Synthesis and Investigation of Swelling Behavior of New Agar Based Superabsorbent Hydrogel As A Candidate For Agrochemical Delivery - Springer

9/1/2015
Synthesis and investigation of swelling behavior of new agar based superabsorbent hydrogel as a candidate for agrochemical delivery - Springer
Journal of Polymer Research
Springer Science+Business Media B.V. 2009

10.1007/s10965-009-9270-2
Original Paper
Synthesis and investigation of swelling

behavior of new agar based superabsorbent
hydrogel as a candidate for agrochemical
delivery
Ali Pourjavadi 1 , Bahareh Farhadpour 1 and Farzad Seidi 1
(1) Polymer Research Laboratory, Department of Chemistry, Sharif University of Technology, P.O. Box 113659516, Tehran, Iran
Ali Pourjavadi
Email: purjavad@sharif.edu
Received: 28 October 2008
Accepted: 27 January 2009
Published online: 25 February 2009
Abstract
In this investigation a new type of superabsorbent hydrogel based on agar was prepared, and
the effect of the feed ratio of some components (acrylic acid, MBA, APS and agar) on the
swelling capacity of the hydrogel was systematically studied. Maximum water absorbency of
the optimized final product was found to be 1,100g/g in distilled water. The structure of the
hydrogel was characterized by FT-IR method and morphology of the samples was examined
by scanning electron microscopy (SEM). Swelling properties of optimized hydrogel sample in
different swelling mediums were investigated. The optimum hydrogel were also loaded with
potassium nitrate and its potential for controlled release of potassium was investigated by
measuring conductivity in various conditions.
Keywords Agar Acrylic acid Hydrogel Swelling behavior Potassium nitrate
http://link.springer.com/article/10.1007/s10965-009-9270-2/fulltext.html
1/25
9/1/2015
Introduction
Polymer networks consist of long macromolecular chains cross-linked with each other by
chemical or physical bonding. Polymer networks swollen in a liquid are called polymer gels.
Hydrogels are polymer gels, which swell extensively in water. The most common hydrogels are
polyelectrolyte gels: their high degree of swelling in water is due to the exerting osmotic
pressure of counter ions. Such gels can acquire up to several hundredweight parts of water per
one part of a dry polymer [1]. Considerable attention has been devoted to the preparation and
application of responsive hydrogels for medical and pharmaceutical fields particularly as
stimuli-sensitive drug delivery [24].
Stimuli-responsive hydrogels undergo a substantial volume change when an environmental
factor such as temperature, pH, or ionic strength is altered. The volume phase transition is
caused by a change in the hydrogels water content. Hydrogels have attracted attention
because of both potential and demonstrated utility of this behavior in a variety of applications
ranging from flow controllers in microfluidic devices to sorbents [57]. Conventional
application of agrochemicals results in ground water contamination. Thus, we need a more
controlled application of agrochemicals to reduce amounts of active ingredients without
diminishing efficiency. The replacement of conventional agrochemical formulations by
controlled release systems not only helps to avoid treatment with excess amounts of active
substances, but also offers the most suitable technical solution in special fields of application.
On the other hand, hydrogels of natural polymers, especially polysaccharides, have recently
found widespread applications because of their unique advantages. Polysaccharides are, in
general, non-toxic, biocompatible, biodegradable and abundant [8, 9].
Hydrogels can be prepared by simultaneous copolymerization and crosslinking of one or more
monofunctional and one multifunctional monomer or by crosslinking of a homopolymer or
copolymer in solution [10, 11]. Hydrogel properties depend strongly on the degree of
crosslinking, the chemical composition of the polymer chains, and the interactions of
network and surrounding liquid.
Agar (Scheme 1) is an alternating copolymer of 3-linked -D-galactopyranose and 4-linked
3,6-anhydro--L-galactopyranose residues. Agar is the most hydrophobic polysaccharide
with the strongest tendency to gel formation that melts at about 40C. Agar forms hydrogels
via intermolecular aggregations prompted by thermal changes [12]. Due to its
biocompatibility, it has generally been used as a cell immobilization matrix, drug delivery
vehicle, or dental impression material [13, 14].
2/25
9/1/2015
Scheme 1
Proposed mechanistic pathway for synthesis of the agar-g-poly (AA-co-AMPS) hydrogel
The purpose of this paper is to synthesize agar-g-poly (acrylic acid-co-2-acrylamido-2methylpropanesulfonic acid) hydrogel. The effect of reaction variables affecting on water
absorbency of the composite and swelling behavior in various solvents, salt and pH solutions
was investigated. The absorbency under load (AUL) of optimized hydrogel was determined by
using an AUL tester [15] in various applied pressures. Dynamic swelling kinetics of the
hydrogel was also determined. Finally, we investigated the release of KNO3 from the optimum
hydrogel as models of ionic fertilizer.
Materials and methods

