Carbohydrate Polymers 84 (2011) 465–470

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Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

Preparation and properties of chitosan derivative/poly(vinyl alcohol) blend film

crosslinked with glutaraldehyde
Qian Yu a , Yanan Song a , Xiaomei Shi a , Chunye Xu b , Yuezhen Bin a,c,∗
a
Department of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Zhongshan Road 158, Dalian 116012, China
b
Hefei National Lab. for Physical Sciences at Microscale, Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei 230026, China
c
State Key laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Zhongshan Road 158, Dalian 116012, China

a r t i c l e i n f o a b s t r a c t

Article history: Novel crosslinked blend films of N-(2-hydroxy)propyl-3-trimethylammonium chitosan chloride (HTCC)
Received 20 July 2010 and poly(vinyl alcohol) (PVA) were prepared by mixing their aqueous solutions followed by crosslinking
Received in revised form with glutaraldehyde (GA). The effects of the GA content and ratio of HTCC to PVA on the appearance,
19 November 2010
swelling, gel content, morphology and antibacterial activities of blend films were studied and a possible
Accepted 2 December 2010
mechanism of crosslinking was proposed based on the results. It was found that the equilibrium degree
Available online 10 December 2010
of swelling (ESD) increased with the increasing content of HTCC, but decreased with the content of
GA. The ESD was a maximum (212%) when the ratio of HTCC/PVA/GA was 60/40/2 (wt). Antibacterial
Keywords:
Chitosan derivative
activities against Staphylococcus aureus and Escherichia coli of the blend films were weakened slightly by
Poly(vinyl alcohol) crosslinking, but still showed substantial antibacterial activity. These results demonstrate that, not only
Crosslinking the PVA, but also the HTCC reacted with GA. It was the amino groups on HTCC that was un-substituted
Swelling by quaternary ammonium salt, which reacted with the aldehyde groups on GA.
Antibacterial © 2010 Elsevier Ltd. All rights reserved.

1. Introduction etrates the cytosol of the microorganisms and, through the binding
of chitosan with DNA, and results in the interference with the syn-
Chitosan, an aminopolysaccharide, is composed of ␤,1-4 gluco- thesis of mRNA and proteins; (5) chitosan, on the surface of the
sidic bonds. Due to its unique polycationic nature, chitosan and its cell, can form an impermeable polymeric layer which alters the cell
derivatives have been proposed for various applications in biomed- permeability and prevents nutrients from entering the cell; and (6)
ical, food, agricultural, biotechnological and pharmaceutical fields finally, chitosan can adsorb the electronegative substances in the
(Arvanitoyannis, Nakayama, & Aiba, 1998; Cardile et al., 2008; Feng cell and flocculate them, it disturbs the physiological activities of
& Huang, 1997; Wang, Turhan, & Gunasekaran, 2004). The antibac- the microorganism leading to their death (Muzzarelli et al., 2000;
terial activity of chitosan and its antibacterial mechanism have Vallapa et al., 2011).
been researched extensively. The six main antibacterial mecha- In general, chitosan of high molecular weight can only be dis-
nisms have been proposed as follow: (1) interactions between the solved in acid solution. Solutions made from chitosan in dilute acid
positively charged moieties on the chitosan molecules and the solution often need a repeated washing process to neutralize the
negatively charged ones on the microbial cell outer membranes acid, which restricts its applications thus the chemical modifica-
leads to changes in the cell membrane structure and permeabil- tion of chitosan to improve its water-solubility is desirable. A series
ity inducing the leakage of proteinaceous and other intracellular of water soluble compounds have been synthesized, hydroxyethy-
constituents; (2) chitosan acts as a chelating agent that selectively lated, N-carboxymethylated, N-alkylated, oxidated, degradation of
binds trace metals and subsequently inhibits the production of tox- chitosan N, O-sulfated, oxygen inorganic acid esterified and qua-
ins and microbial growth; (3) chitosan activates several defense ternary ammonium cationizated chitosan derivatives (Chen, Wang,
processes in the host tissue, acting as a water binding agent and Liu, & Park, 2002; Ji et al., 2009; Ma et al., 2007). N-[(2-hydroxy-3-
inhibits various enzymes; (4) low molecular weight chitosan pen- trimethyl-ammonium)-propyl] chitosan chloride (HTCC) could be
prepared by reacting chitosan with glycidyl trimethylammonium
chloride (GTMAC). The introduction of N-trimethylated quater-
nary ammonium salt group would greatly weaken the hydrogen
∗ Corresponding author at: Department of Polymer Science and Engineering,
bonds between chitosan molecule chains, and improve the water-
School of Chemical Engineering, Dalian University of Technology, Zhongshan Road
solubility, antibacterial activity, moisture absorption and retention
158, Dalian 116012, China. Tel.: +86 411 39893638; fax: +86 411 39893638.
E-mail addresses: [email protected], [email protected] (Y. Bin). capabilities of chitosan. In addition, the reagents used in the prepa-

