity (Xi-Feng et al. 2015); Zirconium and silver co-doped TiO2
nanoparticles for degradation of methyl orange and methylene blue (Saraschandra
et al. 2015).
1.4.3 Desalination
Due to limited resources of fresh water, it is likely that in the near future, desalina-
tion of sea water will become a major source of fresh water. Conventional desalina-
tion technologies like reverse osmosis (RO) membranes are being used but these are
costly due to the large amount of energy required. Nanotechnology has played a
very important role in developing a number of low-energy alternatives, among
which three are most promising. (i) protein-polymer biomimetic membranes, (ii)
aligned-carbon nanotube membranes and (iii) thin film nanocomposite membranes
(Hoek and Ghosh 2009; Victor et al. 2014). These technologies have shown up to
1000 times better desalination efficiencies than RO, as these have high water perme-
ability due to the presence of carbon nanotube membranes in their structure. Some
of these membranes are involved in the integration of other processes like disinfec-
tion, deodorizing, de-fouling and self-cleaning. In another approach, zeolite nano-
membrane can be used for seawater desalination (Liu and Chen 2013). Some of
these technologies may be introduced in the market place in the near future but
scale-up fabrication, practical desalination effectiveness and long-term stability are
the most critical challenges to be considered before their successful commercial-
ization (Yan et al. 2003). Desalination using nanotechnology with the aspects of
carbon nanotubes (Rasel et al. 2014), reverse osmosis (Peng et al. 2011), forward
osmosis for seawater and wastewater (Linares et al. 2014) have been reviewed ear-
lier. Recently many devices with improved efficiency and performance have been
developed- self-sustained webs of polyvinylidene fluoride electrospun nano-fibers
(Essalhi and Khayet 2014); PVA/PVDF hollow fiber composite membrane modified
with TiO2 nanoparticles (Xipeng et al. 2014); novel integrated system coupled
with nanofluid-based solar collector (Kabeel and Emad 2014); zinc oxide micro/
nanostructures grafted on activated carbon cloth electrodes (Myint et al. 2014);
tubular MFI zeolite membranes (Martin et al. 2012); titanium oxide nanotubes/
polyethersulfone blend membrane (Abdallah et al. 2014); Graphene wrapped
MnO2-nanostructures (Ahmed et al. 2014a); thin film nanocomposite membranes
(Arun et al. 2014); Graphene/SnO2 nanocomposite (El-Deen et al. 2014; Ahmed
et al. 2014b); carbon nanotubes (Goh et al. 2013).
1.4.4 Removal of Heavy Metals
Ligand based nanocoating can be utilized for effective removal of heavy metals as
these have high absorption tendency. It becomes cost effective as it can be regener-
ated in situ by treatment with bifunctional self-assembling ligand of the previously
used nanocoating media. Farmen (2009) used crystal clear technology for water
purification in which multiple layers of metal can be bonded to the same substrate
using crystal clear technologies (Farmen 2009). According to, another strategy for
the removal of heavy metals is the use of dendrimer enhanced filtration and it can
bind cations and anions according to acidity (Diallo 2009). Nowadays nanomaterials
have been widely used to remove heavy metals from water/wastewater due to their
large surface area and high reactivity. Metal oxide nanoparticles, including nano-
sized ferric oxides, manganese oxides, aluminum oxides, titanium oxides, magne-
sium oxides and cerium oxides, provide high surface area and specific affinity for
heavy metal adsorption from aqueous systems. To date, it has become a hot topic to
develop new technologies to synthesize metal oxide nanoparticles, to evaluate their
removal of heavy metals under varying experimental conditions, to reveal the under-
lying mechanism responsible for metal removal based on modern analytical tech-
niques (XAS, ATR-FT-IR, NMR, etc.) or mathematical models, and to develop
metal oxide-based nanomaterials of better applicability for practical use i.e. granu-
lar oxides or composite materials (Ming et al. 2012). Additionally, humic acid and
fulvic acid exist ubiquitously in aquatic environments and have a variety of func-
tional groups which allow them to complex with metal ions and interact with nano-
materials. These interactions can not only alter the environmental behaviour of
nanomaterials, but also influence the removal and transportation of heavy metals by
nanomaterials. Thus, the interactions and the underlying mechanisms involved war-
rant specific investigations. Wang-Wang et al. (2014) have given a detailed review
on the effects of humic acid and fulvic acid on the removal of heavy metals from
aqueous solutions by various nanomaterials, mainly including carbon-based nano-
materials, iron-based nanomaterials and photocatalytic nanomaterials. Mainly they
have discussed the mechanisms involved in the interactions and evaluated the poten-
tial environmental implications of humic acid and fulvic acid to nanomaterials and
heavy metals.
1.4.5 Wireless Nanosensors
Crop growth and field conditions like moisture level, soil fertility, temperature, crop
nutrient status, insects, plant diseases, weeds, etc. can be monitored through
advancement in nanotechnology. This real-time monitoring is done by employing
networks of wireless nanosensors across cultivated fields, providing essential data
for agronomic intelligence processes like optimal time of planting and harvesting
the crops. It is also helpful for monitoring the time and level of water, fertilizers,
pesticides, herbicides and other treatments. These processes are needed to be admin-
istered given specific plant physiology, pathology and environmental conditions and
ultimately reduce the resource inputs and maximize yield (Scott and Chen 2003).
Scientists and engineers are working to develop the strategies which can increase
the water use efficiency in agricultural productions, e.g. drip irrigation. This has
moved precision agriculture to a much higher level of control in water usage, ulti-
mately towards the conservation of water. More precise water delivery systems are
likely to be developed in the near future. These factors critical for their development
include water storage, in situ water holding capacity, water distribution near roots,
water absorption efficiency of plants, encapsulated water released on demand, and
interaction with field intelligence through distributed nano-sensor systems (Cross
et al. 2009). Sensing and detection of various contaminants in water at nanoscale
under laboratory and field conditions has remained a hot issue over the last decade.
In the near future, state-of-the-art nanotechnology-based techniques will help in
developing many new technologies that will have better detection and sensing abil-
ity (Chen and Yada 2011). Similar to nanobarcode development – wireless nanosen-
sor development for WQM is one of the vital fields of the research. Sensor networks
are a key technological and economic driver for global industries in the near future,
with applications in health care, environmental monitoring, infrastructure monitor-
ing, national security, and more. Developing technologies for self-powered nano-
sensors is vitally important. Zhong (2012) has given a brief summary about recent
progress in the area, describing nanogenerators that are capable of providing
sustainable self-sufficient micro/nanopower sources for future sensor networks.
Negligible research work has been done in the field of wireless nanosensor develop-
ment (SIAD 2014; SciFinder 2014) out of which mostly are conceptual notes and/
or book chapters and reviews. Mannoor et al. (2013) have done an outstanding work
after developing wireless raphene-based nanosensor for detection of bacteria. In
particular, they have demonstrated integration onto a tooth for remote monitoring of
respiration and bacteria detection in saliva. Since they have developed a wireless
nanosensor to detect bacterial load in saliva which is an aqueous phase – by keeping
this concept in mind one can think about developing such device for bacterial load
detection.
It can be noted that other than food and agriculture, nanotechnology has grown
interest in many fields. Figure 1.1 represents the allied fields and Fig. 1.8 represents
the patents (Edgar et al. 2011). The beneficial properties – increased surface area,
apparent solubility, good retention time, direct uptake of nanomaterials, and
enhanced nutritional quality – open the ample scope for the nanotechnology with
different applications and have best future to cover the market has been summarized
in Fig. 1.9. On contrary, one should not ignore the toxicological aspect of
nanomaterials on humans, animals and its impact on ecosystem, the same has been
discussed in other chapters of this book (Fig. 1.10).
Fig. 1.8 A diagrammatic representation of patents in different applied nanotechnology sector in

previous decade. It represents the sharp increase in use of nantechnology in different sectors
including agriculture and foods (Courtesy: Edger et al. 2011)
1.5 Conclusion
Nanotechnology has not only improved the quality of modern agricultural practices
by making them technical, susceptible, safer and improved quality in agricultural
products nutritious but have also helped a lot in generating new agricultural prod-
ucts, better packaging and storage techniques and improved the quality of the its
allied field such as water quality management. Conversion of materials to its nano
form helps in enhancement of their physiochemical properties and applications e.g.
silver nanoparticles shows antibacterial property and they are being incorporated
into bandages for their beneficiary effect in ailing wound; however the bulk particles
are less effective. Titanium dioxide, used as an intense white pigment is opaque in
nature. However, nanoparticles of titanium dioxide are transparent and due to its
physical nature, they are being used in transparent sunscreens, food packaging or
plastic food containers.
Application of nanotechnology has enhanced the delivery of fertilizers, pesti-
cides, herbicides and plant growth regulators with the help of nanoscale carriers;
also its application in agricultural sector as fabricated xylem vessel, clay nanotubes,
Nano-Food
Benefits Applications Future
∑ increased surface ∑ bio-sensors for detecting ∑ functional foods

area pathogens ∑ time saving
∑ apparent solubility ∑ smart packaging for ∑ taste and flavor
∑ good retention time better preservation (intense
∑ direct uptake of ∑ food traceability experiences)
nano particles ∑ encapsulation for ∑ customized food
∑ enhanced efficient delivery/reduced ∑ authentic
nutritional quality toxicity ∑ hazard
∑ Water quality management
management ∑ protocol
∑ nanobarcode development
Fig. 1.9 The beneficial properties – increased surface area, apparent solubility, good retention
time, direct uptake of nanomaterials, and enhanced nutritional quality – open the ample scope for
the nanotechnology with different applications and have best future to cover the market
Nano-
materials Hazard
identification
Exposure
assessment
Hazard
Characterization
Risk
Characterization
Risk Management
Risk Risk Risk

Prevention Mitigation Communication
Fig. 1.10 The toxicological aspect of nanomaterials on humans, animals, environment and whole
ecosystem. Diagrammatic representation of overview of nano-toxicological analysis
photocatalysis, wastewater treatment, nanobarcode technique, different types of

biosensors, Quantum dots for bacterial staining etc. In addition, nanomaterials are
further researched to keep the product fresher with increased shelf life. Nanoscience
and nanotechnologies have vast applications in water quality managementas heavy
metal removal, nano-bioremediation through nanolignodynamic metals, desalina-
tion, disinfecting process and the sensors to check the quality. Nevertheless, many
of their applications are currently at a beginning stage and most of them require a
high quality of research and development for their safe application. The safety of
nanoparticles in agri-food industry also offers challenge to government and industry
both. The food processing industry must ensure the consumer confidence and accep-
tance of nanofoods safety. When it comes to the application of nanotechnology in
industrial scale, it is important to evaluate the release of nanoparticles into the envi-
ronment and to estimate the subsequent levels of exposure to these materials. As the
nanoparticles can easily penetrate into the human organ and organelles, exposure
time, exposure concentrations, sites of penetration, immune response and accumu-
lation and retention of nanoparticles in body and their subsequent effects should be
assessed carefully.
Even though the research regarding the application of nanotechnology is grow-
ing every day, still insufficient scientific examination of naturally occurring nano-
systems is available. The compulsory testing of nano-modified agricultural products
and/or treated water should be performed before they allowed to be introduced into
the market. Standardized test procedures are required to study the impact of
nanoparticles on living cells for evaluation of the risk assessment on human exposure
to nanoparticles. Toxicology of nanoparticles is poorly understood because of the
lack of validated test methods and the inconsistency in the reported data. The incon-
sistency in the published data is due to the improper characterization of nanoparti-
cles and the interferences induced by the nanoparticles in the available test system.
Hence, the regulatory bodies and the policy makers should provide the guidance
document for the validated protocols, safe uses and the disposal of the nanoparti-
cles. The understanding of the safe application of nanoscience and nanotechnology
in agri-food and water quality management will help in the sustainable growth of
“nanoagri-technology”.
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Chapter 2
Nanotechnology Definitions, Research,
Industry and Property Rights
Namita Ashish Singh
Abstract Nanotechnology uses nanomaterials for human benefit. In this chapter

I present the various nanomaterials such as liposomes, nanowires and carbon
nanotubes. The next section describe nanotechnology research in biomedial, food,
agriculture and environmental sciences. Then I present nanotechnology application in
the oil, textile, food and cosmetic industry. Intellectual property rights are discussed
in the last section.
Keywords Nanotechnology • Biomedical • Agri food • Textile • Oil and gas industry
• Cosmaceuticals • Patents
2.1 Introduction
Nanoscale refers size dimensions between approximately 1–100 nm (or more

appropriately, 0.2–100 nm) because at this scale the properties of materials differ
with respect to their physical, chemical and biological properties from a larger
scale. Any form of a material that has one or more dimensions in the nanoscale is
known as nanomaterial (Sekhon 2014). Nanoparticles have unique biological prop-
erties like small size, large surface area-to-volume ratio which allows them to bind,
absorb and carry compounds such as small molecule drugs, DNA, RNA, proteins,
and probes with high efficiency (Khan et al. 2015; Nandita et al. 2016b).
N.A. Singh (*)

Department of Life Sciences, Institute of applied medicine and research,
9th Km. Stone Delhi-Meerut Road, Ghaziabad, UP 201206, India

44 N.A. Singh
2.1.1 Nanoparticles Types
2.1.1.1 Liposomes
Liposomes are the simplest forms of nanovectors (hollow or solid structured

nanoparticles which can be filled with various anticancer drugs, targeting moieties
and detection agents) which are made up of lipids enclosing water core (Park 2002).
2.1.1.2 Dendrimers
Dendrimers are artificial macromolecules having tree like structures in which atoms
are arranged in many branches radiate from a central core. Dendrimers are self
assembling synthetic polymers which were used in the magnetic resonance imaging
of lymphatic drainage in mouse model of breast cancer (Kobayashi et al. 2004).
2.1.1.3 Nanoshells
Nanoshells are other nanoparticles composed of a gold shell surrounding a

semiconductor.
2.1.1.4 Nanowires
Nanowires are sensing wires coated with antibodies like molecules to bind to pro-
teins of interest. Silicon nanowires are real time detectors for molecular binding
effects.
2.1.1.5 Fullerenes Based Derivatives
Fullerenes are nanostructured arrangement of carbon atoms in specific soccer like

architecture. They may also form nanotubes which are cylindrical carbon atom
assemblies. Fullerenes have found several specific sensing applications.
2.1.1.6 Quantum Dots
Quantum Dots are inorganic fluorescent semiconductor nanoparticles composed of

10–50 atoms with a diameter ranging 2–10 nm (Cai and Chen 2007).
2 Nanotechnology Definitions, Research, Industry and Property Rights 45
2.1.1.7 Gold Nanoparticles
Gold nanoparticles have been used in vitro based on their ability to scatter visible
light (Sokolov et al. 2003).
2.1.1.8 Carbon Nanotube
Carbon nanotubes are cylinders of several graphite layers with a diameter in nano-
meters. They may be classified into single-walled carbon nanotubes and multi-
walled carbon nanotubes. Due to their unique electronic, thermal and structural
characteristics carbon nanotubes they offer a unique approach for drug and gene
delivery (Tanaka et al. 2004).
2.1.1.9 Nanobiosensors
A device used for detection of an analyte through combination of a sensitive

biological component, transducer along with a detector component is termed as a
biosensor (Mody 2011).
Nanotechnology uses include nanoparticle-mediated gene or DNA transfer in
plants for the development of insect-resistant varieties, food processing and storage;
nano feed additives, and increased product shelf life. The agri-food theme focuses
on sustainability and protection of agriculturally produced foods, including crops
for human consumption and animal feeding. Nanotechnology provides new agro-
chemical agents and new delivery mechanisms to improve crop productivity.
Nanotechnology can boost agricultural production, by nanoformulations of agro-
chemicals for applying pesticides and fertilizers for crop improvement. Nanosensors
or nanobiosensors can be used in crop protection for the identification of diseases
and residues of agrochemicals (Sekhon 2014).
Nanoliposome applications in medicine include molecular imaging, disease
diagnosis, bioactive encapsulation and passive or active targeted delivery. Some of
the current nanocarrier systems are nanoscale size of conventional systems, such as
nanocrystals, micelles, nanoliposomes and dendrimers (Park 2007).
An ‘oil-microbe detection tool’, using nano optical fibers has been developed to
detect the by passed oil or the oil left behind after water flooding (Jahagirdar 2008).
Nanotechnology produces nanomaterials with many attractive properties, which
can play an important role in reducing friction, eliminating differential pipe stick-
ing, maintaining borehole stability, protecting reservoir, and enhancing oil and gas
recovery. Nanomaterials also have potential for oil well drilling operations in the
forms of nanoscale drilling fluid additives and nanofluids in petroleum development
(Kasiralvalad 2014).
46 N.A. Singh
2.2 Research Innovations
2.2.1 Nanotechnology Biomedical Applications
Nanoparticles are used for disease diagnosis, drug delivery, gene therapy of cancer,
pulmonary diseases and prevention of other infections also. Cancer is one of the
leading causes of death worldwide. Cancer is malignant neoplasm, there is uncon-
trolled division of cells which enter into normal adjacent tissues and destroy
them (Maddinedi et al. 2015). There are different nanoparticle based delivery
systems are available for therapeutic and diagnostic uses as depicted in Table 2.1.
Liposomes are coated with polyoxyethylene which prevent opsonisation of lipo-
somes and their uptake by macrophages (Senior et al. 1999). The drug is targeted to
the target site passively owing to the physiological conditions of the body. Various
Doxorubin encapsulated liposomal formulations have been clinically utilized for
the treatment of Kaposi’s sarcoma, breast cancer and ovarian cancer (Palao 2004).
Cancer drugs like amphotericin and haymycin, when used as liposomal drugs pro-
duce much better efficacy and safety as compared to conventional preparations.
Majoros et al. (2006) have shown the synthesis, characterization and functionality
of Poly (Amidoamine) dendrimer based anticancer therapeutics.
When nanoshells they reach the cancer cells, they can be irradiated. These irra-
diations make them hot which ultimately kill the cancer cells. This technique has
been successfully utilized in veneral tumours in mice (Hirsch et al. 2003). Nanowire
based arrays are used for early diagnosis of cancer and cancer treatment. Quantum
dots due to their long term, high sensitivity and multicontrast imaging properties
they are used for detection and diagnosis of cancer in vivo (Morrow et al. 2007).
Sokolov et al. (2003) successfully used gold nanoparticles conjugated to anti-
bodies to level cervical biopsies for identification of precancerous lesions. The use
of nanobiosensors in cancer clinical testing have been increased due to high speed,
Table 2.1 Nanoparticle based delivery systems for therapeutic and diagnostic uses
Nanoparticle based delivery systems Therapeutic and diagnostic use
Liposomes Controlled and targeted drug delivery, targeted gene
delivery
Dendrimers Targeted drug delivery
Nanoshells Tumour targeted
Nanowires, fullerenes based As targeting and imaging agents
derivatives
Quantum dots As targeting and imaging agents
Gold nanoparticles Targeted delivery and imaging agents
Carbon nanotube Drug gene and DNA delivery, tumor targeting
Nanobiosensors Early diagnosis of cancer and detection of cancer
agents
reduced cost for diagnosis, automation and multi target analysis (Rasooly 2006;
Wang 2006). Nanobiosensors are useful for early diagnosis of cancer. They can also
effectively be utilized for the detection of cancer agents such as environmental
pollutants, pathogens and carcinogenic gases (Mody 2011).
Nanocarriers can be applied for pulmonary therapies, they penetrate or overcome
blood brain barrier, branching pathways of the pulmonary tract, and the tight epithe-
lial junctions of the skin (Courrier et al. 2002; Hughes 2005). Nanosilver is also
used as a biocide to prevent infection in burns, traumatic wounds, and diabetic
ulcers (Silver et al. 2006).
Fullerene compounds can be employed as antiviral agents, most notably against
human immuno-deficiency virus (Schinazi et al. 1993) antibacterial agents e.g.,
Escherichia coli, Streptococcus, Mycobacterium tuberculosis (Tsao et al. 1999a; b;
Bosi et al. 2000). Fullerene compounds are also used as antioxidant and antiapop-
totic agents for the treatment of amyotrophic lateral sclerosis (Dugan et al. 2000)
and Parkinson’s disease (Cai et al. 2008) and in many other applications.
Cochleates are small lipid-based carriers consist of a negatively charged lipid
and a divalent cation. Cochleates and nanocochleates have been used to deliver
peptides, proteins, DNA for vaccine and gene therapy. Due to their nanometric size,
stability and resistance to degradation in the gastrointestinal tract, nanocochleates
have revealed great potential to deliver bioactive agents both orally and parenterally.
Cochleates containing amphotericin B are now in development for the oral and par-
enteral treatment of fungal infections (Mozafari 2006; Darani and Mozafari 2010).
2.2.2 Nanotechnology in Agri-Food Production
2.2.2.1 Nanotechnology for Crop Improvement
A variety of nanomaterials, mostly metal-based nanomaterials and carbon-based

nanomaterials, have been exploited for their absorption, translocation, accumula-
tion, and effects on growth and development of crop plants (Nair et al. 2010; Rico
et al. 2011). The positive morphological effects included enhanced germination per-
centage and rate, length of root and shoot, their ratio and vegetative biomass of
seedlings in many crop plants, including corn, wheat, ryegrass, alfalfa, soybean,
rape, tomato, radish, lettuce, spinach, onion, pumpkin, cucumber etc. Enhancement
of many physiological parameters such as enhanced photosynthetic activity and
nitrogen metabolism by metal-based nanomaterials in a few crops including soy-
bean (Agrawal and Rathore 2014; Nandita et al. 2015a). Magnetic nanoparticles
coated with tetramethylammonium hydroxide led to an increase in chlorophyll-a
level in maize.
Nanobiosensors can be effectively used for sensing a wide variety of fertilizers,
herbicide, pesticide, insecticide, pathogens, moisture, soil pH, and their controlled
use can support sustainable agriculture for enhancing crop productivity (Guo 2004).
48 N.A. Singh
2.2.2.2 Nanofoods
The agri-food industries have been investing huge money into nanotechnology
research. Food is nanofood when nanoparticles or nanotechnology techniques or
tools are used during cultivation, production, processing, or packaging of the
food (Ranjan et al. 2014). Foods among the nanotechnology-created consumer
products coming onto the market include a brand of canola cooking oil called
Canola Active Oil (Shemen Industries, Tel Aviv, Israel), a tea called Nanotea
(Qinhuangdao Taiji Ring Nano-Products Co., Ltd., Hebei, People’s Republic of
China), and a chocolate diet shake called Nanoceuticals Slim Shake Chocolate
(RBC Life Sciences Inc., Irving, TX, USA). The canola oil contains an additive
called “nanodrops” designed to carry vitamins, minerals, and phytochemicals
through the digestive system and urea (Washington DC 2013).
2.2.3 Nanofertilizers
Traditional fertilizers substitution by nanofertilizers is a way to release nutrients

into the soil gradually thus preventing autrification and pollution of water resources
(Moaveni and Kheiri 2011; Naderi and Abedi 2011). Treatment with TiO2 nanopar-
ticles on maize had a considerable effect on growth, titanium nanoparticles increases
light absorption and photo energy transmission. A compound of SiO2 and TiO2
nanoparticles increased the activity of nitrate reductase in soybeans and intensified
plant absorption capacity, making its use of water and fertilizer more efficient
(Lu et al. 2002; Ranjan et al. 2016).
Nanofertilizers have unique features like ultrahigh absorption, increase in
production, rise in photosynthesis, and significant expansion in the leaves’ surface
area. The use of nanofertilizer leads to an increased efficiency of the elements,
reduces the toxicity of the soil, to at least reach the negative effects caused by the
consumption of excessive consumption of fertilizers, and reduces the frequency of
application of fertilizers (Naderi and Danesh-Shahraki 2013).
2.2.4 Nanotechnological Applications in Agrowaste

Reduction and Biofuels
Nanomaterials could stimulate microorganism metabolism. Nanomaterials could

improve the efficiency of the lipid extraction and without harming the microalgae.
Nanomaterials such as calcium oxide and magnesium oxide nanoparticles have
been used as biocatalyst carriers in oil transesterification to biodiesel. The advances
in application of nanotechnology in microalgae lipid accumulation extraction, and
transesterification were reported (Zhang et al. 2013). Cellulose-based nanomaterials

have been used as potential nanoreinforcing filler into biocomposites for industrial
and biomedical applications (Kumar et al. 2014).
2.2.5 Nanoagrochemicals
Pesticides are commonly used in agriculture to improve crop yield and efficiency.
Nanopesticides are new strategies used to address the problems of agriculture
(Sasson et al. 2007). Nanomaterials serve equally as additives (mostly for controlled
release) and active constituents (Gogos et al. 2012). Controlled-release formula-
tions of imidacloprid, synthesized from polyethylene glycol and various aliphatic
diacids using encapsulation techniques, have been used for efficient pest manage-
ment in different crops. In addition, some of the developed controlled-release
formulations recorded higher yield over commercial formulation and control (Adak
et al. 2012). Researchers have reported different aspects of nanoparticle formulation,
characterization, effect of their characteristics, and their applications in management
of plant diseases (Al-Samarrai 2012).
2.2.6 Nanomaterials Based Biosensor for Bacterial

Contaminants in Milk
An amperometric immunobiosensing strip with conjugating secondary enzyme-

labeled antibodies with gold nanoparticles has been developed to detect to detect
Listeria monocytogenes at two log colony-forming unit (CFU)/g in wild blueberry
samples. This method showed significant specificity over other enteric pathogens
such as Escherichia coli O157:H7 and Salmonella typhimurium (Davis et al. 2013).
2.2.7 Nanotechnology in Oil Industry
Nanotubes have many potential applications within the oil industry. For instance,
nanotubes could be used to create lighter, stronger, and more corrosion-resistant
structural materials. Nanotechnology could help improve oil and gas production by
making it easier to separate oil and gas in the reservoir for instance, through
improved understanding of processes at the molecular level. There are many other
potential clean energy sources that could be enhanced through the use of nanotech-
nology. One specialized petroleum laboratory has developed an advanced fluid
mixed with nanosized particles and superfine powder that significantly improves the
50 N.A. Singh
drilling speed and can eliminate formation damage in near wellbore zone (Abdollah
2009). Subsurface micro and nanosensors could be injected in oil and gas well bores
for recovery (Kong and Ohadi 2010).
2.2.8 Nanotechnology in Gas Industry
Nanotechnology could be used to enhance the possibilities of developing unconven-

tional gas resources. Near-term challenges focus on liquefied-natural-gas infra-
structure, efficiency, quality and developing gas-to-liquids technology. Midterm
challenges include developing superpipelines; constructing floating gas-to-liquids
platforms; production, regasification, and storage issues; and compressed-natural-
gas transport. Long-term issues are production of methane hydrates and gas by wire
producing electricity at the location of the gas source and carrying the electricity by
wire to market rather than the gas to market by pipeline. Nanotechnology can
address the problems associated with accessing stranded natural-gas resources by
developing nano catalysts and nanoscale membranes for gas-to-liquids production
and creating nano structured materials for compressed-natural-gas transport or
long-distance electricity transmission (Abdollah 2009).
The recovery of gas from hydrates requires the dissociation of gas hydrates,
air-suspended Ni-Fe nanoparticles when injected in the hydrate formation they will
penetrate deep into hydrate reservoir by passing through the cavities. The self-
heating of Ni-Fe particles in a magnetic field is caused by hysteresis loss and
relaxation losses. These particles cause a temperature rise up to 42 °C leading to
disturbance in thermodynamic equilibrium and causing the water cage to decom-
pose and release methane (Bhatia and Chacko 2011).
2.2.9 Nanotechnology in Textile Industry
Nanotechnology is applied in textile industry due to the increased durability of fabrics,

comfortness, hygienic properties and reduced production cost. Nanotechnology
also offers many advantages as compared to the conventional process in term of
economy, energy saving, eco-friendliness, control release of substances, packaging,
separating and storing materials on a microscopic scale for later use and release
under control condition (David 2002).
Nanoparticles can provide high durability for treated fabrics as they posses large
surface area and high surface energy that ensure better affinity for fabrics and led to
an increase in durability of the desired textile function. The particle size also plays
a primary role in determining their adhesion to the fibres. It is reasonable to accept
that the largest particle cluster will be easily removed from the fibre surface, while
the smallest particle will penetrate deeper and adhere strongly into the fabric matrix
(Kathiervelu 2003; Wang and Chen 2005). Thus due to the decreasing size of
particles to nano-scale dimensional, changes in the properties of the material occurs.
Table 2.2 Some finishing based developments through nanotechnology in textile industries
Application in textile Nanomaterials used References
Electro conductive and Carbon black, carbon nanotubes Dong and Huang (2002)
antistatic (CNT), Cu, Polypyrrole, Polyaniline and Anonymous (2003)
Increase durability Al2O3, SiO2, CNT, ZnO, Burniston et al. (2004) and
Polybutylacrylate Wong et al. (2006)
Antibacterial Ag, Chitosan, SiO2 Burniston et al. (2004),
(as matrix),TiO2 , ZnO Wong et al. (2006) and
Nandita et al. 2015b
Self-cleaning/dirt and CNT, Fluoroacrylate, SiO2 Lei and Juan (2003) and
water repellent (as matrix), TiO2 Zhang et al (2003)
Moisture absorbing TiO2 Burniston et al. (2004)
UV protection TiO2, ZnO Burniston et al. (2004) and
Wong et al. (2006)
Controlled release of active Montmorillonite (nano clay), SiO2 Harholdt (2003)
agents, medicinal products (as matrix)
or fragrances
Areas where nanotech enhanced textiles are already seeing some applications
include sporting industry, skincare, space technology and clothing as well as materi-
als technology for better protection in extreme environments.
The use of nanotechnology allows textiles to become multifunctional and produce
fabrics with special functions, including antibacterial, UV-protection, easy-clean,
water and stain repellent and anti-odour: Kathiervelu (2003) as shown in Table 2.2.
To impart wrinkle resistance to fabric, resin is commonly used in conventional
methods. However, there are limitations to applying resin, including a decrease in
the tensile strength of fibre, abrasion resistance, water absorbency and dye-ability,
as well as breathability. To overcome the limitations of using resin, some research-
ers employed nano-titanium dioxide and nano-silica to improve the wrinkle resis-
tance of cotton and silk. Nano-titanium dioxide is used with carboxylic acid as a
catalyst under UV irradiation to catalyse the cross-linking reaction between the cel-
lulose molecule and the acid while nano-silica is used with maleic anhydride as a
catalyst to improve the wrinkle resistance (Song et al. 2001; Zhou et al. 2003;
respectively (Wong et al. 2006).
Silver nanoparticles are used in socks and sports clothing because of their ability
to kill bacteria and inhibit unwanted odors (Medero 2013).
2.2.10 Nanotechnology in Food Industry
Nanoscience applications in foods suggested the technologies that create added values
that are most needed and that will have the highest impact on consumers. Four major
types of applications of nanotechnology in the food industry namely agriculture,
food processing, food packaging, and supplements are described in Table 2.3.
52 N.A. Singh
Table 2.3 Application of nanotechnology being researched, tested, and applied in the food
industry
Agriculture Food processing Food packaging Supplements
Nanotechnology Nanocapsules for Fluorescent Nanosize powders for
enabled single improving nanoparticles with increasing absorption
molecule detection for bio-availability of attached antibodies of nutrients
determining enzyme/ neutraceuticals in for detecting
substrate interactions standard ingredients chemicals or
such as cooking oils food-borne pathogens
Nanopsules for Nano encapsulated Biodegradable Cellulose nanocrystal
delivery of pesticides, flavor enhancers nanosensors for composites as drug
fertilizers, and other temperature, carriers
agri-chemicals moisture, and time
monitoring
Nanotechnology Nanotubes and Nanoclays and Nanocochleates (coiled
enabled delivery of nanoparticles as nanofilms as barrier nanoparticles) for
growth hormones in a gela-tion and materials to prevent more efficient nutrient
controlled fashion viscosifying agents spoilage and oxygen delivery to cells
absorption without affecting color
or taste of food
Nanosensors for Nanocapsule Electrochemical Vitamin sprays that
monitoring soil infusions of nanosensors for disperse nanodroplets
conditions and crop plant-based steroids detecting ethylene with better absorption
growth as a replacement for
meat cholesterol
Nanochips for identity Nanoparticles that Nanoparticle
preservation and selectively bind and containing anti-
tracking remove chemicals microbial and
or pathogens from antifungal surface
food coatings
Nanosensors for Nanoemulsions and Lighter, stronger, and
detecting animal and nanoparticles for more heat-resistant
plant pathogens better availability films made of silicate
and dispersion of nanoparticles
nutrients
Pray and Yaktine (2009); Nandita et al. 2015a
Cow udder cell produces casein micelles and fat globules, both key ingredients
of milk, with casein micelles ranging in size from 300 to 400 nm and fat globules
ranging in size from 100 nm to 20 μm. Fat globule membranes have a thickness of
4–25 nm. The dairy industry utilizes these three basic micro and nano-sized struc-
tures to build all sorts of emulsions (butter), foams (ice cream and whipped cream),
complex liquids (milk), plastic solids (cheese) and gel networks (yogurt) (See and
Stanley 1999).
Nanocomposites focus on the development of high barrier properties against the
diffusion of oxygen, carbon dioxide, flavor compounds, and water vapor.
Bionanocomposites suitable for packaging applications include starch and cellulose
derivatives, poly lactic acid, poly caprolactone, poly butylenes succinate and
polyhydroxy-butyrate. Nanoclay (montmorillonite, a hydrated alumina silicate
layered clay consisting of an octahedral sheet of aluminum hydroxide between two

silica layers) minerals are found abundantly in nature and might be incorporated
into the packaging films. The use of nanocomposites with new thermal and gas
barrier properties can prolong the post-harvest life of food and this application
could facilitate the transportation and storage of food.
Nanolaminates, which consist of two or more layers of nano-materials (physi-
cally or chemically bonded to each other), are suitable for use in the food industry.
Nanolaminates can be used for the preparation of edible coatings and films which
are currently used in the food industry such as fruit, vegetables, meats, chocolate,
candies, bakery products and French fries. These coatings or films could be used as
barriers to moisture, lipid, gases and increase the textural properties of foods, or
applied as carriers of functional agents including colors, flavors, antioxidants, nutrients,
and antimicrobials (Phan et al. 2008; Ponce et al. 2008; Cha and Chinnan 2004;
Rhim 2004).
Silver colloids, silver nanoparticles have been found to be effective against numer-
ous species of bacteria, including: E. coli, Enterococcus faecalis, Staphylococcus
(aureus and epidermidis), Vibrio cholera, Pseudomonas (aeruginosa, putida, fluore-
scens), Shigella flexneri , Bacillus (anthracis, subtilis and cereus), Proteus mirabilis,
Salmonella enteric Typhimurium, Micrococcus luteus, Listeria monocytogenes and
Klebsiella pneumoniae (Panacek et al. 2006; Eby et al. 2009; Egger et al. 2009;
Fayaz et al. 2010; Duncan 2011). Silver nanoparticles are also effective against
strains of these organisms that are resistant to potent chemical antimicrobials,
vancomycin-resistant Enterococcus and extended- spectrum b-lactamase. In addition,
silver nanoparticles are toxic to fungi (e.g.,Candida albicans, Aspergillus niger,
Trichophyton mentagrophytes (Kim et al. 2009; Duncan 2011).
2.2.11 Nanotechnology Based Cosmeceuticals
Cosmeceutical is defined as a product between a drug and cosmetics and cosmeceu-

ticals are the fastest growing segment of the personal care industry (Fulekar 2010).
Liposomes are used in a variety of cosmeceuticals because they are biocompatible,
biodegradable, nontoxic, flexible vesicles and can encapsulate active ingredients
easily and liposomes can protect the encapsulated drug from external environment.
One of the main ingredients of liposome is phosphatidylcholine which has been
used in skin care products (moisturizer, lotions, creams, etc.) and hair care products
(shampoo, conditioner) due to its softening and conditioning properties. Several
active ingredients (e.g., vitamins A, E, and K) and antioxidants (e.g. carotenoids,
lycopene and CoQ10) have been incorporated into liposomes which increases their
physical and chemical stability when dispersed in water (Müller-Goymann 2004;
Nandita et al. 2016a).
Various nanotechnology-based cosmeceutical products are in the market used as
moisturizer, cleanser, antiwrinkle, antiaging, sunscreen manufactured by Lancôme,
Kara Vita, Nano-Infinity Nanotech, L’Oreal companies (Lohani et al. 2014).
54 N.A. Singh
2.3 Intellectual Property Rights in Nanotechnology
2.3.1 Intellectual Property Rights Types
It includes patents, copyright, industrial design rights, trademarks, plant variety

rights, trade dress, and trade secrets explained as follows:
2.3.1.1 Patent
A patent is a form of right granted by the government to an inventor, giving the

owner the right to exclude others from making, using, selling, offering to sell, and
importing an invention for a limited period of time, in exchange for the public dis-
closure of the invention. An invention is a solution to a specific technological prob-
lem, which may be a product or a process and generally has to fulfil three main
requirements: it has to be new, not obvious and have an industrial application.
2.3.1.2 Copyright
A copyright gives the creator of original work exclusive rights to it, usually for a
limited time. Copyright may apply to a wide range of creative, intellectual, or artistic
forms, or “works”. Copyright does not cover ideas and information themselves,
only the form or manner in which they are expressed (Stokes 2001).
2.3.1.3 Industrial Design Right
An industrial design right (sometimes called “design right”) protects the visual
design of objects that are not purely utilitarian. An industrial design consists of the
creation of a shape, configuration or composition of pattern or color, or combination
of pattern and color in three-dimensional form containing aesthetic value. An indus-
trial design can be a two- or three-dimensional pattern used to produce a product,
industrial commodity or handicraft.
2.3.1.4 Plant Breeders’ Rights
Plant breeders’ rights or plant variety rights are the rights to commercially use a new
variety of a plant. The variety must amongst others be novel and distinct and for
registration the evaluation of propagating material of the variety is examined.
2.3.1.5 Trademark
A trademark is a recognizable sign, design or expression which distinguishes

products or services of a particular trader from the similar products or services of
other traders.
2.3.1.6 Trade Dress
Trade dress is a legal term of art that generally refers to characteristics of the visual
appearance of a product or its packaging (or even the design of a building) that
signify the source of the product to consumers: Merges et al. (2007).
2.3.1.7 Trade Secrets
A trade secret is a formula, practice, process, design, instrument, pattern, or

compilation of information which is not generally known or reasonably ascertain-
able, by which a business can obtain an economic advantage over competitors or
customers.
2.3.2 Issues and Challenges
The huge investment in nanotechnology research should accelerate the availability

of commercial nanotechnology applications but patenting nanotechnology inventions
is more problematic than other inventions due to following issues (Barpujari 2010):
2.3.2.1 Broad Claims and Patents on Basic Inventions
Since a single invention could be used for a broad range of applications, the patentee
tries to maximize the profit by preferring patent claims which cover many applica-
tions and markets as possible. Due to the constraint of well versed examiners at
patent offices, these types of applications face problem of rejections despite of
overly broad claims.
2.3.2.2 Multi-disciplinary and Multi-industrial Applications
One distinguishing feature of nanotechnology inventions is their multi-disciplinary

nature; most of them involve a vast range of disciplines such as chemistry, biology,
physics, pharmaceuticals, computer science, material science and other disciplines.
56 N.A. Singh
They may also have broad spectrum of industries due to size of nanoparticles e.g.
carbon nanotubes (nanomaterial) have applications in energy, electronics, materials
and life sciences industries due to their unique electrical, mechanical, thermal and
optical properties.
2.3.2.3 Difficulties in Identifying Nanotechnology Patents
The broad definition of nanotechnology creates difficulties for both the inventor
and the patent examiner in classifying new inventions for patent office. A patent
application may use terms such as ‘microscale’ and ‘quantum dots’ to describe
nanotechnology invention instead of using term nanotechnology. Therefore both
inventor and the examiner must take precaution in searching the term in prior art in
nanotechnology area.
2.3.2.4 Difficulties in Fulfilling Patentability Criteria
A patent can only be obtained on an invention if claims are novel, non- obvious over
the prior art and have an industrial application. The novelty and inventive step
requirement have created difficulties for nano-patents even in United States.
2.3.3 Global Scenario of Nanotechnology Patents
Inventions reflected by the number of patent applications filed in the top 50 deposi-
tories was about 13,000 in 2008 as compared to about 1200 in year 2000 (Huang
et al. 2004, 2005).
A study on Indian publications and patents in nanotechnology during 1990–2007
(in foreign patent office’s like the United States Patent and Trade Office, European
Patent Office, Japan Patent Office etc.) arrived at the following conclusions
(Gupta 2008):
• Of the total 167 patents, 64 patents (39 % of the total patents) are owned by
government institutions, 45 patents (27 % of the total) by firms in the industry
and 10 patents (6 % of the total) by academic institutions. There are 37 patents
(22 % of the total) that are owned by individual inventors. The remaining 5 % of
the patents are joint patents in collaboration between government institutions or
firms from industry.
• The leading contributors from the government sector include laboratories of the
Council of Scientific and Industrial Research (CSIR), Defence Research and
Development Organisation (DRDO)
• The academic institutions that have taken patents include the Indian Institute of
Science, Indian Institutes of Technology and Jawahar Lal Nehru University.
Table 2.4 Top assignees in S.No. Company Country

2011 nanotechnology patent
1 GeneASys Australia
literature by healthcare and
medicine sector 2 Boston Scientific United States
3 Merck United States
4 Abbott Laboratories United States
5 Life Technologies Corporation United States
Jordan et al. (2012)
• Firms like Ranbaxy Laboratories, Stempeutics Research Private Limited,

Panacea Biotech Limited and Arrow Coated Products Limited are the leading
owners of industry patents.
• Academic institutions have more number of publications than patents while
reverse is true for industry.
The annual rate of increase for all the patent publications is more pronounced
between 2000 and 2008 (34.5 %). This rate is higher than that of Science Citation
Index’s article publication rate of 20–25 % for the same period when we use the
same keyword “title–abstract” search approach as for patent applications (Dang
et al. 2010). Top assignees in nanotechnology patent literature by medicine sector
are described in Table 2.4.
Nanotechnology emerged as an advance discipline in twentieth century and now
progressing by leaps and bounds. Unite States ranks first position among top 20
countries while India stands on nineteenth position for filing United States Patent
and Trade Office patents related to nanotechnology as shown in Table 2.5. In scien-
tific publications related to nanotechnology Unite States ranks first position among
top 20 countries while India stands on eighth position (Chen et al. 2013).
2.3.4 Copyright, Trademarks and Designs Protection

for Nanotechnology
2.3.4.1 Copyright Protection for Nanotechnology
Copyright protects a wide range of subject matter or works, it has been suggested
that a molecular architecture of nanotechnology may be protected under Canadian
copyright law. Different types of original work are protected provided they are
within the categories specified in the Malaysian and UK Copyright Acts, as well as
meeting the requirements of originality and expression in material form. Copyright-
protected works include literary, artistic, musical and dramatic and other works such
as sound recordings, films, broadcasts, and performer’s rights. The presumption can
be made that the categories of work most relevant to nanotechnology are artistic and
literary works (Norain 2012).
58 N.A. Singh
Table 2.5 USPTO patents filed by top 20 countries during 1991–2012

S.No. Country Total patents 1991–2000 2001–2010 2011–2012
1 United States 23,070 3597 13,947 5526
2 Japan 3332 534 1983 815
3 Korea (South) 1901 32 1114 755
4 Taiwan 1170 62 521 587
5 Germany 1079 119 687 273
6 France 799 160 396 243
7 China 591 1 262 328
8 Canada 408 56 256 96
9 Netherlands 349 30 198 121
10 Switzerland 284 61 156 67
11 Australia 218 28 144 46
12 UK 216 29 142 45
13 Israel 211 17 150 44
14 Sweden 165 21 100 44
15 Italy 161 24 109 28
16 Belgium 144 15 93 36
17 Singapore 126 2 90 34
18 Finland 72 8 43 21
19 India 60 2 28 30
20 Denmark 46 15 28 3
2.3.4.2 Trademarks Protection for Nanotechnology
A team from Monash University has created electron beam lithography instrument
that managed to write or mark nano-sized objects or surfaces to a size less than
10 nm (Press Release 2009). Thus it is possible to mark products at nanoscale,
though visualisation techniques such as atomic force microscopy and scanning tun-
neling microscope are needed to interpret them. Macro marks on packaging can be
used to signify the source of nano products or services.
The law that governs trade mark registration in Malaysia is the Trade Marks Act
1976 and Trade Marks Regulations 1983, both came into effect on 1 September
1983. Trade Marks Act 1976 defines ‘mark’ to include a device, brand, heading,
label, ticket, name, signature, word, letter, numeral etc. Visual perception which
makes it difficult for Malaysian law to be applied to nanotechnology, as nanotech-
nology cannot be seen by the naked eye. Eligibility for protection of non-visible but
perceptible marks such as smells and sounds provides a good consideration on how
nanoscale marks may attract trademarks protection. Indeed, nanotechnology may
help to deliver smell mark; nano-encapsulation methods are available for produc-
tion of aromatic compounds in perfumes using nanoparticles such as gold-palladium.
Nano-encapsulated fragrance may be embedded for example into textiles, shoes and
other materials such as ceramics.
2.3.4.3 Design Protection for Nanotechnology
Design protection is arguably available to protect nanotechnology features although

the arguments experience some difficulties. The argument is that not only the nature
of nanotechnology itself, and its suitability as subject-matter, but also the inherent
nature of overlapping rights in the intellectual property rights regimes as well as
complexity in the design law protection itself, pose problems. In Malaysia, the pro-
tection of industrial design is provided under the Industrial Design Act 1996, or
under copyright law. Examples of design may be appearance of devices such as
nano-bots, or nano-robotics systems in medicine, the functional design of orthopae-
dic devices for arms and joint replacement, the molecular design that mimics nature
called “bio-mimetic”, and the design of bio-compatible dendrimers for cancer diag-
nosis. The non-visibility of nano-creations has indicated that it was unfortunate to
be protected under design law in Malaysia. Even in the UK/EU law, the protection
provided under design is complex not only within different protection under design
law itself but also overlapping rights with other intellectual property rights. Under
UK registered design, the requirement that the design does not mean to be visible to
the eye explained some favourable treatment to protect nano-creations. However,
non-visibility and technical characteristics of nanotechnology proved to be less rel-
evant to be protected under registered design/community (Norain 2012).
2.4 Conclusion
Nanotechnology is widely used in various fields such as medical, agricultural,

industrial etc. due to the specific attributes of nanomaterials. Despite of worldwide
applications of nanotechnology it faces many problems related to patenting due to
broad claims, multidisciplinary applications, and difficulties in identifying nano-
technology patents and fulfilling patentability criteria. The 21-year evolution of
nanotechnology reflected in United States Patent and Trade Office patents and sci-
entific publications shows patents and research papers increased in 2001–2010 four
times, while the 2-year 2011–2012 increases are two times approximately. Unite
States ranks first position among top 20 countries for filing patents and publications
related to nanotechnology while India stands on nineteenth position for filing pat-
ents and eighth position in scientific publications.
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Chapter 3
Green Synthesis and Spectroscopic
Characterization of Nanoparticles
Ashutosh Kumar Shukla and Siavash Iravani
Abstract Nanoparticles have many applications in different fields including food

and agriculture. Synthesis and characterization of nanoparticles have therefore
attracted interest of scientific community. Here we review green methods of synthe-
sis of metal and metal oxide nanoparticles. We describe synthesis using enzymes,
monosaccharides, polysaccharides and biodegradable polymers. We explain the
role of vitamins as reducing and capping agents in green synthesis of nanoparticles.
Microwave assisted synthesis and biobased methods have also been illustrated with
examples. We then discuss nanoparticle characterization using UV-Visible spectros-
copy and Fourier-transform infrared spectroscopy. Applications in diverse fields
including water purification are then highlighted.
Keywords Nanoparticles • Green synthesis • UV-visible spectroscopy • FT-IR

spectroscopy • Water purification • Vitamin • Microwave • Bacteria • Fungi • Yeast
3.1 Introduction
Nanomaterials have enhanced surface to volume ratio as compared to macromateri-

als and therefore a smaller mass of material is required to achieve the same objective
(Crane and Scott 2012; Masciangioli and Zhang 2003). Properties of nanoparticle-
containing materials are quite different to those of their bulk counterparts (El-Sayed
2001). Nanoparticles have attracted considerable interest recently in the field of
food, agriculture and pharmaceuticals (Dasgupta et al. 2015a; Nandita et al. 2015;
Shivendu et al. 2014; Aditi et al. 2016). Improved antioxidant and antimicrobial
activity of nanoemulsions leading to potential application in increasing the shelf life
A.K. Shukla (*)

Physics Department, Ewing Christian College, Allahabad, UP 211003, India
S. Iravani
Faculty of Pharmacy and Pharmaceutical Sciences, Isfahan University of Medical Sciences,
Isfahan, Iran

66 A.K. Shukla and S. Iravani
of fruit juice has also been recently reported (Dasgupta et al. 2015b). Possibility of
use of iron nanoparticles to remove contamination from water and soil is reported
by Crane and Scott (2012). A process to prepare silver– silica nanocomposite for
treatment of waste water is also reported by Das et al. (2013).
Factors mentioned above are few of the many due to which nanoparticle research
has attracted the focus of the masses in general and scientific community in particu-
lar in present times. There are different methods possible for synthesis of nanopar-
ticles. Green synthesis of nanoparticles has become important due to environmental
concerns related with chemical methods of synthesis. Optimum use/application of
nanoparticles for specific purpose depends completely on the detailed information
obtainable from different characterization techniques. Therefore, we have made an
attempt to review the current trends in the green synthesis and spectroscopic char-
acterization of nanoparticles. We have also emphasized some most relevant applica-
tions of nanoparticles so prepared and the future scope in this area.
3.2 Green Methods for Synthesizing Metal

and Metal Oxide Nanoparticles
Green synthesis of nanoparticles using naturally occurring biodegradable materials

such as enzymes, vitamins, polysaccharides, plant extracts, biodegradable poly-
mers, and microorganisms is a very promising area in nanobiotechnology and green
nanotechnology. There has always been a demand for reliable and eco-friendly pro-
cesses to manufacture metal and metal oxide nanoparticles minimizing or even
eliminating the use of toxic and hazardous chemicals. The only way to develop
these “green” processes is to adapt benign synthesis approaches that use mild reac-
tion conditions and non-toxic reaction precursors (Iravani 2011; Iravani and
Zolfaghari 2013; Korbekandi et al. 2013; Korbekandi and Iravani 2013; Korbekandi
et al. 2009, 2012). This section presents an overview of nanoparticle preparation by
“Green chemistry” approaches which have advantages over conventional methods
involving chemical agents associated with environmental toxicity (e.g., biocompat-
ibility, biodegradability, cost-effectiveness and renewability).
3.2.1 Enzymes
Enzymatic method as a green approach has been used for synthesis of metal and
metal oxide nanoparticles. This method has advantages over other biological meth-
ods as enzymes are available in pure form and their structures are also well known.
For instance, silver nanoparticles were synthesized by an enzyme-induced growth
process on solid substrates. Variations in the silver-nanoparticle films depending on
the conditions during synthesis were observed. After an initial growth state, silver
nanoparticles exhibited the so-called desert-rose or nanoflower-like structure
3 Green Synthesis and Spectroscopic Characterization of Nanoparticles 67
(Schneidewind et al. 2012). Moreover, exposing the silver ions to Verticillium

resulted in the reduction of the silver ions and formation of nanoparticles. The
enzymes in the cell wall membrane reduce the silver ions (Mukherjee et al. 2001).
Manivasagan et al. (2015) reported the production of α-amylase for extracellular
synthesis of gold nanoparticles using Streptomyces sp. MBRC-82. The particles
were synthesized using the optimized enzyme activity (~20–80 nm). Furthermore,
Rangnekar et al. (2007) attributed the synthesis of gold nanoparticles to the pres-
ence of enzyme α-amylase. They reported the generation of gold nanoparticles,
using a pure enzyme for the reduction of AuCl4−, with the retention of enzymatic
activity in the complex. The presence of free and exposed S−H groups was essential
in the reduction of AuCl4− to gold nanoparticles. In this study, structural analysis of
the enzymes showed that both α-amylase and EcoRI enzymes have free and exposed
S−H groups in their native form and thus are suitable for the generation of nanopar-
ticles. In another study, Kalishwaralal et al. (2010) studied the optimization of
α-amylase production for the green synthesis of gold nanoparticles (~10–50 nm) by
Bacillus licheniformis. This bacterium is known to synthesize amylase enzyme
which is active in a wide range of temperature and pH (Khemakhem et al. 2009). In
this study, response surface methodology and central composite rotary design
(CCRD) were employed to optimize a fermentation medium for the production of
α-amylase by B. licheniformis at pH 8. The three variables involved in the study of
α-amylase were fructose, peptone and soya meal. Only fructose had a significant
effect on α-amylase production. The most optimum medium containing (%) fruc-
tose: 3, peptone: 1, soya meal: 2, resulted in amylase activity of 201.381 U/ml
(Kalishwaralal et al. 2010).
The enzyme α-amylase was used for the green synthesis of titanium dioxide
nanoparticles (as the reducing and capping agent). Transmission electron micros-
copy (TEM) data showed that the morphology of produced nanoparticles depended
upon the used enzyme concentration. The produced nanoparticles were investigated
for their antibacterial effect on Staphylococcus aureus and Escherichia coli
(Minimum inhibitory concentration (MIC) = 62.50 μg/ml). Jayaseelan et al. (2013)
reported the green synthesis of titanium dioxide nanoparticles using Aeromonas
hydrophilla. The gas chromatography – mass spectrometry (GC-MS) analysis of the
broth showed the major compound found in the A. hydrophilla was glycyl-proline
and other compounds present in lesser amounts areuric acid, glycl-glumatic acid,
and Leucyl-leucine and compounds containing –COOH and –C=O group. They
concluded that glycil-Lproline acted as reducing agent for the synthesis of titanium
dioxide nanoparticles and the water soluble carboxylic acid compounds acted as
stabilizing agents (Jayaseelan et al. 2013).
3.2.2 Monosaccharides and Polysaccharides
Monosaccharides and polysaccharides including plant polysaccharides (starch, cel-

lulose, dextran, and alginic acid), mammalian glycosaminoglycan polysaccharides,
heparin or hyaluronic acid and chitosan can be used for cost-effective, biocompatible,
biodegradable and green synthesis of metallic nanoparticles. For example, silver

nanoparticles were prepared using water as an eco-friendly solvent and polysaccha-
rides as capping/reducing agents (Sathishkumar et al. 2009b). Actually, polysac-
charides have functionalities including hydroxyl groups and a hemiacetal reducing
end which are capable of reducing precursor salts. The oxidation of polysaccharide
hydroxyl groups to carbonyl groups plays a critical role in bioreduction of gold salts
(Mata et al. 2009). Furthermore, the reducing end of polysaccharides can also be
used to introduce an amino functionality capable of complexing to and stabilizing
metal nanoparticles (Nadkarni et al. 1994).
Starch is a mixture of α-amylose and amylopectin. Starch-stabilized and glucose-
reduced silver nanoparticles were prepared via the incubation of silver salt with
starch and glucose at 40 °C for 20 h producing a particle with a mean size of 5.3 nm
(Raveendran et al. 2003b). The produced silver nanoparticles were stable without
any noticeable aggregation even after 2 months of storage. Another thermal method,
an autoclaving method (15 psi, 121 °C, 5 min), was introduced for the synthesis of
stable face-centred cubic silver nanoparticles in the size range of 10–34 nm using
soluble starch as both a reducing and stabilizing agent (Vigneshwaran et al. 2006).
In another study, silver nanoparticles were prepared using starch under sonication.
TEM images indicated the formation of spherical, polydispersed, amorphous, silver
nanoparticles (~23–97 nm). Selected area electron diffraction (SAED) confirmed
partial crystalline and amorphous nature of silver nanoparticles. The optimized
reaction conditions include 10 ml of 1 mM AgNO3, 25 mg starch, 11 pH range, and
sonication for 20 min at room temperature (Kumar et al. 2014).
In one study, synthesis of starch-silver nanoparticles was carried out with starch
(as a capping agent) and β-D-glucose (reducing agent) in a gently heated system
(Raveendran et al. 2003a). The binding interactions between starch and the pro-
duced silver nanoparticles were weak and could be reversible at higher tempera-
tures, allowing separation of the synthesized nanoparticles. In dual polysaccharide
function, silver nanoparticles were synthesized by reduction of silver ions inside of
nanoscopic starch templates (Raveendran et al. 2003a, 2005). The extensive net-
work of hydrogen bands in templates provided surface passivation or protection
against nanoparticle aggregation. Green synthesis of silver nanoparticles using neg-
atively charged heparin (reducing/stabilizing agent and nucleation controller) was
also reported by heating a solution of silver nitrate and heparin to 70 °C for about
8 h (Huang and Yang 2004). TEM micrographs demonstrated an increase in particle
size of silver nanoparticles with increased concentrations of silver nitrate (substrate)
and heparin. Moreover, changes in heparin concentration varied the morphology
and size of silver nanoparticles. The synthesized silver nanoparticles were highly
stable, and showed no signs of aggregation after 2 months (Huang and Yang 2004).
In another study, stable silver nanoparticles (~10–34 nm) were synthesized by auto-
claving a solution of silver nitrate (substrate) and starch (capping and reducing
agent) at 15 psi and 121 °C for 5 min (Vigneshwaran et al. 2006). These nanopar-
ticles were stable in solution for 3 months at about 25 °C. Smaller silver nanopar-
ticles (≤10 nm) were synthesized by mixing two solutions of silver nitrate containing
starch (capping agent), and NaOH solutions containing glucose (reducing agent) in
a spinning disk reactor with a reaction time of less than 10 min (Tai et al. 2008).
Silver nitrate, glucose, sodium hydroxide, and starch could be used, respectively, to
serve as precursor, reducing agent, accelerator, and stabilizer for the reduction syn-
thesis of silver nitrate. Polyethylene glycol (reducing agent and stabilizing agent)
was used to prepare stable monodispersed silver colloids (~10 nm) (Bo et al. 2009).
Biodegradable starch served as a stabilizing agent to synthesize silver nanoparticles
(~5–20 nm). According to High-resolution transmission electron microscopy
(HR-TEM) findings, silver nanoparticles were covered by starch layer and formed
spherical core-shell silver/starch nanoparticles. In addition, X-ray diffraction (XRD)
confirmed the presence of silver nanoparticles with face-centered cubic structure
(Gao et al. 2011).
Hydroxypropyl starch can be used as a reducing and stabilizing agent in the syn-
thesis of stable silver nanoparticles (~6–8 nm) with no aggregation for more than 6
months. In addition, the influences of the reaction parameters, such as the concen-
trations of hydroxypropyl starch and AgNO3, pH, temperature, and duration of the
reaction medium on the size and agglomeration of the formed silver nanoparticles
were studied (El-Rafie et al. 2011). Hydroxypropyl cellulose can also be used to
manufacture silver nanoparticles and as a dopant for visible light active titanium
dioxide. Therefore, optimum conditions for silver nanoparticles preparation were
pH 12.5, 0.3 % hydroxypropyl cellulose solution having molar substitution of 0.42
and carrying out the reaction at 90 °C for 90 min. On the other hand, doped-TiO2
nanoparticles were prepared using a benign “one-pot” synthesis procedure at room
temperature, resulting in stable and effective nanoparticles with average size of
17 nm and Brunauer-Emmett-Teller (BET) surface area of 133.8 m2 g−1 which were
efficient in degrading organic contaminants in the visible-light range (Virkutyte and
Varma 2013; Abdel-Halim and Al-Deyab 2011).
3.2.3 Biodegradable Polymers
Polymers with ion-exchangeable capacity can be used in the fields of nanoscience.