Materials
Agar was obtained from QUELAB/UK. Acrylic acid (AA, from Merck) distilled before use. N,
N'-methylene bisacrylamide (MBA, from Merck), ammonium persulfate (APS, from Merck),
3/25
9/1/2015
2-acrylamido-2-methylpropanesulfonic acid (AMPS, from Fluka), were of analytical grade

and used without further purification. The solvents (all from Merck) were used as received. All
other chemicals were also analytical grades. Double distilled water was used for the hydrogel
preparation and swelling measurements.
Instrumental analysis
The infrared spectra of hydrogel were recorded by ABB Bomem MB-100 FTIR
spectrophotometer (Canada). The dried sample was ground with dried KBr powder and
compressed into a disc, and then was subjected to analysis. In order to prevent the
morphology of hydrogels, the dried samples were coated with gold under reduced pressure and
their scanning electron micrographs were obtained using a Philips (XL30) scanning electron
microscope.
Hydrogel synthesis
In a 200 mL flask, fitted with a mechanical stirrer (Heidolph RZR 2021, 200 rpm), is placed
40 mL of water and variable amounts (0.51.5 g) of agar and the mixture is stirred at 100C
until a clear solution is obtained. Then the reaction flask is cooled until the temperature of
the mixture reaches to 85C. The mixture is heated in a water bath preset at 85C. Then,
appropriate amounts of 2-acrylamido-2-methylpropanesulfonic acid (AMPS, 0.5 g),
partially neutralized acrylic acid (AA, 47 g), and N, N'-methylene bisacrylamide (MBA,
0.030.09 g) in 10 mL H2O were added. After 5 min, ammonium persulfate (APS, 0.03
0.09 g) in 5 mL H2O was added. After 1015 min obtained gel was cooled at room
temperature and poured to excess non solvent ethanol (200 mL) and remained for 3 h to
dewater. Then, ethanol was decanted and the product cut into small pieces. Again, 200 mL
fresh ethanol was added and the composite remained for 48 h. Finally, the filtered gel was
dried in oven at 50C for 24 h. After grinding, the powdered composite hydrogel was stored
away from moisture, heat and light.
Absorbency or swelling measurement

Absorbency of superabsorbent polymers are measured by the free swelling method and
expressed as a water retention value (WRV) calculated in grams of water per grams of dry
polymer. Thus, an accurately weighed quantity of the hydrogel (0.10 g) was immersed in
250 mL of distilled water and allowed to soak for 1 hat room temperature. The sample
particle sizes were 4060 meshes (250400m). The swollen hydrogel was then separated
from unabsorbed water by a tea bag (i.e. a 100 mesh nylon screen). The equilibrium swelling
4/25
9/1/2015
(ES) was calculated according to following equation:
ES(g/g ) =
W2 W1
W1
(1)
Where, W 2 and W 1 are the weights of swollen hydrogel and dry hydrogel in grams,
respectively.
Swelling in various salt solutions

Hydrogel absorbency was evaluated in 0.15 M solutions of NaCl, CaCl2, and AlCl3 according
to the method described above. Moreover, water absorbency of the hydrogel was measured in
different concentration of NaCl salt solutions.
Swelling at various values of pH

Individual solutions with acidic and basic values of pH were prepared by dilution of NaOH
(pH=14.0) and HCl (pH=0.0) solutions to achieve pH6.0 and pH6.0, respectively.
Then, absorbency was measured according to Eq. (1).
pH sensitivity
pH-responsiveness of the hydrogel was investigated in terms of swelling and deswelling of the
final product at two basic (pH 8.0) and acidic (pH 2.0) solutions, respectively. Swelling
capacity of the hydrogels at each pH was measured according to Eq. (1) at consecutive time
intervals.
Swelling kinetics
Hydrogel sample (4060 mesh, 0.10 g) was poured into a weighed tea bag and immersed in
250 mL distilled water. At consecutive time intervals, the water absorbency of the sample was
measured.
Absorbency under load (AUL)

A macro-porous sintered glass filter plate (porosity # 0, d=80 mm, h=7 mm) was placed in
a Petri dish (d=118 mm, h=12 mm), and a weighed, dried hydrogel (0.40 g) was uniformly
placed on the surface of a polyester gauze located on the sintered glass. A cylindrical solid
weight (Teflon, d=60 mm, variable height) which could slip freely in a glass cylinder (d=
60 mm, h=50 mm) was used to apply the desired load (applied pressure 0.3 and 0.6 psi
5/25
9/1/2015
(2,068 and 4,137 Pa)) to the dry hydrogel sample particles. Then, 0.9% NaCl solution was
added so that the liquid level was equal to the height of the sintered glass filter. Whole of the
set was covered to prevent surface evaporation and probable change in the saline
concentration. At consecutive time intervals, the water absorbency of the hydrogel was
measured. After 2 h, the swollen particles were weighed again, and AUL was calculated
according to Eq. (1).
Loading of KNO3
The dry gel was put into a solution of KNO3 and leave to swell for 2 h. The swollen gels were
dried at 50C. The % loading was calculated by the following equation:
%Loading = (m1 m0 /m0 ) 100
(2)
where m 1 and m 0 are the weights of loaded gel and dry gel, respectively.
Determination of KNO3 release

