Synthesis, Characterization, and Drug Release Study
of Acrylamide-Co-Itaconic Acid Based Smart Hydrogel
Rabin Bera, Ayan Dey, Debabrata Chakrabarty
Department of Polymer Science and Technology, University of Calcutta, Kolkata 700009, India
A new kind of pH and temperature responsive poly(acryl-
amide-co-itaconic acid) hydrogel was prepared by free rad-
ical polymerization using ammonium persulfate as initiator
and different comonomer ratios. The hydrogels were char-
acterized in terms of chemical composition, swelling-
deswelling behavior, morphology, crystallographic behavior,
and drug release properties. All the hydrogels showed high
swelling ability in aqueous solutions, the maximum being
at pH 7. Swelling decreased on either side of pH 7 (i.e.,
both in acidic and alkaline region) and increased with
increase in temperature. The hydrogel with 10 mol% ita-
conic acid (IA) absorbed maximum water among the copol-
ymer gels. The cellular structures of the hydrogels were
clearly revealed by microscopic analysis and SEM pictures.
Swelling of the gels in water followed non-Fickian type of
diffusion principle. The hydrogel was proved to be a con-
trolled release vehicle, for example in drug delivery by
using its smart properties. The hydrogel with 10 mol% IA
also absorbed maximum amount of drug (ascorbic acid)
under study. Incorporation of drug in hydrogel matrix was
established from XRD peak analysis. POLYM. ENG. SCI.,
C 2014 Society of Plastics Engineers
00:000–000, 2014. V
INTRODUCTION
Hydrogels are three-dimensional polymeric crosslinked net-
works having a solid-like appearance that do not dissolve in
water but can absorb large volume of water or aqueous solution.
Hydrophilic groups present in the polymer chains assist the
hydrogel to swell in water. However, the mechanical strength of
the gel comes from its crosslinked network [1]. Stimuli-sensitive
polymers can change their structure and physical properties in
response to physical or chemical changes, such as pH [2, 3],
temperature [4–7], ionic strength, electric field [8], magnetic
field [9], concentration, etc. They are also called intelligent or
smart polymers. These smart polymers have a wide range of
applications in pharmaceutical technology and the biotechnology
industry such as drug delivery [10, 11], artificial implants [12],
contact lenses [13], and in solving environmental problems [14].
Among the smart polymers, pH and temperature responsive
polymers are most frequently studied.
pH sensitive hydrogels usually swell due to ionic networks
that contain acidic or basic pendant groups. When these groups
are ionized, a swelling osmotic pressure inside the gel matrix is
built up, and fixed charges are trapped in the gel. As a result of
the electrostatic repulsion, the diffusion of solvent in the net-
work is increased [15, 16]; although large number of ionised
groups may cause deswelling of the gel due to extreme electro-
static repulsion of the like charges, sometimes leading to gel
Correspondence to: Debabrata Chakrabarty; e-mail: chakrabarty_deb@yahoo.com
DOI 10.1002/pen.23874
Published online in Wiley Online Library (wileyonlinelibrary.com).
C 2014 Society of Plastics Engineers
V tubes. In all the cases AAm, itaconic acid, MBA and APS were
POLYMER ENGINEERING AND SCIENCE—2014
collapse. Within the human body also, different compartments
have the different pH and it can therefore be used to direct the
response to a certain tissue or cellular compartment (Table 1).
Temperature-sensitive polymers or hydrogels exhibit a vol-
ume phase transition at a certain temperature, which causes a
sudden change in the solvation state. This is due to the presence
of hydrophilic-hydrophobic interaction in the polymer chain.
Polymers, which become insoluble upon heating, have a lower
critical solution temperature, for example poly(N-isopropyl
acrylamide), and the systems, which become soluble upon heat-
ing, have an upper critical solution temperature. For the corre-
sponding hydrogels, they are known as lower gel transition
temperature or upper gel transition temperature, respectively.
The combination of a thermo-responsive monomer with one of a
pH-responsive monomer yields dual-responsive copolymers or
hydrogels [19]. It is more useful than the monoresponsive one.
Hydrogels can also be made as electric field responsive mate-
rial by using one or more conductive compound. These hydrogels
found applications in many biomedical and technological applica-
tions such as artificial implants, contact lens, pharmaceutical, and
biosensors. Recently, there have been a number of publications
on electrically induced phenomena in charged polyelectrolyte net-
works. Tang et al. prepared polyacrylamide-graphite super
absorbent composite hydrogel with conductivity 0.86 mS cm21
[20]. Polyacrylamide/Cu composite hydrogel of conductivity 1.08
mS m21 was synthesized by Lin et al. [21]. Polyacrylate/polyani-
line and poly(2-acrylamido-2-methyl propylsulfonic acid-acrylic
acid)/polyaniline conducting hydrogels with an interpenetrating
polymer network structure was prepared by Lin et al [22].
In this study, an attempt has been made to synthesis a pH
responsive and temperature responsive (both characteristic being
present in one) smart hydrogel by using copolymers made from
acrylamide (AAm) as nonionic monomer; and an anionic mono-
mer; itaconic acid (IA). The gels have been studied in terms of
its swelling behavior, microscopic study, and drug release
behavior. The effects of pH on swelling and shrinking behaviors
of the prepared hydrogels are studied. Release kinetics of the
hydrogels has also been investigated. Structures of the mono-
mers and crosslinker used are as in Scheme 1. S1
EXPERIMENTAL
Materials
AAm (Merck, Darmstadt, Germany), IA (Aldrich), ammo-
nium persulfate (APS) were used as received. N,N0 -methylenebi-
sacrylamide (MBA) was used without further purification.
Buffer capsules were used as supplied by Merck. Distilled water
was used to synthesis gels and for swelling studies.
Preparation of Gels
All the polymerization reactions were carried out in glass
 TABLE 1. pH in various tissues and cellular compartments [17, 18]. TABLE 2. Composition of the hydrogels.