The polymer often used contained phosphonic acid groups and had a low molecular
weight. For instance, silver nanoparticles were stabilized in the presence of an ion-
exchange polymer. The surface morphology indicated that cubes and rectangular
prism structures were formed (García-Serrano et al. 2011). Co-polymers like cyclo-
dextrin, grafted with poly acrylic acid, were used to produce silver nanoparticles
where potassium per sulfate was used as the initiator. The co-polymer reduced and
stabilized silver ions, which yielded silver nanoparticles. Concentrations of the
alkali, silver nitrate, the co-polymer, and the method of heating, all played an impor-
tant role in determining the size of the produced nanoparticles (Hebeish et al. 2011).
Poly(methyl vinyl ether-co-maleic anhydride) was used as a reducing and stabi-
lizing agent as well. The produced nanoparticles were stable at room temperature
for up to a month and had a 5–8 nm coat of Poly(methyl vinyl etherco-maleic anhy-
dride) surrounding them (Maity et al. 2011). It was reported that the nanoparticles
(~10.2–13.7 nm) were fcc structures, non-aggregating, and very spherical in shape
(Medina-Ramirez et al. 2009). Sarkar et al. (2010) examined the synthesis of silver
nanowires and nanoparticles. Through a polypol process, with the help of a poly-
mer, silver nanowires and nanoparticles were formed. It was reported that the
nanoparticles were 60–200 nm in size and held prismatic and hexagonal shapes
while the nanowires had diameters from 50 to 190 nm and lengths between 40 and
1,000 μm. The reaction occurred at 210 °C when ethylene glycol was used as the
solvent. Different photoluminescence emission from the nano-clusters spread out
through methanol and ethylene glycol at room temperature. The excitation wave-
lengths were measured between 300 and 414 nm (Sarkar et al. 2010). By changing
the reducing and capping agents used to synthesize silver nanoparticles, one can
change morphologies of the nanoparticles, as well. The synthesis yielded nanopar-
ticles which were spherical in shape and around 15–43 nm in size after being heated
at 70 °C for 30 min; while at room temperature, the particles were only 8–24 nm.
Sodium hydroxide reduced the salt in ethylene glycol and the cubes were formed
upon some aggregation. By adding 5 wt.% polyvinylpyrrolidone to 1 wt.% of
starched solution (aq), mixtures of spherical and anisotropic structures were
produced. The reaction took place at 70 °C for 1 h (Shervani et al. 2008).
3.2.4 Vitamins
Silver nanoparticles were prepared from silver nitrate in the presence of vitamin C
derivative 6-palmitoyl ascorbic acid-2-glucoside (PAsAG), via a sonochemical
route (Chandrasekharan et al. 2011). Ag-PAsAG nanocomplex with average size of
5 nm was formed and used to protect DNA from γ-radiation-induced damage. It was
reported that the presence of Ag-PAsAG complexes during irradiation inhibited the
disappearance of covalently closed circular form of plasmid pBR322 with a dose-
modifying factor of 1.78. Ag-PAsAG protected cellular DNA from radiation-
induced damage as evident from comet assay study on mouse spleen cells, irradiated
ex vivo (Chandrasekharan et al. 2011). Moreover, Huang et al. (2007) fabricated
gold nanodogbones with simple seeded mediated growth method in the presence of
vitamin C. It was reported that the morphologies of the formed nanoparticles highly
depended on the amount of added vitamin C (10–40 mL). In another study, mono-
dispersed silver nanoparticles were synthesized by a simple one-step procedure in
the alkaline sub-phase beneath vitamin E Langmuir monolayers. It was reported
that the phenolic groups in vitamin E molecules were converted to a quinone struc-
ture, and the silver ions were mainly reduced to ellipsoidal and spherical nanopar-
ticles. According to the electron-diffraction pattern, silver nanoparticles were
face-centered cubic polycrystalline (Zhang et al. 2006).
In addition, vitamin B2 was also reported to be an effective reducing as well as
capping agent due to its high water solubility, biodegradability and low toxicity in
comparison to other available reducing agents (Nadagouda and Varma 2008a).
In one study, green synthesis of silver and palladium nanospheres, nanowires,
and nanorods by using vitamin B2 (as reducing and capping agent) has been
reported. Importantly, the addition of a solvent along with B2 may alter the sizes of
resulting nanoparticles. The average particle size of nanoparticle was found to be
silver (~6.1 ± 0.1 nm) and palladium (~4.1 ± 0.1 nm) nanoparticles in ethylene
glycol, and silver (~5.9 ± 0.1 nm, and 6.1 ± 0.1) nanoparticles in acetic acid and
N-methylpyrrolidinone, respectively. Interestingly, when water was used as a
solvent, silver and palladium nanoparticles were self-assembled into rod-like
structures. However, in isopropanol, the nanoparticles yielded wire-like structures
with a thickness in the range of 10–20 nm and several hundred micrometers in
length. Finally, in acetone and acetonitrile, the silver and palladium nanoparticles
were self-assembled into a regular pattern making nanorod structures with thick-
nesses ranging from 100 to 200 nm and lengths of a few micrometers (Nadagouda
and Varma 2008a; Virkutyte and Varma 2013).
Nadagouda et al. (2009) reported a green one-step method to synthesize palla-
dium nanobelts, nanoplates and nanotrees using vitamin B1. In this method, water
was used as a solvent and vitamin B1 as a reducing agent. It was reported that pal-
ladium concentration affected the shapes and sizes of the produced nanostructures.
A lower palladium concentration yielded a plate-like structure where thickness of
these plates varied from 100 to 250 nm with a length of several microns. An increase
in concentration of palladium resulted in the formation of tree-like structures. Upon
further increase in palladium concentration, palladium nanoplates started becoming
thicker by vertically aligning themselves together to form ball-like structures. The
produced palladium nanoparticles showed excellent catalytic activity for several
carbon-carbon bond forming reactions such as Suzuki, Heck and Sonogashira
reactions under microwave irradiation conditions.
3.2.5 Microwave-Assisted Synthesis
Microwave-assisted synthesis is a promising method for synthesis of nanoparticles

(Nadagouda et al. 2011). Silver, gold, platinum, and gold-palladium titanium
dioxide nanostructures were prepared using microwave-assisted synthetic
approaches (Shivendu et al. 2016). For instance, it was reported that silver nanopar-
ticles could be synthesized by microwave-assisted synthesis method employing car-
boxymethyl cellulose sodium as reducing and stabilizing agent. The size was
dependent on concentration of sodium carboxymethyl cellulose and silver nitrate
(the substrate). The produced nanoparticles were uniform and stable at room tem-
perature for 2 months without any visible changes (Chen et al. 2008). Production of
silver nanoparticles in presence of Pt seeds, polyvinyl pyrrolidine and ethylene
glycol was also reported (Navaladian et al. 2008). Furthermore, starch was employed
as a template and reducing agent for synthesis of silver nanoparticles with an
average size of 12 nm, using microwave-assisted synthetic method. Starch functions
as a template, preventing the aggregation of the produced silver nanoparticles
(Sreeram et al. 2008).
A bulk and shape-controlled synthesis of noble nanostructures with various

shapes (e.g., prisms, cubes, and hexagons) occurs via microwave-assisted spontane-
ous reduction of noble metal salts using aqueous solution of α-D-glucose, sucrose,
and maltose (Mallikarjuna and Varma 2007). The size of the produced nanoparticles
can be controlled by varying the concentration of the sugars; higher concentration
provides uniformly smaller size particles which increases with decrease in the
concentration of the sugars.
Microwaves in combination with polyol process were applied for synthesis of
silver nanospheroids using ethylene glycol and poly N-vinylpyrrolidone as reducing
and stabilizing agents, respectively (Komarneni et al. 2002). In a typical polyol pro-
cess, inorganic salt is reduced by the polyol (e.g., ethylene glycol which serves as
both solvent and reducing agent) at a high temperature. Yin et al. (2004) reported
that large-scale and size-controlled silver nanoparticles could be rapidly synthe-
sized under microwave irradiation from an aqueous solution of silver nitrate and
tri-sodium citrate in the presence of formaldehyde as a reducing agent. Size and size
distribution of the produced silver nanoparticles were strongly dependent on the
states of silver cations in the initial reaction solution. Silver nanoparticles with dif-
ferent shapes can be synthesized by microwave irradiation of a silver nitrate-ethylene-
glycol-H2[PtCl6]-poly(vinylpyrrolidone) solution within 3 min (Tsuji et al. 2008).
3.2.6 Biobased Methods
3.2.6.1 Bacteria and Actinomycetes
Bacteria and actinomycetes are capable of reducing metal ions into metallic
nanoparticles. For instance, Konishi et al. (2007) reported microbial deposition of
gold nanoparticles by the metal reducing bacterium, Shewanella algae. They dem-
onstrated that harvested cells of S. algae were capable of reducing 1 mM AuCl4−
ions into elemental gold within 30 min at 25 °C over the pH range from 2.0 to 7.0,
when H2 gas was provided as the electron donor (Caccavo et al. 1992). At pH 7.0,
biogenic gold nanoparticles (~10–20 nm), were deposited in the periplasmic space
of S. algae cells. When the solution pH decreased to below 2.8, some gold nanopar-
ticles were deposited extracellularly. At this pH, the biogenic gold nanoparticles
(~15–200 nm), on the bacterial cells exhibited various morphologies. At a solution
of pH 2.0, biogenic gold nanoparticles (~20 nm), were deposited on the bacterial
cells, and larger gold particles approximately 350 nm in size were deposited extra-
cellularly. Thus, it could be concluded that the solution pH is an important factor in
controlling the morphology of biogenic gold nanoparticles and in the location of
gold deposition (Konishi et al. 2007). They observed that the decrease in the soluble
Au (III) concentration was presumably caused by its rapid reduction into insoluble
gold. In the absence of H2 gas, however, S. algae cells were not able to reduce Au
(III) with lactate as an alternative electron donor. Moreover, in a sterile control
medium without S. algae cells, Au (III) was not chemically reduced by H2 gas.
Thus, resting cells of S. algae were able to reduce the soluble Au (III) into insoluble
gold in the presence of molecular H2 as the electron donor (Konishi et al. 2006;
Kashefi et al. 2001). A number of metal-reducing bacteria have been isolated and
characterized from a variety of habitats, and much work has been focused on S.
oneidensis and Geobacter spp. (Lovley 2001).
Fe (Ш)-reducing bacteria and archaea, were capable of precipitating gold by
reducing Au (Ш) to Au (0) (Kashefi et al. 2001). The reaction seemed to be enzy-
matically catalyzed which were dependent on temperature and the presence of a
specific electron donor, hydrogen. It was reported that hyperthermophilic archaea,
Pyrobaculum islandicum, Pyrococcus furiosus and the acetate-oxidizing hyperther-
mophilic strain 234, Thermotoga maritime and mesophilic bacteria, S. algae strain
BRY, Desulfovibrio vulgaris, and Geovibrio ferrireducens were capable of reducing
Au(Ш), while hyperthermophilic Archaea, P. aerophillum, Archaeoglobus fulgidus,
Ferroglobus placidus and mesophilic bacteria, D. palmitatis, Geothrix fermentans,
Desulfitobacterium metallireducens and Geobacter sulfurreducens, could not
reduce Au(Ш) (Kashefi et al. 2001).
CdS nanoparticles can be biologically synthesized by using bacterial cells
(Watson et al. 1999; Zhang et al. 1998; Lee et al. 2004). Clostridium thermoaceticum
showed the ability to grow autotrophically on CO2 and H2, utilizing the so-called
Wood-Ljungdahl pathway to synthesize acetyl coenzyme A (acetyl-CoA), a starting
material for the anabolic processes of these cells (Barondeau and Lindahl 1997).
Cunningham and Lundie (1993) reported that C. thermoaceticum was able to pre-
cipitate cadmium extracellularly at an initial concentration of 1 mM. This process
was energy dependent and required cysteine. The yellow precipitate of CdS appeared
approximately 12 h after the addition of CdCl2 and complete removal of the metal
from the growth medium was accomplished within 72 h. CdS was precipitated from
CdCl2 in the presence of cysteine hydrochloride by C. thermoaceticum at the cell
surface and in the medium (Cunningham and Lundie 1993). Rhodopseudomonas
palustris was capable of producing cadmium sulfide nanoparticles when it was incu-
bated with 1 mM CdSO4 at 30 °C for 72 h (Bai et al. 2009). The researchers of this
study found that C-S-lyase (an intracellular enzyme located in the cytoplasm) was
responsible for the synthesis of nanoparticles. One of the interesting results of this
study was that R. palustris transported CdS nanoparticles out of the cell.
Labrenz et al. (2000) reported that spherical aggregates of 2–5 nm diameter
sphalerite zinc sulfide (ZnS) particles were formed within natural biofilms domi-
nated by sulfate-reducing bacteria of the family of Desulfobacteriaceae. A combina-
tion of geochemical and microbial processes led to zinc sulfidebio-mineralization in
a complex natural system. It is appropriate to mention that the concentration of Zn
was significantly reduced to below-acceptable levels for drinking water with the use
of this method. Rhodobacter sphaeroides was developed for the synthesis of ZnS
nanoparticles with an average diameter of 8 nm (Bai et al. 2006). ZnS and PbS
nanoparticles (~10.5 ± 0.15 nm) were produced by using R. sphaeroides (Bai and
Zhang 2009). It was revealed that culture time could control the size of the produced
lead sulfide nanoparticles. Crystalline, needlelike deposits were formed around the
cells of Pseudomonas aeruginosa in the presence of La (NO3)2 (Mullen et al. 1989).
Silver concentrations up to 25 % of the bacterial dry biomass were reached in a

mixed culture of Thiobacillus ferrooxidans and Thiobacillus thiooxidans after
leaching of a sulphide mineral (Pooley 1982). Brock et al. (1976) reported that T.
ferrooxidans, T. thiooxidans and Sulfolobus acidocaldarius (thermophilic bacte-
rium able to oxidize both sulfur (Brock et al. 1976) and ferrous iron (Shiwers and
Brock 1973)) were able to reduce ferric ion to the ferrous state when growing on
elemental sulfur as an energy source. T. thiooxidans was able to reduce ferric iron at
low pH medium aerobically. The ferrous iron formed was stable to autooxidation
and T. thiooxidans was unable to oxidize ferrous iron, but the reduction of ferric iron
by using T. ferrooxidans was not aerobic because of the rapid bacterial reoxidation
of the ferrous iron in the presence of oxygen (Brock and Gustafson 1976). This
study reported that bacterial catalysis may play a significant role in the reactivity of
ferric iron and the ability of bacteria to oxidize elemental sulfur using ferric iron as
an oxidant. This could be geochemically significant in the leaching of sulfide ores
and in the development of acid mine drainage (Brock and Gustafson 1976). Other
biomineralization phenomena, such as the formation of tellurium in E. coli K12, the
direct enzymatic reduction of Tc (VII) by resting cells of Shewanella putrefaciens
and Geobacter metallireducens (previously known as strain GS-15) (Lloyd et al.
1999) and the reduction of selenite to selenium by Enterobacter cloacea, D. desul-
furicans and Rhodospirillum rubrum (Kessi et al. 1999), have been reported, as
well. Roh et al. showed that metals such as Co, Cr, and Ni might be substituted into
magnetite crystals biosynthesized in the thermophilic iron-reducing bacterium
Thermoanaerobacter ethanolicus (Klaus-Joerger et al. 2001; Yeary et al. 2005; Roh
et al. 2001). This procedure led to formation of octahedral-shaped magnetite
nanoparticles (<12 nm) in large quantities that co-existed with a poorly crystalline
magnetite phase near the surface of the cells (Roh et al. 2001). A more fundamental
investigation in the assembly of single-domain magnetite particles (Fe3O4) into
folded-chain and flux-closure ring morphologies by harvested magnetotactic bacte-
rium, Magnetospirillum magnetotacticum, was carried out by Philipse and Maas
(2002). Magnetic nanoparticles were also assembled into ordered structures when
the motion of M. magnetotacticum (MS-1) was controlled by applying a magnetic
field (Lee et al. 2004).
Sulfate-reducing bacteria were capable of producing magnetic iron sulfide
nanoparticles. Adsorption of radioactive metals by these magnetic iron sulfide
nanoparticles occurred due to high surface area (400–500 m2g−1) which could pro-
vided a suitable matrix for the long-term safe storage of hazardous radioactive
pertechnetate ion (Watson et al. 1999, 2001). GS-15 oxidized simple organic com-
pounds such as acetate, butyrate, and ethanol to carbon dioxide with Fe (III) or Mn
(IV) as the sole electron acceptor (Lovely et al. 1987; Lovley and Phillips 1988).
Iron-reducing microorganism, GS-15, produced copious quantities of ultra fine-
grained magnetite, with size range of 10–50 nm, under anaerobic conditions by
coupling the organic matter to the reduction of ferric iron (Lovely et al. 1987). In
this process, the non-magnetic brown amorphic ferric oxide was converted to a
black solid material which was strongly attracted to a magnet. But, GS-15 was not
magnetotactic because the crystals were clearly external to the cells and were not
aligned in chains.
Lovely et al. (1989) investigated the ability of Alteromonas putrefaciens to
couple the oxidation of potential electron donors (e.g., lactate, pyruvate, hydrogen and
formate) to the reduction of Fe (III) and Mn (IV). Also they reported that Pelobacter
acetylenicus and P. venetianus were able to reduce Fe (III). They demonstrated that
P. carbinolicus was capable of conversing energy to support growth from Fe (III)
respiration as it also grew with H2 or formate as the electron donor and Fe (III) as
the electron acceptor. P. carbinolicus grew with ethanol (ethanol was metabolized
to acetate) as the sole electron donor and Fe (III) as the sole electron acceptor.
Growth was also possible on Fe (III) with the oxidation of propanol to propionate or
butanol to butyrate if acetate was provided as a carbon source (Lovley et al. 1995).
Green synthesis of titanium dioxide (TiO2) nanoparticles was done using
Planomicrobium sp. (Malarkodi et al. 2013). The produced nanoparticles exhibited
antimicrobial activity against B. Subtilis, K. planticola, and A. niger. Furthermore,
it was reported that Shewanella sp. strain PV-4 was able to reduce metals such as Fe
(III), Co (III), Cr (VI), Mn (IV), and U (VI) as electron acceptors while using lac-
tate, formate, pyruvate, or hydrogen as electron donors (Roh et al. 2006). Growth
during iron reduction occurred over the pH range of 7.0–8.9, a sodium chloride
range of 0.05–5 %, and a temperature range of 0–37 °C, with an optimum growth
temperature of 18 °C. Strain PV-4 was able to reduce Fe (III)-citrate, as indicated by
the color change of the culture solution from brownish gray [Fe (III)-citrate]sil to
colorless at 8 °C. Strain PV-4 was also able to reduce Co(III) [Co(III)-EDTA] to
Co(II), Cr(VI) (potassium chromate) to Cr(III), and U(VI) (uranyl carbonate) to
U(IV) with lactate (10 mM) as the electron donor, as indicated by the color change
of the culture solution from purple[Co(III)-EDTA] and yellow (potassium chromate
and uranyl carbonate) to colorless at 8 °C. Furthermore, the strain PV-4 was able to
reduce manganese oxide using lactate (10 mM) as an electron donor and formed
rhodochrosite (MnCO3) at 8 °C under an H2-CO2 atmosphere. However, the cells
did not reduce Fe (III)-EDTA as an electron acceptor using lactate (10 mM) as the
electron donor at 8 °C under N2 atmosphere. Moreover, D. desulfuricans was capa-
ble of enzymatic reduction of U (VI) (Lovley and Phillips 1992; Mohagheghi et al.
1985; Woolfolk and Whiteley 1962). When washed cell suspensions of D. desulfuri-
cans were suspended in bicarbonate buffer containing lactate or hydrogen as the
potential electron donor, U (VI) concentration was decreased and amount of U (IV)
concentration was increased (Lovley and Phillips 1992). Enzymatic reduction of U
(VI) by D. desulfuricans was much faster than non-enzymatic reduction of U (VI)
by sulfide (Mohagheghi et al. 1985), even when cells of D. desulfuricans were
added to provide a potential catalytic surface for the nonenzymatic reaction (Lovley
and Phillips 1992). Microbial reduction of soluble U (VI) to insoluble U (IV) may
play an important role in the geochemical cycle of uranium and serve as a mecha-
nism for the bioremediation of uranium-contaminated waters, as well (Lovley et al.
1991). Reductive precipitation of uranium might also account for the ability of the
bottom sediments of algal ponds to remove dissolved uranium from uranium mine
wastewaters (Brierley and Brierley 1980). Bioreactors containing U (VI)-reducing
microorganisms (such as cells and S-layer proteins of Bacillus sphaericus JG-A12

(Pollmann et al. 2006)), could rapidly remove dissolved uranium from water (Gorby
and Lovley 1991); therefore, D. desulfuricans might show useful and potential
capabilities for recycling and recovering uranium from contaminated waters and
waste waters (Lovley and Phillips 1992).
3.2.6.2 Yeasts and Fungi
Several studies indicated that yeasts extracts could be used to synthesize metallic
nanoparticles. For instance, Kowshik et al. (2003) demonstrated the extracellular
formation of silver nanoparticles (~2–5 nm) by a silver-tolerant yeast strain MKY3.
Furthermore, Saccharomyces cerevisae broth was used to synthesize gold and silver
nanoparticles. The produced gold nanoparticles (20–100 nm, pH 4–6) and silver
(10–20 nm, pH 8–10) were formed extracellularly within 24 h and 48 h, respectively
(Lim et al. 2011). Kumar et al. (2011) showed the applicability of yeast species
Hanensula anomala to reduce gold salt in the presence of amine-terminated poly-
amidoamine dendrimer as the stabilizer; cysteine could also be used as stabilizer.
Furthermore, Candida guilliermondii was used to prepare silver (~10–20 nm) and
gold nanoparticles (~50–70 nm) (Mishra et al. 2011). The produced nanoparticles
were tested against five pathogenic bacterial strains. The highest efficiency for both
gold and silver nanoparticles was observed against S.aureus, which indicated the
applicability of yeast-synthesized nanoparticles for environmental remediation and
medical fields (Mishra et al. 2011).
Spherical and occasionally triangular silver nanoparticles (~5–50 nm) were bio-
logically synthesized using Fusarium oxysporum, with no evidence of flocculation
of the particles even a month after the reaction (Ahmad et al. 2003a). The long-term
stability of the nanoparticle solution might be due to the stabilization of the silver
particles by proteins. Silver nanoparticles have been reported to interact strongly
with proteins including cytochrome c (Cc). This protein could be self-assembled on
citrate-reduced silver colloid surface (Macdonald and Smith 1996; Nandita et al.
2016; Shivendu et al. 2015). Interestingly, adsorption of (Cc)-coated colloidal gold
nanoparticles onto aggregated colloidal Ag resulted Ag: Cc: Au nanoparticle conju-
gate (Keating et al. 1998). In UV-vis spectra from the reaction mixture after 72 h,
the presence of an absorption band at ca. 270 nm might be due to electronic excita-
tions in tryptophan and tyrosine residues in the proteins. In the case of F. oxyspo-
rum, the biological reduction of silver ions was attributed to an enzymatic process
involving NADH-dependent reductase (Ahmad et al. 2003b). The exposure of silver
ions to F. oxysporum resulted in release of nitrate reductase and subsequent
formation of highly stable silver nanoparticles in solution (Kumar et al. 2007). The
secreted enzyme was found to be dependent on NADH cofactor. High stability of
the produced nanoparticles in solution was due to capping of particles by release of
capping proteins by F. oxysporum. Moreover, stability of the capping protein was
found to be pH dependent. At higher pH values (>12), the nanoparticles in solution
remained stable, while they aggregated at lower pH values (<2) as the protein was
denatured. Kumar et al. (2007) demonstrated enzymatic synthesis of silver nanopar-

ticles with different chemical compositions, sizes and morphologies, using
α-NADPH-dependent nitrate reductase purified from F. oxysporum and phytochela-
tin, in vitro. Silver ions were reduced in the presence of nitrate reductase, leading to
formation of a stable silver hydrosol 10–25 nm in diameter and stabilized by the
capping peptide. Use of a specific enzyme in in vitro synthesis of nanoparticles
showed interesting advantages. This would eliminate the downstream processing
required for the use of these nanoparticles in homogeneous catalysis and other
applications such as non-linear optics. The biggest advantage of this protocol based
on purified enzyme was the development of a new approach for green synthesis of
nanomaterials over a range of chemical compositions and shapes without possible
aggregation. Korbekandi et al. (2013) demonstrated the bioreductive synthesis of
silver nanoparticles using F. oxysporum. Previous researchers reported qualitative
production of silver nanoparticles by F. oxysporum, but they did not optimize the
reaction mixture. In Scanning electron microscope (SEM) micrographs, silver
nanoparticles were almost spherical, single (~25–50 nm) or in aggregates (100 nm),
attached to the surface of biomass. The biological reduction of metal ions and stabi-
lization of the silver nanoparticles was confirmed to occur by an enzymatic process.
It seems that the first step involves trapping of the Ag+ ions by F. oxysporum cells.
Furthermore, Ingle et al. (2008) demonstrated the potential ability of Fusarium acu-
minatum Ell. and Ev. (USM-3793) cell extracts in biosynthesis of silver nanoparti-
cles. The nanoparticles produced within 15–20 min and were spherical with a broad
size distribution in the range of 5–40 nm with the average diameter of 13 nm. A
nitrate-dependent reductase enzyme might act as the reducing agent. The white rot
fungus, Phanerochaete chrysosporium, also reduced silver ions to form nano-silver
particles (Vigneshwaran et al. 2006). The most dominant morphology was pyrami-
dal shape, in different sizes, but hexagonal structures were also observed. Moreover,
silver nanoparticles were synthesized using Aspergillus flavus. The prodeced
nanoparticles were found to be stable in water for more than 3 months with no sig-
nificant aggregation because of surface binding of stabilizing materials secreted by
the fungus (Vigneshwaran et al. 2007). Extracellular biosynthesis of silver nanopar-
ticles (~5–25 nm) using Aspergillus fumigatus has also been investigated (Bhainsa
and D’Souza 2006). Most of the nanoparticles were spherical in nature with some
others having occasionally triangular shapes.
The extracellular filtrate of Cladosporium cladosporioides biomass was used to
synthesize silver nanoparticles (Balaji et al. 2009). It was suggested that proteins,
organic acids and polysaccharides released by C. cladosporioides were responsible
for formation of spherical crystalline silver nanoparticles. Kathiresan et al. (2009)
have shown that when the culture filtrate of Penicillium fellutanum was incubated
with silver ions and maintained under dark conditions, spherical silver nanoparticles
could be produced. Penicillium sp. J3 isolated from soil was able to produce silver
nanoparticles. The bioreduction of silver ions occurred on the surface of the cells
and proteins might have critical role in formation and stabilization of the synthe-
sized nanoparticles (Maliszewska et al. 2009).
Sanghi and Verma (2009) investigated the ability of Coriolus versicolor in forma-
tion of monodisperse spherical silver nanoparticles. The time taken for production of
silver nanoparticles was reduced from 72 to 1 h under alkaline conditions (pH 10). It
was indicated that alkaline conditions might be involved in bioreduction of silver
ions, water hydrolysis and interaction with protein functionalities. Findings of this
study have demonstrated that glucose was necessary for the reduction of silver
nanoparticles, and S-H of the protein played an important role in the bioreduction.
3.2.6.3 Algae
Cyanobacteria and eukaryotic alga genera such as Lyngbya majuscule, Spirulina

subsalsa, Rhizoclonium heiroglyphicum, Chlorella vulgaris, Cladophora prolifera,
Padina pavonica, Spirulina platensis, and Sargassum fluitans can be used as cost-
effective means for biorecovery of gold out of the aqueous solutions, as well as the
formation of gold nanoparticles (Chakraborty et al. 2009; Lengke et al. 2006a, b;
Niu and Volesky 2000). Marine algae like Chaetoceros calcitrans, Chlorella salina,
Isochrysis galbana and Tetraselmis gracilis can also be used for reduction of silver
ions and thereby synthesis of silver nanoparticles. Marine cyanobacterium,
Oscillatoria willei NTDM01 has been used for synthesis of silver nanoparticles
(~100–200 nm). The color of silver nitrate solution incubated with washed marine
cyanobacteria was changed to yellow from 72 h onwards, indicating the formation
of silver nanoparticles. When Spirulina platensis biomass was exposed to 10−3 M
aqueous AgNO3, extracellular formation of spherical silver nanoparticles (~7–16
nm) was resulted in 120 h at 37 °C at pH 5.6 (Govindaraju et al. 2008). Proteins
might be responsible for reduction and stabilization of the nanoparticles. In the case
of C. vulgaris, the proteins in the extract had dual function of Ag+ ion reduction, and
shape controlled synthesis of nanoparticles. The silvernano plates were obtained at
room temperature. Reduction of Ag+ ions was done by hydroxyl groups in Tyr
residues and carboxyl groups in Asp/Glu residues. This was responsible for the
anisotropic growth of silver nano plates which yielded rod-like particles with a
mean length of 44 nm and width of 16–24 nm. In one study, a sustained synthesis of
colloidal gold (~9 nm) using Klebsormidium flaccidum green algae was reported.
According to the findings, ca. 16 wt.% of gold was cellular Au and ca. 80 % of it was
metallic Au content, indicating an effective intracellular reduction process
(Dahoumane et al. 2012).
3.2.6.4 Plants and Phytochemicals
Green synthesis of metal and metal oxide nanoparticles by plants and phytochemi-
cals is mainly advantageous in terms of environmental friendliness. But, major
drawbacks associated with this green process are longer reaction times, tedious
purification steps, greater sizes of all nanoparticles and poor understanding of the
underlying mechanisms. Optimization of this green method is critical to for fast and
clean synthesis of nanoparticles with desired sizes and morphologies. Several studies
reported the bioreduction of metallic ions using various plants and phytochemicals
in order to synthesize metallic nanoparticles. For instance, Beta vulgaris (pulp
extract) (Castro et al. 2011), Nycanthes arbortristis (flower extract) (Das et al.
2011), Mangifera indica (leaf extract) (Phillip 2010), Ficus carica (leaf and bark
extracts) (Singh and Bhakat 2012), Sphearanthus amaranthoids (leaf extract)
(Nellore et al. 2012), Putranjiva roxburghii (leaf extract) (Badole and Dighe 2012),
Terminalia catappa (leaf extract) (Ankamwar 2010) and Stevia rebaudiana (leaf
extract) (Mishra et al. 2010) were used for synthesizing metallic nanoparticles.
Moreover, Song and Kim (2009) have elucidated that Pinus desiflora, Diospyros
kaki, Ginko biloba, Magnolia kobus and Platanus orientalis leaves broth synthe-
sized stable silver nanoparticles with average particle size ranging from 15 to 500
nm, extracellularly. In the case of M. kobus and D. kaki leaf broth, synthesis rate and
final conversion to silver nanoparticles became faster, when reaction temperature
increased. But the average particle sizes produced by D. kaki leaf broth decreased
from 50 to 16 nm, when temperature was increased from 25 to 95 °C. They also
illustrated that only 11 min was required for more than 90 % conversion at the reac-
tion temperature of 95 °C using M. kobus leaf broth (Song and Kim 2009). Vilchis-
Nestor et al. (2008) used Camellia sinensis extract to produce gold nanoparticles
and silver nanostructures in aqueous solution at ambient conditions. They also
investigated control of size, morphology, and optical properties of the nanostruc-
tures and reported initial concentrations of metal ions and tea extract as controlling
factors. It was investigated that when the amount of C. sinensis extract was increased,
the resulted nanoparticles were slightly bigger and more spherical. Authors of this
study believed that phenolic acid-type biomolecules present in C. sinensis extract
were responsible for production and stabilization of silver and gold nanoparticles.
Caffeine and theophylline present in tea extracts might be responsible for catalysis
and synthesis of nanoparticles. In another study, black tea leaf extracts were used in
production of gold and silver nanoparticles (Begum et al. 2009). The nanoparticles
were stable and had different shapes, such as spheres, trapezoids, prisms, and rods.
Findings of this study demonstrated that polyphenols and flavonoids were respon-
sible for synthesis of nanoparticles. Moreover, tea leaf extracts in 1-methyl-2-
pyrrolidinone solution were used for fabrication of 20 nm gold nanoparticles (Afzal
et al. 2009). These nanoparticles were incorporated in 1-methyl-2-pyrrolidinone
solution of polyaniline emeraldine base to cast the nanocomposite films. In addi-
tion, green method for synthesizing gold nanoparticles was reported by mixing the
Au(III) ion-dissolved rice wine and soda at pH 6.5 at a slightly elevated temperature
(25–55 °C) in the absence of extra protective agents (Wu and Chen 2007). Rice
wine was used as a solvent and a reducing agent; soda not only functioned as a pro-
tective agent but also played the role of base catalyst. The resultant solution was
quite stable and no precipitation occurred even after several months.
Sathishkumar et al. (2009a) investigated the synthesis of palladium nanoparticles
through reduction process using Cinnamomum zeylanicum bark extract. As a result,
nano-crystalline palladium particles (~15–20 nm) were synthesized. It was demon-
strated that reaction conditions such as pH, temperature, and biomaterial dosage had
no major effects on the shape and size of produced nanoparticles. One-pot biogenic
fabrication of palladium nanoparticles (~3.2–6.0 nm) was also carried out by a sim-
ple procedure using broth of Cinnamomum camphora leaf without extra surfactant,
capping agent and/or template (Yang et al. 2010). The size of palladium nanoparti-
cles could be easily controlled by variation of the initial concentration of Pd (II)
ions. In another study, nano-crystalline palladium particles (~10–15 nm) were syn-
thesized using Curcuma longa tuber extract as biomaterial. Temperature and pH had
no major effect on size and shape of the nanoparticles. It was found that the zeta
potential of formed palladium nanoparticles was negative and it was increased by
increasing the pH (Sathishkumar et al. 2009c). It was also reported that palladium
nanoparticles could be synthesized by using coffee and tea extract. The produced
nanoparticles were in the size range of 20–60 nm and crystallized in face centered
cubic symmetry (Nadagouda and Varma 2008b). It was reported that Gardenia jas-
minoides Ellis’ aqueous crude extract could be used for bioreduction of palladium
chloride. Identified antioxidants, including geniposide, chlorogenic acid, crocins
and crocetin were reducing and stabilizing agents for synthesizing palladium
nanoparticles (~3–5 nm) in aqueous crude extract. The particle size and dispersity
of nanoparticles were temperature dependent, and the best dispersity was revealed
at 70 °C (Jia et al. 2009). Palladium nanoparticles were synthesized under moderate
pH and room temperature using Solanum trilobatum conjugated with lipoic acid
(S-PdNP-LA) and vitamins (S-PdNP-Vitamin-LA). S-PdNP were polydisperse and
of different morphologies ranging from 60 to 70 nm (S-PdNP), 65–80 nm
(S-PdNP-LA), and 75–100 nm (S-PdNP-Vitamin-LA) in size (Kanchana et al.
2010). Moreover, palladium nanoparticles (~15 nm) were synthesized by using a
soybean (Glycine max) leaf extract-mediated biosynthesis process. Protein-rich
soybean leaf extract acted as an effective reducing agent for palladium ions
(Petla et al. 2012).
Platinum nanoparticles (~2–12 nm) could be synthesized using the leaf extract of
Diopyros kaki (as a reducing agent). It was reported that more than 90 % of the plati-
num ions were converted into nanoparticles with a 10 % leaf biomass concentration
at 95 °C (Song et al. 2010). The sizes of the produced nanoparticles were dependent
on the reaction temperature and concentrations of the leaf broth and PtCl62−. The
leaf extract of Ocimum sanctum was used as a reducing agent for the synthesis of
platinum nanoparticles (~23 nm). Fourier-transform infrared (FTIR) spectroscopy
revealed that the compounds such as ascorbic acid, gallic acid, terpenoids, certain
proteins and amino acids act as reducing agents for platinum ions reduction. It was
reported that the reduced platinum showed similar hydrogen evolution potential and
catalytic activity like pure platinum using linear scan voltammetry (Soundarrajan
et al. 2012). In another study, one-pot synthesis of platinum and palladium nanopar-
ticles using lignin isolated from red pine (Pinus resinosa) was reported. Spherical
nanoparticles (~16–20 nm) were observed in the case of palladium, and smaller
ones of not so well defined shapes for platinum. These nanoparticles showed good
catalytic activity in the reduction reaction (Coccia et al. 2012).
In2O3 nanoparticles (~5–50 nm) were produced by using indium acetylacetonate

and Aloe vera plant extracted solution (Maensiri et al. 2008). The nanoparticles
were formed after calcinations of the dried precursor of indium oxide in air at
400–600 °C. The morphology and size of indium oxide nanoparticles were affected by
the temperature of calcination. Moreover, copper nanoparticles were biosynthesized
using Magnolia leaf extract. When aqueous solutions of CuSO4•5H2O treated with
the leaf extract, stable copper nanoparticles (~40–100 nm) were formed. The produced
nanoparticles showed higher antibacterial activity against E. coli cells (Lee et al.
2011). In another study, extracellular production of copper nanoparticles was
carried out using stem latex of a medicinally important plant, Euphorbia nivulia.
The produced nanoparticles were stabilized and subsequently capped by peptides
and terpenoids present within the latex. The copper nanoparticles were toxic to
adenocarcinomic human alveolar basal epithelial cells (A549 cells) in a dose
dependent manner. It was concluded that the non-toxic aqueous formulation of latex
capped copper nanoparticles could be directly used for administration/in vivo deliv-
ery of nanoparticles for cancer therapy (Valodkar et al. 2011). Furthermore, Cu2O
nanoparticles were biologically synthesized by reduction of Barfoedʼs solution,
using agriculture wastes of Arachis hypogaea L. leaf extracts containing reducing
sugars. The aldehyde group present in reducing sugar plays an important role in the
formation of cuprous oxide nanoparticles in the solution. It was demonstrated that
the produced cuprous oxide nanoparticles had antibacterial effects on E. coli
(Ramesh 2011). Furthermore, the synthesis of hexagonal wurtzite ZnO nanoparti-
cles by Zn-hyper-accumulator (Sedum alfredii Hance) plants was reported. The
formed nanoparticles were agglomerated, and single ZnO nanoparticles were
pseudo-spherical in shape with a mean size of 53.7 nm (Qu et al. 2011a). In another
study, crystalline zinc oxide nanoparticles (~72.5 nm) were biologically synthesized
using Physalis alkekengi L. The TEM images demonstrated that the nanoparticles
were polydispersed and not uniformly distributed (Qu et al. 2011b). Moreover,
highly stable and spherical zinc oxide nanoparticles (~25–40 nm) were produced
using zinc nitrate as the substrate and Aloe barbadensis Miller leaf extract as the
biocatalyst. Consequently, greater than 95 % conversion to nanoparticles was
achieved using concentrations more than 25 % of A. barbadensis leaf broth. The
produced nanoparticles were polydispersed (Sangeetha et al. 2011). Green synthe-
sis of ZnO nanoparticles (~30–35 nm) by zinc nitrate and utilizing the leaf extract
of Calotropis giganteahas been reported. The SEM image showed relatively spheri-
cal shape nanoparticles (Vidya et al. 2013).
A green approach for synthesis of titanium dioxide nanoparticles from titanium
isopropoxide solution using N. arbortristis leaves extract was reported. SEM analy-
sis demonstrated that the average size was from 100 to 150 nm, and the shapes were
spherical and uniformed (Sundrarajan and Gowri 2011). Furthermore, green
synthesis of TiO2 nanoparticles (~25–100 nm) by using 0.3 % aqueous extract pre-
pared from latex of Jatropha curcas L. was reported. These nanoparticles were
characterized by X-ray diffraction (XRD), Selected Area Electron Diffraction
(SAED), Transmission Electron Microscopy (TEM), Energy Dispersive Analysis of
X-rays (EDAX) and Fourier Transform Infrared Spectroscopy (FTIR). FTIR were
performed to find the role of curcain (an enzyme), cyclic peptides namely curcacy-
cline A (an octapeptide) and curcacycline B (a nonapeptide) as a possible reducing
and capping agent, present in the latex of J. curcas L. The produced nanoparticles
were mostly spherical in shape (Hudlikar et al. 2012). In one study, Eclipta prostrata
leaf extract was used for green synthesis of titanium dioxide nanoparticles (~36–68
nm) (Rajakumar et al. 2012). FTIR peak implicated the role of carboxyl group O-H
stretching amine N-H stretch in the formation of titanium dioxide nanoparticles.
XRD characterized the crystallographic plane of rutile phase (iv) Atomic Force
Microscopy (AFM) showed uneven surface morphology which indicates the pres-
ence of both individual and agglomerated nanoparticles. The surface of synthesized
nanoparticles was characterized using Field Emission Scanning Electron Microscopy
(FESEM). This analysis showed shape of spherical clusters, quite polydisperse
(Rajakumar et al. 2012).
3.3 Spectroscopic Characterization of Nanoparticles
Most of the nanoparticle characterization techniques can be classified in two broad

categories (Herrera and Sakulchaicharoen 2009).
1. Local probe techniques
(i) Scanning Electron Microscopy (SEM)
(ii) Transmission Electronic Microscopy (TEM)
(iii) Scanning Tunneling Microscopy (STM)
(iv) Atomic Force Microscopy (AFM)
2. Bulk sensitive techniques
(i) Optical absorption spectroscopy
(ii) Fourier Transform Infra-red (FT -IR)spectroscopy spectroscopy
(iii) Electron Spin Resonance (ESR) Spectroscopy
(iv) Raman scattering
(v) X-ray based techniques
This contribution presents review of recent trends in nanoparticle characteriza-
tion using the following two spectroscopic techniques only.
(i) UV-visible spectroscopy
(ii) FT-IR spectroscopy
A brief account of the Electron Magnetic Resonance (EMR) characterization of
nanoparticles has been separately published (Shukla 2015). However detailed
account of different characterization techniques is beyond the scope of this article
and can be found elsewhere (Lungu et al. 2015).
3.3.1 Optical Properties of Nanoparticles and Surface

Plasmon Resonance
Surface Plasmon Resonance is responsible for unique optical properties of metal

nanoparticles. Interaction between the incident electromagnetic radiation and sur-
face electrons of metal nanoparticles is responsible for the surface plasmon reso-
nance. Surface plasmons are generated by the coupling between the oscillation
modes of incident electromagnetic radiation and the oscillations of conduction elec-
trons (Collective oscillations of conduction electrons in resonance with electromag-
netic field). Field is enhanced at the interface and the effect is more significant with
decreasing size though the other parameters like particle shape, composition and
surrounding medium also play their role. Surface Plasmon experiments are mostly
performed using nanoparticles of noble metals like silver, gold and copper as their
Plasmon absorption bands have well defined values in the visible region of the elec-
tromagnetic spectrum (Upstone 2000). Gold and silver nanoparticles of size
5–50 nm show strong absorption band around 520–560 nm and 390–420 nm wave-
length range respectively (Henglein 1999; Henglein and Meisel 1998). Composition
dependence provides another way to tailor the properties using a combination
(nanoalloys) say silver-gold for example. Silver-gold combination is interesting
because of one more reason other than well defined surface Plasmon resonance
bands. Both metals form face centered cubic crystals with similar lattice constants.
Therefore alloy of any composition can be formed at bulk as well as nano level
(Link et al. 1999). Absorption band position also depends on the shape of nanopar-
ticles. When spherical nanoparticles are elongated (nanorods) then two different
resonance modes are observed namely longitudinal surface Plasmon absorption and
transverse surface plasmon absorption depending on the orientation with respect to
the direction of incident electric field.
3.3.2 UV-Visible Spectroscopic Characterization
UV-visible absorption spectroscopy plays very important role to investigate the

optical properties of nanoparticles. Quantitative formation can be monitored and
size of nanoparticles can be studied with the help of this technique. It is basically
study of response to electromagnetic waves in the wavelength range 190–700 nm by
the sample (Upstone 2000). Now we cite some examples from recent literature to
highlight the applications of UV-visible spectroscopy in nanoparticle characterization.
Awaad and Salem (2012) have reported the green synthesis of silver nanoparti-
cles by mulberry leaves extract. They have used UV-visible absorption spectrum in
the wavelength range 200–800 nm to confirm the formation and stability of silver
nanoparticles synthesized by green synthesis. They monitored the reduction of pure
Ag+ ion to Ag0 nanoparticles at regular interval of time and could obtain a peak after
30 min at 425 nm. There was no change in the wavelength in the peak position with
Fig. 3.1 UV-visible 3.0

absorption spectrum
showing the degradation of
2.5
Malachite Green using
Absorbance (a.u)
different types of tea
extracts. It may be noticed 2.0
that Fe nanoparticles MG
synthesized by green tea GT-Fe NPs
1.5
OT-Fe NPs
extracts are best for
BT-Fe NPs
degrading Malachite green.
1.0
GT, OT and BT stands for
green, oolong and black
teas respectively 0.5
(Reproduced with
permission) 0.0
200 300 400 500 600 700 800
Wavelength (nm)
Fig. 3.2 UV-visible

absorption spectrum of
gold nanoparticles
synthesized from Allium
cepa extract. Strong
resonance which arises due
to the excitation of surface
plasmon resonance at
540 nm is clearly noticed
(Reproduced with
permission)
time onwards and it could be concluded that after 60 min there was no increase in
the number and size of the nanoparticles, the reason being depletion of Ag+ ions in
the extract.
Synthesis of iron nanoparticles using green method based on tea extracts, includ-
ing green, oolong and black teas is reported by Huang et al. (2014). With the help of
UV-visible experiments they have been able to state that such iron nanoparticles
synthesized from tea extracts are best for degrading of malachite green (Fig. 3.1).
Parida et al. (2011) have reported UV-visible absorption study of gold nanopar-
ticles synthesized from Allium cepa extract. A strong resonance at 540 nm is clearly
seen and arises due to the excitation of surface plasmon resonance in the gold
nanoparticles (Fig. 3.2).
Maddinedi et al. (2015c) have confirmed the formation of gold nanoparticles
using a natural enzyme Diatase using UV-visible spectrum with a characteristic
UV graph of Biologically synthesized

2
silver nanoparticles
1.8
1.6
1.4
Absorbance
1.2
1
0.8 Bio AgNP
0.6
0.4
0.2
0
0 200 400 600 800
Wavelength
Fig. 3.3 UV-visible spectrum of chemically synthesized silver nanoparticles (Reproduced with
permission)
surface plasmon resonance band at 530 nm. The size of the diastase-stabilized gold
nanoparticles is reported to be controlled by changing the quantity of diastase.
Banerjee et al. (2014) have reported UV-visible characterization of silver
nanoparticles synthesized by green route from three Indian medicinal plants, M.
balbisiana (banana), A. indica (neem) and O.tenuiflorum (black tulsi). Spectra were
recorded with time and the absorption band was found in the range of 425–475 nm
due to surface Plasmon resonance. They could infer that most rapid bioreduction
was achieved using banana leaf extract as reducing agent followed by tulsi and
neem leaf extracts. It was also found from UV-visible analysis that formation of
silver nanoparticles occurred rapidly within the first 15 min only and the nanopar-
ticles remained stable even after 24 h of completion of reaction.
Green synthesis and UV-visible characterization of silver nanoparticles using
fenugreek seed extract have been reported by Angelina et al. (2013). They have
recorded spectra periodically after a day and could find from the broadening and
red shift that particle size increases with time. Nandita et al. have analyzed the
nano-silver and protein (bovine serum albumin) interaction using this technique
(Nandita et al. 2016).
Green synthesis and characterization of silver nanoparticles synthesized from
Morus nigra leaves extract has been reported by Kumar et al. (2013). They could
monitor reduction of Ag+ ions by recording UV-Visible spectrum. From the surface
plasmon band position, they were able to distinguish between chemically synthe-
sized silver nanoparticls (Fig. 3.3) and biologically synthesized silver nanoparticles
(Fig. 3.4). Moreover they were able to estimate the shape of nanoparticles.
UV graph of Biologically synthesized

silver nanoparticles
2
1.8
1.6
1.4
Absorbance
1.2
1
0.8 Bio AgNP
0.6
0.4
0.2
0
0 200 400 600 800
Wavelength
Fig. 3.4 UV-visible spectrum of biologically synthesized silver nanoparticles (Reproduced with
permission)
Green synthesis and characterization of silver nanoparticles synthesized by

aqueous leaf extracts of Cardiospermum helicacabum leaves has been reported by
Mitra et al. (2012). UV visible spectra were recorded for different concentration,
time and temperature. It was concluded that high Plasmon resonance could be
obtained for 20 % concentration.
Pattanayak and Nayak (2013) have reported green synthesis and characterization
of iron nanoparticles from the leaf extract of Azadirachta indica (neem). In their
study they found appreciable surface plasmon resonance in 216–265 nm range of
wavelength.
UV-visible spectrum of synthesized silver nanoparticles using S. xanthocarpum-
berry extract as a reducing and capping agent has been reported by Amin et al. (2012).
They found that high pH value, temperature and molar ratio of S. xanthocarpum
extract to AgNO3 could accelerate the reduction rate of Ag+ and affect the Ag
nanoparticle size.
Monitoring of synthesis of colloidal sliver nanoparticles prepared from different
plant leaves extract using UV-Visible spectroscopy has been reported by Okafor
et al. (2013). The UV-Visible spectrum showed a peak between 417 and 425 nm
corresponding to the plasmon absorbance of the silver nanoparticles. They could
conclude that silver nanoparticles synthesized by green methods at low concentra-
tions are not cytotoxic for human healthy cells but inhibit bacteria growth. Authors
emphasized the need to carry further investigations to determine the minimum
inhibitory concentration of silver nanoparticles for bacterial growth, and cytotoxic

effects of biosynthesized silver nanoparticles on cancerous and other healthy cells.
Senapati et al. (2013) have reported green synthesis and characterization of ZnS
nanoparticles using glucose as capping agent. In their UV-visible absorption study
they have found strong absorption below 300 nm and with the help of blue shift
obtained with respect to the bulk ZnS they have predicted quantum confinement in
the sample. Band gap energy has also been calculated and they have been able to
estimate the size of nanoparticles with the help of blue shift.
3.3.3 FT-IR Spectroscopy and Nanoparticle Characterization
FT-IR spectroscopy is applied to find out information about the different functional
groups from the peak positions in the spectrum. Information about capping and
stabilization of the nanoparticles may also be inferred from this analysis. Now we
cite some examples from recent literature to highlight the applications of FT-IR
spectroscopy in nanoparticle characterization.
FTIR analysis carried out to characterize the silver nanoparticles obtained from
three Indian medicinal plants, M. balbisiana (banana), A. indica (neem) and O.
tenuiflorum (black tulsi) has been reported by Banerjee et al. (2014). In all three
cases, prominent bands of absorbance were observed at around 1025, 1074, 1320,
1381, 1610 and 2263 cm−1. They have concluded that observed peaks denote
-C-OC-, ether linkages, -C-O-, germinal methyls, -C=C- groups or from aromatic
rings and alkyne bonds, respectively. They have suggested that these bands may be
responsible for efficient capping and stabilization of obtained silver nanoparticles.
Awaad and Salem (2012) have reported the FT-IR study of mulberry leaves
extract to investigate the functional groups. They have found that the carboxyl
(-C=O), hydroxyl (-OH) and amine (N-H) groups of mulberry leaves extract are
mainly involved in reduction of Ag+ to Ag nanoparticles.
Shahwan et al. (2011) have reported FT-IR analysis of iron nanoparticles synthe-
sized by green tea before and after degradation reactions with methylene blue and
methyl orange dyes. Spectral features after contact with methylene blue solution
were obtained at 2925 cm−1 and 2818 cm−1 attributable to the stretching vibration of
C–H in the methyl groups, originating from methylene blue and/or its degradation
products (Imamura et al. 2002). Spectral features after contact with methyl orange
solution appeared at 2927 cm−1 and was attributed to asymmetric –CH3 vibrations.
Additional peaks were assigned to –C–S– stretching vibrations (Pashetti et al. 2010).
FT-IR analysis of silver nanoparticles bio-synthesized using Potentilla fulgens
extract has been reported recently to investigate the possible reducing functional
groups present in the P. fulgens root extract (Mittal et al. 2015). The FT-IR spectrum
of nanoparticles showed the involvement of O-H stretching, involvement of C=N in
plane vibrations of amino acids, corresponding to amides I, II and III, aromatic
rings and ether linkages. From the observed peaks authors have suggested the
presence of flavonoid, phenolicsand terpenoids capped on nanoparticles.
Sadeghi and Gholamhoseinpoor (2015) have found the FT-IR spectra (Fig. 3.5)
of the Z. tenuior (Zt) leaf extract before and after bioreduction very different. They
could conclude from the structural changes that the reduction and stabilization of
silver nanoparticles proceeds via the coordination between nitrogen of the amide
group and silver ions. Proteins could possibly form a layer capping of silver
nanoparticles to prevent agglomeration and thereby stabilize the medium.
In another report, Sadeghi et al. (2015) have reported FT-IR result of silver
nanoparticles synthesized using seed aqueous extract of Pistacia atlantica and
found that the extracts containing OH as a functional group act in capping the
nanoparticles.
Molecular interactions of silver nanoparticles obtained with polyethylene glycol
suspension and gluconic acid products by reduction of sugar compound were con-
firmed by FT-IR spectra by Shameli et al. (2012). They have suggested that hydroxyl
group of polyethylene glycol as capping agent can make a cover on the surface of
silver nanoparticles. This is possible because the surface of silver nanoparticles is
positively charged.
The leaf biomass before bioreduction, the biomass residue after bioreduction and
the resulting palladium nanoparticles synthesized by broth of Cinnamomum cam-
phora leaf were analyzed by FT-IR by Yang et al. (2010). Information regarding
chemical transformation of the functional groups involved in reduction of palladium
ions could be obtained and it was inferred that the polyols such as flavones, terpe-
noids, and polysaccharides in the broth played a critical role with dominant role of
the water soluble fractions in reduction of Pd(II) ions.
Senapati et al. (2013) have reported FT-IR characterization of ZnS nanoparticles
synthesized using glucose as capping agent. They have been able to identify the
presence of –CO and –OH groups of glucose which have strong ability to bind
metals.
3.4 Applications and Challenges
Nanoparticles have found their applications in diverse fields. Silver nanoparticles

are popular for their, catalytic, antibacterial and microorganism elimination applica-
tions (Okafor et al. 2013; Awaad and Salem 2012). Other applications of silver
nanoparticles include their use as selective coating material for solar energy absorp-
tion (Bonsak et al. 2011) and as optical receptors for biolabeling (McFarland and
van Duyne 2003). Gold nanoparticles have found their application as bio censors in
living cells and can lead to cancer diagnostics in addition to their other applications
(El-Sayed et al. 2005). Titanium dioxide is a material of great significance in many
fields, e.g., photo catalysis, solar cell devices, gas sensors, and biomaterials. The
non-toxic and biocompatible properties of TiO2 find its applications in biomedical
sciences such as bone tissue engineering as well as in pharmaceutical industries.
Fig. 3.5 FT-IR spectra of Ziziphora tenuior (Zt) powder (a) before and (b) after reaction. Possibly
proteins could form a layer capping of silver nanoparticles to prevent agglomeration and stabilize
the medium (Reproduced with permission)
Titanium dioxide catalysts have been confirmed to be excellent and efficient

photocatalysts for the degradation and inhibition of numerous toxic environmental
contaminants. Different applications of TiO2 include air and water cleaning and
surface cleaning (Malarkodi et al. 2013). II-VI class inorganic semiconductor nano-
materials like CdS, ZnS, CdSe have found important applications in optoelectronic
devices (Senapati et al. 2013). Among these several applications it will be relevant
to cite a few from the field of water purification technology which is no doubt on the
top priority in present days. The technologies in practice for the treatment of waste
water include ion-exchange, reverse osmosis, ultra-filtration, ozonization, oxidation
and adsorption. High operation cost, relatively low efficiency and generation of
toxic products are the prime concerns of these technologies which have led to the
research for new alternatives. Nanomaterials have been explored to provide the
alternative approaches in this area (Das and Mandal 2015). Crane and Scott (2012)
have pointed it out that due to its capability for removal of different chemicals,
nanoscale iron is supposed to serve as a tool to remove contamination from water
and soil. Water purification technique for the treatment of dye bearing contaminated
water through cost-effective and eco-friendly nanocomposite based method is
reported by Das et al. (2013). They have reported a process to prepare silver – silica
nanocomposite for treatment of waste water. However the need to examine the
reversible nature of remediation in water using nanoscale particles seeks further
concentrated efforts to validate the technology and open up/establish the new
dimensions in the area of water purification.
3.5 Conclusion
In this chapter, we have discussed green methods for nanoparticle synthesis and
their characterization through UV-visible and FT-IR spectroscopic techniques. We
have also highlighted their applications in water purification while mentioning some
other reports on their applications in other fields. Green methods eliminate the need
to use harsh, toxic and expensive chemicals. Actually there are several investiga-
tions carried out at research laboratories in small scale but unfortunately there are
few reports on industrial-scale fabrication of nanoparticles using green methods.
Optimization of the reaction conditions and extraction and purification of the pro-
duced nanoparticles and separation according to size and shape are important
aspects for green synthesis of nanoparticles. Therefore it is the need of the hour to
pay attention on scaling up the processes of the preparation of nanoparticles.
Acknowledgement One of the authors (AKS) thanks Dr. Mervin Massey for his constant
encouragement.
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Chapter 4
Nanotechnology to Remove Contaminants
Mitra Naghdi, Mehrdad Taheran, Saurabh Jyoti Sarma, Satinder Kaur Brar,

Antonio A. Ramirez, and Mausam Verma
Abstract Emerging contaminants will be a major challenge for human health and
environment since their concentrations are increasing. Contaminants occur in air,
soil and aquatic media, then finally end up in drinking water. Contaminants cause
many health issues to living organisms, by disruption of endocrine systems and
feminization of male fish, for instance. Therefore, prevention of contaminant
release, and cleaning of contaminated media are needed. Many processes, including
physical separation, biological treatment and chemical transformation have been set
up to remove contaminants. Here we review methods to remove contaminants using
nanomaterials, such as nanoparticles, nanotubes, and nanostructured membranes.
New processes based on nanostructured materials such as TiO2 nanowires or nano-
filtration membrane can achieve up to 95 % removal of contaminants.
Keywords Nanotechnology • Remediation • Sensors • Agriculture • Environment
4.1 Introduction
Emerging contaminants are a number of polluting compounds, which are of emerg-

ing public interest due to potential health or environmental effects. These com-
pounds have been released into environment since their use has commenced (Englert
2007), but they might be beyond the detection limits of analytical methods. In the
past 20 years, by developing sophisticated analytical instrument, researchers have
detected them in different environmental compartment, including water, air, soil and
sediments.
M. Naghdi • M. Taheran • S.J. Sarma • S.K. Brar (*)

INRS-ETE, Université du Québec, 490, Rue de la Couronne, Québec G1K 9A9, Canada
A.A. Ramirez
Centre National en Électrochimie et en Technologie Environnementales Inc.,
2263, avenue du Collège, Shawinigan, Québec G9N 6V8, Canada
M. Verma
CO2 Solutions Inc., 2300, rue Jean-Perrin, Québec, Québec G2C 1T9, Canada

102 M. Naghdi et al.
Fig. 4.1 Distribution of emerging contaminants in the environment. Subsequent to human, veteri-
nary and industrial use and then releasing into wastewater, emerging contaminants can easily find
their ways into soil, ground water, surface water and finally drinking water
The possible routes for transport of emerging contaminants from point of use to
drinking water have been illustrated in Fig. 4.1. In the case of pharmaceutically
active compounds, veterinary drugs find their ways into soil when manure is used
on agricultural field. Later, they can go to groundwater or surface water through
leaching or run-off from livestock slurries, respectively. Also, excess human phar-
maceuticals and other chemical compounds in the customer products end up in
wastewater treatment plants and afterwards, they can enter aquatic media through
effluent or soil via biosolids (Farre et al. 2008). It is noteworthy that compounds
with higher volatility can go to air form soil or water.
Until date, there is limited regulatory status for the majority of emerging contami-
nants and their metabolites (Deblonde et al. 2011) however their effects on ecosys-
tem and human health is becoming more obvious as a result of recent research works.
For example, the increased number of female fish in some aquatic media is attributed
to steroid hormones that find their way into rivers from municipal wastewater treat-
ment systems (Spina et al. 2013). Also, there are reports on the relation of polybro-
minated diphenyl ethers and cancer proliferation (Siddiqi et al. 2003). Until now,
three lists for emerging contaminants are published by the United States Environmental
Protection Agency and the draft of fourth list is prepared. In Table 4.1, different
classes of emerging contaminants with related examples have been presented.
To prevent adverse effects of emerging contaminants, capability of their efficient
removal from different environmental compartments is of high importance. Different
4 Nanotechnology to Remove Contaminants 103
Table 4.1 Classification of different emerging contaminants. Since 1998, US Environmental

Protection Agency updated the list of emerging contaminants four times and the below list is in
accordance to the draft of latest list prepared in 2015
Class of emerging
contaminants Examples Definition
Antibiotics Tetracycline Medications that fight bacterial
Erythromycin infections, inhibiting or stopping
bacterial growth
Disinfectants Alcohols A chemical agent used on non-living
Aldehydes surfaces to destroy, neutralize, or
inhibit the growth of disease-causing
microorganisms
Disinfection Chloroform Chemical substances resulting from
by-products Nitrosodimethylamine the interaction of organic matter in
water with disinfection agents, such
as chlorine
Drugs of abuse Amphetamine Drugs are addictive and have
Cocaine long-lasting changes in the brain
Tetrahydrocannabinol
Hormone mimicking Bisphenol A Natural or synthetic chemicals that
agents can elicit an estrogenic response
Fire or flame Polybrominated diphenyl Any of several materials or coatings
retardants ethers that inhibit or resist the spread of fire
Tetrabromo bisphenol A
Tris (2-chloroethyl) phosphate
Fragrances Galaxolide Chemical substances that impart a
Polycyclic sweet or pleasant odor
Macrocyclic musks
Gasoline additives Dialkyl ethers Chemicals that raise gasoline octane
Methyl-t-butyl ether number or act as corrosion inhibitors
or lubricants
Insect repellants N, N-diethyl-meta-toluamide Chemical substances applied to skin
or other surfaces to discourage
insects from coming in contact with
the surface
Poly-aromatic Benzo(a) pyrene A large group of chemical substances
hydrocarbons Fluoranthene usually found in the environment as a
Naphthalene result of incomplete burning of
carbon-containing materials like
fossil fuels, wood, or garbage
Personal care Para-hydroxybenzoate Chemical substances used in a
products Benzophenone diverse group of personal items
N,N-diethyltoluamide including toiletries and cosmetics
Methylbenzylidene
(continued)
Table 4.1 (continued)
Class of emerging
contaminants Examples Definition
Pesticides or Permethrin Chemical substances or
insecticides Fenitrothion microbiological agents that kill,
Bacillus Thuringiensis incapacitate or otherwise prevent
israelensis pests from causing damage
Pharmaceuticals Carbamazepine Chemical substances used in the
Acetaminophen prevention or treatment of
Diclofenac physiological conditions
Diazepam
Plasticizers Dioctyl Phthalate Chemical additives that increase the
plasticity or fluidity of a material
Reproductive Dihydrotestosterone A group of chemical substances,
hormones Progesterone usually steroids, whose purpose is to
Estrone stimulate certain reproductive
functions
Estradiol
Other hormones Cholesterol A large group of fat-soluble organic
Coprostanol compounds with a characteristic
Progesterone molecular structure, which includes
many natural and synthetic hormones
Diethylstilbestrol
Solvents Ethanol Chemical solutions, other than water,
Kerosene capable of dissolving another
substance
Surfactants and Sodium lauryl sulfate Chemical substances that affect the
metabolites Alkylphenol ethoxylates surface tension of a liquid
Alkylphenols (nonylphenol and
octylphenol)
Alkylphenol carboxylates
processes including filtration, adsorption, biodegradation and chemical oxidation

are suggested to remove these compounds. However, they need much more research
work to satisfy performance and economic requirements. Meanwhile, nanotechnol-
ogy, with its impacts on scientific and technological breakthroughs, is the most
likely tool to revolutionize the purification and remediation processes for contami-
nated media (Bottero et al. 2006; Chirag 2015; Masciangioli and Zhang 2003;
Savage and Diallo 2005; Theron et al. 2008). Nanomaterials exhibit novel physical,
chemical and biological properties due to their larger surface area per unit of vol-
ume and quantum effects. The potential capabilities of nanotechnology are divided
into three classes, including treatment, detection, and prevention (Rickerby and
Morrison 2007; Vaseashta et al. 2007). In this chapter, thus, an overview on recent
advances in nanotechnology for removing emerging contaminants from different
media including water, wastewater and soil is provided. The applications of nano-
materials are critically reviewed based on their structures e.g. nanoparticles, nano-
tubes, among others and related challenges for their application in full-scale and the
research needs for overcoming these challenges are also discussed.
4.1.1 Applications for Water and Wastewater Treatment
At nanoscale, materials show size-dependent properties that are remarkably differ-

ent from large particles. Several of these scalable properties including fast dissolu-
tion, high reactivity, and strong sorption are desirable for water treatment
applications. Also, there are several discontinuous properties, such as superpara-
magnetism, localized surface plasmon resonance, and quantum confinement effect
that can be used for specific applications. In Table 4.2, the application of nanomate-
rials in water treatment processes have been listed. Generally, there are physical
separation methods, such as membrane filtration and adsorption system and chemi-
cal transformation processes, such as photocatalytic degradation and nanotechnol-
ogy could enhance all these processes by novel well-structured materials, such as
nanofibers, nanotubes, nanoplatelets, nanolayers, among others. In the following
sections, the recent research on removal of emerging contaminants using important
classes of nanostructured materials have been summarized.
4.1.2 Nanoscale TiO2
Titanium dioxide (TiO2), also known as Titania, is a well-known semiconductor

with photocatalytic properties. This compound is widely used in advanced oxida-
tion processes for water and air remediation. Nanoscale TiO2 materials attracted the
attention of researchers for their enhanced photocatalytic properties (Dasgupta et al.
2015; Pelaez et al. 2009; Ranjan et al. 2016). As shown in Fig. 4.2, the photocata-
lytic properties of TiO2 originated from absorption of ultraviolet light that lead to
the formation of charge carriers i.e. hole and electron. The generated holes in the
valence band diffuse to the surface of TiO2 and react with water molecules to form
hydroxyl radicals (OH•). On the other hand, oxygen molecule can be reduced by one
of generated electrons to a superoxide radical (O2•−) that can be further reduced by
another electron or reacts with a hydroperoxyl radical (HO2•) to form hydrogen
peroxide (H2O2) (Nakata and Fujishima 2012). Therefore, as a result of light absorp-
tion, reactive species, such as hydroxyl radicals and hydrogen peroxide are formed
which reacts with contaminants in water and transform them into metabolites.
There are several challenges for commercialization of this process at large scale,
such as high operational cost and lack of knowledge on the degradation mechanism.
It is obvious that the metabolites of contaminants degradation should be much less
toxic than the parent compounds, otherwise, only transforming the contaminants to
another unfavorable species will be useless. Measuring the total organic carbon dur-
ing the reaction is a good criterion to assess the performance of degradation system
in transforming the contaminants to non-toxic species. Another challenge for using
photooxidation process is the effect of solution chemistry and presence of other
constituents in aqueous media, such as sulphate ions that can react with the reactive
groups and impede the contaminant degradation.
Table 4.2 Current and potential applications of nanotechnology in water and wastewater treatment (Qu et al. 2013)
106
Representative Investigated emerging