In a typical release experiment, the loaded gel with known weight (0.1 g, mesh 4060) was
placed in measured volume (200 mL) of distilled water (release medium) and was stirred
mildly. The released amount of KNO3 at different time intervals (Mt) was determined by
measuring the conductivity of the release medium using a conductivity meter (Martini
Instruments, Mi 170, EC/TDS/NaCl/Temp Meter). This was related to the amount of KNO3
using a calibration plot.
Result and discussion

Synthesis and spectral characterization
The hydrogel was synthesized by simultaneous graft copolymerization of AA and AMPS on
to agar by using of APS as an initiator and MBA as a crosslinker. The mechanism for
crosslinking graft copolymerization shown in Scheme 1. The persulfate initiator is decomposed
under heating to generate sulfate anionradical. The radical abstracts hydrogen from the
hydroxyl group of the polysaccharide substrate to form alkoxy radicals on the substrate. These
macroradicals initiate AA/AMPS grafting onto agar backbone led to a graft copolymer. Since
a crosslinking agent, e.g. MBA, is presented in the system, the copolymer comprises a
crosslinked structure.
6/25
9/1/2015
FT-IR spectroscopy was used to confirm the chemical structure of hydrogel. The FT-IR
spectra of agar, poly (AA-co-AMPS) and synthesized hydrogel were shown in Fig. 1ac. The
broad band at 3,2003,500 cm1 is due to stretching of these hydroxyl groups. FTIR
spectrum of the hydrogel [Fig. 1(c)] represents several new peaks. The bands observed at 512,
630 and 1,400 cm1 can be attributed to sulfonate group of AMPS, bands at 1,545 and
1,710 cm1 is due to stretching of carboxylate and carboxylic acid groups, respectively. The
small peak at ~930 cm1 is due to the 3,6-anhydro--L-galactopyranose unites. The band
observed at ~890 cm1 is due to the unsubstituted D-galactopyranose unites. Finally the
peak observed at ~1,646 cm1 that is related to of agar is the characteristic absorption band of
polysaccharides.
7/25
9/1/2015
Fig. 1
FTIR spectra of a agar, b poly (AA-co-AMPS), c synthesized hydrogel, d loaded hydrogel and e unloaded
hydrogel
Also the IR transmittance spectra of unloaded (a) and loaded (b) hydrogels are presented in
Fig. 1de. The spectra confirm the presence of KNO3 as evident from vibrational frequency of
nitrate ion at 1,384 cm1.
SEM images of hydrogel are shown in Fig. 2. It is obvious from this Figure; the hydrogel has a
porous structure. It is supposed that these pores are the regions of water permeation and
interaction sites of external stimuli with the hydrophilic groups of the graft copolymers.
Fig. 2
SEM photographs of the optimized superabsorbent hydrogel (Agar 1 g, NU 40%, AA 1.26 mol/L, AMPS
0.044 mol/L, APS 0.0024 mol/L, and MBA 0.006 mol/L, 85C). a 10,000 and b 20,000
Optimization of the grafting conditions

Different variables affect the ultimate swelling capacity. In this research, we selected some of
these variables (i.e. concentration of AA, APS, and MBA, and polysaccharide). These
parameters were systematically varied to achieve maximum water absorbency.
Effect of crosslinker concentration

The effect of the extent of crosslinking on water absorbency of agar-g-poly (AA-co-AMPS)
hydrogel is shown in Fig. 3. The maximum absorbency (820g/g) is achieved at
8/25
9/1/2015
0.0060 mol/L of MBA. At the lower than this amount, the formation of very loosely
crosslinked networks, resulting in highly swollen hydrogels with very low gel strength. Higher
crosslinker concentration produces more crosslinked points in polymeric chains and increases
the extent of crosslinking of the polymer network, which results in less swelling when it is
brought into contact with the solvent.
Fig. 3
Dependency of swelling of the hydrogel vs. the crosslinker concentration employed in the polymerization
process. Reaction conditions: Agar 1 g, NU 40%, AA 1.26 mol/L, AMPS 0.044 mol/L, and APS
0.0040 mol/L, 85C
Effect of APS concentration

