Polymer Degradation and Stability 76 (2002) 211218

www.elsevier.com/locate/polydegstab

Eect of hydrogen peroxide treatment on the molecular

weight and structure of chitosan
C.Q. Qina,b, Y.M. Dua,*, L. Xiaoa
a
Department of Environmental Science, Wuhan University, Wuhan 430072, China
b
Department of Chemistry, Xiaogan University, Xiaogan 432100, China

Received 8 October 2001; received in revised form 8 November 2001; accepted 16 November 2001

Abstract
The degradation of chitosan by hydrogen peroxide was studied. The degradation was monitored by gel permeation chromato-
graphy (GPC). The molecular weight distribution of partially degraded products from homogeneous reaction displayed a single-
modal curve whereas that from heterogeneous reaction was bimodal. The molecular weight (Mw) decreased as the temperature, the
time and/or hydrogen peroxide concentration increased. The dissolution of chitosan (pH 5.5) in minimum hydrochloride enhanced
its degradation, but excessive hydrogen ion potentially inhibited the degradation. The formation of carboxyl group and deamina-
tion in the products indicated that the decrease of Mw was accompanied by structure changes. The degraded chitosans in Mw range
from 51
103 to 1.2
103 were characterized by elemental analysis, X-ray diraction, thermogravimetric analysis (TGA) and dif-
ferential thermal analysis (DTA), Fourier transform infrared (FTIR), carbon-13 nuclear magnetic resonance spectroscopy (13C-
NMR). There was no signicant chemical change in the backbone of chitosan with Mw of 51
103. But degraded chitosan with Mw
of 3.5
103 had 1.71 mmol/g carboxyl groups and lost about 15% of amino groups. Further degradation led to more ring-opening
oxidation of degraded products, the formation of carboxyl groups and faster deamination. The degraded chitosan with Mw of
1.2
103 had 2.86 mmol/g carboxyl groups and lost more than 40% of amino groups. # 2002 Elsevier Science Ltd. All rights
reserved.
Keywords: Chitosan; Degradation; Hydrogen peroxide

1. Introduction available and environmentally friendly. Although the

Chitin, poly-b-(1!4)-linked-N-acetyl-d-glucosamine,
is one of the most abundant, easily obtained, and
renewable natural polymers, second only to cellulose. It
is commonly found in the exoskeletons of crustaceans
and in cell walls of fungi, insects and yeast [1]. Every year
approximately 100 billion tons of chitin is produced on
the earth. Chitosan, the deacetylated derivative of chitin,
is one of the nontoxic and biodegradable carbohydrate
polymers, and has received much attention as a functional
biopolymer for diverse applications from pharmaceu-
ticals to commodity chemicals [2,3]. These functions
undoubtedly depend upon not only their chemical
structure but also the molecular size [4].
Hydrogen peroxide has long been used in the treat-
ment of polysaccharides such as cellulose [5], starch [6]
and hemicellulose [7] because it is easy to handle, easily
treatment of chitosan by H2O2 as a method for the pre-
paration of chitosan with low molecular weight was
reported [810], there are few papers on the relation
between the molecular weight and the structure of the
obtained products in detail. An understanding of chemical
structure and molecular weight of resulting chitosan is
essential for better application. This work is concerned
with the degradation of chitosan using aqueous H2O2.
Factors aecting the reaction are studied. The products
with dierent molecular weights were comparatively
investigated by GPC, FTIR, 13C-NMR,TGA/DTA
and elemental analysis as well as chemical analyses.
2. Experimental
2.1. Materials

