CHAPTER I

INTRODUCTION TO POLYMERIC HYDROGELS

 Abstract

Reported in this chapter, are the detailed explanations on the definition of

hydrogels, their properties and method of formation. The chapter also encapsulates
on various methods of classifying hydrogels as well as their applications in
different fields viz; agricultural, environmental, optical and biomedical
applications.
1. INTRODUCTION

The term ‘hydrogel’ refers to water-absorbing three-dimensional polymeric material

capable of engrossing colossal amount of water ranging from hundreds to tens of
thousands of times its weight [1]. The hydrogel’s insolubility and water withholding
capacity arises from the crosslinked network they possess. The water absorption is
aided by -COOH, -OH, -NH2 and –CN groups present in their structure. The flow of
huge amount of water from the surrounding medium into the polymer network is
engineered by the aforesaid hydrophilic groups through osmotic pressure difference
between the hydrogel and swelling environs [2]. The versatile nature of hydrogels,
their high water absorption properties and their ability to respond differently to
external stimuli informed the viability in various applications namely, agriculture [3],
cosmetic [4], sanitary napkins [5], biomedicine [6], tissue engineering [7], wastewater
treatment [8] and so on.

Conventional superabsorbent hydrogels are polymers of acrylic acid and acrylamide

derived from depletable petroleum resources which are not only exorbitant but also
non-biodegradable, non-biocompatible and injurious to the ecosystem. With global
demand for hydrogels on the hike-1.9 M metric ton in 2015 [9], coupled with the
resentments such as non-biodegradability, cytotoxicity, high cost and non-
renewability associated with the use of synthetic hydrogel, current researches dwell
more on the use of alternative material of purely biological origin.

Although eco-friendly, biomaterials have poor water retention capacity, response to

stimuli and mechanical strength. This aroused from lack of cross-links between their
chains. Research is therefore diversified to modifying polysaccharides either by
physical or chemical cross-linking. Synthetic monomers such as acrylic acid and
synthetic polymers such as polyvinyl alcohol could be cross-linked with
polysaccharide to form hydrogels with high water absorption/retention capacity and
also environmentally benign [10].

The use of different biomaterials such as chitosan [11], gelatin [12], gum-gatti [13],
sodium alginate [14], pullulan [15], deoxyribonucleic acid [16] and cellulose [17] as
host materials in the preparation hydrogels for various applications-environmental,
biomedical and photonics have been investigated. They are user/environmentally
benevolent and are economically viable.

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These biomaterials could be out-sourced from various industrial/agricultural wastes.
DNA could be sourced from salmon milt fish. Cellulose could be obtained from
different agricultural waste namely, wheat straw [18], sugarcane bagasse [19], water
hyacinth [20] and durian rind [21]. Banana pseudo-stem is high cellulose (60 %)
containing agri-waste material which is cultivated throughout India with the annual
production of 14.2 million ton [22]. Cellulose could, therefore, be isolated from
banana pseudo-stem and utilized for the preparation of hydrogel. Out-sourcing these
biomaterials from agricultural/industrial waste could help ameliorate environmental
pollution problems, minimization in operational and material cost, as well as
curtailing the over-usage of commercially driven biomaterials. The use of synthetic
substances as monomer/cross-linkers could be avoided through cross-linking of
natural polymers using bio-based cross-linkers. Their properties could be improved
through electrospinning process to produce nanofibers with a high surface area that
could be used in environmental, biomedical and photonic applications.

1.1. Classification of Hydrogels

There are various ways of categorizing polymeric hydrogels which depend upon the
nature and source of material used in their preparation, polymeric composition,
nature, and type of cross-linking, presence or absence of electrical charges, and
finally, the configuration of hydrogel network [23]. On the basis of origin, hydrogel
could either be natural or synthetic depending on the nature of starting material. Based
on polymeric composition, hydrogels may be classified as homopolymeric,
copolymeric and multi polymeric. On the basis of nature and type of cross-linking,
polymeric hydrogels may be either physically cross-linked or chemically cross-linked
hydrogels [23]. Physical cross-linking could be achieved via hydrogen bonding, ionic
interaction, and freeze-thawing. Meanwhile, chemically cross-linked hydrogels may
be prepared through either of the following processes; chemical cross-linking,
grafting, radical polymerization and condensation. Polymeric hydrogels may be ionic
or neutral depending on the presence or absence of electric charge. Ionic hydrogels
are further sub-divided into anionic, cationic and ampholytic. Under the category of
the configuration of hydrogel network, the polymeric hydrogel may be classed as an
amorphous, crystalline and semi-crystalline hydrogel.