Application nanomaterials Desirable nanomaterial properties Enabled technologies contaminants
Photocatalysis Nano-TiO2 Photocatalytic activity under Photocatalytic reactors Alachlor
ultraviolet and visible light range Solar disinfection systems Fenitrothion
Low human toxicity Trimethoprim
High stability
Low cost
Fullerene derivatives Photocatalytic activity in solar Photocatalytic reactors
spectrum
High selectivity Solar disinfection systems
Adsorption Nanoscale metal High specific surface area Adsorptive media filters Aspirin
oxide Short intraparticle diffusion Slurry reactors Acetaminophen
distance Diclofenac
More adsorption sites Arsenate
Compressible without significant Polychlorinated biphenyls
surface area reduction Trichloroethylene
Easy reuse
Superparamagnetic properties
Nanofibers with core Tailored shell surface chemistry Reactive nano-adsorbents
shell structure for selective adsorption Reactive
core for degradation
Short internal diffusion distance
Carbon nanotubes High specific surface area Contaminant preconcentration/detection
Highly assessable adsorption sites adsorption of recalcitrant contaminants
Tunable surface chemistry
Easy reuse
M. Naghdi et al.
Membranes Nano-magnetite Tunable surface chemistry Forward osmosis Trimethoprim
processes Superparamagnetic properties Norfluoxetine Atorvastatin
Nano-TiO2 Photocatalytic activity Reactive membranes Escherichia coli
Hydrophilicity High performance thin film
High chemical stability nanocomposite membranes
Nano-zeolites Molecular sieve High permeability thin film
Hydrophilicity nanocomposite membranes
Nano-Ag Strong and wide-spectrum Anti-biofouling membranes
antimicrobial activity
Low toxicity to humans
Carbon nanotubes Antimicrobial activity (unaligned Aligned Carbon nanotubes membranes
Carbon nanotubes)
Small diameter
4 Nanotechnology to Remove Contaminants
Atomic smoothness of inner surface

Tunable opening chemistry
High mechanical and chemical
stability
(continued)
107
108

Sensing and Quantum dots Broad absorption spectrum, Optical detection Aspirin
monitoring narrow, bright and stable emission Acetaminophen
which scales with the particle size Diclofenac Ibuprofen
and chemical component
Noble metal Enhanced localized surface Optical and electrochemical detection
nanoparticles plasmon resonances
High conductivity
Dye-doped silica High sensitivity and stability Optical detection
nanoparticles Rich silica chemistry for easy
conjugation
Magnetic Tunable surface chemistry Sample pre-concentration and
nanoparticles Superparamagnetism purification
Carbon nanotubes Large surface area Electrochemical detection Sample
high mechanical strength and pre-concentration
chemical stability Excellent
electronic properties
Disinfection and Nano-TiO2 Photocatalytic ROS generation Point of use to full scale Escherichia coli
microbial control decontamination Staphylococcus aureus
High chemical stability
Low human toxicity and cost
Nano-Ag Strong and wide-spectrum Point of use water disinfection
antimicrobial activity Anti-biofouling surface
Low toxicity to humans
Ease of use
Carbon nanotubes Antimicrobial activity Point of use water disinfection
Fiber shape Anti-biofouling surface
Conductivity
M. Naghdi et al.
Oxygen
O2
Reduction
e− O2*− Superoxide radical

light (Disproportionation)
TiO2 e−
reduction
excitation
H2O2 Hydrogen peroxide
e−
Reduction
H2O2 h+
h+ OH*
Hydroxyl radical
H2O
Water
Fig. 4.2 Formation of reactive species as a result of light absorption by TiO2 photocatalyst. O2 is
reduced by one electron to form superoxide radical (O2⋅−) that can react with a hydroperoxyl radical
(HO2⋅) to form hydrogen peroxide (H2O2). One-electron reduction of H2O2 produces hydroxyl radi-
cal (OH)
In recent years, researchers have tried to thoroughly investigate the dominants

parameters of this process in order to develop an efficient system for removal of all
organic contaminants from water. For example, Mahmoodi and Arami immobilized
TiO2 nanoparticles on the walls of their reactor to act as nanophotocatalyst in the
presence of ultraviolet irradiation for degradation of two agricultural organic pollut-
ants including Alachlor and Fenitrothion. The results showed that after 180 min of
reaction, both compounds degraded and after 240 min complete mineralization was
achieved (Mahmoodi and Arami 2010). Hu et al. developed a dense TiO2 membrane
nanowire of 10–20 nm in diameter directly on Ti-atom substrates at 180 °C to pre-
pare a nanophotocatalyst for degradation of trimethoprim, norfluoxetine and atorv-
astatin as a model pharmaceutical compounds in presence of ultraviolet light
irradiation. Their results showed more than 95 % degradation of model compound
after 25 min of reaction (Hu et al. 2011).
To investigate the effect of pH and temperature, Liang et al. produced TiO2 nano-
belts with 30–100 nm in width and tens of um in length to use as nanophotocatalyst
for degradation of persistent pharmaceutical compounds such as naproxen, carbam-
azepine and theophylline in water treatment effluents. According to their results,
higher temperature and higher pH favors the photodegradation of theophylline in
presence of TiO2 nanobelts and ultraviolet light. They also observed that after
90 min of reaction, more than 95 % of three compounds were degraded (Liang et al.
2013). Shirazi et al. used the TiO2 nanoparticles with the average size of 21 nm to
degrade carbamazepine from water in the presence of ultraviolet light. They
achieved 85 % degradation after 36 min for carbamazepine in distilled water, but
they observed that the removal efficiency declined to 30 % when the source of water
was changed to groundwater. They attributed this reduction to the presence of diva-
lent ions, such as SO42− and CO32− since these ions may adsorb onto the surface of
the TiO2 and prevent the generation of superoxide anion O2•− and hydroxyl radical
OH• (Shirazi et al. 2013). In Table 4.3, the reaction constants and water matrices in
different degradation systems, which follow the pseudo-first order reaction, are
listed. According to this table, the value of K largely influences the economy of the
systems. For example, when K is higher than 0.1 min−1, more than 95 % of the com-
pound can be degraded within 30 min whereas for K less than 0.01 min−1, only 16 %
of the contaminant can be degraded within the same time. Therefore, developing
systems with higher K value can decrease the capital and operational costs to a
remarkable extent.
Table 4.3 Chemical transformation systems which follow a Pseudo-first-order kinetic model. The
highest rate constant was reported for degradation of norfluoxetine by TiO2 nanobelts and the
lowest one was for polychlorinated biphenyls by zero-valent iron nanoparticles
Nanomaterials Emerging
(conc. g/L) contaminants K1 Water matrices References
TiO2 (4 g/L) Alachlor 0.0017– Distilled Mahmoodi and
0.0152 Arami (2010)
Fenitrothion 0.0015–
0.0230
TiO2 nanowire Trimethoprim 0.0269 Milli Q Hu et al. (2011)
membranes (1.25 Norfluoxetine 0.1239
g/L) Atorvastatin 0.0688
TiO2 nanobelts (0.2 Naproxen 0.0616 Milli Q Liang et al. (2013)
g/L) Carbamazepine 0.0291
Theophylline 0.0912
TiO2 nanoparticles Carbamazepine 0.017 Groundwater Shirazi et al. (2013)
(0.02 g/L) 0.050 Distilled
FeFNS-doped TiO2 Diazinon 0.0162 Deionized Hossaini et al. (2014)
(0.03–0.3 g/L)
Nitrogen and Caffeine 0.0146 Milli Q Barndõk et al. (2013)
fluorine codoped Carbamazepine 0.0125
TiO2 (5 g/L) Atrazine 0.0109
Nano-magnetite Carbamazepine 0.00303 Distilled Sun et al. (2013)
(Fe3O4) (1–1.8 g/L) Ibuprofen 0.00201
Nanoscale zero Polychlorinated 0.00183 Deionized Chen et al. (2014)
valent iron (10 g/L) biphenyls
Pd-Fe nanoparticles Polychlorinated 0.002 Deionized Chen et al. (2014)
(10 g/L) biphenyls
Nanoscale iron Perchlorate 0.0253 Deionized Cao et al. (2005)
particles (10 g/L)
Au-Pd-TiO2 Malathion 0.0158 Twice-distilled Yu et al. (2010)
nanotube film (n.d.)
The Pseudo-first-order equation can be expressed as:
Ln(Ct / C0 ) = − k1t
Where: C0 and Ct (mol/L) are concentrations of contaminant at different time, t (min) and k1 (1/
min) is reaction constant
4.1.3 Doped TiO2
In order to increase the performance of TiO2 nanophotocatalyst, researchers investi-

gated the effect of doping TiO2 with other elements such as iron, carbon and nitro-
gen. For example, Wang et al. synthesized anatase TiO2 nanoparticles doped with
iron and carbon (Fe/C-TiO2) to degrade bisphenol A and clofibric acid in a photo-
catalytic process. They observed that Fe and C had synergistic effects on improving
photocatalytic activities of Fe/C-TiO2 as compared to C-TiO2, Fe-TiO2 and TiO2
nanoparticles under simulated solar light and visible light irradiation. According to
their results, no bisphenol A or clofibric acid could be detected after 4 h of irradia-
tion with visible light by Fe/C TiO2, and 61 % and 71 % of the total organic carbon
were mineralized, respectively (Wang et al. 2011). Hossaini et al. doped TiO2 with
a mixture of iron and non-metal elements i.e. N, S and F for use in light emitting
diodes-activated photocatalysis process for degradation of diazinon pesticide. Their
analysis showed that the nanophotocatalyst comprised of mesoporous nanocrystals
with the average size of 6.7 nm. They observed that the new nanophotocatalyst can
improve the degradation of diazinon by 52.3 % compared to plain TiO2 at neutral
pH. Also, they reported that diazinon degradation increased from 44.8 to 96.3 %
when the concentration of nanophotocatalyst increased from 25 to 300 % at a reac-
tion time of 100 min (Hossaini et al. 2014).
Pelaez et al. used nonionic fluorosurfactant as pore template material to dope
TiO2 nanoparticles with nitrogen and fluorine. The new material employed con-
tained mesoporous structure with pore size of 2–10 nm in photocatalytic process
under visible light with λ higher than 420 nm for destruction of microcystin. They
achieved the highest degradation rate of 70 % after 2 h at pH 3, and the electrostatic
interactions between compound and the TiO2 nanoparticles with nitrogen and fluo-
rine nanosystem favored photocatalytic degradation. They concluded that co-doping
TiO2 with nitrogen and fluorine increased photocatalytic activity compared to TiO2
nanoparticles with only fluorine or nitrogen doping (less than 20 % degradation)
(Pelaez et al. 2009). In a similar study, Barndok et al. synthesized a nanosystem of
TiO2 nanoparticles (50 nm) doped with nitrogen and fluorine to remove atrazine,
carbamazepine, and caffeine from water through a photocatalytic process using
solar light. They performed their tests in synthetic water and also in an effluent from
a hybrid biological concentrator reactor. The results showed that after 2 h of reac-
tion, about 70, 75, and 80 % removal in synthetic water and about 50, 70, and 70 %
removal in the biological concentrator reactor effluent was obtained for atrazine,
carbamazepine, and caffeine (Barndõk et al. 2013). The presence of various com-
plex ions, such as sulfate and chloride compete with target compounds in the pho-
tocatalytic process and therefore the efficiency of such system under real conditions
is less than the one obtained under controlled conditions in laboratory.
TiO2 nanoparticles are also studied for their adsorption capacity for contami-
nants. For example, Hristovski et al. studied the capabilities of aggregated TiO2
nanoparticles for adsorption of arsenate from four different water matrices in a
packed bed column. In their batch tests, TiO2 nanoparticles achieved 98 % removal
rate in all water matrices which is remarkable (Hristovski et al. 2007). In another
study, Hristovski et al. transformed TiO2 into bundle-like titanate nanofibers of rect-
angular in shape with ∼4 um long and 30–100 nm thick in order to increase the
adsorption capacity for arsenate. However, their experiment showed that commer-
cial TiO2 had 40 times more capacity in comparison to synthesized nanofibers and
therefore they were less suitable for arsenate removal though they have unique sur-
face chemistry and porosity (Hristovski et al. 2008a). In Tables 4.4 and 4.5, a sum-
mary of nanostructured adsorbent with their related parameters are listed. In
Freundlich model, there is no maximum adsorption capacity because adsorbates can
form multilayers around adsorbent. But in Langmuir and Polanyi-Manes models,
there are maximum values for adsorption or sorption. Many of the proposed nano-
Table 4.4 Physical adsorption systems which follow Freundlich isotherm model. In Freunlich
model. if n < 1, then adsorption is a chemical process and if n > 1, then adsorption is a physical
process (Desta 2013). Therefore all of the processes in this table are physical except carbon
nanotubes
Emerging
Nanomaterials contaminants KFa 1/n Water matrices References
TiO2, Fe2O3, ZrO2 Arsenic 1.37– 0.21–0.52 10 mM Hristovski et al.
and NiO 12.09 NaHCO3 (2007)
nanopowders nanopure
waterb
Titanate Arsenic 5–26 0.51–0.66 10 mM Hristovski et al.
nanofibers NaHCO3 (2008a)
buffered
nanopure water
Nanostructured Perchlorate 2.5–34.7 <0.6 Distilled Hristovski et al.
iron hydroxide Arsenate (2008b)
Nanofiltration Atrazine 0.04– 0.5633– Groundwater Tepus et al.
11.58 1.1196 (2009)
Deethylatrazin 0.05– 0.5825–
0.75 0.8387
Carbon nanotubes 2-naphthol 0.128– 1.1988– Milli-Q Xu et al. (2015)
0.222 1.5193
Graphene oxide Aniline 5.2–14.4 0.526– Distilled Yan et al. (2015)
0.7519
Nitrobenzene 6.8–11.1 0.4386–
0.4673
Chlorobenzene 0.78– 0.7407–
1.80 0.8130
Magnetic Arsenic 4.32 0.3584 Deionized Zhu et al. (2012)
graphene
nanoplatelets
a
The freundlich isotherm model can be expressed as:
Q e = K F Ce1/ n
Where: Ce (mg/L) and Qe (mg/g) are the equilibrium concentration of adsorbate in liquid and solid
phase, n and KF (mg/g)(L/mg)1/n are the adsorption equilibrium constant
b
Conductivity <1μS cm−1
Table 4.5 Physical adsorption systems which followed Langmuir or Polanyi-Manes isotherm
models. The maximum adsorption capacity was reported for Triclosan on single-walled carbon
nanotubes and the lowest one was reported for Trichlorophenol on magnetic nanoparticle
Maximum
Emerging Adsorption adsorption KL or Water
Nanomaterials contaminants model capacity log K matrices References
Magnetic 2,4,6-Trichlorophenol Langmuir 75.49 n.d. n.d. Pan et al.
nanoparticles (2011)
MWCNT Polychlorinated Langmuir 235–261 n.d. Milli-Q Shao et al.
biphenyls (2010)
SWCNT Ibuprofen Polanyi- 231.5 5.61 Milli-Q Cho et al.
Triclosan Manes 558.2 6.52 (2011)
MWCNT Ibuprofen Polanyi- 81.6 4.43 Milli-Q Cho et al.
O-MWCNT Ibuprofen Polanyi- 19.4 3.89 Milli-Q Cho et al.
The Langmuir isotherm model can be expressed as: Qe = ( K LQmCe ) / (1 + K LCe )
Where: Qm is the maximum adsorption capacity of the sorbent (mg/g), and KL is the affinity con-
stant
The Polanyi-Manes model (PMM) equation can be expressed as: Qe = Q p0 exp(a( RT Ln( S w / Ce )))b
Where: Qp0 is maximum sorption capacity (mg/g). a and b are model constants, R is the universal
gas constant (8.314 × 10−3 kJ/mol/K), T is absolute temperature (K), and Sw is the solubility of the
adsorbate in water at 20 °C
MWCNT Multiwalled carbon nanotubes, SWCNT Single-walled carbon nanotubes, O-MWCNT
oxidized multiwalled carbon nanotubes
structured materials showed superior performance compared to their conventional

counterparts. However the high cost of nanomaterials production and their limited
life cycles are important challenges for their scale-up.
4.1.4 Magnetic Nanoparticles
Magnetic nanoparticles consist of magnetic elements, such as iron, cobalt and nickel
in their chemical structure. Since these nanomaterials combine high surface area
with magnetic properties, they can be easily isolated from solution by applying a
magnetic field. Because of these interesting properties, magnetic nanoparticles have
been the focus of much research in recent years for their potential use in catalysis
and adsorption. For example, Shen et al. synthesized magnetic Fe3O4-C18 compos-
ite nanoparticles with the size of 5–10 nm for using in the clean-up and enrichment
procedures of measuring organophosphorous pesticides by gas chromatography
technique. According to their results, the composite nanoparticles have comparable
recovery of 80–93 % to conventional C18 materials that is 82–94 % recovery while
clean-up and enrichment procedures are faster and easier. They also observed that
Fe3O4-C18 composite nanoparticles is recyclable up to ten times with negligible

loss of properties (Shen et al. 2007). In a similar study, Moliner-Martinez et al.
incorporated Fe3O4 magnetic nanoparticles in a silica matrix for extraction and pre-
concentration of pharmaceutical compounds, such as aspirin, acetaminophen,
diclofenac and ibuprofen from water without need of clean-up process. The recov-
ery of this nanostructured sorbent was reported to be in the range of 80–110 % with
relative standard deviation less than 12 %. Under the optimum conditions, the new
sorbent material demonstrated suitable reusability during 20 uses with no loss in
efficiency (Martínez et al. 2011).
Zhu et al. developed graphene with strong magnetic properties composites by
decorating nanoplatelets with core-shell Fe-Fe2O3 nanoparticles. The new
nanomaterial was used for removal of arsenate from water. They observed that at
optimum pH (~7), the maximum adsorption capacity is around 11.34 mg/g that is
much higher than other magnetic nanoparticles i.e. 1 mg/g (Zhu et al. 2012). Ghosh
et al. studied the adsorption naproxen, carbamazepine and bisphenol A from aque-
ous solutions onto Fe3O4 nanoparticles that were coated with thiodiglycolic acid.
They also grafted 6-deoxy-6-ethylenediamino-β-cyclodextrin onto the magnetic
nanoparticles to compare the adsorption capacities. According to their results, the
adsorption capacities of thiodiglycolic acid-coated nanoparticles with and without
6-deoxy-6-ethylenediamino-β-cyclodextrin graft were in the range of 0.24–0.38
mg/g and 0.90–1.30 mg/g. They suggested that Fe3O4 nanoparticles serve as
magnetic separators and 6-deoxy-6-ethylenediamino-β-cyclodextrin provides the
capability to adsorb pollutants through inclusive host-guest interactions (Ghosh
et al. 2013).
Beside adsorption, magnetic Fe and Fe3O4 nanoparticles can act as catalyst in the
degradation of emerging contaminants. Sun et al. used magnetic Fe3O4 nanoparti-
cles with the average size of 30 nm for degradation of the carbamazepine and ibu-
profen in aqueous suspensions. They concluded that at neutral pH, hydroxyl radical
(•OH) produced form the decomposition of H2O2 on the Fe3O4 nanoparticle surface
plays the major role in the degradation of carbamazepine and ibuprofen. They also
observed that the degradation of carbamazepine and ibuprofen fitted with pseudo-
first-order kinetics model with the rate constants (k) of 0.182 and 0.121 h−1, respec-
tively. In addition, the presence of montmorillonite can reduce the rate constant for
carbamazepine due to adsorption at neutral pH, while it has no effect on ibuprofen
due to electrostatic repulsion (Sun et al. 2013). In another investigation carried out
by Cao et al. Iron nanoparticles showed capability to reduce perchlorate (ClO−4) to
chloride. Under same conditions, they reported no reduction using microscale iron
powder. They observed that by increasing temperature from 25 to 75 °C, the rate
constant will increase from 0.013 to 1.52 (mg perchlorate/(g nanoparticles × h))
(Cao et al. 2005). Unfortunately, higher activation energy of perchlorate-iron reac-
tion i.e. 79.02 ± 7.75 kJ/mol is not favorable for large scale applications.
Palladium is known for its catalytic properties towards conversion of harmful
gases in automobile exhaust to less harmful compounds. Also, nickel is widely used
as a catalyst in organic chemistry for hydrogenation. Therefore, the idea of using
these two metals in combination with iron nanoparticles for degradation of contami-
nants has led to interesting results. Chen et al synthesized iron/palladium (Fe/Pd)
bimetallic nanoparticles to catalyze the degradation of 2, 2′, 4, 4′, 5, 5′-hexachloro-
biphenyl in deionized water. According to their results, the degradation efficiency
for bimetallic nanoparticles and iron nanoparticles were 93.8 % and 74.9 % after 20
h of reaction. Later, they applied the results to the two soil samples collected from
an electrical waste recycling area that was contaminated with polychlorinated
biphenyls. They observed 53.4–81.5 % removal efficiency of polychlorinated biphe-
nyls from soil by Pd/Fe nanoparticles that was higher than 48.3–64.6 % removal
efficiency reported for iron nanoparticles (Chen et al. 2014).
In a similar study, Lien et al. produced iron nanoparticles in the size range of
1–100 nm for catalytic transformation of chlorinated methanes e.g. CCl4, CHCl3,
CH2Cl2 and CH3Cl. They also deposited palladium at the loading of 0.05–1 % Pd by
weight on the surface of iron and compared the capabilities of these two nanopar-
ticles and also commercial iron particles with the average size of 10 μm in reaction
with chlorinated methane. They observed that after 1 h of reacting 0.1 mM of CCl4
or CHCl3, there was no detectable reactant in the case of palladized iron nanoparti-
cles. In these reactions, methane and CH2Cl2 were the major end products at the
yields of 52 % and 23 %, respectively. However, iron nanoparticles and commercial
iron particles exhibited much slower reactions of chlorinated methanes. The kinetic
analyses revealed that the surface area-normalized rate coefficients (kSA) for palla-
dized iron nanoparticles was two orders of magnitude greater than those for iron
nanoparticles and commercial iron particles (Lien and Zhang 1999). In another
attempt, Vijayakumar et al. synthesized iron-nickel (Fe-Ni) nanoparticles in the size
range of 36–41 nm and immobilized them on to a polysulphone support to use as a
catalyst for the reduction of dichloroethane (C2H4Cl2) and trichloroethylene
(C2HCl3). They observed 90 % removal after a 36 h reaction with the initial concen-
tration of 26.81 and 682.81 ppb for C2H4Cl2 and trichloroethylene C2HCl3 respec-
tively. According to their study, in alkaline pH, Fe–Ni nanoparticles lose their
catalytic properties and cannot get involved in the hydrodechlorination of target
compounds (Vijayakumar et al. 2012). Shirazi et al. used iron nanoparticles in the
size range of 8–18 nm for degradation of carbamazepine in water in the presence of
H2O2. They obtained 78.5 % total organic carbon removal after only 5 min in the
presence of 10 ppm iron nanoparticles and 25 ppm H2O2. In contrast to their result
for TiO2/ultraviolet process, no difference in performance was observed when water
source was changed from distilled water to groundwater (Shirazi et al. 2013).
4.1.5 Precious Metal Nanosystems
Gold (Au) and Silver (Ag) nanoparticles are widely used in different applications,
such as sensors, catalysis, electronics and medicals. Removal of emerging contami-
nants from water sources is another application of precious metals that has attracted
the attention of researchers (Jain et al. 2016; Dasgupta et al. 2016a, b). For example,
Das et al. produced gold nanoparticles with 10 nm in diameter through biosynthesis
and used them for adsorption of organophosphorous pesticide, such as malathion

and parathion from aqueous solutions. They observed that synthesized nanoparticles
could remove almost all of the tested pesticides after 30 min (Das et al. 2009). In
another study, Suman et al. produced Ag nanoparticles and embedded them within
the porous concrete pebble particles. They also synthesized nanocellulose by acid
hydrolysis of cellulose and used these two nanoparticles for removal of microbes
(Escherichia coli) from water. They used a column with two beds of nano embedded
Ag nanoparticles and one bed of nanocellulose in between for continuous purifica-
tion of water and observed 99 % decontamination of microbes at pH 6. According to
their proposed mechanism, Ag nanoparticles kill microorganisms and prevent for-
mation of biofilm and nanocellulose can adsorb dye and heavy metals and the col-
umn can be reused up to five cycles with no loss in performance (Suman et al. 2014).
Li et al. observed that the gold Au-coated TiO2 nanotube arrays show recyclabil-
ity as a substrate for surface-enhanced Raman spectroscopy. Interestingly, this new
system can clean itself through photocatalytic degradation under ultraviolet light.
However, recycling process is time consuming (30 min), and only highly trained
staff can performed test with this new substrate (Li et al. 2010). Yu et al. developed
a nanosystem by modification of TiO2 nanotube film with Au and Pd (Au-Pd-TiO2)
to degrade malathion, which is an organophosphorus pesticide, through photocata-
lytic process in the presence of ultraviolet light. Their experiments showed that Au
and Pd can increase the degradation rate by 172 % compared to naked TiO2 nano-
tube film and attributed this behavior to effective separation of generated charge
carriers and also the higher generation rate of H2O2 (Yu et al. 2010). Han et al.
formed Ag nanoparticles with a diameter of 5.9 ± 1.2 nm on TiO2 aggregates to use
for the photocatalytic degradation of the antibiotic oxytetracycline under ultraviolet
-visible light irradiation. They observed that by increasing the load of Ag, the
absorption in the visible light region increased. However, under both ultraviolet
-visible light and visible light illumination, the highest photocatalytic activity for
the degradation of oxytetracycline was observed at 1.9 wt.% of Ag loading so that
it took 2 h for ultraviolet -visible and 3 h for visible light to reach below the detec-
tion limit of gas chromatography analysis (Han et al. 2014).
4.1.6 Carbon Nanotubes
Carbon nanotubes are categorized into single-walled carbon nanotubes and multi-
walled carbon nanotubes according to their atom layers in the walls of carbon nano-
tubes. The diameter of single-walled carbon nanotubes range from 0.3 to 3 nm,
whereas the multi-walled carbon nanotubes have concentric arrangement of cylin-
ders and their diameters can reach up to 100 nm (Balasubramanian and Burghard
2005). Carbon nanotubes have attracted attention of many researchers due to their
outstanding structural, chemical and mechanical properties (Miyagawa et al. 2005;
Popov 2004). Besides application in electronics, sensors, catalysis, and composite
materials, carbon nanotubes showed a promising application as adsorbent material
for different contamination due to their large surface area and also tubular structure
(Balasubramanian and Burghard 2005; Polizu et al. 2006). However, there are dif-
ferent parameters including surface chemistry of carbon nanotubes, the chemical
properties of contaminants, and the chemistry of aqueous solution including pH,
ionic strength and presence of other compounds that can affect the adsorption of
contaminants onto carbon nanotubes.
Zhou fabricated a column of multi-walled carbon nanotubes as a sorbent for
atrazine and simazine in the pre-concentration process for measuring these com-
pounds using HPLC in water samples. The recovery of two compounds were in the
range of 82.6–103.7 % in spiked samples (Zhou et al. 2006). Shao et al. used multi-
walled carbon nanotubes grafted with β-cyclodextrin to remove polychlorinated
biphenyls from water under ambient conditions. In their experiments, multi-walled
carbon nanotubes grafted with β-cyclodextrin showed higher adsorption capacity
(95 % removal) compared to multi-walled carbon nanotubes (90 % removal) (Shao
et al. 2010). In a similar study, Salipira et al. tried to adsorb p-nitrophenol from
water using a copolymer of cyclodextrin cross linked by 5 % of functionalized car-
bon nanotubes. The new material could remove 99 % of model compounds from 10
ppm spiked samples, whereas granular activated carbon and native cyclodextrin
could remove only 47 % and 58 %, respectively. The new nanomaterial could main-
tain its adsorption capacity after at least 18 cycles (Salipira et al. 2007). In another
study, they used the new copolymer to adsorb trichloroethylene and achieved 98 %
removal efficiency (Salipira et al. 2008).
Chen et al. combined TiO2 nanoparticles with multi-walled carbon nanotubes to
enhance the photocatalytic degradation of atrazine under microwave irradiation
rather than ultraviolet light. According to their results, the new composite material
showed 20–30 % higher efficiency compared to TiO2 alone. They attributed this
improvement to the strong capability of the new material to absorb microwaves
(Chen et al. 2011). Cho et al. studied the adsorption of ibuprofen and triclosan by
single-walled, multi-walled and oxidized multi-walled carbon nanotubes from
water under conditions close to natural environment and water treatment systems.
They concluded that for hydrophobic compounds, single-walled carbon nanotubes
have higher adsorption capacity than multi-walled ones due to larger specific sur-
face area, while oxidized multi-walled carbon nanotubes showed lower capacity
compared to not oxidized ones due to higher surface oxygen. They also indicated
that for pHs below pKa, adsorption capacity was higher due to lack of electrostatic
repulsion (Cho et al. 2011).
Zhang et al. studied the sorption kinetics of tetrabromobisphenol A onto raw and
functionalized multi-walled carbon nanotubes in aqueous solutions using a pseudo-
second-order model, an intraparticle diffusion model and Boyd model. According
to their results, both types of multi-walled carbon nanotubes showed rapid binding
for tetrabromobisphenol A within 20 min and the kinetics could be described by the
pseudo-second-order model. Also, the external diffusion (boundary layer diffusion)
was considered as the rate-limiting step (Zhang et al. 2014).
Xu et al. developed a new adsorbent by self-assembling carbon nanotubes onto
CaCO3 micro-particles in shell-core structure and studied its capacity for removing
2-naphthol, naphthalene and 4-chlorophenol from aqueous solutions. They observed

that with increasing carbon nanotubes loading, the adsorption coefficient (Kf)
increased but the normalized adsorption coefficient (KfCNT) decreased (Xu et al.
2015). Srivastava et al. fabricated carbon nanotube filter that consisted of hollow
cylinders with radially aligned carbon nanotubes walls and used it for removal of
bacterial pathogens (Escherichia coli and Staphylococcus aureus) and Poliovirus
sabin 1 from water. This new filter was easily re-usable by ultrasonication or auto-
claving (Srivastava et al. 2004).
4.1.7 Graphene Nanoplatelets
Graphene is a new member of the carbonaceous nanomaterials group that has a 2D

(Fig. 4.3) honeycomb structure (sp2-hybridization) with a thickness of one carbon
atom. Graphene can be considered as a building block for other carbonaceous nano-
materials, such as fullerene and nanotubes. Due to large theoretical specific surface
area and especially highly hydrophobic surface, graphene shows strong adsorption
affinity to hydrophobic organic pollutants, such as polycyclic aromatic hydrocar-
bons, chlorobenzenes, antibiotics, pesticides and phenols (Liu et al. 2014; Wang
et al. 2014). After increasing awareness about the potential threats of emerging con-
taminants, researchers considered graphene as a promising solution to address the
problem of removing these contaminants at lower concentrations.
Fig. 4.3 Schematic of the structure of graphene nanoplatelets. The carbon-carbon bond length in
graphene is around 0.142 nm and Graphene sheets stack to form graphite with an interplanar spac-
ing of 0.335 nm. Owing to its two-dimensional structure, Graphene has a theoretical specific sur-
face area of more than 2600 m2/g which is much larger than that reported to date for carbon black
or carbon nanotubes (Bonaccorso et al. 2015)
For example, Al-Khateeb et al. studied the removal of aspirin, acetaminophen,

and caffeine from aqueous solution by graphene nanoplatelets. Their results showed
that pH 8 is the optimum pH and more than 94 % of all compounds can be removed
within 10 min at the graphene loading of 1 g/L. They also calculated the thermody-
namic parameters (ΔG, ΔH and ΔS) of adsorption process and concluded that for
the studied compounds, the process is spontaneous at all temperatures (Al-Khateeb
et al. 2014).
Several researchers tried to compare the performance of graphene with other
adsorbent materials, such as granular activated carbon, carbon nanotubes and also
other graphene based nanomaterials. For example, Rizzo et al. coupled conventional
sand filtration with graphene adsorption system to remove pharmaceutical com-
pounds from municipal wastewater. Using this system, they achieved more than
95 % removal for caffeine, carbamazepine, ibuprofen and diclofenac while in same
conditions, granular activated carbon showed only 63 % removal for mixture of
pharmaceutical compounds. They also observed that graphene treatment can
decrease toxicity towards Daphnia magna with 0–50 % immobilization (Rizzo et al.
2015). In a similar investigation, Zhu et al. compared graphene with granular acti-
vated carbon system for adsorption of ciprofloxacin and observed 77 % greater
adsorption capacity for graphene (323 mg/g) compared to granular activated carbon
(180 mg/g). According to the FTIR spectroscopy, they suggested that adsorption of
ciprofloxacin on graphene primarily occurred through π-π interaction. Interestingly,
they observed that ionic strength, presence of natural organic matter, and different
water sources were less important for graphene than granular activated carbon (Zhu
et al. 2015). In another study, Balamurugan and Subramanian compared the adsorp-
tion of the homologues series of chlorobenzenes with the molecular formula of
C6HmCln where m and n = 0−6, and m + n = 6 onto graphene sheet and single-walled
carbon nanotube. They found that graphene has higher adsorption capacity for chlo-
robenzenes compared to single-walled carbon nanotube that is due to planar geom-
etry of graphene that facilitates the surface adsorption of compounds (Balamurugan
and Subramanian 2013). Also, Liu et al. compared three different graphene with
single-walled carbon nanotube to remove ketoprofen, carbamazepine, and bisphe-
nol A from water under different solution conditions. They observed that the
adsorption isotherms were consistent with the orders of the surface areas and micro-
pore volumes of adsorbents and therefore in all cases, single-walled carbon nano-
tube showed the best performance. Their results also suggested incomplete
occupation onto adsorption sites of graphene as a result of the aggregation of sheets
and the presence of remaining oxygen-containing functionalities (Liu et al. 2014).
Some researchers attached oxygen containing groups to graphene using strong
oxidizers to enhance the functionality of graphene as adsorbent. These new nano-
materials are called “graphene oxide”, however in several cases; they are reported to
have lower adsorption capacity compared to pristine graphene. For example, Wang
et al. synthesized graphene and graphene oxide nanosheets and compared their per-
formance for adsorption of naphthalene from water. They observed that attaching
oxygen-containing groups to graphene can severely decrease the affinity of polycy-
clic aromatic hydrocarbons to graphene which is dominated by π-π interactions and
the sieving effect formed by wrinkles on graphene surfaces. In fact, by attaching the
new groups, the grooves on the graphene surface disappeared and π-π interactions
will be restricted (Wang et al. 2014). Also, Yan et al. synthesized graphene oxide for
the removal of aniline, nitrobenzene, and chlorobenzene, from water. They con-
cluded that hydrophobic interactions (π-π stacking and hydrophobic effects)
between graphene oxide and adsorbates played major role in the whole adsorption
process. Also, they studied the effect of oxidizing extent of graphene on adsorption
capacity and observed that moderately oxidized graphene with around 50 % gra-
phitic zone had the best adsorption performance due to good dispersibility and
enough activated adsorption sites (Yan et al. 2015). Kyzas et al. synthesized a nano-
composite from graphite oxide, which is the precursor of graphene, and modified
chitosan for the removal of dorzolamide, that is a pharmaceutical compound, from
biomedical synthetic wastewaters. They suggested that the reactive groups of graph-
ite oxide and chitosan have interaction with the amino groups in dorzolamide mol-
ecule which enhanced adsorption capacity. The maximum adsorption at optimum
pH (~3) was 334 mg/g which was superior compared to graphite oxide (175 mg/g)
and chitosan (229 mg/g) (Kyzas et al. 2014).
4.1.8 Polymeric Nanosponge
Mhlanga et al. produced cyclodextrin polymer with nanosponge structure using
bifunctional isocyanate linkers to remove a series of chlorinated disinfection by-
products and an odor-causing compound, in water 2-methylisoborneol. The as-
synthesized polymer could adsorb the pollutants with more than 99 % efficiency at
ng/l level which was superior to granular activated carbon (Mhlanga et al. 2007).
Later, they reported the removal of n-nitrosodimethylamine from drinking water,
using this nanosponge polymer with 80 % efficiency (Mhlongo et al. 2009). The
high efficiency of this polymer was due to the inclusive host-guest interactions
between polymer and contaminants which is shown in Fig. 4.4. However, nano-
sponge structures will be saturated after sometime and researchers should also
investigate their recyclability.
Arkas et al. impregnated TiO2 porous ceramic filter with nanosponge made from
functionalized poly (propylene imine) dendrimer, poly (ethylene imine) hyper-
branched polymer, and β-cyclodextrin derivatives to remove contaminants from
water at ppb level. Their results showed that by using this new class of filter sys-
tem, polycyclic aromatic hydrocarbons can be removed efficiently (higher than
95 %) and other contaminants, such as trihalogen methanes, monoaromatic hydro-
carbons, and pesticides were also removed efficiently (higher than 80 %) (Arkas
et al. 2005, 2006).
Hydrophobic cavity
OH OH
Cl Cl Cl Cl
+ Cl Cl Cl Cl
Cl Cl
Cyclodextrin Organic molecule Inclusion complex

(host) (guest)
Fig. 4.4 A schematic for host-guest interaction. In this mechanism, the host material has free
spaces in its structure which is perfect for retaining the guest molecules through non-covalent
forces including hydrogen bonds, ionic bonds, van der Waals forces, and hydrophobic
interactions
4.1.9 Nanofiltration Membranes
Separation processes through nanofiltration membranes have been increasingly

considered as an affordable and reliable technology for the purification of water
from unconventional sources, such as contaminated surface water, brackish water,
and secondary effluent of wastewater treatment plants where micropollutants should
be removed according to regulations. Nanofiltration membrane has pore size of less
than 2 nm or molecular weight cut-off in the range of 200–500 Da. Therefore, nano-
filtration membranes are capable of removing pollutants having molecular weights
larger than molecular weight cut-off of membrane. In Fig. 4.5, the performance of
different filtration technologies is illustrated. According to this figure, reverse osmo-
sis membrane retained all the solutes, even monovalent ions, which was not neces-
sary and their operational costs are also high. On the other hand, ultrafiltration
membranes can only retain microorganisms and proteins and they are not capable of
filtering molecules with MW of less than 2000. Therefore, nanofiltration mem-
branes could fill this gap with reasonable cost and reliable performance. At the pres-
ent time, nanofiltration membrane modules are working in some water treatment
plants in the world for removing or reducing contaminants. For example, in Cooper
city, Florida, a drinking water treatment plant was upgraded in 1998 with nanofiltra-
tion membrane module with the capacity of 11,000 m3/day and is capable of pro-
ducing high quality drinking water.
In some cases, the removal efficiency for certain compounds with nanofiltration
membranes is more than 98 %. However, besides size exclusion, there are several
parameters, such as electrostatic charge repulsion, hydrophobic interaction and
membrane fouling that can increase or decrease the rejection of contaminants. In
Fig. 4.5 Performance of nanofiltration membrane compared to other filtration technology.

Nanofiltration can retain up to 98 % of the organic contaminants but let the ions pass through the
membrane. Therefore it can be implemented for drinking water decontamination
recent years, many researchers tried to understand the mechanisms of solute trans-
port in nanofiltration membranes so that they could select the best option for reme-
diation of specific water source (Nghiem et al. 2005, 2010; Simon et al. 2012;
Verliefde et al. 2007a; Yüksel et al. 2013; Zhang et al. 2006). For example, Verliefde
et al. studied the removal of different emerging contaminants using a nanofiltration
system with negatively charged surface. They concluded that the size exclusion is
the dominants mechanism for rejection of neutral compound such as carbamaze-
pine, but for negatively and positively charged compounds such as ibuprofen and
atenolol, electrostatic repulsions and attractions can affect the rejection (Chellam
and Taylor 2001; Verliefde et al. 2007b). Interestingly, Nghiem et al. observed by
increasing the pH to above the pKa of the compounds, they transform from neutral
to negatively charged species and therefore the rejection of the compounds will be
higher through nanofiltration membranes with negatively charged surface (Nghiem
et al. 2005, 2006).
Zhang et al. used nanofiltration membrane to remove bisphenol A from drinking
water and observed that at the beginning of filtration the rejection rate was more
than 90 % but after several hours, due to the saturation of membrane, the rejection
rate decreased to 50 % (Zhang et al. 2006). Tepus et al. studied the effect of pressure
on rejection rate of atrazine through nanofiltration membrane and observed that by
increasing the pressure from 2 to 12 bar, the rejection rate will decrease from 60 to
50 % (Tepus et al. 2009). Also Yuksel et al. used nanofiltration membrane for
removal of bisphenol A from water and achieved 80 % removal during 4 h of filtra-
tion (Yuksel et al. 2013). In another study, Ahmad et al. investigated the perfor-
mance of four different nanofiltration membranes for removal of atrazine and
observed that the rejection rate was in the range of 60–95 % for different mem-
branes. They also observed that increasing the transmembrane pressure can lead to
enhanced solute rejection and permeate flux (Ahmad et al. 2008). Therefore, the
characteristics of membranes including material, molecular weight cut-off and sur-
face charge are very important in determining the rejection rate of membrane for
each compound.
To sum up, nanofiltration membranes can show high rejection efficiency for a
wide range of emerging contaminants, although their performances are impacted by
different parameters. But as a rule of thumb, bigger molecules with negative charge
and higher hydrophilicity are rejected more efficiently.
4.2 Conclusion
Emerging contaminants are going to become a big challenge to the environment and
human health in the near future and therefore, to prevent from their adverse effects,
having efficient methods for their removal from different media, especially water
and wastewater is of higher importance. Conventional wastewater treatment plants
are not able to remove these contaminants from wastewater or they only shift them
to soil through biosolids. Hence, novel methods are necessary to remove them at
maximum level. Meanwhile, nanotechnology is the most likely tool to develop the
solutions for contaminated media and there are numerous research works in this
field. Generally there are physical methods, such as adsorption systems and chemi-
cal methods, such as photocatalytic degradation which enhance their performance
through nanostructured materials. For example, carbon nanotubes with their large
specific surface areas showed a promising performance in adsorbing contaminants
even at low concentrations and TiO2 nanophotocatalyst proved to be capable of near
complete mineralization of contaminants. Also, nanofiltration membranes showed
the ability to filter some emerging contaminants with more than 95 % efficiency.
However, there are several drawbacks including the high cost of nanomaterials pro-
duction, limited recyclability, sensitivity to interferences and toxicity of by-products
that should be addressed before commercialization. Therefore, further research may
result in better understanding of the mechanisms controlling emerging contami-
nants removal in different processes and finding solutions for current issues. Also,
developing combinational systems which integrate physical separation and chemi-
cal transformation into one solution may attract the attention of researchers in future
due to their potential to overcome the drawbacks of single process methods.
Acknowledgement The authors are sincerely thankful to the Natural Sciences and Engineering
Research Council of Canada (Discovery Grant 355254and NSERC Strategic Grant), and Ministère
des Relations internationales du Québec (coopération Québec-Catalanya 2012–2014) for financial
support. The views or opinions expressed in this article are those of the authors.
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Chapter 5
Nanosensors for the Detection of Pathogenic
Bacteria
Anurag Jyoti, Rajesh Singh Tomar and Rishi Shanker
Abstract The consumption of microbiologically unsafe water poses major health

threats and leads to several diseases like diarrhea, typhoid and cholera. Hence, the
management of water quality is a growing need for public health and environment
in the developing world. Existing methods for pathogen detection face challenges
of inadequate monitoring in terms of specificity, rapidity and simplicity. Molecular
methods including polymerase chain reaction (PCR) and its advanced version real-
time PCR can detect pathogens at low levels. However, the requirement of sophis-
ticated instrumentation and trained personnel makes these methods less applicable
to field situations. The detection of target pathogens needs improvements to over-
come existing drawbacks and should be based on simple, rapid, sensitive and spe-
cific methodologies.
Here, nanotechnology provides solutions such as biodiagnostics, where
nanoparticle-based assays allow to specifically detect bioanalytes of clinical inter-
est. Gold nanoparticles are promising materials because they have unique optical
properties and high surface areas. Nanobiosensors are specific molecular-recognition
probes that target an analyte, then convert that recognition into a measurable signal.
Aptamers are single-stranded oligonucleotides that can fold into three-dimensional
conformations. Aptamers have the unique property of binding specifically to a tar-
get molecule. As molecular recognition probes, aptamers in conjugation with gold
nanoparticles have binding affinities and specificities that are can be explored to
capture and identify specific pathogens. This chapter reviews practical applications
of aptamer-conjugated nanoparticles for the detection of pathogenic bacteria.
Keywords Aptamers • Detection of pathogenic bacteria • Nanosensor • Gold

nanoparticle • Salmonella • Escherichia coli • Immunoassay • Real-time PCR
A. Jyoti (*) • R.S. Tomar

Amity Institute of Biotechnology, Amity University Madhya Pradesh, Gwalior, MP, India
e-mail: [email protected]; [email protected]; [email protected]
R. Shanker
Institute of Life Sciences, School of Science and Technology, Ahmedabad University,
Ahmedabad, Gujarat, India

130 A. Jyoti et al.
5.1 Introduction
The degradation in the microbiological quality of water and food adversely affects
human health worldwide. Rapid population growth has placed new challenges on
management of the frequency of food and water-borne disease outbreaks. The
majority of water and food borne infectious diseases occur include diarrhea, typhoid,
and cholera among others (Tomar and Jyoti 2015). An estimated 94 % of the diar-
rheal burden of disease is attributable to the environment, and associated with risk
factors such as unsafe drinking water, lack of sanitation and hygiene (Prüss-Üstün
and Corvalán 2006). Diarrhea is among the three most common causative agents of
death in children under-5. It is responsible for almost 13 % deaths in this age-group,
killing approximately 300,000 children in India each year (Lakshminarayanan and
Jayalakshmy 2015). Approximately, 20 million episodes of travelers’ diarrhea occur
annually and out of which 80 % of cases are due to bacterial agents. Diarrheagenic
Escherichia coli, including enterotoxigenic E. coli and enteroaggregative E. coli,
are responsible for approximately 50 % of cases. Globally, the three regions can be
alienated depending upon the risk of acquiring travelers’ diarrhea for visitors. India
is categorized under the high risk area, having 30–50 % chances of acquiring diar-
rhea (DuPont 2005). Enterotoxigenic E. coli is among the most common E. coli
diarrheal pathotypes. In the developing countries about 0.7 million childhood deaths
due to ETEC diarrhoea are reported every year (Pavankumar and Sankaran 2008).
Enterohemorrhagic E. coli, a potential pathovar of E. coli, causes bloody diarrhea
and hemorrhagic colitis. They can cause hemolytic uremic syndrome, an important
cause of childhood acute renal failure (Tarr et al. 2005).
It has been documented that countries in south Asia, particularly south-east Asia,
exhibit high burden of typhoid fever. India and neighboring countries have been
identified as high risk sites for infections caused by Salmonella spp. Ochiai et al.
(2008).
Despite ongoing efforts, the 2002 Millennium Development Goal of halving the
population without clean water or sanitation by 2015 is unlikely to be achieved.
Therefore, infectious waterborne diseases acquired through these uses are of
supreme importance. Recent reports indicate that waterborne diseases of fecal-oral
origin (mostly acute gastroenteritis) are the most common based on the number of
people affected (WHO 2008; Stevens et al. 2009). The outbreaks have an enormous
impact on the burden of diseases and sustainable development in developing coun-
tries. In contrast, the populations of developed countries are generally protected by
legislation and regulations regarding water quality usage.
Globally, the source of almost the two third of the drinking water consumption is
surface water, which may easily be contaminated by sewage discharges, animals
defecation, faulty infected channels, municipal wastes and industrial effluents
(Ahmed et al. 2005; Hamelin et al. 2006; Orsi et al. 2007). These surface waters
harbor a variety of pathogens such as Shiga Toxin producing Escherichia coli,
Enterotoxigenic Escherichia coli and Salmonella (Belanger et al. 2002; Shelton
et al. 2006; Lothigius et al. 2010; Sur et al. 2007; Fong et al. 2007; Jyoti et al. 2010).
Diseases caused by food-borne microbial hazards constitute a world-wide public
5 Nanosensors for the Detection of Pathogenic Bacteria 131
health concern, despite the enormous volume of food produced and consumed
safely throughout the world on a daily basis. During the past decades, the incidence
of certain food-borne diseases has increased in many parts of the world despite the
many improvements made to public health and food safety systems. Statistics indi-
cate that even in industrialized countries one out of every three people has a food-
borne microbial illness event every year (WHO 2003). It is recognized that food
safety is not an absolute but rather a continuum of more or less safety and also that
food-borne microbial hazards are likely to remain or (re-)emerge over time for a
number of reasons. These include microbial adaptation, changes in the food produc-
tion systems, changes in human demographics and behaviour, international travel
and trade.
Global data indicate that the epidemiology of food-borne diseases is changing
and that an increased range of microorganisms and foods are the leading cause of
food-borne illness. A better understanding of the distribution, epidemiology and
threat posed by emerging and uncharacterized pathogens is needed due to rapid,
poorly controlled global spread through the food chain and ultimately and commu-
nities. The detection, reporting and characterization of food- and water-borne ill-
nesses play an important role in identifying the origins and incidence of disease
when links can be made to the causative agents and the foods involved.
Prevalence of pathogenic bacteria is well documented in drinking water. A better
understanding of monitoring and detection system can lead to the minimization of
risks imposed by the consumption of drinking water. Recently more emphasis has
been given on the detection of pathogens in water. A number of methods exist for
the detection of pathogenic bacteria in water having their own pros and cons
(Fig. 5.1).
These include culture based and biochemical methods. These methods are labour
intensive and time taking. Often these are qualitative which limit their applicability
in recommendations in therapeutics (Li and Gu 2011). Polymerase Chain Reaction
(Navas et al. 2006) and immunological techniques like Enzyme Linked
Immunosorbent Assay are restricted to the laboratory set up (Crowther 1995).
Quantitative real time Polymerase Chain Reaction assays have proved to be sen-
sitive and specific for the detection of E. coli and Salmonella serovars (Ram et al.
2008a; Jyoti et al. 2010). Due to the requirements of specialized instrumentation
and trained personnels this technique has been limited to lab conditions only.
Nanomaterials mediated DNA detection are attractive alternative to the existing
methods. Replacing fluorescently labeled DNA probes with metallic nanoparticles
conjugated DNA probes are promising because they minimize the necessity of
using expensive and complex instrumentation. Nanomaterials are attractive probe
candidates because of their contrasting physical and chemical features. Their small
size leads to unique large surface-to-volume ratio, often make them feasible to
attach with nucleic acids. Gold nanoparticles, in particular, have surface plasmon
resonance related optical absorption at around 525 nm and possess a red colour in
an aqueous suspension. The gold nanoparticles are attached with the single stranded
DNA (complementary to target DNA) to generate probe. Synthesised gold
nanoparticle probes are allowed to hybridise with target DNA. As a result of
132 A. Jyoti et al.
Culture based technique

-Time consuming
-Labour intensive
-Non specific
Molecular method: PCR based

-DNA based detection
-Expensive instrumentation
-Trained personnel required
-Not fit for field conditions
Nanobiotechnology: Nanoprobes for detection

-DNA based detection (PCR products)
-Needs PCR to generate targets
-Not fit for field conditions
Strip based detection device

-Detects whole bacteria
-Rapid and Simple
-Highly specific and sensitive
Suitable for field conditions
Fig. 5.1 Schematic representation of the development of pathogen detection systems
hybridization, a polymer network is formed. This condensed network brought the

conjugated gold nanoparticles self assemblies into aggregates leading to change in
colour from red to purple (Jyoti et al. 2011). The aforesaid reports track only the
short synthetic oligonucleotides (up to 20–30 bp) targets, which again do not repre-
sent the sequences of a pathogenic DNA or PCR product.
In order to enhance the target detection capabilities, a number of gold nanopar-
ticle based lateral flow immunoassays have been reported for the detection of bacte-
rial pathogens but most of these assays are not in actual use. Applications of
aptamers have proven to be very useful in the detection system. Gold nanoparticles
conjugated with aptamers have unique capability to detect whole of the target bac-
teria without isolating its DNA.
Therefore, this paper intends to review the existing methods for the detection of
pathogenic bacteria. The review also focuses onto the applications of gold nanopar-
ticle and aptamer for the development of diagnostic device useful in field conditions
for point-of-care diagnostics. It discusses the challenges and opens the avenues for
future research. Therefore, the recent focus is on the development of rapid detection
techniques, which are user friendly, require less technical expertise and time
efficient.
5.2 Prevalent Water and Food Borne Pathogenic Bacteria
Water and food-borne bacterial agents have been the most well investigated and
monitored causes of intestinal infectious disease. In developed countries, the risk
assessment is being regulated, but still the disease burden is substantial. For the past
two decades, Salmonella spp. and E. coli are among the three most persistant food
borne pathogens. The serotypes of both these pathogens are responsible for major-
ity of burdens of food and water borne illnesses (Newell et al. 2010).
5.2.1 Salmonella
Salmonella spp. is one of the most prevalent food and water borne pathogens, which
causes morbidity and mortality in rural and urban settings. The pathogen causes
salmonellosis, leads to significant medical and economic losses throughout the
world (Voetsch et al. 2004). The causative organism can pass through the food chain
from primary production to ultimate consumers and causes gasteroenterititis.
Salmonellae are gram-negative, rod-shaped, non-spore forming, mainly motile
enterobacteria. They are facultative anaerobes; belong to Enterobacteriaceae family
having dimensions around 0.7–1.5 μm (diameters) and 2–5 μm (lengths) (Madigan
et al. 2009). Salmonellae can grow at optimum temperature between 35 and 37 °C,
but growth has also been observed at temperatures ranging from 5 to 47 °C. The
optimum pH for growth is near 7.0, but growth may occur between pH 4.0 and pH
9.0 (Lanata 2003). Salmonellae produce hydrogen sulfide, decarboxylate lysine and
ornithine, and do not hydrolyze urea. They are oxidase negative and catalase posi-
tive and can grow on citrate as the sole carbon source.
The Centre for Disease Control and Prevention has distinguished two Salmonella
species (or subgenera): S. enterica and S. bongori. S. enterica is further divided into
six subspecies, of which S. enterica subsp. enterica is the most clinically signifi-
cant, causing 99 % of Salmonella infections (Brenner et al. 2000). WHO report con-
firms there are 2579 serovars of Salmonella, out of which approximately 59 %
belong to S. enterica subsp. enterica (Grimont and Weill 2007).
The pathogenicity of Salmonella serotypes vary widely. Most Salmonella viru-
lence factors are clustered on chromosome referred as Salmonella pathogenicity
islands (Shea et al. 1996). So far five Salmonella pathogenicity islands have been
identified which encode different secretion systems required by pathogenesis
(Schmidt and Hensel 2004). Typhimurium, Enteritis, Newport, and Heidelberg
were among the top four most commonly isolated serotypes from human infections.
These are also the most frequently isolated serotypes from food samples (CDC
2003). The pathogenicity of Salmonella requires the expression of virulent genes.
Serotypes, not possessing the invABC genes are unable to invade mammalian cells
(Galan 1996). Virulent chromosomal genes such as invA sequences unique to this
genus and has been proved to be a suitable Polymerase Chain Reaction target with
134 A. Jyoti et al.
potential diagnostic application (Malorny et al. 2003; Zahraei et al. 2007; Jamshidi
et al. 2008). This gene is recognized as an international standard for detection of
Salmonella genus (Malorny et al. 2003).
Infection of Salmonella in immune-compromised persons causes Salmonellosis.
The symptoms including diarrhea, fever and abdominal cramps develop within
3 days after infection, the illness may last 4–7 days (FDA/CFSAN 2008). In severe
cases, the Salmonella infection may become systemic and spread from intestines to
other body sites through blood stream and can cause death. The type of Salmonella
usually associated with infections in humans is non-typhoidal Salmonella. It is usu-
ally spread from sources such as: infected poultry, eggs, egg products, cattle, milk
and contaminated fruits and vegetables. Another form of Salmonella, typhoidal
Salmonella can lead to typhoid fever. It is carried only by humans and is usually
spread through direct contact with the infected person and its fecal matter. The
infectious dose of Salmonella varies and depends upon serovars, source of infection
and host susceptibility. In general, the minimum infective dose of Salmonella is 106
and S. Typhimurium 10–100 cells (Lanata 2003).
Salmonella is constantly released into the environment from infected humans,
farm animals, pets, and wildlife (Baudart et al. 2000). The organism is frequently
isolated from surface and potable water which serve as bacterial reservoirs (Chao
et al. 1987; Jyoti et al. 2010). Salmonella has the ability to grow and survive in
harsh conditions too as it can survive for 10–15 days in a septic system (Parker and
Mee 1982).
5.2.2 Diarrheagenic Escherichia coli
E. coli is gram-negative, facultative anaerobic and non-sporulating bacterium and is

generally rod-shaped. E. coli generally grows at 37 °C but some strains can grow
upto 49 °C (Fotadar et al. 2005). Diarrheagenic E. coli causes the diarrhea in infants,
children and immuno-compromised people. E. coli colonise the gastrointestinal
tract of infants just after birth and is the predominant throughout lives. The bacte-
rium is responsible for a variety of diseases like gastroenteritis, urinary tract infec-
tions, and meningitis. Infections due to pathogenic E. coli may be limited to the
mucosal surfaces or can disseminate throughout the body.
5.2.2.1 Enterotoxigenic E. coli
Enterotoxigenic E. coli is the most common diarrheal agent among the six recog-
nized pathovars of DEC, particularly in the developing world. produces at least one
member of two defined groups of enterotoxins: ST (heat-stable enterotoxin) and
heat-labile enterotoxin and colonization factors which allow the organisms to colo-
nize the small intestine causes diarrhea in infants as well as adult human beings
(Qadri et al. 2005).
The heat labile enterotoxin is oligomeric toxin which resembles in structure and
function to the cholera enterotoxin of Vibrio cholerae. The toxin exists in two forms,
namely. LT-I is pathogenic for both humans and animals. LT-II has only been found
in ETEC strains infecting animals. LT-I consists of one A subunit and five identical
B subunits (Nagy and Fekete 2005). After the colonization of the small intestine by
the LTB subunits bind to ganglioside GM1, and the A subunit activates for the enzy-
matic activity of the toxin by activating adenylate cyclase which results in increases
in cyclic adenosine monophosphate concentrations. This inhibits neutral sodium
chloride in the villus tips and stimulates chloride secretion in the crypt cells thereby
resulting in osmotic diarrhea (Nataro and Kaper 1998; Kaper et al. 2004).
Heat stable enterotoxin (ST) is small, monomeric toxin in comparison to LT. Heat
stable enterotoxin can be categorised into two groups: STa (or STI) and STb (or
STII). STa is produced by ETEC strains infecting both humans and animals whereas
STb is primarily associated with disease in animals, and not oftenly human disease
(Nataro and Kaper 1998). The receptor for the ST toxins is guanylate cyclase in the
small intestine. Binding to the receptor results in increased intracellular cyclic gua-
nylate monophosphate levels which stimulate chloride secretion and inhibit NaCl
absorption, resulting in subsequent net intestinal fluid secretion leading to diarrhea
(Qadri et al. 2005). ETEC has great importance for developing countries due to its
association with surface and potable water borne diarrheal disease outbreaks.
5.2.2.2 Enterohemorrhagic E. coli
Enterohemorrhagic E. coli, Verotoxin producing E. coli or Shiga-toxin producing E.