Tissue/cellular compartment pH Hydrogel AAm (mol%) IA (mol%) MBA (mol%) APS (mol%)

Blood 7.35–7.45 AI0 100 0 2 0.1

Stomach 1.0–3.0 AI5 95 5 2 0.1
Duodenum 4.8–8.2 AI10 90 10 2 0.1
Early endosome 6.0–6.5 AI20 80 20 2 0.1
Late endosome 5.0–6.0 AI30 70 30 2 0.1
Colon 7.0–7.5
Lysosome 4.5–5.0 Water retention was measured by the equation:
Golgi 6.4
Wt2Wd
Water retention : Wr5 3100% (2)
W
dissolved in water separately, and then mixed. The total mono-
mer concentration was kept constant in each case. Then the where Wt is the weight of the gel sample at time t, Wd is the
solution was kept at 70 C for 8 h under constant stirring. The weight of the dry gel, and W is the weight of the water absorbed
details of the monomers taken are given in Table 2. by the gel in fully swollen condition.

CHARACTERIZATION OF POLY(AAM-IA) HYDROGELS Drug Encapsulation and Release Study

Fourier Transform Infrared Spectroscopy (FTIR)
The FTIR spectra of the dried gel samples were recorded by
making KBr pellets on a Perkin–Elmer BX II spectrophotometer.
The FTIR spectra were recorded in the range of 4000–400 cm21.
The FTIR spectra of the copolymer gels are given in Fig. 1.
Swelling Measurement
Dried hydrogel samples were allowed to swell in distilled
water at different temperatures and in different pH solutions.
The swelled gels were taken out at certain time intervals, wiped
on its surface with tissue paper, and then weighed and the pro-
cess is repeated until the constant weight was reached.Equili-
brium swelling was measured by the equation:
Ws2Wd
Equilibrium swelling ES5 3100%
Wd
where Ws is the weight of the swollen gel and Wd is the weight
of the dry gel.
Deswelling Measurement
The gel samples were allowed to swell in distilled water at
room temperature (27 C) and then dropped in pH 4 medium to
deswell (as all the hydrogels under study swell in pH 4 medium
in much lesser amount compared to that in pH 6.5). At regular
time intervals, gel samples were taken out, wiped with tissue
paper on its surface, and weighed again.
Previously weighed dry hydrogels were loaded with ascorbic
acid by immersing them in an aqueous solution of a drug (ascor-
bic acid in this case) until equilibrium was reached. Swelling
was carried out by keeping the electrode of a pH meter
immersed in it. Amount of ascorbic acid uptake was determined
from the decrease of conductivity of the solution using Conduc-
tivity vs. ascorbic acid concentration calibration curve, which
was obtained using standard ascorbic acid solutions at 27 C.
The loaded hydrogels were then dried at room temperature for 3–
4 days and weighed to obtain the concentration of drug in the hydro-
gels. To study the drug delivery kinetics, the loaded hydrogels were
immersed in 25 ml of distilled water at 27 C, which were continu-
ously stirred. To follow the delivery kinetics, the conductivity of the
solution was measured at certain time interval. The amount of drug
released at any given time was obtained from the calibration curve.
(1)
Optical Microscopic Studies
The internal or cross-sectional morphology of the swollen
gels were determined by using optical microscope, Kruss, A.
Kruss Optronic, Germany, at different magnification. The dried
gels were first swollen to equilibrium and then thin strips of the
gel sample were placed under microscope.
Scanning Electron Microscope (SEM)
The SEM of the dried gels were taken by using SEM appara-
tus, S-3400N Hitachi, Japan. The samples were gold coated
with coating time of 45 s using gold coater Hitachi E1010.

SCHEME 1. Structures of the monomers and the crosslinker.

2 POLYMER ENGINEERING AND SCIENCE—2014 DOI 10.1002/pen


FIG. 1. FTIR spectra of copolymer gels (AI0-AI30).
X-Ray Diffraction (XRD)
Identification of crystalline planes in itaconic acid, pure
hydrogel and drug loaded hydrogel were investigated by wide
angle x-ray scattering study by using XPERT-PRO Diffractome-
ter system, Goniometer PW3050/60 (Theta/Theta; XRD PANa-
lytical, Netherland). Studies were undertaken from 5 to 70
2Theta using continuous scan with 0.0330 2Theta step size.