0144-8617/$ – see front matter © 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbpol.2010.12.006
466 Q. Yu et al. / Carbohydrate Polymers 84 (2011) 465–470

ration of HTCC were of low cost, and the processing was relatively
simple. This method has been widely used in the production of
chitosan derivatives (Chiellini, Cinelli, Chiellini, & Imam, 2004; Jia,
shen, & Xu, 2001; Kim, Choi, Chun, & Choi, 1997; Qin et al., 2004).
Poly(vinyl alcohol) (PVA) is one kind of hydrophilic semi-
crystalline polymer. It has been widely used in biomedical
applications because of its non-toxicity, biocompatibility, excellent
chemical resistance and mechanical strength (Peppas & Wright, Fig. 1. Synthetic scheme of HTCC.
1998).
Up to now, much work has been done on the prepara-
2.2. Sample preparation and measurement
tion and study of chitosan/chitosan derivatives and PVA blend.
Arvanitoyannis, Kolokuris, Nakayama, Yamamoto, and Aiba (1997)
2.2.1. Preparation of HTCC
have prepared the blend of chitosan/PVA plasticized with sorbitol
Chitosan was dissolved in a 2 wt% acetic acid solution, and then
and sucrose for using as a food packaging material, and stud-
the solution was adjusted with NaOH solution (0.1 mol/L) to pH = 9,
ied the effect of plasticizer on the structure, thermal, mechanical
kept for 6 h to allow sedimentation. The precipitate was then fil-
property and CO2 permeability and also reviewed the preparation,
tered out and dissolved in isopropanol, and heated to 60 ◦ C under
physical properties, and potential as food packaging materials of
a nitrogen atmosphere. GTMAC was then added into the solution,
this kind of blend based on natural and synthetic macromolecules
and stirred for 6 h at 80 ◦ C. After that the clear viscous solution
(Arvanitoyannis, 1999). Some studies have focused on the applying
was cooled to ambient temperature and deposited in isopropanol,
of a series of crosslinking methods, e.g. irradiation, freeze-thawing
then the filtered out precipitate was washed three times by iso-
and chemical methods. These studies include the combination of
propanol and dried at 80 ◦ C. The synthetic scheme was represented
two crosslinking methods to prepare the hydrogel of PVA and
in Fig. 1. Hydrogen atoms of –NH2 on chitosan were substituted
chitosan, and the results showed that hydrogels made by irradi-
by the quaternary ammonium salt group, and the proportion of
ation followed by freeze-thawing show larger swelling capacity
hydrogen atom being substituted was expressed by the degree of
and mechanical strength, higher thermal stability, lower water
substitution (DS).
evaporation rate, and are less turbid than those made by pure
To measure the DS of HTCC, a certain quality of HTCC was dis-
freeze-thawing and freeze-thawing followed by irradiation. Hydro-
solved in deionized water, and Cl− in solution was titrated with
gels made by irradiation alone cannot be used as wound dressing
silver nitrate solution using potassium chromate as the indicator.
due to their poor mechanical strength. (Shen, Ruan, & Ga, 2009;
DS of the quaternary ammonium salt groups was calculated as fol-
Yang, Liu, Chen, Yu, & Zhu, 2008). The chemical crosslinking method
lowing:
has the advantages of improving the mechanical strength, ther-
mal stability, keeping the intrinsic opaque appearance and swelling VM
DS% = (1)
capacity (Bai, Xie, & Zhu, 2007). Most of studies focused on the effect VM + (W − VM × 314)/161
of chemical crosslinking on the mechanical, thermal and swelling