coli are the synonyms for the same group of organism. Infections in humans can
result in bloody diarrhea and hemorrhagic colitis (Nataro and Kaper 1998). In
severe infections the hemorrhagic colitis progresses to hemolytic uremic syndrome,
an important cause of acute renal failure in children and morbidity and mortality in
adults (fatality rate in elders: 50 %). E. coli O157:H7 has been recognized as the
most commonly occurring member of this group. Infections in humans can be
acquired by direct contact with animal carriers, their feces, ingestion of under-
cooked ground beef and contaminated water, vegetables and fruits. The low infec-
tious dose (1–100 CFU) enhances the risk of occurrence of disease (Paton and Paton
1998; Sharma 2006).
The pathogenicity of is determined by pathogenic factors. The most important
factors are the phage-encoded Shiga toxins (stx) elements on the chromosome
which inhibit protein synthesis (Nataro and Kaper 1998). Shiga toxin contains two
major toxins, called Stx1 and Stx2, which share approximately 55 % amino acid
homology, these are similar to the one produced by Shigella dysenteriae serotype 1,
Nakao and Takeda (2000) and Gourmelon et al. (2006). Epidemiological studies
have revealed that Stx2 is 1000 times more cytotoxic than Stx1 towards human renal
endothelial cells. Isolates producing Stx2 are more associated with serious diseases
than isolates producing Stx1 or Stx1 and Stx2 (Louise et al. 1995; Boerlin et al.
1999; Paton and Paton 1998). The pathogen enters the human body through con-
136 A. Jyoti et al.
taminated food or water. The ability of bacterium to survive at lower pH (up to 2–3)
facilitates survival through the acidic condition of the stomach. In the colon, the
virulence genes are turned on by environmental signals. Secretion of Shiga toxins
leads to local damage blood vessels in the colon result in bloody diarrhea.
Absorbance of sufficient Stx in circulation causes damaging and impaired function
of vascular endothelial sites. The kidneys and central nervous system are frequently
affected, and hemolytic uremic syndrome may develop (Gyles 2007).
Environmental reservoirs are the potential sources of pathogenic E. coli. These
are ideal habitat for survival, growth, and proliferation of E. coli as they are rich in
nutrients. A wide range of different animals harbor pathogenic E. coli, which are
consistently associated with human and animal diarrheal infection (Chapman et al.
1994). Infected cattle typically excrete (>103 CFU/g of feces) pathogenic E. coli
(Robinson et al. 2004; Topping et al. 2008). These discharges may be released
directly into the aquatic environment or indirectly through storm water runoff. The
surface water carries a number of pathogenic bacteria when used for the drinking
and bathing purposes. Apart from these, the water is treated in municipal treatment
plants and supplied through pipelines for drinking purposes. The processed clean
water sometimes also gets contaminated due to leakage of nearby sewer lines (Ram
et al. 2008a).
E. coli can also survive in estuarine sediment environments (Brettar and Hofle
1992). Two highly prevalent diarrheagenic E. coli variants have been reported in
surface and potable waters as well as in macrophytes in India. The multiple antibi-
otic resistant Enterotoxigenic E. coli (ETEC) and Shiga toxin producing E. coli
have been reported in surface waters of river Ganga and its tributaries Gomti and
Saryu (Ram et al. 2007, 2008a, b, c). Potentially pathogenic isolates of Escherichia
coli serotype O157:H7 have been isolated from the Ganges river near Varanasi
(Hamner et al. 2007).
5.3 Conventional Methods for Pathogen Detection
The detection of Salmonellae faces several challenges, such as the low concentra-
tion of target bacteria in foods, high amount of other bacteria and inhibitory compo-
nents in samples.
5.3.1 Culture Based Methods
The traditional confirmation and identification of Salmonella spp. are usually based
on the colony appearance on chromogenic and other selective agar media, followed
by confirmation using classical biochemical and serological testing. The biochemi-
cal tests include fermentation of glucose, negative urease reaction, lysine decarbox-
ylase activity and H2S production. In the European Union, the reference detection
methods are published by the International Organization for Standardization. The

procedure for the detection of food borne Salmonella includes non-selective enrich-
ment in buffered peptone water broth for 16–20 h followed by selective enrichment
cultivation in selective media and incubation on two different selective agar plates
for isolation of colonies. The colonies are then identified by means of biochemical
tests. This procedure takes at least 72 h to complete. In Bacteriological Analytical
Manual, published from the United States, the procedure for the detection of
Salmonella includes non-selective enrichment in nutrient broth for 16 h and fol-
lowed by 16 h selective enrichment cultivation in either Rappaport–Vassiliadis or
tetrathionate brilliant green broth (Andrews and Hammack 2007). The colonies are
isolated by using selective agar plates and identified biochemically.
The traditional method of detection of enterotoxigenic E. coli involves cultiva-
tion of bacteria in selective media. This includes the cultivation in MacConkey or
Eosin Methylene Blue (EMB) agar followed by overnight incubation. The charac-
teristic colonies are typical pink to red color for E. coli. Further confirmation is done
by Indole, Methyl red, Voges-Proskauer and Citrate test which examine the ability
to produce indole and sufficient acid to change the color of a methyl red indicator
(Todar 2008). These assays are laborious and time consuming.
The identification of enterohemorrhagic E. coli in accurate manner is still a
major issue. The inability of most E. coli O157 to ferment sorbitol is exploited in
sorbitol McConkey agar. The Inernational Odranisation for Standardisation proto-
col (ISO 16654) recommends addition of Cefixime and potassium tellurite to sorbi-
tol McConkey agar may increase the selectivity in samples. E. coli O157 generally
produces colourless colonies when cultured on this media, thus distinguishing it
from other enterohemorrhagic E. coli serogroups.
5.3.2 Immunoassays
In general, the immunoassays use antisera for detection of flagellar (H) and somatic
(O) antigens. Isolates with a typical biochemical profile, which agglutinate with
both H and O antisera, are identified as Salmonella spp. Cudjoe et al. (1995),
Valdivieso et al. (2001), and Magliulo et al. (2007). Further, the positive isolates are
often confirmed by serotyping and using techniques such a phage typing and pulsed-
field gel electrophoresis. The immunoassays are capable of detecting 104–106 cells
of Salmonella in foods per assay. The antibodies may cross-react with antigens in
closely related bacteria, while showing low reactivity with some Salmonella
serotypes.
Enzyme Linked Immunosorbent Assay has been widely used for detection of
heat labile toxin using microtiter ganglioside methods. It requires culturing of the
bacteria before testing for presence of enterotoxins. Although, the immunoassays,
based upon the antigen-antibody interactions are established techniques, they often
lack specificity. Serotyping has also been used to identify and characterize entero-
138 A. Jyoti et al.
toxigenic E. coli strains. The ETEC has more than 78 O groups and 34 H groups
identified; therefore the determination of O serogroups associated with the lipopoly-
saccharides in the cell wall and H serogroups of the flagella is difficult (Qadri et al.
2005). A huge number of combinations of O and H groups make serotyping less
suitable for identification of enterotoxigenic E. coli.
Enterohemorrhagic E. coli O157:H7 colonies are confirmed with biochemical
tests and immunoassays having the O157 somatic antigen and H7 flagellar antigen.
A variety of tests including enzyme-linked immunosorbent assays, agglutination,
immunoblotting or Vero cell assay can be used to detect the verocytotoxin.
5.3.3 DNA Amplification Method
Polymerase Chain Reaction, a molecular technique has been used most frequently
for the detection of Salmonella (Malorny et al. 2007; Chen et al. 2010; O’Regan
et al. 2008; McGuinness et al. 2009; Jyoti et al. 2010). The virulence invA gene has
been extensively used for the detection of Salmonella in water and food. Most of
these methods which are in routine use provide results in approximately 24 h.
PCR can be used for differentiating diarrheagenic strains from nonpathogenic
strains in both clinical and environmental samples (Sjöling et al. 2007). This
approach to ETEC detection relies on the presence of the genes encoding heat labile
and/or heat stable enterotoxins. The E. coli O157:H7 specific virulent genes such as
stx1 and stx2 are used for the reliable and accurate detection (Ram et al. 2011).
5.3.4 Real Time Polymerase Chain Reaction
Real Time PCR, a recent advancement in PCR technology simultaneously amplifies

and detects target DNA in samples. It uses fluorescent detection strategies for the
quantification of nucleic acid in a reaction without post-PCR processing. With the
addition of an optical module, real time PCR allows the capture of fluorescent sig-
nals from amplified PCR products. Computer software records and displays the
amount of fluorescence in relative fluorescence units (RFU). The amplification
cycle at which the fluorescence exceeds the cutoff level is known as threshold cycle
(CT) Corless et al. (2000). This threshold is calculated as a function of the amount
of background fluorescence and is plotted at a point in which the signal generated
from a sample is significantly greater than background fluorescence (Kubista et al.
2006; Espy et al. 2006). With increasing concentration of target DNA, the threshold
of the sample fluorescence will be achieved earlier. The amount of initial copy num-
ber of the target in unknown sample can be calculated by comparing the CT obtained
of that sample with a standard curve, generated from serial dilutions of a known
amount of the target DNA (Ibekwe et al. 2002).
One of the major probe chemistries is Molecular Beacon (MB) probe, which is
widely used for the detection of target nucleic acids in samples. It is a short single-
stranded oligonucleotide molecule that forms a hairpin with a loop and stem. The
loop is designed to hybridize to a 15–20 nucleotide fragments of the target DNA
sequence while the stems are composed of five to seven self complementary nucleo-
tides. A fluorescent reporter molecule is attached at the 5′- end of the molecular
beacon and a dark quencher at 3′- end. In the native state, the MB is closed and both
the reporter and quencher are in close proximity of each other. The signal released
by reporter is masked by the quencher. During annealing step of PCR, the binding
of molecular beacon to its target leads to increased fluorescence, due to separation
of reporter and quencher, which directly corresponds to accumulation of product
(Fig. 5.2) (Kubista et al. 2006).
The possibility of cross-contamination between analyses is reduced due to closed
tube format, and provides rapid, continuous data collection and reduction in time
required to obtain results. These salient features have made real time PCR a potential
alternative to conventional culture-based or immunoassay-based testing methods
used for diagnosing infectious diseases.
Fig. 5.2 Mechanism of target binding of molecular beacon probe (above). As a result of target
hybridization the Cycle Threshold (CT) is generated (below)
140 A. Jyoti et al.
5.4 Gold Nanoparticle Probes for Detection of DNA
Currently, nano-biotechnology is evolving with the simultaneous developments in

nanoscience, biology and medicine. The potential applications of nanotechnology are
becoming increasingly important for the development of ultrasensitive DNA detection
systems. Organic fluorophores have been used to achieve the recognition of different
targets. These fluorophores often suffer from quenching and limited multiplexing.
Apart from these, the need of expensive instrumentation makes them unsuitable for
point-of-care diagnostics. Gold nanoparticles possessing unique and outstanding opti-
cal properties have been explored for bio-diagnostics (Storhoff et al. 2004; Sato et al.
2007). GNP-based DNA detection has high sensitivity as compared to conventional
fluorescence based assays due to the extremely its high molar absorptivity of (approxi-
mately 1000 times higher than that of organic dyes) (Zhao et al. 2008).
The optical properties of gold nanoparticles are governed by collective oscilla-
tion of electrons at surfaces known as surface plasmon resonance. The Gold
nanoparticles have a high surface to volume ratio, therefore the surface electrons are
sensitive to change in the dielectric (refractive index) of the medium. Any changes
to the environment of these particles including surface modification, aggregation
and medium refractive index lead to colorimetric changes of the dispersions (Rosi
and Mirkin 2005). The aggregation behaviour of Gold nanoparticles has been
widely explored for different applications. This has further facilitated the applica-
tion in bio-detection via numerous detection methods (Boyer et al. 2002; Niemeyer
2001). Due to its outstanding conjugation ability various analytes such as nucleic
acids, sugars, proteins via the strong affinity of gold surface with thiol Ligands can
bind for target detection (Schofield et al. 2007).
The colloidal solution of gold nanoparticles is monodisperse red and exhibit a
narrow surface plasmon absorption band centered on 520 nm (depends upon parti-
cle size) in the UV-Visible spectrum. The colorimetric change pointed to a simple
and inexpensive way of diagnosing disease, suggested that assays based upon such
nanostructures should have higher selectivities than the conventional molecular
fluorophore-labeled structures. The properties and application of gold nanoparticles
in nano-diagnostics have received a lot of attention for the detection of DNA, using
the well-known chemistry of thiol adsorption to gold.
5.4.1 Principle
5.4.1.1 Gold Nanoparticles Probes for DNA Detection
The Gold nanoparticles are bio-functionalized with the thiol modified single
stranded DNA (ssDNA) to generate probe for DNA detection (Lu and Liu 2006).
The computational exercises for the selection of ssDNA probe strand are done to
create a complementarity with target of interest. Gold nanoparticles are conjugated
with the synthesized ssDNA having thiol group. After hybridization with the target,
the probes come in the close proximity, which leads to change in color. As a result,
the particles aggregate and the solution appear purple/blue, corresponding to a char-
acteristic red shift in the surface plasmon resonance towards higher wavelength
(Storhoff et al. 2004). A number of factors viz. size and shape of the nanoparticle,
refractive index of the surrounding media and inter-particle distance are taken into
account for use in colorimetric detection of DNA (Baptista et al. 2008). The Gold
nanoparticles obtained by citrate-reduction present in solution are charged particles
and they are sensitive to changes in solution dielectrics. Hence, with the addition of
NaCl the surface charge is shielded leading to a decrease in inter-particle distance
and particle aggregation.
Mirkin and co-workers reported the colorimetric detection of DNA targets based
on the cross-linking mechanism use of Gold nanoparticles probes. Two different
batches of ssDNA are designed to detect target DNA. During hybridization, a poly-
meric network of Gold nanoparticles probes is generated due to aggregation, turn-
ing the solution from red to blue (Mirkin et al. 1996). This aggregation process is
slower and capable to detect smaller targets (Sato et al. 2003).
Another mechanism of analyte detection has been well demonstrated by Sato
and coworkers. The thiol modified single stranded DNA can be immobilized on
Gold nanoparticles. With the addition of Gold nanoparticles probes aggregate
together and detect the target DNA. As a result, there is significant change in colour
of the solution from red to blue (Sato et al. 2007).
The basic steps of DNA detection using gold nanoparticle probes include
(Fig. 5.3):
+
Gold nanoparticles Thiolated ssDNA
GNP conjugated ssDNA probes
Target DNA
GNP probes hybridize with target DNA
Fig. 5.3 Schematic representation of synthesis of Gold nanoparticle probes and target DNA
detection
142 A. Jyoti et al.
1. Synthesis of Gold Nanoparticles: Gold nanoparticles are synthesized using

citrate reduction method (Pandey et al. 2008). Aqueous solution of Hydrogen
tetrachloroaurate (1 mM HAuCl4) is brought to the boiling with stirring in a
round bottomed flask fitted with a reflux condenser. Trisodium citrate solution is
added rapidly when the solution begins to reflux. The solution is further boiled
for another 15 min. In due course, the colour of the solution is changed from pale
yellow to deep red. This red solution is allowed to cool at room temperature with
continuous stirring.
2. Functionalization of gold nanoparticles with thiol-modified DNA: The single
stranded oligonucleotides (complementary to some parts of target) are used for
synthesizing probes by immobilizing onto the gold nanoparticles. These oligo-
nucleotides are modified with thiol group (-SH) at their 5′/3′-ends. The single
stranded DNA (ssDNA) stabilized Gold nanoparticles are prepared by the
method with slight modification reported previously (Lu and Liu 2006). The
gold nanoparticles (selected size ~20 ± 0.2 nm diameter) are incubated with dif-
ferent batches (number varies with the target size) of thiol modified ssDNAs
separately. The solution is buffered with the Tris-acetate and salt. After this the
unbound ssDNA is removed by centrifuging the solution. The ssDNA grafted
Gold nanoparticles is resuspended in buffer and room temperature. The absorp-
tion spectra of the bio-functionalized Gold nanoparticles are recorded in UV-
visible spectroscopy.
3. Hybridization of Gold nanoparticles probes with targets and detection: The syn-
thesized Gold nanoparticles probes are allowed to hybridize with the target DNA
under controlled conditions. The hybridization mixture includes target DNA,
Gold nanoparticles probes and monovalent salt. Hybridization and target detec-
tion is examined for change in solution colour by naked eye and the change in
surface Plasmon resonance band is recorded in UV-visible spectroscopy. The
reduction in interparticle distances and aggregate formation is observed in
Transmission Electron Microscopy.
5.5 Aptamers for Pathogen Detection
Aptamer is single-stranded nucleic acid (DNA or RNA) that usually possesses high
affinity and results in a significant conformation change upon binding with a wide
range of targets. Aptamers are generally selected from the pools containing ran-
domly created sequences through an in vitro systematic evolution of ligands by
exponential enrichment (SELEX). Compared to antibody-based biosensors,
aptamer-based biosensors (aptasensor) possess unprecedented advantages with high
productivity, affinity, selectivity, and stability (Zhou et al. 2014).
Aptamers, with appropriate secondary structures that function as ligands, are
emerging as new analytical reagents, which can be coupled with different transduc-
tion systems. Possibly, the most important advantages of aptamers from an analyti-
cal point of view are the high affinity and binding specificity for their targets, ease
to be labeled with different reporter molecules, and their relatively low production
cost, which make them ideal reagents for the development of sensors. Although
aptamer applications are dominated by clinical or medical diagnostics market so far,
first steps have already been taken for the application of aptamers to ensure food
safety.
Several bacterial aptamers had been isolated and recently used in identification
of bacteria, including Escherichia coli, Mycobacterium tuberculosis, Salmonella
enterica and Bacillus anthracis (Maeng et al. 2012).
Gold nanoparticles are gold particles that range in size from 1 nm to several
hundred nanometers and possess strong light scattering properties. The intensity of
light scattering is based on the size of the particle. Moreover, Gold nanoparticles
can be easily conjugated with protein or modified DNA molecules through sulfhy-
dryl linkages. These properties make Gold nanoparticles a useful tool for ultrasensi-
tive molecular detection (Jyoti et al. 2011). Moreover, a GNP-based amplification
method has been developed and the system was shown to be capable of detecting
prostate-specific antigen with sensitivity in the attomolar range.
5.5.1 Advantages of Aptamers Over Antibodies
Principally, biosensor consists of a biological recognition component and a signal-

ing component. The recognition element detects the target molecule while that the
signaling component converts the biological recognition into detectable signals.
The specificity, binding affinity and sensitivity of recognition molecules are the
utmost important for biosensors performance. A number of recognition molecules
have been used including the antibodies due to varying reasons. Inspite of different
applications and uses, antibodies face certain lacunae. Being proteinacious in
nature, the antibodies are highly sensitive towards temperature variations. The spec-
ificity and binding with the target also faces variations. The irreproducibility of
results due to instability makes it difficult for working with antibodies. Therefore, it
is highly desirable for potential alternative ligands as a new platform for diagnosis.
DNA Aptamers are attractive for biosensor development due to their small size,
high stability, high binding affinity and specificity, and ease of modification.
5.5.2 Detection of Whole Bacteria
Detection of target bacteria as an analyte will be a major breakthrough. This will

remove the steps involved in isolation of genomic DNA and amplification of PCR
product. Aptamers have also been involved in developing lateral flow assays for the
direct detection of bacterial pathogens. Such aptamers are developed using
Systematic Evolution of Ligands by Exponential Enrichment technique. In this
approach, one of the aptamer specific to the analyte is immobilised on the nitro
144 A. Jyoti et al.
cellulose membrane as test line directly or through biotin–avidin interaction.

Another aptamer is conjugated to colloidal nanoparticles. The bacterial pathogen
(analyte) is put on the sample pad which interacts with the nanoparticle conjugated
aptamer. As the complex moves along the strip, the aptamer immobilised at test line
will also interact with the bacterial pathogen to form a sandwich and the gold
nanoparticles get captured at the test line producing a red colour.
5.5.3 Method
1. Synthesis of Aptamer conjugated Gold Nanoparticle probes: The single stranded

aptamers are used for synthesizing probes by immobilizing onto the gold
nanoparticles. The aptamers are modified with thiol group (-SH) preferably at
their 5′-ends. The gold nanoparticles are incubated with thiol modified aptamers.
The final concentration of aptamers is 2 μM. The solution is incubated with the
Tris-acetate and NaCl. The unbound thiolated aptamers are removed by wash-
ing. This is followed by resuspension of aptamers-conjugated GNP at room tem-
perature for further characterization.
2. Colorimetric detection of target bacteria using Aptamer-conjugated Gold
Nanoparticle probes: Different concentrations of target bacteria are added to the
aptamer-conjugated Gold nanoparticles solution. After incubation the monoso-
dium salt (NaCl) is introduced to the mixtures, followed by UV–vis
characterization.
5.6 Development of Nanoaptasensors Pathogen Detection
5.6.1 Strip Based Lateral Flow Device
Strip assays are extremely versatile and are available for an enormous range of ana-
lytes including mycotoxins, blood proteins and bacterial pathogens. Lateral flow
assays are essentially immunoassays adapted to operate along a single axis to suit
the test strip format. There are a number of variations of the technology that have
been developed into commercial products for detection of bacterial pathogens
(Singh et al. 2015).
5.6.2 Working of Lateral Flow Assay (Fig. 5.4)
A lateral flow rapid test strip consists of the following components:

Sample pad- It is an adsorbent pad onto which the test sample is applied.
Sample pad
Conjugate pad Reaction membrane Wick or waste

reservoir
Target bacteria Aptamer conjugated GNP Anti-aptamer
Fig. 5.4 Schematic representation of strip based lateral flow device
Conjugate pad- It contains aptamers conjugated gold nanoparticles specific to the

target pathogen.
Reaction membrane- A nitrocellulose membrane onto which anti-target aptamers
are immobilized in a line that crosses the membrane to act as a capture zone or
test line. This is followed by a control zone which contains oligonucleotides
complementary to the aptamer.
Wick or waste reservoir- Another absorbent pad designed to draw the sample across
the reaction membrane by capillary action and collect it.
The components of the strip are usually fixed to an inert backing material and
may be presented in a simple dipstick format or within a plastic casing with a sam-
ple port and reaction window showing the capture and control zones.
5.7 Challenges of Aptamer-Based Biosensors
Although, a number of aptamers are being used for sensing the pathogens and these
have potentials to replace existing technologies in near future, a number of challenges
can be faced. The lack of high quality DNA aptamers for many important targets,
such as bacterial pathogens, glucose and many others is the foremost challenge. Most
of the aptamers in use lack characterization, which makes it difficult for practical util-
ity. The main challenge lies in the target detection in a complex sample matrix.
5.8 Conclusion
The present scenario of over population, urban crowding and stressed rural–urban
interfaces in developing nations has created an urgent need to develop an ideal
detection system which overcomes drawbacks in existing methods for detection of
146 A. Jyoti et al.
water-borne pathogens and risk assessment. Various conventional and analytical

methods exist to detect bacterial pathogens in different matrices including environ-
mental and clinical settings. Very often they suffer from limitations such as poor
sensitivity, selected specificity, time consuming costly instrumentations, trained
personnel etc. The detection system or device needs to be based on simple, rapid,
highly sensitive and specific methodology for detection of pathogens in a single
assay. Aptamers have been shown to be versatile and effective as molecular probes
for molecular recognition. Since E. coli and Salmonella are major prevalent organ-
isms in water, there exists a scope for developing such rapid and simple strip based
detection system. With the deteriorating water quality in the developing countries
and looking at the occurrence of water borne infections, it becomes indispensable to
have some point-of-care diagnostic system for water quality assessment.
Acknowledgement We wish to express our sincere acknowledgement to Dr. Ashok Kumar

Chauhan, President, RBEF parent organization of Amity University Madhya Pradesh (AUMP), Dr.
Aseem Chauhan, Additional President, RBEF and chairman of AUMP; Lt. Gen. V.K. Sharma,
AVSM (Retd.), Vice Chancellor of AUMP, Gwalior, for providing their valuable support, neces-
sary facilities and encouragement throughout.
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Chapter 6
Nanotechnology in Food Packaging
Bambang Kuswandi
Abstract Nanotechnology promises many interesting changes for better life.

Nanotechnology can be used to improve health, wealth, products and quality of life.
Food nanopackaging is still a rather unexplored field of nanoscience and food sci-
ence. Here I review developments in nano-packaging. This chapter describes first
biobased food packaging for biodegradable packaging. Biobased packaging is
indeed an alternative to conventional packaging with non-degradable plastic poly-
mers that are a threat to the environment. Biobased packaging reduces waste, extend
the shelf life, and enhance food quality. The next section discusses nanomaterials
that improve packaging, such as better barrier properties, mechanical strength, flex-
ibility and stability. Active packaging refers to the use of active materials such as
antimicrobials and oxygen scavenging reagents. Smart packaging is the use of
nanosensors and nanodevices that detect freshness or contaminants in foods or
monitor changes in packaging conditions or integrity. The last section discusses
safety issues and heath concerns of nanopackaging.
Keywords Nanotechnology • Food packaging • Sensors • Nanocomposites •

Nanoparticles
6.1 Introduction
Nanotechnology involves the fabrication, manipulation and characterization of

structures, devices or materials at the nano size, approximately 1–100 nm in length,
that have at least one dimension. When particle size of material is reduced into nano
size, the resulting material exhibits physical and chemical properties that are signifi-
cantly different from the properties of macroscale materials composed of the same
substance. Therefore, it would seem illogical that structures in the size of 1–100 nm
would not only exist but would also have implications and applications that could
B. Kuswandi (*)
Chemo and Biosensors Group, Faculty of Pharmacy, University of Jember,
Jl. Kalimantan 37, Jember 68121, East Java, Indonesia

152 B. Kuswandi
Fig. 6.1 Key functions of packaging systems, i.e. container of the product, preservation and
protection of the product quality, presentation and identification of the product as sales element,
facilitation for transportation and distribution of the product, and information of the product to
the consumers
be essential to humankind (Sozer and Kokini 2009; Ravichandran 2010).

Nanotechnology promises many interesting changes to improve health, wealth and
quality of life, as well as reducing impact on the environmental.
Packaging systems are those products which are manufactured with any material
in order to protect, to contain, to manipulate, to distribute, to transport and to iden-
tify each article along its supply chain, from raw materials to end users (Fig. 6.1).
These functions are compulsory to define accurately any kind of packaging, how-
ever, according to the types of products which have to be packed and preserved, a
wide range of requirements are also needed, such as mechanical, thermal and bar-
rier properties. Due to the range of advanced functional properties of nanomaterials
that can bring to packaging materials, therefore, nanomaterials are increasingly
being used in the food packaging industry. It was reported that around 500 nano-
packaging products are estimated to be in commercial use, while nanotechnology is
predicted to be used in the manufacture of 25 % of all food packaging within the
next decade (Reynolds 2007). In nano-packaging, it can also be designed to release
antimicrobials, antioxidants, enzymes, flavors and nutraceuticals to extend shelf life
(Cha and Chinnan 2004). The new nanotechnology products for food packaging
were in the pipeline and some anti-microbial films to improve the shelf life of food
and dairy products, have already been entered the market (El Amin 2005).
Novel food packaging technology is by far the most promising benefit of nano-
technology in the food industry in the near future, as described very recently by
Dasgupta et al. (2015) regarding application of nanotechnology in the agro-food
sector, as one of the fastest growing fields in nano-research. Furthermore, it showed
6 Nanotechnology in Food Packaging 153
by recent research trends in food processing, packaging, nutraceutical delivery,

quality control and functional food. In this field many organizations, scientists,
inventors as well as industries are coming up with new techniques, protocols and
products that have a direct application of nanotechnology in agriculture and food
products (Dasgupta et al. 2015). In food packaging, by applying nanotechnology,
companies are already producing packaging materials that are extending the life of
food and drinks and improving food safety. Food packaging and monitoring are
major focus of food industry–related nanotechology research and development
(Brody 2003). The leading development in food packaging is active and smart pack-
aging that promises to improve food safety and quality and optimizes product shelf
life (Kuswandi et al. 2011). In active and smart packaging, many companies and
universities are developing packaging that would be able to alert if the packaged
food becomes contaminated, respond to a change in environmental conditions, and
self-repair holes and tears.
Currently in packaging industries, the largest part of materials used is non-
degradable petroleum based plastic polymer materials. As a result, this non-
degradable food packaging materials, represent a serious problem on the global
environmental (Kirwan and Strawbridge 2003). Therefore, the use of bio-based
packaging materials, such as edible and biodegradable films from renewable
resources (Tharanathan 2003), could at least to some extent solve the waste problem
by reducing packaging waste and also extend the shelf life, which in turn, enhance
food quality. In this respect, by means of the correct selection of materials and pack-
aging technologies, it is possible to keep the product quality and freshness during
the time required for its commercialization and consumption (Stewart et al. 2002;
Kuswandi et al. 2011).
However, the use of bio-based materials for food packaging has been very lim-
ited currently. This is due to natural polymers have the poor barrier and weak
mechanical properties. Therefore, these natural polymers were frequently blended
with other synthetic polymers or chemically modified with the goal of extending
their applications in packaging (Petersen et al. 1999). In addition, like conventional
packaging, bio-based packaging must serve a number of important functions, such
as containment and protection of food, maintaining its sensory quality and safety,
and communicating information to consumers (Robertson 1993). Other nanotech-
nology that could help to reduce waste of the packaging associated with processed
foods is the application of nanocomposites in packaging. The application of nano-
composites promises to enhance the use of edible and biodegradable films in pack-
aging (Lagaron et al. 2005; Sinha Ray and Bousmina 2005) and will support the
preservation of fresh foods, which in turn, extending their shelf life (Vermeiren
et al. 1999).
Nanotechnology was used to create tiny particles in the film, to improve the
transportation of some gases through the plastic films to pump out unwanted carbon
dioxide that would shorten the shelf life of the foods. In addition, they are also look-
ing at whether the film could also provide barrier protection and prevent gases such
as oxygen and ethylene from deteriorating foods (Silvestre et al. 2011; Duncan
2011). Nowadays, numerous food and pharmacy researchers are working to applied
154 B. Kuswandi
Fig. 6.2 Food nano-packaging, classification, functions and features, including: bio-based pack-
aging for biodegradable, biocompatible, low-waste and eco-friendly; improved packaging in term
of mechanical strength, durability and flexibility, and temperature and moisture stability; active
packaging based nanocomposites as active material, e.g. antimicrobial and other properties, e.g.
antioxidant, UV absorbance etc.; and smart packaging with nanosensors as intelligent function in
packaging for the detection of food relevant analytes (gasses and small organic molecules), active
tag and product identification and anticounterfeiting. Biobased packaging can also be used in
improved and active packaging
nanotechnology with the aim to improve delivery of medicines, vitamins or fragile

micronutrients in the daily foods by creating tiny edible capsules based nanoparti-
cles that release their contents on demand at targeted spots in the body. Therefore, it
will provide significant health benefits, such as reduced risk of heart attack, stroke,
neurodegenerative diseases and cancer (Koo et al. 2005; Yan and Gilbert 2004). In
addition, nanoparticles may be used to introduce multiple functionalities like color
and odors but also to act as reservoirs for the controlled release functions of drugs
or fungicides (Lee et al. 2003). Although promising results were obtained, the road
to successful bio-nanocomposites is still long development (Sorrentino et al. 2007).
Despite a tremendous growth in this field, food packaging nanotechnology is still
rare subfield of the nanotechnology spectrum as well as in the food science and
technology. This article addresses to fill this knowledge shortage by providing a
comprehensive review of current developments in nano-packaging technology as it
applies to foods and food-related systems, focusing specifically on applications
which are most likely to enjoy consumer acceptance and regulatory attention in the
immediate future as given in Fig. 6.2. Covered topics include bio-based packaging
for biodegradable packaging for environmental concern; improved packaging for
improved barrier properties, mechanical strength and flexibility as well as stability;

active packaging for antimicrobials, and oxygen scavenging; smart packaging for
intelligent functions, such as sensors/indicators that detect freshness or contami-
nants in foods or monitor changes in packaging conditions or integrity. Safety issues
on specific health concerns related to these various applications are also briefly
discussed. The article concludes with a brief overview of the outlook of the nano-
packaging materials in the future.
6.2 Biobased Packaging
Biobased packaging is biodegradable packaging films that are applied to food prod-
ucts to control moisture transfer and/or gas exchange in order to improve safety and
preserve the nutritional and sensory quality (Siracusa et al. 2008). These packaging
materials are perceived to be more environmental friendly than the other conven-
tional packaging films. Like any kind of packaging, bio-based packaging provides a
barrier between a food product and its environment, thereby protecting it against
unwanted effects of microorganisms, ambient relative humidity and gas conditions.
The specific characteristic that distinguishes biodegradable packaging films from
other packaging solutions is that they are capable of decaying through the action of
living organisms (Del Nobile et al. 2009). This packaging type is generally per-
ceived to be more environmental friendly as the breakdown products are all com-
pletely natural, i.e. carbon dioxide, biomass and water. Bio-based packaging does
not (or less) use fossil fuels to produce the materials, but uses renewable sources,
upon disposal energy can be recovered by incineration.
Commonly, biodegradable plastics that used as materials in bio-based packag-
ing, are polymeric materials in which at least one step in the degradation process via
naturally occurring organism’s metabolism. Under appropriate conditions of mois-
ture, temperature and oxygen availability, this biodegradation leads to fragmenta-
tion or disintegration of the plastics with no toxic or environmentally harmful
residue (Chandra and Rustgi 1998). These biodegradable polymers can be classified
according to their source: (i) Polymers directly extracted from biomass, such as
polysaccharides, proteins, polypeptides, polynucleotides. (ii) Polymers produced
by chemical synthesis of bio-based monomers or mixed biomass and petroleum,
such as polylactic acid or bio-polyester. (iii) Polymers produced by micro-organism
or genetically modified bacteria, such as polyhydroxybutyrate, bacterial cellulose,
xanthan, curdian and pullan.
The success concept of bio-based nanocomposite in the area of synthetic
polymers has stimulated new research on nanocomposites based on biodegradable
polymers for food packaging applications (Sorrentino et al. 2007). Description of
biopolymers is available in literature (Kaplan 1998; Doi and Steinbuechel 2002;
Steinbuchel 2003; Mohanty et al. 2005; Sorrentino et al. 2007). The problems asso-
ciated with biodegradable polymers are performance, processing, and cost. This is
due to “performance and processing” are common to all biodegradable polymers in
156 B. Kuswandi
Layered silicate Polymer
a b c
Phase separated Intercalated Exfoliated

(microcomposite) (nanocomposite) (nanocomposite)
Fig. 6.3 Three types of composites when layered clays are incorporated with the polymer: (a)
tactoid, phase-separated microcomposite; (b) intercalated nanocomposite and (c) exfoliated, poly-
mer–clay nanocomposite (Courtesy of Alexandre and Dubois 2000)
spite of their origin (Trznadel 1995; Scott 2000). The problem particularly, brittleness,
low heat distortion temperature, high gas and vapor permeability, poor resistance to
protracted processing operations have strongly limited their applications. The appli-
cation of nanotechnology to these polymers could open new possibilities for
improving both the properties and the cost-price-efficiency.
Three main types of composites can be formed when the layered clay is incorpo-
rated with a polymer, as given in Fig. 6.3 (Alexandre and Dubois 2000). Types of
composites formed mostly depend on the nature of the components used (i.e. lay-
ered silicate, organic cation and polymer matrix) and the method of preparation.
Micro-composites are formed when the polymer chain is unable to intercalate into
the silicate layer, which therefore phase separated polymer/clay composites are
formed as shown in Fig. 6.3a. Intercalated nano-composite is obtained when the
polymer chain is inserted between clay layers such that the interlayer spacing is
expanded, but the layers still bear a well-defined spatial relationship to each other as
shown in Fig. 6.3b. Exfoliated nano-composites are formed when the layers of the
clay have been completely separated and the individual layers are distributed
throughout the polymeric matrix as shown in Fig. 6.3c.
Due to nanometer-size particles obtained by dispersion, these bio-nanocomposites
can remarkably improved mechanical, thermal, barrier and physico-chemical prop-
erties, when compared with the starting polymers and microscale composites. As an
example, it shows great promise in providing excellent barrier properties, due to the
presence of the clay layers able to delay the molecule pathway making the diffusive
path more tortuous (Bharadwaj 2001). In addition, the preparation and characteriza-
tion of various kinds of biodegradable polymer nanocomposites showing properties
Fig. 6.4 Terminology of nanomaterial used in nano-packaging: (a) nano-object, and (b) nano-
structured material. Nano-object consist of nanofibre, nanoplate and nanoparticle, while nano-
structured material consist of nanocomposite, material with nanostructured surfaces, assembled
nanomaterial and shell structure
suitable for a wide range of applications (Sinha Ray and Bousmina 2005). Currently,
the most studied bio-nanocomposites suitable for packaging applications are starch
and derivates, i.e. polylactic acid, poly(butylene succinate), polyhydroxybutyrate,
and aliphatic polyester. Thus, bio-based packaging can also be used for improved
packaging and active packaging.
In general, the application of the nanotechnology in polymer based packaging
that used nanoparticles can be divided into two categories: (i) nano-object materials
(materials with nanoscale dimensions less than 100 nm) and (ii) nano-structured
materials as shown in Fig. 6.4. In nano-objects, mostly nanomaterials used as a filler
(nano-reinforcement), which involves the use of nanoplate, nanoparticles and nano-
fibers (such as metal oxides nanoparticles, nanoclays, carbon nanotubes and other
fillers like metallic nanoparticles). While in nano-structured materials, the nanoma-
terials are dispersed into a polymer matrix as nanocomposites.
Actually, the applications of nanomaterial materials in packaging are developed
mainly into three applications: (i) improved packaging, such as barrier performance
pertaining to gases such as oxygen, carbon dioxide, and ultraviolet rays, as well as
to add strength, stiffness, dimensional stability, and heat resistance; (ii) active pack-
aging, such as antimicrobial or other properties (e.g. antioxidant, UV absorbance)
with intentional release into- and consequent effect on the packaged food in term of
taste, freshness and self life; (ii) smart/intelligent packaging, such as oxygen indica-
tors, freshness indicators and pathogen. The three main applications of nanomate-
rial in food packaging was also described as the research trends of food packaging
with the help of nanotechnology (Ranjan et al. 2014), where in food packaging
mainly related with nano-reinforcement, nanocomposite active packaging and
nanocomposite smart packaging. Table 6.1 gives an overview of these potential
applications of the nanotechnology in food packaging. In improved packaging, the
presence of nanoparticles in the polymer matrix materials improves the properties
158 B. Kuswandi
Table 6.1 Packaging applications of nanomaterials: (a) improved packaging, (b) active packaging
and (c) smart packaging
Applications Descriptions Key nanomaterials
Improved Incorporation of nanomaterials into the packaging to Clays, SiO2
packaging improve physical performance, durability, barrier
properties, biodegradation, biocompatibility and
environmental friendly
Active Incorporation of nanomaterials with antimicrobial or Ag, TiO2
packaging other properties (e.g. antioxidant, UV absorbance) with
intentional release into- and consequent effect on the
packaged food in terms of taste, freshness and self life
Smart Incorporation of nanosensors to monitor and report on High variability
packaging the condition of the food (e.g. oxygen indicators,
freshness indicators and pathogen)
of the material. Besides barrier properties, strength, stiffness, dimensional stability

and heat resistance of materials can be improved due to nanoclays or SiO2 nanopar-
ticles addition. In active packaging, nanoparticles as active agents are being
developed specially for antimicrobial packaging applications; silver, gold and metal
oxide nanoparticles are the most studied nanoparticles with antimicrobial function,
with silver nanoparticles already found in several commercial applications.
Moreover, they can be suitable for other active packaging fields such as ethylene
removers. In intelligent packaging, nanoparticles can be applied as reactive particles
in packaging materials to inform about the state of the packaged product.
The so-called nanosensors are able to respond to external stimuli change in order to
communicate, inform and identify the product with the aim to assure its quality
and safety. The recent developments for polymer nanomaterials for smart food
packaging include oxygen indicators, freshness indicators and pathogen.
6.2.1 Starch
Starch is a potential raw material and renewable source, due to its cyclic availability
from many plants and excessive production related to current needs and its low cost
(Smits et al. 1998; Gonera and Cornillon 2002). There are many ways to using
starch as packaging material (Kim and Pometto 1994). Starch alone does not form
films with appropriate mechanical properties without chemically modification or
plasticized. If starch is treated in an extruder by both thermal and mechanical energy,
it can be converted to a thermoplastic material. In the thermoplastic starches pro-
duction, plasticizers are used to reduce intra-molecular hydrogen bonds and to
provide stability to product properties. Corn is the primary source of starch for
bioplastics, although more recent global research is evaluating the potential use in
bioplastics for starches from potato, wheat, rice, barley, oat and soy sources.
Since its hygroscopic nature, starch-based absorbent pads are used as a potential
alternative to conventional absorbent for meat exudation (Smith et al. 1995). Films
based starch, could be employed as packaging for perishable foods (such as fruits
and vegetables, snacks or dry products). However, in these applications, efficient
mechanical, oxygen and moisture protection is needed. Thermoplastic starch (TPS)
alone often cannot meet all these requirements. Due to its hydrophilicity, its perfor-
mance changes during and after processing, due to changes in the water content. To
overcome this drawback, the used of clay as filler have been reported as follows.
Clay, as potential filler, has been used for improving the properties of TPS in
such applications (De Carvalho et al. 2001; McGlashan and Halley 2003; Wilhelm
et al. 2003; Chen and Evans 2005; Yoon and Deng 2006). Starch/clay nanocompos-
ite films have been obtained by dispersing montmorillonite nanoparticles via poly-
mer melt processing techniques. It has been shown that both the tensile strength and
the elongation at break of TPS were increased with the presence of small amounts
(>5 %) of sodium montmorillonite. Furthermore, the temperature of decomposition
was increased, while the relative diffusion coefficient of water vapor was decreased
(Park et al. 2003). Mechanical characterization results also show an increase of
modulus and tensile strength. In addition, the conformity of the resulting material
samples with actual regulations and European directives on biodegradable materials
was verified by migration tests (Avella et al. 2005).
6.2.2 Polylactic Acid
The conventional chemical synthesis used for the production of polymers gives a
wide variety of biopolyesters. Polylactic acid is thermoplastic aliphatic polyester,
biodegradable and the polymer with the highest potential for a commercial major
scale production of renewable packaging materials. Polylactic acid is derived from
renewable resources by means of a fermentation process using sugar from corn, fol-
lowed by either ring-opening polymerization or by condensation polymerization of
lactic acid. It is one of the most important biocompatible and biodegradable poly-
mers in a group of degradable plastics. Polylactic acid represents a good candidate
to produce disposable packaging due to its good mechanical properties and process
ability (Murariu et al. 2008).
The properties of the polylactic acid material are highly related to the ratio
between the two forms (L or D) of the lactic acid monomer. L- polylactic acid is a
material with a very high melting point and high crystallinity, whereas a mixture of
D- and L- polylactic acid results in an amorphous polymer with a low glass transi-
tion temperature. Although polylactic acid is an eco-friendly boiplastic with good
biocompatibility, poor hardiness, slow degradation, hydrophobicity, and lack of
reactive side-chain groups limit its application (Rasal et al. 2010). Therefore, the
tailoring of its properties to reach end-users demands is required. In addition,
mechanical properties being better than or comparable to conventional plastics,
controlled surface properties such as hydrophilicity, roughness, and reactive
160 B. Kuswandi
functionalities are the successful implementation of polylactic acid as material in

food packaging. Many has been reported for the preparation of polylactic acid/clay
nanocomposite materials (Choi et al. 1997; Ogata et al. 1997; Bandyopadhyay et al.
1999; Pluta et al. 2002; Sinha Ray et al. 2002a, b, 2003; Chang et al. 2003; Paul
et al. 2003).
The incorporation of clays in the polylactic acid to produce a polylactic acid-clay
nano-composite to improve polylactic acid’s mechanical and properties as well as to
accelerate its degradation rate have been developed (Bandyopadhyay et al. 1999).
Solvent casting of mixtures of polylactic acid and organophilic clay in chloroform
resulted in materials with an enhanced crystallization tendency and increased
Young’s modulus (Ogata et al. 1997). However, the glass transition temperature
increases only slightly with increasing clay content. This may be due to the micro-
composite structure rather than nanocomposite structure. As a matter of fact, a
strong tendency of tactoids formation was observed. The polylactic acid/layered
silicate nanocomposites, prepared by simple melt extrusion, exhibited remarkable
improvement of material properties in both solid and melt states compared to the
matrix without clay (Sinha Ray et al. 2002a).
The combination of polylactic acid and clays, at the nano-scale, often results in
remarkably improved mechanical and functional properties compared with pure
polylactic acid or conventional composites (Okamoto et al. 2001). Different poly-
lactic acid/silicate nano-composites have been explored: montmorillonites and
fluorohectorites clays, were blended with the polylactic acid (Oliva et al. 2007;
Aguzzi et al. 2007). Nanocomposites of the polylactic acid and polylactic acid/
polycaprolactone blends were obtained by melt-mixing with a properly modified
kaolinite (Cabedo et al. 2006). In this case, all nanocomposites showed an improvement
in the gas barrier, mechanical and thermal properties with regard to the polymers
and blends without clay.
6.2.3 Polyhydroxybutyrate
Polyhydrobutyrate has been the subject of extensive studies as an environmentally

friendly polymeric material which is the most popular polyhydroxyalkanoate used
in food-packaging. Polyhydrobutyrate is a polymer belonging to the polyesters
class that are of interest as bio-derived and biodegradable plastics (Frieder 2010).
Polyhydrobutyrate is produced by microorganisms (such as Ralstonia eutrophus or
Bacillus megaterium) (Lenz and Marchessault 2005) and is utilized as an energy
storage molecule within the microorganism’s cellular structure. Due to its biode-
gradability and biocompatibility, this biopolyester may easily find industrial appli-
cations (Weber 2000; Lenz and Marchessault 2005). Potentially, polyhydrobutyrate
offers many advantages over traditional petrochemically derived plastics in packag-
ing applications, since it is compatible with many foods, such as dairy products,
beverage, fresh meat products and ready meals. In addition to its complete biode-
gradability, it possesses better physical properties than polypropylene for food
packaging applications and is completely non-toxic. However, as polyhydrobutyrate

is a partially crystalline polymer with a high melting temperature and a high degree
of crystallinity, then it is brittle and has limited applications (Hankermeyer and
Tjeerdema 1999). The poor low-impact strength of polyhydrobutyrate is solved
by incorporation of hydroxyvalerate monomers into the polymer to produce
polyhydroxybutyrate-co-valerate (Liu et al. 2002). Polyhydroxybutyrate-co-valerate
completely degrades into carbon dioxide and water under aerobic conditions (Lenz
and Marchessault 2005).
Many papers report the use of polyhydrobutyrate for the preparation of polymer/
clay nanocomposite materials (Park et al. 2001; Liu et al. 2002; Maiti et al. 2003;
Chen et al. 2004). Instead, the formation of nanocomposite materials from polyhy-
drobutyrate seems to be difficult, and rather moderate improvements in properties
have been reported in the case of polyhydrobutyrate as matrix material (Maiti et al.
2003). These results still have low mechanical properties with a low extension at
break, which limits its range of applications. If the properties of the polyhydrobutyr-
ate can be further improved by the addition of a small quantity of an environmen-
tally benign material, this polymer will find numerous applications in packaging.
6.2.4 Polycaprolactone
Polycaprolactone is linear polyester prepared by either ring opening polymerization

of 3-caprolactone using a variety of anionic, cationic and co-ordination catalysts or
via free radical ring-opening polymerization of 2-methylene-1-3-dioxepane (Pitt
1990). It is a semicrystalline polymer with a high degree of crystallinity (around
50 %). Polycaprolactone exhibits high elongation at break and low modulus. Its
physical properties and commercial availability make it very attractive as a material
for packaging applications. Polycaprolactone is also interesting for applications in
the biomedical (Chandra and Rustgi 1998; Okada 2002; Nair and Laurencin 2007)
and agricultural areas (Nakayama et al. 1997).
Because of its low melting point, in conventional applications it must be blended
with other polymers (Ishiaku et al. 2002; Lee et al. 2002; Lim et al. 2002). The
blended of polycaprolactone with the fillers nanocomposites have been reported
literature. The nanocomposites based on polycaprolactone/organically modified
layered silicate with better physical properties have been developed (Bharadwaj
et al. 2002; Di et al. 2003; Gorrasi et al. 2002, 2004; Tortora et al. 2002).
6.3 Improved Packaging
In improved packaging development, nanomaterials are mixed into the polymer

matrix to improve the gas barrier properties, as well as temperature and humidity
resistance of the packaging. A variety of nanoparticle reinforced polymers, also
162 B. Kuswandi
termed as nanocomposites have been developed, which typically contain up to 5 %

w/w nanoparticles with clay nanoparticle composites with improved barrier proper-
ties (80–90 % reduction) for the manufacture of bottles for beer, edible oils and
carbonated drinks and films (Chaudhry et al. 2008; Brody 2007). United States
Food and Drug Administration (USFDA) have approved the use of nanocomposite
in contact with foods (Sozer and Kokini 2009).
6.3.1 Nanocoatings
Coating in food can be defined as thin/film of edible material placed between food
components to provide a barrier to mass transfer (Guilbert et al. 1997). These coat-
ings could serve as moisture, lipid, and gas barriers. Coatings are applied and
formed directly on the food product either by addition of a liquid film forming solu-
tion or by molten compounds (Baldwin et al. 1996). Components of edible coatings
can be divided into two categories: water-soluble polysaccharides (hydrocolloids)
and lipids. Suitable polysaccharides include cellulose derivatives, alginates, pectins,
starches, chitosan and other polysaccharides (El Ghaouth et al. 1991). Many lipid
compounds such as animal and vegetable fats have been used to make edible films
and coatings. Suitable lipids include waxes, acylglycerols, and fatty acids. Lipid
films have excellent moisture barrier properties or as coating agents for adding gloss
to confectionery products. Waxes are commonly used for coating fruits and vegeta-
bles to retard respiration and lessen moisture loss (Avena-Bustillos et al. 1997).
Edible coatings are currently extensively used on a wide variety of foods,
including fruits, vegetables, meats, chocolate, cheese, candies, bakery products, and
French fries (Morillon et al. 2002; Cagri et al. 2004; Rhim 2004). However, until
now only few research works reported the incorporation nano-particles toward coating
films, in order to improve their physical properties. In order to lower the diffusion
of oxygen, clay montmorillonite has been added into pectins (Mangiacapra et al.
2005). Similarly, a nanocomposites prepared by gelatin and montmorillonite has
been used for considerable improvement of the physical properties (Zheng et al.
2002). An appreciable increase in stability of chitosan/layered nanocomposites was
also developed (Darder et al. 2003).
Despite the lack of specific literature data, there is sufficient evidence to establish
the beneficial effects of inorganic nanofiller on these materials, among which there
are improved retention of flavor, sugars, acids, texture and color, increased stability
during shipping and storage, improved appearance and reduced spoilage.
Nanoparticles can be used as carrier of antimicrobials and additive. It can also be
used to stabilize the additives and efficiently control their diffusion into the food and
in the different regions, i.e., surface vs. bulk of a food system. This control can be
interesting for long-term storage of foods or for imparting specific desirable charac-
teristics, such as flavor to a food system. In this regards, an edible antibacterial
nanocoating, which can be applied directly to bakery goods has also been developed
by the U.S. Company Sono-Tec Corporation (El Amin 2007).
6.3.2 Nanolaminates
Nanotechnology provides food scientists with a number of ways to create novel

nanolaminate films that suitable to be used in the food industry. Generallay, a nano-
laminate consists of two or more layers of materials with nanometer dimensions that
are physically or chemically bonded to each other. One of the most powerful meth-
ods in nanolaminated, is based on the layer by layer deposition technique, in which
the charged surfaces are coated with interfacial films consisting of multiple nano-
layers of different materials (Decher and Schlenoff 2003). Nanolaminates offer
some advantages for the preparation of edible coatings and films over conventional
technologies and may thus have a number of important applications within the food
and dairy industry (Weiss et al. 2006).
A variety of different adsorbing substances could be used to create the different
layers, including natural polyelectrolytes (proteins, polysaccharides), charged lipids
(phospholipids, surfactants), and colloidal particles (micelles, vesicles, droplets)
(Dasgupta et al. 2016a). It would be possible to incorporate active functional agents
such as antimicrobials, anti browning agents, antioxidants, enzymes, flavors, and
colors into the films. These functional agents would increase the shelf life and quality
of coated foods. The basic functional properties of laminated films depend on the
characteristics of the film-forming materials used for their preparation. Like nano-
coating, these nanolaminated coatings could be created entirely from edible materials
ingredients (proteins, polysaccharides, lipids) by using simple processing operations
such as dipping and washing. The composition, thickness, structure, and properties
of the multilayered laminate formed around the object could be controlled in a num-
ber of ways, including changing of the type of adsorbing substances in the dipping
solutions, the total number of dipping steps used, the order that the object is intro-
duced into the various dipping solutions, the solution and environmental conditions
used, such as pH, ionic strength, dielectric constant, temperature, etc (Dasgupta
et al. 2016b, c; Ranjan et al. 2015, 2016; Maddineni et al. 2015).
6.3.3 Clay Nanoparticles and Nanocristals
Nanoclays can be used to improved barrier properties of the food packaging materi-
als by incorporating and embedding inside them. The layered silicates commonly
used in nanocomposites consist of two-dimensional layers, which are 1 nm thick
and several microns long depending on the particular silicate. Its presence in poly-
mer formulations increases the tortuosity of the diffusive path for a penetrated
molecule (Fig. 6.5), which in turn, providing excellent barrier properties (Bharadwaj
et al. 2002; Cabedo et al. 2004; Mirzadeh and Kokabi 2007). The interaction
between layered silicates and polymer chains may produce two types of ideal
nanoscale composites as shown in Fig. 6.3. The intercalated nanocomposites result
from the penetration of polymers chains into the interlayer region of the clay,
164 B. Kuswandi
Fig. 6.5 Illustration of the “tortuous pathway” created by incorporation of exfoliated clay nano-
platelets into a polymer matrix film. In a film composed only of polymer (a), diffusing gas mole-
cules on average migrate via a pathway that is perpendicular to the film orientation. In a
nanocomposite (b), diffusing molecules must navigate around impenetrable particles/platelets and
through interfacial zones which have different permeability characteristics than those of the virgin
polymer. The tortuous pathway increases the mean gas diffusion length and, thus, the shelf-life of
spoilable foods (Adapted from Adame and Beall 2009)
resulting in an ordered multilayer structure, with alternating polymer/inorganic

layers at a repeated distance of a few nanometers (Weiss et al. 2006). The exfoliated
nanocomposites involve extensive polymer penetration, with the clay layers delami-
nated and randomly dispersed in the polymer matrix (Luduena et al. 2007).
Exfoliated nanocomposites were the best properties due to the optimal interaction
between clay and polymer (Adame and Beall 2009; Alexandre et al. 2009).
The most widely studied type of clay fillers is montmorillonite, an hydrated
alumina-silicate layered clay consisting of an edge-shared octahedral sheet of alu-
minum hydroxide between two silica tetrahedral layers (Weiss et al. 2006). The
imbalance of the surface negative charges is compensated by exchangeable cations
(typically Na+ and Ca2+). The parallel layers are linked together by weak electro-
static forces (Tan et al. 2008). This type of clay is characterized by a moderate
negative surface charge, which is an important factor to define the equilibrium layer
spacing. The charge of the layer is not locally constant as it varies from layer to
layer and must rather be considered as an average value over the whole crystal
(Alexandre and Dubois 2000). Montmorillonite is an effective reinforcement filler,
due to its high surface area and large aspect ratio (50–1000) (Uyama et al. 2003).
Mostly nanoclays have been reported to improve the mechanical strength of
several polymers (Avella et al. 2005; Chen and Evans 2005; Jawahar and
Balasubramanian 2006; Mangiacapra et al. 2006; Russo et al. 2007; Cyras et al. 2008;
Yu et al. 2003) and also of biopolymers, making their use feasible as packaging
materials (Dean et al. 2007; Marras et al. 2008: Park et al. 2003; Petersson and
Oksman 2006; Weiss et al. 2006; Xu et al. 2006). Other benefits have been reported
on the performance of a diversity of polymers as resulting from using clay nanopar-

ticles, including increased glass transition (Cabedo et al. 2004; Petersson and
Oksman 2006; Yu et al. 2003) and thermal degradation temperatures (Bertini et al.
2006; Cabedo et al. 2004; Cyras et al. 2008; Paul et al. 2003; Yu et al. 2003).
Furthermore, the advantage of clay nanocomposite in the packaging material offers
improved shelf life, shutter proof, light in weight and heat resistant (Ravichandran
2010).
The minor disadvantages of nanoclays on polymers were decreased transparency
(Yu et al. 2003). Some companies in the USA (e.g. Nanocor Inc. and Southern Clay
Products, Inc.) was making plastics lighter, stronger, more heat-resistant and with
improved barrier against gases, moisture and volatiles by incorporating montmoril-
lonite in nanocomposite production (Moraru et al. 2003). Some industries have
incorporated clays in nylon- 6, which is fluid and easily penetrates small spaces
between layers. Nylon-6 nanocomposites can achieve oxygen transmission rates
almost four times lower than that of neat nylon-6 (Brody 2003). Nanocor and
Mitsubishi Gas Chemical (New York) have developed Imperm, a nanocomposite
nylon MXD6 with much improved barrier properties, to be used in films and poly-
ethylene terephthalate bottles (Brody 2006, 2007). The nanocomposite material can
be used as an oxygen barrier layer in the extrusion manufacturing of bottles for
fruit juices, dairy foods, beer and carbonated drinks, or as nanocomposite layers in
multilayer films to enhance the shelf life of a variety of foods such as processed
meats, cheese, confectionery, cereals, and boil-in-bag foods (Brody 2007; Moraru
et al. 2003).
6.4 Active Packaging
In active packaging development, nanomaterials are used to interact directly with

the food or the environment to allow better protection of the product. For example,
silver nanoparticles and silver coatings can provide anti-microbial properties, with
other materials being used as oxygen or UV scavengers. Nano silver, Nano magne-
sium oxide, nanocopper oxide, nano titanium dioxide and carbon nanotubes are also
predicted for future use in antimicrobial food packaging (Chaudhry et al. 2008;
Doyle 2006, Miller and Senjen 2008). Antimicrobial packaging for food products
which absorbs oxygen has been developed and commercialized by Kodak company
(Asadi and Mousavi 2006). Oxygen scavenging packaging using enzymes between
polyethylene films have also been developed (Lopez-Rubio et al. 2006). An active
packaging application could also be designed to stop microbial growth once the
package is opened by the consumer and rewrapped with an active-film portion of
the package (Brody 2007).
166 B. Kuswandi
6.4.1 Antimicrobial Films
The incorporation of antimicrobial compounds (e.g. silver nanoparticles and silver

coatings) into food packaging materials has received considerable attention cur-
rently. The films with antimicrobial activity could help control the growth of patho-
genic and spoilage microorganisms. An antimicrobial film is particularly desirable
due to its acceptable structural integrity and barrier properties imparted by the nano-
material, and the antimicrobial properties contributed by the antimicrobial agents
impregnated within the film (Rhim and Ng 2007). Here, the film allows nanomateri-
als to be able to attach more copies of biological molecules, which confers greater
efficiency (Luo and Stutzenberger 2008).
Nanomaterials have been studied for antimicrobial activity so that they can be
used as growth inhibitors (Cioffi et al. 2005), killing agents (Huang et al. 2005;
Kumar and Munstedt 2005; Lin et al. 2005; Qi et al. 2004; Stoimenov et al. 2002),
or antibiotic carriers (Gu et al. 2003). The most common antimicrobial films for
food packaging are based on silver nanoparticles, which are well known for its
strong toxicity to a wide range of microorganisms, with high temperature stability
and low volatility (Kumar and Munstedt 2005). Film based on silver nanoparticles
has been produced and their antimicrobial affectivity has been reported.
Nanocomposites with low silver nanoparticles content presented a better
increased efficacy against E. coli than microcomposites with much higher silver in
polyamide 6/silver-nano- and microcomposites (Damm et al. 2007, 2008). Moreover,
silver nanoparticles absorbs and decomposes ethylene (Hu and Fu 2003), which
may contribute to its effects on extending shelf life of fruits and vegetables. Indeed,
nanocomposite polyethylene film with silver nanoparticles retarded the senescence
of jujube, a Chinese fruit (Li et al. 2009). A coating containing silver nanoparticles
was effective in decreasing microbial growth and increasing shelf life of asparagus
(An et al. 2008). Silver nanoparticles increased modulus and strength of a poly(vinyl
alcohol) matrix, and improved its thermal properties, enhancing its stability and
increasing its Tg (Mbhele et al. 2003). Nanostructured calcium silicate has also
been used that adsorb Ag+ from solution down to the 1 mg/kg level (Johnston et al.
2008) as antimrobial film.
Other materials that have been used as antimicrobial materials are titanium diox-
ide (TiO2), carbon nanotubes, nisin and chitosan. TiO2 is widely used as a photo-
catalytic disinfecting material for surface coatings (Fujishima et al. 2000). TiO2
photocatalysis, which promotes peroxidation of the polyunsaturated phospholipids
of microbial cell membranes (Maness et al. 1999), has been used to inactivate sev-
eral food-related pathogenic bacteria (Kim et al. 2003, 2005; Robertson et al. 2005).
A TiO2 powder-coated packaging film has been verified its ability to reduce E. coli
contamination on food surfaces, suggesting that the film could be used for fresh cut
produce (Chawengkijwanich and Hayata 2008).
Carbon nanotubes have also been reported to have antibacterial properties. Direct
contact with aggregates of carbon nanotubes was demonstrated to be fatal for E.
coli, possibly because the long and thin carbon nanotubes puncture microbial cells,
causing irreversible damages (Kang et al. 2007). On the other hand, there are studies
suggesting that carbon nanotubes are cytotoxic to human cells, at least when in
contact to skin (Monteiro-Riviere et al. 2005) and lungs (Warheit et al. 2004), which
would affect people working directly with carbon nanotubes in processing stages
rather than consumers. Nevertheless, it is mandatory to know eventual health effects
of carbon nanotubes when ingested, since the risk of ingestion of particles incorpo-
rated to a food packaging material must be taken into account because of the pos-
sibility of migration to food.
Antimicrobial peptides, such as nisin, could also be integrated with layer by
layer structures to develop antimicrobial films (Haynie et al. 2006). Nisin acts as a
depolarization agent on bacterial membranes and creates pores in lipid bilayers
(Sahl et al. 1987). Multilayer peptide nanofilms, which intercalated different
peptides designed to be oppositely charged at neutral pH which was much more
stable than when the peptide film was stabilized only by electrostatic interactions
(Li et al. 2006).
Antibacterial activity of nanoscale chitosan has also been reported (Qi et al.
2004). One possible antimicrobial mechanism involves interactions between
positively charged chitosan and negatively charged cell membranes, increasing
membrane permeability and eventually causing rupture and leakage of intracellular
material. This is consistent with the observation that both raw chitosan and engi-
neered nanoparticles are ineffective at pH values above 6, which would be due to the
absence of protonated amino groups (Qi et al. 2004).
6.4.2 Oxygen Scavenging Film
Oxygen (O2) is responsible for the deterioration of many foods either directly or
indirectly. For example, direct oxidation reactions result in browning of fruits and
rancidity of vegetable oils. Food deterioration by indirect action of O2 includes food
spoilage by aerobic microorganisms. Therefore, the incorporation of O2 scavengers
into food package can maintain very low O2 levels, which is useful for several appli-
cations, since it will enhance self-life of the food.
Oxygen scavenger films were successfully developed by adding titania nanopar-
ticles (TiO2) to different polymers (Xiao-e et al. 2004). So that they can be used for
packaging a wide variety of oxygen-sensitive products. Attention has particularly
focused on the photocatalytic activity of nanocrystalline titania under ultraviolet
radiation. Since TiO2 act by a photocatalytic mechanism, and its major drawback is
the requirement of UVA light (Mills et al. 2006).
6.4.3 UV Absorbing Films
Commonly used material as UV absorbing is film based on nanocrystalline titania

