UNIT 4: Polymers

Conducting polymers/ Conjugated polymers/ π-conjugated polymers

Conjugated polymers are macromolecules that possess alternating single and double bonds
along the main chain. Some common conjugated polymers are poly(acetylene) (PA),
poly(thiophene) (PT), poly(pyrrole) (PPy), poly(p-phenylene) (PPP), poly(p-
phenylenevinylene) (PPV) and poly(fluorene) (PF), which are illustrated in Figure 1.1.

The potential use of conjugated polymers in electronic devices was realized in the late 1970s
when electrically conductive polymers were discovered; i.e. PA doped with iodine.

• Professor Alan J. Heeger at the University of California at Santa Barbara, USA

• Professor Alan G. MacDiarmid at the University of Pennsylvania, USA and

• Professor Hideki Shirakawa at the University of Tsukuba, Japan

rewarded the Nobel Prize in Chemistry for 2000 “for the discovery and development of
electrically conductive polymers”.

• In the early 1970s Shirakawa and co-workers make well-defined films of

polyacetylene. They produced a copper-coloured film of all-cis-polyacetylene and
also silvery all-trans-polyacetylene. Their conductivities were:

cis-polyacetylene 10–8-10–7 S.m–1 (siemens /meter)

trans-polyacetylene 10–3-10–2 S.m–1

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 • MacDiarmid wanted to modify the polyacetylene by iodine treatment. Conductivity of
3000 S.m–1 was measured for iodine-modified trans-polyacetylene, an increase of
seven orders of magnitude over the undoped material.

• The seminal paper received for publication in 1977, had the title: Synthesis of
electrically conducting organic polymers: Halogen derivatives of polyacetylene
(CH)x.

• Doping cis-polyacetylene with AsF5 (Arsenic pentafluoride) resulted in an increase

of conductivity by a factor of 1011. The high conductivity found by Heeger,
MacDiarmid and Shirakawa clearly opened up the field of “plastic electronics”.

Many conjugated polymers that were studied in the early 1980s were based on heterocyclic
compounds which were synthesized using chemical and electrochemical means. Chemically
synthesized conjugated polymers resulted in powders which were insoluble and
uncharacterizable using conventional analytical techniques. The primary interest in these
powders was their electrical conductivity and their corresponding electronic structure.
Alternatively, electrochemical synthesis of conjugated polymers was a more attractive
approach because films were formed on the electrode. Significant research on these polymer
films was therefore performed to understand their spectro electrochemical properties. In the
mid 1980s, Elsenbaumer reported the ground breaking synthesis of soluble conjugated
polymers by attaching an alkyl side chain on PT. The solubility of the polymers allowed
structural characterization and polymer processing using spin or drop cast methods.

To date, a surge of research on soluble conjugated polymers has been performed, due to their
potential use as components in electronic applications, such as field effect transistors (FETs),
light emitting diodes (LEDs), actuators, and solar cells. The development of these soluble
conjugated polymers has lead to significant improvement in their properties, including their
high electrical conductivity (up to 2000 S/cm), high field effect mobility (~0.12 cm2 V-1 s-1)
with excellent on/off ratios in FETs (107), high solid state photoluminescent and LED
efficiencies (10% photons/electrons, external), and significant solar energy conversion
efficiencies (4.2%).

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(An antistatic agent is a compound used for treatment of materials or their surfaces in order to
reduce or eliminate buildup of static electricity.)

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Films of polypyrrole are yellow but darken in air due to some oxidation. Doped films are blue

or black depending on the degree of polymerization and film thickness. They are amorphous,

showing only weak diffraction. Undoped and doped films are insoluble in solvents but

swellable. Doping makes the materials brittle.

Applications

1. Polypyrrole is a potential vehicle for drug delivery. The polymer matrix serves as a

container for proteins.

2. Polypyrrole has been investigated as a catalyst support for fuel cells and to sensitize

cathode electrocatalysts.