properties of PVA/chitosan blend, but the changes in antibacte- where W is the weight of HTCC in grams, V (mL) and M (mol/L)
rial activity as a result of crosslinking have been seldom studied. are the volume and concentration of silver nitrate solution used
Although some studies had demonstrated that the amino groups for titration, respectively. The numbers 314 and 161 corresponded
on chitosan might react to the aldehyde groups on GA through the to the molecular weight of the repeat structural unit of HTCC and
FTIR spectrum, the changing of the absorption bands of N–H and CS. When the hydrogen atoms of –NH2 on chitosan were fully sub-
characteristic peak of other groups were not so obvious, and there stituted, the DS of HTCC was 200%, since there were two hydrogen
was no other evidence to support this mechanism (Milosavljević atoms on each amino group which could be substituted by the qua-
et al., 2009). ternary ammonium salt groups. And the measured DS of HTCC was
Our research aims at prepare the HTCC and HTCC/PVA blend 124%, which indicates that 76% of the hydrogen atoms of –NH2 on
films crosslinked by glutaraldehyde (GA), investigate the swelling chitosan were not substituted.
properties, degree of crosslinking and antibacterial activities, and
explore the crosslinking mechanism. 2.2.2. Preparation of sample films
PVA pellets were added into deionized water (PVA/water = 1/10
in weight) and dissolved under continuous stirring at 100 ◦ C. Then
the HTCC was added into the PVA solution, and an absolutely clear
2. Experiments mixture was obtained for a while. After that the diluted GA aqueous
was added into the flask, and the mixture was stirred for 15 min at
2.1. Materials 70 ◦ C. Then the solution was cooled down and poured into the dish,
dried at ambient temperature to form the crosslinked PVA–HTCC
Chitosan (K-03) used in this work was provided by FUNAKOSHI film. Pure PVA films and HTCC films crosslinked with GA were also
Co. (Japan). The viscosity-average molecular weight (M v ) was prepared with the same method.
35,000 and the degree of deacetylation was 90%. PVA was pur-
chased from Sinopharm Chemical Reagent Co., Ltd. (China) with 2.2.3. Measurement of the swelling properties of the films
a degree of polymerization of 1750 ± 50. GA was prepared in The swelling properties of PVA–HTCC blend films in buffer
the lab. Analytical-grade sodium hydroxide (NaOH), acetic acid solutions (pH = 7.4) at 37 ◦ C were studied. The swelling degree
(CH3 COOH), isopropanol and GA aqueous (25 wt%) were used (SD) and equilibrium swelling degree (ESD) of films with differ-
without further purification. Nutrient broth and agar culture ent contents of HTCC and GA were determined gravimetrically.
medium (Hangzhou Microbial Reagent Co., Ltd., China), agar pow- Dried films of appropriate size were weighed and then immersed
der (Sinopharm Chemical Reagent Co., Ltd., China), meat-extract in NaH2 PO4 –Na2 HPO4 buffer solutions, and NaOH solutions were
(Dainippon Pharmaceutical Co., Ltd., Japan) and polypeptone used to adjust pH to be 7.4. Sodium chloride was used to adjust
(Wako Pure Chemical Industries, Ltd., Japan) were used for the the ionic strength of the solutions to be 0.15 mol/L. To ensure
antibacterial activity test. complete equilibration, the samples were allowed to swell for
 Q. Yu et al. / Carbohydrate Polymers 84 (2011) 465–470 467

Fig. 2. Photographs of different films. (a) PVA film; (b) HTCC film; (c) HTCC–PVA blend film; (d) crosslinked PVA film; (e) crosslinked HTCC film; and (f) crosslinked HTCC–PVA
blend film.