The relationship between the initiator concentration and water absorbency were studied by
varying the initiator concentration from 0.0012 to 0.0096 mol/L (Fig. 4). Figure 4 shows
that the absorbency is increased with increasing the APS concentration from 0.0012 up to
0.0024 mol/L and then, it is decreased considerably with a further increase in the amount of
initiator. The maximum absorbency (1,100g/g) is achieved at concentration of 2.4 mmol/L
of the initiator. The initial increase in water absorbency may be ascribed to the increase in the
active sites on the backbone of the agar, arising from the attack of sulfate anion-radical.
Decrease in swelling is originated from an increase in terminating step reaction via bimolecular
collision which, in turn, causes to enhance crosslinking density. This possible phenomenon is
referred to as self-crosslinking by Chen and Zhao [16]. In addition, the free radical
degradation of polysaccharide backbones by sulfate radicalanions is an additional reason for
swelling-loss at higher APS concentration. A similar observation is recently reported in the
case of polysaccharides such as chitosan [17] and carrageenan [18].
9/25
9/1/2015
Fig. 4
Dependency of swelling of the hydrogel vs. the initiator concentration employed in the polymerization
process. Reaction conditions: Agar 1 g, NU 40%, AA 1.26 mol/L, AMPS 0.044 mol/L, and MBA
0.006 mol/L, 85 C
Effect of AA concentration
The effect of AA concentration on the swelling capacity of the hydrogel was studied by
varying the AA concentration from 0.76 to 2.02 mol/L (Fig. 5). Maximum swelling
(1,100g/g) was obtained at 1.26 mol/L of AA concentration. Enhanced acrylic acid
concentration increases the diffusion of AA molecules into the agar backbone that
consequently causes an increase in water absorbency. In addition, higher AA content
enhanced the hydrophilicity of the hydrogel that it caused a stronger affinity for more
absorption of water. The swelling decrease after the maximum may be attributed to (a)
preferential homopolymerization over graft copolymerization, (b) increase in viscosity of the
medium which hinders the movement of free radicals and monomer molecules, (c) the
enhanced chance of chain transfer to monomer molecules and (d) non-neutralized acid
groups of grafted and non-grafted polyacrylic acid chains.
10/25
9/1/2015
Fig. 5
Dependency of swelling of the hydrogel vs. the monomer (AA) concentration employed in the
polymerization process. Reaction conditions: Agar 1 g, NU 40%, APS 0.0024 mol/L, AMPS 0.044 mol/L,
and MBA 0.006 mol/L, 85C
Effect of agar weight on swelling

The effect of agar weight on the swelling capacity of the hydrogel was studied by varying the
agar weight from 0.5 to 1.5 g (Fig. 6). Figure 6 shows that the water absorbency of the
hydrogel was increased by increasing agar content up to 1 g then decreased with any further
increase. As the agar weight was increased in the mixture feed (0.5 up to 1 g), the active sites
can react easily with monomers. Increasing agar content more than 1 g, results in a high
viscosity of the medium and a decrease in the diffusion of monomers to active sites to
produce crosslinked hydrogels.
Fig. 6
11/25
9/1/2015
Dependency of swelling of the hydroegl vs. agar weight employed in the polymerization process. Reaction
conditions: NU 40%, AA 1.26 mol/L, APS 0.0024 mol/L, AMPS 0.044 mol/L, and MBA 0.006 mol/L, 85C
The environmental sensitivity

Salt effect
The swelling degree of the hydrogel in saline solutions was significantly decreased as compared
with the values measured in deionized water. This result ,commonly observed in the swelling
of ionic hydrogels [19], is often attributed to a charge screening effect of the additional
cations causing a non-perfect anionanion electrostatic repulsion, led to a decreased osmotic
pressure (ionic pressure) difference between the hydrogel network and the external solution.
Figure 7 showed the change of the swelling ratio as a function of NaCl concentration. It
showed that initially the equilibrium swelling ratio dropped down quickly as NaCl added, then
flattened out after NaCl concentration exceeded 0.15 mol/L.
Fig. 7
Swelling capacity variation of the optimized hydrogel in saline solutions with various concentrations
The effect of cation type (cations with different charge) on swelling behavior is shown in
Fig. 8. In the case of salt solutions with multivalent cations, ionic crosslinking causes an
appreciable decrease in swelling capacity. Therefore, the absorbency for the hydrogel in the
studied salt solutions is in the order of monovalent>divalent>trivalent cations. Similar results
have been reported in similar previous studies [20, 21].
12/25
9/1/2015
Fig. 8
Swelling capacity of the optimized hydrogel in different chloride salt solutions (0.15 M)
Solvent-induced phase transition

We examined the swelling changes of the optimized hydrogel in different water-solvent
systems. The swelling-loss in these mixtures related to decrease of slovatation of ionic groups
in water-solvent systems. Sodium carboxylate and solfonate groups are easily solvated by
water molecules. However, it is widely restricted in these organic solvent-water systems
because the organic solvent molecules (ethanol and isopropanol) cannot solvate these ionic
groups. As a consequence, the swelling capacities are considerably decreased.
Figure 9 shows that in a fixed ratio of solventwater (e.g., a 30:70 w/w solvent-water
mixture), the swelling is decreased in order of ethanol<2-propanol. This can be explained by
the Hildebrand eq. (3) [22]:
Hm/(V 1 2 ) = ( 1 2 )
(3)
where H m is the enthalpy change on mixing of a polymer and a solvent, V is the whole
volume of the solution, 1 and 2 are the volume fractions for the solvent and the polymer,
1 and 2 are the solubility parameters for the solvent and the polymer, respectively.
13/25
9/1/2015
Fig. 9
Sensitivity of the optimized hydrogel swelled in different solventwater media with varied composition
It can be concluded from this equation that to dissolve a polymer in a solvent, the values
must be close to each other. As swelling absorbency of the superabsorbent hydrogels in water
is maximum, the value of water (23.4 (cal/cm3)1/2) can be regarded as the solubility
parameter of it. The solubility parameter for solvent-water mixtures ( mix ) can be calculated
using following eq. (4)
mix = 1 1 + 2 2
(4)
where 1 and 2 are the volume fraction, and 1 and 2 are the solubility parameters of the
two solvents.
It can be seen from Table 1 that with increasing of mix values toward 23.4, the hydrogel can
be highly swollen as in pure water. In other words, the swelling capacity of the hydrogel in the
solventwater mixture will be close to that in pure water if mix is close to water . A similar
observation is recently reported by Zohuriaan-Mehr and co-workers [23].
14/25
9/1/2015
Table 1
Solubility parameters for solvents [22]. Symbols and mix [(cal/cm3)1/2] are the solubility parameters for
the solvent and the solventwater mixture, respectively
Solvent
(or mix)a
Swelling capacity (g/g)
Acetone
9.9
2-propanol
11.5
Ethanol
12.7
Water
23.4
1,100
Ethanol- water (30:70)
20.19
571
2-propanol- water (30:70)
19.83
495
Equilibrium swelling at various pH solutions

