Materials Sciences and Applicatio ns, 2011, 2, 1741-1748
doi:10.4236/msa.2011.212232 Published Online December 2011 (
Copyright © 2011 SciRes. MSA
Grafting Vinyl Monomers onto Chitosan:IV:Graft
Copolymerized of Acrylicacid onto Chitosan Using
Ceric Ammonium Nitrate as the Initiator—
Characterization and Antimicrobial Activities
Manoj Kumar Pati, Padmalochan Nayak*
Research Foundation, Neelachal Bhavan, Cuttack, Odisha, India.
E-mail: *
Received October 20th, 2011; revised November 24th, 2011; accepted December 2nd, 2011.
Acrylicacid was grafted onto chitosan by using the ceric ammonium nitrate as the initiator. The effect of initiator con-
centration, monomer concentration, time & temperature on % G and % GE were studied. The grafted samples were
characterized using FTIR, TGA, SEM and XRD methods. From the FTIR data it was ascertained that grafting has oc-
curred considerably. The morphology of the grafted polymer was observed from the SEM picture. The thermal analysis
indicated the different stages of degradation of the grafted copolymer. Evidence of grafting was obtained from com-
parison of SEM, XRD, and FTIR of the grafted and nongrafted chitosan as well as solubility characteristics of the
products. The antibacterial and antifungal activities of the grafted polymer have also been investigated.
Keywords: Chitosan, Acrylicacid, Graftcopolymerization, Antifungal, Antibactarial
1. Introduction
Grafting vinyl monomers onto natural and synthetic
polymers is a challenging field of research with unlim-
ited future prospects. During the last four decades Nayak
and co-workers have studies the graft copolymerization
of several monomers onto a multitude of natural and
synthetic polymers like wool, silk, cellulose, nylon and
PET, rubber to enhance their properties using various
initiators like hexavalent chromium, quinquevalent vana-
dium, tetravalent cerium, trivalent manganese, peroxydi-
sulphate and peroxydiphophate ions [1-16].
Chitosan is a partially deacetylated polymer of acetyl
glucosamine obtained after alkaline deacetylation of the
chitin. It displays interesting properties such as biocom-
patibility, biodegradability [17-21] and its degradation
products are non-toxic, non-immunogenic and non-car-
cinogenic [22-24]. Therefore, chitosan has prospective
applications in many fields such as biomedicine, waste
water treatment, functional membranes and flocculation.
However, chitosan can only soluble in few dilute acid
solutions, which limits its wide applications. Recently,
there has been a growing interest in chemical modifica-
tion of chitosan to improve its solubility and widen its
applications [25-31]). Among various methods, graft
copolymerization is most attractive because it is a useful
technique for modifying the chemical and physical prop-
erties of natural polymers. Chitosan bears two types of
reactive groups that can be grafted. First, the free amino
groups on deacetylated units and secondly, the hydroxyl
groups on the C3 and C6 carbons on acetylated or
deacetylated units. Grafting of chitosan allows the for-
mation of functional derivatives by covalent binding of a
molecule, the graft, onto the chitosan backbone. Recently,
researchers have also shown that after primary deviation
followed by graft modification; chitosan would obtain
much improved water solubility and bioactivities such as
antibacterial and antioxidant properties [32]. Grafting
chitosan is a common way to improve chitosan properties
such as increasing chelating [33] or complexation prop-
erties [34), bacteriostatic effect [35] or enhancing ad-
sorption properties [36,37]. Although the grafting of chi-
tosan modifies its properties, it is possible to maintain
some interesting characteristics such as mucoadhesivity
[38], biocompatibility [39] and biodegradability [40].
Many investigations have been carried out on the graft
copolymerization of chitosan in view of preparing poly-
Grafting Vinyl Monomers onto Chitosan:IV:Graft Copolymerized of Acrylicacid onto Chitosan
Using Ceric Ammonium Nitrate as the Initiator—Characterization and Antimicrobial Activities
saccharide-based advanced materials with unique bioac-
tivities and thus widening their applications in biomedi-
cine and environmental fields. A few review articles on
the potential applications of chitosan for pharmaceutical,
veterinary medicine, biomedical and environmental field
have already been reported [41-49]. However, there is no
review available on the graft copolymerization of chito-
san and its applications, despites the considerable amount
of works have been published in this field. Moreover, the
potential applications of grafted chitosan in the various
fields such as drug delivery, biomedical, tissue engineer-
ing and environmental is also discussed.