24 h. The excess surface-adhered water drops were removed by 0.4 mL of the bacteria inocula was diluted with 20 mL liq-
filter paper rapidly, and the swollen films were weighed (Costa- uid medium and shaking cultured for 4 h. And then diluted
Júnior, Pereira, & Mansur, 2009; Costa-Júnior, Barbosa-Stanciolib, 10,000 times with buffer solution, the number of bacteria was
Mansurc, Vasconcelosc, & Mansurc, 2009; SanlI, Ay, & IsIklan, 2007). 1.5–3 × 104–5 cfu/mL.
The SD and ESD were calculated as follows: (4) Antibacterial activity test: the sample films were added into the
Ms − Md conical beaker with 70 mL culture medium, then the diluted
SD% = 100% (2) inocula (5 mL) was added and shaking cultured at 36 ◦ C for
Md
18 h. After that 1 mL of the above inocula was transferred by
Ms − Md pipette to the Petri dish, 15 mL standard agar medium was
ESD% = 100% (3)
Md added and cooled down. Next, the Petri dish was put into the
where Ms and Md are the weights of the swollen film and dry film, constant temperature incubator and cultured for 24 h. Finally,
respectively. Ms is the weight of the film swollen for 24 h. the growing status of bacteria was observed and the num-
ber was counted. Based on the standard of QB/T 2591:2003
2.2.4. Measurement of gel content of films (Antimicrobial plastics-Test for antimicrobial activity and effi-
Films with different compositions and crosslinking agent con- cacy) from China, which mainly referenced the standards of
tents were dried sufficiently at 105 ◦ C and weighed. Then the films ASTM G 21-1996 (Standard Practice for Determining Resistance
were wrapped in a stainless steel net (150 mesh) and extracted with of Synthetic Polymeric Materials to Fungi, NEQ) and JIS Z 2801-
Soxhlet extractor at 90 ◦ C for 12 h where water was used as solvent. 2000 (Antimicrobial products-Test for antimicrobial activity
Afterward, the stainless steel net encapsulated residue was taken and efficacy), the antibacterial rate was calculated as the fol-
out, then dried and weighed. lowing formula:

M2 B−C
gel content = 100% (4) antibacterial rate (%) = 100% (5)
M1 B
where M1 is the weight of film before extracted and M2 is the weight where B: average bacterial number per plate in the control film
of film after extracted. after 24 h incubation. C: average bacterial number per plate in
the PVA or blend films after 24 h incubation.
2.2.5. Antibacterial activity test I Antibacterial rate > 99% (good antibacterial efficacy).
The antibacterial activity test was carried out using the film II Antibacterial rate > 90% (normal antibacterial efficacy).
adhering method. Staphylococcus aureus (S. aureus) ATCC 6538 III Antibacterial rate < 90% (no antibacterial efficacy).
(NBRC 13276) and Escherichia coli (E. coli) ATCC 25922 (NBRC
15034) were used as the test bacteria. 3. Results and discussion