(TiO2). The efficacy of TiO2-coated films exposed to sunlight to inactivate fecal coli
forms in water has been demonstrated (Gelover et al. 2006). Metal doping improves
168 B. Kuswandi
visible light absorbance of TiO2 and increases its photo catalytic activity under UV
irradiation (Anpo et al. 2001). It has been reported that doping TiO2 with silver
greatly improved photo catalytic bacterial inactivation (Page et al. 2007; Reddy
et al. 2007). This combination was resulted good antibacterial properties of TiO2/
Ag+ nanoparticles in a nanocomposite with PVC (Cheng et al. 2006).
6.5 Smart Packaging
In smart/intelligent, nanomaterials are used for sensing biochemical or microbial

changes in the food, for example detecting specific pathogens developing in the
food, or specific gases from food spoiling (Kuswandi et al. 2011). In terms of smart
packaging, nanoparticles can be applied as reactive particles in packaging materials
to inform about the state of the packaged product. The so-called nanosensors are
able to respond to external stimuli change in order to communicate, inform and
identify the product with the aim to assure its quality and safety. The recent develop-
ments for polymer nanomaterials for smart food packaging include spoilage indica-
tors, oxygen indicators, product identification and traceability.
6.5.1 Nanosensors
Packaging equipped with nanosensors is also designed to track either the internal or
external conditions of food products, pellets and containers, throughout the supply
chain. For example, such packaging can monitor temperature or humidity over time
and then provide relevant information of these conditions, for example by changing
color. Nanosensors in plastic packaging can detect gases given off by food when it
spoils and the packaging itself changes color to alert you. The so-called nanosensors
are able to respond to environmental changes (e.g., temperature or humidity in stor-
age rooms, levels of oxygen exposure), degradation products or microbial contami-
nation (Bouwmeester et al. 2009).
Usually, producers estimated the expiration date of food by considering distribu-
tion and storage conditions, especially temperature to which the food product is
predicted to be exposed. However, such conditions are not always known, and foods
are frequently exposed to temperature abuse; this is particularly worrying for prod-
ucts which require a cold chain. Furthermore, sealing defects in packaging systems
can lead food products to an unexpected high exposure to oxygen, which can result
in undesirable changes. Nanosensors, when integrated into food packaging, can
detect certain chemical compounds, pathogens, and toxins in food, being then use-
ful to eliminate the need for inaccurate expiration dates, providing real-time status
of food freshness (Liao et al. 2005).
They have also been reported that nano-biosensors already have been developed
and commercialized to detect pathogens, spoilage, chemical contaminants, or
product tampering, or to track ingredients or products through the processing chain

(Nachay 2007). Nanosensors based on carbon nanotubes have also been pointed out
to have several advantages over conventional detection methods such as high per-
formance liquid chromatography. Carbon nanotubes based nanosensor is rapid and
high-throughput detection; simplicity and cost effectiveness; reduced power require-
ments and easier recycling; and the un-necessity of exogenous molecules or labels.
Furthermore, a multiwalled carbon nanotubes based biosensor have also been devel-
oped that can detect microorganisms, toxic proteins, and degraded products in food
and beverages (Nachay 2007).
Engineered nanosensors have also been developed in packages to change color
to warn the consumer if a food is beginning to spoil, or has been contaminated by
pathogens using electronic “noses” and “tongues” to “taste” or “smell” scents and
flavors (Joseph and Morrison 2006, Asadi and Mousavi 2006; Scrinis and Lyons
2007; Sozer and Kokini 2009). In real market applications, Nestlé, British Airways,
MonoPrix Supermarkets are using chemical nanosensors that can detect color
change (Pehanich 2006).
6.5.2 Freshness and Spoilage Indicators
Based on applied studies of the surface properties of materials, several types of gas
sensors have been developed, which translates chemical interactions between par-
ticles on the surfaces into a response signal. Conducting polymers or electro active
conjugated polymers, which can be synthesized either by chemical or electrochemi-
cal oxidation, are very important because of their electrical, electronic, magnetic
and optical properties, which are related to their conjugated p electron backbones
(Ahuja et al. 2007; Kuswandi et al. 2012). Polyene and polyaromatic conducting
polymers such as polyaniline, polyacetylene, polypyrrole have been widely studied
(Ahuja et al. 2007; Kuswandi et al. 2012). Electrochemically polymerized conduct-
ing polymers have a remarkable ability to switch between conducting oxidized
(doped) and insulating reduced (undoped) state, which is the basis of many applica-
tions (Rajesh and Kaneto 2004). On-package indicator contains polyaniline film,
that responds through visible color change to a variety of basic volatile amines
released during fish spoilage period has been developed (Fig. 6.6) (Kuswandi et al.
2012). Color changes, in terms of total color difference of polyaniline, correlated
well with total volatile amine levels and microbial growth patterns in fish samples
(milkfish). These responses enabled the real-time monitoring of fish spoilage either
at various constant temperatures or with temperature fluctuations.
Food spoilage is caused by microorganisms, whose metabolism produces gases
which can be detected by conducting polymer nanocomposites or metal oxides,
which can be used for quantification and/or identification of microorganisms based
on their gas emissions as well as for food freshness detection. Sensors based on
conducting polymer nanocomposites consist on conducting particles embedded into
an insulating polymer matrix. The resistance changes of the sensors produce a
170 B. Kuswandi
Fresh fish
Spoilage fish
not
fresh still fresh fresh
Fig. 6.6 Freshness sensor for smart packaging based on nanofibre of polyaniline. Left is sensor
reference color change for detection of fish freshness, and right is sensor response towards fresh
fish and spoilage fish (Courtesy of Kuswandi et al. 2012)
pattern that corresponds to the gas under investigation (Arshak et al. 2007; Kuswandi
et al. 2012). Conducting polymer nanocomposites sensors containing carbon black
and polyaniline have been developed to detect and identify food borne pathogens by
producing a specific response pattern for each microorganism. Three bacteria, such
as Bacillus cereus, Vibrio parahemolyticus and Salmmonella spp. could be identi-
fied from the response pattern produced by the sensors (Arshak et al. 2007). Chicken
meat freshness was evaluated based on the smell when the output data of metal,
such as tin and indium oxide gas sensors were processed with a neural network
(Galdikas et al. 2000). An “electronic tongue” incorporated in food packaging have
also been developed (Joseph and Morrison 2006). The device consists of an array of
nanosensors extremely sensitive to gases released by spoiling microorganisms, pro-
ducing a color change which indicates whether the food is deteriorated.
6.5.3 O2 Indicators
Oxygen allows aerobic microorganism to grow during food storage. There has been
an increasing interest to develop non-toxic and irreversible oxygen sensors to assure
oxygen absence in oxygen free food packaging systems, such as packaging under
vacuum or nitrogen. An UV-activated colorimetric oxygen indicator using UVA
light has been developed, which uses nanoparticles of titania (TiO2) to photosensi-
tize the reduction of methylene blue by triethanolamine in a polymer encapsulation
medium (Lee et al. 2005). Upon UV irradiation, the sensor bleaches and remains
colorless, until it is exposed by oxygen, when its original blue color is restored. The
rate of color recovery is proportional to the level of oxygen exposure. Nanocomposite
thin films deposited methylene blue/TiO2 on glass by liquid phase deposition, a soft
chemical technique which has been applied to deposition of oxides to several
substrates have been developed for oxygen indicator packaging systems in a variety
of oxygen-sensitive foods (Gutierrez-Tauste et al. 2007).
Nanocrystalline SnO2 has been used as a photo sensitizer in a colorimetric O2
indicator comprising a sacrificial electron donor (glycerol), a redox dye (methylene
blue), and an encapsulating polymer (hydroxyethyl cellulose) (Mills and Hazafy
2009). Exposure to UVB light led to activation (photo bleaching) of the indicator
and photo reduction of methylene blue by the SnO2 nanoparticles. The color of the
films varied according to O2 exposure – bleached when not exposed, and blue upon
exposed.
6.5.4 Product Identification and Anti-counterfeiting
Some smart packaging has also been developed to be used as a tracking device for
food safety or to avoid counterfeit. BioMerieux have developed a multi-detection
test – Food Expert ID® for nano surveillance response to food scares. The nanotech
company pSiNutria are also developing nano-based tracking technologies, includ-
ing an ingestible BioSilicon which could be placed in foods for monitoring pur-
poses and pathogen detection, but could also be eaten by consumers (Scrinis and
Lyons 2007; Miller and Sejnon 2008). A United States company Oxonica Inc, has
been developed nano-barcodes to be used for individual items or pellets, which
must be read with a modified microscope for anti-counterfeiting purposes (Roberts
2007). Commercially available Nanobarcodes® manufactured by electroplating
inert metals-such as gold, nickel, platinum, or silver- into templates that define the
particle diameter, and then releasing the resulting striped nanorods from the tem-
plates (www.nanoplextech.com).
6.5.5 Active Tags and Traceability
Generally, active tags in packaging are radiofrequency identification. The tags are
electronic information-based systems that uses radio frequency to transfer data
from a tag attached to an object to trace and identify the object automatically.
Radiofrequency identification is an improvement to the previous manual tracking
systems or barcodes. Furthermore, it has a longer reading range, it is very strong and
can work under extreme temperatures and different pressures, it can be detected at
distances of more than 100 m, and many tags can be read simultaneously (Abad
et al. 2007, 2009). Nanotechnology is also enabling sensor packaging to incorporate
cheap radio frequency identification tags. The nano-enabled radiofrequency
identification tags are much smaller, flexible and can be printed on thin labels.
This increases the tags versatility and thus enables much cheaper production
(www.thefreelibrary.com/).
172 B. Kuswandi
6.6 Safety Issues
In terms of consumer safety, it is important to evaluate the potential migration of

packaging constituents into food and to assess their potential hazard for a compre-
hensive risk assessment. However, to date very few studies have been published
regarding the effects of nanomaterials upon ingestion, or the potential interaction of
nanomaterial-based food contact materials with food components (Silvestre et al.
2011; Jain et al. 2016). In Europe, the legislation currently applies an overall
migration limit of 10 mg constituent per dm2 surface area to all substances that can
migrate from food contact materials to foodstuffs (Commission Regulation (EU)
No. 10/2011). For a liter cubic packaging containing 1 kg of food, this equates to a
migration of 60 mg of substance per kg of food. However, with the exception of a
few materials specifically listed in Annex 1 of the legislation, nanomaterial risk
assessment has to be performed on a case-by-case basis (Silvestre et al. 2011;
Commission Regulation (EU) No. 10/2011).
The migration of silver from three different types of nanocomposites into food
stimulants, including an analysis of the form of silver migrating (ions or particles)
has been studied (Echegoyen and Nerín 2013). Their results showed that silver
migrated into food stimulants and that acidic food presented the highest level of
migration. Moreover, heating was observed to increase migration, with microwave
heating inducing more migration than a classical oven. The authors suggest that
migration of silver could occur through two different mechanisms: the detachment of
silver nanoparticles from the composites, or the oxidative dissolution of silver ions.
The migration of silver and copper from nanocomposites, used for their anti-
microbial properties in food packaging has also been studied (Cushen et al. 2014).
The study showed that the percentage of nanofiller in the nanocomposites was one
of the most critical parameters driving migration, more so than particle size,
temperature or contact time. A model to study migration of particles from food
packaging has also been developed in this study. This model was a good predictor
of the level of migration of nanosilver and to a lesser extent of nanocopper into food
stuff and, when further developed and validated, could potentially be of benefit to
industry by reducing the time and costs usually associated with migration studies.
More recently, the migration and toxicological profile of an organo-modified
clay polylactic acid nanocomposite to be used as a food contact materials was evalu-
ated. Migration studies indicated that less than 10 mg per dm2 of the nanocomposite
migrated in water, under the conditions of the experiment (Maisanaba et al. 2014a).
Further analysis of the food stimulant indicated that the levels of metals measured
were below the permitted values. In addition, the authors evaluated the potential
toxicity of migration extracts both in vitro and in vivo. Assessment of the potential
cytotoxicity of the migration extracts in vitro, on two cell types representative of the
digestive system and their ability to induce DNA mutations, did not reveal any evi-
dence of in vitro toxicity compared to control (Maisanaba et al. 2014a). Furthermore,
exposure of rats to the same migration extracts for 90 days in drinking water did
Fig. 6.7 Relevant regulation for nano-packaging, including food product legislation and product
safety directive, chemical safety regulation, and environmental regulation
not show evidence of toxicity in terms of oxidative stress, inflammation, clinical

biomarkers and histopathological analysis (Maisanaba et al. 2014b).
These studies indicate the potential for nanomaterials to migrate from food
contact materials into foodstuffs, with the rate of migration potentially associated with
the percentage of nanofiller present in the composite material. There remains is a
need for further migration and toxicological studies in order to ensure safe develop-
ment of nanotechnologies in the food packaging industry. Thus, safe and successful
implementation of nano-packaging applications need to fulfill three regulations, i.e.
(i) food regulation, (ii) health regulation and (iii) environmental regulation as shown
in Fig. 6.7. These are needed to ensure that society can benefit from novel applica-
tions of nano-packaging, whilst a high level of protection of health, safety and the
environment is maintained. Furthermore, these are needed to ensure the safety use
of these nano-packaging, with special emphasis in the enhancement of knowledge
regarding their eventual toxicological effects, migration potential and levels of
exposure for both workers and consumers, with special emphasis on the effects on
the selected nanomaterials to human health following chronic exposure. In addition,
it is necessary for the producers not only to assure product quality ensuring regula-
tory compliance but also to involve the consumer providing clear information in
174 B. Kuswandi
regard to benefits/possible risks balance and protection of the environment. If all

regulation fulfils, then the fruitful of incorporation of nanomaterial into food
packaging would play an important role in making the world’s food supply health-
ier, safer, and tastier and more nutritious as well as environmental friendly.
6.7 Conclusion
Based on all the research conducted during last decade, clearly nanotechnology
offers tremendous opportunities for innovative developments in food packaging that
can benefit both consumers and industry. The application of nanotechnology shows
considerable advantages in improving the properties of packaging materials, even in
the early stages and will require continued investments to fund the research and
development to better understand the advantages and disadvantages of nanotechnol-
ogy use in packaging materials. The use of nanotechnology to fabricate food pack-
aging can give numerous benefits in the range of advanced functional properties.
They can bring to packaging materials with enhanced processing, health and pack-
aging functionalities, shelf-life, transportability, and reduced costs.
Nanotechnology has the potential to improve foods, making them tastier, health-
ier, and more nutritious, to generate new food packaging functions, new food pack-
aging, and storage. However, many of the applications are currently at an elementary
stage, and most are aimed at high-value products, at least in the short term. In addi-
tion to this, nanomaterials can be used to make packaging that keeps the product
inside fresher for longer extending the life of food and improving food safety. Smart
packaging, incorporating nanosensors, could even provide consumers with informa-
tion on the state of the food inside. Food packages are embedded with nanosensors
that alert consumers when a product is no longer safe to eat. Sensors can warn
before the food goes spoil or can inform consumers the exact nutritional status
contained in the contents. In fact, nanotechnology will be change the fabrication of
the entire packaging industry.
In spite of the great possibilities existing for food packaging based on nanomate-
rials, it is hoped that simple traditional packaging will be replaced with multi-
functional smart packaging. The next generation of packaging materials will be able
to fit the requirements of preserving perishable foods and other food products. By
adding appropriate nanoparticles, it will be possible to produce packages with
stronger mechanical, barrier and thermal performance. Nano-structured materials
will prevent the invasion of bacteria and microorganisms as a concern for food
safety. The nanosensors embedded in the packaging may alert the consumer if a
food has deteriorated and cannot be consumed any more.
Regardless of how applications of nanotechnology in the food packaging sector
are ultimately marketed, governed, or perceived by the public, it seems clear that the
integrating of nanoscale material in packaging will continue to yield exciting and
unforeseen packaging products. However, the potential dangers and ethical ques-
tions, that the use of this new technology should be responded wisely with more
research and development regarding these issues. Therefore, successful and safe
implementation of nanotechnology applications will require constant dialogue
between the scientists and companies who invent them and the consumers who
purchase them. If it succeeds, then the fruitful of incorporation of nanomaterial into
food packaging may play an important role in making the world’s food supply
healthier, safer, tastier, more nutritious and plentiful as well as environmental
friendly.
Regulatory bodies, should author guidance with respect to the criteria to be fol-
lowed in evaluating the safety of food packaging, uses of nanomaterials with novel
properties and functions. Novel methods, approaches and standardized test proce-
dures to study the effects of nanomaterials upon ingestion, or the potential interac-
tion of nanomaterial-based food contact materials with food components are
urgently needed for the evaluation of potential hazards relating to human exposure
to nanoparticles. Even though, it is widely expected that nanotechnology-derived
food packaging will be available increasingly to consumers worldwide in the
coming years.
Acknowledgment The author gratefully thanks the Higher Education, Ministry of Science,
Technology & Higher Education, Republic of Indonesia for supporting this work via the
Competency Grant (Hibah Kompetensi 2015/2016).
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Chapter 7
Nanotechnology in Food Processing
and Packaging
Preetam Sarkar, Syed Irshaan, S. Sivapratha, and Ruplal Choudhary
Abstract Food products are complex mixtures including proteins, carbohydrates

and lipids that are shaped at the nanoscale. These food nanomaterials are either
naturally present within foods or created during transformation of initial products.
Recent research has revealed several applications of food-based nanomaterials for
food processing and packaging. For instance nanoparticles protect and control the
delivery of antimicrobial compounds, lipid-soluble vitamins, flavours and antioxi-
dants. Nanoparticles are also used as delivery vehicles such as pickering emulsions,
multi-layered emulsions and solid-lipid nanoparticles. Nanosensors can detect
rapidly toxic substances in food. In food packaging, nanoparticles can protect func-
tional ingredients such as antimicrobials or vitamins. Chitosan nanoparticles are
used as antimicrobial compounds to enhance food safety.
Keywords Nanoparticles • Nanocomposites • Food packaging • Nanosensors •

Product quality
7.1 Introduction
7.1.1 Food Systems and Structures
In the modern world with urbanized lifestyle, food habit of people has become
responsible for many disorders which were not a big concern a few decades back.
People have to be conscious of what food they consume and how much they
consume. Hyperglycaemia and obesity are two such disorders that are strangling
millions of people directly or indirectly. A necessity is felt to produce foods that are
P. Sarkar (*) • S. Irshaan • S. Sivapratha

Department of Food Process Engineering, National Institute of Technology Rourkela,
Rourkela 769008, Odisha, India
R. Choudhary
Department of Plant Soil and Agricultural Systems, Southern Illinois University Carbondale,
Carbondale, IL, USA

186 P. Sarkar et al.
nutritionally superior; at the same time safe, affordable and tasty. Although nutritious
food can be delivered at the expense of organoleptic quality, humans always give
preference to the food that satisfies their tongue. When food technologists develop
food that is nutritionally superior and that has satisfactory mouth feel, the cost of
such preparations shoot up and hence, their availability is restricted only to a narrow
category of people (Boland et al. 2014). The task of making available nutritious,
tasty and affordable food is hindered by a lot of interlinked factors. The in-depth
understanding of food systems and structures are necessary to overcome these
hindrances.
In general, food from animal and plant origin in their pristine form, are observed
to have a ‘fibre matrix’ composite structure. A fibre is described as the one whose
length to width ratio is more than 100. It implies that fibres are arranged in a certain
fashion, like parallel, spiral, which may vary from commodity to commodity. These
fibres provide the mechanical strength to hold the matrix material. Both the fibre
and matrix are composed of polysaccharide and protein polymers. Polysaccharide
polymers are cellulose and hemicellulose while protein fibres include actin, myosin,
to name a few. Combination of proteins and polysaccharides like glucose aminogly-
cans act as matrix material that bind to the fibre (Vincent 2008).
Most of the food commodity from natural origin undergo milling, polishing,
refining and numerous other processes, all meant to disturb the native fibre matrix
structure. Therefore, food in consumable form is a derivative of the natural raw
materials whose structure is spoken in terms of emulsion, particle, gel, and foam;
indicating that the perspective used to view food structure could be colloidal (Boland
et al. 2014). Emulsions that use solid nanoparticles to stabilise their structure are
referred to as Pickering emulsion (Chevalier and Bolzinger 2013). Studies also
make use of nanoparticles to stabilise foams in the food area and such foams have
better stability (Bournival and Ata 2015; Rodríguez et al. 2015). There are several
attempts to produce food innovations using nanotechnology.
Currently, more interest is drawn in the application of nanotechnology to food
and agricultural sector. With the emergence of concepts such as green nanotechnol-
ogy, more engineered nanomaterials are expected to hit the market. But the scien-
tific community is yet to understand the new properties of engineered nanoscale
materials (Chen et al. 2014b). Majorly work was carried in the area of application
of nanoscale science to various sectors such as food packaging for extension of shelf
life, sensors for detection of harmful compounds and to ensure food safety.
With the progress of food nanotechnology various novel methods for smart
delivery of multifunctional components to target sites are being investigated.
Currently, research is heading at creation of food systems with optimized delivery
system and acceptance (physical, visual and sensory appeal) for providing human
health care (Ravichandran 2010).
Recently, there is an enormous increase in the number of patents, publications
and intellectual property rights in the budding field of agri-food nanotechnology
(Dasgupta et al. 2015). Fortified ‘canola active oil’ enriched with phytosterols is
developed by Shemen Industries Ltd. (Haifa, Israel). Fat soluble nutrients are
converted to water soluble nutrients and its absorption is increased by products
developed by Nutri-Nano™, CoQ-10 Solgar (Leonia, NJ, USA) (Ranjan et al. 2014).
7 Nanotechnology in Food Processing and Packaging 187
Various products in the market related to food nanotechnology are Slim Shake
Chocolate (based on Nanoclusters™ system), in which silica nanoparticles are
coated with cocoa for enhancement of chocolate flavour. Similarly, Nano cluster™
is another delivery system based product from RBC Life Sciences® Inc (Dasgupta
et al. 2015). FDA has approved the carotenoids and lycopene of tomato (particle
size of 100 nm, from BASF’s US patent US5968251) produced synthetically and
are GRAS (Ranjan et al. 2014). Nano-micelle based products with intended use in
food applications are produced by Novasol® from Aquanova® AG (Darmstadt,
Germany). They are used to encapsulate the functional ingredients such as beta-
carotene, vitamin A and lutein (Ranjan et al. 2014).
7.1.2 Food Packaging
Packaged articles are everywhere and packaged food is no exception. Literally

everything in the market comes suitably packed for easy transportation from the
centralized manufacturing facility, convenient transportation, comfortable handling,
attractive displaying, easy costing, controlled dispersing and disposing. Therefore,
packaging is inevitable in food industry.
Packaging is a process in which food products are well contained and protected
from outside contamination for the ultimate convenience of the consumer and also
communicates about the contents it possesses within (Robertson 2012). Packaging
should deliver the food to the customer in a form most suitable for its use (Lockhart
1997). Packaging could be primary- the package that acts as a barrier between the
food and the immediate environment. A primary packaging material contacts the
food directly. The packages over primary package meant for the convenience of
handling and transportation are referred to as secondary and tertiary packaging.
Unitisation of primary packages is achieved using secondary package. For example,
extruded snack foods packed in multilayer pouches is considered a primary package
and it put into corrugated paperboard cartons is secondary packaging. A stretch
wrapping over the corrugated cartons would be tertiary packaging. Metal shipping
containers and crates are referred to as tertiary packaging which may or may not be
used (Robertson 2012).
Large scale production, distribution and the success of delivering the food prod-
uct in the intended form to the customers have covered up the added cost of manu-
facturing the packaging material, filling and sealing. Packaging ensures safe delivery
of billions of food packs all over the world thus reducing food wastage. Food wast-
age not only means loss of product due to spoilage but additional cost gets piled up
due to disposal issues (Coles et al. 2003).
The drive for packaging development in earlier days was largely given by
military requirements during the world wars I and II. Packaging innovations such as
polyethylene, aluminium foil, polyvinylchloride, beer cans, aseptic packaging,
flexographic printing and packaging machinery were brought to use to cater to the
food requirement of military personnel performing at harsh climates (Brody et al. 2008).
The present day drive for accelerating packaging innovation is changing lifestyle
where people prefer to spend less and less time on preparing food from fresh
produce. As of now we require ready-to-eat foods, microwavable foods and snacks
that taste good and are nutritious. Such food distribution systems are provided by a
variety of corporations around the world and packaging material, their graphics and
information serve as platforms to advertise their respective brands (Yam and Lee 2012).
The most common packaging material in use these days are paper based,
polymer based, metal based or the combination (laminates and co-extrudates) of the
aforesaid. A single polymer used alone may not sufficiently give the adequate barrier
properties under all situations. Therefore, multilayer packaging materials came into
play. New innovations happen to come with a new problem. Multi-layered packages
have many additives and layers making recycling difficult over the widely known
trouble of non-degradability of polymer packages (Duncan 2011).
Bio-based packaging material claim degradability. These include starch fillers or
gelatinised starch incorporated up to 75 % to low density polyethylene along with
pro-oxidative additives. The fact that they don’t actually degrade but just fragment
have left many consumers with a deceived feeling. It should be noted that paper is
not included under bio-based packaging material as the raw material should be
annually renewable. Paper wood takes about 25–65 years to develop adequately
(Chiellini 2008). Endless are the beneficial uses of packaging, yet, they are consid-
ered as an unnecessary cost. Some customers view it as a nuisance to the environ-
ment. This is because by the time the package is received by the consumer most of
its functions are already over (Robertson 2012).
7.1.3 Introduction to Nanotechnology
7.1.3.1 Basics of Nanomaterials
The manufacture of structures in the size range of 1–100 nm and their use in various
applications is termed as nanotechnology (Coles and Frewer 2013). Nanotechnology
is an association of various disciplines like physics, chemistry and engineering and
involves manipulation of the matter at the nanoscale (Tarver 2006). A structure that
has at least one dimension in the nanometre range is called a nanostructure. A num-
ber of nanostructures have been made which are quantum dots (Tsakalakos et al.
2012), wires, wells, carbon nanotubes, and spherical nanoparticles that have a wide
range of applications. Natural food components like protein and carbohydrates from
natural resources can form nanoparticles. Cellulose is a natural polymer carbohy-
drate. Cellulose nanocrystals are synthesised by acid hydrolysis of cellulose from
natural sources like wood and cotton (Khan et al. 2012).
7.1.3.2 Properties of Nanomaterials
What makes nanomaterials so special? The answer is different optical, electrical,

and magnetic properties. The large surface energy associated with a high surface
area of nanoparticles is responsible for special properties. The large surface area to
volume ratio becomes very significant at the lower scales of nanometers. If an iron
cube was cut from 1 cm3 into smaller cubes, until the cube dimension was 1 nm3, the
ratio of number of surface atoms to bulk atoms would change from 1:106 to 1:0. The
latter implies that every atom of the 1nm3 nanocube is a surface atom. As number of
atoms on the surface increases and so does the surface area with respect to the vol-
ume of the nanoparticle (Cao 2004).
Depending on the nature of nanoparticle the measured properties are varied.
Nanospheres and nanofibrils have been associated with different food applications
and hence different properties. Also, peptide and polysaccharide nanomaterial prop-
erties have variation from the properties of metal and metal oxide nanoparticles. For
instance, persistence length and contour length are the properties of nanofibrils
(protein based). Contour length is the maximum length at completely extended form
while persistence length is the length of the polymer bent by thermal fluctuations
(MacKintosh 1998). The high aspect ratio of protein fibrils affects the rheological
property of the food solution. Gelling and thickening is enabled at comparatively
low concentration of protein nanofibrils (Loveday et al. 2011). Metal oxide, food
grade TiO2 was characterised with crystal structure, surface composition, size and
elemental composition (Yang et al. 2014).
7.2 Nanoscience in Food Processing
Nanoscience is the study of behaviour and properties related to nanostructures

(Hochella 2008). Structuring of food systems at nanoscale will modify their inher-
ent characteristics which will, in turn, assist in modulation of food quality at mac-
roscale. Along with formulation and preparation, processing is an important unit
operation that influences the physicochemical properties of food. It has a significant
effect on altering the structure of food which influences their characteristics such as
texture, flavour release profile, stability and other physicochemical properties
(Huang 2012). In order to optimize the characteristics of food systems at nanoscale,
in-depth knowledge on relationship between structure and properties of food is a
prerequisite (Aguilera and Lillford 2008). This chapter reviews the various effects
of food processing on quality and safety of foods systems.
7.2.1 Role of Nanotechnology in Food Quality
The structure and quality of food systems is greatly altered during food processing
and it relies upon the various unit operations or processing conditions (temperature,
pressure and mechanical forces) they are subjected to. Processing mainly influences
the internal components of food namely protein, starch, and lipids (Raynes et al.
2014). The stabilization of bioactive materials encapsulated in nano-carrier systems
against deleterious environmental conditions can be achieved by food nanotechnology
and thus increase the nutrition and quality of food systems.
Eugenol extract is found to possess antibacterial and antifungal properties. It also
possesses antioxidant properties which makes it suitable for preservative action. But
it is susceptible to adverse environmental conditions such as heat and light. Thus to
uphold the preservative action research has been carried for the formation of
thermally stable eugenol by its encapsulation in (α, β and γ) cyclodextrin inclusion
complex (Gong et al. 2016).
7.2.1.1 Encapsulation and Delivery Systems
Improper diet selection and poor eating patterns have led to very less or limited
consumption of bioactive nutrients. As a consequence, health related issues like
cancer, and cardiovascular diseases are prevailing. Currently, more emphasis has been
drawn on improved food processing techniques to deliver the bioactive nutrients to
overcome these health problems (Lindsay and Saarela 2011).
Encapsulation is the science of entrapment of desired functional component in a
shielding material by mechanical or physicochemical process which results in the
production of encapsulates ranging in diameter of few nanometers to millimetres
(Chen and Chen 2007). It is widely used in agro-food industries for improving the
quality and safety of food systems and has various functions such as masking and
controlled release of flavours, inhibition of oxidation for enabling prolonged
shelf life, smart delivery of nutrients and protection of probiotic microorganisms
(Burgain et al. 2011).
Nano structuring and encapsulation of food systems is done for improved stabil-
ity, controlled release of bioactive components (lipids and nutrients) to targeted sites
(Huang 2012). Bioactive ingredients are entrapped and shielded inside the second-
ary matrix which will be released upon stimulus by the outside chemical environ-
ment (Onwulata 2012). Currently, special focus has been drawn at designing of
colloidal delivery systems for effective delivery of hydrophobic bioactives for their
use in food applications (McClements 2015). The design of encapsulation systems
for delivery of core active ingredients to liquid food systems is demanding research
as these functional components are hardly soluble in liquid medium or prone to
degradation due to incompatibility between functional component and surrounding
matrix (Sagalowicz and Leser 2010). Various nano delivery systems are available for
the smart delivery of bioactives. In the recent years, mainly emphasis has been given
Table 7.1 Nano particle based delivery systems for nutrient encapsulation
Components forming
Sl no. Bioactive nutrient Delivery vehicle delivery vehicle Reference
1 Docosahexanoic Nano-micelles Casein Zimet et al.
acid (DHA) (2011)
2 Vitamin B2 Nano-capsule Alginate/chitosan Azevedo et al.
(riboflavin) (2014)
3 β-carotene Lipid nanoparticles Cocoa butter and/or Qian et al.
hydrogenated palm oil, (2013)
surfactant -Tween 80
4 Vitamin D Nanoemulsion Tween 20, 40, 60, 80 and Guttoff et al.
85 and medium chain (2015)
triglycerides (MCT)
5 Vitamin E Nanoemulsion MCT oil and surfactant Laouini et al.
mixture Tween 80/Brij 35 (2012)
6 Vitamin E Nanoemulsion Whey protein isolate and Dasgupta et al.
gum arabic and edible (2016a) and
mustard oil with Tween Ozturk et al.
surfactant. (2015a)
7 Vitamin D3 Nanoemulsions Surfactant- Ozturk et al.
quillajasaponin (2015b)
8 Lycopene Nanoemulsions Tween 20 Ha et al.
(2015)
9 Curcumin Core–shell Protein (zein) as the core Hu et al.
nanoparticles and polysaccharide (2015)
(pectin) as the shell
on delivery systems such as liposomes, nanoliposomes, nanoemulsions, nanostruc-

tured lipid carriers, nanosuspensions, nanoparticles, micelles, Pickering emulsion, solid
lipid nanoparticles and are discussed as follows (Table 7.1; Fig. 7.1):
1. Liposomes: A liquid core is enclosed in a phospholipid bilayer in a spherical
shell-like structure and is called as liposomes (Singh et al. 2012) (Table 7.2).
2. Nanoliposomes: Liposomes having dimensions of less than 200 nm are termed
as nanoliposomes (Livney 2015).
3. Nanoemulsions: The colloidal dispersion made by a combination of several min-
ute liquid droplets leads to the formation of nanoemulsions, which have a diam-
eter <100 nm. They are classified as oil-in-water or water-in-oil or combination
of both (bi-continuous). Similarly, it can be liquid in solid, or liquid in liquid.
Nanoemulsions are produced by homogenization method such as high shear
homogenization (Walker et al. 2015).
4. Nanostructured lipid carriers: These are combinations of different types of lipids
mixed together, aimed at reducing the degree of crystallinity to control the
microstructure and release profile (Davis et al. 2015).
5. Nanosuspensions: The systems in which solid nanoparticles are distributed in a
continuous liquid medium and are stabilized by amphiphiles are termed as nano-
suspensions (Livney 2015).
Fig. 7.1 An overview of different delivery vehicles in food nanotechnology
6. Pickering emulsion: Emulsions which are stabilized by particles are called as

Pickering emulsions. The various particle stabilizers used for formation of
Pickering emulsions are namely alumina, clay particles, chitin, silica, wax (Song
et al. 2015).
7. Solid lipid nanoparticles: These are composed of lipids having melting point
above room or body temperature (Davis et al. 2015).
7
Table 7.2 Delivery of antimicrobial compounds using nanostructured vehicles

Sl. Antimicrobial Components used to form
no. component Delivery vehicle delivery vehicle Tested species References
1 Nisin Liposomes Marine lecithin and soy lecithin Listeria monocytogenes Imran et al. (2015)
2 Nisin Nanocapsule Chitosan-carrageenan Micrococcus luteus, Pseudomonas Chopra et al. (2014)
aeruginosa, Salmonella enterica and
Enterobacter aerogenes
3 Pediocin Nanocomposite film Methyl cellulose film and ZnO Staphylococcus aureus and Listeria Espitia et al. (2013)
nanoparticles monocytogenes
4 Pediocin Nanovesicles Soybean phosphatidylcholine Listeria monocytogenes, Listeria de Mello et al. (2013)
(phospholipid) innocua and Listeria ivanovii
5 Thymol and eugenol Co-encapsulated Spray-dried zein–casein Escherichia coli O157:H7 and Listeria Chen et al. (2015)
nanocapsule monocytogenes,
6 Thymol and thyme oil Inclusion complexes β-cyclodextrin Escherichia coli Tao et al. (2014)
7 Thymol Nanospheres Ethylcellulose/methylcellulose Staphylococcus aureus, Escherichia Wattanasatcha et al.
coli and Pseudomonas aeruginosa (2012)
Nanotechnology in Food Processing and Packaging
8 Eugenol Nanoliposomes – Staphylococcus aureus, Escherichia Peng et al. (2015)

coli, Salmonella enterica serovar
Typhimurium, and Listeria
monocytogenes
9 Carvacrol Nanoemulsion Peanut oil (carrier) and fluid Escherichia coli Donsì et al. (2014)
soy lecithinpolysorbate Tween
20 and monoolein
10 Carvacrol Nanoemulsion Medium chain triglyceride Salmonella enterica serovar Enteritidis Landry et al. (2014)
(MCT) oil and Tween 80 and Escherichia coli
11 Trans-cinnamaldehyde Nanoemulsion Sunflower oil and Tween 20 S. cerevisiae and L. delbrueckii Donsì et al. (2012)
and glycerol monooleate,
12 Trans-cinnamaldehyde Nanoemulsion Cinnamon oil and Tween 20 Salmonella Typhimurium and Jo et al. (2015)
Staphylococcus aureus
193
Flavour Encapsulation
In recent times, one of the major challenges faced by food industries is to limit the
loss of flavour, which is attributable to unstable processing conditions and occur-
rence of several undesirable reactions such as chemical degradation and oxidation.
Significant efforts have been made to resolve this issue, among which major
approaches are encapsulation of aroma compounds using formation of starch-aroma
inclusion complex, usage of emulsion as a delivery vehicle (Kasemwong and
Itthisoponkul 2013). Similarly, efforts to control Maillard reaction in different food
products was carried out so as to produce desired flavour and colour and to reduce
toxicity (Troise and Fogliano 2013).
It is well-known fact that loss of flavour compounds increases with higher pro-
cessing temperatures. Ultimately, novel food processing techniques are emerging
with time to resolve these issues. Significant research was carried out to entrap
aroma compounds in starch matrix for shielding them during thermal processing.
Native starch and aroma compounds such as menthol and menthone were able to
form V amylose inclusion complexes and were found to be stable at higher process-
ing temperatures, varied conditions of pH and had prolonged storage time at high
water activities (Ades et al. 2012). The complexation was found to increase with the
increase in amylose content, as amylose has the ability to form more molecular
inclusion complexes among both glucose polymer units of starch, amylose and
amylopectin. The helical structure of amylose has a hydrophobic cavity in which the
volatiles (Kasemwong and Itthisoponkul 2013) and essential oils (Marques 2010)
were entrapped.
The study to evaluate the flavour release profile with the presence and absence of
α-amylase enzyme revealed that the amylose-flavour complex gets hydrolysed dur-
ing chewing mechanism in the presence of enzymes and leads to complete release
of aroma. It is also seen that the encapsulation efficiency between amylose-flavour
complexes can modulate the release and retention of aroma compounds (Ades
et al. 2012).
In another study, use of cyclodextrins for encapsulation of aroma compounds
was emphasised. A general schematic of flavour encapsulation with cyclodextrins is
demonstrated in Fig. 7.2. Commercially three types of cyclodextrins are available:
α, β and γ cyclodextrins (Astray et al. 2009). Structurally, these are cyclic oligosac-
charides produced as a result of starch degradation and own a truncated cone shape
with hydrophobic cavity, whose diameter ranges from 5.7 to 9.5 Ao and hydrophilic
exterior. This cavity enables flavour molecules to get trapped inside and form an
inclusion complex with polyphenolic compounds (Pinho et al. 2014).
An experimental study was conducted to evaluate the retention of flavours (benz-
aldehyde, l-menthol, citral and vanillin) in various thermally processed food appli-
cations like candy, fruit leather and angel cakes. The flavours were made to form a
molecular inclusion complex with β-cyclodextrins and they were compared with
that of normal liquid formulations. As a consequence, it was found that flavour loss
was minimised owing to increased heat stability due to complexation of flavours
with β- cyclodextrins. The flavours benzaldehyde, citral and menthol had 20, 26 and
Fig. 7.2 Schematic representation of molecular inclusion complex between cyclodextrin and a
flavour molecule
86-fold retention, respectively while complexing with β-cyclodextrins when

compared with liquid formulations (Reineccius et al. 2004).
Thymol is a volatile phenolic compound, although it is found to be an antimicro-
bial in nature and effective against Salmonella Typhimurium, it has low acceptance
owing to unpleasant bitter taste (Si et al. 2006). Another phenolic compound, resve-
ratrol has a role in improving human health attributable to functional properties
such as anti-carcinogenic, anti-inflammatory and protects heart functioning
(Davidov-Pardo and McClements 2014). Research was performed to mask the
undesirable taste of thymol by encapsulating it in cyclodextrins (Nieddu et al. 2014).
Encapsulation technique is used to mask the unpleasant taste caused due to phenolic
compounds and which influences the acceptance of a commodity. It even helps
to enhance the stability and bioavailability of phenolic compounds (Fang and
Bhandari 2010).
Electrospinning technique is used widely in recent times for formation of nano
fibrous polymeric membranes (Mascheroni et al. 2013). Vanillin-cyclodextrins (α, β
and γ) inclusion complex was formed in polyvinyl acetate nano-web by the use of
electrospinning technique. The results suggested that vanillin and γ- cyclodextrins
had slow and prolonged release of vanillin and was thermally stable when compared
to other types of cyclodextrins (Kayaci and Uyar 2012).
In another study, carbohydrate polymers of pullulan and β-cyclodextrins were
blended by electrospinning technique for production of encapsulates containing
aroma compounds which are thermally stable and whose aroma release triggers on
stimulus of humidity in surrounding environment (Mascheroni et al. 2013).
Similarly, emulsion electrospinning process is used for encapsulation of limonene
in polyvinyl acetate fibrous membranes (Camerlo et al. 2013).
Great attention has been paid to encapsulation of citral flavour attributable to its
enormous application in beverages. Citral flavour is prone to degradation with time
due to oxidation and results in loss of aroma intensity (Maswal and Dar 2014). The
flavour release behaviour of six fragrances such as citronellal, camphor, eucalyptol,
menthol, limonene and 4-tert-butylcyclohexyl acetate was evaluated after encapsu-
lating them in various polymer based blends using solvent displacement technique.
The process resulted in good fragrance loading capacity and encapsulation efficiency
of more than 40 % and 80 %, respectively. Limonene showed the fastest release
while menthol had the slowest release profile (Sansukcharearnpon et al. 2010).
Some recent studies have been carried on aroma partition properties of oil–gel
complexes. The gel structure made of monoglycerides forms a basis for encapsula-
tion of oil. The gel was subjected to characterization and by application of head-
space gas chromatography analysis the aroma partition properties were evaluated
(Calligaris et al. 2010).
Nutrient Encapsulation
Carotenoids, mainly β carotene is the precursor of vitamin A and it plays a major

role as an antioxidant (Böhm et al. 2002). It eradicates occurrence of health associ-
ated risks such as cancer, night blindness and cardiovascular diseases (Fikselova
et al. 2008). These functional components are lost during processing since they are
sensitive to heat and light (Rodriguez-Amaya 1999). Several methods have been
deployed for increasing stability, smart delivery and bioavailability of β-carotene in
food systems by nanoencapsulation. Novel carrier systems such as lipid nanoparti-
cles, solid lipid nanoparticles and nanostructured lipid carriers are designed having
improved functions such as increased bioavailability of active components, mem-
brane permeability for controlled release (Gutiérrez et al. 2013).
Proteins and polysaccharides are used as carriers of active ingredients such as
vitamins, ω-3 oils (Matalanis et al. 2011). Electrospray technique is used to produce
microcapsules which assists to encapsulate proteins (Fukui et al. 2010). Carbohydrate
particles are used for the encapsulation and improving bioavailability of catechins
(Peres et al. 2011).
Microencapsulation technology has been a solution to solve the issues pertaining
to stability of oils. The recommended daily intake for adults for both docosahexae-
noic acid and eicosapentaenoic acid for maintaining cardiovascular health and
coronary heart disease is 500 mg and 900 mg, respectively (Shi 2006).
Bioactive Lipids
Nanoliposomes are lipid vesicles which act as nanocarriers systems for the delivery
of bioactive lipids. The lipid vesicles are composed of phospholipid molecules,
main components in naturally occurring bilayers and show amphiphilic character
(Siegel and Tenchov 2008). The presence of both lipid and aqueous phase makes it
suitable for entrapment and controlled release of water and lipid soluble as well as
amphiphilic materials (Mozafari and Mortazavi 2005). Liposomes are available in
our natural diet, such as milk, eggs and can be easily approved for food use by regu-
latory bodies (Reza Mozafari et al. 2008).
In recent decades, the functional properties of lipids have been studied

extensively. Functional lipids are encapsulated into nanoparticles for enhancing the
bioavailability. Emulsification has been found to be one of the best technique for
effective delivery of lipid molecules (Neves et al. 2015). Novel methods such as
microchannel emulsification and nanochannel emulsification were proposed for
production of droplets of very narrow size (Kobayashi et al. 2002).
Delivery of Probiotic Microorganisms
Probiotic encapsulation aims at protection and delivery of beneficial microorgan-

isms from adverse environmental conditions. The study of yeast encapsulation
reveals that the electrospray technique can encapsulate a physiologically active
substrate in the polyelectrolyte microcapsule and maintain its activity (Fukui et al.
2010). Bioactive food components are classified into two types, molecules which are
functional (bioactive molecules) and living cells which are beneficial (probiotics)
(de Vos et al. 2010).
7.2.1.2 Sensory and Texture Improvement
Application of nanotechnology to food has led to improvement in sensory aspects

such as taste, color, texture and modulation of consistency in food systems (Restuccia
et al. 2010).
Color
Not much of research has been progressed in this field, recent research suggests the
application of β-carotene, a fat soluble pigment to manipulate the colour of food
systems by the application of nano-emulsion technology. The colour of food system
varies from yellow to dark orange, and varies with the concentration of β-carotene
in the nanoparticles (Cushen et al. 2012). Transparent and thermally stable disper-
sions which are of nano size are produced by encapsulation of eugenol using
Maillard-type conjugates. Study was conducted for delivery of lipophilic compo-
nents without affecting the visual characteristics (Shah et al. 2012).
Viscosity
Change in viscosity of food systems influences the flavour perception. With the
increase in viscosity of foods there is a decrease in flavour release profile and thus
leads to decrease in overall flavour intensity. It also delays the tastant signals of taste
buds which lead to modulation of flavour perception (Taylor et al. 2009).
Size
Oil droplet size distribution is an important emulsion property which controls the
release of aroma compounds. A study carried out to determine the effect of droplet
size on aroma release profile has revealed that in the case of hydrophobic esters (e.g.
geranyl acetate) with a decrease in droplet size of emulsion there was a significant
increase in the release of aroma compounds while maintaining the oil content of
emulsion. But the same trend was not found in case of ethyl butanoate which
happens to be more hydrophilic ester (Weel et al. 2004).
7.2.2 Role of Nanoscience in Food Safety
Microbiological safety and security of food systems is a high priority issue in recent
times as they are prone to contamination with pathogenic and spoilage microorgan-
isms. Many costly and conventional methods, such as modification of atmosphere,
high temperature and pressure are in use for ensuring food safety aspects. In the last
decade, novel techniques are used in the delivery of entrapped active components
such as nanoparticles, emulsion and hydrogels (Onwulata 2012).
7.2.2.1 Delivery and Protection Systems of Antimicrobial Agents
The Centre for Disease Control and Prevention has estimated in their findings that
out of every six American people, one gets sick and hospitalized attributable to
foodborne diseases. In terms of estimated number of illness, the main pathogens
leading to hospitalizations and deaths each year are Norovirus, Salmonella,
Clostridium perfringens, Campylobacter spp., Staphylococcus aureus. Recently,
with rapid consumer awareness on food safety and quality related issues there is
demand for natural antimicrobials in food applications (Weiss et al. 2009). Thus, great
attention is paid for protection of antimicrobial compounds present in natural
sources to enhance food safety and security. Researchers have focused on design
and development of novel delivery vehicles such as phytoglycogen based Pickering
emulsions for the prolonged protection and release of bioactive agents such as nisin
(Bi et al. 2011).
Antimicrobial silver nanoparticles with a size range of 20–30 nm were synthe-
sized from dry roasted Coffea arabica seed extract by bio-reduction (Dhand et al.
2016). Silver nanoparticles with bactericidal potential were synthesized by chemical
reduction method from the bark extracts of the plant species Ficus benghalensis and
Azadirachta indica. An indication of formation of silver nanoparticles was the
color change to dark brown, an observation further confirmed by ultraviolet-visible
spectroscopy (Nayak et al. 2016). Cu-chitosan nanoparticles demonstrated anti-
fungal activity, reduction of mycelial growth and inhibition of spore germination in
tomatoes (Saharan et al. 2015).
Fig. 7.3 Schematic representation of different types of oil-in-water emulsions with single and
multiple interfacial layers
Emulsions
Various lipid-based vehicles have been proposed as delivery systems and for
application in food system such as conventional emulsions, multiple emulsions, mul-
tilayered emulsions (McClements et al. 2009). These emulsion systems are used for
prolonged delivery of antimicrobial compounds in food applications (Fig. 7.3).
Emulsion formulation and droplet size have been regarded as major parameters
for evaluating the antimicrobial efficacy (Speranza et al. 2015). With the application
of high pressure homogenization technique with an applied pressure of 300 MPa,
nanoscale emulsions were prepared by encapsulation of D-limonene and terpenes
mixture and these emulsions were evaluated for their antimicrobial activity against
Lactobacillus delbrueckii, Saccharomyces cerevisiae, and Escherichia coli. The
parameters taken into consideration were minimum bactericidal concentration and
minimum inhibitory concentration and it was found that there was an increase in
antimicrobial activity and was influenced by mean diameter and formulation (Donsì
et al. 2011).
In another study, the effect of mean diameter and formulation was studied on rate
of infusion of carvacrol into food matrices (Donsì et al. 2014). Microcapsules have
been found to have excellent protection properties against degradation for encapsu-
lated essential oils and do not influence the antimicrobial activity. In contradiction to
that, nanoscale capsules owning to smaller size, passive cellular absorption function
may increase leading to reduction in mass transfer resistance. As a consequence, the

antimicrobial activity is increased for nanoscale materials and this was witnessed by
increase in antimicrobial activity of oils entrapped in liposomes (Gortzi et al. 2007).
Nowadays, wide application of oil-in-water emulsions have been noticed for the
protection and delivery of oils, for instance, thyme oil (Wu et al. 2014) and their
antimicrobial efficacy is evaluated. Similarly, oil-in-water emulsions are used
for encapsulation of essential oil components from clove, lemongrass, thyme and
palmarosa and tested for their antimicrobial activity against Escherichia coli
(Odriozola-Serrano et al. 2014).
Functional nanoemulsions of Eugenol were prepared using sesame oil and sur-
factants such as Tween-20 and Tween-80 and their antimicrobial efficacy was tested
in orange juice system. The study showed that Staphylococcus aureus could be
effectively inhibited by the nanoemulsion loaded with eugenol (Peng et al. 2015).
Nanoparticles
Nanoparticles use an ingredient has been extensively increased in food industries on

account of their physicochemical and functional properties (Joye and McClements
2014). Till date nanoparticles were used profusely in various fields like electronics,
medicine and automation. With the experience and knowledge attained from these
fields, it can be applied to food science for enhancing food safety (Ravichandran
2010). Nanoparticles of alginate, chitosan and pluronic were combined with nisin
and were tested for their antimicrobial efficacy in nutrient broth and tomato juice
system. The study confirmed that nano-encapsulated nisin demonstrated greater
antimicrobial efficacy compared to free nisin (Chopra et al. 2014).
Usage of peppermint oils has potential benefits such as antifungal and antibacte-
rial properties (Mehri et al. 2015). Essential oils of Menthapiperita were encapsu-
lated in chitosan-cinnamic nanogel and tested for their antimicrobial activity and
stability against Aspergillus flavus and it was found to be effective and inhibit A.
flavus (Beyki et al. 2014). Chitosan nanoparticles were prepared for encapsulation
of polyphenols and tested for antimicrobial activity against various food pathogens
and found to more effective against Bacillus cereus, Escherichia coli O157:H7 and
less efficacy was reported against Salmonella Typhimurium (Madureira et al. 2015).
In case of coatings, metal-based materials with antimicrobial functions are utilized
as nanoparticles (Bastarrachea et al. 2015). Silver nanoparticles are enclosed in cel-
lulose pads and kept in contact with beef and tested for microbial load. It was found
that the microbial load decreased in the meat extracts (Smolkova et al. 2015).
Nanoparticles of phytoglycogen derivatives were used as carriers of nisin, which
represented peptide model and was tested for antimicrobial efficacy against patho-
gen Listeria monocytogenes. The study found that with the degree of substitution of
phytoglycogen with β-amylolysis, and octenyl succinate lead to increase the reten-
tion of nisin activity for a longer time (Bi et al. 2011).
In most applications including food, nanomaterial synthesis is perceived in two

approaches; these are top-down and bottom-up approaches (Nasr 2015). In the
bottom-up method, the required nanomaterial is synthesised by building atom-by-
atom or cluster-by-cluster. This allows the surface topography to be uniform and
can be manipulated very specifically to the required final nanoparticle structure. The
top-down approach involves the breakdown of a bulk substance by chemical or
physical means to nano-sized particles. Thus, a top-down approach is characterised
by surface imperfections (Thakkar et al. 2010). A bottom-up approach is favoured
over top-down method as the surface properties are very important to design nano-
materials in the desired way.
Halloysite clay nanotubes were synthesized at ambient temperature by size
reduction using high energy ball milling with no specific solvent (Gorrasi et al.
2014). A dilute slurry of cellulose was subjected to high- pressure homogenization
to convert it to microfibrillated cellulose. The structure consisted of interconnected
microfibrils having diameter in the range 10–100 nm (Herrick et al. 1983). Cellulose
nanocrystals were formed from cellulose nanofibres by sulphuric acids hydrolysis
(Robles et al. 2015).
Phase separation method, also known as coacervation has been used to form
nanoparticles. A study synthesized gelatin nanoparticles by the phase separation
method using binary non-solvent system yielding 94 % of particles. A size as small
as 55.67 nm in dry state could be achieved by modified coacervation of gelatin
(Patra et al. 2016). Cu- chitosan cross-linked nanoparticles were synthesized using
ionic gelation approach (Saharan et al. 2015). Chemical methods were used to pre-
pare chitosan nanoparticle by a series of steps- amidation, grafting and cross-linking
(Atta et al. 2015).
Films and Edible Coatings
Surface coating method is commonly employed during the fabrication of food pack-
aging films for attaining antimicrobial functions. In order to achieve food packaging
materials with antibacterial function, silver nanoparticles coating was suggested.
The surface of polyethylene film was modified with corona discharge technique and
dipped in silver nanoparticle based colloidal solution. The fabricated nanostruc-
tured films were tested for antimicrobial activity against Staphylococcus aureus and
Escherichia coli (Sadeghnejad et al. 2014).
With the emergence of nano-encapsulation technique, coating materials are
incorporated with nutrients and bioactive agents possessing potential health benefits
can be delivered to targeted sites. In second generation coating, use of chemicals,
microorganisms or enzymes in coating food surfaces is done which are prone to
oxidation and degradation (Falguera et al. 2011).
7.3 Nanoscience in Food Packaging
The packaging criteria required for food is very varied. A very important criterion
that a food packaging must accomplish is to provide the necessary barrier proper-
ties. Respiring foods like fruits and vegetables will decay-off if the food were to be
packed in a packaging material completely impervious to oxygen. Instead, they
require a membrane that selectively allows oxygen to enter the packaging, at the
same time retains moisture within the packaging material. Non-respiring foods like
carbonated beverages have to be stored in containers highly impervious to gas trans-
fer so as to prevent decarbonation of the drink. Not only the sophisticated require-
ment of food material makes packaging a challenge, the packaging material’s
behaviour also creates complication in food system (Fig. 7.4). For example, ethyl-
ene vinyl alcohol has good oxygen barrier property at low humidity ranges.
However, as the humidity goes beyond 75 %, the oxygen transmission rate of ethyl-
ene vinyl alcohol shoots up (Duncan 2011).
The behaviour of food cannot be modified as food is expected to be delivered in
a fresh state. So the packaging material is to be modified to accommodate the com-
plex characters of food systems. Polymers made into laminates or co-extrudates can
obtain suitable barrier properties but recycling them is difficult (Duncan 2011).
Polymer nanocomposites are believed to offer a possible solution to the problem of
packaging material as the barrier properties of the polymers can be improved by
using a single polymer material (polyolefin) or suitable biopolymers (cellulose)
intercalated with natural clays in pristine or modified form.
7.3.1 Food Quality
Food quality is associated with food perishability. Perishable products must be

stored so as to reduce the loss in food during transportation and storage (Rong et al.
2011). Perishability can be controlled to some extent by carefully monitoring the
Fig. 7.4 Illustration of Gas barriers Oxygen scavenger

nano-packaging in food
safety and security
Food Quality
FOOD NANO PACKAGING
Food Safety
Metal reinforcement Immobilized enzymes
Functional antioxidant Nano-sensors

food’s exposure to degrading substances like oxygen, light, ethylene (in the case of
fruits) and various other factors. Packaging materials are required to contribute to
the food quality by influencing barrier properties to form a conclusive food
environment.
7.3.1.1 Barrier Properties
The most important property of packaging material is the barrier ability. A sug-
gested technique to tackle the barrier issue is the use of polymer nanocomposites
such as silica and clay nanoparticles embedded within the polymer matrix. The
primary mechanism by which the permeability of the polymer material is altered
is by forcing the diffusant to traverse a ‘tortuous pathway’ (Bharadwaj 2001).
The diffusing material could be oxygen entering the system of packaged material or
could be water vapour, carbon dioxide, flavours and other substances entering or
leaving the packaging system enclosing the food. In a packaging material consisting
of only the polymer material, the diffusing particle would travel a straight unhin-
dered path through the thickness of the packaging material, perpendicular to the
surface. By embedding polymer nanoparticles of sufficient aspect ratio, the mean
path travelled by the diffusing material is long and undefined, a path described as
‘tortuous pathway’ as illustrated (Fig. 7.5). The long path buys more time for the
diffusing material to diffuse through the packaging material and the effective film
thickness increases by the incorporation of nanoparticles in polymers. The nanopar-
ticles thus, embedded into the polymer is called filler while the pure polymer is
referred to as matrix. The filler is mostly an inorganic impermeable crystal that
Fig. 7.5 The migrating substance while travelling through a segment of nanocomposite film has
to take an undetermined, long and round about path, as the filler material hinders the free
movement
makes it necessary for the diffusing material to go around (Duncan 2011). Fillers
may include starch nanocrystals (Haaj et al. 2014; Rajisha et al. 2014; Tehfe et al.
2015), chitosan or chitin nanoparticles (Biswas et al. 2015; Chen et al. 2014a;
Herrera et al. 2015), carbon nanotubes (Kavoosi et al. 2014; Yu et al. 2014),
silicate nano-platelets (Baouz et al. 2015; Decker et al. 2015), silica nanoparticles
(Farhoodi et al. 2014; Holt et al. 2014), clay nanoparticles (Bodaghi et al. 2015;
Wakai and Almenar 2015) and cellulose-based nanofibres (Ghaderi et al. 2014;
Khan et al. 2014a).
The first success story of polymer nanomaterials was that of nano-clays such as
montmorillonite. It is naturally formed clay obtained from volcanic debris. This
clay has a nano-layered structure, in which layers are spaced by interlayer galleries.
In case of montmorillonite, the galleries are bound on either side by silicate layers
(de Paiva et al. 2008). Montmorillonite being hydrophilic easily does not solubilise
in polymer. This constraint was overcome by the use of alkyl-ammonium group that
act as a surfactant and brings down thermodynamic barrier posed by the immiscibil-
ity of clay and polymer. Certain other methods have been employed to evenly dis-
tribute the clay within the polymer matrix like clay modification and polymer
modification with or without the addition of compatible agents. Structures resulting
from dispersion of nanoclays into polymer are intercalated nanocomposite, non-
intercalated nanocomposites, flocculated nanocomposites and exfoliated nanocom-
posites. Of the aforementioned probable structures of nanocomposites, exfoliated
structure is favoured by researchers due to improved barrier effect and reduced filler
loading (Silvestre et al. 2011).
Polylactic acid has been known as a biodegradable polymer. It consists of lactic
acid (CH3CH(OH)COOH) monomer units esterified to form the thermoplastic poly-
mer. On a large scale lactic acid is produced from corn starch by fermentation.
Polylactic acid films have been commercially used to package ‘relatively short shelf
life’ food in cups, lamination films and overwraps. Cellulose, a widely available
nanoparticle forming substance was added to polylactic acid as reinforcement filler
material to form the nanocomposite (Herrera et al. 2015). Cellulose was chosen
because it was a widely available, low-cost material which permitted high level of
polymer filling. Cellulose being hydrophilic, poses difficulty in dissolving with
polylactic acid. Therefore, suitable solvent like chloroform had to be employed to
cope up with the non-compatibility of polylactic acid and cellulose nanocrystals.
Polylactic acid composite films prepared by adding 1 wt.% cellulose nano-crystals
exhibited 9 % reduction in oxygen transmission rate and those polylactic acid com-
posite films prepared by inclusion of 5 % cellulose nano-crystals exhibited 43 %
reduction in oxygen transmission rate. Surfactant modified-cellulose nano-crystals
incorporated film exhibited oxygen transmission rate reduced by 48 % in compari-
son with unmodified cellulose nano-crystals film. The above findings indicated that
cellulose nanocrystals, in pristine and modified forms, could be used to make films
with polyvinyl acetate that had improved barrier effect with respect to oxygen. The
same result did not hold true for water vapour barrier property (Fortunati et al. 2012).
Biodegradable composite packaging material was prepared from a polymer blend of

apple peel powder and carboxymethyl cellulose with different nanoclay reinforce-
ment to improve mechanical and barrier properties of the film (Shin et al. 2014).
7.3.1.2 Oxygen Scavenging Properties
Oxygen is held responsible for most of the deteriorative reactions in food. Be it

oxidation of lipids, growth of fungi or proliferation of aerobic bacteria, oxygen is
the main degrading agent. It is utmost necessary to eliminate oxygen from food
packages so that shelf life is extended. Gas flushing techniques of vacuum packag-
ing and modified atmospheric packaging target controlling the oxygen levels within
the sealed packages. However, these techniques do not create a packaged space
completely devoid of oxygen due to the fact that the porous food material will hold
oxygen and there is permeation of gases through sealed membranes. There came the
use of sachets and pads capable of scavenging oxygen within the enclosed space.
Oxygen scavenging systems were mostly iron powder based sachets involved in
chemical reaction with the moisture within the system (Han 2005; Nakata 2015). It
should be noted that scavenging involves chemical or enzymatic reactions to quench
oxygen. Sachets posed the problem of accidental consumption with food and their
non-compatibility with beverages. Researchers then turned to find other means of
putting an oxygen scavenging material inside the package. One such approach is
making the packaging film that quenched oxygen and nano-materials seem to have
vast potency in this regard (Ahvenainen 2003).
Films co-deposited with nano-crystalline TiO2, and consequently compressed
formed films that could consume oxygen from a packaged environment. TiO2
required the use of ultraviolet illumination and a sacrificial electron donor, obtained
from the organic food for active removal of oxygen. Further, high-pressure com-
pression of the film ensured that the film was non-scattering to light. Good final
deoxygenation was observed even when the initial oxygen concentration was very
low, indicating that oxygen depletion was feebly dependent on concentration
(Xiao-e et al. 2004). Oxygen-sensitive luminophore coated glass beads were used to
study the rate of oxygen depletion of film utilizing TiO2 and UV light. Oxygen scav-
enging rate of TiO2was found to be 0.017 cm3 O2h−1 cm−2 over a period of 24 h
(Mills et al. 2006).
Active packaging films to quench oxygen were prepared using poly (lactic acid)
as matrix, modified montmorillonite as filler and thymol as additive. Images
obtained from TEM and X-ray scattering patterns convinced the existence of an
intercalated structure that improved mechanical properties and oxygen barrier prop-
erties. Thymol addition brought good antioxidant property to the packaging mate-
rial in addition to superior physical properties, thus bringing forth promising active
packaging material (Ramos et al. 2014).
7.3.2 Food Safety
In the past few decades food safety has become a major concern all around the
world. Recent consumer demand for organic food is the evidence that consumers
are careful about the food they consume. Microbial safety is very crucial to develop
trust among the consumers that the packed food is safe for consumption (Grunert
2005). Foodborne diseases and safety issues was estimated to affect the US econ-
omy by $77.7 billion annually (Hakovirta et al. 2015). The recent food safety ideas
involve control of food-borne microbes affecting humans and continuous surveil-
lance (Fox et al. 2015). Antimicrobial nanocomposites and nano-laminates aids in
preventing pathogen multiplication while nanotracers and nanosensors assist in
tracking the product safety.
7.3.2.1 Nanocomposites
Nanocomposites filled with metal nanoparticles are known to possess antimicrobial