In the present research program, we wish to report the
graft copolymerization of Acrylicacid onto chitosan us-
ing ceric ammonium nitrate as the initiator. The graft co-
polymrization was studied by varying the initiator, time,
temperature and concentration of monomer. The grafted
polymers were characterized by SEM, XRD and FTIR
studies. The antibacterial and antifungal activity of the
grafted samples have been reported.
2. Material and Method
Chitosan with more than 95% deacylated was obtained as
Gift sample from India Sea food, Kerala, India.
Acrylicacid (Riedel) was extracted with an aqueous
solution of 5% NaOH/20% NaCl to remove the hydro-
quinone stabilizer. The monomer was distilled and the
middle fraction were used Inhibitor free Acrylicacid
(Fluka puriss) was also used.
Reagent-grade ceric ammonium supplied by Merck
was used to prepare the initiator solution, and was used
without further purification. Other reagents were of ana-
lytical grade and were used without further treatment.
2.1. Graft Copolymerization
The chitosan powder sample was dispersed in a definite
volume was dissolved in 2% acetic acid, in a thermo-
stated reaction flask for 60 min. The ceric ammonium
nitrate in 0.5 M nitric acid solution was then loaded into
the reactor under continuous stirring. Then a known
weight of Acrylicacid was also injected into the reactor.
The reaction was assumed to have started at the moment
the monomer was injected.
Graft copolymerization was carried out at room tem-
perature under constant stirring in nitrogen atmosphere
for a particular time period. At the end of grafting co-
polymerization the reaction mixture was neutralized with
a 1 M NaOH solution, and the reaction products (graft
copolymer and homopolymer) were filtered and thor-
oughly washed with distilled water, and then dried to
constant weight. The homopolymer was subsequently
removed by extraction with N,N-dimethethyl formamide
for 6 hrs. The remaining product, after drying to a con-
stant weight, was considered to be a graft copolymer.
Grafting percentage (%G) which designates the amount
of polymer grafted on the substract backbone (chitosan)
and grafting efficiency (%E), which indicates the effi-
ciency of conversion of the initial Acrylicacid to the
grafted PAN, were calculated from the increase in weight
of the chitosan after graft copolymerization in following
2.2. Evidence of Grafting
It has been seen that the amidecarbonyl absorption band
from grafted chains appears at 1649 cm–1. The band is
located at 1670 cm–1 for acrylamide homopolymer. On
the other hand, the most typical absorption bands of chi-
tosan situated at 1558 cm–1 and 1661 cm–1 corresponding
to amide-I and amide-II bands respectively, are not
clearly visible since they are hidden by strong carbonyl
absorption band of PAA in this spectrum region. How-
ever the CHI amide-I absorption can be observed as a
shoulder at 1540 cm–1. The shift of the carbonyl absorp-
tion band of PAA amide-I band of chitosan to lower fre-
quencies could be due to inter—and/or intramolecular
interacting though hydrogen bonding. Naturally, the in-
solubility of PAA grafted CHI samples, inspite of con-
taining a large number of amide groups, is produced by
the cross linking (Figure 1).
2.3. X-Ray Diffraction Studies
The formation and quality of compounds were checked
by X-ray diffraction (XRD) spectrum. The XRD pattern
was measured by drop coated grafting compound on
glass plate and employed with X-ray diffractometer
(INEL X-ray diffractometer) of characteristic Co-kα1
radiation (λ = 1.78 Å) in the range of 20˚ to 90˚ at a scan
rate of 0.05˚/min with the time constant of 2 s.
2.4. SEM Analysis of Grafting Compound
Scanning Electron Microscopic (SEM) analysis was done
using Hitachi S-4500 SEM machine. The sample were
prepared on a carbon coated copper grid by just dropping
a very small amount of the sample on the grid, extra so-
lution was removed using a blotting paper and then the
sample on the SEM grid were allowed to dry by putting it
under a mercury lamp for 5 min.