(1) The samples were cut to small pieces (50 mm × 50 mm), and 3.1. Appearance of the films
pure PVA film was used as the control and cover film. All the
films were rinsed with 70 wt% ethanol solution, and then fully Fig. 2 shows the photographs of films including the non-
dried and sterilized under ultraviolet light. crosslinked and crosslinked films with GA in which GA was 2 wt%
(2) Test bacteria were cultivated in nutrient agar at 36 ± 1 ◦ C for of sample. The color of pure PVA, HTCC and HTCC/PVA blend films
16 h. An aliquot was transferred into nutrient broth and culti- was transparent as also the PVA film crosslinked by GA, but the
vated at 36 ± 1 ◦ C for 16 h. This cultivation broth was diluted HTCC and HTCC–PVA blend films crosslinked by GA are dark yel-
500 times with 1/500 nutrient broth (pH = 7.0 ± 0.2). low. This was not reported in the previous studies. Some studies
(3) Cultivation of test bacteria: a transferring loop of S. aureus or referenced above only reported that the aldehyde group on GA
E. coli was taken and dispersed on the surface of slope medium could react with the amino group on chitosan/chitosan derivatives
evenly, then cultured at constant temperature (36 ◦ C) for 24 h. formed the –C N– group. In the present study, the amino groups
Afterward, a transferring loop of bacteria was moved to the on HTCC were not substituted totally by the quaternary ammonium
liquid culture medium, and shaking cultured in an oscillating salt groups. And the residual amino groups might react with GA and
incubator at 36 ◦ C for 16 h. The bacteria content was 108 cfu/mL. formed the –C N– group, a chromophore. The adsorption band of
468 Q. Yu et al. / Carbohydrate Polymers 84 (2011) 465–470

Fig. 3. The swelling kinetics (a) and EDS (b) of PVA–HTCC blend films with different compositions in buffer solutions (pH = 7.4). (GA content was the 2 wt% of the total weight
of PVA and HTCC.)

–C N– is in the extreme ultraviolet, and cannot be observed in pared with the results obtained in the previous studies (Shen et al.,
the range of visible light. However, a cyclic group i.e. glucosamine 2009; Yang et al., 2008). On one hand, the high swelling rate and
with –OH, –OR is conjoint with –C N–, which can act as an aux- ESD should be attributed to the good hydratability of HTCC with
ochrome. This resulted in the adsorption band of –C N– shifting large amounts of quaternary ammonium salt groups. Introduction
to the range of long wave, and chromogenic in the range of vis- of HTCC increased the number of positive charge, which attracted
ible light. Therefore, the color of crosslinked blend film became hydroxyl ion in the external environment of cross-linking net-
darker. works; on the other hand, PVA was a polymer with high percentage
of crystallinity, and the micro-molecular, e.g. water, CO2 , O2 was
3.2. Results of swelling measurement difficult to permeate through because of the strongly hydrogen
bond interaction between the molecular chains. The introduction
Swelling properties in vitro test are of paramount importance of an amorphous polymer, e.g. chitosan (Arvanitoyannis et al., 1997,
for prospective evaluation of biomaterials. The swelling capacity of 1998) or HTCC would dilute the PVA, which induced the decrease of
biomaterial can be affected by many factors, such as the crosslink- hydrogen bonds interaction and the percentage of crystallinity as
ing density, the hydratability of the materials, the ionic strength and well as improved the gas/water permeability of blend films. There-
pH value of the media, as well as the temperature of the environ- fore, both of the swelling rate and ESD increased. When swollen,
ment (Yang et al., 2008). In this research the swelling capacity was the non-crosslinked molecular chains in the coiled state hindered
studied for PVA–HTCC blend films with different compositions and the inhalation of liquid to a certain extent, and the stretching of
dosages of crosslinking agent in NaH2 PO4 –Na2 HPO4 buffer solu- HTCC molecular chains prolonged the time reached equilibrium
tions. swelling.
Fig. 3 shows the effect of HTCC content on the swelling capac- Fig. 4 shows the effect of GA dosage on the swelling capacity
ity of blend films when the dosage of GA was fixed to be 2 wt% of blend films containing 10 wt% HTCC. The ESD of different films
against the total quantity of PVA and HTCC. More rapid swelling decreased with increasing dosage of GA. This could be ascribed to
was observed for the films with higher HTCC content. When the the fact that when the dosage of GA is increased, more hydrophilic
swelling degree of the film attained 80%, 40 min was needed for the hydroxyl and amino groups were crosslinked thus the hydratabil-
pure PVA film, but only 20 min and 10 min for the films with 10 wt% ity of samples was weakened. When the GA dosage was more than
and 40 wt% HTCC, respectively. And equilibrium state of swelling 0.1 wt%, the swelling rate was higher than that for the samples
was achieved within 100 min for the film with 10 wt% HTCC while crosslinked with 0.045 wt% GA. However, the swelling rate and the
more than 250 min was required for the film with 40 wt% HTCC. time reached swelling equilibrium of different films have no much
ESD also increased with the HTCC content. When the ratio of difference. But as a whole, the effect of GA content on the swelling
HTCC/PVA/GA was 60/40/2 (wt), ESD of the blend films reached kinetics of films was not so obvious compared to the content of
212%. A higher ESD and shorter response time were observed com- HTCC.