Ionic superabsorbent hydrogels exhibit swelling changes at a wide range of pH values. Since the
swelling capacity of all ionic hydrogels is appreciably decreased by addition of counter ions
to the swelling medium, no buffer solutions were used. Therefore, stock NaOH (pH14.0) and
HCl (0.0) solutions were diluted with distilled water to reach desired basic and acidic pH
values, respectively.
Figure 10 shows the effect of pH on the swelling ratio of hydrogel. The results clearly indicate
that the hydrogel exhibits extremely low degree of swelling in the media with low pH (pH<
2), whereas the gel demonstrates extensive swelling in the swelling media of pH~6. The low
swelling in the media with low pH may be attributed to the fact that the COOH and SO3H groups present along the macromolecular chains in the matrix remain almost unionized
(since pKa of the acrylic acid is 5.4), thus resulting into almost nil osmotic swelling pressure as
there are no mobile/counter ions present inside the gel matrix [17]. In addition, there occur
H-bonding interactions among the carboxylic groups within the matrix, thus providing a
compact H-bonded structure to the hydrogel [18], which ultimately restricts the movements
of polymeric segments and highly discourage the solvent entrance. However, when the gel is
put in the medium of pH6, the ionization of COOH and -SO3H groups not only increases
the osmotic swelling pressure but it also results in relaxation of polymeric chains due to
15/25
9/1/2015
repulsion among similarly charged COO- and -SO 3 - groups along the macromolecular
chains. This causes extensive swelling of the hydrogel as indicated by higher water uptake of
value of the gel. The swelling-loss in the highly basic solutions may be attributed to the
charge screening effect of excess Na+ in the swelling media, which, in turn, shields the
carboxylate and sulfonate anions and prevents effective anion-anion repulsion.
Fig. 10
Effect of pH of solutions on swelling capacity of the hydrogel
pH-responsiveness behavior of the hydrogel

The pH-dependent swelling reversibility of the hydrogels was examined by immersing the
hydrogel in solutions with pH2 and pH8 and the swelling ratio was measured at relevant
intervals (Fig. 11). Since the pH of the working solutions may be changed by protonation
deprotonation process of superabsorbent hydrogel, a fresh solution was used in each cycle. At
pH8, the hydrogel swells up to 1,080g/g due to anionanion repulsive electrostatic forces,
while at pH2, it shrinks within a few minutes due to protonation of carboxylate groups. As
illustrated in Fig. 11 the hydrogel sample exhibited an excellent reversibility. The swelling rate
and swelling capacity was almost no losing even after many times of oscillation. Such on-off
switching behavior as reversible swelling and deswelling has been reported for other ionic
hydrogels [2427].
16/25
9/1/2015
Fig. 11
Onoff switching behavior as reversible pulsatile swelling (pH8) and deswelling (pH2) of the optimized
hydrogel
Swelling kinetics
Figure 12(a) represented the dynamic swelling behavior of optimized hydrogel sample with
certain particle sizes (4060 mesh) in water. The samples swelled rapidly and reached
equilibrium within about 25 min. Power law behaviors were obvious from Fig. 12(a). The
initial swelling rate can be calculated using Voigt-based equation (Eq. (5)) [28].
/
S t = S e (1 et )
(5)
where S t (g/g) is swelling at time t, S e (g/g) is equilibrium swelling; t(min) is time for
swelling S t , and (min) stand for the "rate parameter". To find the rate parameter for
superabsorbent sample, Ln[1-S t /S e ] versus time (t) was plotted [Fig. 12(b)]. The slope of
the line passing the point zero and the point of 60% fractional swelling was determined (slope
=l/, gives the rate parameter). Therefore, the rate parameter for the superabsorbent
composite was found to be 2.1 min in distilled water.
17/25
9/1/2015
Fig. 12
Representative swelling kinetics of the optimized hydrogel with certain particle sizes (4060 mesh) (a), and
the rate parameter (s) calculating graph (b)
Absorbency under load (AUL)

