Materials Science and Engineering C 64 (2016) 428435

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Materials Science and Engineering C

journal homepage: www.elsevier.com/locate/msec

Fabrication of chitosan-g-poly(acrylamide)/CuS nanocomposite for

controlled drug delivery and antibacterial activity
Deepak Pathania a,, Divya Gupta a, Shilpi Agarwal b, M. Asif d, Vinod Kumar Gupta b,c,
a

School of Chemistry, Shoolini University of Biotechnology and Management Sciences, Solan, H.P., India
Department of Applied Chemistry, University of Johannesburg, Johannesburg, South Africa
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, 247667, India
d
Chemical Engineering Department, King Suad University Riyadh, Saudi Arabia
b
c

a r t i c l e

i n f o

Article history:
Received 4 December 2015
Received in revised form 15 March 2016
Accepted 21 March 2016
Available online 08 April 2016
Keywords:
Chitosan
Nanocomposite
Ooxacin
Acrylamide
Drug delivery
Antibacterial

a b s t r a c t
In present study, we reported the synthesis of chitosan-g-poly(acrylamide)/CuS (CPA/CS) nanocomposite for
controlled delivery of ooxacin. The CPA/CS nanocomposites were characterized by Fourier transmission infrared
spectroscopy (FTIR), UVvisible spectroscopy (UV), scanning electron microscopy (SEM), X-ray diffraction (XRD)
analysis. From the FTIR spectra, the various groups present in CPA/CS nanocomposite were monitored. The
homogeneity, morphology and crystallinity of the CPA/CS nanocomposite were ascertained from SEM/EDX and
XRD data, respectively. The kinetics of ooxacin drug delivery was investigated at different pH. The drug released
studies were investigated at different pH (2.2, 7.4 and 9.4) and time intervals (2, 4, 6, 8, 10, 12, 14, 16 h). The drug
release behavior depends upon the pH of medium and the nature of matrix. The maximum drug loading efciency of 85% was recorded for CPA/CS. The maximum drug release of 76% was observed at 2.2. pH after 18 h onto
CPA/CS. Nanocomposites were also tested for antibacterial activity against Escherichia coli bacteria. About 97%
killing of E. coli was observed after 24 h.
2016 Elsevier B.V. All rights reserved.

1. Introduction
During the past decades many biodegradable polymeric materials
have been developed for biomedical applications. Degradable polymeric
biomaterials have been used for controlled drug delivery vehicles [47]. A
wide range of natural or synthetic polymers have been being investigated for biomedical applications [13,48,49]. In recent years, biodegradable
polymers have been used as carriers for drug delivery systems [9,24,27,
29,32,33,36,37,42,55]. Drug delivery has been emerged as a powerful
tool for the treatment of various pathologies carrier-mediated diseases.
Due to their stability and controlled physicochemical properties the
polymer composites have enhanced loading capabilities and can be
used as drug carriers [15].
Polymer based nanocomposites due to their unique structures and
properties are of great importance as controlled drug delivery materials.
As compared to bulk counterparts these polymer based nanocomposites
have controlled release behavior [44]. They also possess improved mechanical properties, swelling properties and better drug loading
efciency.

Corresponding author.
Correspondence to: V.K. Gupta, Department of Applied Chemistry, University of
Johannesburg, Johannesburg, South Africa.
E-mail address: dpathania74@gmail.com (D. Pathania).

http://dx.doi.org/10.1016/j.msec.2016.03.065
0928-4931/ 2016 Elsevier B.V. All rights reserved.

Nanocomposites are nano-materials of high performance which exhibit unusual and unique properties. They are considered as the materials
of the 21st century. These materials are of great importance for many industries. The growing demand for nanocomposite material shows a
promising future. The applications of composite materials at nano scale
have strongly inuenced the medicine and pharmacy industries [43,46].
Chitosan is a natural linear biopolyaminosaccharide. It has been
obtained by the alkaline deacetylation of chitin [21,52]. Chitin is a
homopolymer composed of (1.4)-linked N-acetyl-glucosamine
units, whereas chitosan comprises of copolymers of glucosamine
and N-acetyl-glucosamine [11,23,54]. One primary amino and two
free hydroxyl groups are present in chitosan. Chitosan carries a positive charge due to the easy availability of free amino groups. Thus, it
undergoes chelation with metal ions by reacting with many negatively charged surfaces/polymers [5,40]. Chitosan is soluble in dilute
aqueous acidic solutions and is insoluble in water and organic solvents [7]. For the treatment of waste water it acts as occulant [17].
Chitosan has been received a great deal of attention in the pharmaceutical eld due to its promising properties such as biodegradability, biocompatibility and antibacterial nature.
Polyacrylamide hydrogels have been widely used as biomaterials
due to their high water retention property. They have been extensively
studied for biomedical applications, such as drug delivery systems [3,6,
10]. Polyacrylamide due to different polymeric networks have been
used in various a eld [26,34]. Semi-interpenetrating polymeric