* Corresponding author. Fax: +86-27-8768-6402. Chitosan (CS-0) from shrimp shell, whose degree of
E-mail address: duyumin@whu.edu.cn (Y.M. Du). deacetylation was 90.5%, was purchased from Yuhuan
0141-3910/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S0141-3910(02)00016-2
212 C.Q. Qin et al. / Polymer Degradation and Stability 76 (2002) 211218
Biochemical Co. (Zhejiang, China), and was used after
passage through a 200 mesh sieve. All other chemicals
were of reagent grade.
2.2. Characterizations
The number average molecular weight (Mn) and
weight average molecular weights (Mw) were measured
by gel permeation chromatography (GPC). The GPC
system was a TSP P100 instrument. Two columns in ser-
ies (TSK G5000-PW and TSK G3000-PW) were used.
The eluent was 0.2 mol l1 CH3COOH/0.1 mol l1
CH3COONa. The ow rate was maintained at 1.0 ml
min1. The temperature of the columns was maintained
at 30  C. The eluent was monitored by a RI 150 refrac-
tive index detector. The sample concentration was ca.
0.4% (w/v). The standards used to calibrate the column
were TOSOH pullulan. All data provided by the GPC
system were collected and analyzed using the Jiangshen
Workstation software package.
The elemental analyses were performed with an
Elemental Analyzer-MOD 1106 apparatus.
13
C-NMR spectra were recorded on a Varian Mercury
V
300 spectrometer. Water-soluble samples were dis-
solved in D2O and water-insoluble samples were dissolved
in D2O in the presence of CD3COOD.
IR spectra were taken on KBr pellets on a Shimadzu
FTIR-8210 spectrophotometer.
X-ray diraction patterns of the degraded chitosan
fractions were measured by a Dmax-ray diractrometer
and used a CuKa target at 40 KV and 50 mA.
TGA and DTA of sample (5.3 mg) were performed by
a dierential thermal Analyzer Model WCT-1 (Beijing
Optical Instruments Factory, China) under a nitrogen
atmosphere with a ow of 30 ml/min from 25500  C at
a heating rate of 5  C/min.
2.3. Degradation of chitosan
Unless otherwise stated, the degradation was carried
out as follows: the chitosan powder was introduced into
a reactor containing liquor adjusted to the desired con-
centration of HCl. A Chitosan to liquor ratio of 1:50
was used. After the reactor was kept in a thermostatic
water bath for 2 h with stirring, hydrogen peroxide was
added. Details of the reaction conditions are given in
the text. At various intervals, 0.5 ml of the reaction
mixture was taken out. After adding sodium bisulte,
the product was analyzed by GPC.
At the end of a predetermined time, the mixture was
adjusted to pH 9.0 with dilute ammonia liquor, and
then subjected to vacuum ltration. The solid was then
washed with deionized water, and was nally collected
by drying in vacuum at 30  C. The ltrate was con-
centrated to about one-tenth with a rotary evaporator
under diminished pressure at 40  C, and a precipitate
was obtained by adding ethanol to the mixture. The
precipitate was treated with 1% ammonia solution of
ethanol (85%), and then was washed thoroughly with
ethanol. The water-soluble chitosan was collected after
drying over phosphorus pentoxide in vacuum. These
obtained products were used for the determination of
carboxyl content.
Some of the above product was dispersed in aqueous
NaOH solution of pH 12, reprecipitated with ethanol
and then washed with ethanol to obtain the chitosan
sodium salt. The dried sample was used for NMR, TG/
DTA and X-ray diraction analysis.
Some degraded chitosan was reprecipitated with eth-
anol from HCl aqueous solution, and then washed with
ethanol to obtain the chitosan hydrochloride salt. The
dried chitosan hydrochloride samples were used for FT
IR analysis.
2.4. Determination of content of carboxylic groups
The tested chitosans were the products treated with
ammonia after degradation and separated as water-
soluble and water-insoluble chitosans. The dried sample
