Research Article

Received: 16 July 2010 Revised: 28 September 2010 Accepted: 22 October 2010 Published online in Wiley Online Library: 2 February 2011

(wileyonlinelibrary.com) DOI 10.1002/pi.3021

Effects of starch gelatinization and oxidation

on the rheological behavior of chitosan/starch
blends
Marilia M Horn, Virginia CA Martins and Ana MG Plepis∗

Abstract
Chitosan/starch blends represent an interesting alternative for the preparation of biocompatible drug delivery systems, packing
materials and edible films. This paper reports on the effects of starch gelatinization and oxidation on the rheological behavior of
chitosan/starch blends. The results show that the modifications in the starch structure cause changes in G (storage modulus) and
G (loss modulus) as a function of frequency. For chitosan/starch, G is higher than G , showing a viscous behavior. However, for
chitosan/gelatinized starch and chitosan/oxidized starch, an increase in the angular frequency promotes a modulus crossover
at ω = 0.02 and 0.04 rad s−1 , respectively. The viscosity curves as a function of shear rate show that both modifications cause
an increase in viscosity, and all blends show a non-Newtonian behavior.

c 2011 Society of Chemical Industry

Keywords: chitosan; starch; rheology; oxidation

INTRODUCTION attempt to further understand the relationship between the struc-

Starch is a biodegradable polymer with excellent biocompat-
ibility and non-toxicity, and has found various uses because
of its properties such as film-forming ability suitable for the
food industry1 and biomedical applications.2 Chitosan is ob-
tained from N-deacetylation of chitin, and both polysaccharides
are copolymers of β-(1 → 4)-linked N-acetyl-D-glucosamine and
D-glucosamine units.3 Chitosan shows excellent biological proper-
ties, such as biocompatibility, biodegradability and lack of toxicity,
being favorable for a large variety of industrial and biomedical
applications.4
Starch, which is a basic food product, is also widely used
in adhesives, packaging and the pharmaceutical industry when
functionally modified. In order to withstand modern processing
and storage conditions as well as to provide special functionality
to end products, native starch can be chemically modified.5
When starch powders are mixed with water and heated at
or above the gelatinization temperature, the granules absorb
large quantities of water and form a viscous paste.6 Dialdehyde
starch, which has considerable further industrial potential,5
is a polymeric aldehyde obtained by the reaction of native
starch with periodic acid.7 Dialdehyde starch (Fig. 1) not only is
biocompatible and biodegradable, but also has greater chemical
activity than starch, as it can react with amine groups of
chitosan. The resulting chitosan/starch blends are widely used
in medicine.8 – 10
The rheological behavior of chitosan/starch blends can be
changed by chemical modification of the starch structure. In
the study reported here, two experiments were performed to an-
alyze these modifications: (i) investigation of the effect of starch
gelatinization, which is characterized by the disorganization of
crystalline granule arrangement and (ii) oxidation with the forma-
920
ture and properties of chitosan/starch after starch modifications.
MATERIALS AND METHODS
Materials
Chitosan (degree of acetylation of 16%) was obtained in our
laboratory as previously described,11 based on the method
of Kurita et al.12 A 1 wt% chitosan solution was prepared by
dissolution in 1 wt% acetic acid.
Starch powder (Sigma-Aldrich; 73% amylopectin/23% amylose)
and 50 mL of deionized water were mixed with mechanical stirring
and gelatinized at 90 ◦ C for 30 min, and then cooled to room
temperature, forming a homogeneous solution.13 An aqueous
solution of 2% (w/w) of corn starch was used in the preparation of
blends.
Starch (1 g in 30 mL water) was oxidized with a 5 wt% periodic
acid (H5 IO6 ) solution for 24 h at room temperature under stirring.
The resulting products were dialyzed against distilled water for
72 h to remove the low-molecular-weight products,7 and then
lyophilized. Structural analysis of the oxidized starch was carried
out using Fourier transform infrared (FTIR) spectrophotometry,
which showed an additional band at 1735 cm−1 , confirming that
dialdehyde starch had been prepared successfully.7
∗ Correspondence to: Ana MG Plepis, S Carlos Chemical Institute, University of
São Paulo, USP, Av. Trab. São-carlense, 400, CP 780, CEP 13560-970, São Carlos,
SP, Brazil. E-mail: amplepis@iqsc.usp.br
S Carlos Chemical Institute, University of São Paulo, USP, Av. Trab. São-carlense,

tion of dialdehyde starch. Rheological studies were performed in an 400, CP 780, CEP 13560-970, São Carlos, SP, Brazil