D. Pathania et al. / Materials Science and Engineering C 64 (2016) 428435

networks of polyacrylamide/poly(itaconic acid) has been prepared with

the polyacrylamide gel by hydrogen bonding with poly(itaconic acid)
and formation of interpolymer complex [26]. Due to unique properties
of chitosan and polyacrylamide several works have been reported on
polyacrylamide/chitosan blend.
Due to quantum size effect semiconductor nanoparticles
immobilized in a polymer matrix show different properties compared
to their bulk form [19,39,45,53]. Due to number of interesting optical,
catalytic and electronic properties, transition metal suldes have been
an innovative eld of research. Copper sulde (CuS) is an important ptype semiconductor [56] which is extensively used as cathode materials
in lithium rechargeable batteries, solar cells, optical lters, sensors and
super conductor at low temperature below 1.6 K [12,20,28,57]. Copper
compounds are the most important materials [31] and copper based
nanomaterials have broad applications in electronics, catalyst, antibiotics, tissue imaging and photothermal cancer therapy.
Ooxacin is a new class of uoroquinolone whose activity is similar
to other uoroquinolone. It is used in chlamydial infections, in treating
mycobacterial infections such as leprosy. Ooxacin is a second generation uorinated quinolone, a pyridone carboxylic acid derivative having
antimicrobial effect in a variety of systemic infections [1,8,30,35,41].

429

A survey of the literature reveals that chitosan-g-poly(acrylamide)/

CuS (CPA/CS) nanocomposite, has not been used for controlled delivery
systems. In this communication we reported the preparation of
chitosan-g-poly(acrylamide)/CuS (CPAC) nanocomposite. The nanocomosite have been characterized using FTIR, TEM, SEM/EDX, XRD.
The drug delivery systems using ooxacin has also been studied at
different pH and drug loading. The antibacterial study of CPA/CS has
also been investigated against Escherichia coli bacteria.
2. Materials and methods
2.1. Materials
The chemicals used in this study were of analytical grade. The
chemicals chitosan, sodium sulde, acrylamide, copper nitrate, aceticacid and ammonium persulfate were procured from E. Merck Pvt. Ltd.,
India. The drug ooxacin used for drug delivery was obtained from
Ranbaxy Pvt. Ltd., India. The glass wares of borosil make were used during the study. Chromic acid, detergent and acetone were used to clean
the glass wares before use. Double distilled water was used for all preparations and dilutions.

Fig. 1. FTIR spectra of (a) pure chitosan (b) CPA/CS nanocomposite.

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D. Pathania et al. / Materials Science and Engineering C 64 (2016) 428435

Fig. 2. XRD pattern of (a) pure chitosan (b) CPA/CS nanocomposite.

Fig. 3. (a) SEM micrograph of CuS nanoparticles (b) SEM micrograph of CPA/CS nanocomposite (c) SEM micrograph of chitosan (d) TEM micrograph of CPA/CS nanocomposite (e) EDX
pattern of CuS nanoparticles (f) EDX pattern of CPA/CS nanocomposite.

D. Pathania et al. / Materials Science and Engineering C 64 (2016) 428435

431

Fig. 4. (a) Release prole of ooxacin from ooxacin-loaded CPA/CS nanocomposites in buffer solutions of 2.2, 7.4 and 9.4 pH (b) Plot of conc. v/s time.

2.2. Synthesis of CuS nanoparticles

Co-precipitation method was used for the synthesis of CuS nanoparticles. In this method, 20 mL of 0.1 M copper nitrate was added drop

wise with continuous stirring into 10 mL of 0.1 M sodium sulde solution. A white precipitated solution was formed after proper mixing
and stirring. The solution along with precipitates was stirred for 57 h
on a magnetic stirrer at 60 C65 C. The product obtained was ltered

Fig. 5. UVvis spectra of (a) CPA/CS nanocomposites (b) CuS nanoparticles (c) Tauc plot for CPA/CS nanocomposite (d) Tauc plot for CuS nanoparticles.