3. Together with other conjugated polymers such as polyaniline,

poly(ethylenedioxythiophene) etc., polypyrrole has been studied as a material for

"artificial muscles", a technology that offers advantages relative to traditional motor

actuating elements.

4. Polypyrrole was used to coat silica and reverse phase silica to yield a material capable

of anion exchange and exhibiting hydrophobic interactions.

5. Polypyrrole was used in the microwave fabrication of multiwalled carbon nanotubes,

a rapid method to grow carbon nanotubes.

6. A water-resistant polyurethane sponge coated with a thin layer of polypyrrole absorbs

20 times its weight in oil and is reusable.

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Mechanism for polypyrrole and polythiophene synthesis

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Electrons are delocalized along the conjugated backbones of conducting polymers, usually
through overlap of π-orbitals, resulting in an extended π-system with a filled valence band.
By removing electrons from the π-system ("p-doping"), or adding electrons into the π-system
("n-doping"), a charged unit called a bipolaron is formed

Reduction of the conducting polymer, n-doping, is much less common than p-doping. An
early study of electrochemical n-doping of poly(bithiophene) found that the n-doping levels
are less than those of p-doping, the n-doping cycles were less efficient, the number of cycles
required to reach maximum doping was higher, and the n-doping process appeared to be
kinetically limited, possibly due to counterion diffusion in the polymer.

Polythiophenes are conductive after doping, and have excellent environmental stability
compared with some other conducting polymers such as polyacetylene, but are intractable
and soluble only in solutions like mixtures of arsenic trifluoride and arsenic pentafluoride.

Applications

Potential applications include field-effect transistors, electroluminescent devices, solar cells,

photochemical resists, nonlinear optic devices, batteries, diodes, and chemical sensors. In
general, there are two categories of applications for conducting polymers. Static applications
rely upon the intrinsic conductivity of the materials, combined with their ease of processing
and material properties common to polymeric materials. Dynamic applications utilize
changes in the conductive and optical properties, resulting either from application of electric
potentials or from environmental stimuli.

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Polymer composites

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Polymer blends

Mixture of polymer with chemicals or other polymer(s) is called blend. The basis of polymer
blends is to exploit certain unique properties of individual polymers for multicomponent
systems for the benefit of the overall properties. Polymer blends are gaining greater
importance due to their unique properties different from the basic polymers. Blending of one
polymer with another polymer is a very common practice.

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Liquid-crystal polymers (LCP)

Most of us trained in science, since our years in school, have been conditioned into

recognizing three states of matter - solid, liquid and gas. Our everyday experience strongly

reinforces these concepts. A solid may be either crystalline or amorphous. The most

important property which differentiates between solids and liquids is flow. The liquids flow

and adopt the shape of container, whereas solids do not flow and tend to retain their shape.

The optical properties of some solids and liquids can also be very different. For instance,

some solids change the polarization of light whereas liquids do not. Due to these concepts in

mind, the early investigators could not think about the existence of other phases, although

they found substances which did not neatly fall into these categories.

At that time it was anticipated that if we take a crystalline solid and heat it then it will step

through the phases solid-liquid-gas, unless it sublimes and evaporates before the gas phase is

reached.

The interconversion of phases, particularly, in case of organic compounds, usually takes

place at well defined temperatures. Contrary to it an unusual sequence of phase transition was

observed by an Austrian Botanist Reinitzer in the year 1888. While investigating some esters

of cholesterol he observed two melting points. At 145.5 ˚C cholesteryl benzoate melted from

a solid to a cloudy liquid and at 178.5 ˚C it turned into a clear liquid. Some unusual colour

behaviour was also observed upon cooling; first a pale blue colour appeared as the clear

liquid turned cloudy and then a bright blue-violet colour as the cloudy liquid crystallised.