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Figure1.1: Sharma G. (2018). Classification of hydrogels Retrieved from https://doi.org/10.1007/s10311-
017-0671-x

1.1.1 Classification based on the source

a) Natural polymeric hydrogels
Natural polymeric hydrogels are driven from biological macromolecules such as
proteins, nucleic acids, and polysaccharides. The commonest protein polymers are
collagen and gelatin. Examples of polysaccharide polymers include starch, alginate,
pullulan as well as cellulose and its derivatives. The most important polymer driven
from nucleic acids is deoxyribonucleic acid (DNA). Hydrogels derived from natural
sources possess various advantages over their synthetic analog because of their
inherent biodegradability, biocompatibility, low cost, and renewability. However,
although useful in the field of biomedicine-owing to their similarities to living tissues,
hydrogels derived from natural sources have poor mechanical strength,
absorption/retention capacity and possess less sensitivity to external stimuli [10].
These properties are integral for a material to be used in wastewater treatment,
photonics, and biomedical applications. Natural polymers could be modified via
physical or chemical means in order to achieve the desired properties. This could be
done either by blending two or more natural polymer in a binary/ternary settings or
incorporating synthetic polymers through chemical approach [24]. The process
provides an eco-friendly material which could be utilized in various applications. Wu
and Imai [25] for an instance, reported the enhancement of mechanical strength of k-

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Carrageenan through chemical cross-linking of same with pullulan. The PVA being
mechanically strong was also reported to have been used in the improvement of
mechanical stress and strain of pullulan by cross-linking same using glutaraldehyde.
Investigation on the improvement of water absorption capacity of carboxymethyl
cellulose via chemical modification with synthetic polymer was documented [26].
According to them, the overall water absorption/retention capacity of the prepared
material depended upon the amount of synthetic polymer.

b) Synthetic polymeric hydrogels

Synthetic hydrogels are hydrogels derived from a by-product of petroleum called
petrochemicals. The origin of synthetic hydrogel could be traced back to 19th century
when Wichterle and Lim synthesized the first synthetic polymeric hydrogel network
through polymerization of 2-hydroxyethyl methacrylate (HEMA) to form poly 2-
hydroxyethyl methacrylate (PHEMA). The hydrogel was used in the fabrication of
contact lenses. Over the fast decades, sundry synthetic hydrogels such as acrylic,
acrylamide, and acrylates were developed which are intended to finding alternative
material with good water absorption/retention capacity, high mechanical strength and
sensitivity to change in external conditions. Shukla and Madras [27] for example
reported the preparation of a poly 2-methacryloyloxyethyl trimethylammonium
chloride for water absorption and dye removal studies. Report on the fabrication of
synthetic copolymer made from two synthetic polymers i.e acrylic acid and 2-
acrylamido-2-methyl-1-propane sulfonic acid was documented [28]. The copolymer
was used for the removal of cationic dyes from aqueous solution. The study revealed
that the prepared hydrogel could chelate five different dyes from aqueous solution.
Whereas alas, polymeric hydrogels derived from synthetic sources are costly and
injurious to the ecosystem. Current researches are therefore directed to finding eco-
friendly materials whose properties could match those of synthetic hydrogels.

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1.1.2. Classification based on nature and type of cross-linking

a) Physically cross-linked hydrogels

Because of their low toxicity, biocompatibility, biodegradability and low cost of
production, physically cross-linked polymeric hydrogels have drawn the attention of
researchers to finding bio-based material to be utilized in food packaging and
pharmaceutical industries. Their preference over chemically cross-linked hydrogels
might be due to the fact that physically cross-linked polymeric hydrogels are
biomaterials devoid of any chemical cross-linking agents. The structure of physically
cross-linked hydrogel is prevented from collapse due to the physical interactions
existing between their polymer chains [29].

Physically cross-linked polymeric hydrogels may be obtained through various

methods. These include freeze-thawing, hydrogen bonding, ionic interaction, and
stereo-complex formation. Freeze-thawing is a method in which microgels are formed
via successive freeze-thaw cycles which could be achieved using freeze-dryer. The
notable hydrogel formed via freeze-thawing is polyvinyl alcohol derived hydrogel.
Hydrogels prepared through freeze-thawing appeared to be spongy, rubbery and more
porous than the ones obtained from other methods. Polymeric hydrogels prepared in
this fashion are being utilized in the field of biotechnology [30].

Another way of forming physically cross-linked polymeric hydrogels is through

hydrogen bonding. In this approach, cross-linking is achieved through hydrogen
bonding between the hydroxyl groups of one polymer with a hydroxyl/carboxyl/amine
group of the other. The commonest example of such interaction could be observed
between the carboxymethyl cellulose network and hydrochloric acid wherein, the
hydrogen atom in the acid replaces the sodium ions in carboxymethyl cellulose [31].