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D. Pathania et al. / Materials Science and Engineering C 64 (2016) 428435

The morphological images of nanocomposite were obtained using

Scanning electron microscope (SEM). The instrument (Model: JEOL
Stereoscan 440, Cambridge) was used to analyze the surface morphology of CPA/CS nanocomposite and CuS nanoparticles. Energy dispersive
X-ray was used to conrmed the elemental constituents and purity of
the sample.
Transmission electron microscopy (TEM) is an electron based technique used to study the anatomy of nanocomposites. The Techai F12
(Tokyo, Japan) TEM system is used for the characterization of samples.
Optical and band gap studies have been investigated by recording
UVvis transmission spectra. In this, 5 mg of CPA/CS was dispersed in
water and the suspension was then ultrasonicated for 1 h. The UVvis
spectrum was then recorded using double beam spectrophotometer.
Fig. 6. The graph showing antibacterial activity of CPA/CS nanocomposite against E. coli
bacteria.

and washed with distilled water many time. The product was nally
dried in a hot air oven at 50 C.
2.3. Synthesis of chitosan-g-poly(acrylamide)/CuS (CPA/CS) nanocomposite
CPA/CS nanocomposite was synthesized by co-precipitation method
in a microwave reactor. 2 g of chitosan dissolved in 1% aqueous acetic
acid (100 mL) was added dropwise with constant stirring into 50 mL
of 0.1 M acrylamide solution. The CuS nanoparticles prepared above
were dispersed into the reaction mixture. The reaction mixture was
stirred for 10 min. The resultant mixture was placed in a microwave
reactor for 1520 min at 15 psi pressure at 60 C. The product was
taken out, ltered and washed with double distilled water. The product
was dried at 50 C in a hot air oven for 6 h. The product (CPA/CS) was
then grounded to powder and stored for further studies.
2.4. Characterization
CPA/CS nanocomposite was characterized by Fourier transform
infrared (FTIR) spectroscopy. FTIR spectrum was obtained using (Bruker
IFS 66 V Ettlingen, Germany) spectrophotometer. FTIR provides the
useful information about the structure and bonding of the molecule.
FTIR spectra were recorded in the region between 4000 and 400 cm1.
CPA/CS nanocomposite was analyzed using Model D/Max-2500Pc Xray diffractometer Rigagu, Tokyo, Japan. It is used for the identication
and quantitative analysis of various crystalline forms of molecules.

2.5. Drug loading and drug release behavior

1000 mg/L stock solution of ooxacin was prepared in distilled
water and maximum wavelength was recorded. 100 mL of ooxacin
solution was taken from stock solution. 750 mg of the CPA/CS nanocomposite sample in the form of pellet was immersed in ooxacin solution
for 24 h. The loading efciency of ooxacin in nanocomposite sample
was monitored spectrophotometrically. The sample was then taken
out from the solution. The drug-loaded samples were then washed
with distilled water to remove any surface adhered impurities and
then dried. Drug loading % was calculated using Eq. (1) as:
%Drug Loading

Weight of drug in a sample

 100:
Weight of drug

The drug release studies were carried out spectrophotometrically by

placing ooxacin loaded drug in a suitable buffer medium of different
pH (2.2, 7.4 and 9.4). The experiment was performed at 37 C to check
the body specic or colon specic behavior of the sample. The concentration of the drug released at different pH (2.2, 7.4 and 9.4) and time
intervals (2, 4, 6, 8, 10, 12, 14, 16 h) was investigated. The release of
ooxacin by the sample matrix exhibited different behaviors at different
pH media with respect to time interval.
2.6. Mathematical analysis of drug release
The drug release behavior of nanocomposite has been studied using
a mathematical model as reported earlier in the literature [4,25,38,41].
The uptake of the sample was described by using Eq. (2) as follow:
Ms ktn

where, Ms is the uptake of sample, k and n are the constants. The values
of n = 0.5 reveals the normal Fickian diffusion and the value of n = 1.0
signies case II diffusion. The value of n between 0.5 and 1.0 indicate
Fickian or anomalous diffusion. The drug release mechanism was evaluated using power law Eq. (3) as given in literature [50,51].
Mt =M ktn

where Mt/M is the fraction of drug released at time t, k is the release

rate constant and n is the release exponent, which is used to characterize the mechanism of drug released. The value of n determines the
nature of release mechanism. The slope and intercept of the plot
between Mt/M give the value of n and k.
2.7. Antibacterial activity

Fig. 7. The graph showing log reduction.