Differential Scanning Calorimetry (DSC)
The DSC studies were performed on a Perkin–Elmer DSC 7.
The samples were heated from 50 to 300 C, with a heating rate
of 20 C per min in an inert condition.
RESULTS AND DISCUSSION
FTIR Spectra of the Gel
The FTIR analysis of the different gel samples (Fig. 1)
showed the presence of peaks corresponding to the functional
groups of the monomeric units used in preparing the copoly-
meric gels. The characteristic absorption peaks of AAm and ita-
DOI 10.1002/pen
conic acid units appear at their usual wave numbers. The peaks
at 1650 and 1710 cm21 are assumed to be due to the C@O
group of AAm and itaconic acid part respectively [23]. The
peak corresponding to OAH bond of ACOOH group of itaconic
acid part was observed around 2929 cm21 and NAH peak of
AAm part was observed at around 3445 cm21. The broad nature
of NAH peak reveals that the H-atom is involved in making
hydrogen bond. The absence of peak at 1610–1640 cm21 (for
conjugated C@C) and at 3000–3100 cm21 (for @CAH) ensures
complete polymerization with the formation of gels of copoly-
mers and/or blends of two homopolymers [24]. The above IR
analysis indicates the presence of all monomeric units in the
crosslinked network, and as such no functional groups are lost
during crosslinking.
Swelling Properties of the Gels
Swelling in Water. Poly(AAm-co-IA) hydrogels absorb large
amount of water compared to the conventional polyacrylamide
hydrogel. On increasing the itaconic acid content in the copoly-
mer network swelling increases. In case of hydrogel with 10%
itaconic acid (sample AI10) swelling is maximum. The % swel-
ling then falls with further increase in itaconic acid content (Fig.
2). Introduction of polar ACOOH group in the polymer network
increases the hydrophilicity of the gel. Carboxylic acid
(ACOOH) group of the itaconic acid part ionizes partially in
contact with water to form ACOO2 ion, which attracts the polar
water molecules in the crosslinked network and thus imparting
development in swelling properties of the gel [25]. The behavior
of the two ACOOH group present in the IA is not identical; the
primary one being the most reactive readily ionizes whereas the
secondary ACOOH group undergoes dissociation rather slowly.
However under any circumstances the dissociation of the
ACOOH group is never completed. Beside, there is a probabil-
ity of formation of inter molecular H-bonding between the car-
bonyl oxygen atom of ACONH2 (amide) group of the AAm
unit with the hydrogen atom of the ACOOH (carboxylic acid)
functionality of the itaconic acid unit, which results in cage like
structure that can hold large amount of water in it (Scheme 2). S2
With increase in content of IA beyond 10% the surface area
available for cage formation due to crosslinking of the poly
AAm chains (the content of which decreases with increase in
IA) also decreases. Consequently, the volume accessible for
swelling gradually diminishes.
It is assumed that with increase in IA content during the
copolymer formation the statistical probability of intramolecular
and intermolecular crosslinking amongst the IA moieties and
between the IA and poly AAm increases. As a result of which
the cage structure undergoes a substantial reduction in sizes.
The reduction in swelling with increasing IA beyond 10% may
possibly be explained by the following schematic representation.
pH Dependent Swelling of the Gel. To determine the pH sensi-
tivity of the poly(AAm-IA) hydrogels, the dried hydrogel samples
were allowed to swell to equilibrium in buffer solutions (by using
standard buffer capsules) having different pH at room temperature
(25 C). Equilibrium swelling of poly AAm hydrogel is independ-
ent on pH. However, equilibrium swelling of all the poly(AAm-
IA) hydrogels were strongly dependent on the pH of the medium
as revealed in Fig. 3a. Swelling of hydrogel first increases with
POLYMER ENGINEERING AND SCIENCE—2014 3
FIG. 2. Variation of swelling with itaconic acid content in the crosslinked
network.