property and the most promising results have been obtained by the inclusion of
silver nanoparticles. Gold and zinc nanoparticles are also studied for their antimi-
crobial function (Silvestre et al. 2011; Maddineni et al. 2015).
Silver is known to be a wide spectrum antibacterial. It has been found to be effec-
tive against a large range of bacteria, algae, fungi and some viruses. With the pro-
gressing trend of development of resistance by microbes against several molecular
antimicrobials, research suggests that silver is very potent antimicrobial (Duncan
2011). Mechanisms that account for silver’s bactericidal effect include mainly the
ability of silver to bind with oxygen, nitrogen and sulphur atoms of functional
species present in biomolecules; the result may be cell wall damage and cell fluid
loss. Silver may also bind with proteins including enzymes and affect the normal
metabolism of the bacterial cell (Dasgupta et al. 2016b, c). Cell reproduction may
be hindered if silver interacts with DNA, which accounts for bacteriostatic effect
(Cavaliere et al. 2015). The cytotoxicity level of silver ions per litre of water is
10 mg. When such is the case, a concentration as low as a few micrograms of silver
ions are capable of destroying bacteria present in water (Damm et al. 2008).
Studies have indicated that when silver was filled into polyamide-6 (nylon/poly-
caprolactam, a polymer) in nanoparticle form exhibited more bactericidal effect
than the same polyamide filled with silver microparticle. This effect was justified by
the fact that nanosilver held larger surface area and so the release of silver was
higher. Also, the study discovered that 9.5 × 10−4 mg l−1 cm−2 day−1 of silver release
could eliminate E.coli totally in 24 h (Damm et al. 2008).
The chemical behaviour of silver ions was held responsible for the antibacterial
property of silver. The inability of silver nanoparticles to be harmless to silver
resistant strains of E. coli supported the belief that silver nanoparticles were mere
delivery vehicles of silver ion. This theory was in opposition to the another research
which found silver nanoparticles to be effective against of P. mirabilis and E. coli,
both silver resistant organism (Duncan 2011). There may be other factors affecting
the antimicrobial activity of silver like the presence of salts, continuous ion release,
size, shape and much more (Kim et al. 2007). Antimicrobial nanocomposite films
from chitosan- gold nanoparticles and chitosan- silver nanoparticles were prepared
and the microbial destruction was studied against gram positive bacteria, gram neg-
ative bacteria, fungi and yeast (Youssef et al. 2014).
Extensive research over the killing of microbes by using Titanium dioxide started
following the findings of Matsunaga in 1985 (Mirhoseini and Salabat 2015;
She et al. 2015; Ranjan et al. 2015, 2016). Matsunaga and the associated team had
discovered that near UV activated TiO2–Pt catalyst was capable of microbes present
in water. Several researches followed this finding to explore the antimicrobial effect
of photoactivated TiO2 against numerous fungi, algae, bacteria, viruses and cancer
cells (Kim et al. 2003). Most of the researches, even today try to combine photoac-
tivated TiO2 and other antimicrobials like silver to achieve effective antimicrobial
action in a film or coating.
Nano-TiO2 doped with Ag and iron and modified by using methacryloxypropyl-
trimethoxysilane was used to prepare a multifunctional fluorocarbon coating.
Research showed that such a modified film exhibited an antimicrobial property of
92 % if activated using light. The bactericidal ability was attributed to a variety of
combined factors that included quantum of TiO2, light doses and effects of doping
materials (Wang et al. 2010).
Semiconductor-metal composite nanoparticles formed from TiO2 semiconductor
and doping metals like vanadium and gold were dispersed in solution. This solution
formed by sol-gel method was claimed as antimicrobial (with killing efficiency of
60–100 %) coating against the organisms studied, which are, gram-negative E. coli
and gram-positive Bacillus megaterium. General techniques employed for studying
nanoparticles include transmission electron microscopy, atomic force microscopy,
X-ray diffraction and some spectroscopic methods (Fu et al. 2005).
Several studies have indicated that TiO2 on photocatalysis achieves microbial
killing by the formation of reactive oxygen species like O2 (superoxide anion radi-
cal) and .OH (hydroxyl radical). These free radicals cause mineralisation by react-
ing with organic compounds of membrane and cell wall of the pathogens, resulting
in death (Foster et al. 2011). Nano size just seems to accelerate this antimicrobial
effect of TiO2 by exposing more active sites due to a high surface area that favors
catalytic reactions (Fu et al. 2005). Deacetylation of chitin forms chitosan, a posi-
tively charged natural biopolymer that is non-toxic. Chitosan nanoparticles, in con-
junction with Ag (Pinto et al. 2012), Cu (Pinto et al. 2013; Qi et al. 2005) and clay
nanoparticles (Rhim et al. 2006), have been attempted to prepare food compatible
films with cytotoxic ability. The mode of action of chitosan is suggested that cell
membrane is disturbed causing rupture of the cell due to the interactions between
chitosan and cell membranes that possess opposite charges (Qi et al. 2004). A com-
parative study performed to compare the antibacterial effect of chitosan/cellulose
and chitosan/cellulose–AgNPs nanocomposite films indicated that chitosan in
association with silver nanoparticles performed better in terms of antimicrobial

activity compared to just chitosan/cellulose film (Lin et al. 2015).
Nisin has been attempted to be incorporated into nanocomposite films to make it
a functional film. In a poly lactic acid-cellulose nanocrystals nanocomposite system
nisin was reinforced using the method of adsorption coating to inhibit the propaga-
tion of L. monocytogenes in sliced cooked ham (Salmieri et al. 2014). In a similar
meat system, experimented with nisin immobilized cellulose nanocrystal embedded
chitosan films increased the lag phase of Listeria (Khan et al. 2014b). The matrix
forming materials of nanocomposites like food-grade montmorillonite readily pick
up nisin into the interlayer space of the clay as indicated by X-ray powder diffrac-
tion studies (Meira et al. 2015). Immobilized systems prepared using montmoril-
lonite intercalated with nisin were found to have bactericidal activity against
Enterococcus faecium C1 (Ibarguren et al. 2014). Nanocomposites with mont-
morillonite and nisin at less than 5 % (w/w) in a polypropylene film could inhibit
gram- positive Staphylococcus aureus, Listeria monocytogenes and Clostridium
perfringens (Meira et al. 2014).
In another study, two types of nanoclays were used to deliver essential oils like
thymol, eugenol and carvacrol by blending with linear low-density polyethylene to
form nano-composite films. The layered structure of the first nano-clay, montmoril-
lonite allowed the loading of essential oil on the interface and tubular structure of a
second nano-clay, halloysite allowed filling into the nano-channels. Tween 80, a
food grade surfactant assisted the loading of nano-clays with antimicrobial oil. Such
nano-reinforcement made the packaging material active and enabled delivery of the
antimicrobial essential oils over a prolonged period in meat-based food system
(Tornuk et al. 2015). Halloysite nano-tubes were described as nano-containers
owing to their ability to hold model antimicrobial sodium benzoate, with the nano-
tubes embedded within a Poly (ethylene terephthalate) matrix. High chemical load-
ing, around 1–7 % was achieved within halloysite nano-clay tubes by using simple
procedure, thus, eliminating the need for hazardous chemicals. This study indicated
that antimicrobial composite packaging had its bactericidal effect for prolonged
time when loaded into halloysite as compared to the antimicrobial release after sim-
ple dispersion of active compound into the polymer matrix (Gorrasi et al. 2014).
A novel filler material, microfibrillated cellulose was made from blue agave
bagasse to check the release of natural antimicrobial lysozyme and was incorpo-
rated into polylactic acid polymer matrix after modification. In this study, the ability
to retain lysozyme associated with the microfibrillar cellulose by the probable
hydrogen, electrostatic and ion-dipole interactions was analysed by fitting the diffu-
sion data with Fick’s law (Robles et al. 2015). The amount of antimicrobial required
to bring about effective killing of microorganisms is considerably less when the size
of antimicrobial agent, eg, chitosan, benzoic acid and sorbic acid, is reduced to
nanoparticle size. The author proposes their potential for applications in smart and
active packaging (Cruz-Romero et al. 2013).
7.3.2.2 Nanolaminates
Nanolaminates, with regard to food packaging, refer to several layers of edible film
coatings applied over food itself or polymer/surface with the layers bonded together
by physical or chemical interactions. It is mandatory for the film so formed to lie
within the nanometre range of 1–100 nm for the laminate to be called a nanolami-
nate. The edible substances used for coating include polymers of carbohydrate, pro-
tein and lipid. Nanolaminates of precise thickness are formed by ‘layer by layer’
deposition technique (Ravichandran 2010). This technique uses polyelectrolytes
like polysaccharides and proteins (Mishra 2012) to be deposited on the prepared
surface by making use of electrostatic interaction (attraction between the opposite
charges) or similar interactions and thus, holds the multiple layers intact. In actual
practice, the formation of nanolayered structure is achieved by spraying the layer
forming material and then washing, and again spraying and washing, until the
required number of layers is formed. In an alternate method, cyclic dipping and
washing are used to form the specified nanolayers. A number of functional com-
pounds like flavours, antimicrobials, colours and antioxidants can also be incorpo-
rated into the nanolaminate film (Weiss et al. 2006).
Polysaccharides, namely sodium alginate and chitosan were used to form a lami-
nate made of five layers through layer by layer deposition. The laminate coating was
made over aminolyzed/charged polyethylene terephthalate film with the objective
of improving the water vapour permeability and mechanical property. One of the
alginate layers had a thickness of 19.55 nm. The water vapour permeability of the
laminated film was (0.85 ± 0.04) × 10−11 g−1 s−1 Pa−1 and the hardness raised by
0.245 ± 0.06 GPa (Carneiro-da-Cunha et al. 2010). Polysaccharide nanolayers had
significantly contributed to improve the barrier properties of the nanolaminated
film. The general opinion is that polysaccharide and protein polymers form a coat-
ing that has good gas barrier property but poor water barrier ability. On the other
hand, lipids being hydrophilic are good moisture barriers but lack the necessary gas
barrier capability (Weiss et al. 2006).
Lipids can also be used as nano coatings. In a study lipid nanolayer was formed
over a hydrophilic film made up of starch. Sunflower oil could be coated over the
starch film due to favourable interfacial interactions. In nanolaminated films it was
found that permeation phenomenon is reduced and that coefficient of water diffu-
sion had dropped down considerably for the oil laminated film when compared with
the corresponding starch film (Slavutsky and Bertuzzi 2015).
Immobilisation of antimicrobial on food contact surface is another approach that
nanoscience takes for improved safety of food. Nanoemulsion based edible coatings
were prepared using lemon grass oil as a preservative and compared with the edible
coatings prepared from conventional emulsion on fresh-cut Fuji apples.
Nanoemulsion based coating performed better coating at a concentration of 0.1 %
lemongrass oil. It inhibited the natural microflora and slowed the proliferation of
psychrophilic bacteria for a storage period of 2 weeks (Salvia-Trujillo et al. 2015).
A 15 layer film was fabricated using edible protein hen egg white lysozyme and
poly (L-glutamic acid) by layer by layer deposition. Thickness per layer in the study
was 1–10 nm. The model organism Microccocus luteus in the ambient liquid
medium was inhibited by lysozyme immobilized in the laminate (Rudra et al. 2006).
Biopolymer- based mats were fabricated using electrospinning technique that con-
sists of nano-fibres with unique functions. In food sector, they could be manipulated
for preparing transparent barriers and active packaging of preservatives (Torres-
Giner 2011). On a template of nanofibrous mats, lysozyme-pectin bilayers were
coated and antimicrobial ability was tested (Zhang et al. 2015). Inhibition against
Escherichia coli and Staphylococcus aureus were observed by the immobilization
of lysozyme and gold nanoparticles. The strong attractive interaction between nega-
tively charged gold nanoparticles and positively charged lysozyme favoured their
layer by layer assembly on negatively charged cellulose nanofiber mat (Zhou et al.
2014). Cinnamaldehyde formed into nano-liposomes by using polydiacetylene-N-
hydroxysuccinimide bilayers were immobilized on glass surfaces. The study
showed evidence of antimicrobial activity of immobilized cinnamaldehyde against
Escherichia coli W1485 and Bacillus cereus ATCC 14579 (Makwana et al. 2014).
7.3.2.3 Nano-biotracers
Food safety issues of the recent days have led to increased tracing methods along
the food supply and distribution channel. Food traceability is necessary edible sub-
stances like for grains and processed food (Ceruti et al. 2006). Food product may
move a long and complex path from farm to customers. When such is the case, food
traceability ensures that the product is identified with respect to origin and quality.
Such an identification system creates trust in customers. Traceability also ensures
that the producers take their responsibility seriously (Ceruti et al. 2006). Barcodes
and radio-frequency identification are the popularly used identification tags. The
radio-frequency identification tags were found to be not very economical (Véronneau
and Roy 2009), while the bar codes suffer the possibility of being erased off leading
to non-readability. Nanotechnology opens new gates in product identification and
tracking by putting forth the technology of nanobarcodes.
Machine-readable sub-micron sized tags called nanobarcodes have been devel-
oped for use as identification devices in many applications including tracing food
along the supply chain. These ID devices are durable and must be encoded to use.
The structure of nanobarcode is mostly a cylinder with length 0.04–15 mm long and
the diameter between 20 and 500 nm. Nanobarcodes are made by electroplating
inert metals like gold, silver, platinum and nickel over templates of pre-defined size
and the formed nano-rods are released into suspension from templates (Warad and
Dutta 2005).
Nanobarcodes made up of different segments were fabricated. A magnetic and
non-magnetic segment over a single nanowire will allow both magnetic and optical
responses to be produced by the barcode, thus improving the detection capability.
The template used to manufacture the nanobarcode was anodised aluminium oxide
membrane as this membrane has nano-channels. Two segments of the barcode, one
of CoFe (an alloy) and the other segment of Au were fabricated on a single barcode
using one-bath pulsed electro-deposition. Electron microscopic images of the so
formed nanobarcodes exhibited well-differentiated interfaces between segments
(Yoon et al. 2012).
Along with appropriate detection and storage devices, nanosensors can be used
as a quality assurance technique by tracking the food microbes, heavy metals and
harmful chemicals. For assurance of safe produce, the sensors can help by detect-
ing, capturing and recording process and storage condition along the path of pro-
cessed food. Even low-cost nanosensors can be inserted into every package to
monitor quality up to consumption during long shipments especially in cases of
highly perishable food commodities, for example, prevention of temperature abuse
(Neethirajan and Jayas 2011). Nanosensors in food are basically miniature biosen-
sors. A biosensor consists of a biological recognition component, referred to as
bioreceptor. This bioreceptor is linked to a transducer. The receptor conceives the
analyte of interest and forms electronic signal, enabling the measurement of the
analyte of interest (Viswanathan and Radecki 2008). Nanosensors have been studied
for various sensing applications including detection of microbes, toxins, pesticides,
volatile compounds and gases like oxygen and carbon dioxide.
Microbial detection is generally done by plating techniques and only these are
considered reliable E. coli was detected by a sensor that used streptavidin-coated
ferrofluid (Fe3O4) nanoparticles to amplify the feeble frequency change produced in
the probe while detection. The probe had a single-stranded DNA (ssDNA) as recep-
tor connected to transducer. The signal obtained had a quantitative relation with the
E. coli concentration. The improved sensitivity was associated with large mass of
nanoparticles compared with DNA targets (Valdés et al. 2009).
Hexanal is a volatile compound that indicates oxidation in food. A novel method
to detect even minute concentrations of hexanal was devised which was olfactory-
nanovesicle-fused carbon nanotube-transistor biosensor. It was meant to mimic the
canine olfactory senses to detect hexanal precisely without confusing with similar
volatile compounds like heptanal, octanal and pentanal. Its construction was done
by mounting receptor on carbon nanotube channel, in which conductance change
was produced when hexanal contacted the receptor. Concentration as low as 1 fm
was detected by this sensor (Park et al. 2012).
Pesticide detection is achieved by nanosensors meant for organophosphorus pes-
ticides by the use of up conversion nanoparticles and gold nanoparticles. Very low
levels up to 0.67, 23 and 67 ng/L were achieved for organophosphorus pesticides-
parathion-methyl, monocrotophos and dimethoate, respectively (Long et al. 2015).
The up conversion nanoparticles are a new range of fluorescent nanomaterials that
work by converting infrared radiations to visible light (Wang et al. 2011). Several
researches have attempted to make nanosensors for oxygen detection as well.
Gas detection is possible by measuring resistivity changes of carbon nanotubes
in response to the adsorption of gas molecules on them. Carbon nanotubes consist
of a single layer of cylindrical graphene sheet. Since every atom of a graphene sheet
is a surface atom, detection of least levels of gas becomes theoretically possible
(Vanderroost et al. 2014). Carbon nanotube was made to transfer charge due to the
adsorption of NH3 and it was found to be influenced by environmental oxygen (Peng
et al. 2009). Several detectors based on carbon nanotubes were attempted to prepare
for identification of trace levels of SO2, H2, H2S, O2, CO2, SO2 and other organic
compounds (Kauffman and Star 2008). Hindrances from contaminants during
detection of a specific gas is an issue to be addressed (Vanderroost et al. 2014).
Electro-catalytic activity of cobalt nitroprusside nanoparticles had improved even in a
matrix consisting of interfering organic and inorganic, ions and acids when prepared
by drop by drop method. This electrochemical behavior helped the quantification of
sulphite in water and food at trace levels (Devaramani and Malingappa 2012).
7.4 Nanotechnology in Agriculture and Food Industry
The public perception of food derived from nanotechnology is similar to that of GM

foods as the consumer needs to be explained clearly the advantages of opting nano-
technology engineered foods. A survey was done to record the view of public
whether they would opt a food (tomatoes) protected by a nanostructured packaging
material or a food which itself is nano-engineered (bread fortified with nanocap-
sules of omega-3 fatty acids). The survey suggested that public would opt for a food
wrapped in nanostructured packaging material rather that of nano-engineered food
(Sozer and Kokini 2009).
Extracellular secretions of Aspergillus fumigatus TFR-8 were used in the pro-
duction of ZnO nanoparticles (Fig. 7.6). Effect of these biologically transformed
ZnO nanoparticles on clusterbean (Cyamopsis tetragonoloba L.) was investigated
to increase the amount of native phosphorous mobilizing enzymes. It also enhanced
the gum content in beans by 7.5 % indicating that ZnO nanoparticles can be used in
industrial and medical applications along with agricultural sector A significant
increase in the root and shoot length was found i.e. 66.3 % and 31.5 % respectively
(Raliya and Tarafdar 2013).
Researchers indicate the possible hazards that can occur when the nanoscale
materials will interfere with the environment. Literature survey reveals the possible
risks associated with the exposure of engineered nanomaterials to the environment
as well as their reaction in human digestive tracts (Chen et al. 2014b). Researcher’s
main goal is to understand the behaviour of these nanomaterials and do detailed risk
assessment related to them so that on can distinguish between the engineered nano-
materials and its background particles and investigate the level of toxicity due to
these products. Debate is on among researchers to make these engineered nanoma-
terials sustainable and safe (Koelmans et al. 2015).
Future prospects include study of models for the prediction of the interactional
effects of engineered nanomaterials with living cells and tissues (Oksel et al. 2015).
The use of nanomaterials in agriculture is reviewed. Its effect on the plants and the
produce from it is investigated. A research conducted in this aspect showed that
when sand was mixed with silver nanoparticles and wheat plants were grown on it,
Fig. 7.6 TEM image of

ZnO nanoparticles
the result was found to decrease in the growth of shoots and roots with respect to
given dose (Dimkpa et al. 2013).
MgO nanoparticles (Fig. 7.7) synthesized from Aspergillus flavus, strain TFR-12
was used to study its effect on the chlorophyll content present in the leaves of
Clusterbean (Cyamopsis tetragonoloba L.). A detailed study of reports suggested
significant improvement in growth of shoot-root length (18.2–49.2 %). MgO
nanoparticles were found to be phenomenal for the enhancement of chlorophyll
photosynthetic pigment by 76.1 % at a concentration of 15MgL−1 (Raliya et al.
2014). The combined effect of Cu-chitosan nanoparticles (Fig. 7.8) on the growth
Fig. 7.7 TEM image of MgO nanoparticles
Fig. 7.8 TEM images of Cu-chitosan complexes

Fig. 7.9 TEM images of TiO2 nanoparticles
promotion and anti-fungal efficacy of tomato was studied and it was found to
enhance various factors such as seed germination and seedling length and exhibited
significant antifungal property (Saharan et al. 2015).
Biosynthesized TiO2 nanoparticles (Fig. 7.9) was found to have many benefits
such as procured at low cost and is eco-friendly in nature, as it is produced from
Aspergillus flavus TFR 7. Influence of characterized TiO2 nanoparticles on mung
bean was investigated and it was found that it increased the shoot length and root
length by 17.02 % and 49.6 % respectively (Raliya et al. 2015). Concept of green
nanotechnology should be implemented for controlling the treatment and risk asso-
ciated with nano-engineered products and can lead to sustainable development
(Bergeson 2013).
7.5 Regulatory Aspects
Regulations for nanotechnology are widely framed in many countries (Takeuchi

et al. 2014; Jain et al. 2016). Regulation on Registration, Evaluation, Authorisation
and Restriction of Chemicals in the European Union is the main regulation body
that covers nanotech-derived materials (Parliament and Union 2006). European
commission has recognized nanotechnology as one among its major six key enabling
technologies that significantly contribute for development of industrial sectors
(Parisi et al. 2014). Discussions on the definition regarding the size range of
nanoparticles in between 1 and 100 nm is being reviewed (Rauscher et al. 2012).
There are wide ranges of nanotechnology produced food products which are avail-
able in global market but are not confining to safety testing standards. Thus, there is
a dire need of toxicological research and risk assessment in food sector. Current
toxicity testing standards which are approved for conventional foods can be used as
a base regulation for drafting the toxicity testing of nanotech-derived food products.
However modifications are required to be done as greater difference occurs between
conventionally produced materials and nanomaterials (Cushen et al. 2012). US has
the largest nano products in the global market when compared to Europe and East
Asia (Chau et al. 2007). Currently, the negative impacts of nanotech-derived food
products on public health is unclear and thus proactive measures are taken to dictate
precautionary terms so as to limit the toxicity of nanomaterials. In order to fill the
knowledge gap, more research studies supporting the safety of nano-derived foods
are yet to be proved and a through risk and benefit analysis is the needed for proac-
tively avoid upcoming unpredicted health hazard. In another study it is observed
that public opinion about nanotechnology and its derived products is not negative if
they are clearly explained regarding the benefits of opting them (Parisi et al. 2014).
7.6 Toxicological Effects of Nanomaterials
As nanomaterials have a high surface area they are presumed to have large toxic
effects when compared to bulk materials, although no evidence has been recorded
as such regarding the potential negative impacts of using of nanomaterials in food
packaging. A detailed research on the effect of nano-engineered food on the micro-
bial flora of mouth and gut is required to know the risk associated with it and update
the current regulations (Sozer and Kokini 2009). Food products containing engi-
neered nanoparticles are launched into the global market, yet the consumers are
completely unaware of their properties and behaviour (Chen et al. 2006). In spite of
lacking strong regulations to vigil the production and risk assessment of these nano-
materials, notable food products containing additives of nanoscale are being circu-
lated in the global market namely iron, phytochemicals and zinc oxide in the case of
nutritional drinks, oils and breakfast cereals, respectively (Sozer and Kokini 2009).
A recent survey states that nanotech foods are applied almost in all food application
fields and draws more attention for having a regular check of toxicology. Even
though health benefits are claimed for nano-engineered foods, little attention has
been paid to acknowledge the risk assessment due to toxicity and potential threats
of nanomaterials (Bouwmeester et al. 2009). In case of agricultural sector, the nano-
engineered fertilizers and pesticides are presumed to post health risk to small farm-
ers (Dasgupta et al. 2015).
Even though US Food and Drug Administration legislates the manufacturers to
declare their product to be free from harmful additives, this does not specifically
cover nanoparticles which draw thought of safety of nano engineered foods (Sozer
and Kokini 2009). Knowledge on the physicochemical properties of nanoparticles is
a prerequisite to know the toxicity caused by it, as variation in toxicity between
particulate and nanoscale materials has been witnessed. There is need for the regu-
latory bodies to dictate strict terms and regulations to the manufactures of nano
engineered foods. As a result the foods claiming false allegations of being “Nanotech
foods” will be minimized in market. Instruments and human intervention is required
for verification and validation of nano-products (Bouwmeester et al. 2009).
7.7 Conclusion
There is an unlimited number of applications of nanotechnology in processing and

packaging of foods. Nanotechnology has already entered the packaging world with
improved physical and mechanical functionality; however use of nanotechnology in
active packaging and tracking is being researched actively. Nanotechnology has a
greater potential in food processing in terms of using nano-structured ingredients as
delivery systems for improved delivery of nutrients or antimicrobials to create a new
generation of health foods with better retention of key nutrients and natural flavours
with added safety against food pathogens. Significant research is already in progress
toward improved processing and packaging of food by the discovery of new nano-
structures with novel functionalities. Lastly, nanotechnology has also shown prom-
ising applications in delivering novel methods of real-time food quality and safety
indicators for improved consumer confidence. Needless to say that nanotechnology
will soon be encompassing all aspects of the food manufacturing industry.
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Chapter 8
Nanomaterials for Soil Fertilisation
and Contaminant Removal
Mrudula Pulimi and Sangeetha Subramanian
Abstract Expanding population and increasing consumption is inducing higher

pressure on agricultural resources and food production. Agriculture depends to a
large extent on the quality of soil and water resource availability. Soils should ensure
water retention, provide sufficient nutrients and not contain any contaminants.
However, anthropogenic and natural factors are responsible for the deterioration of
soil quality in the form of erosion, loss of water retention capacity and nutrients, and
contamination. Large scale use of agrochemicals in the form of fertilisers and pes-
ticides has given rise to increase in the levels of contaminants in soil and ground
water. Here we review the application of nanomaterials to improve nutrient quality
and to remove soil contaminants. Nanomaterials such as nanoclays, nanozeolites
and nanominerals have been used to enhance water retention and as nutrient carri-
ers. These nanomaterials promoted seed germination, plant growth, phosphorus and
nitrogen fixation, versus conventional methods. Nanoparticles have also been used
for remediating soils contaminated by herbicides, pesticides, organic pollutants and
heavy metals. Conventional soil remediation methods such as phytoremediation,
thermal treatment and electrokinetic degradation, have been improved using
nanoparticles.
Keywords Nanoremediation • Contamination remediation • Soil quality •

Sustainable agriculture
M. Pulimi (*)
Centre for Nanobiotechnology, VIT University, Vellore 632014, Tamilnadu, India
S. Subramanian
School of Bio Sciences and Technology, VIT University, Vellore 632014, Tamilnadu, India

230 M. Pulimi and S. Subramanian
8.1 Introduction
Material with particle size of nanometer ranging between 1 and 100 are considered
as nanoparticles and any technology that deals on nanoscale means nanotechnology.
The growth of nanotechnology has considerably inflated its application of nanoma-
terial in different area (Khot et al. 2012). Different engineered carbon based
nanomaterial (single and multi-walled carbon nanotubes), metal (quantum dots,
nanogold, nanosilver) and metal oxide (titanium oxide, zinc oxide and cesium oxide)
based nanomaterial, nano sized polymer material called dendrimers and nano com-
posites material are built for different functional properties. The major advantages of
nanomaterial over bulk material include decrease in melting point and surface area,
increase in dielectric constant and mechanical strength (Nagi et al. 2012; Maddineni
et al. 2015; Dasgupta et al. 2016a, b; Ranjan et al. 2016). In addition, size of
nanoparticles enables them to absorb exceptionally on to other material (Nagi et al.
2012; Dasgupta et al. 2015; Ranjan et al. 2014, 2015, 2016). Because of all these
unique behaviour and properties, nanoparticles have wider application in textiles,
clothing, and cosmetics, pharmaceutical, electronic and paint industry. Also they are
widely used for development of health care products and remediation of contami-
nated environment. In addition to its wider application in major industries, nanoma-
terials are also applied for the prospects of agriculture in several ways (Jain et al.
2016; Baruah and Dutta 2009; Handford et al. 2014; Sastry et al. 2010; Taghiyari
et al. 2015; Dasgupta et al. 2016c). Figure 8.1 represents some of the applications of
nanomaterials in different fields.
Fig. 8.1 Applications of nanomaterials in various fields

8 Nanomaterials for Soil Fertilisation and Contaminant Removal 231
Escalation of human population has led to decrease in productive land to less

than 11 % of total earth area (Mermut and Eswaran 2012). With limited availability
of resources, development in agriculture has to be attained by increasing the fertility
of a soil. Although conventional soil management methods are available,
nanotechnology is reported by many researchers currently as an alternate technol-
ogy for sustainable soil management. Fertility and quality of the agricultural soils
primarily depends on quality and quantity of water available, micro and macro
nutrients present in the soil. The depletion of nutrient quality in soil is predomi-
nantly caused due to man-made or natural soil erosion and accumulation of toxic
pollutant in the soil. This paper reviews on application of different nanomaterials for
improvement and remediation of soil.
8.2 Soil Amendments
Soil amendments are materials used to improve the physical properties of soil such
as water retention capacity, nutrient availability, structure, drainage in order to pro-
duce better crop yields. Several soil amendments have been in use historically as
fertilizers and soil conditioners. The purpose of fertilizers is to provide adequate
nutrients for plant growth. Whereas, soil conditioners have minimum nutrient con-
centration but are added to enhance the biological, physical or chemical nature of
soils. The indiscriminate and ineffective use of soil amendments can lead wastage
of nutrients, hence nanotechnology was proposed to enhance the effective use of
nutrients. The application of nanotechnology for agriculture includes (i) nanomate-
rials as enablers for delivery of agrochemicals (ii) sensors to monitor plant stress
and soil conditions and (iii) improvement of plant traits against environmental stress
and plant diseases. In this review, we will discuss about nanoparticles which are
specifically used as nanofertilizer or as carriers for fertilizers. A summary of various
types of nanomaterials used as soil amendments is given in Table 8.1.
8.2.1 Nanoclays
Clays are an integral part of soil mainly consisting of phyllo-silicate minerals with
varying water retention capacities. Clays offer high surface area and have a net
negative charge which helps clays in retaining plant nutrients and act as a pH buffer
in soil. Clays lose their plasticity and become brittle when the water content is
reduced. Nanoclays are generally prepared from the smectite group of clays which
includes montmorillinate. Nanoclays have been extensively used in preparing poly-
mer nanocomposites which have been applied in paints, cosmetics, drug delivery
and water treatment. Nano-clay polymer composites have also been used as nutrient
carriers for enhancing plant growth and for enhancing the water retention capacity
of soils.
Table 8.1 Nanomaterials used as soil amendments

Type of nanomaterial Purpose Reference
Polymer nanoclays Slow release of Sarkar et al (2013, 2014,
nitrogen and 2015)
phosphorus
Poly(acrylamide-co-acrylic acid)/AlZnFe2O4 Water retention Shahid et al. (2012)
superabsorbent hydrogel nanocomposite
Acid phosphatase immobilized on nanoclays Phosphorus Calabi-Floody et al.
mineralization (2012)
Phytase immobilized on nanoclays Phosphorous Menezes-Blackburn et al.
mineralization (2014)
Nanoporous zeolite Nitrogen release Manikandan and
Subramanian (2014)
Nanocomposite PAAm/methyl Carrier for urea Bortolin et al. (2013)
cellulose/montmorillonite hydrogel
Nanozeolite based urea Nitrogen release Thirunavakkarasu and
Subramanian (2014)
Aminopropyltrimethoxysilane-zeolite Nitrogen release Hidayat et al. (2015)
based urea
Carbon nanoparticles Water retention Saxena et al. (2014)
Magnetite (Fe3O4) Growth of ocimum Elfeky et al. (2013)
basilicum
Hydroxyapatite Growth of chickpea Bala et al. (2014)
Nano hydroxyapatite P fertilizer Montolvo et al. (2015)
Nano-hydroxyapatite To resist Cd stress Li and Huang (2014)
in Cd contaminated
soils
Urea-modified hydroxyapatite Slow release N Kottegoda et al. (2011)
nanoparticles encapsulated wood fertilizer
Nanosilica Nutrient Karunakaran et al. (2013)
Nano silica Silica availability Rangaraj et al. (2014)
and biomass
content of soil
Nano silica Silica fertilizer Suriyaprabha et al. (2012)
Mesoporous silica nanoparticles with urea Urea Wanyika et al. (2012)
Nano Zn Growth of pearl Tarafdar et al. (2014)
millet
Zn encapsulated in Mn core shell Zinc Yuvaraj and Subramanian
(2014)
ZnO nanoparticles Zinc and Watts-Williams et al.
phosphorus uptake (2014)
Nano iron, phosphorus and potassium Fertilizer for saffron Amirnia et al. (2014)
flowering
Nitrogen fertilizer and nanocarbon Nitrogen use in Fan et al. (2012)
saline-alkaline soils
Nano TiO2 Phosphorus uptake Hanif et al. (2015)
NanoN2 chelate; sulfur coated N2 chelate Nitrogen release Zareabyaneh and
Bayatvarkeshi (2015)
A series of nanoclay-polymer composite nutrient carriers were prepared by the

reaction of different types of clays such as kaolinite, mica and montmorillonite with
partially neutralized acrylic acid and acryl amide with N,N-methylene bisacryl-
amide as a crosslinker and ammonium persulfate as an initiator. Six different types
of nanoclays were used with different types of clays with and without amorphous
aluminosilicate. Among the different nano-polymer composites, the percentage
release of nutrients at 48 h ranged from around 70 % in the polymer/clay (montmo-
rillonite) composite to 90 % in the polymer/clay (kaolinite) composite proving that
these nanoclays can be utilised for slow release of nutrients. Further the nanopoly-
mer composites were loaded separately with di-ammonium phosphate and urea
solution. Release of phosphorous and total mineral nitrogen from the polymer com-
posites loaded with diammonium phosphate and urea, respectively, were compared
with corresponding conventional fertilizer. Release of Phosphorous and Nitrogen
were studied independently with a factorial experiment under four types of fertilizer
in combination with three types of soils alfisol, inceptisol and vertisol. Cumulative
Phosphorus and total mineral Nitrogen recovery significantly increased over con-
ventional fertilizer. The increase in recovery was +88.3 % and +27.3 % for phospho-
rous and nitrogen respectively with nanomontmoillonite. Higher Recoveries were a
result of slow release property of nanopolymers which reduced nutrient losses
(Sarkar et al. 2014, 2015).
Nano-sized AlZnFe2O4/poly (Acrylamide-co-acrylic acid) superabsorbent nano-
composite was synthesized and the effects of different levels of nanocomposite
were studied to evaluate the moisture retention properties of sandy loam soil. The
soil amendment with 0.1, 0.2, 0.3 and 0.4 w/w% of nanocomposite enhanced the
moisture retention significantly at field capacity compared to the untreated soil.
Seed germination and seedling growth of wheat was found to be notably improved
with the application of the nanocomposite. A delay in wilting of seedlings by 5–8
days was observed for nanocomposite-amended soil, thereby improving wheat
plant growth and establishment (Shahid et al. 2012).
8.2.2 Nanominerals
Natural zeolites are hydrated aluminosilicates based on an infinite three-dimensional

structure of tetrahedrons such as SiO4, AlO4, FeO4 joined by oxygen atoms. Zeolites
consist of interconnected channels and cavities of molecular dimensions where cat-
ions allowing the ion exchange exist. Zeolite materials allow an introduction of new
functional groups through several processes of modification, improving substan-
tially its activity and selectivity on the removal several substances (Inglezakis et al.
2002). Sulphate loaded nano zeolites were prepared and its activity was analysed in
a percolation reactor (Thirunavakkarasu and Subramanian 2014). Sulphate release
from fertilizer-loaded nanozeolite was available even after 912 h of continuous per-
colation, whereas sulphate from Ammonium sulphate was exhausted within 384 h.
The effectiveness of micro and nanoporous zeolite as a carrier for urea for slow
release of nitrate was investigated by Manikandan and Subramanian (2014). Results
revealed that the nitrogen release from the urea blended with nanozeolite (1:1) was
up to 48 days while the conventional Zeolite – urea (1:1) mix was up to 34 day and
the Nitrogen release ceased to exist in urea within 4 days without the presence of
Zeolites.
Growth of Maize on sandy loam soil with and without the presence of porous
silica nanoparticles was studied by Suriyaprabha et al. (2012).The increased surface
area of silica nanoparticles led to accumulation of nanosilica in the plants and also
increased the leaf size thereby leading to larger surface area for photosynthesis.
Similarly, the effect of nano Si on growth characteristics of tomato was studied
under salinity levels and has delivered promising results in salt tolerance (Haghighi
et al. 2012). Using mesoporous silica as carrier for urea for slow release of nitrogen
resulted in a fivefold increase in the availability period (Wanyika et al. 2012).
The supplement of the nanoscale hydroxyapatite was found to increase the level
of chlorophyll and vitamin C and decrease the level of malondialdehyde in pakchoi
plant shoots grown on Cd contaminated soil. The level of antioxidant enzymatic
activity in the plant also increased as result of the addition of hydroxyapatite. The
results confirmed that nanohydroxyapatite can be applied to reduce the plant uptake
of Cd and resist the Cd stress (Li and Wu 2013). Nanohydroxyapatite was evaluated
as a potential fertilizer to improve phosphorous availability in comparison with bulk
hydroxyapatite and triplesuperphosphate for the growth of wheat (Montalvo et al.
2015). Although nanohydroxyapatite performed better than bulk hydroxyapatite,
most likely because of faster dissolution, triplesuperphosphate was still a more effi-
cient phosphorous fertilizer.
8.2.3 Metal and Metal Oxide Nanoparticles
Metal and Metal oxide nanoparticles such as Zinc, Iron, Titanium and their oxides
have shown potential in promoting plant growth. Biosynthesized protein encapsu-
lated, crystalline natured nano Zn (15–25 nm) was evaluated as a nanofertilizer for
enhancing the growth of pearl millet. Beneficial effects were observed on shoot and
root lengths, chlorophyll content leading to a grain yield of 37.7 % over the control
without nano Zn (Tarafdar et al. 2014). Release of Zn to the soil using a nano-sized
manganese hollow core shell was evaluated in a percolation reactor system. The
results showed that the Zn-fortified core shell released Zn for more than 696 h while
Zn release ceased after 408 h in ZnSO4-fertilized soil (Yuvaraj and Subramanian
2014).
Beneficial effect of individual nano Fe, P and K on saffron flowering was anal-
ysed by Amirnia et al. (2014). Results indicated that nanofertilizers were effective
in enhancing the flowering traits of saffron plant. Magnetite (Fe3O4) nanoparticles
were synthesized and applied as foliar spray and soil additive to basil plant.
Nanoparticles applied were effective in increasing all the measured traits such as
chlorophyll content, carbohydrate content, oil content shoot/root length etc. for both
foliar spray and soil additive methods (Elfeky et al. 2013).
8.3 Soil Remediants
Anthropogenic activities have led to soil contamination is various parts of the world.
Mining, agriculture, Industries, waste disposal are some of the factors which lead to
soil pollution. An estimated 3,000,000 potentially contaminated sites are present
globally which not only pose risk to human health, ecosystem but also pose a huge
economic loss (Singh and Naidu 2012). Common contaminants include petroleum
hydrocarbons, chlorinated solvents, persistent organic pollutants, pesticides, inor-
ganics, heavy metals and radioactive constituents (Naidu 2013). Soil remediation
methods are well established and have been in use for decades. Remediation tech-
nologies could be exsitu or insitu. Table 8.2 gives a summary of the remediation
technologies available and the contaminant classes treated.
Nanomaterials with their enhanced reactivity towards contaminants and better
mobility could be a potential choice for remediating soils. The application of nano-
materials for mitigating soil pollution includes degradation of pollutants, detection
and sensing of pollutants, enhancers for remediation processes. Table 8.3 gives a
summary of the research work carried out for evaluating the role of nanoparticles
for soil remediation.
Table 8.2 Methods used for soil remediation and the contaminant classes
Method Contaminant classes
Physical/chemical methods
Soil vapor extraction Halogenated and nonhalogenated organic compounds;
inorganics; radionuclides; explosives
Stabilization Halogenated and nonhalogenated organic compounds;
hydrocarbons; explosives; inorganics
Chemical oxidation/reduction Halogenated and nonhalogenated organic compounds;
hydrocarbons; explosives; inorganics; radionuclides
Soil washing Halogenated and nonhalogenated organic compounds;
hydrocarbons; explosives; radionuclides
Electrokinetic seperation Halogenated and nonhalogenated organic compounds;
hydrocarbons; explosives; radionuclides; inorganics
Biological treatment
Bioremediation Organic compounds; inorganics; radionuclides
Bioventing Organic compound; explosives; radionuclides; inorganics
Phytoremediation Halogenated and nonhalogenated organic compound;
hydrocarbons; explosives; Radionuclides; inorganics
Thermal treatment Explosives; radionuclides; inorganics
Table 8.3 Nanoparticles used for soil remediation

Degradation/
Nanoparticles Purpose treatment method Reference
Manganese Polyaromatics Transformation Acevedo et al. (2010)
peroxidase hydrocarbons
immobilized on
nanoclay
Apatite with Lead Immobilization Liu and Zhao (2013)
carboxy methyl
cellulose stabilizer
Apatite Atrazine Dechlorination Satapanajaru et al. (2008)
Hydroxyapatite Lead Immobilization Shaheen and Rinklebe
and reduce lead (2015)
accumulation in
plants
Hydroxyapatite Cadmium/lead Enhance Wang et al. (2014)
phytoremediation
Hydroxyapatite Cadmium, Adsorption Chen et al. (2010)
Zinc
Lead
Copper
Nanosilicone Lead Stabilization Liu et al. (2015)
Carbon black Copper/zinc Immobilization Wang et al. (2009)
Surface modified Copper/zinc Immobilization Cheng et al. (2014)
carbon black
Nano Ca/CaO Radioactive cesium Ball milling for Mallampati et al. (2012,
immobilization 2013)
Nano zero valent Triethylene Enhancing Martínez-Fernández
iron phytoremediation et al. (2014), (2015)
by immobilizing
triethylene
Chlorpyrifos Degradation Reddy et al. (2013)
Lead polychlorinated Gao and Zhou (2014)
biphenyls
Cr (VI) Electrokinetics and Shariatmadari et al.
PRB (2009)
DDT Degradation El-Temsah et al. (2013)
Pyrene Degradation Chang et al. (2007);
Chang and Kang (2009)
Degradation Alidokht et al. (2011)
Degradation Chrysochoou et al.
(2012)
Molinate Electrokinetic Gomes et al. (2014)
Trichloroethylen Permeable reactive Katsenovich and
barrier Miralles-Wilhelm (2009)
TiO2/CeO2 Cu Reduce Wang et al. (2015)
phytotoxicity
(continued)

Degradation/
Nanoparticles Purpose treatment method Reference
CMC stabilized Pentachlorophenil Electrokinetic Yuan et al. (2012)
nano Pd/Fe reduction
Nanomaghemite Cd, Cu, Pb Stabilization Michalkova et al. (2014)
and magnetite
CMC-Pd/nFeO HCH (pesticides) Degradation Singh et al. (2012, 2013)
Nano Ca/CaO Radioactive cesium Immobilization by Mallampati et al. (2015)
thermal treatment
Nanomaghemite Fe/Al/Mn Immobilization/ Vitkova et al. (2015)
phytostabilization
Fe/Ca/Cao Cesium Grinding Mallampati et al. (2015)
Pd/nFe Polychrorinatedbiphenyls Dechlorination Le et al. (2015)
Nano Ca/CaO Heavy metals Mallampati et al.
(2013a, b) and
Mallampati et al. (2014)
Polyurethene Phynethrene Soil washing Kim et al. (2003, 2004)
ZnO, Al Heavy metals Sorption Mahdavi et al. (2015)
TiO2 Pyrene Photocatalytic Chang et al. (2011)
Phenanthrene Photocatalytic Gu et al. (2012)
MnO2 Pyrene Photooxidation Chang et al. (2011a, b)
8.3.1 Nanomaterials for Contaminant Stabilization
Stabilization techniques effectively reduce the hazard potential of a contaminant by

converting it into less soluble, mobile or toxic forms. Stabilization could be done
either by physical methods or chemical reactions. The mobility of organic and inor-
ganic compounds can be reduced through various precipitation, complexation, and
adsorption reactions. The potential of Fe nano oxide (maghemite and magnetite)
and amorphous Mn oxides for stabilizing Cd, Cu and Pb in contaminated soils was
investigated by Michálková et al. (2014). Results from batch and column experi-
ments coupled with adsorption tests proved that the amorphous MnO was the most
effective treatment for the stabilization of metals in the studied soil samples at the
given w/w ratios (1 and 2 %, w/w). Metal stabilization was a result of combined
specific adsorption onto the oxide surface together with an increase in soil pH pro-
moting the adsorption of metallic cations. Nano TiO2 and CeO2 were utilized to
adsorb Cu(II) and mitigate its bioavailability and toxicity to Tobacco plants (Wang
et al. 2015a, b). The addition of the nanoparticles along with humic acid resulted in
increased the root length by 90 % and 100 % for nano TiO2 and nano CeO2 respec-
tively. The results indicated that nanoparticles were successful in reducing the
Cu(II) phytoxicity by reducing the bioavailable soluble Cu(II). The study also
reported no phytotooxicity by individual TiO2 and CeO2 nanoparticle which makes
their usage more amenable.
The effect of nano zero valent iron (nZVI) coated with carboxy methyl cellulose
on the degradation of DDT in soil columns was investigated by El-Temsah et al.
(2013). Addition of nZVI and subsequent leaching with water led to a reduction in
DDT concentrations in soil of almost 50 % compared to controls without
nZVI. However the use of nZVI resulted in negative effects on plant growth. It was
also observed that the oxidation of nZVI with aging reduces the negative effects of
the presence of nanoparticles. Le et al. (2015) developed an integrated remediation
system for dechlorination of aroclor 1248 using chemical catalysis and biodegrada-
tion. Dechlorination was achieved by treatment with bimetallic nanoparticles Pd/
nFe under anoxic conditions. Dechlorination efficiency was 99 %, 92 %, 84 %, and
28 % of tri-, tetra-, penta-, and hexachlorinated biphenyls, respectively. The resulting
biphenyl was found to be biodegraded rapidly by Burkholderia xenovorans LB400.
8.3.2 Nanomaterials in Thermal Treatment
Thermal treatments for soil remediation include incineration, steam injection and
extraction and vitrification. Vitrification is a high temperature process in which
organic matter is incinerated and mineral matter is melted and a slag is quickly
cooled to obtain the contaminant entrapped in a matrix. Nano Ca/Cao mixtures were
used to immobilized radionuclides 133 Cesium from contaminated soil through vitri-
fication. The removal efficiency achieved with the nanoparticles was 96 % at 1,200
°C. The investigation results have showed that a certain amount of 133Cs was the
entrapped inside new aggregates, produced during the thermal treatment with nCa/
CaO (Mallampati et al. 2015a, b).
Thermal desorption of polychlorinated biphenyls in the presence of nZVI was
evaluated by Liu et al. (2014). The presence of nZVI gave improved efficiency of
desorption at 300 °C. The desorption efficiency was dependent on nZVI concentra-
tion and temperature. Nano Zerovalent Iron was also used to enhance thermal
degradation of polychlorinated dibenzo-. p-dioxins and dibenzofurans at low
temperatures (Lundin et al. 2013).
8.3.3 Nanomaterials for Enhancing Phytoremediation
Phytoremediation is a low cost and effective insitu remediation method for contami-
nated soil reclamation. Phytoremediation involves uptake, containment, degrada-
tion of contaminants by plants. Several reports are available in literature evaluating
the effect of nanomaterials for enhancing phytoremediation Gao and Zhu 2014;
Wang et al. 2014, 2015) . The effect of nanosilicon on lead toxicity, uptake and
accumulation in rice varieties Yangdao 6 and Yu 44 grown on lead contaminated soil

was analysed by Liu et al. (2015). The biomass increased by 3.35–11.8 % higher
and lead concentration in shoots and grains was reduced by 27–54 % and 21–41 %
respectively by adding nanosilicone to lead contaminated soil. The results indicate
that nanosilicone was effective in preventing the lead transfer from rice roots to
aboveground parts by complexation with lead.
E-waste contaminated soil containing Pb and polychlorobiphenyls was remedi-
ated by phytoextraction using Impatiens balsamina in the presence of three different
nanozerovalent iron particles – free, vermiculite supported and activated carbon
supported zerovalent iron. Free and vermiculite supported nanozero valent iron
were found to increase accumulation of Pb in plants and activated carbon supported
nano zero valent iron reduced the bioavailability of Pb (Gao and Zhou 2013, 2014).
8.3.4 Nanomaterials for Electrokinetic Remediation
Electrokinetic remediation is an emerging technology which involves application of

a low-intensity, direct current through the soil to separate and extract contaminants
from soil. The current is applied across electrode pairs that have been implanted in
the ground on each side of the contaminated soil. During the process positively
charged chemical species, such as metals, ammonium ions, and some organic com-
pounds, move toward the cathode, and negatively charged chemicals, such as chlo-
ride, cyanide, fluoride, nitrate, and negatively-charged organic species, migrate
toward the anode. Various additives such as surfactants can be added to enhance the
remediation process. The combined effect of nanozerovalent iron and electrodialy-
sis of polychlorinated biphenyls (PCB) was evaluated by Gomes et al. (2014a, b).
H+ generated near the anode in electrodialytic chamber solubilized the transition
metal from soils which in turn aided in dechlorination of PCB to biphenyl com-
pound (Gomes et al. 2014a, b). Yang and Chang (2011) evaluated the treatment
efficiency of combining emulsified nano zerovalent iron and electrokinetic remedia-
tion for Trichloroethylene (TCE) on contaminated soil. Electro kinetic remediation
enhanced transport of nanoparticles through the soil matrix from anode to cathode
chamber. During the transport, hydrophobic TCE diffuses into nano zerovalent iron
present in the inner aqueous region through emulsion and becomes dechlorinated.
8.4 Conclusion
Nanotechnology has the potential to provide solutions for better soil management
through improving nutrient quality of soil and alleviating soil pollution. Although
the efficacy of Nanomaterials as plant growth promoters and remediation agents has
been proved, knowledge of the fate and effect of nanomaterials in soil has to be
careful considered. Nanomaterials have been reportedly toxic to various organisms
Fig. 8.2 Application of nanomaterials for soil management
and also effect human health (Mukherjee et al. 2014; Zou et al. 2014; Smulders
et al. 2015). In this context, any new development involving the application of
nanoparticles directly into the environment has to take into consideration the fate,
transport and effect on the soil ecosystem, plant toxicity. Several researchers have
attempted to understand the fate and transport of nanoparticles (Anjum et al. 2015;
Sun et al. 2015) but many more investigations have to be carried out on the stability
of the various types of nanoparticles alone and in combination with various con-
taminants (Fig. 8.2).
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Chapter 9
Nanofertilisers, Nanopesticides
and Nanosensors in Agriculture
Hemraj Chhipa and Piyush Joshi
Abstract Nanotechnology has potentially promising applications to improve

agriculture. Here we review the application of nanofertilizers, nanopesticides and
nanosensors in agriculture. Nanofertilisers include Fe, Mn, Zn, Cu, Mo, Ti and carbon
nanotubes. Nanofertilisers improve plant growth and save money because they are
more efficient. Nanopesticides for plant protection include Ag, Cu, SiO2 and Zn.
Nanopesticides also save money because they are more efficient. Nanosensors are
useful in precision agriculture, for instance to detect pests and weeds locally in real
time, and thus to apply pesticides fast and locally. We also discuss toxicity and risk
assessment of nanoparticles.
Keywords Agriculture • Nanotechnology • Nanofertilizer • Nanopesticide • Pest

control • Nanotoxicity • Risk assessment
9.1 Introduction
Increasing global population is poignant on the yield of agricultural products and

demanding innovations in global food security for fulfillment of daily need (Mura
and Dudas 2013). The yield of agriculture is increasing, but the primary concern is
safely and sustainable production. Previously, many applied technologies has been
innovated in the agriculture sector for improvement of production such as, the usage
of synthetic chemicals, genetically modified crops by biotechnology and evolution
of pest resistant and hybrid varieties, but still a gap between the requirement and
contentment of agriculture production looking for new technology (Zamir 2001;
Zhu et al. 2000). The research and development give rise to several new technologi-
cal innovations and the recent public figure in the limelight is nanotechnology
(Mura and Dudas 2013; Appell and Jackson 2013; Handford et al. 2014).
Nanotechnology is a prominent technology in various fields such as electronic,
electrical, optical, sensing, food and medical (Rai and Ingle 2012; Sozer and Kokini
2009). These tiny particles have specific physical, optical, chemical and mechanical
H. Chhipa (*) • P. Joshi