Copyright © 2011 SciRes. MSA
Grafting Vinyl Monomers onto Chitosan:IV:Graft Copolymerized of Acrylicacid onto Chitosan
Using Ceric Ammonium Nitrate as the Initiator—Characterization and Antimicrobial Activities
Copyright © 2011 SciRes. MSA
Figure 1. (a) FTIR spectra of pure chitosan; (b) FTIR spectra of grafted chitosan with acrylic acid (monomer).
2.5. FTIR
FTIR spectra were taken by using a Bruker IFS-28 in-
strument. The samples were prepared as KBr pellets.
3. Antimicrobial Susceptibility Test
The disc diffusion method was used to screen the antim-
icrobial activity. In vitro antimicrobial activity was
screened by using Mueller Hinton Agar (MHA) obtained
from Himedia (Mumbai). The MHA plates were pre-
pared by pouring 15 ml of molten media into sterile Petri
plates. The plates were allowed to solidify for 5 min and
0.1% inoculum (0.5 McFarland standard) suspension was
swabbed uniformly and the inoculum was allowed to dry
for 5 min. 50 μl concentration of test sample was loaded
on 0.5 cm sterile disc. The loaded disc was placed on the
surface of medium and the compound was allowed to
diffuse for 5 min and the plates were kept for incubation
at 37˚C for 24 h. At the end of incubation, inhibition
zones formed around the disc were measured with trans-
parent ruler in millimeter. For each bacterial strain, nega-
tive controls were maintained where pure solvents were
used instead of the extract. The control zones were sub-
tracted from the test zones and the resulting zone diame-
ter and the result obtained was tabulated and Ampicillin
(10 mcg/disc) were used.
4. Result and Discussion
4.1. Solubility Tests
The solubility of PACN has been furnished in Ta bl e 1. It
is evident that the grafted polymer are insoluble in many
Table 1. Results of solubility tests on 45% grafted chitosan.
Solvent Observation
1% Acetic acid Soluble
Ethanol Insoluble
1% Acetic acid: ethanol Cloudiness
Glacial acetic acid:ethanol (1:1) swelling
Glacial acetic acid:ethanol (1:2) swelling
DMF Insoluble
DMSO Insoluble
THF Insoluble
Distilled water Soluble
Grafting Vinyl Monomers onto Chitosan:IV:Graft Copolymerized of Acrylicacid onto Chitosan
Using Ceric Ammonium Nitrate as the Initiator—Characterization and Antimicrobial Activities
protic and aprotic solvents. This behaviour may be at-
tributed to a slight crosslinking at higher grafting yields.
Although PNVI is soluble in organic solvents such as
ethanol, DMF, DMSO and THF, grafted chitosans were
found to be insoluble in these solvents. This shows that
chitosan’s nature is predominant over PACN in these
solvents for samples studied.
4.2. The Effect of Initiator Concentration
Table 2 shows the effect of the concentration of the ini-
tiator Ce4+ on grafting of Acrylicacid. It was observed
that the miximum percentage of grafting occurred at 5.70
× 10–3 M. A further increase in the Ce4+ concentration
leads to a decrease in the grafting percentage of Acryli-
cacid. This could be explained by the fact that ceric ion
at a higher concentration causes the termination of graft-
ing polymeric chain growth since ceric ion is a very good
terminator ( ). Another factor which could contribute to a
decrease in the grafting percentage at higher concentra-
tion of initiator is the increase the homopolymer forma-
tion, which competes with the grafting reaction for the
available monomer.
4.3. The Effect of Monomer Concentration
The effect of the Acrylicacid concentration on the graft
yield obtained with chitosan is shown in Table 3. An
increase in the monomer concentration is accompanied
by significant increase in grafting up to 0.75 M. However
with the further increase in the concentration of mono-
mer, grafting is found decrees. This could be ascribed to
the substantial amount of polymer grafted on the sub-
stract backbone, which inhibit the diffusion of Ce4+ and
the monomer into chitosan for further grafting.
4.4. The Effect of Tempertaure
The dependence of grafting yield on temperature in the
range of 25˚C - 52˚C is shown in Table 4 . The maximum
grafting of Acrylicacid occurs at 35˚C within 180 min. A
further increase in temperature reduces the percentage
grafting. This is to be expected since at higher tempera-
ture various chain transform reaction are accelerated
which leads to a decrease in the percentage of grafting on
in other words the formation of more homopolymer.