of chitosan (0.2 g) was dissolved in VB1 ml (15 ml) of
0.1 mol l1 NaOH and was evaporated to dryness under
vacuum at 40  C. The mixture was dissolved in 10.0 ml
of 0.1 mol l1 HCl. The solution was then titrated with
0.1 mol l1 NaOH and the volume of consumed NaOH
VB2 ml was determined by the titration curve recorded
on a Delta-320-S pH meter. The content of carboxylic
group of sample was calculated by X=(VB NB
10.0
NA)/W, where NA is the HCl concentration;
VB=VB1+VB2; NB is the NaOH concentration; W is
the sample weight.
3. Results and discussion
3.1. Reduction in Mw
Samples were taken at intervals during the degradation.
Fig. 1 shows the GPC proles of chitosans degraded with
H2O2 in 0.9% HCl solution (Fig. 1a) and in distilled water
(Fig. 1b) at 60  C. The shift toward higher elution volumes
as a consequence of the degradation could be observed for
all samples. Obviously the extent of degradation
increased by prolonging the duration. These proles
give information on the degradation, indicating that the
degradation of the backbone occurred in a random
fashion. A rapid decrease in the viscosity of HCl solution
of chitosan was seen in 0.5 h. When the Mw of ethanol-
insoluble product reduced from 49.8
104 to 5
104, the
yield was more than 95%. The data also revealed that
H2O2 caused the scission of chitosan chain.
Fig. 2 shows the eect of the HCl of the oxidizing
medium on the rate of degradation, which corresponds
 C.Q. Qin et al. / Polymer Degradation and Stability 76 (2002) 211218
to the Mw of resulting chitosan. For every HCl con-
centration, the reaction was conducted with 0.75%
H2O2 at 70  C for 2 h. The rate of degradation of chit-
osan was apparently not proportional to the concentra-
tion of HCl. In 0.23% HCl solution, the mole ratio of
HCl to chitosan was 0.56 corresponding to pH 5.5, the
chitosan was more rapidly degraded and its Mw drop-
ped to 2.64
103 in 2 h. But in 9% HCl solution, the Mw
only declined to 21.2
104. In general, homogenous
reaction was more rapid than heterogeneous reaction.
Too low HCl concentration was not enough for the
dissolution of chitosan, but strong acidity inhibited the
degradation. The protonation of NH2 restrained the
degradation [11], suggesting that the reduction of Mw
came from the oxidative cleavage of main chain.
Fig. 3 shows the dependence of the extent of degra-
dation on the temperature of reaction when 0.3% H2O2
was used in all cases for 2 h. The data clearly demon-
strate that high temperature enhanced the rate of
degradation. At low temperature, the degradation in
Fig. 1. GPC proles of chitosan degraded with H2O2 in 0.9 % HCl (a)
and distilled water (b).
Fig. 2. Eect of concentration of HCl solution on the Mw of degra-
ded chitosan.
213
distilled water was slightly faster than in 0.45% HCl
solution, indicating that the H+ inhibited the oxidative
degradation of chitosan. But at temperature higher than
40  C, the degradation in 0.45% HCl solution increased
faster than in distilled water. Higher temperature increased
the deprotonation of NH+ 3 and the concentration of
oxidizing species. Nevertheless, when mole ratio of HCl to
NH2 is much more than 1, the degradation was inhibited
even at high temperatures, such as 70  C in Fig. 2.
Fig. 4 shows the eect of concentration of H2O2 on
the extent of degradation at 70  C for 2 h. A high con-
centration of H2O2 accelerated the cleavage of glycosi-
dic bond. Chitosan was degraded into small molecules
with Mw lower than 4
103 in distilled water, and was
water-soluble. When the H2O2 concentration was more
than 1.2% H2O2, the later stage of degradation in dis-
tilled water was homogenous as in HCl solution. For
the same reason of protonation, the Mw of resulting
chitosan degraded in HCl solution was higher than in
distilled water.
Fig. 3. Dependence of Mw of degraded chitosan on the temperature

