Experiment 11: Smart materials

Definition:
Smart materials or responsive materials, the properties of which can be significantly
changed or altered in a controlled fashion by external stimuli like stress, light,
temperature, pH, moisture, electrical or magnetic fields.
Classification of Smart materials:
Smart materials are classified into various types depending on the properties.
a. Shape memory materials: i. Shape memory alloys ii. Shape memory polymers
b. Piezo electric materials
c. pH sensitive materials
d. Chromo active materials
e. Photo active materials

[11] Smart materials for Bio-medical applications

1. Certain materials like poly-electrolyte gels are being experimented for artificial-
muscle applications, where a polymer matrix swollen with a solvent that can expand or
contract when exposed to an electric field or other stimulation.
2. In addition, due to biodegradability of these materials, it may make it useful as a
drug-delivery system.
3. Healthcare field: Biosensors made from smart materials can be used to monitor
blood sugar levels in diabetics and communicate with a pump that administers
insulin as required. However, the human body is a hostile environment and sensors are
easily damaged. Some researches on barrier materials are going to protect these sensors.
4. Smart Membranes for Separation of Biomolecules
Compared with chromatography processes, for high-resolution separation and analysis of
biomolecules such as proteins, smart membranes combining the advantages of low-
pressure drop, short processing time, high flow rate, accessible equipment and excellent
anti-fouling properties can help to reduce production energy consumption and equipment
cost, and improves production efficiency and product yield of biomolecules, which is
of great significance in the healthcare field.
5. For cell and tissue culture, porous membranes with good permeability of oxygen and
nutrients, ease of handling for cell culture and co-culture of heterogeneous cells are
widely applied to prepare culture inserts.
Moreover, for tissue engineering, smart membranes enable rapid and non-destructive
harvest of cell sheets from culture media, effectively reducing the harmful enzymatic
hydrolysis and mechanical scraping compared with traditional cell and tissue culture,
which is beneficial to cell protection and process simplification.
6. Smart membranes for biomedical applications
Smart membranes could self-adjust their physical/chemical properties (such as pore size
and surface properties) in response to environmental signals such as temperature, pH,
light, magnetic field, electric field, redox and specific ions/molecules.
Such smart membranes show great prospects in biomedical applications ranging from
controlled drug release to bio-separation and tissue engineering.
 For controlled drug release, traditional drug delivery systems are difficult to avoid the
risk of toxicities and drug waste. Through rational structural design and selection of
responsive materials, smart membranes can precisely control the drug release time and
location, thus effectively solving these problems.
7. The rapid development of nanotechnology paved the way for further expansion of
polymer chemistry and the fabrication of advanced polymeric membranes. Such
modifications allowed enhancing or adding some unique properties, including
mechanical strength, excellent biocompatibility, easily controlled degradability, and
biological activity.
It is intended to highlight here possible ways of improvement the properties of polymeric
membranes, by modifying with other polymers, functional groups, compounds, drugs,
bioactive components, and nano materials.
8. Stimuli-Responsive Smart Gating Membranes

Inspired by the natural cell membranes with stimuli-responsive channels, artificial

stimuli-responsive smart gating membranes are developed by chemically/physically
incorporating stimuli-responsive materials as functional gates into traditional
porous membranes to provide advanced functions and enhanced performances for
breaking the bottlenecks of traditional membrane technology.

The smart gating membranes, integrating the advantages of traditional porous membrane
substrates and smart functional gates, can self-regulate their permeability and selectivity
via flexible adjustment of pore sizes and surface properties based on the "open/close"
switch of the smart gates in response to environmental stimuli.

With self-regulated membrane performances, the smart gating membranes show great
power for global sustainable development as follows:

(1) Combination of traditional porous membranes and smart polymeric gating materials
creating stimuli-responsive smart gating membranes.

(2) Chemical science of strategies for creating smart gates in membranes and the stimuli
responsive conformational switch and mechanism of functional gates in molecular
level.

(3) Self-adjustment of the pore sizes and/or the surface properties with functional gates
for manipulating the permeability and selectivity of membranes.

(4) Chemical technologies of stimuli-responsive smart gating membranes for wide applications
in not only the traditional, but also the extended or even brand new fields.