Table 2. The effect of redox initiator concentration on the
grafting of Acrylicacid onto chitosan.
No Chitosan (g) Ce4+ × 103 (M) % G % E
1 5.03 3.90 55.6 36.9
2 5.07 5.70 106.3 76.1
3 5.07 7.88 53.07 35.2
4 3.00 9.50 44.4 26.6
Acryonitrile 6.00 g, temperature of 25˚C reaction time of 180 min.
4.5. The Effect Time
The effect of the reaction time on the percentage of
grafting and grafting efficiency is shown in Table 5. The
percentage of grafting was found to increase linearly with
time and then approximately constant. The initial increase
in the rate due to the increase in the number of grafting
site, but this number remain constant with further in-
crease of time.
The following mechanism has been suggested for the
graft copolymerization of Acrylicacid onto chitosan.
Table 3. The effect of monomer concentration on the graft-
ing of Acrylicacid onto chitosan.
No.Chitosan (g) Acrylicacid (Mol/L) % G % E
1 2.00 0.5 11.0 12
2 2.00 1.00 33.0 31
3 2.00 2.00 69.3 68
4 2.00 3.00 10.5 7
Ce4+ = 30.9 × 10–3 M, temperature of 25˚C reaction time of 180 min.
Table 4. The effect of temperature on grafting of acrylicacid
onto chitosan.
No. Chitosan (g) Temper a ture (˚C) % G% E
1 2.10 25 10 7
2 2.04 35 54 36
3 2.04 40 24 22
4 2.05 50 13 11
Ce4+ = 30.9 × 10–3 M, temperature of 25˚C reaction time of 180 min.
Table 5. The effect of time on the grafting of acrylicacid
onto chitosan.
Time (min) %G %E
30 12 11
60 33 22
90 38 26
150 42 25 - -
Ce4+ = 30.9 × 10–3 M, chitosan 2.00 g, acryolonitrile = 3.00 g temperature of
Copyright © 2011 SciRes. MSA
Grafting Vinyl Monomers onto Chitosan:IV:Graft Copolymerized of Acrylicacid onto Chitosan 1745
Using Ceric Ammonium Nitrate as the Initiator—Characterization and Antimicrobial Activities
Production of Free Radical: Oxidation.
CS CeComplexCSCeH
 
4+ 3++
Ce+ M Compex M + Ce+ H
 
n1 n1
(Graft Copolymer)
 
n1 n1
M CeM+ Ce
(Homopolymer) Chain Transfer
CS Mn CeCS Mn Ce H
 
CS Mn MCS Mn M.
where CH, m, CH(M)n + 1 and (M)n + 1 represent chitosan
Acrylicacid, the graftcopolymer and homopolymer, re-
5. X-Ray Diffraction Studies
The grafting was also supported by XRD (Figure 2). The
X-ray diffraction spectra of the grafted chitosan show
many crystalline areas between 2
20˚ - 32˚ and 38˚ -
45˚ (due to polyAcrylicacid grafts at the chitosan back-
bone), while no such peaks are visible in the XRD of the
chitosan itself.
5.1. SEM
Figure 3 shows the SEM micrographs of chitosan 1) and
chitosan/PAA (Acrylic Acid) 2) blend. It provides direct
evidence that phase separation occurred in chitosan/PAA
(Acrylic Acid) blend. This sample has a distinct two-
phase morphology, i.e., a continuous PAA (Acrylic Acid)
phase with a dispersed chitosan phase indicates poor in-
terfacial adhesion between terpolyamide and chitosan
phases. It is well known that chitosan has the good ability
of degradation. Therefore, PAA (Acrylic Acid) interfered
with chitosan can improve its biodegradability.
5.2. TGA Studies
The TGA of pure chitosan and chitosan-g-AA (Acrylic
Acid) is given in Figure 4.
The grafting was also supported by thermogravimetric
Figure 2. (a) XRD of pure chitosan; (b) chitosan-g-AA (Ac-
rylic acid) graft copolymer.
Figure 3. SEM picture of grafted chitosan.