Fig. 4. The swelling kinetics (a) and EDS (b) of PVA–HTCC blend films with different GA dosages in buffer solutions (pH = 7.4). (GA content was percentage of the total weight
of PVA and HTCC.)
 Q. Yu et al. / Carbohydrate Polymers 84 (2011) 465–470 469

Fig. 5. Gel content of films with different HTCC–PVA compositions and 2 wt% of GA (a) and different dosages of GA while HTCC–PVA composition was fixed to be 10/90 (b).

3.3. Gel content of the cross-linked films crosslinking degree of HTCC was low and its effect on the crosslink-
ing of PVA was not clear.
Gel content is one important parameter for characterizing the When the composition of HTCC–PVA was fixed, the gel content
crosslinking degree of polymer. Fig. 5 displays the gel content increased with the increase of GA dosage, especially in the range
of different blend films. The gel contents of films with different of GA dosage of 0.045–1.0 wt% (Fig. 5b). This variation tendency
HTCC–PVA proportions (2 wt% GA) are showed in Fig. 5a (curve a). became unobvious with further increasing of GA dosage. When the
The gel content of the blend films decreased when the HTCC con- crosslinking agent content was low, the crosslinking degree was
tent increased. Due to most of the hydrogen atoms of –NH2 on HTCC also low, and the molecular chains were in a coiled state which did
being replaced, and the reactivity of hydroxyl on HTCC was lower not form a fixed passage, thus reducing the liquid absorption rate
than that of PVA because of steric effects, and the molecular chains and prolonged the time of reaching the swelling equilibrium. With
of HTCC hindered the crosslinking of the nearby molecular chains increasing GA dosage, the crosslinking degree of film increased,
of PVA, thus the overall crosslinking degree of films decreased. As and the crosslinked networks took a basic structure which could
previously mentioned when swollen, the non-crosslinked molecu- form a fixed imbibitions’ passage. Therefore, as shown in Fig. 4,
lar chains in the coiled state hindered the inhalation of liquid to a the swelling rate of blend films increased and samples reached the
certain extent, and stretching process of HTCC molecular chains swelling equilibrium. But the difference in the swelling kinetics
prolonged the time reached equilibrium swelling. These results of the blend films was not significant for the blends while the GA
coincided with the swelling kinetics of blend films (Fig. 3). dosage was over 0.1 wt%.
Considering the higher crosslinking reactivity of PVA compared
with HTCC, we first assumed that only PVA was crosslinked by GA. 3.4. The antibacterial activity of blend films
In this case the residual gel after extracted was the crosslinked PVA
networks, and then the theoretical gel content of PVA could be Based on the QB/T 2591:2003 the antibacterial efficacies of the
calculated followed formula (4) (where M1 should be the weight films were evaluated. Table 1 shows the results of antibacterial
of PVA in the films before extracted). Based on this assumption efficacies against S. aureus and E. coli for the samples. As can be
the calculated gel contents for the blends with different HTCC/PVA seen, pure PVA has no antibacterial activity, and the HTCC–PVA
compositions were plotted as curve b in Fig. 5a. The gel content blend film shows a strong antibacterial activity against both of
of PVA was up to 63.3% when the content of HTCC was 40 wt%, S. aureus and E. coli. After crosslinked, the antibacterial efficacy
which was even higher than that of the crosslinked pure PVA (61%). of blend film was slightly weakened. This is attributed to the
The inconsistency indicates that the assumption was unreasonable, ammonium group with strong antibacterial activity, which had
and HTCC molecules in the blends were surely crosslinked by GA not been substituted fully by quaternary ammonium salt groups,
at the same time. When the content of HTCC was low, the mea- reacted with GA (Rosa, Laranjeira, Riela, & Fávere, 2008). And
sured gel content of blend films and calculated gel content of PVA this experiment provided an evidence for that the HTCC in the
were decreased substantially by the addition of HTCC, which can blend was crosslinked by GA. However, the crosslinked blend
be attributed to the high DS of HTCC and entanglements between films still showed a high antibacterial activity. The reactivity of N-
molecular chains of PVA and HTCC. The gel content of PVA might trimethylated quaternary ammonium salt groups in HTTCC with
be lower when the content of HTCC was higher only if PVA was GA was lower than –NH2 due to steric effect, and much lower
crosslinked by GA. However, when the content of HTCC was up than hydroxyl group in PVA. Thus much of groups with strong
to 30 wt%, the gel content of PVA increased in contrast. This indi- bacterial activity in HTCC had not reacted with aldehyde groups
cated that when the HTCC content was high, a portion was involved of GA and showed a high antibacterial efficacy. The high antibac-
in crosslinks which resulted in an increase in gel content. But the terial efficacy and its controllability of the crosslinked PVA–HTCC