The method as described earlier in the literature with some modications was used for the determination of antimicrobial activity of CPA/
CS nanocomposites. Nutrient agar plates were prepared to check the
susceptibility of bacteria to different nanoparticles. Three tubes of
5 mL bacterial suspension of concentration 107 CFU/mL of E. coli

D. Pathania et al. / Materials Science and Engineering C 64 (2016) 428435

cultured in nutrient broth were prepared. Two tubes of bacterial suspension were supplemented with different amounts of nanosized particles (with a concentration of 0.4 mg/mL and 2 mg/mL of nanoparticles).
From each tube a 100 L sample of bacterial suspension was then plated
in three different nutrient agar plates. Nanoparticle free bacterial suspension was used as control. The plates were then incubated at 37 C.
The tubes of bacterial suspension were incubated at 37 C on a rotatory
shaker at 200 rpm for 24 h. The numbers of resultant colonies were
counted after 24 h of incubation. The counts were averaged from
three independent experiments plated at 0 h, 24 h, 48 h for a particular
sample. Percent reduction and log10 reduction were calculated using
the following equations:
Initial count CFU=CarrierTest result CFU=Carrier

433

Fig. 3d shows the TEM picture of CPA/CS nanocomposites. TEM results conrmed the size of particles in the range between 5 nm and
15 nm.
The optical properties of CPA/CS and CS were investigated from UV
vis spectra and results were shown in Fig. 5ab. The dispersion was prepared in distilled water and ultrasonicated for 1 h in ultrasonicator. The
UVvis spectra were recorded using double beam spectrophotometer
and curve of absorbance vs wavelength has been plotted. From the absorbance values, absorption coefcient () was calculated using the formula.
2:303 A=l

=Initial count CFU=Carrier  100 percent reduction

Log10 Initial count CFU=CarrierLog10 Test results CFU=Carrier
Log10 reduction:
5

where, A is the absorbance and l is the length of the light passed through
the sample in cm.
Fig. 5cd shows the Tauc plots of CuS nanoparticles and chitosan-gpoly(acrylamide)/CuS nanocomposite. UVvis spectral data was used
for the determination of the band gap using the Tauc relation as.

3. Results and discussion

3.1. Characterization of CPA/CS nanocomposites
The FTIR spectra of chitosan and CPA/CS nanocomposite were shown
in Fig. 1ab. A strong peak has been observed around 3419 cm1 in chitosan, due to the stretching vibration of O\\H, and the extension vibration of N\\H. Fig. 1a shows the observation peaks at 1422 cm1 and
1384 cm 1 due to N\\H stretching of the amide and ether bond. In
grafted sample the reduction in the intensity of peak (at 3401 cm1)
was recorded due to overlapping of O\\H stretching of chitosan and
N\\H stretching of amide groups [14,16]. The peak observed at
1599 cm 1 was due to the carbonyl (C_O) stretching of secondary
amide. The reduced intensity of peak indicated the presence of polyacrylamide chains with chitosan. The peak at 467 cm1 in CPA/CS nanocomposite was originated from the stretching mode of CuS (Fig. 1b). The
occurrence of new peaks and change in the intensity of old peaks
conrmed the polymerization of monomer and synthesis of nanocomposite under microwave radiations.
Fig. 2ab illustrates the X-ray diffraction spectra of the pure chitosan
and CPA/CS nanocomposite. Crystalline areas between 10 and 80 at 2
in was observed in Fig. 2b may be due to presence of polyacrylamide in
the chitosan backbone. A broad peak seen at 2 ranging from 24 to 32
attributed to diffraction peak of acrylamide. Seven different peaks at
2 = 12, 15, 17, 21, 25,30 and 32 clearly indexed as the cubic
CuS phase by comparing with data from JCPDS no. 24-0060. The crystalline nature of the CPA/CS was also indicated by the presence of strong
and sharp peaks. The broadening of peaks suggested size of copper
sulde particle in nanoscale [22]. The mean size of the particle was
calculated to be about 8 nm according to Scherrer's equation based on
XRD data. XRD spectra of pure chitosan shows two characteristic
peaks at 10.9 and 19.8 which correspond to hydrated crystalline and
amorphous peaks of the chitosan [18].
Fig. 3ab shows the morphology of CuS nanoparticles and CPA/CS
nanocomposite at different magnications. It has been conrmed that
polymerization of acrylamide modied the surface morphology of chitosan. The SEM images clearly indicated the porous structure of the
CPA/CS nanocomposite. The successful coatings by polymer particles
and crystalline structure have also been conrmed. SEM image indicated the uniform distribution of polyacrylamide improving the characteristic nature of chitosan as well as acrylamide [15]. The some of the
particles was observed triangular in shape which is the best crystalline
structure shape for antibacterial activity due to higher atomic density
[2]. EDX spectra of CuS nanoparticles and CPA/CS nanocomposite were
shown in Fig. 3c. EDX results inferred the amount of different constituents present in the nanocomposite.