increasing pH upto pH 7, then it falls on further increase of pH

of the medium. That is the hydrogels swell to its maximum at pH
7 solution in all the cases. Itaconic acid being a weak acid the
ACOOH groups introduced in polymer backbone ionizes little
forming ACOO2 (carboxylate) ions. These carboxylate ions
attract the polar water molecules to enter into the crosslinked net-
work. The cage structure formed by the intermolecular H-bonding
between carbonyl group of the amide functionality with the acid SCHEME 2. Structure of the hydrogen bonded crosslinked network devel-
functionality of the itaconic acid unit can hold the large amount oped in the gel matrix.
of water molecules. Ionization of the ACOOH group is arrested
in acidic medium (pH < 7) as the medium contains excess H1 which may remain in equilibrium with the ionized ACOO2
ions. Even amide group may undergo protonation in this medium, group may form a sheathing layer or screen through which the
which results on the whole breakage of H-bonding structure and diffusion of water molecule towards the cage structure is inhib-
decrease in equilibrium swelling. In basic medium ionization of ited to a great extent.
the acid group increases with the formation of large amount of
ACOO2 ions, which repel each other resulting disruption of cage Temperature Dependent Swelling of the Gel. It is quite appa-
structure and decrease in swelling. rent that like the insensitive behavior exhibited by virgin poly
It can be assumed that at the high acid concentration the ion- AAm gel in different pH media the said gel is also almost
ization is somewhat arrested. The unionized –COOH group, insensitive to changes in temperature. The copolymer gels are

FIG. 3. (a) Swelling of the copolymer gels in different pH medium (AI0-AI30) and (b) Swelling of the gels at differ-
ent temperatures (AI0-AI30). [Color figure can be viewed in the online issue, which is available at wileyonlinelibrary.
com.]