in 0.45% HCl ( ) and distilled water (&).
Fig. 4. Eect of concentration of H2O2 on the Mw of degraded chit-

osan in 0.45% HCl ( ) and distilled water (&).
214 C.Q. Qin et al. / Polymer Degradation and Stability 76 (2002) 211218

3.2. Molecular weight distribution Table 1

Properties of degraded chitosan
Elution proles of a single-modal distribution were Sample Mw
103 PD C% N% N/C COOH
observed for chitosan degraded with H2O2 in dilute acid (mmol/g)
solution (Fig. 1a). Chitosan could dissolve in acid solution,
CS-0 498 5.13 42.93 7.78 0.181 0
so the degradation in acid solution was homogeneous. CW-S1 51 2.51 43.30 7.84 0.181 0.03
In distilled water, the partially degraded samples dis- CW-S2 12 1.73 42.82 7.18 0.168 0.30
played bimodal molecular weight distribution (Fig. 1b). CW-L3 3.5 1.29 39.70 6.61 0.166 1.71
Chitosan with high molecular weight did not dissolve in CW-L4 1.2 1.17 32.67 4.46 0.147 2.86
distilled water, so the degradation was heterogeneous. CH-S2 11 1.56 42.66 7.18 0.168 0.35
CH-L4 1.9 1.19 38.55 5.79 0.150 2.11
The elution curves of the most degraded samples shifted
closer to the second peak (dissolved fraction) and trans-
formed to a single peak. At the same time, the dissolved
molecules proceeded with the homogeneous degradation. 19.8 , which coincided with the pattern of the L-2 poly-
Fig. 5 shows the relation between the Mw and poly- morph of shrimp chitosan reported previously [12,13].
dispersity index PD (Mw/Mn). For heterogeneous For CW-S1 the pattern had three main peaks. A peak at
degradation, the polydispersity increased at the earlier 2
=22 rose and the peak at 2y=10.4 also increased.
stage, suggesting that the degradation occurred rstly Such a pattern characterized a chitosan polymorph,
on the surface. which is referred to as the tendon hydrate polymorph
The partially degraded chitosan was separated into [14]. The rise in crystallinity of CW-S1 showed the pre-
two fractions according to their water-solubility. The ferential degradation of amorphous parts of chitosan,
Mw and PD of the main fraction measured by GPC are whereas the crystalline are ones more or less preserved.
listed in Table 1. CW series of samples were pre- But for CW-S2 the peaks at 2
=10.4 decreased, and
pared from degradation in distilled water and CH the peaks at 2
=22 disappeared. For CW-L3, only a
series from degradation in 0.45% HCl solution. CS-0 is decreased wide peak at 2
=19.8 was left. The crystal-
the initial chitosan; CW-S1, CW-S2 and CH-S2 are the linity was in the order CS-0 < CW-S1> CW-S2 > CW-
water-insoluble fraction of degraded chitosan; CW-L3, L3. The water-soluble fraction became amorphous [15].
CW-L4 and CH-L2 are the water-soluble fraction. Thus, it was assumed that the degradation rst took
place preferentially in the amorphous region and then
3.3. X-ray analysis proceeded very moderately from the edge to the inside
of the crystalline. That was to say, the chitosan in
Fig. 6 shows the X-ray diraction patterns of main amorphous region was rst degraded to water-soluble
fraction of chitosan resulting from the degradation in molecules, and dissolved in the water. With deeper
distilled water. These samples had been treated with
dilute NaOH solution.
The WAXD pattern of the initial chitosan CS-0
exhibited its two characteristic peaks at 2
=10.4 and

Fig. 5. Plot of polydispersity versus Mw of degraded chitosan in Fig. 6. X-ray diraction patterns of initial chitosan and degraded