The Energy and Resources Institute, IHC, Lodhi Road, New Delhi 110003, India

248 H. Chhipa and P. Joshi
characters which make them highly useful in comparative their bulk compounds.
In the nanometer size range they are well composed which provides high volume to
surface ratio for any application (Guo 2013).
Agriculture field is also looking towards this newly growing technology with
great hope for future sustainability. The use of nanotechnology in agriculture is in
the initial phase and need more research to provide a suitable solution for produc-
tion improvement in sustainable manner (Lyons et al. 2011). It is hypothesized that
nano-formulation/nanoparticles mediate delivery will provide site specific and con-
trolled release of agriculture inputs e.g. fertilizer and pesticide, which will reduce
the cost and the amount of agricultural input and make agriculture practices more
productive through water and nutrient management (Bhattacharyya et al. 2010;
Mukhopadhyay 2014). Reduction of chemical fertilizer and pesticide will be help-
ful in maintaining natural eco-balance of Geo-biological cycles, which have been
destroyed or imbalanced by the use of synthetic chemicals (Alexander 1973). The
continuous use of chemical in agriculture practices developed many disorders into
growers and feeders and destroyed soil and water health also, making them toxic for
the next generation. So the need of the time is to improve such drastic situation into
a sustainable state of implementation of nanotechnology.
The use of metal nanoparticles, polymer based nano-formulation and encapsula-
tion of fertilizers and pesticides is in nascent phase (Kashyap et al. 2015; Parisi et al.
2014). Many researchers have developed nano-formulation and encapsulation of
agriculture inputs and applied on different agriculture crops in vitro and in vivo
conditions. Kuzma et al. (2006) explained that nanotechnology can have different
applications in agri-food sector such as food packing in the food industry, detoxifi-
cation and nano-medication in animal husbandry, plant protection and fertilizer
application, plant genetic modification, pollutant and water remediation in the envi-
ronment and nano-sensing.
On the other side, as we know the negative impact of biotechnology in resistance
development or genetic manipulation, similarly nanotechnology also has some
adverse effect on biological and chemical environment (Sharma et al. 2004; Herdt
2006). So the environmental impact assessment is also necessary of nanotechnology
before adopting in agricultural practices.
In the current article we reviewed the use of nanotechnology tools e.g. nanofertil-
izer, nano pesticide, nano sensor and nano herbicide in agriculture and their effect
as growth promoters, nutrient supplement, pest controller and their environmental
impact assessment. The advantage of nanotechnology in comparison to conven-
tional farming practices is also summarized.
9.2 Need of Advancement in Agriculture
It had been centuries, since when the agricultural technology was continuously in
developing approaches and thus has created huge changes in farmers live and con-
tributed a lot in countries development, which can be clearly monitored through the
9 Nanofertilisers, Nanopesticides and Nanosensors in Agriculture 249
countries per capita income. The expansion of towns and cities in the urbanized
world has previously reinstate farmland with shopping malls, parking lots and hous-
ing developments. Thus, the needs of agriculture production uplifted and so increase
the monetary value of crops and agricultural food items. Moreover, the major
challenges faced by agricultural world include changing climate, sustainable use of
natural resources and environmental issues like runoff and accumulation of pesti-
cides and fertilizers. These troubles are further heightened by an alarm, increase in
food demand that will be needed to feed an estimated population of 6–9 billion by
2050 (Chen and Yada 2011). Besides, it is widely acknowledged that global agricul-
tural productivity must increase to feed a rapidly developing world population.
Today, there is increasing trend of Peri-urban agriculture and home gardening,
which is becoming very significant in the developing world as a consequence of
rapid urban growth. Therefore, new cultivar technology is required to fit into exhaus-
tive construction systems, which may supply the food compulsory to fulfill urban
world demands of the next century. The scientist is in the process to develop several
new technologies for plants that are tolerated to urban pollution, proficient nutrient
uptake and crop getting new substrates for growth. Also with the higher income,
these clients may demand a more diverse diet. Food crops with low fats and high in
specific amino acids may be needed to satisfy people who wish to change their
eating habits (Naseer et al. 2014).
In modern agricultural systems farmers believe they own much more fundamen-
tal roles and are eager to use technology and information to control most parts of the
agriculture system, a very different perspective from that of traditional farmers. In
contrast to the isolation inherent in traditional systems, modern agriculture tends to
ensure its success as dependent on linkages-access to resources, technology, man-
agement, investment, markets and supportive government policies.
As a result, much of the success of modern systems depends on the development
and maintenance of soil fertility through the specific provision of nutrients when
they are depleted, machine power and technology to make soil conditions to pro-
mote plant growth with minimal disturbance and minimal soil loss, the use of
improved genetics for crops and livestock to enhance yields, quality and reliability
and use of modern genetic and other techniques to protect plants and livestock from
losses to competing plants diseases, drought insects and other threats.
Further, this could only become possible by adopting the latest technologies like
biotechnology, which has been delivered specific agronomic trait development to
overcome production constraints for perhaps 12 million of the world’s farmers. This
has resulted in improved productivity and profitability and has made important posi-
tive socioeconomic and environmental contributions even though only a limited
range of agronomic traits have been commercialized so far for a small number of
crops. The technology has delivered economic and environmental gains through a
combination of their inherent technical advances and by facilitating the use of tech-
nology in more cost effective and environmentally friendly farming practices as
suggested by Motes (2010) in its pre-publication draft.
Likewise, there are several profound structural changes occurred in the agricul-
tural sector due to the fast development of technological innovations, but these also
pose challenges such as sustainable production considering food security, poverty

reduction and public health improvement. The agriculture and food production is of
vital importance, as it has been one of the primary drivers of economy. The agricul-
tural practices are often in the public eye because climate change, energy and
resource constraints and rapidly growing global population are placing extraordi-
nary pressure on food and water resources. By now scientific advances have touched
all the facets in the field of agriculture. Thus we can witness a radical makeover for
decades from handheld apparatus in the modern day Glass house/ Poly house,
computer-controlled and GPS-monitored programs that virtually negate the need
for human intervention. Moreover, attaining global food and nutrition security for
9.2 billion people by 2050 which means that food production will need to be
increased by 70 % from current levels in a sustainable way while the environmental
footprint of agriculture is reduced. Small field holder farmers in developing coun-
tries are expected to meet the food demand of emerging rural and urban regions.
This demand is likely to increase to almost 90 % of total food demand by 2050
(Ghasemzadeh 2012). Traditional strategies like integrated pest management used
in agriculture are insufficient nowadays and excess use of chemical pesticides like
DDT has adversative effects on animals and human beings apart from the decline in
soil fertility.
Consequently, If we talk about the current scenario in developing countries,
where agriculture is considered as the backbone of the national economy, the
countries are facing several serious issues such as lack of fertile agricultural soil,
reduction of land due to competing infrastructural development activities, poverty
and malnutrition, which need to be solved on a sustainable basis. The developing
countries advancement in science and technology can offer potential solutions for
discovering value addition in their current production systems. Therefore, these
countries should enthusiastically contribute in research and development of these
latest advance technologies, which have already greatly shown its impact on the
agriculture industry. For example, earlier the farmers improved their crop produc-
tion by inventing the first hoes, but today, they improve crop production through the
use of global positioning systems. Nowadays, agricultural technology is also making
inroads with the help of new but very promising fields of nanotechnology and
genetic engineering. In past several scientific innovations also have led to the way
of revolutionizing agriculture, which includes irrigation techniques, farm equip-
ment, fertilization, and plant breeding. One of the most revolutionary agricultural
innovations has been the development and use of biotechnology to increase crop
protection and yield. Today, farmers in more than 30 countries around the world are
planting seeds containing biotechnology traits. Seeds that utilize new breeding and
biotechnology advances have helped these growers increase yields, reduce inputs
and dramatically improve their profits (Fraley 2012).
Similarly, the results are expected from the flourishing applications of nanotech-
nology in agriculture, which will continue to rely on the problem-solving ability of
the material and are unlikely to adhere very rigidly to the upper limit of 100 nm.
This is because nanotechnology for agricultural applications will have to address
the large-scale inherent imperfections and complexities of farm production systems
(e.g. Use efficiency at extremely low input), that might require nanomaterials with
flexible dimensions, which nevertheless perform tasks efficiently in agricultural
production systems. This is in contrast with nanomaterials that might be working
well in well-knit factory-based production systems (Mukhopadhyay 2014). With
nano fertilizers emerging as alternatives to conventional fertilizers, build-up of
nutrients in soils and thereby eliminating the chances of eutrophication and con-
tamination of drinking water may be eliminated (DeRosa et al. 2010).
Moreover, the agricultural researchers and farmers worldwide will be facing the
challenge during the next 25 years of developing and applying technology that can
increase the global cereal yields by 50–75 %, and to do so in ways that are economi-
cally and environmentally sustainable is a great task.
Here the ray of hope lies in the application of nanotechnology in agriculture,
which is astonishing till date. Research on the applications of nanotechnology in
agriculture is less than a decade old. Nevertheless, as conventional farming practices
become increasingly inadequate, and needs tremendous improvement, we have little
option but to adopt and explore the latest technology such as nanotechnology in all
sectors of agriculture.
Nanotechnology promises a breakthrough in improving our presently appalling
nutrient use efficiency through nano-formulation of fertilizers, breaking yield and
nutritional quality barriers through bio-nanotechnology, surveillance and control of
pests and diseases, understanding the mechanism of host-parasite interactions at the
molecular scale, development of new-generation fertilizers and pesticides. Moreover
the nanotechnology applications in agriculture can be successful if natural pro-
cesses are simulated in greater scientific sophistication/articulation for successful
implementation.
9.3 Definition of Nanomaterial
The nano is defining the size of the matter in 10−9 m range. The Nanoparticles have
the dimension of particles in the range of 1–100 nm. In this range each particle has
specific mechanical, electrical and optical properties in comparison with their bulk
matter which could be possible due to surface area per unit weight or volume
increased enormously in the nano form. Due to their Surface Plasma Resonance
(SPR), Enhanced Rayleigh Scattering and Surface Enhanced Raman Scattering
(SERS) characteristics of nanoparticles have more advantage to bulk material and
these properties make them the building blocks of optoelectronics, electronics and
chemical and biochemical sensors of next generation (Gmucov 2012; Hahn et al.
2011; Gloskovskii et al. 2010).
Nanotechnology is viewed as “the next industrial revolution” by taking the
advantages of these properties in order to develop new products (Lane 2002; Miley
2005). Nanotechnology has been explored in different applications due to their
novel properties such as creating lighter and stronger material, ground water reme-
diation, in substitution of harmful toxic chemicals in various applications, solar cell
efficiency enhancement and as targeted drug delivery (Yan et al. 2012; Banik and
Sharma 2011; Appell and Jackson 2013; Nakache et al. 2000). In this century the
trend is toward miniaturization of the materials and nanotechnology is based on
nano scale material with specific functionalities. The functionalization of the
nanoparticles surface is one method for development of particle for specific applica-
tion. Different shaped nanoparticles have been synthesized using different materials
as spheres, nanotubes, nanohorns, nanoflowers and nanocages. The surface modifi-
ers such as molecules, particles and polymers have different task, such as described
by Guo (2013).
1. Stabilization of nanoparticles in solutions by controlling the growth at an embry-
onic stage and determine their shape
2. Provide functional groups on the surface
3. Increase solubility of nanoparticles in different solvents
4. Creating capping layer on the surface that modify physical and chemical proper-
ties of nanoparticle
5. Improve the assembling capacity of nanoparticles in specific array
6. Decrease the environmental toxicity of nanoparticles
The synthesis of nanomaterial for farming practices can be developed by top
down and bottom-up method of understanding of the nano-dynamics of interacting
nanomaterials and interfacing nanostructures. The synthesis of metallic nanoparti-
cles has different routes of synthesis such as physical, chemical and biological but
another type of nano-formulation using biopolymer, nano-capsulation and polymer-
metal nano-composite also in developing stage (Fig. 9.1).
Fig. 9.1 Synthesis of nanomaterial using different routes including physical, chemical and bio-
logical. Chemical is based on solid and wet chemical method while, physical is mainly based on
pyrolysis and attrition method and biological method is based on use of fungal, bacterial and plant
extracts in reduction of bulk metal compounds
Physical method includes attrition and pyrolysis, while chemical method includes
wet chemical and solid state interaction method. Physical and wet chemical meth-
ods are widely used in the synthesis of nanoparticles but these methods have some
disadvantages. These procedures use enormous consumption of energy in order to
maintain high pressure and temperature and uses of toxic solvents and generation of
hazardous bi- products in chemical methods. So, cost effective, non-toxic and envi-
ronmentally benign procedures for the synthesis of metallic nanoparticles are being
used in the form of biological approaches (Thakkar et al. 2010).
In biological synthesis metallic nanoparticle has been synthesized by different
species of bacteria such as Pseudomonas, Lactobacillus, Escherichia and
Thermomonospora, different fungal strains such as Aspergillus, Fusarium, Phoma,
Verticillium and different plant species as Alfa-Alfa, Aloe Vera, Azadirachta,
Solanum and Lemon grass and algal strains such as Sargassum, Chlorella.
Fungi are the main biological matter, among bacteria, algae, virus and plants in
the biosynthesis of nanoparticles due to their tolerance and bioaccumulation capac-
ity of metal (Shankar et al. 2003). The fungus produces different type of extracel-
lular enzymes, which is useful in large scale production of ecofriendly biomaterial,
which provides economic viability and easy handling of the synthesis process (Jain
et al. 2011).
9.4 Nanotechnology in Agriculture
Uncontrolled and longer time application of different conventional fertilizers would

be dangerous for the agriculture sector and will raise environmental issue near
future. It has been reported that heavy use of phosphorus and nitrogen fertilizer rais-
ing the eutrophication problem into surface water bodies world-wide (Conley et al.
2009), provide nutrition to phototrophic microorganism and help them into devel-
opments of algal bloom. Dubrovsky et al. (2010) reported that high use of manure
and nitrogen fertilizer in agriculture zone increased the nitrate content, more than
83 % of shallow ground water zones in US have higher level of nitrate salt than
maximum containment level (10 ppm) regulated by United state Environmental
protection Agency (USEPA) in the United State.
Similarly, Rosenstock et al. (2014) reported that high nitrogen loading or uncon-
trolled use of fertilizer in agriculture accumulating the residues longer and their
concentration increased rapidly in the ecosystem. In California nitrogen loading has
increased from 81 to 163 kilo tonne per year within four decades (1971–2010). It is
a serious concern about the continuous increasing residual concentration of fertil-
izer and pesticide in soil and water, which have crossed the limit and polluting
environment. The conventional fertilizers have only 30–50 % efficiency. So,
Researchers are looking for a sustainable solution to solve this critical condition,
which is increasing with the time.
Fig. 9.2 Application of

nanotechnology in
agriculture:
nanotechnology applies in
the form of nano-fertilizer,
nano-pesticide, nano-
herbicide and nano-sensor
for controlling nutrition,
pest detection and
management
Lal (2008) emphasized that nanotechnology could be a panacea for agriculture,

like other sectors of development of a nano form of agriculture inputs e.g. nano-
fertilizers and nano-pesticide, which have the greater capacity to provide site spe-
cific delivery of plant nutrients and improve the crop production in a sustainable
manner. Similarly, many agricultural experts (DeRosa et al. 2010; Nair et al. 2010;
Ghormade et al. 2011; Khot et al. 2012) interested in the development of nanotech-
nology based fertilizers. The output of nanoparticle application on plants at lab
scale experiments developed a white hope for agriculture sector.
It is expected that nanotechnology covert conventional farming practices into
precision farming practices. Chen and Yada (2011) concluded that “Precision farm-
ing is one of the most important techniques utilized for increasing crop productivity
by monitoring environmental variables and applying targeted action”. So there is
need to search a vital solution for sustainable agriculture development by innovat-
ing new agriculture inputs that provide high crop production, increase plant effi-
ciency to nutrient use and reduce environmental destruction.
The nanotechnology will provide nano-supplement fortified feed and antimicro-
bial agents for animal production and nano-biosensor for diagnostic and precision
farming practices. It would be possible that using nanotechnology, we can offer
required quantity of nutrients and pest control agent to crop to maintain eco-balance
and reduce excess runoff. In the form of nano-formulation, nano encapsulation and
functionalized nanoparticles, this new technology provides lots of new opportuni-
ties in the development of new fertilizers, pesticides, herbicides, insecticide and
sensor, which would have a capacity of controlled release and site specific delivery
(Fig. 9.2).
The advantage of nano-formulation increases the solubility of poorly active
ingredient by release of active ingredient in controlled manner and protection
against premature degradation (Kah et al. 2013). Similarly, more advancement has
been seen in pesticide sector, agrochemical companies also utilizing the advantage
of nanotechnology by the development of chemical emulsion at nano-scale or nano-
capsules contain active ingredients, which have the function of split open in response
of the insect’s alkaline condition or presence of heat and sunlight. Such advanced
functionality of nano-pesticide will improve the efficiency and reduce the chemical
dose and provide sustainable solutions for agro sector. Further, in the food sector,
nanotechnology has the capability to solve many problems of food supply system.
In the form of food polymers and polymer assemblage nanotechnology can contrib-
ute to the improvement of food safety and quality.
9.5 Use of Nano Tools in Sustainable Farming Practices
Nanotechnology is growing field of the current decade and it is widely applicable in

the field of electronics, medicine, energy, automobiles, cosmetics, construction,
food packing and paint industry. Likewise, agriculture is also touched by the use of
nanotechnology in the form of nano-pesticide, nano-herbicide, nano-fertilizer and
nano-sensor. The development of smart delivery system using nanomaterials has
been open up new modes of novel applications in bringing the sustainability of the
Agri-sector (Robinson and Morrison 2009; Joseph and Morrison 2006; Scott and
Chen 2013).
9.5.1 Nanoparticles as Smart Delivery Agent
Nanotechnology could play a great role in sustainable agriculture practices by

developing smart delivery system which is useful in environmental balance. Smart
delivery system can provide a natural interaction between soil, plant and microbial
communities of terrain. These advanced materials facilitate the nutrient manage-
ment and control the nutrient transport such as Zn2+, HPO42−, H2PO4− and NH4+ in
soil-plant system according demand.
Subsequently, nanoparticles are applying as smart delivery agent for fertilizers
and pesticides in agriculture sector. These agriculture inputs are used with poly-
mers, encapsulation or metal surface (ionic or weak bond) attachment. These smart
delivery agents improve the stability and reduced the amount of product needed to
be distributed. So excess chemical runoff can reduce and maintain the environmental
balance. The nano-formulation of 100–250 nm sized nanoparticles has been attract-
ing in agriculture by increasing the stability, ability to dissolve in water and increase
activity. Similarly, nano-emulsion of 200–400 nm sized nanoparticles with pesti-
cides and herbicide also attracting agriculture sector by enhancing their integration
properties in different distribution medium (Solanki et al. 2015; Liu and Lal 2015).
Further, nano-capsules are also an attractive tool of delivery in agriculture and the
pharmaceutical industry. Nano-capsules are organic polymer or micelles based
Table 9.1 Recent breakthroughs of nanotechnology in agriculture sector; different type of

products have been developed for agricultural applications by nanotechnology
S.No. Product Application
1. Agricultural waste Nano-fibers from cotton waste for improved strength of clothing
2. Buckyball fertilizer Ammonia from buckyballs
3. Food packing Airtight plastic packing with silica nanoparticle
4. Nanocides Nano-pesticide encapsulate in nanoparticle for controlled
release
Nano-emulsion for greater efficiency
5. Nano-sensor Pathogen detection, toxin detection, pesticide residue detection
6. Precision Framing Nano-sensor linked to soil condition and crop growth
Sastry et al. (2007)
nanostructure, which has the one lipophilic and other polar side. They contain the
active ingredient inside the shell and release in the response of physiological change
(Ali et al. 2011).
In contrast, such nanomaterials as zero valent iron or nanoparticle from iron rust
have been used for remediation of soil, contaminated by heavy metals and pesti-
cides. Iron nanomaterials also take part in soil aggregation and improve the soil
binding capacity.
In the form of nano-formulation, these nanomaterials improve the nutrient effi-
ciency of nano fertilizer by higher surface area. Similarly, nanomaterials are highly
applicable in surveillance and pest and disease control, understanding of host-
parasite interactions at the molecular level (Mukhopadhyay 2014). Some of the uses
of nanotechnology in agriculture are listed in Table 9.1.
For enhancement of global agriculture production, one of the nano technological
tools in the form of “nanofertilizer” is the potential tool which could helpful in ful-
fillment of the demand of a growing population by increasing the crop production.
According to Liu and Lal (2015) nano-fertilizers are nanomaterials (NMs) which
can supply one or more nutrients to the plants and enhance their growth and yields,
which facilitate the improvement in the performance of conventional fertilizers.
Primarily nano-fertilizers are divided into two categories based on plant nutrient
requirement.
9.5.1.1 Macronutrient Nanofertilizers
In this category different macronutrient are included such as Nitrogen (N),

Phosphorus (P), Potassium (K), Magnesium (Mg), Sulfur (S) and Calcium (Ca)
which are essential for plant growth. In the conventional farming practices those
macronutrients are heavily used on the farm and large amount of unused chemicals
transported into ground water and surface water bodies, which increasing the threat
to human health and aquatic life by disturbing the ecosystem balance. Therefore,
development and innovation of nanofertilizer in the field of macronutrient supply in
an ecofriendly and sustainable manner are much needed. Many researchers are
working on the development of environmental friendly nanomaterial which can
ensure the protection of environment and high crop yield. There are a few examples
for instance, Liu and Lal (2014) developed a Ca and P based nanoparticles in the
form of hydroxyapatite (Ca5 (PO4) 3OH) and applied on Glycine max (Soybean) in
greenhouse experiment and recorded 20 % and 33 % increment in seed yield and
growth rate in comparison of regular phosphorus fertilizer. Similarly, Liu et al.
(2004) reported that when 20–80 nm sized Ca NP in the form of CaCO3 was applied
at 160 ppm concentration on Arachis hypogaea (peanut), seedling growth was
observed significantly. The total 15 % increase was measured in dry biomass in
comparison to control. Magnesium (Mg) and iron (Fe) nanoparticles were used on
Vigna unguiculata (Black eyed pea) by the foliar method (Delfani et al. 2014). In
the seed weight of black eyed pea increased by 7 % when measured in comparison
to bulk Fe and Mg salt and without Fe and Mn nanoparticle growing plants. Delfani
et al. (2014) concluded that Fe and Mn nanoparticle could helpful in the improve-
ment of photosynthetic efficiency.
9.5.1.2 Micronutrient Nanofertilizers
Micronutrients are the trace elements which are required to plant in minute quantity
for different metabolic activities. There are different elements included such as iron
(Fe), magnesium (Mn), Zinc (Zn), Copper (Cu), Molybdenum (Mo), Nickel (Ni),
Boron (B) and Chlorine (Cl) as micronutrient (Table 9.2). Generally, these micronu-
trients are added with the macronutrients in the concentration of 5 ppm in composite
fertilizers (Jones et al. 2012).
Iron Nanoparticles
Fe is the most important metal for plant growth, base of chlorophyll development
and helped as a carrier of important elements circulation as blood stream. Researchers
have been focusing on the development of such nanoparticles and their adaptability
in agriculture worldwide. Ghafariyan et al. (2013) used Fe nanoparticle in the
greenhouse experiment on Glycine max (Soybean) and observed that chlorophyll
was increased in leaves significantly. They suggested that Fe nanoparticle could be
used as iron supplement for soybean, which may helpful in preventing chlorotic
symptoms of leaves. Similarly Delfani et al. (2014) reported that numbers of pods
were increased in black eyed pea plant on the use of foliar spray of Fe nanoparticle
at 500 ppm and Fe content was increased up to 34 % and chlorophyll up to 10 % in
leaves in comparison to control.
Table 9.2 Effect of micronutrients on agricultural crop: different types of micronutrients have
been developed in nano form and their effect on plant growth and physiology is summarized below
S.No Nanoparticle Crop Concentration Effect References
1. FeO Soybean 30–60 ppm Chlorophyll increased Ghafariyan
et al. (2013)
Pea 250–500 ppm Seed weight and Delfani et al.
chlorophyll increased (2014)
2. Mn Mung Bean 0.05–1 ppm Shoot length, Pradhan et al.
chlorophyll content and (2013)
the photosynthesis rate
increased
3. ZnO Mung Bean 1–2000 ppm Plant growth increased Mahajan et al.
and Chick at 20 ppm in mung (2011)
Pea bean and in check
pea at 1 ppm
Cucumber 400–800 ppm Root dry weight and Mahajan et al.
in soil fruit gluten increased (2011)
Rap seed 1–2000 ppm Root elongation Lin and Xing
(2007)
4. Zn Rye grass 1–2000 ppm Root elongation Lin and Xing
(2008)
5. CuO Edodea 0.023–5 ppm Photosynthetic rate Nekrasova et al.
Densa planch increased (2011)
6. Cu Lettuce seed 130–600 ppm Shoot and root length Shah and
increased Belozerova
2009
7. Mo Chick Pea 8 ppm Plant mass and number Taran et al.
of modules increased (2014)
Manganese Nanoparticles
Manganese (Mn) is the component of superoxide dismutase enzyme and is required

at water splitting step in photosynthesis. Pradhan et al. (2013) used, Mnnanoparticle
on Vigna radiata (Mung bean) and observed enhancement in growth and an increase
in photosynthesis. They measured a 52 % increase in root length, 38 % shoot length,
71 % in the number of rootlets, 38 % in fresh biomass and 100 % increase in dry
biomass at very low (0.05 ppm) concentration of Mn nanoparticle and suggested
that Mn nanoparticle could be a better alternative of Mn micronutrient in compari-
son to bulk MnSO4.
Zinc Nanoparticles
Zinc is the essential component of different enzymes such as RNA polymerase,

alcohol dehydrogenase, carbonic anhydrase and superoxide dismutase and it is an
essential element for chlorophyll biosynthesis in plant. Mahajan et al. (2011) applied
ZnO nanoparticle on Vigna radiata and Cicer ariatium (chickpea) seedlings at

different concentration. They observed that ZnO nanoparticle at 20 ppm showed
growth in term of root enhancement up to 42 % and 41 % in biomass, similarly in
shoot length enhancement up to 98 % in comparison to control. In the case of chick-
pea at 1 ppm concentration root length was increased up to 53 % and shoot length
up to 6 %. ZnO nanoparticle was also shown growth enhancement in Cucumis sati-
vus (Cucumber) at 400–800 mg Kg−1 concentration in soil (Zhao et al. 2013a).
Similarly, Lin and Xing (2007) applied ZnO nanoparticle on Raphanus sativus
(Radish) and Brassica napus (Rape) and reported enhancement in root at 2 ppm.
Subsequently, Raliya and Tarafdar (2013) used biosynthesized nanoparticles on
cluster bean and measured significant improvement in plant growth at 10 ppm con-
centration. They reported that in the presence of ZnO nanoparticle cluster bean
showed 27.1 % increment in biomass, 31.5 % in shoot length, 66.3 % in root length,
73.5 % in the root area, 276.25 in chlorophyll, 27.1 % insoluble protein and 73.5 %
in phosphatase enzyme activity.
On the other hand, toxic or inhibitory effect of ZnO nanoparticle also assessed
at higher concentration (400 to 2000 ppm) by many researchers (Lee et al. 2010;
Lin and Xing 2007; López-Moreno et al. 2010; Zhao et al. 2013b).
Copper Nanoparticles
Copper is also a component of many plant enzymes and essential for plant growth.
Nekrasova et al. (2011) reported that at low concentration (0.25 ppm) Cu nanopar-
ticle improved the photosynthesis by 35 % in Elodea densaplanch (waterweed). As
same Shah and Belozerova (2009) also reported improvement in seedling growth of
lettuce by 40 % at 130 mg Kg−1 of Cu nanoparticle in soil. In contrast, at 200 to 1000
ppm Cu nanoparticle showed toxic effects on mung bean, Triticum aestivum (Wheat)
and Cucurbita pepo (Yellow Squash) (Lee et al. 2008; Musante and White 2012;
Stampoulis et al. 2009).
Molybdenum Nanoparticles
Molybdenum (Mo) nanoparticle is an important element of nitrogen fixation system

in plants. Many scientists have been working on development of Mo nanoparticle.
In this context Taran et al. (2014) reported that Mo nanoparticle with nitrogen fixing
bacteria treatment to chickpea seed showed enhanced growth two to three times in
comparison to water, only Mo nanoparticle, only nitrogen fixing bacterial incuba-
tion treatment and concluded that this combination could be the optimal treatment
for better plant nutrition and Mo nanoparticle increases the microbial activity.
Another type of nanoparticle such as TiO2, SiO2 and CNT also used as growth pro-
moters in plants except micro and macro nutrients.
TiO2 Nanoparticles
Titanium oxide nanoparticle also showed good agreement with plant enzyme activ-
ity, enhance plant growth. On the exposure of sunlight, it improves the photosynthe-
sis activity and helpful in chemical nitrogen fixation in the air. Lu et al. (2001)
reported that TiO2 and SiO2 nanoparticle mixture accelerate germination and growth
of Glycine max (soybean) by increased nitrogen fixation by enhancing the activity
of nitrate reductase in the rhizosphere. Gao et al. (2006) used TiO2 nanoparticle in
seed treatment and foliar spray in Spinacia oleracea (Spinach). They first socked
the spinach seeds in TiO2 nanoparticle solution at 250 ppm for 48 h under light and
after germination of seedlings sprayed TiO2 nanoparticle solution once a week for
35 days in green house experiment. They reported that use of TiO2 nanoparticle
increased the total nitrogen, chlorophyll and protein content by 23 %, 34 % and
13 %, respectively, weight of the plant also increases two times in comparison to
control. Further, Gao et al. (2006) and Song et al. (2013) showed growth enhance-
ment only at low concentration, higher than 50 ppm.
Carbon Nanotubes
Carbon nanotubes (CNT) also applied as growth promoter in different plant systems
(tomato, soybean, cabbage, carrot, rye-grass, rape and corn) and showed a positive
and negative impact on plant growth at different concentrations. Lin and Xing
(2007) used multi walled carbon nanotubes on rye-grass, rape and corn and reported
enhancement in root elongation of germinated seed at 200 ppm. Similarly, Cañas
et al. (2008) also reported incensement in root length of Allium cepa and cucumber
seed at an exposure of single walled carbon nanotubes at different concentration. In
the other hand, no positive result was measured on cucumber, radish and lettuce
seed. carbon nanotubes also showed positive impact on production of crops by
effected water channel protein expression through surface charges of carbon nano-
tubes in a tomato plant, which increase the water uptake capacity and utilization
efficiency (Villagarcia et al. 2012). Subsequently, Khodakovskaya et al. (2012)
reported that carbon nanotubes increased the tomato production by twofold at 50
ppm concentration in comparison to control. Srinivasan and Saraswathi (2010)
applied carbon nanotubes on tomato and explained that carbon nanotubes facilitate
water uptake capacity and plant growth by entering into germinating tomato seeds.
9.5.2 Dynamics of Nanofertilizer
In the recent review by Liu and Lal (2015) described the thermo dynamical concept
of nanofertilizer penetration inside the plant cell. They proposed that the entropy
of a single particle is based on randomness and in emulsion form, nano colloids have
more suspension compared to ordinary fertilizer grade due to high entropy. Entropy
is directly proportional to Gibbs free energy. Movement of particle depend on Gibbs
free (G) energy and increase in Gibbs energy of colloidal particles will increase
their movement which increases the permeability of colloidal particles across the
semi-permeable membrane and after penetration nanoparticle enter inside the xylem.
According to rule of thermo dynamics G = H-TS (G = Gibbs Free energy; H =
Enthalpy; S = entropy and T = Temperature) If Gibbs energy is negative, the reaction
is spontaneous and moves in a forward direction. If Gibbs energy is zero, the reaction
is at equilibrium and if Gibbs energy is positive, then the reaction is non-spontaneous.
Nanoparticles enter into the plant through binding with carrier proteins and transfer
by aquaporin, endocytosis, ion channels and pores (Rico et al. 2011).
9.5.3 Nanoporous Nanomaterial
Nano-porous nanomaterial provides a new advantage of carrier nanoparticles. They

have uniform pore size, well established pore channels, high surface area and spe-
cial liquid permeability, which provide benefits to agriculture and food sector (Dai
and Ju 2012). The pore size of mesoporous material contains between 2 and 50 nm,
while in macro-porous material it is approx 50–1000 nm and in micro-porous mate-
rial they possess from 0.2 to 2 nm (Ravikovitch and Neimark 2001). Nano-porous
material is applicable in the detection of pathogen, detection of toxin, catalyst and
controlled release material for pesticide and fertilizer delivery. These nanomaterials
have control on delivery of bioactive compounds to target points in needed amount.
Functionalization of such material provides additional feature in the form of tuning
of release rate. Use of these materials in agriculture fields reduces the quantity of
fertilizers and improves efficiency. Further, Zhang et al. (2011) reported that nano-
porous material, pore size, wall thickness and structure significantly influence the
release rate. They investigated the ability of nano-porous silica to release menthol
and describe that functionalization of surface with hydrophobic groups reduce the
release rate of menthol by nano-porous silica in aqueous solution. Subsequently,
Yan et al. (2012) also explained that the release rate of nano-porous material depends
on external factors such as ionic strength, pH and salt concentration in the medium.
They worked on multilayer microcapsule of poly (L-glutamic acid) /Chitosan and
investigate the release rate of 5-fluorouracil compound in different conditions. They
reported that pH and salt concentration also affected the loading capacity of the
drug in nano-porous capsules and acidic condition promotes the continuous release
of the drug.
9.5.4 Nanosensors
Nanotechnology has more promising application in the field of agriculture in the

form of nanosensor. Nanosensors provides real time information about detection or
location of the pathogen, pesticides and beneficial in prediction of environmental
condition, field condition and real time monitoring of the crop (Chen and Yada
2011). Such information would be useful in protecting the crop from pathogens,
pests, viruses, weeds and improve production by proving suitable nutrients to the
soil. These sensing systems make the conventional agriculture system into precision
farming practices. Yao et al. (2009) synthesized fluorescent nano-probes of silica
nanoparticles conjugated with goat anti rabbit secondary antibody for detection of
plant pathogen Xanthomonas axonopdis, which produce bacterial spot disease in
Solanaceous plants. Further, in these probes Yao et al. (2009) use Tris-2, 2′-bipyri-
dyl dichloro ruthenium hexa hydrate dye on to the core surface of silica nanoparti-
cles which produce fluorescence. Carbon nanoparticles are also used in nanosensor
development. Sharon and Sharon (2008) developed carbon nanomaterial based
chemical sensor for detection of pesticide residue in plants.
9.5.5 Role of Nanotechnology in Plant Protection and Pest

Management
In current decade nanotechnology is getting more attention in controlling pest and

diseases of crops plants. Nano-formulation with metal nanoparticles or polymer
based formulation of pesticides is in demand in the pesticide research field.
Nanoparticle has been used for DNA and chemical delivery into plant tissue for
protection from pathogens showing promising application of nanotechnology in
nanoparticle mediate gene transfer (Torney et al. 2007). Another form of the nano
tool as nano-encapsulation of pesticide is known for controlled and slow release of
the active compound by manipulation of the outer shell of the capsule, which pro-
motes the release of pesticide with low dosage over a prolong period and prevent
unwanted pesticide runoff in the environment (Agrawal and Rathore 2014; Khot
et al. 2012).
Similarly, Nair et al. (2010) concluded that these nano carriers have the ability to
provide controlled and site targeted delivery of Agrochemicals in the plants. The
synthesis of such nanomaterial is based on polymer encapsulation with lipid, viral
capsid and clay have ecofriendly and biodegradable material which release the
agrochemicals under structural manipulation. Nano-capsule and nanoparticles have
the size in the range of 0.1–1000 nm is most relevant in plant protection. The nano –
capsule has the shell which contains bioactive compounds in his core. This nano-
capsule are helpful in penetration of agrochemicals in plant tissue, provides stability
to active compounds and release slowly, gradually or completely after the shell
opening. Shell opening is based on the outer circumstance of nano-capsules and
depends on the change in physiological pH or enzymatic degradation. Additionally,
Wang et al. (2007) synthesized nano-emulsion of pesticide using oil and water used
against different insect pest and found effective to control pests. Further, solid-lipid
nanoparticles loaded with essential oil also used for nano-pesticide formulation (Liu
et al. 2006). Subsequently, Pérez‐de‐Luque and Rubiales (2009) reported that nano
encapsulated herbicide reduced the eco-toxicity of herbicide against parasitic weed.
Nano-silica is also used to control different insect pests (Rahman et al. 2009). The
advantage of nanocapsule in agriculture application is given below
1. Absence or less of phytotoxicity
2. Reduction of harmful residues in soils
3. Reduction of chemical compounds uses for nutrition and protection of crops
4. High selectivity towards the crops treated
5. High quality and no harmful residues in the final products
6. Low production costs
Recently different type of nanoparticles used in pest management and further
research is going on for their efficiency improvement (Table 9.3). Description of
some nano pesticides is given below.
9.5.5.1 Silver Nanoparticles
Silver is a highly known antimicrobial metal in ionic and nanoparticle forms since
long back. Kim et al. (2007) reported that silver kills the unicellular microorganism
by inactive their enzyme system. Silver is also reported as a plant growth promoter
(Kumar et al. 2010). Silver nanoparticles are reported as controlling agent against
different plant pathogen such as Fusarium culmorum, Rhizoctonia solani,
Scalerotinia sclerotiorum, Biploaris sorokiniana, Colletotrichum gloeosporioides,
Magnaporthe grisea, Phythium ultimum Botrytis cinerea, Phoma and Magnaporthe
grisea (Gopal et al. 2011; Park 2006; Gajbhiye et al. 2009). Further, Park et al.
(2006) demonstrated spray of silica–silver nanoparticles on powdery mildew
infected leaves of pumpkin and observed silica-silver alloy prevented powdery mil-
dew disease of pumpkin within 3 days of spraying. Similar, Kumar et al. (2010)
studied the antifungal effect of silver nano colloids against powdery mildew patho-
gen of rose (Sphaerotheca pannosa). Likewise, Kim et al. (2007) synthesized three
types of Ag nanoparticle and used as an antifungal agent against Raffaelea sp., a
pathogenic fungus of oak tree in Korea. They observed that Ag nanoparticle showed
detrimental effects on fungal mycelia as well as on conidial germination. Jo et al.
(2009) tested Ag nanoparticle on fungal pathogens of spot blotch of wheat (Bipolaris
sorokiniana) and rice blast (Magnaporthe grisea) and reported that comparatively
M. grisea showed more inhibition to silver nanoparticles. In another study on
Lolium perenne (rye-grass) showed significant reduction by silver ions and nanopar-
ticle. Gajbhiye et al. (2009)) investigated the effect of biological synthesized silver
nanoparticle and observed enhancement in antifungal activity of trizole against
Phoma glomerata, Trichoderma sp. and Candida albicans.
Table 9.3 Use of nanomaterials as pathogens control agent: different types of nano-pesticides showed significant impact in pest control. The effect of these
264
nano-pesticides are summarized in the table

S.No. Nanomaterial Application Act against Effect Reference
1. Nano silver Antibacterial activity of Xanthomonas campestris Significant reduction of Gan et al. (2010)
nano-silver towards the pv. campestris cabbage, black rot in the
control of cabbage pot experiment
black rot
2. Validamycin loaded Controlled release of Rhizoctonia solani Better germicidal efficacy Qian et al. (2011)
nano sized calcium validamycin loaded and slow releases of nano
carbonate nano sized calcium formulation of
carbonate (50–200 nm) validamycin upto 2 weeks
3. Thiamine di-lauryl Antifungal activity of C. gloeosporioides 80 % growth inhibition of Seo et al. (2011)
sulfate (TDS) nano TDS nano-particles C. gloeosporioides and
particles (258.6 nm) against TDS nano particles
fungus associated with showed destruction of the
pepper anthracnose Haifa
4. Chitosan nano particles Efficacy of CSNPs on Rhizopus sp. Colletotrichum Delayed mycelia growth Chookhongkha et al.
(CSNPs) fungal growth and chili capsici, C. gloeosporioides, in comparison to control (2012)
seed quality and Aspergillus Niger
5. Nano copper Antibacterial activity, Xanthomonas axonopodis Nano copper inhibited the Mondal and Mani (2012)
the causative of pv. punicae growth >10,000 times
pomegranate bacterial efficiently than that
blight usually recommended
dose of Cu-oxychloride
6. Light activated Nanoscale formulations Xanthomonas perforans High photocatalytic Paret et al. (2013)
nanoscale formulations of TiO2 with Ag and Zn activity as compared to
of TiO2 on towards the control control and the
of bacterial spot of significantly reduced
tomato bacterial spot without
causing any adverse
effects on yield
H. Chhipa and P. Joshi
9
7. Copper nano particles Cu-based NPs (11–55 Phytophthora infestans More effective than the Giannousi et al. (2013)
nm) were tested on commercial
tomato (Lycopersicon Agrochemicals at lower
esculentum) work for concentrations and
their antifungal activity drastically reduced the
active ingredient rate
8. DNA directed silver Antibacterial activity of Xanthomonas performance Reduced the bacterial spot Ocsoy et al. (2013)
nano particles on nano particles disease compared to
graphene oxide untreated tomato
transplants
9. Light-activated nano Nano composite for Bacteria Significantly reduced Paret et al. (2013)
particle formulation of management of bacterial spot compared
Titanium dioxide with bacterial leaf spot on with the untreated control
zinc Rosa ‘Noare’ and other commercial
bactericides
10. Chitosan based In vitro evaluation of Alternaria alternata, Most effective in Saharan et al. (2013)
nanoparticles (Chitosan, Chitosan based nano Macrophomina phaseolina inhibiting spore
Chitosan- saponin and particles and Rhizoctonia solani germination and showed
Cu-Chitosan 89.5 %, 63.0 % and 60.1 %
nanoparticles) growth inhibition of A.
alternata, M. phaseolina
and R. solani respectively
Nanofertilisers, Nanopesticides and Nanosensors in Agriculture
Chowdappa and Gowda (2013)

265
9.5.5.2 Copper Nanoparticles
Cu nanoparticle is also reported effective against disease spread by Xanthomanas

sp. such as rice bacterial blight disease (Xanthomonas oryzae) and leaf spot of
mung by Xanthomonas campestris. Esteban-Tejeda et al. (2009) reported that Cu
nanoparticles have broad spectrum antimicrobial activity against Gram positive and
negative bacteria and fungi, at low concentration it can be used as a fungicide
(Giannousi et al. 2014). Similarly, Cioffi et al. (2005) measured antifungal activity
of nano-composite of copper with polymer against plant pathogens.
9.5.5.3 Silica Nanoparticles
Silica is recognized as a vital element in plant physiological activities and growth

inducer (Kanto et al. 2004) which would helpful in proliferation of the stress resis-
tance capability of diseased plants (Brecht et al. 2004). Silica nanoparticles have
reported effective in control of insects like Trialeuroded vaporarium (white fly),
Dermanyssus gallinae (Coconut mite), Phaedon weevil (mustard weevil), Sitophilus
oryzae (rice weevil). There has been no report of silica nanoparticle as antimicrobial
agent, but in combination with Ag (Ag-Si) nanoparticle showed anti-bacterial and
anti-fungal activity (Park et al. 2006). They reported at 10 ppm concentration Si-Ag
nanoparticle showed 100 % inhibition of fungal growth while in the case of bacterial
concentration was 100 ppm. Further, Si-Ag nanoparticles showed 100 % control of
powdery mildew disease in cucurbits and these nanoparticles showed phyto-toxicity
at 3200 ppm concentration in cucumber and pansy plant (Park et al. 2006). In
another form, silica is highly applicable in transformation (targeted delivery of
DNA and gene of interest) and chemicals through its mesoporous structure (Wang
et al. 2002). In mesoporous form nanoparticle have well organized pores which
increase their surface. Liu et al. (2006) also reported that pesticide validamycine
loaded into porous hollow silica nanoparticle (PHSN) can be efficient delivery sys-
tem. These PHSN can provide controlled delivery of pesticide according to need of
the plant. Barik et al. (2008) used nano-silica as a pesticide against insect and
reported that nano-silica absorbed into the cuticle lipid of insects by physio-sorption
and kill insects.
9.5.5.4 Zinc Nanoparticles
Zinc nanoparticles has been used as nanofertilizer on many crops and its showed
positive results in optimal concentration, but the ZnO as fungicidal against fungal
plant pathogen is less studied. He et al. (2011) applied ZnO nanoparticle against
fruit mold Penicillium expansum and Botrytis cinerea and measured significant
reduction in growth of pathogen. Similarly, growth reduction was observed
against Aspergillus flavus and Aspergillus niger by Jayaseelan et al. (2012).
Table 9.4 Application of nano-formulations as carrier and pest controlling agent for crop
protection; use of different base materials in formation of nano capsules are summarized below
Delivery of
Type of nano capsule compound Application Reference
Vernonia oil 2,4 D Delivery through plant Wiesman et al.
Barrier (2007)
Lipid nano disc Amphotericin B Delivery in plants Pérez‐de‐Luque and
Hermosín (2013)
Chitosan Pesticide Delivery in plants Ding et al. (2011),
Feng and Zhang
(2011), and ad Yin
and Zhang (2010)
Alginate-chitosan Paraquat Transport of herbicide Dos Santos Silva
et al. (2011)
Starch Plant oil Encapsulation of plant Glenn et al. (2010)
oil
Cyclodextin complex Soil amendment for Morillo et al. (2001)
decreasing herbicide
photo-degradation
Poly Atrazine and Controlled release of Grillo et al. (2010)
(hydroxybutyrate-co- ametryn herbicides and (2011)
hydroxyvalerate
Ethylcellulose Nonflurazon and Controlled release Sopeña et al. (2005,
alachor 2007)
Virus Viral protein Bio insecticide Summers (2006)
Pérez‐de‐Luque and Hermosín (2013)
ZnO nanoparticle showed less toxicity in comparison to Ag nanoparticle to the

plant and can be applicable as nano pesticide.
In the same context, nano-sulfur and nano formulation of conventional pesticide
(hexaconzole) also used against plant fungal pathogens. Plant fungal pathogen
Rhizoctonia solani and Erysiphe cichoracearum could be controlled by use of nano-
formulation of hexaconzole and nano sulfur. Nano sulfur is also active in controlling
red spider mite (Tetranychus urticae) which is ten times more effective as compared
to commercial sulfur. In the other study, Yang et al. (2009) used PEG coated
nanoparticles loaded with essential oil of garlic against Tribolium castaneum insect
and observed 80 % control of insect based on slow and continuous release of essen-
tial oil of garlic from nanoparticles.
In the recent review by Rai and Ingle (2012) described the use of nanotechnology
in pest management (Table 9.4). Many researchers used different type of nanopar-
ticle to control the insect pest. Comparative study on the effectiveness of different
type of nanoparticles such as AgNP, ZnO, TiO2, and aluminium oxide nanoparticle
against rice weevil, Sitophilus oryzae and baculovirus were done by Goswami et al.
(2010). They measured that aluminium nanoparticle showed 100 % mortality
while Ag NP showed 95 % mortality after 7 days. Similarly, Stadler et al. (2010)
showed insecticidal activity of nano alumina against Rhyzopertha dominica and
S. oryzae and reported that nano alumina is the reliable and cheap alternative of
commercial insecticides.
A lot of product has been come into market for different applications, but the
impact of these nanoparticles in the environment should be monitored. Further, the
regulation for product registration by Federal insecticide, fungicide and rodenticide,
Act of Nano-pesticide is required so the product will not generally cause unreason-
able adverse effect on the environment. All nanotechnology based products should
complacence with Toxic substance control act (TSCA). TSCA is the act which regu-
lates the chemicals by providing a regulatory framework for chemical production,
use and their disposal method. It applies to any persons which has the relation to
manufacturing, processes and distribution of chemical substance at commercial
level.
9.6 Nanotechnology Versus Conventional Practices
As compared to the conventional practices the use of nanotechnology can play an

important role in improving agricultural productivity by decreasing agricultural
consumption of water and decreasing environmental pollution caused by agricul-
tural runoff. If we talk about the role of nanotechnology in modern agriculture sys-
tem, it can be considered as one of the most significant tools and can be predicted to
become a driving economic force in the near future. Nanotechnology has a tremen-
dous potential to revolutionize agriculture and allied fields, including aquaculture
and fisheries. Nano agriculture focuses currently on target farming that involves the
use of nano sized particles with unique properties to boost crop and livestock pro-
ductivity (Batsmanova et al 2013; Scott and Chen 2013). There are several examples
where the scientists have tested the efficiency of the nanoparticles in plant experi-
ment and shown that there are significant increases in the physiological parameters
of the plant, as compared to the conventional technologies. For the significant
results, the foresight and patience are essential for applying nanotechnology in agri-
culture because generation of data in most agricultural fields is time-consuming and
expensive, and success is uncertain due to the involvement of a large number of
variables in farm production systems and because of the complex intrinsic relation-
ship between nanomaterials and nature. It is worthwhile to recognize that a large
number of nanomaterials have existed since time immemorial in soils, plants, and
the atmosphere (Li et al. 2012; Wilson et al. 2008; Theng and Yuan 2008).
The traditional practices used for the seed germination, plant growth promotion
and crop improvement, including breeding and use of microbial inoculation was
now being reported successfully replaced by the application of carbon nanotubes as
regulators of seed germination and plant growth (Khodakovskaya et al. 2013; Zheng
et al. (2005). Thus, there are several such examples showing that there is the start of
new genera, with the use of nanotechnology as the effective tool, which can be used
in the field of plant growth and improvement.
Similarly, in disease management technologies, such as bacteriophages and

systemic acquired resistance inducers, have been under investigation for several
years as alternatives to Cu bactericides (Obradovic et al. 2005; Huang et al. 2012).
Additional, the use of Bacteriophages, have also shown promising as biological
alternatives to conventional Cu bactericides. However, ensuring the efficacy of bac-
teriophages is challenging in field conditions due to limited phage viability and the
specific environmental requirements for their multiplication. In recent years, nano-
technology has been increasingly applied to the development of novel antimicrobi-
als for the management of pathogenic bacteria affecting agricultural crops, humans
and animals. In particular, significant development in nanomaterials synthesis, such
as polymers, carbon-based and metallic, has attracted researcher’s attention towards
applications in managing plant diseases caused by bacteria. Toxicity considerations,
including negative environmental effects, have also led to the redesign of nanoma-
terials by tuning the size and shape and by surface modification, leading to increased
antimicrobial activity and decreased ecological toxicity (Neal 2008; Dasgupta et al.
2016a, b, c; Ranjan et al. 2014, 2015, 2016; Maddineni et al. 2015; Dasgupta et al.
2015; Jain et al. 2016).
9.7 Risk Assessment of Nanotechnology
The purpose of every newly developed mechanism is facilitated to the complex

system and the welfare of the society. The development of nanotechnology is aim-
ing to reduce size and improvement in the functionality of any application, but the
safety of society is on high priority. The nanoparticles have a natural tendency to
group together to form large particle which is called agglomeration. (Ostiguy et al.
2006), but for their application purpose they are required in unagglomerate form or
individual particle form. Similarly the surface of nanoparticles is also modified for
specific use by chemicals. In such context the manufacturer uses post synthetic
strategies to prevent aggregation of particles. Uses of those chemicals and surface
modifier materials have a major impact on the safety and toxicity of nanomaterial
(Rana and Kalaichelvan 2013).
Therefore, the Eco-toxicity study is advised, as these includes natural uptake
mechanisms and the influence of environmental factors on bioavailability.
Nanotechnology is applied in different areas which have a direct relation to living
beings such as health care and agriculture sector (Nel et al. 2009). Thus the use of
nanotechnology improving the quality of life, but the impact of nanotechnology on
human health is also a major concern regarding human health and the environment.
Use of nanomaterial in agriculture is the direct root of entry of nanoparticle into
soil system and plants and after consumption, in living beings. So there is need to
determine the impact assessment of manufactured nanomaterials.
The effect of nanoparticles on in biological and chemical environment is deter-
mined by different factors such as size of the nanoparticle, chemical composition,
surface chemistry, pH, ionic strength and ionic composition of environment, hydro-
dynamic condition and residence time (Ray et al. 2009). Nanoparticles have size in
the range of 1–1000 nm. Small nanoparticles have fast diffusion rate and easy to
coagulate on large particles, deposit on the surface and facile binding with biologi-
cal components.
In a review article by Auffan et al. (2009) explained the toxicity assessment of
nanoparticles in chemical and biological environment. The effect of nanoparticle
accumulation in the plant is very less studied and their impact on agriculture crops
has been deliberate only in vitro: hydroponics (López-Moreno et al. 2010; El‐
Temsah and Joner 2012; Stampoulis et al. 2009; Kumari et al. 2009; Lin and Xing
2007), agar culture medium (Lee et al. 2008) and in Hoagland medium (Schwabe
et al. 2013). Very less crops have evaluated for nanomaterial toxicity and their
accumulating studies such as wheat, cucumber, corn, onion, pumpkin, tomato, rice,
soyabean, lettuce and tobacco specially Cucurbita pepo and Cucumis sativus
(Deng et al. 2014; Cui et al. 2014).
Nanoparticles journey starts in the food chain from soil via agriculture crop and
its feeder and increase of bioaccumulation of nanoparticles in the food chain could
be harmful for the environment (Zhu et al. 2008). It is reported that 20 nm sized
TiO2 nanoparticle is more toxic in comparison to 250 nm nanoparticles (Auffan
et al. 2009). Similarly, 7 nm CeO2 nanoparticles produced more oxidative stress in
comparison to 300 nm sized nanoparticles and induce DNA and chromosome dam-
age in vitro experiment. Different mechanisms such as transformation of chemical
species, reactive oxygen species (ROS) development and toxic ion release play
important role in toxicity of inorganic nanoparticles (Auffan et al. 2009). The effect
of functionalized and non-functionalized carbon nanotubes were studied by Cañas
et al. (2008) on cabbage, carrot, cucumber, onion, lettuce and tomato. They were
found that in tomato non-functionalized carbon nanotubes inhibit root growth, but
the enhancement in cucumber and onion, while functionalized carbon nanotubes
inhibit the root growth in lettuce. Rest two crops were unaffected with both types of
carbon nanotubes. Similarly, Yang and Watts (2005) reported that alumina nanopar-
ticles showed inhibition of root at 2000 ppm concentration in corn, cucumber, soy-
bean, cabbage and carrot, while Lin and Xing (2007) used multi walled nanotubes,
zinc, zinc oxide alumina and aluminium to check their toxicity in rape, radish, let-
tuce, corn and cucumber and reported that only zinc and zinc oxide inhibit the seed
germination. Shaw and Hossain (2013) reported the presence of CuO nanoparticle
showed impaired germination and growth by oxidative damage. Similarly Dimkpa
et al. (2013) and Shaw et al. (2014) showed the negative impact of CuO nanoparticle
on wheat, maize and barley growth reduction and change in DNA integrity also have
correlated with toxicity of CuO nanoparticle in radish, rye grass and buckwheat
(Lee et al. 2010; Atha et al. 2012).
9.7.1 Accretion of Nanoparticle in Chemical and Biological

Environment
Transportation, adsorption and accumulation of nanoparticles in agriculture crops

depends on plant species and nanoparticle type, their interaction, size, chemical
composition and long term stability of nanoparticle (Rico et al. 2011). The com-
parative study of different metal oxides (CeO2, Fe2O3, SnO2 and TiO2 nanoparticle)
and Ag, Co and Ni metal nanoparticles on tomato plant were carried out by Antisari
et al. (2015). They reported that SnO2 decreased the dry biomass up to 63.1 % and
accumulation of Ag, Co and Ni nanoparticle occurred in root, stem and leaves of the
plant additionally, Ag nanoparticle in fruit too. They concluded that size, shape,
type of nanoparticle and surface chemistry is responsible for uptake, translocation
and occurrences of nanoparticles in different organ. In contrast, nanoparticle also
have advantageous role of absorbing the pollutant and reduce the toxicity by
decrease the free concentration of pollutants in the environment (Nowack and
Bucheli 2007).
The engineered nanoparticles usually occurred in agricultural field due to use of
nanoparticles containing agrochemical or nano-formulations for crop protection
and production improvement. When engineered nanoparticle release in to the envi-
ronment they persist in air, water and soil after discharge and plant root is directly
exposed to engineered nanomaterial present in soil and irrigation water, while leaves
and stem tissue come in direct contact with atmospheric nanoparticles. The interac-
tion of engineered nanoparticle in a biological environment with different type of
biomolecules such as cellular organelles, lipid, nucleic acid and protein is basically
depends on size and surface reactivity of nanoparticle (Auffan et al. 2009; Fadeel
et al. 2007).
Zhang et al. (2011) reported that different type of interaction phenomena used
such as electrostatic, mechanical adhesion, adsorption and hydrophobic affinity by
engineered nanoparticles. In the cell the pore size of cell wall presents is in the
range of 5–20 nm (Tepfer and Taylor 1981), nanoparticle or their cluster less than
the pore size of cell wall could diffuse through pore and enter via symplastic or
apoplastic flow. Sometimes nanoparticle sorption on to root surface create a struc-
tural damage and enter into the root tissue also, from there nanoparticles diffuse in
space between the cell wall and plasma membrane (intracellular space) (Lin and
Xing 2008). Engineered nanoparticles enter into inter cellular space through apo-
palstic pathway. Similarly, through apoplast (through cell wall), particles may enter
in to epidermal and cortical cell to reach endodermis and accumulate there and
sometime form aggregates of engineered nanoparticles, because waxy Casparian
strip work as barriers for further movement of nanoparticles in the vascular system
(Larue et al. 2012; Zhao et al. 2013a).
On the other hand Rico et al. (2011) hypothesized that symplastic (through cyto-
plasm) route is more organized and regulated pathway for movement of engineered
nanoparticles in to plants. They proposed that binding of nanoparticle with carrier
protein is helpful in cell internalization and easy to move through ion channels,
aquaporins and endocytosis. In the experiment carried out by Khodakovskaya et al.

(2012) supported the hypothesis by reported that presence of nanoparticles, expres-
sion of aquaporin proteins enhanced along with up regulation of water channel
genes. Li et al. (2008) and Stark (2011) reported that in the interaction of nanopar-
ticles also depend on hydrophobic and hydrophilic nature of particles. Hydrophobic
nanoparticle embedded into the hydrophobic core of membrane without any dam-
age, but hydrophilic nanoparticles absorb on the surface of the membrane. In the
cell, nanoparticle surrounded by different type of biomolecules, forms a corona and
smaller nanoparticle complex move through plasmodesmata to neighboring cells.
The effect of nanoparticles on cell internal structure in plants has been studied.
Wang et al. (2011) and Larue et al. (2012) reported that during intercellular move-
ment through plasmodesmata TiO2 nanoparticles showed toxicity and disturb the
micro tubular network in Arabidopsis thaliana. Additionally, Cifuentes et al. (2010)
hypothesized that the presence of Rab protein determined the movement to specific
areas near plasmodesmata. Transportation of engineered nanomaterial through sim-
plistic flow showed highly effective into stele and then vascular tissue.
The toxicity by nanoparticle basically depends on generation of reactive oxygen
species (ROS). When nanoparticles exposed to the light they generate excited elec-
trons by photochemical response. These electrons form superoxide radicals in the
presence of oxygen. Such situation where the organism exposed to light and
nanoparticles, the simultaneous could be toxic to the organism (Cañas et al. 2008).
Recently lot of work has been going on the mobility of nanoparticle into the envi-
ronment, but more important is how they behave within the chemical or biological
environment (Nowack and Bucheli 2007).
The biggest challenge is to find that in what concentration these engineered
nanoparticles are beneficial or after what quantities they show toxicity in the envi-
ronment. Presence of nanoparticles in the soil might be interacted with microbial
community and effected microbial dynamics, soil ecosystem and carbon sequester-
ing. Further, they can be influence different functional assay such as the decomposi-
tion of organic matter, nitrogen transformation and mycorhizal association. Still the
research on interaction of engineered nanomaterial with soil microbial community
and crop, transmission of engineered nanoparticles from plant to human begins and
interaction with soil pollutant is very limited, so to understand the assessment of
nanomaterial on ecosystem required more knowledge on engineered nanoparticles
and crop interaction, safety of food products derived from the nanomaterial contain-
ing environment.
9.8 Conclusion
Nanotechnology is a fascinating technology, a door for the next revolution in the

field of agriculture and Agri-technology. It can reduce the amount of chemical
inputs to enhance the agricultural productivity and develop a healthy relationship
between chemical inputs with eco-balance. Reduction of chemical fertilizer and
pesticide is very much required for a sustainable future. Continuous uses of uncon-
trolled chemicals are disturbing the environment, microbial diversity, geo-biological
cycles and human health. Long time residues of such inputs also affected the soil
health and their nutrition system. So sustainability of nature is much required for
our future generation and using nanotechnology we can control the chemical disas-
ter in the agriculture field. The use of encapsulated and metal nanoparticle have
been evidenced their promising approach in agriculture as fertilizer and pest control
agents. The site specific feature and controlled release capacity of these carriers
makes them more advantageous in agriculture. Their use as biosensor also will
change the conventional farming practices and convert it into precision farming,
which will provide the information about soil health, pest and nutritional require-
ment of the crop and helpful to reduce excessive input and agricultural cost and
develop the smarter agriculture practice. On the other side, we need to assess the
impact of nanotechnology in agriculture before commercialization of products.
Accumulation of nanomaterial and their adverse effect on the environment is also a
major concern. These nanoparticles showed toxicity after a certain limit against
plant and human health. It is important more research is required for environmental
impact assessment of nanomaterial and determine the non-toxic concentration for
each crop.
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Chapter 10
Nanoparticles, Soils, Plants and Sustainable
Agriculture
Tarek A. Shalaby, Yousry Bayoumi, Neama Abdalla, Hussein Taha,

Tarek Alshaal, Said Shehata, Megahed Amer, Éva Domokos-Szabolcsy,
and Hassan El-Ramady
Abstract Humanity faces major challenges involving energy, water, food, environ-
ment, poverty, diseases, education, democracy and population. Green nanotechnol-
ogy could be a solution for providing sustainable energy, clean water and a better
environment. Various nanomaterials can sustain the agricultural sectors. Here we
review the applications of nanoparticles for soil security and plant nutrition.
Keywords Nanoparicles • Terrestrial environments • Sustainable agriculture • Soil

security • Plant nutrition
T.A. Shalaby
Horticulture Department, Faculty of Agriculture, Kafrelsheikh University,
Kafr El-Sheikh, Egypt
College of Agricultural and Food Sciences, King Faisal University,
31982 Al-Hassa, Saudi Arabia
Y. Bayoumi
Horticulture Department, Faculty of Agriculture, Kafrelsheikh University,
N. Abdalla • H. Taha
Plant Biotechnology Department, Genetic Engineering Division,
National Research Center, 33-El-Behouth St., Dokki, Cairo, Egypt
T. Alshaal • H. El-Ramady (*)
Soil and Water Department, Faculty of Agriculture, Kafrelsheikh University,
S. Shehata
Vegetable crops Department, Faculty of Agriculture, Cairo University, Giza, Egypt

284 T.A. Shalaby et al.
10.1 Introduction
Green nanotechnology is the nascent area of research involving the design of nano-
scale substances, materials, and processes through green chemistry and green engi-
neering that results in the development of new performance without adverse
consequences to humans and the biosphere (McKenzie and Hutchison 2004). It has
been said that green nanotechnology in its simplest form is preserving the applications
while minimizing or eliminating the negative implications of nanomaterials (Eckelman
et al. 2008). It could be noted that this kind of nanotechnology is (1) environmentally
benign and sustainable, (2) is intended to contribute to the solution of some environ-
mental problem or (3) at a minimum it should perform better than alternative non-
green nanotechnologies (Geoffrey and Granqvist 2011). Recently, several publications
focused on the field of green nanotechnology (e.g., McKenzie and Hutchison 2004;
Eckelman et al. 2008; Dhingra et al. 2010; Geoffrey and Granqvist 2011; Guo 2012;
Virkutyte and Varma 2013; Rickerby and Morrison 2014; Basiuk and Basiuk 2015).
Literally nanotechnology means any technology on a nanoscale that has applica-
tions in the real world (Bhushan 2010). The term “nanotechnology” was invented by
Professor Norio Taniguchi at the University of Tokyo in 1974 with the following
definition: Nano-technology is the production technology to get the extra high accu-
racy and ultra fine dimensions, i.e. the preciseness and fineness on the order of 1 nm
(nanometer), 10−9 m in length. According to NASA’s definition, “nanotechnology is
the creation of functional materials, devices and systems through control of matter
on the nanometer length scale (1–100 nanometers), and exploitation of novel phe-
nomena and properties (physical, chemical, biological, mechanical, electrical…) at
that length scale” (Meyyappan 2004). It could be defined nanotechnology as a
promising field of interdisciplinary research. It can open up a wide array of oppor-
tunities in various fields like agriculture, pharmaceuticals, medicine and electronics.
Therefore, the potential benefits and uses of nanotechnology are enormous.
Concerning the application of nanotechnology to agriculture is also getting atten-
tion nowadays (Prasad et al. 2014; Shapira and Youtie 2015; Resham et al. 2015;
Nath 2015). It has been widely recognized that, reducing the impact of industry on
the environment as an important priority for achieving sustainability. As a conse-
quence, products and production methods are being modified, supply chains are
evolving and increased attention is paid to the disposal of waste and recycling.
Therefore, nanotechnology can play a key role in these developments because it has
the potential to confer substantial societal, economic, and environmental benefits
through more efficient energy generation and storage systems, reduction of emis-
M. Amer
Soil, Water and Environment Research Institute (SWERI), Agricultural Research
Center (ARC), Egypt
É. Domokos-Szabolcsy
Plant Biotechnology Department, Debrecen University, Böszörményi Útca. 138, 4032
Debrecen, Hungary
10 Nanoparticles, Soils, Plants and Sustainable Agriculture 285
sions, resource saving, and substitution of hazardous substances (Rickerby and

Morrison 2007; Rickerby and Morrison 2014). In developing countries, a large pro-
portion of people face daily food shortages as a result of environmental impacts or
political instability, whereas in the developed world there is surplus of food. The
drive for developing countries is to develop drought and pest resistant crops, which
also maximize yield. The potential of nanotechnology to revolutionize textile, mate-
rials, information and communication technology, the health care and energy sec-
tors has been well publicized (Prasad et al. 2014).
Therefore, the role of nanoparticles in enhancing soil security, different effects
on plants as well as the significance of these nanoparticles for plant nutrition and
hence sustainable agriculture will be highlighted.
10.2 Nanoparticles for Sustainable Agriculture
Humankind faces a lot of challenges. These challenges can be listed according to