Reinitzer sent the samples of this substance to a German Physicist Lehmann who was

studying the crystallisation properties of various substances. Lehmann observed the sample

with his polarising microscope and noted its similarity to some of his own samples. He

observed that they flow like liquids and exhibit optical properties like that of a crystal. The

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subsequent studies established that these observed intermediate phases represent a new

thermodynamic state of matter that are quite distinct from the isotropic liquid. The

mechanical and symmetry properties of these phases are intermediate between those of a

crystalline solid and an isotropic liquid. Lehmann first referred to them as flowing crystals

and later used the term "liquid crystals". The molecules in a crystal are ordered whereas in a

liquid they are not. The existing order in a crystal is usually both positional and orientational,

i.e., the molecules are constrained both to occupy specific sites in a lattice and to point their

molecular axes in specific directions.

Schematic arrangement of molecules in various phases.

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When a molecular material composed of anisotropic molecules is heated from the solid phase

following possibilities exist at the melting point (see above Figure) :

(i) Both types of order (positional and orientational) disappear simultaneously and

the resulting phase will be an "isotropic liquid (IL)".

(ii) Only orientational order disappears leaving the positional order intact and the

corresponding phase is called a "plastic crystal (PC)". The materials in this phase

are said to exhibit rotator phases; the molecules freely rotate along one or more of

their molecular axes, whereas their centers of mass are fixed in a lattice.

(iii) The positional order either fully or partially disappears while some degree of

orientational order is maintained. The phase thus derived is called as "liquid

crystal (LC)". An other name in use is mesophase (meaning intermediate phase) or

mesomorphic phase. In this phase the unique axes of the molecules remain, on

average, parallel to each other, leading to a preferred direction in space.

A question that has persisted throughout the development of science has been: "What is the

structure of the condensed phase?" In the earliest stage of knowledge

about atoms backed by experiment, states that: "The essential distinction between liquids and

solids, perhaps consists in this, that heat changes the figure of arrangement of the ultimate

particles of the former continually and gradually, whereas they retain their liquid form;

whereas in the latter, it is probable, that change of temperature does no more than change the

size, and not the arrangement of the ultimate particles."

This microscopic description of a solid as a material with fixed atomic arrangement is still

valid today. The "ultimate particles" one would describe today as motifs, i.e. as the atoms,

ions, molecules or parts of molecules which represent the crystallographic repeating units.

The "change in size" one relates today to the asymmetric increase in vibrational amplitude.

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When asking about the types of arrangement possible in a solid, we can make the obvious

subdivision into order and disorder. This leads to the distinction of crystalline and amorphous

solids (glasses).

The crystals have long range order, the glasses do not. In this, we want to concentrate on the

in-between states of order, those of "mesomorphic order"

Mesomorphic is a term proposed by Friedel in 1922, for the materials of "middle" (Grk.

mesos) "form" (Grk. morphe). Because of their in-between microscopic structure, mesophase

crystals (Grk. phasis = appearance) may be in-between liquid and solid in macroscopic

appearance. It thus becomes difficult to identify mesophases as solid or liquid.

To give a base for discussion, one can make use of the following operational definition of

liquids and solids. A solid is either a crystal (stable below its melting or crystal-to-crystal

transition temperature) or a glass, which changes at its glass transition temperature to a liquid.

The glass is an amorphous solid, metastable relative to the crystalline state. Both, the melting

temperature and the glass transition temperature, are easily identified by thermal analysis, for

example. Figure 1 shows thermal analysis traces through the melting and glass transitions.

The transition

temperatures (melting temperature (Tm) and glass transition temperature (Tg)) provide thus a

precise, operational definition for solids and liquids.

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Classification and Structure of Liquid Crystals (LCs)

Liquid crystals (low mol. Wt. compounds) can be distinguished as thermotropic or lyotropic

LCs, depending on whether the LC state is achieved by melting or in solution.

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For thermotropic LCs, the transition to the liquid crystal state is induced by a purely thermal

process. Thermotropic LCs form thermally activated mesogenic phases that extend from the

crystal melting temperature up to the clearing temperature. Thermotropic LCs have found

wide application in the electro-optical displays. For lyotropic LCs, the transition is induced

by the influence of solvents. Lyotropic LCs exhibit their phase transitions through the

addition or removal of solvent.