Physically cross-linked polymeric hydrogels could also be formed through ionic

interaction. This involves cross-linking of polyelectrolyte polymers through the
dispersion of di or trivalent counterions. The notable hydrogel falling under this
category is chitosan-glycerol phosphate salt.

On the other hand, stereo-complex formation is a method whereby, L-lactyl unit and
D-lactyl unit interact to form hydrogels. Hydrogels formed in this fashion opened up a

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new generation of materials for drug delivery. One good example of polymeric
hydrogels formed through stereo-complexing is polylactic acid. However, the
limitation of this method of hydrogel formation is its restriction to enantiomeric
polymers [24].

b) Chemically cross-linked hydrogels

Chemically cross-linked polymeric hydrogel are types of hydrogels whose network is

held together by covalent bonding. Chemically cross-linked polymeric hydrogels are
mechanically robust with excellent rigidity and elasticity. Unlike physically cross-
linked hydrogels, chemically cross-linked hydrogels are hard to dissolve not until the
covalent bonds holding their network are cleaved. Chemically cross-linked hydrogels
may be obtained through various methods which include; chemical cross-linking,
grafting, radical polymerization and condensation reaction [32].

Chemical cross-linking employs the use of various cross-linking agents such as

glutaraldehyde [10], epichlorohydrin [24], arginine [33], boric acid [32] and glyoxal
[34] to aid the cross-linking of one or two polymers. Chemical cross-linking might
also ensue through a reaction between different functional groups in polymer chains.
The notable example of this sort is the study on the preparation of glutaraldehyde
cross-linked chitosan/pullulan reported [35].

Grafting is a technique involving the use of natural polymers with different monomers
which could be polymerized. Grafting could be achieved via the use of chemicals or
radiation depending upon the nature of activation used. Chemical grafting goes via
activation of the polymeric backbone with chemical reagents followed by addition of
monomer. The simplest example of this type of grafting is the study on the
preparation of polyacrylic acid-co-acrylamide grafted carboxymethyl cellulose
hydrogel reported [36]. Radiation grafting is employed to avoid the excessive use of
chemicals in the preparation hydrogels. This involves the use of radiation sources
such as gamma radiation to facilitate the activation of the polymeric backbone [14].

Radical polymerization is virtually the most reported method for the preparation of
chemically cross-linked hydrogels. It involves the use of low molecular weight
monomers which are cross-linked to form the hydrogel. Radical polymerization
involves the use of initiators such as persulfates and ceric ammonium nitrate [36].

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Chemically cross-linked hydrogels could also be fabricated via condensation
polymerization. In condensation polymerization, the participating monomers
belonging to different functional groups are condensed to form the hydrogel. This
goes via the elimination of small molecule-mostly water. Condensation
polymerization could proceed via elimination of water molecule from amine group of
one monomer and hydroxyl or carboxyl group of the other [34].

1.1.3. Classification based on network electrical charge

Depending upon the availability of electrically charged particles in their network,

polymeric hydrogels may be sub-divided into four basic groups. These include;
neutral, cationic, anionic and ampholytic polymeric hydrogels [23]. This sub-division
aroused from polymerization techniques leading to their preparations.

a) Neutral hydrogels
Neutral polymeric hydrogels which are often referred to as non-ionic hydrogel are
forms of hydrogel having no charge particles on their network. Neutral hydrogels
could be synthesized through different polymerization techniques or by the
transformation of existing polymers. Neutral hydrogels possess various physical and
chemical properties which depend upon the chemical composition of monomers used.
Neutral hydrogels have high water absorption capacity due to the osmotic pressure
difference between the hydrogel and the surrounding medium. It is imperative to note
that, unlike ionic hydrogels, neutral hydrogels hardly response to changes in external
stimuli. The notable examples of neutral hydrogels are polyacrylamide and poly N, N-
dimethyl acrylamide. Sadeghi et al. [37] for instance, reported the grafting of
acrylamide onto the cellulose backbone to form neutral cellulose graft copolymer
acrylamide hydrogel.

b) Ionic hydrogels

Ionic polymeric hydrogels which are often referred to as polyelectrolytes are forms of
hydrogel possessing charged particles on their network. Ionic hydrogels could be
synthesized from monomers having ionic charges through different polymerization
techniques. They may be positively or negatively charged which are sub-grouped into
cationic and anionic hydrogels respectively. Combination of both charges on the same
hydrogel might be possible and the hydrogels of this sort are referred to as ampholytic