Figure 4. (a) TGA of chitosan; (b) TGA of chitosan-g-AA
(Acrylic Acid) graft copolymer.
analysis (Figure 4). TGA of chitosan (a) shows a weight
loss in two stages. The first stage ranges between 10 and
100˚C and shows about 12% loss in weight. This may
correspond to the loss of adsorbed and bound water. The
second stage of weight loss starts at 210˚C and continues
up to 360˚C during which there was 44% weight loss due
to the degradation of chitosan. However, the TGA of the
Copyright © 2011 SciRes. MSA
Grafting Vinyl Monomers onto Chitosan:IV:Graft Copolymerized of Acrylicacid onto Chitosan
Using Ceric Ammonium Nitrate as the Initiator—Characterization and Antimicrobial Activities
grafted product is different. The latter has three stage of
weight loss between 10˚C and 550˚C. The first stage of
weight loss starts at 180˚C and continues up to 340˚C,
during which there was 22% weight loss due to the deg-
radation of chitosan. The second stage from 340˚C to
420˚C and the third stage from 420˚C to 500˚C may con-
tribute to the decomposition of different structure of the
graft co-polymer. Below 430˚C the copolymer had lower
weight loss than chitosan. These mean that the grafting
of chitosan increases the thermal stability of chitosan in
some extent.
6. Antibacterial Activity of Graft
Copolymerized of Acrylicacid on Chitosan
A preliminary study has been carried out to compare the
antibacterial activity of grafted chitosan hydrochloride
film samples with that of chitosan. The study was carried
out against P. aeruginosa, E. coli, B. subtilis and S.
aureus using the inhibition zone method. The results are
shown in Table 3. It was observed that grafting of NVI
improved the antibacterial activity of chitosans. While
the inhibition zone diameter for chitosan film ranged
between 9 and 11 mm against indicated bacteria, the in-
hibition zone increased up to 17 mm (against B. subtilis)
by grafting. Although the difference is not significant,
activity of gram-positive bacteria seems to be more pro-
nounced; increase in the inhibition zone diameter is 4 - 5
mm in gram-negative ones whereas it is 5 - 7 mm in
gram-positive ones. Grafted samples showed an increas-
ing antibacterial activity as the degree of grafting in-
creased for all of gram-negative and gram positive bacte-
rias; a minimum of 2 mm increase was observed consis-
tently when the grafting percentage increased from
82.5% to 145%. Average film weight (thickness) also
effected the degree of antimicrobial activity of both chi-
tosan and grafted chitosan samples. And 3 - 4 mm in-
crease was observed when the average film weight was
increased from 134 to 296.
Table 6. Antifungal activities of GRAFTING compounds
minimal inhibitory concentration (MIC) mg/ml.
Fungus MIC (mg/ml)
C. albicans 15.22 ± 0.04
C. tropicalis 17.32 ± 0.07
C. krusei 20.28 ± 0.00
C. Kefyr 11.33 ± 0.44
A. flavus 18.63 ± 0.64
7. Antifungal Activity
Further the grafting compound were found to be highly
toxic against clinically isolated fungal species. At a con-
centration of 50 μl grafting compound revealed a higher
antifungal activity against C. albicans, Candida kefyr,
Aspergillus niger whereas intermediated activity were
showed against C. tropicalis, C. krusei, A. flavus, A. fu-
migatus. The inhibitory activities of all the grafting
compound are reported in Table 6. The data results were
compared with the standard antimicrobics of Ketocona-
zole (30 mg) and Itraconazole (30 mg).
8. Conclusions
The grafting of acrylicacid onto chitosan, in the absence
of N,N-methylenebisacrylamide as crosslinking agent,
leads to slightly soluble products. When N,Nmethylene-
bisacrylamide was used as crosslinker insoluble grafted
chitosan was obtained which could be easily separated
from the reaction medium and purified. Moreover, the
insoluble grafted chitosan showed characteristics of SEM,
XRD and FTIR. This study has demonstrated that graft-
ing compound showed a higher antibacterial and fungal
activity. Grafting compound markedly inhibited the gr-
owth of most bacteria and fungal tested although their
inhibitory effects differed.
9. Acknowledgements
This work was supported by Bio-Lab (A-41, Janpath,
Ashok Nagar, Bhubaneswar, India-751009).
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