4 POLYMER ENGINEERING AND SCIENCE—2014 DOI 10.1002/pen

 FIG. 4. (a) Extent of swelling of the gels (AI0-AI30) with time and (b) Swelling kinetics plot according to Fick’s
law equation. [Color figure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]
however very much sensitive to changes in temperature as can
be seen from the Fig. 3b. Here also we can find that the copoly-
mer gel with IA content of 10 mol% gives the highest swelling
at all temperatures under study. Moreover, this gel is observed
to undergo a drastic jump in swelling efficiency.
To determine the temperature sensitivity of the poly(AAm-
IA) gel, the samples were subjected to swell in distilled water,
kept at different temperatures. Swelling of the gel increases with
temperature in all the cases (Fig 4). This can be explained by
considering the effect of temperature on the ionization of weak
acids. According to the equation:
DG0 52RTlnKa
where DG0 is standard Gibbs free energy change, R the univer-
sal gas constant, T the temperature (kelvin), and Ka the ioniza-
tion constant. With the increase in temperature the ionization
constant increases, that is, more ACOOH group ionizes to form
ACOO2 (carboxylate) ions, which drag larger number of water
molecules in network causing higher rate of diffusion at ele-
vated temperatures.
Swelling Kinetics. The rate of swelling is very fast initially for
all the poly(AAm-IA) gels, then it slows down with time and
reaches equilibrium (Fig. 4a). The rate and extent of swelling is
highest in case of hydrogel AI10. To determine the nature of
water diffusion into hydrogels, the equilibrium swelling data
were fitted to the following exponential equation [26, 27]:
F5Mt =M1 5ktn
where, F is the fraction of water uptake at time t, Mt , and M1
represent the weight of the swelled hydrogels at time t and at
equilibrium respectively, k is a characteristic constant of the
hydrogel, and n is the diffusional exponent, which is indicative
of the transport mechanism; n 5 0.5, represents a Fickian diffu-
sion, when the rate of diffusion is much slower than the rate of
relaxation. In case of n 5 1, it is case II transport, the diffusion
is very fast, contrary to the rate of relaxation, and the third case
corresponds to an anomalous diffusion (or non-Fickian diffu-
sion) with n values lying between 0.5 and 1. A representative
DOI 10.1002/pen
plot of log t versus log F is shown in the Fig. 4b for all the
samples. The n exponents are calculated from slopes of the lines
and are given in Table 3. In case of poly AAm gel (sample
AI0), n is close to 0.5 though they are not exactly equal to 0.5.
It can be said that the process is quasi-Fickian diffusion with
partly anomalous behavior, that is, chain relaxation controlled
process. However, the swelling of copolymer gels (samples AI5-
AI30) is anomalous having n value between 0.5 and 1. The
strong interchain interactions via the formation of intermolecular
H-bonding leading to a compact structure may play a significant
role in the anomalous diffusion behavior.
(3) Swelling in Salt Solutions. The effect of salt concentration on
the swelling capacity of the hydrogel samples was examined
with sodium chloride solution (Fig. 5). Swelling of all the
hydrogels in salt solutions are lower compared with that of pure
water. This is because, the swelling of polyelectrolyte hydrogels
ismainly due to the electrostatic interactions among the charge
centers present on the polymer chain, so the extent of swelling
is influenced by any change in physical parameters, such as pH,