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hydrogels. Because of the possession of charged particles, ionic hydrogels are
sensitive to changes in the external stimuli. Their response to stimuli depends upon
the nature of pendant groups. This makes them useful in biomedical applications [24].
Anionic hydrogels are negatively charged polymeric hydrogels derived from either
polymerization of anionic monomer or copolymerization of neutral and anionic
monomers. In any case, the net charge on the polymer network is negative. Anionic
hydrogels may also be prepared by adding polyanions onto the network of existing
neutral hydrogel or by partial hydrolysis of polyhydroxy alkyl methacrylate. The
swelling ratio of anionic hydrogels is pH-dependent and is expected to increase with
an increase in pH value. The notable examples of anionic hydrogels are polyacrylic
acid, poly (acrylic acid-copolymer acrylamide), etc

Cationic hydrogels, on the other hand, are positively charged polymeric hydrogel
derived from homopolymerization of cationic monomer or copolymerization of the
cationic monomer with neutral monomer. They may also be derived via partial
hydrolysis of neutral polymer or through polyelectrolyte complexation reaction by
adding polycations. Cationic hydrogels swell more at lower (acidic) pH owing to the
electrostatic repulsion with positively charged hydroxonium ions. The notable
examples of cationic hydrogels are poly 3-acrylamidopropyl trimethylammonium
chloride, poly 2-acryloyloxyethyl trimethylammonium chloride copolymer N, N-
dimethyl acrylamide [23].

Polyampholytic hydrogels are polymeric hydrogels having both positively and

negatively charged particles in their network. Polyampholytic hydrogels may be
prepared from copolymerization of anionic and cationic monomers [24].
Polyampholytic hydrogels could do well in every pH environment hence, possess a
wide range of applications in biomedical and environmental applications. The notable
example of Polyampholytic hydrogel is carboxymethyl cellulose grafted poly (3-
acrylamidopropyl trimethylammonium chloride copolymer N, N-dimethyl
acrylamide).

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1.1.4. Classification based on polymeric composition

a) Homopolymeric hydrogels

Homopolymeric hydrogels are class of hydrogel whose structure is built upon single
monomer species through a polymerization reaction. Various cross-linking agents
may be used to provide cross-linking in homopolymer [23]. This, however, depends
on the type of monomer and polymerization technique. Homopolymers are employed
in the fabrication of contact lenses, drug delivery devices, photonics and so forth. The
notable examples of homopolymers include; polyacrylic acid, polymethyl
methacrylamide, poly (2-hydroxyethyl methacrylate), etc. preparation of un-
crosslinked homopolymers such as poly (N-vinyl-2-pyrrolidone), polyethylene glycol
and polyvinyl alcohol have also been reported. Polyvinyl alcohol, for example, is
found useful as a matrix in the fabrication of films and electrospun nanofibers.

b) Copolymeric hydrogels

Copolymeric hydrogels are class of hydrogel which are built upon more than one
monomer species through a process known as copolymerization reaction. Either of the
two monomers must be hydrophilic [23]. The assembly of these monomers along the
chain of polymer network could be random, alternating or block configuration.
Copolymeric hydrogels are water-insoluble because of the covalent/ionic cross-linked
nature of their network. The notable examples of copolymeric hydrogels are poly
(acrylic acid-copolymer acrylamide), poly 2-acryloyloxyethyl trimethylammonium
chloride copolymer N, N-dimethyl acrylamide, etc.

Copolymeric hydrogels are designed in order to achieve a desired property such as pH

sensitivity, mechanical strength and so forth. Abdel-Halima [38] for example,
prepared a copolymer hydrogel via free radical graft copolymerization of acrylic acid
onto hydroxyethyl cellulose. The prepared copolymer according to the author
exhibited better swelling capacity relative to non-cross linked hydroxyethyl cellulose.

c) Multipolymers

Multipolymers, otherwise known as interpenetrating polymer network is a class of

polymeric hydrogel formed as a result of cross-linking of two independent natural and
or synthetic components arranged in the form of network. Semi-interpenetrating

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polymer network, on the other hand, comprises one cross-linked polymer and non-
cross linked polymer [31]. Multipolymers are designed to prevent phase separation
through an increase in compatibility. Because of the absence of covalent or ionic bond
between the components of multipolymers, multipolymers are found to be both
temperature and pH-sensitive. Rao and his group [31] demonstrated a study on the
preparation of IPN hydrogel containing polyvinyl alcohol and carboxymethyl
cellulose for controlled release of anti-cancer drug.

1.2. Methods of Synthesis of Hydrogels

The various classical techniques used in the preparation of hydrogel are as described
in the following sections.