0.45% HCl ( ) and distilled water (&). chitosans.
 C.Q. Qin et al. / Polymer Degradation and Stability 76 (2002) 211218
degradation, the crystalline structure was destroyed and
the crystallinity decreased.
3.4. Thermal analysis
Fig. 7 shows the TG/DTG and DTA curves of CS-0,
CW-S1, CW-S2 and CW-L3. The greatest weight loss
point of CS-0 was at 298  C, and the chitosan showed
an exothermic peak at around 300  C due to the degra-
dation of the main chain [16]. The lowest decomposition
temperature was in the order CS-0, CW-S1> CW-S2
> CW-L3. The DTG curve of CW-S1 resembled the CS-0
curve. Although the temperature of maximum active pyr-
olysis of CW-S1 was slightly higher than that of CS-0, the
peak decreased. Curves of CW-S2 and CW-L3 were
dierent from CS-0. CW-L3 showed the least thermal
stability of the samples studied, starting to decompose
from 140  C, and there was no obvious peak of the great-
est weight loss. Reasons for this could be the dierence in
their structures and molecular weights [17]. When chit-
osan was treated with H2O2, the thermostability
decreased. The degradation with H2O2 led to the disin-
tegration of intramolecular interaction and partial
breaking of the molecular structure. The change in DTA
curves was in agreement with the change in DTG curves.
These data coincided well with the X-ray analysis.
3.5. Chemical and elemental analysis
The pH of the solution gradually decreased during the
reaction, suggesting that chitosan was oxidized to pro-
duce carboxylic acid. Addition of NaOH to the reaction
solution produced ammonia gas, indicating that the
reduction of Mw was accompanied by deamination.
The data from elemental analysis of degraded chit-
osan samples treated with NaOH are listed in Table 1.
The mass ratio of N/C is in the order of CS-0 > CW-
Fig. 7. TG and DTG (a) and DTA (b) of initial chitosan and degraded chitosans.
215
S1 > CW-S2> CW-L3> CW-L4, and CS-0 > CH-S2 >
CH-L4. Nitrogen and carbon contents of CW-S1 were
almost the same as the CS-0, but the mass ratio of N/C
slightly decreased. With further degradation with H2O2,
nitrogen and carbon contents obviously decreased, sug-
gesting increased oxygen content; the mass ratio of N/C
decreased, conrming the loss of nitrogen in the
degradation.
The samples for the carboxylic acid test were the
samples that were treated with ammonia. The content of
new carboxyl group in the resulting chitosan is also lis-
ted in Table 1. The data show that the content of car-
boxylic groups increased with decreasing Mw of the
resulting chitosan. CW-S1 had only 0.03 mmol/g car-
boxyl group. But CW-L4 had 2.86 mmol/g, suggesting
that not only the terminal units but also the middle
residues were broken by partial ring-opening oxidation.
The results indicated that treatment with H2O2 not only
reduced Mw but also modied the chemical structure of
original chitosan.
3.6. FTIR spectra
FT-IR spectroscopy has been shown to be a powerful
tool for the study of the physicochemical properties of
polysaccharides. The spectra of hydrochloride salts of
the degraded fractions are shown in Fig. 8. The spectral
proles and relative intensities of the bonds exhibited
correlation with Mw of chitosan. As can be seen, the
spectral proles of CW-S2 and CH-S2 are similar to
that of CS-0 though some dierences exist, indicating
that the main macromolecular structure of resulting
chitosan with Mw > 10
103 still remained. For CW-L3,
the intensity of the NH+3  related band at 1 520 cm
1
is
much lower than that of CS-0. For CW-L4, not only the
intensity of the NH+ 3  related band decreases, but also
the new band at 1735 cm1 assigned to the carboxylic
216 C.Q. Qin et al. / Polymer Degradation and Stability 76 (2002) 211218
Fig. 8. FTIR spectra of hydrochloride of initial chitosan and result-
ing chitosans.
group obviously is seen [18]. The results also give us the
following important information. The reaction was mainly
the oxidized cleavage of b-glycosidic linkages, while the
NH2 was removed and the COOH was formed. Thus, the
structure of reducing end residue changed.
13
3.7. C-NMR spectra
To further conrm the structural changes of the chit-
osan during the H2O2 treatment process, the isolated
chitosans were analyzed by 13C-NMR spectroscopy in
D2O or CD3COOD-D2O. The 13C-NMR spectra of the
chitosans are shown in Fig. 9. The main units of CW-S2
and CH-S2 are obviously characterized by the signals at
56.1, 60.1, 70.4, 75.1, 77.2 and 97.9 ppm, which are
attributed to C-2, C-6, C-3, C-5, C-4 and C-1 respec-
tively. The assignments of signals are based on data found
in the literature [1921]. The spectra of CW-S2 and CH-S2
are almost the same as the initial chitosan (spectrum not
shown) and the reported data. The similar spectra
demonstrate that the chemical structure of resulting chit-
osan with Mw> 10
103 was not changed to any notice-
able extent. For CW-L3 and CH-L4, dierences in the
spectra from that of CW-S2 and CH-S2 are seen. Weak