ionic strength, and type of counter-ions present in the swelling
medium, which may alter these electrostatic interaction [28].
Thus, with the increase in concentration of counter-ions, that is,
salt concentration in the external media, the osmotic swelling
pressure responsible for swelling decreases, which ultimately
results in a decrease in the water uptake of the hydrogel sam-
ples. This is supported by the fact that the swelling of the
hydrogel AI0 with no itaconic acid is not at all affected by salt
concentration.
(4)
TABLE 3. Diffusion constant (n) values of the swelling process of poly
(AAm-IA) gels.
Hydrogel n-Value Type of swelling
AI0 0.49 Quasi-Fickian diffusion
AI5 0.73 Non-Fickian diffusion
AI10 0.85 Non-Fickian diffusion
AI20 0.698 Non-Fickian diffusion
AI30 0.563 Non-Fickian diffusion
POLYMER ENGINEERING AND SCIENCE—2014 5
FIG. 5. Swelling of the copolymer gels (AI0-AI30) in NaCl salt solutions
of different strengths. [Color figure can be viewed in the online issue, which
is available at wileyonlinelibrary.com.]
Deswelling Kinetics of the Gel with pH Changes
Deswelling of the gel was studied by using its pH sensitive
behavior. The hydrogel samples were first allowed to swell to
reach equilibrium in pH 8 solutions and subsequently dropped
in medium of pH 4 to deswell. The nature of water retention
kinetics was more or less same for all the cases as shown in
Fig. 6 irrespective of compositions of the copolymer gels.
Drug Encapsulation and Release Study
We are choosing ascorbic acid as a representative of water
soluble molecule to characterize the effectivity of the delivery
vehicle. Ascorbic acid or vitamin C is a weak acid. The aqueous
solution of ascorbic acid is conductive of electricity and its con-
ductivity value is linearly related with its concentration.
During swelling of poly(AAm-IA) hydrogel in aqueous
ascorbic acid solution the polar acid molecule along with water
enters into the crosslinked cage like structure formed by the
FIG. 7. (a) Absorbtion of ascorbic acid by copolymer gels (AI5-AI30) with time and (b) Release kinetics of ascor-
bic acid by the copolymer gels (AI5-AI30). [Color figure can be viewed in the online issue, which is available at
wileyonlinelibrary.com.]
6 POLYMER ENGINEERING AND SCIENCE—2014
FIG. 6. Deswelling of the swelled copolymer gels (AI5-AI30) with time.
[Color figure can be viewed in the online issue, which is available at
wileyonlinelibrary.com.]
interchain H-bonding in copolymer gel structure and gets
trapped by electrostatic attraction of the polar ACOOH and
ACOO2 group of the itaconic acid unit. With increase of ita-
conic acid content in the polymer network, the polar environ-
ment in the network as well as possibility of formation of H-
bonded cage structure increases. This is evidenced by the
increase in ascorbic acid uptake by the gel with increase in ita-
conic acid content and gets maxima for sample AI10 (Fig. 7a).
Further increase of itaconic acid content, reduces the size of the
cage structure resulting lesser amount of ascorbic acid uptake.
This is again reflected in ascorbic acid release behavior. Rate
and extent of release is slowest in case of gel AI10, that is,
hydrogel with 10% itaconic acid (Fig. 7b).
Microscopic Study
Figure 8 shows the porous cross sectional structure of the gel
AI0, AI5, AI10, and AI20 in swollen condition. In Fig. 8a,
DOI 10.1002/pen
 FIG. 8. Optical microscopic pictures of the gel (a) AI0, (b) AI5, (c) AI10, and (d) AI20. [Color figure can be
viewed in the online issue, which is available at wileyonlinelibrary.com.]