Inverse
polymerization

Radiation Graft
polymerization Hydrogel copolymerization

Electrospinning

Figure 1.2: Methods of synthesis of hydrogel

1.2.1. Solution polymerization technique

Solution polymerization is a form of polymerization technique in which neutral/ionic

monomers are blended together in the presence of multifunctional crosslinker [23].
Solution polymerization may be initiated by employing the use of initiators/radiation.
Solution polymerization is exothermic in nature and therefore, excess heat is liberated
to the surrounding. This excess heat is absorbed by the solvent which makes it more
advantageous over bulk polymerization. The commonest solvents used in solution

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polymerization include; water, benzoyl alcohol, ethanol, ethanol-water solvent
mixture, etc. hydrogels prepared using solution polymerization may contain unreacted
monomers, cross-linking agent, initiator and some unreacted entities which may be
removed by repeatedly washing the hydrogel with water until the pH of the eluent is
neutral [24]. Hydrogels prepared using this technique include polyacrylic acid,
polyacrylonitrile and sodium polyacrylate to mention but few. The limitation of
solution polymerization is the difficulty involved in obtaining high molecular weight
hydrogel due to chain transfer reaction with the solvent. This chain transfer reaction is
likely to happen regardless of the inertness of the solvent [39].

1.2.2. Bulk polymerization technique

Bulk polymerization, otherwise known as mass polymerization is a technique of

forming hydrogel which involves the dissolution of soluble initiator into the
monomer. Like solution polymerization, bulk polymerization may be initiated by heat
or radiation. As time goes on, the solution becomes viscous and subsequently, the
purest form of the hydrogel may be obtained from this technique. Unlike solution
polymerization, bulk polymerization does not involve the use of solvent and so, the
tiresome washing steps are avoided. Moreover, bulk polymerization does not amount
to the chain transfer reaction. The heat released during bulk polymerization reaction
may be suppressed by the use of coolants [40].

1.2.3. Inverse suspension polymerization technique

Inverse suspension polymerization otherwise known as heterogeneous polymerization

is a technique of forming a hydrogel in powdered form or beads (microspheres). The
process takes place in oil-in-water phases which are non-solvents for both the
monomers and the prepared hydrogels. Thus, the name “inverse suspension”
Hydrocarbons are usually used as a solvent in which the initiators and monomers are
distributed. The size and shape of the hydrogel beads are controlled by the solution
viscosity and stirring speed. The notable examples of polymers prepared via inverse
suspension polymerization include but not limited to; poly (methyl methacrylate),
poly (styrene-co-acrylonitrile) and polystyrene [41].

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1.2.4. Radiation-induced polymerization technique

Radiation-induced polymerization is a technique that is devoid of chemical species to

provide cross-linking or initiate the polymerization reaction. It is therefore considered
a green approach of hydrogels preparations. Free radicals are generated as a result of
the application of radiation from high energy sources. The commonest radiation
sources include; electron beam radiation, gamma rays, X-rays and so forth. The
formation of radicals on polymer chains due to radiation could be via homolytic
fission of C-H bond or radiolysis of water molecules. This result in the formation of
hydroxyl groups which later attack the polymer chain to generate macro radicals.
Subsequently, cross-linked hydrogels are formed due to the covalent bonding between
macro radical and polymer chains. The major setback of radiation-induced
polymerization might be the degradation of bioactive material such as drugs when
added in the process of making hydrogel. There is also, the possibility of having non-
biodegradable C-C bonds in the hydrogel network [23].

1.2.5. Graft copolymerization technique

Unlike radiation-induced polymerization, graft copolymerization involves the use of

chemical species to initiate the reaction and to provide cross-linking in the polymer
network. Initiators such as potassium persulfate, ammonium persulfate, and ceric
ammonium nitrate are used for the generation of active radical species whilst cross-
linking agents such as N, N-methylene-bis-acrylamide, glutaraldehyde and citric acid
may be used to provide cross-linking in hydrogel network. The overall idea of graft
copolymerization is to improve the mechanical properties of hydrogel which can be
done by attaching the polymerizing monomer onto the surface of stronger support-
usually polysaccharides. The active radicals are generated on the support which later
results in the formation of covalent bonding between the surface of the support and
the polymerizing monomers to produce a cross-linked hydrogel. Sadeghi et al [37] for
example demonstrated the graft copolymerization of acrylamide monomer onto the
surface of carboxymethyl cellulose using ceric ammonium nitrate as initiator and
MBA as cross-linker. The prepared hydrogel exhibited high mechanical strength and
swelling property.