h AhEgn

where is the absorption coefcient and d is the thickness of the sample and Eg is the band gap energy, n (1/2, 1, 2) is a constant dependent
on the degree of transition, n = 1/2 for direct band gap semiconductors,
h is incident photon energy. The band gap is evaluated by plotting h vs
(h)2 and extrapolating the tangent on X-axis (Tauc plots).
3.2. Drug loading efciency and release
The drug release behavior of ooxacin using CPA/CS nanocomposite
at different pH (2.2, 7.4 and 9.4) was studied in triplicate. The maximum
drug loading efciency of 85% was recorded for CPA/CS nanocomposite.
A plot of cumulative percent release (average triplicate set) verses time
for ooxacin loaded CPA/CS nanocomposite was shown in Fig. 4a. The
release studies were performed at different pH such as 2.2, 7.4 and 9.4
for more than 24 h. The swelling of sample membrane caused from
drug diffusion was responsible for initial burst effect of the drug [16,
42]. It may be due to reason that the drug at the surface of the CPA/CS
was released much faster than the drug incorporated deeply into the
pores of the sample.
The maximum drug release was observed in acidic pH (pH = 2.2,
drug release 76%, after 18 h). It is evident from Fig. 4a and b that the
nanocomposite exhibited 61.2 mg/L initial release of ooxacin (pH =
2.2) followed by 19.8 mg/L in neutral medium (pH = 7.4) and
18.1 mg/L in basic medium (pH = 9.4). It has been revealed from the effect of time that initially the drug release was increased with time and
attained a constant rate after reaching the maximum.
3.3. Antibacterial activity
The antibacterial activity CPA/CS nanocomposite was investigated
against E. coli. The results of antibacterial activity of CPA/CS were
shown in Fig. 6. It has been observed that the CPA/CS nanocomposite inhibits the growth of E. coli bacteria, through binding of nanocomposite
to the outer membrane of E. coli. The antibacterial effect was more pronounced at high concentration. The antibacterial effect of nanocomposite against E. coli bacteria may also be due to the inhibition of
dehydrogenase enzyme, periplasmic enzyme activity and active transport [46]. Fig. 7 illustrates the impact log reductions have on a surface
harboring 1,000,000 microbes. A 3-Log Reduction on a surface with
1,000,000 microbes would leave 1000 microbes, which equates to a
99.9% reduction in potentially harmful microorganisms.

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4. Conclusion
In this study, CPA/CS nanocomposites were prepared using microwave irradiations for drug delivery and antibacterial activity. Spectral
analysis indicated the size of the particles in nanoscale. In vitro ooxacin
drug release was studied using CPA/CS nanocomposite at different pH.
The maximum drug release was observed in acidic medium. Initially
higher and faster release of drug was observed which decreased with
time. The combination of chitosan grafted acrylamide chains and CuS
nanoparticles can be envisaged in the eld of drug delivery. CPA/CS
nanocomposite was successfully explored for antibacterial activity
against E. coli bacteria.
Acknowledgment
We would like to thank Shoolini University and Dr. B.R. Ambedkar
NIT Jalandhar for providing the infrastructure and lab facilities to carry
out the research work. We are also grateful to IIT Roorkee, for providing
SEM facility, IIT Ropar for XRD Characterization and Panjab University
for providing with FTIR facilities.
M. Asif appreciates the support of the Deanship of Scientic Research
at King Saud University for the Prolic Research Group PRG-1437-31.
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