FIG. 9. SEM image of hydrogels (a) AI5, (b) AI10, (c) AI20, and cry SEM images of hydrogels (d) AI5 and
(e) AI10. [Color figure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]

DOI 10.1002/pen POLYMER ENGINEERING AND SCIENCE—2014 7

 FIG. 10. XRD pictures of the samples (a) ascorbic acid, (b) pure hydrogel AI10, (c) hydrogel AI10 imbibed with
vitamin C, and (d) DSC thermogram of gel AI10.
some surface porosity is seen, but these pores are considerably
smaller at the same magnification (103). With the incorporation
of IA in the crosslinked network, the cellular structure becomes
more prominent and ordered. There seems an orientation and
elongation of voids at the surfacein case of gel AI10. Figure
10c indicating the cellular structure of AI10 shows that many of
the cells remain no longer nonintercommunicating and some-
times they reveal an intercommunicating type of cellular struc-
ture. Moreover, the large proportion of the cellular body in the
swelled condition appears to be tattered and sometimes the poly-
mers walls contain a large number of minute cells and thus ena-
bling it to absorb maximum amount of water.
8 POLYMER ENGINEERING AND SCIENCE—2014
Scanning Electron Microscope
Figure 9 shows the SEM pictures of the gel AI5, AI10, and
AI20. The SEM picture (Fig. 9d) of the gel AI5 (i.e., copolymer
gel with 5% IA) is almost a reflection of its microscopic picture
as given in Fig. 8b. The bulk of the surface of the particular
copolymer gel contains swollen blisters distributed almost
throughout the network. On increasing the proportion of IA in
the copolymer, the number of cells and the shape of the cells
also undergo a tremendous change. The blister sides appear to
be substituted by alarge number of holes and pit marks distrib-
uted throughout the surface in an irregular manner (Fig. 9b).
Thus, this gel appears to be capable of swelling to a much
DOI 10.1002/pen
larger extent than the previous one. In the SEM image of AI20,
we can find a blend of blisters and closed swelled holes distrib-
uted in a random manner (Fig. 9c). The sizes of both undergo a
decrease remarkably.
From the cryo SEM (Fig. 9d and e), the reticulum of the cell
structure, which consists of random combinations of cells of dif-
ferent sizes is being distinctly observed. Moreover, the gel with
15% of IA exhibits cells having greater depth than those of the
gel with 10% of IA.
X-Ray Diffraction
Ascorbic acid is a crystalline organic compound. When
bound to the copolymer, the crystalline structure will disappear
because ascorbic acid molecule gets entrapped into the hydro-
philic cage structure formed by the intermolecular H-bonding
between the amide group and the carboxylic acid group. This
has been confirmed by the wide angle X-ray diffraction
(WAXD). Figure 10 shows the WAXD spectrum of pure ascor-
bic acid, dried hydrogel sample and the dried hydrogel contain-
ing ascorbic acid. The sharp peaks in the spectrum of pure IA
indicate its crystalline structure. No peaks were visible in the
WAXD spectrum of the dried hydrogel sample containing ascor-
bic acid. This result suggests that the ascorbic acid is absorbed
by the hydrogel.
Differential Scanning Calorimetry
The poly AAm gel has glass transition temperature Tg in the
region 179–190 C [29]. As copolymerization is said to be a pro-
cess of internal plasticization, it leads to a drustic reduction in
Tg. This phenomenon has been observed with the gel discussed
in this work. The modification of poly AAm with itaconic acid
has reduced the Tg to about 118 C (Fig. 10c) due to the incorpo-
ration, which prove copolymer formation during the formation
of the gel.
Evidences on Copolymerization
(a) Itaconic acid is a monomer, which does not undergo homopoly-
merization [24]. It seems that the reactivity of the radical
formed from the monomer towards its own monomer is far less
than the reactivity with the other olefinic monomers. This leads
to the possibility of complete copolymer formation with remote
possibility of any homopolymer.
(b) The possibility of entrapment of monomeric itaconic acid with
the network of poly AAm can be considered negligible as ita-
conic acid is highly soluble in water and the complete removal
of the acid monomer has been ensured through repeated wash-
ing of the gel.
(c) The % swelling ability of the gel under study has been remark-
ably enhanced with reference to the neat poly AAm gel. This
great enhancement can only be explained by a suitable copoly-
mer formation.
(d) The poly AAm gel is neither pH sensitive nor temperature sensi-
tive. The copolymer gel under investigation is however strongly
pH sensitive as has been discussed in our present manuscript.
(e) The poly AAm gel has glass transition temperature Tg in the
region 179–190 C [29]. As copolymerization is said to be a pro-
cess of internal plasticization it leads to a drustic reduction in
Tg. This phenomenon has been observed with the gel discussed
DOI 10.1002/pen
in this work. The modification of poly AAm with itaconic acid
has reduced the Tg to about 118 C due to the incorporation.
These substantially prove copolymer formation.
CONCLUSION
pH responsive and temperature sensitive poly(AAm-IA)
hydrogels were prepared successfully by free radical polymer-
ization using APS as initiator and MBA as crosslinker. Swel-
ling of the gel increased with increasing itaconic acid content
in the polymer network upto 10 mol%. Swelling of the
hydrogel was strongly pH dependent as it contains an anionic
monomer. Swelling was increased with pH up to pH 7 and
then it falls. Therefore, the gel can be used as controlled
release vehicle and pH responsive switches by using its smart
properties.
ABBREVIATIONS
AAm Acrylamide
IA Itaconic acid
MBA N,N0 -Methylenebisacrylamide
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