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1.2.6. Electrospinning technique

Electrospinning is a technique of making hydrogel which employs the uses electric

force to draw charged threads of polymer solution/melt into fine fibers with diameters
in the range of some hundreds of nanometers. Electrospinning is a composite of
electrospraying and conventional solution dry spinning of fibers. Electrospinning
technique does not require the use of coagulation chemistry or high temperatures to
produce solid threads from solution. This makes the process particularly suited to the
production of fibers using large and complex molecules. Electrospinning from molten
precursors is also practiced; this method ensures that no solvent be carried over into
the final product [42]. Electrospinning has been recognized as an efficient technique
for the fabrication of polymer nanofibers. Various polymers have been successfully
electrospun into ultrafine fibers in recent years mostly in solvent solution and some in
melt form. Potential applications based on such fibers specifically their use as
reinforcement in nanocomposite development has been investigated by different
researchers [43]. Gül Şener and co-workers [44] for example documented a study on
the effects of applied voltage on morphologies of electrospun nanofibers containing
polyvinyl alcohol and sodium alginate.

1.3. Properties of Hydrogels

Hydrogels possess some excellent properties such as swelling, biocompatibility, and

response to fluctuations in external stimuli enabling them to be used in various
applications. Some of the properties of hydrogels are as highlighted in the following
sections.

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 Biocompatibility

Swelling properties

Surface properties
Hydrogels

Mechanical
Response to stimuli
properties

Figure 1.3: Properties of hydrogels

1.3.1. Swelling properties

One of the distinctive properties of hydrogels is their ability to swell and retain a
colossal amount of water or fluid. Hydrogels, when placed in water, could swell and
absorb hundreds to thousands of times their initial weight without getting dissolved in
the swelling medium. The swelling of the hydrogel, when soaked in water, is
occasioned by the hydration of hydrophilic groups of hydrogels. This causes the
swelling of hydrogel linkages which later result in the exposure of hydrophobic
groups to intermingle with water molecules. The water associated with hydrophobic
groups in the hydrogel network is called “secondary bound water” while that
associated with the hydrophilic group is known as “primary bound water.”
Combination of ‘primary and secondary bound water” is termed as total bound water
[24]. Another driven factor responsible for the influx of water into the hydrogel
matrix is the hydrophilic groups they possess. This happens through an osmotic
pressure difference. Excess water in the hydrogel network is prevented from making
the hydrogel to collapse because of the presence of chemical or physical cross-links.
The swelling ability of hydrogel makes it resemble body tissues and so, could be used
in biomedical applications. Another important swelling property of hydrogel is
entrapment of some dissolved solutes such as heavy metals and dyes which might
diffuse through the swelling medium into the hydrogel network [23].

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1.3.2. Mechanical properties

Except for biodegradable applications, the mechanical property of hydrogel is an

important property that is required in the design of hydrogel for both water
purification and biomedical applications. Hydrogels intended to be used as drug
carriers, for example, has to be mechanically stable in order to protect the drug from
harsh environmental conditions such as body pH and temperature for it to be released
to the intended site/target. Similarly, the mechanical properties of hydrogels are also
an important factor to be considered when designing hydrogel for wastewater
purifications. This is because the hydrogel has to be mechanically stable enough to
prevent its collapse when excess water is absorbed. Mechanical properties of
hydrogels could be enhanced either by addition of various crosslinking agents,
increasing the cross-link density or by addition of monomer with high mechanical
strength [40].

1.3.3. Biocompatibility

Biocompatibility of hydrogel can be referred to as the ability of the hydrogel to co-

exist with the host system without causing the problem to the latter. Biocompatibility
of hydrogel could be evaluated by conducting cytotoxicity or in-vivo cytotoxicity
studies on the hydrogel. Biocompatibility is an important property to be considered
while designing hydrogel for biomedical applications such as drug delivery, wound
healing and tissue engineering. Polymers are themselves not expected to be toxic.
Their toxicity arises from the presence of unreacted monomer, radicals or initiators
which might be released amidst usage. Hydrogel’s toxicity may be reduced by
avoiding the use of chemical species as initiators or cross-linker through radiation
polymerization techniques or by a thorough washing of the prepared hydrogel with
water to remove unreacted chemical species. Another means of avoiding hydrogel’s
toxicity is through the achievement of higher conversion rates by evaluating the
kinetics of polymerization. This diminishes the chances of having unreacted chemical
species as well as the side products [24].