With increasing levels of mesogenic order, liquid crystals (LCs) can be classified into three

basic types: nematic, smectic, and cholesteric.

The nematic phase is the most commonly observed liquid crystalline phase. The term

“nematic” has its origins in the Greek word for “thread,” which describes the appearance of

this mesomorphic phase between crossed polars. In the nematic phase, the centers of the

molecules are arranged at random; hence, no long-range order exists. However, within a

microscopic volume element, the axes of all molecules are oriented in a specific direction, as

shown in following Figure. In this state, the intermolecular forces are very small, so

molecules can easily pass by each other.

The smectic phase is more complex to describe because a number of symmetry variants exist.

The term “smectic” also has a Greek origin, from the word meaning “soap.” Smectic phases

are characterized by layer structures, with additional order possible in each layer. Within the

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layers, the centers of molecules are arranged in equidistant planes. The planes are allowed to

move perpendicular to the layers, and, within the layers, different arrangements of molecules

are possible. The smectic modifications are labeled according to the arrangement of the

molecules within the layers. The two most common smectic phases are smectic A and

smectic C. The smectic A phase is the least ordered of all the smectic phases, with the

molecules with their overall long axis perpendicular to the layer plane. In smectic C phase,

the orientation axis of the molecules is tilted with respect to the layer phase. In the smectic B

phase, the molecules are arranged with an even higher degree of order; they have

twodimensional long-range order and positional order within the layer. Similar to smectic A,

the molecules are perpendicular to the layer plane.

The cholesteric phase is similar to that of the nematic phase on a local scale. As in the

nematic phase, the molecules can be described by a director. However, the director in the

cholesteric phase is twisted about an axis normal to the molecular orientation, following a

helical path (Figure 1.3). Iridescent colors (that is colors that seem to change when seen from

different angles) are characteristic of cholesteric phases.

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Classifications of LCPs into various categories have been proposed, based on molecular

geometry and the nature of the mesogen attachment. LCPs are broadly divided into main-

chain LCPs and side-chain LCPs, reflecting how the mesogens are attached to the polymer

backbone. Some recently developed LCPs have more complicated structures, such as the

combined side-chain main-chain LCPs, LC elastomers, and LC networks.

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For Example:

Aromatic Main Chain Liquid Crystalline Polymers

Aromatic main chain liquid crystalline polymers consist of a sequence of directly connected

aromatic moieties, namely, polyarylenes, or a sequence of aromatic moieties linked by an

even number of atoms or heterocyclic units. Typical linkage groups in combination with

aromatic moieties are, for example, ester and amid groups.

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The properties, in particular the solubility and fusibility and as consequence the

processability, are controlled by the molecular architecture and chemical structure of the

aromatic moieties.

Improvement of the solubility and the fusibility are of fundamental interest in order to fully

exploit the potential of aromatic liquid crystal polymers (LCPs). Therefore, in the past two

decades considerable effort has been made to obtain tractable aromatic LCPs by different

structural modification concepts.

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Smart polymers/ Stimuli-responsive polymers/ Intelligent polymers

The scientific community tries to mimic nature in the way that living organisms adopt their

behavior as a function of environmental conditions to improve survival. In this sense, smart

polymers offer materials that respond to numerous stimuli (temperature, pH, electric and

magnetic fields, light intensity, biological molecules, etc.), and scientists must devise the best

way to apply them in all research areas.

Smart polymers or stimuli-responsive polymers undergo large reversible changes, either

physical or chemical, in their properties as a consequence of small environmental variations.

They can respond to a single stimulus or multiple stimuli such as temperature, pH, electric or

magnetic field, light intensity, biological molecules, etc., that induce macroscopic responses

in the material, such as swelling/collapse or solution-to-gel transitions, depending on the

physical state of the chains.