The AUL is an effective factor to investigate the swollen gel strength in the practical
application of superabsorbents, which is usually given in the patent literature and technical
data sheets offered by industrial hydrogel manufacturers. The AUL of hydrogel samples is
determined by using an AUL tester according to a procedure reported earlier [29]. Figure 13
represented the AUL of the hydrogel in saline solution (NaCl 0.9%) at r.t. It is obvious that
the minimum time needed for the highest AUL in the case of each load was determined to be
20 min. After this time, the swelling values under load were approximately unchanged.
Fig. 13
18/25
9/1/2015
Time dependence of the AUL values for optimized sample
Release study of KNO3

The release of an active agent from swellable polymeric matrix is an important aspect of
hydrogel. The release of solute from loaded hydrogel involves the sorption of water into the
matrix and simultaneous release of solute via diffusion. The concentration difference of solute
between medium and hydrogels drives the solute out of the loaded hydrogel, but the special
space arrangements of function groups constructed by hydrogen bonds hinder solute to
migrate out. The release kinetics of a loaded hydrogel is closely related to its water sorption
kinetics, that is, initially; the rate of release sharply increases and then begins to level off. As a
result a highly swelling hydrogel should release a greater amount of solute entrapped within
the gel. (The results for all of the conductivities is fitted to 1 gr of loaded or unloaded
hydrogel)
Influence of loading on the release

One of the primary factor in the use of hydrogels as the carrier of active compounds is the
effect of percent loading on the rate of solute release. For this purpose, the optimum hydrogel
sample was equilibrated with KNO3 solution of varying concentrations (0.1, 0.5 and 1 M) for
2 h. The dry loaded hydrogel was mildly stirred in release medium and the progress of the
release process was monitored conductometrically. Also the conductivity of swelling medium
for 0.1 g of unloaded optimum hydrogel was determined. At consective time intervals, the
conductivity of solution was measured and these values were detracted from the conductivity
values of the release medium of loaded hydrogel at each time; After 2 h the increment in
conductivity of this solution was only 4s (equals to 1.44 mg KNO3). The results are
represented in Fig. 14 and Table 2. The release results indicate that the amounts of KNO3
released increases with increasing percent loading of the hydrogel. The results are as expected
because larger the initial load, the faster is the movement of the solvent front penetrating the
surface of the loaded hydrogel [30]. A larger loading of the hydrogel may also facilitate the
relaxation of macromolecular chains.
19/25
9/1/2015
Fig. 14
Influence of loading on the release rate of KNO3
Table 2
Loading condition, loading percent and release percent after 24 h
Entry
Morality of KNO3 in loading medium
% load
% release after 24 h
0.1 M
44.6%
78%
0.5 M
83.7%
67%
1M
132.6%
47%
Influence of pH on the release

Since pH of the swelling medium is a key factor in the application of hydrogels in agriculture
field, the investigation of this parameter is of prime significance. For this purpose, the
optimum hydrogel sample was equilibrated with 1 M KNO3 solution for 2 h. Then the
amount of released KNO3 in phosphate buffer solutions with various pH (concentration of
phosphate buffer was 0.05 mM) was determined by measuring the conductivity of the release
medium. The results are shown in Fig. 15. There is a burst release initially for the first hour
both in acidic and basic medium, followed by an almost constant release of KNO3 from the
hydrogel for the studied period of time. The initial burst release may be attributed to the
20/25
9/1/2015
release of potassium nitrates loaded near the surfaces of the hydrogel. This figure clearly
indicates that the release in highly basic or acidic solutions is low but in pH=5.7 maximum of
released is observed. This can be explained by this fact that the active agent in the hydrogel
could be released as a result of the hydrogel volume change. According to the Fig. 10, the
maximum swelling of hydrogel is in pH~6 and according to the Fig. 15, maximum release is
in pH=5.7. This result indicates that the higher swelling ratios of the hydrogel create larger
surface areas to diffuse the KNO3.
Fig. 15
Effect of pH on KNO3 release
Conclusion
In the present study, we prepared a novel superabsorbent hydrogel by simultaneous graft
copolymerization of AA and AMPS onto agar. Crosslinking graft copolymerization of AA
and AMPS onto agar was performed in an aqueous medium using a persulfate initiator and a
bifunctional hydrophilic crosslinker. Variations in the reaction parameters affecting the
ultimate swelling capacity of the final product optimized the synthesis of superabsorbent
hydrogel. The maximum water absorbency (1,100g/g) was achieved under the optimum
conditions, which were found to be AA 1.26 mol/L, AMPS 0.044 mol/L, MBA
0.0060 mol/L, APS 0.0024 mol/L, neutralization percent 40%,agar weight 0.5 g, and at a
reaction temperature of 85C. Swelling measurement of the optimized hydrogel in different
salt solutions showed appreciable swelling capacity in comparison with our previous works.
Moreover, the synthesized hydrogel exhibited high sensitivity to pH. Furthermore, the
absorbency under load (AUL) of optimized hydrogel was investigated at various applied
21/25
9/1/2015
pressures. Dynamic swelling kinetics of the hydrogel was also determined. Therefore, this
hydrogel may be considered as an excellent candidate for different applications in the future.
Finally, the dry hydrogel loaded with potassium nitrate swells in aqueous medium releasing
the salt entrapped within the matrix. The release rate was related to pH and KNO3 percent
loading of hydrogels. Therefore, this hydrogel may be considered as a candidate for fertilizer
delivery in agriculture.
We express our appreciation to Hamid Salimi (Ph.D student of Sharif University) for his
patient and unflagging assistance.
References
1.
Osada Y, Khokhlov AR (2005) Polymer Gels and Networks. Marcel Dekker, Inc.; p. iii
iv
2.
Ruel-Gariepy E, Leclair G, Hildgen P, Gupta A, Leroux JC (2002) J Contro Rel 82:373
383. doi:10.
1016/
S0168-3659(02)00146-3
CrossRef
3.
Ryu JM, Chung SI, Lee MH, Kim CK (1999) J Control Release 59:163172. doi:10.
1016/
S0168-3659(98)00189-8
CrossRef
4.
Joshi R, Arora V, Desjardins JP, Robinson D, Himmelstein KJ, Iversen PL (1998) Pharm
Res 15:11891195. doi:10.