1.3.4. Surface properties

The hydrogel’s surface morphology is an important property in determining the

behavioral pattern of hydrogel designed for a particular application. The behavior of

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hydrogel for a particular application depends on the morphology of hydrogels.
Hydrogel designed for environmental applications such as a dye or metal uptake
studies should be porous enough to allow for the penetration of excess water along
with dyes or metal as the case may be, into the hydrogel’s network. The same can be
said of hydrogel designed for drug delivery studies. Excess pores must be present on
the hydrogel for drug molecules to diffuse through hydrogel network. Dai and Huang
[36] studied the surface morphology of kaolin loaded pineapple peel graft polyacrylic
acid and found that the well-distributed kaolin particles provided free space for the
diffusion of water molecules into the hydrogel.

1.3.5. Response to changes in external stimuli

Stimuli sensitive hydrogels otherwise known as “smart” or “intelligent” materials are

second-generation hydrogels designed to be able to respond to change in external
environments such as pH, temperature, ionic strength and electric field with respect to
swelling or de-swelling behavior in a given medium. The stimuli-responsive hydrogel
is useful in biomedical applications. The ability of the hydrogel to respond to change
in pH environment largely depends on the presence of acidic/basic pendant groups in
their structure which either accept or release proton in response to change in pH of the
environment [45]. This is a very important property expected of a hydrogel to be used
in drug delivery. Thermo-responsive hydrogels, on the other hand, are sensitive to
change in temperature and therefore undergo either hydration or dehydration due to
change in temperature. The notable examples of thermo-responsive hydrogels are
poly (vinyl methyl ether), poly (2-isopropyl-2-oxazoline) and so forth.

1.4. Applications of Hydrogels

Hydrogels because of their ability to absorb a large volume of water, find application
in agriculture-for slow release of agrochemicals, in biomedicine-for drug delivery and
in wastewater treatment-as adsorbent for dye/heavy metal ions.

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 • As water reservoir
• Slow release of fertilizers, pesticides,
In Agriculture insecticides, etc

• Tissue engineering
• Wound healing
Biomedical • Drug delivery

• Adsorption of metal ions

• Adsorption of dyes
Water Purifn

Figure 1.4: Applications of hydrogels

1.4.1. Agricultural applications

Apparently, it is known fact that the biological processes of all plants are to a larger
extent dependent on water and that the plant growth is highly affected under water-
stressed conditions due to a tremendous decrease in transpiration and photosynthesis.
To overcome all such troubles, modern methods such as water-shed management drip
irrigation are used along with other water-holding alterations. The use of hydrogel as
a water reservoir could serve as a replacement to the existing high cost and high tech
methods of keeping the soil moist in times of drought. One of the works which were
undertaken during the research [45] revealed that hydrogel can absorb and retain
water hundred times of their own weight and can, therefore, be utilized as a water
reservoir in the soil thereby amplifying the level of water uptake by the plants. In
addition, they improve aeration and seepage through the soil and reduce the moisture
stress of the plants. A recent study indicates that sand mixed with hydrogel retained
40 times more water as compared to the sand without hydrogels. Their ability to
respond to change in temperature makes them able to slowly release water to the
plants in time of water shortage and so, could be used as water reservoirs in soil.
Furthermore, the hydrophilic groups in hydrogel enable the hydrogel to adsorb
fertilizers and agrochemicals such as pesticides and insecticides through physical

17
forces and slowly released same due to change in soil pH and temperature condition
[46].

1.4.2. Biomedical applications

The development of poly 2-hydroxyethyl methacrylate for use in contact lenses as

reported by Wichterle and Lim way back in 1950 formed the basis for the application
of polymeric hydrogels in biomedical fields. Afterward, the fabrication hydrogels for
different types of biomedical applications such as tissue engineering, drug delivery,
and wound healing-anti-bacterial and antifungal were reported elsewhere. Hydrogels
behave like living tissues because of its high water content and rubbery like texture.
The ability of the hydrogel to be utilized as a drug carrier lies in its stimuli-sensitive
nature. Ionic hydrogels, for example, are used in the preparation of “smart” hydrogels
that can respond differently to different pH and temperature condition and so, could
be used as drug carriers. Ionic hydrogels could also be used as anti-bacterial agents
because of their ability to form a complex with bacterial cell walls which destroy the
bacterial cells. Ferrera-Harrar et al [11] demonstrated a study on preparation of
superabsorbent hydrogel composite made by grafting acrylamide monomer onto
chitosan followed by incorporating carboxymethyl cellulose. The hydrogel composite
portrayed excellent swelling and activity against both Gram-positive and Gram-
negative bacteria.