Types of smart polymer

Polymers that respond to temperature changes and, more specifically, those that undergo a

phase transition in aqueous solution are currently gaining special attention due to their

potential applications in the biomaterials field, architecture or water-recovery strategies

amongst others. Temperature-sensitive polymers present low critical solution temperature

(LCST) or upper critical solution temperature (UCST) depending on their transition behavior

from monophasic to biphasic when temperature is raised or, on the contrary, from biphasic to

monophasic when temperature is raised, respectively. LCST polymers have been widely

investigated whereas UCST polymers are quite rare. Most common LCST polymers are the

poly(N-substituted acrylamide), poly(vinyl amide) and poly(oligoethylene glycol

(meth)acrylate) families.

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Tg, Tg,1 and Tg,2 are the glass transition temperatures.

pH-sensitive polymers bear weak polyacidic (poly(acrylic acids) or poly(methacrylic acids))

or polybasic (poly(N-dimethylaminoethyl methacrylate), poly(N-diethylaminoethyl

methacrylate), poly(ethyl pyrrolidine methacrylate)) moieties in their structure that protonate

or deprotonate as a function of the surrounding pH. Drug delivery systems, gene carriers or

glucose sensors are three of the multiple applications described for this kind of smart

polymer.

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pH-responsive polymers contain either weakly acidic (e.g., carboxylic acid) or basic (e.g.,

ammonia) groups, these either release protons or accept free protons, respectively, in

response to environmental pH. Under certain pH conditions the functional groups presented

along the backbone and side chains of the polymer undergo ionization that leads to a

conformational change in the polymer resulting in its swelling or dissolution. For example,

poly(acrylic acid) (PAA) has a dissociation constant (pKa 4.25) and above this pH the

carboxylic group becomes ionized.

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All pH-sensitive polymers contain pendant acidic or basic groups that either accept or donate

protons in response to the environmental pH.

Photo-sensitive polymers undergo a reversible or irreversible change in conformation,

polarity, amphiphilicity, charge, optical chirality, conjugation, etc., in response to a light

stimulus. Reversible chromophores or reversible molecular switches (e.g., azobenzenes,

spiropyran, diaryl ethane or coumarin) undergo a reversible isomerization upon light

irradiation while irreversible chromophores are cleaved from the polymer chain upon light

exposure (e.g., ο-nitrobenzylphotolabile protecting group) or induced reactivity resulting in

the coupling of two species (e.g., 2-naphthoquinone-3-methides). Both molecular switches

and irreversible chromophores have been applied in multiple applications such as drug

delivery systems, functional micropatterns, responsive hydrogels, photodegradable materials

or photoswitchable liquid crystalline elastomers for remote actuation.

Photo-responsive polymers undergo a change in their properties in response to a light

stimulus. Different molecular properties can be light-regulated, including conformation,

polarity, amphiphilicity, charge, optical chirality, conjugation, etc. The light-induced

molecular change is reflected in a macroscopic change of material properties like shape (i.e.,

contraction or bending), wettability, solubility, optical properties, conductivity, adhesion and

so on.

In order to obtain photo-responsive polymers, a photo-response functional group

(chromophore) needs to be incorporated into the polymer chain. Depending on the type of

chromophore used, the response can be reversible or irreversible. Reversible systems can

alternate material properties in two photostationary states and are used as switches.

Reversibility is important in many applications such as information storage, artificial

muscles, and actuators. Irreversible chromophores are mainly applied to photodegradable

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materials and used in systems for drug delivery. The advantage of irreversible chromophores

is the possibility of 100% photoconversion, since no equilibrium between two states is

involved. This leads to effective release of drugs or to drastic decrease of the molecular

weight in applications requiring degradation.

Magnetically responsive polymer gels and elastomers are composites based on magnetic

nanoparticles dispersed in a high elastic polymeric matrix. Magnetic field quickly deforms

the polymer matrix with no noise, heat evolution or exhaustion which makes these materials

ideal for the preparation of sensors, micromachines, energy transducing devices, controlled

delivery systems or even artificial muscles. One of the limiting steps in the development of

these materials has been the precise coupling of magnetic nanoparticles to the gel; however,

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this problem has been overcome when magnetic nanoparticles form the cross-linking nodes

of the hydrogel.