Nobel Laureate Richard E. Smalley (1996) including the following top ten prob-
lems: (1) energy, (2) water, (3) food, (4) environment, (5) poverty, (6) terrorism and
war, (7) disease, (8) education, (9) democracy, and (10) population. Furthermore, it
could be used this list according to the green nanotechnology for providing energy,
clean water and a good environment in a sustainable way (Geoffrey and Granqvist
2011). It could be noticed that, about 50 % from these previous challenges in close
relation with the agriculture.
Starting with agriculture, it is the basic activity by which humans live and survive
on the Earth (Reddy 2015). This activity has a lot of systems including conventional,
conservation or sustainable and organic agricultural systems. Concerning conven-
tional agriculture, it has largely been characterized by tillage, which leaves soil vul-
nerable to erosion. It could be also characterized by minimal soil disturbance,
diversified crop rotations, and surface crop residue retention to reduce soil and envi-
ronmental degradation while sustaining crop production. These both tillage and
crop residue burning as conventional farming practices have substantially degraded
the soil resource base, with a concomitant reduction in crop production capacity.
Due to the conventional farming practices, continued loss of soil is expected to
become critical for global agricultural production. This conventional mode of agri-
culture through intensive agricultural practices achieves production goals, but
simultaneously degrades the natural resources (Farooq and Siddique 2015).
On the other hand, conservation agriculture is a new paradigm for achieving
sustained agricultural production and is a major step in the transition to sustainable
agriculture. Conservation agriculture is widely recognized as a viable approach to
creating a sustainable agriculture (Farooq and Siddique 2015). It is a resource-
saving agricultural production system that aims to achieve production intensifica-
tion and high yields while enhancing the natural resource base through compliance
with four interrelated principles viz. minimal soil disturbance, permanent residue
cover, planned crop rotations and integrated weed management, along with other
good production practices of plant nutrition and pest management. Conservation
agriculture is a set of technologies, including minimum soil disturbance, permanent
Fig. 10.1 Plants can sustain our life: composting from leaves (from September till snowing by
February in Böszörményi Street, Debrecen, Hungary; photo 1), whereas photo 2 represents some
steps explaining how the ancient Egyptian used the papyrus plant (Cyperus papyrus) for making
papyrus paper (Photos by El-Ramady)
soil cover, diversified crop rotations, and integrated weed management (Friedrich
et al. 2012), aimed at reducing and/or reverting many negative effects of conven-
tional farming practices such as soil erosion, soil organic matter decline, water loss,
soil physical degradation, and fuel use (FAO 2008; Farooq and Siddique 2015).
Therefore, the growing concerns for sustainable agriculture are in response to the
limitations of both low-input, traditional agriculture and intensive modern agricul-
ture relying on high levels of inputs for crop production (Figs. 10.1 and 10.2).
Sustainable agriculture relies on practices that help to maintain ecological equilib-
rium and encourage natural regenerative processes such as nitrogen fixation, nutri-
ent cycling, soil regeneration, and the protection of natural enemies of pest and
Fig. 10.2 Soils suffer from salinity and/or alkalinity (salt-affected soils) in field (photo 1) or in
green house under drip irrigation (photo 2), pollution and water logging in Kafr El-Sheikh (photo
3) and sandy storm on February 11, 2015 (photo 4) in Giza (Photos by El-Ramady)
diseases as well as the targeted use of inputs. Agricultural systems relying on such
approaches not only support high productivity, but also preserve biodiversity and
safeguard the environment (Farooq and Siddique 2015).
Concerning nanoparticles and its behavior in frame of sustainable agriculture, it
is an emerging issue all over the world. Whereas, there are several publications
including book chapters, reviews, books such as Anandaraj et al. (2011), Chen and
Yada (2011), Ditta (2012), Prasad et al. (2012, 2014), Tarafdar et al. (2013), Thul
et al. (2013), El Beyrouthya and El Azzi (2014), Takeuchi et al. (2014),
Mukhopadhyay (2014), Ngô and Van de Voorde (2014), de Oliveira et al. (2014),
Wigger et al. (2015), Ditta et al. (2015), Thul and Sarangi (2015), Patil et al. (2016),
Salamanca-Buentello and Daar (2016), Hasegawa et al. (2016), and Lourtioz et al.
(2016). It is worth to mention that, recently the American Chemical Society pub-
lished some publications concerning this subject e.g., Shamim and Sharma (2013),
Doong et al. (2013), Park and Appell (2013), and Hu et al. (2014a).
Regarding to soil, it is biogeochemically dynamic entities that play an important
role in sustaining life forms within the Earth’s critical zone by regulating processes
in terrestrial ecosystems. Furthermore, soils can provide critical support essential for
life on the earth, regulate processes across diverse terrestrial ecosystems, and interact
with the atmosphere (Adewopo et al. 2014). Concerning the most important and
emerging research area in soil sciences, it is well established some thematic areas for
this subject including soils as a key regulator of ecosystem functions, role of soils in
public health and human well-being, soils mediating nutrient cycling, transport pro-
cesses, and plant-soil – microbial interactions, soil formation and degradation and
soil information systems (Figs. 10.1 and 10.2). Therefore, identifying priority
research challenges within a scientific area is a daunting task, but the outcomes could
present unparalleled opportunities for advancing the science. However, the unique-
ness of soil science lies in its rich blend of biology, chemistry, pedology, physics,
mathematics, and social sciences as well as communication (Adewopo et al. 2014).
Therefore, it could be concluded that, nanoparticles or nanomaterials can be used
in sustaining the agricultural sectors including food, energy, water, and soils, within
food security, energy security, water security and soil security. We should broaden
our view on nanoparticles or nanomaterials considering different potentials for a
sustainable materials management.
10.3 Enhancing Soil Security
Soil security has been defined in analogy with food security, which aims at the long
term sustainable production of sufficient quantities of food, providing a permanent
feeling of security to world citizens. This implies, however, much more than striving
for a higher production as such, as many socioeconomic, institutional, and ethical
aspects also play a key role (Bouma et al. 2015). The security concept is more com-
plicated when applied to soils. Rather than relate to a sustainable, daily need in
terms of food intake, soil security relates to what might happen if soils degrade to
the extent that sufficient food production is not feasible anymore. Soil degradation
is a long-term process, very much related to varying socioeconomic conditions.
Except for erosion, its effects are often gradual and difficult to communicate and
translate into environmental and economic values. However, when soils degrade to
the extent that they cannot anymore provide certain ecosystem services, of which
food production is only one provisioning service, the consequences for society are
devastating. To mitigate degraded soils is very difficult and even impossible when
soil has been removed by erosion. The challenge, therefore, is to create early aware-
ness about the dangers of soil degradation that may, in the end, terminate many
ecosystem services the soil can provide (Bouma et al. 2015).
A side from soil security, food security was and will remain a major among global
issues of the twenty-first century. Furthermore, principal determinants of food secu-
rity include the availability and quality of soil resources, and their interactions with
water resources as well as vegetation (crop species) through energy-based inputs
using managerial skills for optimizing the net primary productivity (Lal 2015). This
net primary productivity is specifically affected by critical linkages that govern some
specific functions of nexuses. These nexuses include the first one, soil and water for
the plant, available water capacity by influencing water retention and transmission,
conversion of blue and grey into green water, and moderating the effects of pedologic
and agronomic droughts (Lal 2015). The second includes soil and vegetation for
biogeochemical cycling, which determines elemental budgets (i.e., C, N, P, and S),
nutrient use efficiency, root distribution and turnover and soil/root respiration.
Whereas, the third is vegetation and energy for energy/mass transformation and influ-
encing energy productivity, ecosystem C budget, and biomass feedstocks for biofuel
production. Finally, the fourth one is energy and water affecting the hydrological
cycle with specific impacts on water and energy balance on a landscape, energy use
in irrigated systems, and moderation of the hydrological/meteorological droughts.
These nexuses affect and are affected by climate changes and variability on the one
hand and anthropogenic perturbations (human demands) on the other (Lal 2015).
Lal (2015) reported about the importance of nexuses and their inter-connectivity.
He mentioned that, there is a close relationship between soil security, water security,
climate security, energy security, economic security and political security. Concerning
the food security, it includes availability, access, nutritional quality, and retention,
which strongly depends on soil security (quality, resilience), water security (quality,
renewability, availability), energy security (dependability, supply, price), climate
security (optimal temperature and moisture regimes, and low frequency of extreme
events), economic security (income and access to resources), and political stability
(peace and harmony). Therefore, the co-productivity generated by the anthropogenic
use of primary resources (soil, water, climate) and secondary inputs (amendments,
fertilizers, irrigation, tillage) must be optimized. Understanding and judiciously
managing the water-soil-waste nexus for food security is important to enhancing
human wellbeing, achieving the sustainable use of natural resources, improving the
environment and sustaining ecosystem functions and services (Lal 2015).
10.4 Nanoparticles and Plants
Nanotechnology is a new emerging and fascinating field of science. Nanotechnology

permits advanced research in many areas and nanotechnological discoveries could
open up novel applications in the field of biotechnology and agriculture (Siddiqui
et al. 2015a). Nanomaterials, as a term is based on the prefix “nano,” which origi-
nates from the Greek word meaning “dwarf.” More precisely, the word nano means
10−9 or one billionth of a meter (Huang et al. 2015). The word nanomaterial is gen-
erally used for materials with a size ranging between 1 and 100 nm (Rai and Ingle
2012). Generally, nanomaterials refer to a colloidal particulate system, in which size
ranging from 10 to 1000 nm, possessing unique properties, such as size dependent
qualities, high surface-to-volume ratio, and promising optical properties (Aslani
et al. 2014). It could be also defined nanoparticles, which refer to a category of
nanomaterials, a submicron or even ultramicron size particles obtainable as high
performance radiant resistant materials, magnetic materials, solar battery materials,
packaging materials, and magnetic fluid materials (Aslani et al. 2014). Furthermore,
it could be divided nanoparticles into natural and anthropogenic (manufactured or
engineered) particles. Depending on their chemical composition, these particles can
be further separated into carbon-containing and inorganic nanoparticles. Hence, the
C-containing or inorganic nanoparticles can be formed using biogenic, geogenic,
atmospheric and pyrogenic processes (Nowack and Bucheli 2007).
Due to their great surface area per mass unit, nanoparticles are expected to be
more biologically active than larger sized particles of the same chemical composition
(Sozer and Kokini 2009). Beside a very large specific surface area, nanoparticles
high unique properties including surface energy, and quantum confinement (Ma et al.
2010). These unusual properties may result in substantially different environmental
fate and behaviors than their bulk counterparts. Hence, an emerging area of research
nowadays is focused on short and medium term studies of the environmental and
ecological impact of released nanoparticles. Due to the interaction between nanopar-
ticles and plants, many morphological and physiological can be changed, depending
on the properties of these nanoparticles (Siddiqui et al. 2015b). Furthermore, efficacy
of these nanoparticles is determined by their chemical composition, size, shape, sur-
face covering, reactivity, and most importantly the dose at which they are effective in
the terrestrial environments (Khodakovskaya et al. 2012; Dasgupta et al. 2015,
2016a, b, c; Ranjan et al. 2014, 2015, 2016; Jain et al. 2016; Maddineni et al. 2015).
Several positive and negative effects of nanoparticles on plant growth and devel-
opment have been already reviewed by many researchers from their findings (e.g.,
Nowack and Bucheli 2007; Ju-Nam and Lead 2008; Handy et al. 2008; Mueller and
Nowack 2008; Stampoulis et al. 2009; Ruffini and Cremonini 2009; Kahru and
Dubourguier 2010; Ma et al. 2010; Nair et al. 2010; Peralta-Videa et al. 2011;
Menard et al. 2011; Khot et al. 2012; Pan and Xing 2012; Smita et al. 2012; Ma
et al. 2013; Gardea-Torresdey et al. 2014; Deng et al. 2014; Aslani et al. 2014;
Hudson and Roberta 2015; Huang et al. 2015; Siddiqui et al. 2015b; Chichiriccò
and Poma 2015; Aliofkhazraei 2016; Abd-Alla et al. 2016; Gil-Díaz et al. 2016; Le
Van et al. 2016; Wen et al. 2016). They found that, the impact of engineered nanopar-
ticles on plants depends on the composition, concentration, size and physical and
chemical properties of engineered nanoparticles as well as plant species. Efficacy of
these engineered nanoparticles depends on their concentration and varies from plant
to plant. However, this review covers plausible role nanoparticles in seed germina-
tion, plant growth (shoot and root biomass) and photosynthesis.
A recent trend in nanotechnology has been known as nano-bio interactions to
investigate the interactions of nanomaterials with biological systems like plants
(Albanese et al. 2012). Plant growth and development starts from the germination
of seeds followed by root elongation and shoot emergence as the earliest signs of
growth and development. Therefore, it is important to understand the plant growth
and development in relation to nanoparticles. The reported data from various studies
suggested that effect of nanoparticles on seed germination dependent on their con-
centrations. There are several authors studied the effects of nanoparticles on plants
including many metals/metaloids or metal oxide such as:
1. Cerium (Zhao et al. 2013b, 2014; Rico et al. 2015; Hong et al. 2014),
2. Copper (Shaw and Hossain 2013; Ouda 2014; Lalau et al. 2014; Nair and
Chung 2014; Perreault et al. 2014; Shi et al. 2014; Da Costa and Sharma 2015),
3. Gold (Zhai et al. 2014; Gunjan et al. 2014; Dan et al. 2015),
4. Iron (Ghafariyan et al. 2013; Faria et al. 2014; Pardha-Saradhi et al. 2014;
Burke et al. 2015; Libralato et al. 2016),
5. Nickel (Faisal et al. 2013; Oukarroum et al. 2015),
6. Selenium (Domokos-Szabolcsy et al. 2012; Husen and Siddiqi 2014; El-
Ramady et al. 2015a, b, c, 2016),
7. Silicon (Li et al. 2012; Suriyaprabha et al. 2012a, b; Hussain et al. 2013;
Siddiqui et al. 2014; Siddiqui and Al-Whaibi 2014; Kalteh et al. 2014;
Roohizadeh et al. 2015; Wang et al. 2015b),
8. Silver (Kaveh et al. 2013; Silva et al. 2014; Larue et al. 2014a, b; Boenigk et al. 2014;
Geisler-Lee et al. 2014; Ouda 2014; Meena and Chouhan 2015; Razzaq et al. 2016),
9. Titanium (Foltete et al. 2011; Gao et al. 2013; Burke et al. 2015), and
10. Zinc (Prasad et al. 2012; Pokhrel and Dubey 2013; Hu et al. 2014b; Zhao et al.
2013a, 2014; Tyagi et al. 2014; Bandyopadhyay et al. 2015; Vochita et al. 2016),
It could be listed some toxic and beneficial effects of both nano-SiO2 and nano-
ZnO in the following Tables (Tables 10.1 and 10.2). Concerning these effects, it
could be concluded some findings as follows:
Table 10.1 Beneficiary concentration(s) of zinc and silicon nanoparticles for plants (Siddiqui
et al. 2015b) comparing with nano-Se
Nanoparticle (plant Beneficiary
species) concentration Part of plant/process Reference(s)
Nano-ZnO 400 mg kg−1 Micronutrients: Cu, Mn Zhao et al. (2014)
(Cucumis sativus) and Zn
fruit
Nano-ZnO (Cicer 1.5 mg kg−1 Shoot dry weight Burman et al. (2013)
arietinum L.) (foliar spray)
Nano-ZnO (Vigna 20 mg kg−1 (foliar Biomass Dhoke et al. (2013)
radiate) spray, suspension)
Nano-SiO2 (Zea 15 kg ha−1 Growth parameters Yuvakkumar et al. (2011)
mays L.) and Suriyaprabha et al.
(2012a)
Nano-Se (Nicotinia 100 mg kg−1 Callus initiation and Domokos-Szabolcsy et al.
tabacum L.) microshoot formation (2012)
Nano-Se (Arundo 100 mg kg−1 Rooting and other Domokos-Szabolcsy et al.
donax L.) growth parameters (2014)
Nano-Se (Triticum 100 mg kg−1 Production of biofortified El-Ramady et al. (2016)
aestivum L.; sprouts using micro-farm
Raphanus sativus L.) system
Table 10.2 Effect of nano-ZnO and nano-SiO2 on germination and growth of some plants or
microbes
Comments (toxicity or
Nano- enhancement according to
particle Crop/plant/microorganism nanoparticles concentration) References
Nano- Peanut (Arachis hypogaea) Improved growth and yield (up Prasad et al.
ZnO to 1000 mg kg−1) (2012)
Cluster bean (Cyamopsis Improved shoot-root growth, Raliya and
tetragonoloba L.) chlorophyll (photosynthetic Tarafdar (2013)
pigment), total soluble leaf
protein content, rhizospheric
microbial population, and P
nutrient-mobilizing enzymes
including phytase, acid and
alkaline phosphatase (foliar up
10 mg kg−1)
Ryegrass (Lolium perenne) Reduced biomass, shrank root Lin and Xing
tips, epidermis and root cap (2008)
broken, highly vacuolated and
collapsed cortical cells (up to
1000 mg kg−1 in Hoagland
solution)
Cabbage (Brassica oleracea Dose-dependent inhibition of Pokhrel and
var. capitata L.) germination in aqueous Dubey (2013)
suspension (1000 mg kg−1)
Bacteria (Bacillus subtilis) Mild toxicity due to reactive Adams et al.
(Escherichia coli) oxygen species (ROS) (2006)
production (up to 5000 mg L−1)
Bacteria (Pseudomonas Inhibition of bacterial growth (up Li et al. (2011)
putida) to 100 mg L−1)
Bacteria (Rhizobiales, Decline in bacterial communities Ge et al. (2012)
Bradyrhizobiaceae, and reduced diversity (500 mg
Bradyrhizobium) kg−1 soil for nano-ZnO)
Nano- Maize (Zea mays L.) Enhanced plant dry weight and Suriyaprabha et al.
SiO2 levels of organic compounds (2012a, b)
such as proteins, chlorophyll and
phenols (up to 15 kg ha−1)
Tomato (Lycopersicum Improved seed germination (up Siddiqui and
esculentum Mill) to 8 g L−1) Al-Whaibi (2014)
Mouse-ear cress Increased root length at 400 mg Lee et al. (2010)
(Arabidopsis thaliana) L−1, but reduced root length at
2000 and 4000 mg L−1
Lupin (Lupinus sp.) and No signs of toxicity were Hussain et al.
wheat (Triticum spp.) observed and did not affect seed (2013)
germination and did not show
phytotoxicity (2000 mg L−1)
Bacteria (Bacillus subtilis) Mild toxicity due to reactive Adams et al.
(Escherichia coli) oxygen species (ROS) (2006)
production (up to 5 g L−1)
Source: Ditta et al. (2015), Li et al. (2015), Mura et al. (2015), and Thul and Sarangi (2015)
(a) It is found that, the application of nano-SiO2 (up to 8 g L−1) significantly

improved seed germination of tomato, seed germination index, seed vigor
index, seedling fresh weight and dry weight. Due to this application of nano-
SiO2, an increase in germination parameters may be effective for the growth and
yield of crops. It could be suggested that, nano-SiO2 could be used as a fertilizer
for the crop improvement (Siddiqui and Al-Whaibi 2014).
(b) It is also reported that, nano-SiO2 enhanced seed germination and stimulated
the antioxidant system under NaCl stress in case of tomato (Haghighi et al.
2012) and for squash (Siddiqui et al. 2014).
(c) Under salinity stress, nano-SiO2 improves leaf fresh and dry weight, chloro-
phyll content and proline accumulation. Due to the application of nano-SiO2, it
is found an increase in the accumulation of proline, free amino acids, content of
nutrients, antioxidant enzymes activity, thereby improving the tolerance of
plants to abiotic stress (Haghighi et al. 2012; Li et al. 2012; Siddiqui et al. 2014;
Kalteh et al. 2014).
Several studies suggested that, zinc oxide nanoparticles (nano-ZnO) increased
plant growth and development such as peanut (Prasad et al. 2012), soybean (Sedghi
et al. 2013), wheat (Ramesh et al. 2014) and onion (Raskar and Laware 2014).
These previous authors reported that, lower concentration of nano-ZnO exhibited a
beneficial effect on seed germination. It is also found using different concentrations
of nano-ZnO on cucumber, alfalfa and tomato, that only cucumber seed germination
was enhanced (de la Rosa et al. 2013). Helaly et al. (2014) found that, nano-ZnO (up
to 200 mg L−1) supplemented with MS media promoted shooting, somatic embryo-
genesis, regeneration of plantlets, and also induced proline synthesis, activity of
some enzymes including superoxide dismutase, catalase, and peroxidase thereby
improving tolerance to biotic stress. Therefore, some researchers have been studied
different toxicological effect of nanoparticles on plants due to their unique proper-
ties. Whereas, their research focused on the realization of the beneficial effects of
nanoparticles on plant remains incomplete. Furthermore, few studies have shown a
positive effect of nanoparticles on plant growth and development. It is proved that,
effect of nanoparticles varies from plant to plant depending on their mode of appli-
cation, size and concentrations by Siddiqui et al. (2015b).
It could be concluded that, nanoparticles have different effects on plants depend-
ing on several factors including plant species, nanoparticles and environmental fac-
tors. Further research is needed to confirm whether nanoparticles are essential for
plants as well as the current researches are in the beginning. To understand bio-
chemical, physiological and molecular mechanisms of nanoparticles in plants, more
hard works are required.
10.5 Nanoparticles for Plant Nutrition
The applications of nanotechnology concerning applied materials sciences and bio-

mass conversion technologies can be considered the basis of providing food, feed,
fiber, fire, and fuels in agriculture. Therefore in agriculture, management of
Fig. 10.3 Closed hydroponic system (vegetables and fish production) and solar energy system can
be used in the experimentation farm in Kafrelsheikh Uni., (photo 1), intensive crop production
(photo 2), livestock production system in Kafrelsheikh (photo 3) and sediments (NOT soil profile)
from Burullus Lake (sandy soils) and main Gharbia drain (clay soils) during the cleaning process
(photo 4) in Kafr El-Sheikh Governorate (Photos by El-Ramady)
Fig. 10.4 Soil management of salt-affected soils can be performed in strawberry (photo 1) and
pepper (photo 2) production under green house (drip irrigation), to overcome their problems using
soil amendments and solarization in Kafrelsheikh Uni (Photos by El-Ramady)
optimum plant nutrients for sustainable crop production is the priority-based area of
research (Figs. 10.3 and 10.4). In this regard, much progress in the area of plant
nutrition has come forward and nano-nutrition is one of the most interesting research
areas for sustainable agriculture production (Ditta et al. 2015). Plant nano-nutrition
is the application of nanotechnology for the provision of nano-sized nutrients for the
crop production. It could be used of nanoparticles or nano-nutrients under two cases
including biotic and abiotic forms. In regard to the abiotic form of nano-nutrients, it
is prepared from inorganic sources like salts but due to many of them non-
biodegradable, it is not safe. Concerning the biotic one, it is prepared from organic
sources which are definitely environment friendly and biodegradable (Ditta et al.
2015). Therefore, a few attempts or studies have been made in the field of
nano-nutrition and a lot more are expected in the near future because this field of
plant nutrition is efficient and sustainable. Hence, it could be increased the effi-
ciency of micro- as well as macro-nutrients for plants using this nano-nutrition
(Ditta et al. 2015; Mastronardi et al. 2015; Servin et al. 2015; Thul and Sarangi
2015).
It is well documented that, nanotechnology has the potential to revolutionize the
agricultural sector with novel tools for enhancing the productivity of the crop plants
through efficient nutrients in the form of nanofertilizers, nanopesticides, or nano-
herbicides by the plants (Tarafdar et al. 2013). Whereas, it could be enhanced the
agricultural productivity by using of such nano-nutrients for formulation of nanofer-
tilizers, nano-porous zeolites for slow release, enhanced germination, as well as
efficient nanocapsules for herbicide delivery and vector; efficient dosage of water
and fertilizer; pest management and nano-sensors for pest detection (Scrinis and
Lyons 2007). These previous applications would definitely be helpful for the solu-
tions of the limitations and challenges facing large scale and intensive farming sys-
tems (Ditta et al. 2015).
It is also reported that, nanomaterials have great implications in sustainable agri-
cultural crop production and many studies reported their positive impact on various
crops, whereas the main effect has been reported to be improved in these reports is
the germination of various crops (Ditta et al. 2015). Concerning this effect on the
germination of plants, some studies have been involved in improving the growth of
crops by the application of different nano-nutrients such as nano-SiO2 in maize and
tomato (Suriyaprabha et al. 2012a, b; Siddiqui and Al-Whaibi 2014), carbon nano-
tubes in tomato, mustard and rice (Khodakovskaya et al. 2009; Nair et al. 2010;
Ghodake et al. 2010), nanao-TiO2 in spinach and wheat (Lei et al. 2008; Feizi et al.
2012; Larue et al. 2012), and nano Si, Pd, Au, Cu in lettuce (Shah and Belozerova
2009). Therefore, it could be summarized the effects of nanonutrients or nanofertil-
izers on the growth, germination rate, phytotoxicity and other physiological charac-
terizations for certain common vegetable and field crops as follows:
1. Barley (Hordeum vulgare L.): Chauhan et al. (2013), Gruyer et al. (2014), Rico
et al. (2015), and Feichtmeier et al. (2015);
2. Chickpea (Cicer arietinum L.): Burman et al. (2013), Mohammadi et al. (2013,
2014), Nair and Chung (2015b), and Hasanpour et al. (2015);
3. Cabbage (Brassica pekinensis L.): Baskar et al. (2015) and Xiang et al. (2015);
4. Cucumber (Cucumis sativus L.): Kim et al. (2012), Shams et al. (2013), Cui
et al. (2014), Haghighi and da Silva (2014), and Zhang et al. (2015);
5. Green pea (Pisum sativum L.): Huang et al. (2014), Mukherjee et al. (2014),
and Nair and Chung (2015a);
6. Lettuce (Lactuca sativa L.): Song et al. (2013), Gruyer et al. (2014), Gui et al.
(2015b), Doolette et al. (2015), Hong et al. (2015), and Zahra et al. (2015);
7. Maize (Zea mays L.): Suriyaprabha et al. (2012a, b), Sun et al. (2014), Liu et al.
(2015), and Zhang et al. (2015);
8. Oil seed rape (Brassica napus L.): Song et al. (2013), Kouhi et al. (2015a, b),
Palmqvist et al. (2015), and Sarabi et al. (2015);
9. Onion (Allium cepa L.): Golubkina et al. (2012), Haghighi and da Silva (2014),
Laware and Raskar (2014), Konotop et al. (2014), and Taranath et al. (2015);
10. Rice (Oryza sativa L.): Nair et al. (2011), Shaw and Hossain (2013), Rico et al.
(2013a, b), Gui et al. (2015a), Da Costa and Sharma (2015), and Wang et al.
(2015b);
11. Tomato (Solanum lycopersicum L.): Haghighi et al. (2012), de la Rosa et al.
(2013), Faisal et al. (2013), Haghighi and da Silva (2014), Siddiqui and
Al-Whaibi (2014), Shankramma et al. (2015), Antisari et al. (2015), and
Mehrian et al.(2015);
12. Turnip (Brassica rapa ssp. rapa L.): Thiruvengadam et al. (2015);
13. Wheat (Triticum aestivum L.): Du et al. (2011), Larue et al. (2012), Feizi et al.
(2012), Cui et al. (2014), Yanık and Vardar (2015), Wang et al. (2015a), and
Watson et al. (2015).
An increase in the germination rate of the previous stated crops is an important
aspect of the nanomaterials however, the application of these nanomaterials as a
nutrient source for the entire growth cycle of two crop plants needs to be explored
yet. So, the evaluation of these materials as a nutrient source, their critical concen-
tration, and their phytotoxic effects, if any need to be explored in future (Ditta et al.
2015).
Recently, several studies have been focused on the interaction between nanopar-
ticles and different plant species including the physiological, phytotxicological and
biochemical aspects as well as plant nutrition (Patra et al. 2013; Seabra et al. 2014;
Taran et al. 2014; El-Ramady et al. 2014a, b, 2015b, c, d, 2016; Ditta et al. 2015;
Subramanian et al. 2015; Dimkpa et al. 2015; Da Costa and Sharma 2015,
Mastronardi et al. 2015; Monreal et al. 2015; Solanki et al. 2015). So, plant nano-
nutrition and nanofertilizers as well as nanophytoremediation are emerging issues
should be considered in frame of sustainable agriculture. Extensive studies had been
undertaken to study different nanoparticles containing nutrients in frame of plant
nutrition as follows:
1. Nitrogen-nanofertilizers (Subramanian and Sharmila Rahale 2013; Mohanraj
2013; Manikandan and Subramanian 2014; Seabra et al. 2014),
2. Phosphate-nanofertilizers (Bansiwal et al. 2006; Adhikari 2011; Behnassi et al.
2011; Liu and Lal 2014),
3. Potassium-nanofertilizers (Subramanian and Sharmila Rahale 2012),
4. Sulfur-nanofertilizers (Patra et al. 2013; Selva Preetha et al. 2014;
Thirunavukkarasu 2014),
5. Calcium oxide nanoparticle (Deepa et al. 2015), iron oxide nanoparticle (Kim
et al. 2015),
6. Magnesium nanofertilizers (Delfani et al. 2014),
7. Copper oxide nanoparticles (Da Costa and Sharma 2015; Dimkpa et al. 2015),
8. Manganese nanoparticles (Pradhan et al. 2014),
9. Zinc oxide nanoparticles (Subramanian and Sharmila Rahale 2012; Patra et al.
2013; Tarafdar et al. 2014; Dimkpa et al. 2014, 2015; Watson et al. 2015),
10. Silicon nanoparticles (Siddiqui and Al-Whaibi 2014; Kalteh et al. 2014; Le
et al. 2014; Abdul Qados and Moftah 2015; Abdul Qados 2015),
11. Molybdenum (Aubert et al. 2012; Taran et al. 2014; Kanneganti and Talasila
2014),
12. Iron oxide (Alidoust and Isoda 2013; Ghafariyan et al. 2013; Lebedev et al.
2014; Soliman et al. 2015; Shankramma et al. 2015),
13. Nickel oxide (Faisal et al. 2013; Oukarroum et al. 2015; Antisari et al. 2015)
and
14. Selenium nanoparticles (Golubkina et al. 2012; Husen and Siddiqi 2014; El-
Ramady et al. 2015b, c, d, 2016; Papkina et al. 2015).
For more an efficient use of agricultural natural resources like water, nutrients,
and chemicals during farming, nanotechnology (like nano-sensors) gave us the abil-
ity to develop and maximize the benefits of these resources management. Moreover,
these nano-sensors, which have been proved to be user friendly, have not only been
used as nano-biosensors but also for the control of soil nutrients and these have
helped in the reduction of fertilizer consumption and environmental pollution
(Ingale and Chaudhari 2013; Ditta et al. 2015; Kah 2015).
Therefore, it is well established that, nanotechnology has great potential in
improving the quality of life through its applications in various fields including
agriculture production and food system. Moreover, the nanomaterials have been
applied as nano-nutrients (in the form of nanofertilizers) for crop production and as
crop protectants in the form of nanopesticides and nano-herbicides, as well as nano-
sensors in precision agriculture. In this regard, the importance of nano-nutrition in
the sustainable agricultural production and its future scenario could be possible to
apply on a large scale. Nevertheless, nanotechnology has a great potential in various
walks of life, but we must be very careful about any new technology to be intro-
duced for its possible unforeseen related risks that may come through its positive
potentials. Therefore, potential applications of nanotechnology in agricultural pro-
duction for the welfare of humans and hence sustainable environment, challenges,
and opportunities for developing countries should be kept in mind.
It could be concluded that, nanoparticles are emerging issues for plant nutrition
in the frame of sustainable agriculture. These nanoparticles can be considered an
important source for nano-nutrition of plants and nanofertilizers. Otherwise, there
are some open questions still in needing to answer including: (1) are nano-nutrients
or nanofertilizers enough or sufficient sources for crop production instead of normal
mineral fertilizers? (2) To what extent are the different effects of nanofertilizers cur-
rently taken into account? (3) Can different risks and benefits associated with the
use of nanofertilizers be assessed? (4) Which nanofertilizer types are ready to
emerge in the forseen future under different regulations?
10.6 Conclusion
The aim of this review is to explore the potential of the field of nanoparticles with
respect to sustainable agriculture. This main focus is on the currently applied uses
of nanoparticles for agriculture including different effects in enhancing soil secu-
rity, using of nanoparticles for plant nutrition as well as nanoparticles and its effects
on plants. Nanoparticles have emerged as a versatile platform, which could provide
cost-effective, efficient and environmentally acceptable solutions to the global sus-
tainability challenges facing society. Nanoparticles have a significant influence on
the economy and the environment by improving both fertilizers and energy. So,
these nanoparticles have a high potential for achieving sustainable agriculture.
Therefore, the agri-nanotechnology might take a few decades to move from labora-
tory to land.
Acknowledgements Authors thank the outstanding contribution of STDF research teams

(Science and Technology Development Fund, Egypt) and MBMF/DLR (the Federal Ministry of
Education and Research of the Federal Republic of Germany), (Project ID 5310) for their help.
Great support from this German-Egyptian Research Fund (GERF) is gratefully acknowledged.
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Index
A Auffan, M., 270

Abdalla, N., 283–299 Awaad, A.M., 87
Acevedo, F., 236
Actinomycetes, 72
Activated carbon supported nanozero valent B
iron particle, 239 Bala, N., 232
Active packaging Balamurugan, K., 119
antimicrobial films, 166–167 Bandyopadhyay, S., 16
oxygen scavenging film, 167 Banerjee, A., 85
UV absorbing film, 167–168 Banerjee, P., 87
Adams, L.K., 292 Barik, T., 266
Agrowaste reduction, 48–49 Barndok, H., 111
Ahi, H., 12 Baskar, V., 296
Algae, 78, 206, 207, 253 Bayatvarkeshi, M., 232
Alidokht, L., 236 Bayoumi, Y., 283–299
Al-Khateeb, L.A., 119 Belozerova, I., 258, 259
Alshaal, T., 283–299 Bioactive food components, 197
Al-Whaibi, M.H., 292 Biobased packaging
Amer, M., 283–299 polycaprolactone, 161
Amirnia, R., 232, 234 polyhydroxybutyrate, 160–161
Ammonium sulphate, 233–234 polylactic acid, 159–160
Amylose, 194 starch, 158–159
Anandaraj, M., 288 Bio-based packaging material, 153, 188
Ankita, K., 17 Biobased synthesis, metal oxide nanoparticles
Antisari, L.V., 271, 297 algae, 78
Appell, M., 288 bacteria and actinomycetes, 72–76
Aptamers plants and phytochemicals, 78–82
advantages over antibodies, 143 yeasts and fungi, 76–78
challenges, 145 Biodegradable polymers, 66, 69–70, 155, 159
colorimetric detection, 144 Biosensors, 21–22
synthesis, 144 aptamers, 145
whole bacteria detection, electronic nose, 23
143–144 enzymatic, 22–23
Arami, M., 109 nanosensor, 45, 168–169, 211
Aroma compounds, 194, 195, 198 rapid detection, 22

Sustainable Agriculture Reviews 20, DOI 10.1007/978-3-319-39303-2
314 Index
Bortolin, A., 232 pH and temperature, 109

Brar, S.K., 101–123 photocatalyst properties, 105, 109
Burman, U., 291, 296 pseudo-first order reaction, 110
Co-precipitation reaction, 8
Corless, C.E., 138
C Cosmeceuticals, 53
Cai, D., 15 Crane, R.A., 66
Calabi-Floody, M., 232 Cu-chitosan nanoparticles, 198, 213, 214
Cañas, J.E., 260, 270 Cudjoe, K.S., 137
Canola active oil, 186 Cui, D., 296, 297
Carbon nanotubes, 116–118, 212, 260 Cyclodextrins, 194, 195
Carlos, R.R., 16
Carotenoids, 196
Cellulose nanocrystals, 188 D
Chakraborty, A. R., 1–31 da Silva, J.A.T., 296, 297
Chang, M.C., 236 Daar, A.S., 288
Chang, Y.-I., 239 Da Costa, M.V.J., 297
Chang Chien S.W., 237 Das, S.K., 115
Chauhan, N., 296 Dasgupta, N., 1–31, 152
Chaw, L.J., 10 Dechlorination, 238, 239
Chen, J.H., 117, 236, 254, 288 de la Rosa, G., 297
Chen, X., 115 de Oliveira, J.L., 288
Cheng, J.M., 236 Delfani, M., 257, 258
Chhipa, H., 247–273 Dendrimers, 14, 18, 44, 45, 59, 230
Cholera, 130, 135 Desalination, 26
Chookhongkha, N., 264 Dhoke, S.K., 291
Choudhary, R., 185–217 Diarrhea, 130, 134–136
Chowdappa, P., 265 Dimkpa, C.O., 270
Chrysochoou, M., 236 Ding, X., 267
Chung, I.M., 296 Disinfectants, 18–19
Cifuentes, Z., 272 Ditta, A., 288, 292
Cioffi, N., 266 DNA
Citral flavour, 195 amplification method, 138
Clay nanotubes, 16 gold nanoparticles for detection, 140–142
Closed hydroponic system, 294 Domokos-Szabolcsy, É., 283–299
Coffea arabica seed, 198 Doolette, C.L., 296
Conservation agriculture, 285–286 Doong, R.V., 288
Contaminants removal. See also Emerging Dos Santos Silva, M., 267
contaminants Du, W., 297
carbon nanotubes, 116–118 Dubey, B., 292
graphene, 118–120 Dubrovsky, N.M., 253
magnetic nanoparticles
chlorinated methanes, 115
Fe-Fe2O3, 114 E
Fe3O4, 114 Eco-toxicity study, 269
Fe3O4-C18 composite, 113–114 El Azzi, D., 288
palladium, 114–115 El Beyrouthya, M., 288
nanofiltration membranes, 121–123 Electrokinetic remediation, 239
polymeric nanosponge, 120, 121 Electronic nose, 23
precious metal nanosystems, 115–116 Electrospinning technique, 195
titanium dioxide (TiO2) Electrospray technique, 196
commercialization challenges, 105 Elfeky, S.A., 232
doped, 111–113 El-Ramady, H., 283–299
Index 315
El-Temsah, Y.S., 236, 238 UV absorbing film, 167–168

Emerging contaminants. See also advantages, 174
Contaminants removal biobased
challenges, 123 polycaprolactone, 161
classification of, 103–104 polyhydroxybutyrate, 160–161
distribution of, 102 polylactic acid, 159–160
preventing adverse effects, 102, 104 starch, 158–159
Emulsification, 197 disadvantages, 174–175
Emulsion inversion, 12–14 easy transportation, 187
Encapsulation food quality
bioactive lipids, 196–197 barrier properties, 203–205
flavour, 194–196 oxygen scavenging properties, 205
nano delivery systems, 190–193 perishability, 202–203
nutrient, 196 food safety
probiotic, 197 nano-biotracers, 210–212
Engineered nanoparticles, 271, 272 nanocomposites, 206–208
Enterohemorrhagic E. coli, 135–136 nanolaminates, 209–210
Enterotoxigenic E. coli, 134–135 improved
Enzymatic biosensors, 22–23 nanoclays, 163–165
Enzyme Linked Immunosorbent Assay, 131 nanocoatings, 162
Enzymes, 66–67 nanocristals, 163–165
Escherichia coli, 16, 47, 49, 67, 116, 118, 130, nanolaminates, 163
134–136, 143, 199–201, 210 innovations, 187–188
Esteban-Tejeda, L., 266 material, 188
Eugenol, 190 military requirements, 187
nano-packaging, 202
non-respiring foods, 202
F primary package, 187
Fabricated xylem vessels, 15–16 respiring foods, 202
Faisal, M., 297 safe delivery, 187
Fan, L., 232 safety issues
Fat soluble nutrients, 186 nano-packaging regulation, 173
Feichtmeier, N.S., 296 nanoparticle migration limit, 172
Feizi, H., 297 secondary package, 187
Feng, B.H., 267 smart
Fibre matrix composite structure, 186 active tags, 171
Fick’s law, 208 anti-counterfeiting, 171
Finke, J.H., 11 freshness detection, 169–170
Flame spray synthesis, 7 nanosensors, 168–169
Flavour encapsulation, 194–196 oxygen indicators, 169–171
Food and water borne pathogens, 130–132 product identification, 171
conventional methods detection spoilage indicators, 169–170
culture based methods, 136–137 traceability, 171
immunoassays, 137–138 Food processing
PCR, 138 in food safety, antimicrobial agents
real time PCR, 138–139 Coffea arabica seed, 198
E. coli Cu-chitosan nanoparticles, 198
enterohemorrhagic, 135–136 films and edible coatings, 201
enterotoxigenic, 134–135 nanoparticles, 200–201
Salmonella, 133–134 oil-in-water emulsions, 199–200
Food packaging in quality
active encapsulation (see Encapsulation)
antimicrobial films, 166–167 sensory and texture improvement,
oxygen scavenging film, 167 197–198
316 Index
Food systems and structures, 185–187 H

Food traceability, 210 Haghighi, M., 296, 297
Free nanozero valent iron particle, 239 Halloysite clay nanotubes, 201, 208
Freundlich isotherm model, 112 Han, D., 20
FT-IR spectroscopy, 87–88 Hanif, H.U., 232
Fullerenes, 44, 47, 118 Hasanpour, H., 296
Functional lipids, 197 Hasegawa, H., 288
Fungi, 76–78, 253 He, L., 266
Heavy metals removal, 27
Helaly, M.N., 293
G Hemolytic uremic syndrome, 130
Gajbhiye, M., 263 Hermosín, M.C., 267
Gan, L., 264 Hexanal, 211
Gao, F., 260 Hidayat, R., 232
Gao, Y., 236 Hong, J., 296
Gas detection, 23, 211 Hossain, Z., 270, 297
Gas flushing techniques, 205 Hossaini, H., 111
Gas industry, 50 Hristovski, K., 111, 112
Ge, Y., 292 Hsu, H-L., 17
Geo-biological cycles, 248 Hu, A., 109
Ghafariyan, M.H., 257, 258 Hu, Y.H., 288
Gholam, R.M., 7 Huang, J., 232
Gholamhoseinpoor, F., 88 Huang, L., 84
Giannousi, K., 265 Huang, Y.C., 296
Glenn, G.M., 267 Hussain, H.I., 292
Gold nanoparticles, 23, 45, 206 Hydrophobic nanoparticle, 272
α-amylase, 67 Hydroxyapatite, 234
contaminants removal, 115–116 Hyperglycaemia, 185
DNA detection, 131, 132, 140–142
plants and phytochemicals, 79
UV-visible spectrum, 84, 85 I
Golubkina, N.A., 297 Immunoassays, 137–138
Gomes, H.I., 236, 239 Impatiens balsamina, 239
Goswami, A., 267 Improved packaging
Gourmelon, M., 135 nanoclays, 163–165
Gowda, S., 265 nanocoatings, 162
Graphene nanoplatelets, 118–120 nanocristals, 163–165
Grasielli, C.O., 10 nanolaminates, 163
Green synthesis, metal oxide nanoparticles Ingle, A., 267
biobased methods Inorganic nanoparticles
algae, 78 co-precipitation method, 8
bacteria and actinomycetes, 72–76 flame spray synthesis, 7
plants and phytochemicals, 78–82 laser induced gas evaporation method, 7–8
yeasts and fungi, 76–78 plasma based nanoparticles production, 8
biodegradable polymers, 69–70 silver, 5, 6
enzymatic method, 66–67 sol-gel method, 8
microwave-assisted synthesis, 71–72 Intellectual property rights
monosaccharides, 67–69 copyright, 54
polysaccharides, 67–69 difficulties fulfilling patentability
vitamins, 70–71 criteria, 56
Grillo, R., 267 difficulties in identifying patents, 56
Gruyer, N., 296 industrial design right, 54
Gu, J., 237 issues and challenges, 55
Gui, X., 296, 297 multi-industrial applications, 55–56
Guo, K.W., 252 patent, 54
Index 317
plant breeders’ rights, 54 Li, M., 292

trade dress, 55 Li, X., 116
trademark, 55 Li, Y., 272
trade secrets, 55 Li, Z., 232
Iravani, S., 65–90 Liang, R., 109
Irshaan, S., 185–217 Lien, H.L., 115
Limonene, 196
Lin, D., 258–260, 270, 292
J Listeria monocytogenes, 49
Jayaseelan, C., 67, 266 Liu, F.F., 119
Jesus, M.D.L.F. (2012), 7 Liu, J., 236, 238, 239
Jheng, J-M., 28 Liu, R., 236, 256, 257, 260
Jo, Y.-K., 263 Liu, X., 257, 296
Jordan, C.C., 57 Liu, X.-M., 266
Joshi, P., 247–273 Lourtioz, J.-M., 288
Jyoti, A., 129–146 Lovely, D.R., 75
Lu, C., 260
K
Kalishwaralal, K., 67 M
Kang, H.Y., 236 Maas, D., 74
Karunakaran, G., 232 Macronutrient nanofertilizers, 256–257
Kathiervelu, S.S., 51 Maddinedi, S.B., 84
Kathiresan, K., 77 Magliulo, M., 137
Katsenovich, Y.P., 236 Magnetic nanoparticles, 113–115
Khodakovskaya, M.V., 260, 272 Magnetite (Fe3O4) nanoparticles, 234
Kim, J.S., 263 Mahajan, P., 258
Kim, J.Y., 237 Mahdavi, S., 237
Kim, S., 296 Mahmoodi, N.M., 109
Konishi, Y., 72 Maillard reaction, 194
Konotop, Y.O., 297 Majoros, I.J., 46
Kottegoda, N., 232 Mallampati, S.R., 236, 237
Kouhi, S.M.M., 296 Mani, C., 264
Kowshik, M., 76 Manikandan, A., 232, 234
Kumar, A., 1–31, 85 Manivasagan, P., 67
Kumar, R., 263 Mannoor, M.S., 28
Kumar, S.A., 76, 77 Martínez-Fernández, D., 236
Kuswandi, B., 151–175 Mehrian, S.K., 297
Kuzma, J., 248 Membrane emulsification, 12–13
Kyzas, G.Z., 120 Menezes-Blackburn, D., 232
Merges, R.P., 55
Metal and metal oxide nanoparticles
L green synthesis
Labrenz, M., 73 biobased methods (see Biobased
Lal, R., 254, 256, 257, 289 synthesis, metal oxide
Langmuir and Polanyi-Manes isotherm nanoparticles)
models, 112–113 biodegradable polymers, 69–70
Larue, C., 272, 297 enzymatic method, 66–67
Laser induced gas evaporation method, 7–8 microwave-assisted
Laware, S.L., 297 synthesis, 71–72
Le, T.T., 237, 238 monosaccharides, 67–69
Lee, C.W., 292 polysaccharides, 67–69
Li, K.-E., 292 vitamins, 70–71
318 Index
Metal stabilization, 237 Nano-clay polymer composites, 231, 233

MgO nanoparticles, 213, 214 Nanoclays, 9–10, 157, 158, 163–165, 204,
Mhlanga, S.D., 120 208, 231–233
Michálková, Z., 237 Nano cluster™, 187
Microbial detection, 211 Nanoemulsions, 209
Microcapsules, 199 characteristics, 10
Microccocus luteus, 210 emulsion inversion, 13–14
Microencapsulation technology, 196 high-pressure homogenization, 11
Microfibrillated cellulose, 208 high-speed devices, 12
Micronutrients nanofertilizers membrane emulsification, 12–13
carbon nanotubes, 260 phase inversion point, 13–14
nanoparticles production, 11
copper, 257, 259 solvent displacement, 13
iron, 257, 258 spontaneous emulsification, 13
manganese, 258 ultrasound, 11–12
molybdenum, 257, 259 Nanofertilizers, 48, 234, 256–261, 296–298
titanium oxide, 257, 260 dynamics of, 260–261
zinc, 258–259 macronutrient, 256–257
Microwave-assisted synthesis, 71–72 micronutrients
Miralles-Wilhem, F.R., 236 carbon nanotubes, 260
Mohammadi, R., 296 copper nanoparticles, 257, 259
Moliner-Martinez, Y., 114, iron nanoparticles, 257, 258
Mondal, K.K., 264 manganese nanoparticles, 258
Monosaccharides, 67–69 molybdenum nanoparticles, 257, 259
Montalvo, D., 232 titanium oxide nanoparticle, 257, 260
Montmorillonite (MMT), 9–10, 52, 114, 159, zinc nanoparticles, 258–259
160, 162, 164, 165, 204, 205, 208, Nanofiltration membranes, 121–123
231, 233 Nanohydroxyapatite, 234
Morillo, E., 267 Nanolignocellulosic materials, 16
Motes, W., 249 Nanoliposomes, 196
Mukherjee, A., 296 Nanomaterials
Mukhopadhyay, S.S., 288 application, soil management, 240
Multi-layered packages, 188 basics of, 188
Mura, S., 292 beneficial properties, 30
definition of, 251
in different fields, 230
N farming practices, 252
Naghdi, M., 101–123 fungi, 253
Nair, P.M.G., 296 metallic nanoparticle, 253
Nair, R., 262, 297 nanoclays, 9–10
Nakao, H., 135 nanoemulsions
Nandita, D., 52, 85 characteristics, 10
Nanoagrochemicals, 49 emulsion inversion, 13–14
Nanobarcode technology, 210–211 high-pressure homogenization, 11
biological applications, 20–21 high-speed devices, 12
non-biological applications, 21 membrane emulsification, 12–13
quantum dots, 21 phase inversion point, 13–14
SIAD, 20 production, 11
Nanobioremediation, 18 solvent displacement, 13
Nanocapsules, 5, 6, 212, 296 spontaneous emulsification, 13
plant protection and pest management, ultrasound, 11–12
262–263 nanoparticles (see Nanoparticles)
smart delivery system, nanomaterials, physical and wet chemical methods, 253
255–256 properties of, 189
Index 319
soil amendments (see Soil amendments) Nanoscale carriers, 14–15

soil remediants (see Soil remediants, Nanoshells, 44, 46
nanomaterials) “Nanotech foods,” 217
surface modifiers, 252 Nanotechnology
synthesis of, 252 in agriculture
toxicological effects of, 30, 216–217 advantage, 248–251
Nanominerals, 233–234 antimicrobial agents, 254
Nano-oligodynamic metallic particles, 24–25 application of, 254
Nanoparticles conventional fertilizers, 253
applications and challenges, 88, 90 nano-formulation, 254–255
definition, 290 nano-supplement fortified feed, 254
inorganic panacea for, 254
co-precipitation method, 8 phosphorus and nitrogen fertilizer, 253
flame spray synthesis, 7 precision farming, 254
laser induced gas evaporation risk assessment of, 269–272
method, 7–8 sustainable farming practices (see
plasma based nanoparticles Sustainable farming practices)
production, 8 vs. conventional practices, 268–269
silver, 5, 6 in agriculture and food industry
sol-gel method, 8 Cu-chitosan nanoparticles, 213, 214
organic, 5 MgO nanoparticles, 213, 214
and plants TiO2 nanoparticles, 215
closed hydroponic system, 294 ZnO nanoparticles, 212, 213
metals/metaloids/metal oxide, 292 in agri-food production
nutrition (see Plant nano-nutrition) crop improvement, 47
salt-affected soil management, 295 nanofoods, 48
seed germination, 290, 291 agrowaste reduction, 48–49
toxicological effect, 293 bacterial contaminants in milk, 49
ZnO and SiO2, 291–293 biofuel, 48–49
spectroscopic characterization biomedical applications, 46–47
FT-IR spectroscopy, 87–89 biosensors
optical properties, 83 electronic nose, 23
surface plasmon resonance, 83 enzymatic, 22–23
UV-visible spectroscopy, 83–87 gold nanoparticles, 23
sustainable agriculture rapid detection, 22
composting from leaves, 286 clay nanotubes, 16
conservation agriculture, 285–286 copyright protection, 57
conventional agriculture, 285 cosmeceuticals, 53
green house under drip irrigation, 287 design protection, 59
natural regenerative processes, 286 disinfectants, 18–19
salt-affected soils, 287 fabricated xylem vessels, 15–16
soil, 288 food and agriculture, 3, 15, 51–53
types gas industry, 50
carbon nanotubes, 45 global scenario of patents, 56–57
dendrimers, 44 green (see Green synthesis, metal oxide
fullerenes, 44 nanoparticles)
gold nanoparticles, 45 intellectual property rights
liposomes, 44 copyright, 54
nanobiosensors, 45 difficulties fulfilling patentability
nanoshells, 44 criteria, 56
nanowires, 44 difficulties in identifying patents, 56
quantum dots, 44 industrial design right, 54
unique properties, 290 issues and challenges, 55
320 Index
multi-disciplinary nature, 55–56 Ocsoy, I., 265

multi-industrial applications, 55–56 Oil industry, 49–50
patent, 54 Optical properties, nanoparticles, 83
plant breeders’ rights, 54 Oxygen scavenging systems, 205
trade dress, 55
trademark, 55
trade secrets, 55 P
nanoagrochemicals, 49 Packaging innovations, 187–188
nanobarcode Palmqvist, N.G., 296
biological applications, 20–21 Paret, M.L., 264, 265
non-biological applications, 21 Parida, U.K., 84
quantum dots, 21 Park, B., 288
SIAD, 20 Park, H.J., 263
nanobioremediation, 18 Patel, P.D., 22
nanofertilizers, 48 Pathogenic bacteria
nano-food-packaging, 4 conventional methods detection
nano-food processing, 3 culture based methods, 136–137
nanolignocellulosic materials, 16 immunoassays, 137–138
nanomaterials (see Nanomaterials) PCR, 138
nanoscale carriers, 14–15 real time PCR, 138–139
NASA’s definition, 284 detection
oil industry, 49–50 aptamers (see Aptamers)
photocatalysis, 17–18 DNA probes and gold nanoparticles,
regulations for, 215–216 131, 132, 140–142
removing contaminants (see Contaminants enzyme linked immunosorbent assay,
removal) 131, 132
safe application, 31 polymerase chain reaction assays,
solar system model, 2 131, 132
textile industry, 50–51 E. coli
trademarks protection, 58 enterohemorrhagic, 135–136
wastewater treatment, 19–20 enterotoxigenic, 134–135
water quality management limitations, 146
desalination, 26 nanoaptasensors
heavy metals removal, 27 lateral flow assay, 144–145
nano-oligodynamic metallic particles, Salmonella, 133–134
24–25 Patil, S.S., 288
photocatalysis, 25–26 Pattanayak, M., 86
wireless nanosensors, 27–28 Pelaez, M., 111
Nanowires, 23, 44, 70 Peppermint oils, 200
Nano zero valent iron (nZVI), 238 Pérez-de-Luque, A., 263, 267
Native starch, 194 Perishability, 202–203
Natural food components, 188 Pesticide detection, 211
Nayak, P.L., 86 Phase inversion point, 13–14
Nekrasova, G.F., 258, 259 Phase separation method, 201
Nghiem, L.D., 122 Philipse, A.P., 74
Ngô, C., 288 Photocatalysis, 17–18, 25–26
Nisin, 208 Phytoremediation, 238–239
Non-solvent induced phase separation Pickering emulsion, 186
(NIPS), 10 Pigeot-Rémy, 17
Nutrient encapsulation, 196 Plant nano-nutrition
abiotic form, 295
benefits, 298
O biotic form form, 295–296
Obesity, 185 effects, 296–297
Ochiai, R.L., 130 germination, 296, 297
Index 321
nanoparticles interaction, 297–298 Rotor/stator devices, 12

productivity enhancement, 296 Rubiales, D., 263
risks, 298
Plant protection and pest management
copper nanoparticles, 266 S
nano-capsule, 262–263 Sadeghi, B., 88
nano-encapsulation, 262 Saharan, V., 265
silica nanoparticles, 266 Salamanca-Buentello, F., 288
silver nanoparticles, 263 Salem, N.M, 87
types of, 264–265 Salipira, K.L., 117
zinc nanoparticles, 266–268 Salmonella spp., 130, 133, 136, 137
Plants and phytochemicals, 78–82 Sanghi, R., 78
Plasma based nanoparticles production, 8 Sarabi, M., 296
Pokhrel, L.R., 292 Sarangi, B.K., 288
Polychlorinated biphenyls (PCB), 239 Saraswathi, R., 260
Polylactic acid, 204 Sarkar, P., 185–217
Polymerase chain reaction assays, 131 Sarkar, R., 70
Polymeric nanosponge, 120, 121 Sarkar, S., 232
Polysaccharide polymers, 186 Sarma, S.J., 101–123
Polysaccharides, 67–69 Sastry, R.K., 256
Pradhan, S., 258 Satapanajaru, T., 236
Prasad, R., 288 Sathishkumar, M., 79
Prasad, T.N.V.K.V., 292 Sato, K., 141
Pray, L., 52 Saxena, M., 232
Precious metal nanosystems, 115–116 Scopus indexed article database (SIAD), 20
Precision farming, 254 Scott, T.B., 66
Probiotic encapsulation, 197 Senapati, U.S., 87, 88
Protein polymers, 186 Seo, Y., 264
Pseudo-first-order kinetic model, 110 Shah, V., 258, 259
Pulimi, M., 229–240 Shaheen, S.M., 236
Shahid, S.A., 232
Shahwan, T., 87
Q Shalaby, T.A., 283–299
Qian, K., 264 Shameli, K., 88
Quantum dots, 21, 26, 31, 44, 46, 56, 188, 230 Shamim, N., 288
Shams, G., 296
Shams, K., 12
R Shanker, R., 1–31, 129–146
Rai, M., 267 Shankramma, K., 297
Raliya, R., 259, 292 Shariatmadari, N., 236
Ramalingam, C., 1–31 Sharma, P.K., 297
Ramirez, A.A., 101–123 Sharma, V.K., 288
Rangaraj, S., 232 Sharon, M., 262
Rangnekar, A., 67 Shaw, A.K., 270, 297
Ranjan, S., 1–31 Shehata, S., 283–299
Rapid detection biosensors, 22 Shen, H.Y., 113
Raskar, S., 297 Shirazi, E., 115
Real time polymerase chain reaction, 138–139 Shukla, A.K., 65–90
Reddy, A.V.B., 236 Siddiqui, M.H., 292, 293, 297
Respiring foods, 202 Silica nanoparticles, 234, 266
Rico, C.M., 271, 296, 297 Silver nanoparticle, 206, 263
Rinklebe, J., 236 Singh, N.A., 43–59
Rizzo, L., 119 Singh, R., 237
Rosenstock, T.S., 253 Single-stranded DNA (ssDNA), 211
322 Index
Sivapratha, S., 185–217 Sulphate, 233

Slim Shake Chocolate, 187 Summers, M.D., 267
Smalley, R.E., 285 Sun, D., 296
Smart Fields, 22 Sunflower oil, 209
Smart packaging Suprakas, S.R., 17
active tags, 171 Surface coating method, 201
anti-counterfeiting, 171 Surface plasmon resonance, 83–86, 105, 131,
freshness detection, 169–170 140–142
nanosensors, 168–169 Suriyaprabha, R., 232, 234, 291, 292, 296
oxygen indicators, 169–171 Sustainable agriculture
product identification, 171 composting from leaves, 286
spoilage indicators, 169–170 conservation agriculture, 285–286
traceability, 171 conventional agriculture, 285
Sodium montmorillonite (Na-MMT) green house under drip irrigation, 287
nanoclay, 9 natural regenerative processes, 286
Soil amendments salt-affected soils, 287
metal and metal oxide nanoparticles, 234 soil, 288
nanoclays, 231, 233 Sustainable farming practices
nanominerals, 233–234 nano-porous nanomaterial, 261
physical properties, 231 nanosensors, 261–262
types of, 231, 232 plant protection and pest management
SoilNet, 22 copper nanoparticles, 266
Soil remediants nano-capsule, 262–263
method and contaminant classes, 235 nano-encapsulation, 262
nanomaterials silica nanoparticles, 266
for electrokinetic remediation, 239 silver nanoparticles, 263
phytoremediation, 238–239 types of, 264–265
for stabilization techniques, 237–238 zinc nanoparticles, 266–268
in thermal treatment, 238 smart delivery system, nanomaterials
nanoparticles of, 235–237 fertilizers and pesticides, 255
Soil security, 288–289 nano-capsules, 255–256
Sokolov, K., 46 nanofertilizers (see Nanofertilizers)
Sol-gel method, 8 uses of, 256
Solvent displacement, 13 Systematic evolution of ligands by exponential
Song, U., 260, 296 enrichment (SELEX), 142, 143
Sopeña, F., 267
Spectroscopic characterization
FT-IR spectroscopy, 87–89 T
optical properties, 83 Taha, H., 283–299
surface plasmon resonance, 83 Taheran, M., 101–123
UV-visible spectroscopy Takeda, T., 135
Fe nanoparticles, 84 Takeuchi, M.T., 288
gold nanoparticles, 84 Tarafdar, J., 259
silver nanoparticles, 85–86 Tarafdar, J.C., 232, 288, 292
ZnS nanoparticles, 86 Taran, N.Y., 258, 259
Spontaneous emulsification, 13 Taranath, T.C., 297
Srinivasan, C., 260 Tepus, B., 122
Stadler, T., 267 Teresa, APR-S, 22
Stark, W.J., 272 Terrestrial environments, 288, 290
Strip based lateral flow device, 144–145 Textile industry, 50–51
Subramanian, K.S., 232, 234 Thermal treatments, soil remediation, 238
Subramanian, S., 229–240 Thiol group, 140–142, 144
Subramanian, V., 119 Thirunavakkarasu, M., 232
Index 323
Thiruvengadam, M., 297 Wang, L., 262

Thul, S.T., 288, 292 Wang, P., 297
Thymol, 195 Wang, S., 272, 297
Titania. See Titanium dioxide (TiO2) Wang, X., 111
Titanium dioxide (TiO2) Wang, Y., 236
commercialization challenges, 105 Wang-Wang, T., 27
doped Wanyika, H., 232
Freundlich isotherm model, 112 Wastewater treatment, 19–20
Langmuir and Polanyi-Manes isotherm Water purification, 5, 9, 27, 90
models, 112–113 Water quality management
nitrogen and fluorine, 111 desalination, 26
pH and temperature, 109 heavy metals removal, 27
photocatalyst properties, 105, 109 nano-oligodynamic metallic particles,
pseudo-first order reaction, 110 24–25
Titanium oxide nanoparticle, 215, 257, 260 photocatalysis, 25–26
Tomar, R.S., 129–146 wireless nanosensors, 27–28
Tortuous pathway, 203 Watson, J.-L., 297
Toxic substance control act (TSCA), 268 Watts, D.J., 270
Trichloroethylene (TCE), 239 Watts-Williams, S.J., 232
Typhoid fever, 21, 130, 134 Wiesman, Z., 267
Wigger, H., 288
Wireless nanosensors, 27–28
U
Ullmann, M., 7
Ultra-Turrax, 12 X
United state Environmental protection Agency Xiang, L., 296
(USEPA), 253 Xing, B., 258–260, 270, 292
UV-visible spectroscopy Xiqi, Z., 22
Fe nanoparticles, 84 Xu, L., 117
gold nanoparticles, 84
silver nanoparticles, 85–86
ZnS nanoparticles, 86 Y
Yada, R., 254, 288
Yaktine, A., 52
V Yan, H., 120
Valdivieso-Garcia, A., 137 Yan, S., 261
Van de Voorde, M.H., 288 Yang, F.-L., 267
Vardar, F., 297 Yang, G.C.C., 239
Verliefde, A.R.D., 122 Yang, L., 270
Verma, M., 101–123 Yanik, F., 297
Verma, P., 78 Yao, K.S., 262
Vermiculite supported nanozero valent iron Yeasts, 76–78
particle, 239 Yin, X.-d., 267
Vidya, K.S., 17 Yuan, S., 237
Vijayakumar, N.S., 115 Yuksel, S., 122
Vitamins, 70–71 Yuvakkumar, R., 291
Vítková, M., 237 Yuvaraj, M., 232
W Z
Wang, F., 236 Zahra, Z., 296
Wang, H.W., 236 Zareabyaneh, H., 232
Wang, J., 119 Zeolites, 233, 234
324 Index
Zhang, J., 261, 271 Zhong, L.W., 28

Zhang, R., 296 Zhou, Q., 117, 236
Zhang, X., 5, 22 Zhu, J., 114
Zhang, Y., 117, 122 Zhu, X., 119
Zhang, Z.Y., 267 ZigBee™, 22
Zhao, D., 236 ZnO nanoparticles, 81, 212, 213, 259, 266,
Zhao, L., 291 267, 291, 293

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What are some of the publications and series discussed in the document?

What are some of the publications and series discussed in the document?

What is sustainable agriculture and what issues does it address?

What is sustainable agriculture and what issues does it address?

Sustainable Agriculture Reviews 20

More information about this series at http://www.springer.com/series/8380

ISSN 2210-4410 ISSN 2210-4429 (electronic)

Library of Congress Control Number: 2016947716

© Springer International Publishing Switzerland 2016

Printed on acid-free paper

This Springer imprint is published by Springer Nature

Fig. 2 Major applications of nanotechnology in agriculture. Dasgupta et al. Chap. 1

remediation such as phytoremediation and electrokinetic degradation. Chhipa and

Vellore, TN, India Shivendu Ranjan

1 Nanoagriculture and Water Quality Management . . . . . . . . . . . . . . . . . 1

10 Nanoparticles, Soils, Plants and Sustainable Agriculture . . . . . . . . . . 283

Neama Abdalla Plant Biotechnology Department, Genetic Engineering Division,

Syed Irshaan Department of Food Process Engineering, National Institute of

Namita Ashish Singh Department of Life Sciences, Institute of applied medicine

Shivendu Ranjan is currently working as DBT-

Nandita Dasgupta is currently serving as Research

Eric Lichtfouse, 56, is a soil scientist at the French

the french-english newsletter Publier La Science.7 He has published the book

Nandita Dasgupta, Shivendu Ranjan, Arkadyuti Roy Chakraborty,

Abstract Nanomaterials have rapidly gained importance in many fields of science

Keywords Nanotechnology • Nanomaterials • Agriculture • Water quality manage-

N. Dasgupta • A.R. Chakraborty • C. Ramalingam

© Springer International Publishing Switzerland 2016 1

- Novel pesticides Agriculture

Agricultural products influence most aspects of life, including everyday materials,

1.2 Classification of Nanomaterials

1.2.1.1 Inorganic Nanoparticles

Inorganic ingredients manufactured at the nanoscale with variations of compounds

exhibited an improved bactericidal and nanocomposite properties. Further it has

1.2.1.2 Flame Spray Synthesis

1.2.1.3 Laser Induced Gas Evaporation Method

Instead of combustion of a liquid precursor giving access to oxidic nanoparticles,

nanoparticles of around 10 nm particle diameter at a production rate of 10 mg/min

1.2.1.4 Plasma Based Nanoparticles Production

1.2.1.5 Co-precipitation Method

In a first step of a typical co-precipitation reaction, the conditions are adjusted to

1.2.1.6 Sol-Gel Method for Inorganic Nanoparticles Synthesis

Another inorganic nanoparticles synthesis method based on liquid precursors is the

They are naturally occurring aluminium silicate, primarily composed of fine-grained

Nanoemulsion consists of a lipid phase dispersed in an aqueous continuous phase,

1.2.3.1 Production of Nanoemulsion

Nanoemulsion can be produced using a variety of methods, which are classified as

1.2.3.2 High-Pressure Homogenization

1.2.3.4 High-Speed Devices

1.2.3.5 Membrane Emulsification

1.2.3.6 Spontaneous Emulsification

1.2.3.7 Solvent Displacement

This method consists of mixing a water-miscible organic solvent containing lipo-

1.2.3.8 Emulsion Inversion and Phase Inversion Point

It involves variation of system composition at a constant temperature. The structures

1.3 Nanotechnology and Research Trends in Agriculture

1.3.1 Nanoscale Carriers

1.3.2 Fabricated Xylem Vessels

Recent advancement in nanofabrication and characterization tools has enabled the