1023/
A:
1011979505697
CrossRef
5.
Bromberg L, Temchenko M, Alakhov V, Hatton TA (2005) Langmuir 21:15901598.
doi:10.
1021/
la047893j
CrossRef
6.
Beebe DJ, Moore JS, Bauer JM, Yu Q, Liu RH, Devadoss C, Jo BH (2000) Nature
404:588590. doi:10.
1038/
35007047
CrossRef
7.
Peppas NA, Huang Y, Torres-Lugo M, Ward JH, Zhang J (2000) Annu Rev Biomed Eng
2:929. doi:10.
1146/
annurev.
bioeng.
2.
1.
9
22/25
9/1/2015
CrossRef
8.
Cascone MG, Barbani N, Cristallini C, Giusti P, Lazzeri L (2001) Biomater Sci Polym
12:267281. doi:10.
1163/
1568562017501808
07
CrossRef
9.
Chen J, Jo S, Park K (1995) Carbohydr Polym 28:6976. doi:10.

1016/
0144-
8617(95)00080-1
CrossRef
10.
Andrade JD (1976) Hydrogels for medical and related applications. ACS Symposium
Series, No. 31. American Chemical Society, pp. 137

11.
Peppas NA, Mikos AG (1986) In: Peppas NA (ed) Hydrogels in medicine and pharmacy,
vol. 1. CRC, oca Raton (FL), pp 223

12.
Dumitriu S (2005) Polysaccharides: Structural Diversity and Functional Versatility.
Marcel Dekker, Inc., pp. 229, 280 and 848.

13.
Uludag H, De Vos P, Tresco PA (2000) Adv Drug Deliv Rev 42:2964. doi:10.
1016/
S0169-409X(00)00053-3
CrossRef
14.
Wang N, Wu XS (1998) Int J Pharm 166:114. doi:10.

1016/
S0378-5173(97)00339-6
CrossRef
15.
Ramazani-Harandi MJ, Zohuriaan-Mehr MJ, Yousefi AA, Ershad-Langroudi A, Kabiri K
(2006) Polym Test 25:470474. doi:10.

1016/
j.
polymertesting.
2006.
01.
011
CrossRef
16.
Chen J, Zhao Y (2000) J Appl Polym Sci 75:808814. doi:10.

1002/
(SICI)1097-
4628(20000207)75:
6<808:
:
AID-APP10>3.
0.
CO;2-3
CrossRef
17.
Hsu SC, Don TM, Chiu WY (2002) Polym Degrad Stabil 75:7383. doi:10.
1016/
S0141-
3910(01)00205-1
CrossRef
18.
Hosseinzadeh H, Pourjavadi A, Mahdavinia GR, Zohuriaan-Mehr MJ (2005) J Bioact
Compat Polym 20:475490. doi:10.

1177/
0883911505055164
23/25
9/1/2015
CrossRef
19.
20.
Flory PJ (1953) Principles of polymer chemistry. Cornell University Press, Ithaca, NY

Pourjavadi A, Farhadpour B, Seidi F (2008) Starch/Strke 60:457466
CrossRef
21.
Pourjavadi A, Barzegar S, Zeidabadi F (2007) React Funct Polym 67:644654. doi:10.
1016/
j.
reactfunctpolym.
2007.
04.
007
CrossRef
22.
Grulke EA (1992) In: Brandrup J, Immergut EH, Grulke EA (eds) Polymer Handbook,
4th edn. Wiley, New York, pp VII/675VII/697

23.
Zohuriaan-Mehr MJ, Motazedi Z, Kabiri K, Ershad-Langroudi A, Allahdadi I (2006) J
Appl Polym Sci 102:56675674. doi:10.