Composite materials consisting of rather rigid polymeric matrices filled with magnetic

particles have been known for a long time and are called magnetic plastics. Since the particles

cannot leave the polymer matrix, all of the forces acting on the particles are transmitted

directly to the polymer chains resulting in either locomotion or deformation. Shape distortion

occurs instantaneously and disappears abruptly when external fields are applied or removed,

respectively.

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Biointeractive polymers: Macroscopic transitions can also be triggered by ‘biology-to-

material’ interactions in the so-called biointeractive polymers. These materials incorporate

receptors for biomolecules which, when stimulated, cause localized or bulk modifications in

the material properties. Those polymers that respond to selective enzyme catalysis are known

as enzyme responsive polymers. These materials represent an important advance in the

integration of artificial materials with biological entities as they link together the polymer

properties with specific biological processes controlled naturally by either regulating enzyme

expression levels or availability of cofactors. Enzyme responsive polymers can also display

reversible and dynamic responses to a stimulus, thus being of great interest in the formulation

of new biomaterials such as cell supports, injectable scaffolds or drug delivery systems.

Enzyme-responsive polymers are unique in their ability to interact with biological

surroundings through mechanisms that enable dynamic responses by signal amplification

under constant conditions. Research into enzyme-responsive polymers is gaining more

impetus that will see the development of increasingly sophisticated systems and their

integration in biomedical applications. Enzyme-responsive polymers stand apart from other

stimuli-responsive polymers in their ability to respond to a biological molecule to regulate the

function of natural materials.

Research on stimuli-responsive biomaterials aims to integrate the material and its function

into a biological surrounding, that is, interface artificial materials with living organisms, and

has applications in drug delivery, regenerative medicine, cell engineering and biomedicine.

Shape memory polymers represent one of the most active areas in material science due to

their easier processability and lower cost when compared with shape memory metals or

ceramics. These kind of smart polymers have the ability to recover their (permanent)

predefined shape when stimulated by an external stimulus. A stable network and a reversible

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switching transition of the polymer are the two pre-requisites for shape memory effect. The

stable network is responsible for the original shape, and reversible switching transition fixes

the temporary shape, which can be crystallization/melting transition, liquid crystal

anisotropic/isotropic transition, reversible molecule cross-linking (such as photodimerization,

Diels – Alder reaction, oxidation/redox reaction of mercapto groups), and supramolecular

association/disassociation (such as hydrogen bonding, self-assembly metal–ligand

coordination and self-assembly of β-cyclodextrin). In addition to the reversible switches

mentioned, other stimuli that change chain mobility can also trigger shape memory effect,

such as light, pH, moisture, electric field, magnetic field, pressure, etc. Shape memory

polymers allow large, recoverable strains; however, they normally present poor mechanical

properties and do not support great shape-recovery stresses. As a result, great efforts are

being made in the development of shape memory composites with reinforced properties.

Shape memory polymers present numerous actual and potential applications in medicine,

aerospace, textiles, engineering, microfluidics, lithography and household products.

Shape memory materials are able to change their shape in a controlled way upon application

of an external stimulus such as temperature, light, application of electric or magnetic fields,

etc.

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Self-healing or restoration of lost functionalities without external help is a dream come true

with self-healing polymers. Healing mechanisms can be extrinsic (the healing compound is

isolated from the polymer matrix in capsules, fibers or nanocarriers) or intrinsic (the polymer

chains temporarily increase mobility and fl ow to the damaged area) and are responsible for

restoration of properties such as structural integrity, surface aesthetics, electrical

conductivity, hydrophobicity and hydrophilicity, mechanical properties, etc.