signals assigned to carboxylic carbons are observed in
downeld shifts from 160185 ppm [22]. The broadening
Fig. 9. 13C-NMR spectra of degraded chitosans. CW-S2 and CH-S2
in CD3COODD2O; others in D2O.
and splitting of C-1, C-4 and C-3 signals may be due to
change of surroundings. These signals show that
hydrogen peroxide treatment aected the molecular
structure. But signal of C-6 does not weaken, suggesting
the primary hydroxyl group of C-6 was not pre-
dominantly oxidized. For CW-L4, the more compli-
cated signals make interpretation of this spectrum more
dicult. Several signals appear in upeld shift range 30
45 ppm, indicating that the formation of C-CH2C. It is
certain that the molecular structure of the CW-L4 was
severely destroyed. In addition, there are not obvious
signals in low eld of 190210 ppm, suggesting that less
carbonyl group nally existed in the resulting chitosan.
1
H-NMR analysis of the reaction mixture also indicates
no signal of aldehyde group from 8.510 ppm except
formic acid at 8.1 ppm (data not shown)
3.8. Mechanistic discussion
Hydrogen peroxide is substantially more acidic than
water, with a pKa of 11.6. The perhydroxyl anion is
instable. The decrease in stability of H2O2 is caused by
the instability of the HOO+. Heat and base will increase
the decomposition of H2O2. The perhydroxyl anion
reacts with H2O2 to form the highly reactive hydroxyl
radical (HO.)[7].
 C.Q. Qin et al. / Polymer Degradation and Stability 76 (2002) 211218
H2 O2 ! H HOO
HOO ! OH O
H2 O2 HOO ! HO
O2 
H2 O The changes such as formation of carboxyl groups and
The basic amino group can increase the instability of
H2O2 and lead to the rapid formation of HO radicals.
The presence of minute amounts of metal salts will cat-
alyze the decomposition of H2O2 and the resulting OH
radical will attack substrates. HO radical is a much
more powerful oxidant. The reactions of radicals are
thought to be not very selective [23]. Studies show that
hydroxyl radical reacts with carbohydrates exceedingly
rapidly, abstracting a C-bonded H atom according of
the general equation:
RH HO
! R
H2 O and had lost more than 40% of amino groups. The
These radicals then undergo further reactions before
ending up as products.
Like other natural polysaccharides, chitosan also
contained measurable traces of Fe (35.3 mg/kg) and Cu
(2.9 mg/kg) [24]. Therefore, even when no transition
metal was deliberately added, Fenton reactions would be
feasible. The analyses of degraded products suggested
that the degradation of chitosan was predominantly
caused by radical reactions.
Model studies on cellobiose [25] suggest that H-
abstraction from C-1, C-4 or C-5 of a sugar residue in a
(1!4)-linked polysaccharide chain leads to scission of
the glycosidic bond [24]. The acid or base catalysed
rearrangement of radical formed at C-2 resulting in the
cleavage of the glycosidic bond is also proposed [23]. H-
abstraction from C-1 to C-3 and possibly the amino
group leads to the deamination of 2-amino-2-deoxy-d-
glucose [26].
The reduction of Mw and the increase of carboxyl
group content in degraded chitosan were in close rela-
tion to the deamination, suggesting that the scission of
glycosidic bond was predominantly from H-abstraction
at C-1 and C-2 that both led to the deamination [26].
Oxidative scission produced diverse termini, which
could be further oxidized to produce carboxyl acid and
release formic acid [27]. Some splitting of C-C bonds
within sugar residues also occurred, which led to ring-
opening oxidation and formation of carboxyl groups
[28,29].
4. Conclusion
The treatments of chitosan with H2O2 led to a
decrease in the degree of polymerization, even at ambi-
ent temperature. The macromolecular chitosan degra-
ded most rapidly in the lowest acid concentration just
for the formation of chitosan solution. Higher tem-
perature and H2O2 concentration accelerated the
217
degradation. Moreover, the treatments of chitosan with
H2O2 also resulted in change in the chemical structure.
deamination increased with the decrease of Mw. Chit-
osan with Mw more than 50
103 retained almost the
backbone of macromolecular chitosan; for Mw between
50
103 and 10
103, the change was dicult to see
clearly by FTIR and 13C-NMR, but detectable by ele-
mental analysis and chemical analysis; substantial
structure changes existed in the chitosan with Mw
smaller than 3.5
103. Degraded chitosan with Mw of
3.5
103 had 1.71 mmol/g carboxyl groups and lost 15%
of amino groups. Ring-opening oxidation increased
with the further reduction of Mw; degraded chitosan
with Mw of 1.2
103 had 2.86 mmol/g carboxyl groups
modied chitosan is currently under investigation in our
laboratory as novel material for application in cosmetics,
food additives and medical aids.
Acknowledgements
The authors are grateful for the nancial support of
the National Natural Science Foundation of China and
China Capital Investment, Ltd., in Shanghai to this
research.
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