1002/
app.
25033
CrossRef
24.
Lowman AM, Peppas NA (1999) In: Mathiowitz E (ed) Encyclopedia of controlled drug
delivery. Wiley & Sons, New York, p 139

25.
Mahdavinia GR, Pourjavadi A, Zohuriaan-Mehr MJ (2004) Polym Adv Technol
15:173180. doi:10.
1002/
pat.
408
CrossRef
26.
Gan LH, Roshan DG, Gan YY, Tam KC (2001) Eur Polym J 37:14731478. doi:10.
1016/
S0014-3057(00)00250-0
CrossRef
27.
Richter A, Bund A, Keller M, Arndt K (2004) Sens Actuators B Chem 99:579585.
doi:10.
1016/
j.
snb.
2004.
01.
011
CrossRef
28.
Omidian H, Hashemi SA, Sammes PG, Meldrum I (1998) olymer (Guildf 39:6697
6704. doi:10.
1016/
S0032-3861(98)00095-0
CrossRef
29.
Pourjavadi A, Seidi F, Salimi H, Soleyman R (2008) J Appl Polym Sci 108:32813290.
doi:10.
1002/
app.
27998
CrossRef
24/25
9/1/2015
30.
Kim SW, Bae YH, Okano T (1992) Pharm Res 9:283290. doi:10.
1023/
A:
1015887213431
CrossRef
Over 8.5 million scientific documents at your fingertips
Springer International Publishing AG, Part of Springer Science+Business Media
25/25

Synthesis and Investigation of Swelling Behavior of New Agar Based Superabsorbent Hydrogel As A Candidate For Agrochemical Delivery - Springer

Загружено:

Сведения о документе

Оригинальное название

Авторское право

Доступные форматы

Поделиться этим документом

Поделиться или встроить документ

Параметры публикации

Этот документ был вам полезен?

Это неприемлемый материал?

Авторское право:

Доступные форматы

Synthesis and Investigation of Swelling Behavior of New Agar Based Superabsorbent Hydrogel As A Candidate For Agrochemical Delivery - Springer

Загружено:

Авторское право:

Доступные форматы

9/1/2015

Journal of Polymer Research

Springer Science+Business Media B.V. 2009

Synthesis and investigation of swelling

Materials and methods

2-acrylamido-2-methylpropanesulfonic acid (AMPS, from Fluka), were of analytical grade

Absorbency or swelling measurement

(ES) was calculated according to following equation:

Swelling in various salt solutions

Swelling at various values of pH

Absorbency under load (AUL)

%Loading = (m1 m0 /m0 ) 100

Determination of KNO3 release

Result and discussion

Optimization of the grafting conditions

Effect of crosslinker concentration

Effect of APS concentration

Effect of agar weight on swelling

The environmental sensitivity

Solvent-induced phase transition

Swelling capacity (g/g)

Ethanol- water (30:70)

2-propanol- water (30:70)

Equilibrium swelling at various pH solutions

pH-responsiveness behavior of the hydrogel

Absorbency under load (AUL)

Time dependence of the AUL values for optimized sample

Release study of KNO3

Influence of loading on the release

Morality of KNO3 in loading medium

Influence of pH on the release

Ruel-Gariepy E, Leclair G, Hildgen P, Gupta A, Leroux JC (2002) J Contro Rel 82:373

Res 15:11891195. doi:10.

Bromberg L, Temchenko M, Alakhov V, Hatton TA (2005) Langmuir 21:15901598.

Chen J, Jo S, Park K (1995) Carbohydr Polym 28:6976. doi:10.

Series, No. 31. American Chemical Society, pp. 137

vol. 1. CRC, oca Raton (FL), pp 223

Dumitriu S (2005) Polysaccharides: Structural Diversity and Functional Versatility.

Marcel Dekker, Inc., pp. 229, 280 and 848.

Wang N, Wu XS (1998) Int J Pharm 166:114. doi:10.

Ramazani-Harandi MJ, Zohuriaan-Mehr MJ, Yousefi AA, Ershad-Langroudi A, Kabiri K

(2006) Polym Test 25:470474. doi:10.

Chen J, Zhao Y (2000) J Appl Polym Sci 75:808814. doi:10.

Hosseinzadeh H, Pourjavadi A, Mahdavinia GR, Zohuriaan-Mehr MJ (2005) J Bioact

Compat Polym 20:475490. doi:10.

Flory PJ (1953) Principles of polymer chemistry. Cornell University Press, Ithaca, NY

Pourjavadi A, Barzegar S, Zeidabadi F (2007) React Funct Polym 67:644654. doi:10.

4th edn. Wiley, New York, pp VII/675VII/697

Zohuriaan-Mehr MJ, Motazedi Z, Kabiri K, Ershad-Langroudi A, Allahdadi I (2006) J

Appl Polym Sci 102:56675674. doi:10.

delivery. Wiley & Sons, New York, p 139

Mahdavinia GR, Pourjavadi A, Zohuriaan-Mehr MJ (2004) Polym Adv Technol

Richter A, Bund A, Keller M, Arndt K (2004) Sens Actuators B Chem 99:579585.

Pourjavadi A, Seidi F, Salimi H, Soleyman R (2008) J Appl Polym Sci 108:32813290.

Вам также может понравиться