Applications of smart polymers

Most of the important developments were registered in the biomedical field and use smart

polymers in the development of new therapies for the treatment of several diseases or

sophisticated medical devices that react to the environment of the surrounding tissues (pH,

temperature, enzymes, analyte concentration, etc.) or external stimuli (light, magnetic

radiation, etc.).

Responsive polymeric substrates or instructive substrates regulate cell behavior in response to

external factors and are of signifcant importance in tissue engineering applications. Cell

behavior (adhesion, migration and proliferation) is conditioned to substrate surface

properties. Tunable surface properties such as stiffness and wettability, surface

functionalization with bioactive molecules or the design of 3D patterns at the micro- or

nanoscale in hydrogels are interesting strategies actually being developed in order to obtain

specific cell responses to smart surfaces for tissue engineering applications.

Temperature-sensitive polymers and more specifically shape memory polymers have been

used in the preparation of minimally invasive surgery medical devices. The unique properties

of these materials allow the introduction of the medical device in a compressed form

followed by expansion once located in the desired place by minimally invasive surgery

procedures. One of the most relevant applications using this kind of polymer is the

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development of stents for either vascular or urologic procedures. Polymeric stents are

considered a promising option when compared to the conventional metallic stents due not

only to their mechanical properties but also to the possibility of incorporating a drug to be

eluted in the functional place (e.g., to reduce restenosis and/or thrombosis after implantation

in vascular stents or to minimize infections in urinary stents.

Smart polymers have played a key role in the fabrication of new medical devices for cancer

diagnosis and therapy. In this sense, magnetic nanoparticles have been used in the

development of hyperthermia treatments, magnetic separation, immunoassay, cellular

labeling and magnetic resonance imaging diagnosis. Biosensors based on smart polymers

have been used in clinical diagnosis and forensic analysis because alterations in the

concentration of certain analytes (e.g., glucose in diabetes or in physical variables such as

temperature or pH (e.g., pH sensor for the quantification of partial pressure of CO2 in the

stomach for the diagnosis of gastrointestinal ischemia occur in several diseases.

Smart polymer nanocarriers for drug delivery applications play an important role in the

development of highly active and selective treatments, as they permit a controlled delivery of

the drug in the right place at the right time.

Smart polymers have also been used for bioseparation and other biotechnological

applications such as purification techniques. New smart polymers have brought about

progress in affinity precipitation, aqueous polymer two phase partitioning, controlled

permeation membranes.

Textiles have also experienced great improvements through the incorporation of different

kinds of smart polymers to their formulations. Temperature, pH, moisture or light were

responsible for the variable aesthetic appeal, smart controlled drug release, wound monitoring

or smart wetting properties of new textiles. Moreover, protection against extreme variations

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in environmental conditions or textiles with medical properties were also achieved with the

use of smart polymers.

Another sector clearly benefiting from smart polymers is the food industry as smart micro- or

nanoparticles have been used for incorporating active ingredients (e.g., ascorbic acid or olive

oil) in food or antimicrobial polymers such as chitosan, which have been used to fabricate

edible coatings.

Information and communication technologies and more specifically data storage devices have

improved amazingly in recent years due to the fabrication of new smart materials. In this

way, volume holographic storage will give rise to the next generation of data storage devices,

due to their much higher storage capacity and much higher transfer rate.

The skin of humans and animals constitutes a specialized complex system which captures the

electromagnetic, mechanical, thermal and chemical energy inputs (external stimuli) and

transformed them into real world information content. The outer surface layers of human skin

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provides very complex and diverse functions, such as energy harvesting, thermal control,

protection from external agents, and exchange with the external environment, camouflage

and even surface mediation of mobility. It also plays a role as sensor. In the last decades,

these properties of human skin have inspired researchers to design artificial skin by using

biomaterials and polymers for a variety of applications. The fingertips contain a large number

of corpuscles and free nerve endings which show sensitivity to a mechanical stimulus. The

tactile functions of fingertips enable it to detect the object features, such as surface texture

and fi ne form discrimination. A tactile unit is a combination of a peripheral sensory neuron

and its specialized receptors.

Introduction part

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