Table 1
The antibacterial activity of different films.

Samples S. aureus E. coli

Bacterial numbers (cfu/plate) Antibacterial rate (%) Bacterial numbers (cfu/plate) Antibacterial rate (%)

Pure PVA 2.80 × 105 26.32 3.10 × 105 3.13

PVA/HTCC = 90/10 (wt) 2.00 × 101 99.99 4.20 × 101 99.99
PVA/HTCC/GA = 90/10/2 (wt) 1.10 × 103 99.71 3.50 × 103 98.91
470 Q. Yu et al. / Carbohydrate Polymers 84 (2011) 465–470

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the action ofchitosan-N-2-hydroxypropyl trimethylammoniumchloride on the
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SanlI, O., Ay, N., & IsIklan, N. (2007). Release characteristics of diclofenac
Acknowledgements sodium from poly(vinyl alcohol)/sodium alginate and poly(vinyl alcohol)-
grafted-poly(acrylamide)/sodium alginate blend beads. European Journal of
Pharmaceutics and Biopharmaceutics, 65(2), 204–214.
This work was sponsored by Scientific Research Foundation Shen, J. N., Ruan, H. M., & Ga, C. J. (2009). Preparation and characterization of
for the Returned Overseas Chinese Scholars, State Education Min- CMCS/PVA blend membranes and its sorption and pervaporation performance
istry of China. The authors would like to thank Professor Teruo (I). Journal of Applied Polymer Science, 114(6), 3369–3378.
Vallapa, N., Wiarachai, O., Thongchul, N., Pan, J., Tangpasuthadol, V., Kiatkamjorn-
Nakashima in Kinki University (Japan) for his kind help and advice wong, S., et al. (2011). Enhancing antibacterial activity of chitosan surface by
in measurement and evaluation of antibacterial activity of the sam- heterogeneous quaternization. Carbohydrate Polymers, 83(2), 868–875.
ples. Wang, T., Turhan, M., & Gunasekaran, S. (2004). Selected properties of pH-sensitive,
biodegradable chitosan–poly(vinyl alcohol) hydrogel. Polymer International,
53(7), 911–918.
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