1.4.3. Water purifications

Undoubtedly, water is one of the indispensable commodities not only for human
survival but for perpetual prosperity of both developed and developing nations [47].
Albeit 75 percentage of the earth is covered by water, only about 2.5 percent of
world’s total water content is freshwater of which just one percent is accessible for
domestic, agricultural and industrial usage [48]. This limited amount of the world's
freshwater is stagnant and the world’s population is drastically increasing resulting in
enormous evolution of chemical industries. The evolution of various industries brings
about the pollution of both surface and groundwater reservoirs owing to the discharge
of contaminants from municipals, agricultural and industrial sources [48]. The
enormous amount of dye-containing effluents from various chemical industries like
textile industries poses a serious esthetic and toxicological threat to water bodies [49].

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The annual consumption and production of dye by the chemical industries particularly
the textile industry is reported to be to the tune of 7 X 105 [50]. A greater percentage
of about 10-15 % of the dye consumed by the textile industries ended of being
discharged into the water bodies in the course of dyeing processes with 2 X 105 being
oozed out as effluvia [50]. This constitutes inauspicious effects on aquatic lives and
by extension, human health. The curious thing about the presence of dyes in water is
its stability and difficult removal conferred to it by the aromatic structure it possesses.
The aromatic and azo group such as benzidines and naphthalenic derivatives present
in dye structure are associated with toxic, mutagenic and sometimes carcinogenic
implications in human. Moreover, the presence of a minute quantity of azo dye
unfavorably affects the plant’s photosynthetic activities thereby preventing the
penetration of light and oxygen [51]. Among the various substrate used as an
adsorbent for removal of dyes from wastewater, hydrogels may be regarded as the
most preferred material because of their low cost, high efficiency, user-friendliness
and recyclability [52]. Hydrogel, when soaked in dye-containing water swells and
retain water alongside the dissolved dye in their network. The beauty of using
hydrogel as an adsorbent for dye removal is its ability to be re-used after several
successive cycles.

Another source of water pollution is the presence of different kinds of toxic heavy
metals (e.g., Cr, Pb, Cu, Ni, Cd, Fe, etc.) which are either accidentally or deliberately
discharged into these surface waters by commercial and industrial establishments. The
resulting environmental hazards are undesirable and therefore heavy metal ions must
be appropriately removed using new/improved techniques. Currently, many methods
are being used to remove heavy metal ions from wastewaters such as chemical
precipitation, reverse osmosis, membrane filtration, and electrochemical treatment
technologies [53]. However, the effectiveness of these methods is limited in the case
of low metal ion concentration. Adsorption method using polymeric hydrogel is one
of the most important approaches available for this purpose [54]. The process is akin
to the removal of dye from wastewater. Wang and his team [54] documented a study
on preparation of polyvinyl alcohol/carboxymethyl cellulose composite hydrogel
through the freeze-thawing method. The prepared hydrogel was employed as an
adsorbent for removal Ag+, Ni+, Cu2+ and Zn2+ ions from aqueous solutions. The

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authors revealed that the prepared hydrogel could excellently chelate the tested metal
ions from a solution with a preference towards Ag+.

1.4.4. In photonics

Aside the use of hydrogels in agriculture as a soil conditioner and biomedicines as a

drug carrier, thermo-stable hydrogels such as poly (methyl methacrylate) has attracted
much attention as a host material in the fabrication of photoluminescent materials for
lasing technology, optical polymer fibers for data transmission and luminescent solar
concentrators. The use of hydrogels in photonics aroused from its low cost and
unmatched optical transparency from near UV to the near IR regions. Luminescent
hydrogels could emit light when exposed to UV radiation or visible light radiation.
Fluorescent dyes or metal complexes could be incorporated into the hydrogel matrix
through physical or chemical cross-linking. This results in hydrogel composite with
an excellent photoluminescent property that could be used in photonics. Choi et al
[55] demonstrated the use of polyacrylic acid hydrogel as host for fluorescent dyes for
enhanced fluorescence emission. Although not as effective as DNA-CTMA host, dye-
doped polyacrylic acid hydrogel shows excellent luminescence property.

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1.5. CONCLUSION

The review on the classification and application of hydrogels from synthetic and
natural origin leads to the understanding that there exists an ample scope to continue
this field of study. This study might lead to justifiable findings which will cater to the
need for smart functional materials.

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1.6. STUDY OBJECTIVES

Based on the literature review conducted, it is contemplated that the following

objectives could be undertaken.

1. To extract cellulose from banana pseudo-stem.

2. To transform the isolated cellulose into water-soluble carboxymethyl cellulose
for use in the preparation of hydrogels
3. To use the cellulose-based hydrogels for wastewater purification and drug
delivery
4. To fabricate dye-doped electrospun nanofibers and use them as matrix for use
in optoelectronics.

The specific work based on these objectives forms the basis of this thesis.

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