(5) Potential self-cleaning functions of the new-generation membranes based on the

stimuli responsive pore sizes and surface properties.

For example, the membrane-based ethanol fermentation usually requires constant

ethanol concentration in the reactor for efficient continuous fermentation. Therefore,
with increased ethanol concentration during the fermentation, increased membrane
 permeability is needed to instantaneously remove the additional ethanol for
concentration maintaining.

For example, for membrane fouling, such as those induced by silt, protein, and
bacteria, the permeability of gating membranes can be increased by "opening" the gates
to enlarge pore size for flux enhancement. Meanwhile, the membrane surface property
can also be adjusted by changing the wettability of the gates; thus, the affinity between
the fouling components and membrane surface can be weakened for reducing or even
eliminating the fouling.

Moreover, the stimuli-responsive affinity adjustment can also be applied for

controlling the interaction between proteins and the pore surfaces that grafted with
stimuli-responsive polymers such as poly (N-isopropyl acrylamide) (PNIPAM) for
protein separation. Therefore, such gating membranes with self-regulated permeability
and selectivity enable enhanced and advanced performances for wide applications in not
only the traditional, but also the extended or even brand new fields such as detection of
harmful pollutants for environment protection and stimuli-responsive controlled
release of drugs for biomedical application.

9. For example, PNIPAM, with LCST (~32 °C) close to human body temperature, is
widely used as positively thermo-responsive gates.
At temperatures below the LCST, PNIPAM chains are swollen and hydrophilic due to
the hydrogen bonding between the amide groups and water molecules, thus the
membrane pores "close".

While increasing temperature above the LCST, the PNIPAM chains become shrunken
and hydrophobic due to the hydrogen bonding cleavage, thus the membrane pores
"open". Since the LCST can be tuned by incorporating hydrophilic or hydrophobic
groups into the PNIPAM chains, gating membranes with tunable triggering temperatures
for gating can be achieved for more flexible applications.

10. pH-responsive gating.

Typically, polymers containing weak alkaline groups, which can be protonated or

deprotonated for configuration change, can be used as positively pH responsive
gates.

For example, poly (N,N-dimethylaminoethyl methacrylate) (PDM) can swell in acidic

environment due to the electrostatic repulsion between protonated -N(CH3)2 groups; by
contrast, in basic environment, the PDM can shrink due to the deprotonation of the amine
groups.

11. For examples, the polymer chains of negatively pH-responsive PAAc gates can
shrink due to the formation of intermolecular hydrogen bonding between their carboxylic
groups at low pH basic environment, the PAAc chains can extensively swell due to the
electrostatic repulsion between the protonated carboxylic groups.
12. Ion-responsive gating:
 For example, pH-responsive gating membranes can selectively reject dextran
molecules with proper molecular weight from their mixtures with different molecular
weights of 10, 40 and 70 k Da, depending on the environmental pH
13. Temperature-responsive gating membranes enable fast permeation of small
molecules such as NaCl (hydrodynamic radius ~0.1 nm), showing large diffusional
coefficients at both 25 oC and 40 oC ; while large molecules such as VB12
(hydrodynamic radius ~2 nm) can only permeate through the membrane with opened
pores at 40 oC.
14. Similarly, Ba2+-responsive gating membranes can sieve molecules with different sizes
such as dextran molecules with radius of 2~30 nm
15. UV-light-responsive gating: The positively UV-light-responsive gates usually
utilize azobenzene-based materials, which can undergo a trans-cis isomerization
transition in response to UV light . Upon UV irradiation, the azobenzene groups can
change their planar configuration into a non-planar one, with a drastic decrease in the
distance between the para carbon atoms from 9.0 Ǻ to 5.5 Ǻ. Such configuration
changes of azobenzene groups effectively control the membrane pore size.
16. Ion-responsive gating: As a typical example, negatively ion-responsive gates can be
fabricated by incorporating PNIPAM with 18-crown-6 groups.
The 18-crown-6 moiety can selectively recognize certain ion such as Pb2+ to form stable
1:1 host-guest complex. When Pb2+ ions appear, the opened pores can close due to the
ion-responsive isothermal swelling of the gates, causing the change of pore size from 159
nm to 94 nm.