Polym Int 2011; 60: 920–923 www.soci.org

c 2011 Society of Chemical Industry
Effect of starch modification on starch blend rheology
Figure 1. Oxidation of starch to yield dialdehyde starch.
Blend preparation
Chitosan/starch blends were prepared by adding chitosan (1
wt%) to starch (2 wt%) in a 1 : 2 ratio under stirring for 30 min
at 25 ◦ C. The blends were designated as chitosan/starch (CS),
chitosan/gelatinized starch (CSGE) and chitosan/oxidized starch
(CSOX). At the end of the preparation, the blends were immediately
transferred to the rheometer plate for measurement of rheological
properties.
FTIR characterization
FTIR analysis was performed using films obtained by casting the
blends in silicon molds and drying at room temperature. FTIR
spectra were obtained using a Bomem Michelson Series in the
range 400–4000 cm−1 with a resolution of 4 cm−1 .
Rheological characterization
The rheological properties of the blend solutions were investigated
using a stress-controlled rheometer (AR-1000N, TA Instruments),
fitted with a stainless steel cone/plate geometry (30◦ angle, 60 mm
cone diameter) with a gap of 15 µm. The viscoelastic region was
investigated with stress sweeps between 0.01 and 100 Pa with
constant frequency (1.0 Hz) and temperature (25 ◦ C) to obtain
the storage modulus (G ) and loss modulus (G ) as a function
of deformation. Frequency sweeps were performed from 0.1
to 200 rad s−1 at 25 ◦ C and a constant strain of 10%. Dynamic
temperature sweep tests were conducted after equilibration at
the initial temperature and heating from 25 to 75 ◦ C at a rate of
5 ◦ C min−1 with constant frequency (1.0 Hz) and strain (10%).
RESULTS AND DISCUSSION
In order to investigate the chitosan/starch interactions based
on starch modifications, FTIR spectra (Fig. 2) were obtained
for CS, CSGE and CSOX. The FTIR spectra of CS and CSGE
have the characteristic absorption bands of chitosan and starch
without any additional bands, suggesting that the interactions
between polysaccharides are purely electrostatic. For chitosan
the characteristic bands are: 1560 cm−1 (amide II); 1323 cm−1
(–CO–N–group); 3450 cm−1 (O–H stretching). For starch the
characteristic absorption bands are at 1080 and 1157 cm−1 related
to C–O bond stretching of the C–O–H group. In the spectrum of
CSOX, an additional peak is observed at 1650 cm−1 . As suggested
by Tang et al.,9 this band is due to the formation of a Schiff base
between amino groups of chitosan and dialdehyde groups of
oxidized starch.
Rheological studies are useful for understanding the chi-
tosan/starch blend characteristics and consequently the possible
applications of the blends. Initially, the linear viscoelastic region
was determined with a stress sweep between 0.01 and 100 Pa at
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c 2011 Society of Chemical Industry
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Figure 2. FTIR spectra: (a) CSOX; (b) CSGE; (c) CS.
a constant frequency of 1.0 Hz. All the subsequent measurements
were conducted within the linear viscoelastic region, where the
dynamic elastic modulus (G ) and viscous modulus (G ) are inde-
pendent of the strain amplitude. The strain value selected for the
subsequent measurements was 10%.
The rheological behavior of starch before and after modification
(gelatinization and oxidation) was investigated in order to compare
the behavior before and after addition of chitosan. Figure 3 shows
the angular frequency (ω) dependence of G and G of starch before
addition of chitosan. The curves show that non-modified starch
(S) and gelatinized starch (SGE) have similar behavior, whereas for
oxidized starch (SOX) a higher modulus is observed. This suggests
that oxidization affects significantly the rheological behavior.
In all tests (oscillatory, frequency and temperature) the curves
obtained show that chitosan addition promotes an increase in
G and G values (Table 1). In addition, gelatinized and oxidized
starches have higher G and G than starch without modification.
Figure 4 shows the behavior of G and G as a function of
temperature after chitosan addition. For SOX the modulus is
almost constant, whereas for chitosan an increase in the modulus
is observed as temperature increases. For the CSOX blend there is
a greater increase in the modulus suggesting network formation
through interactions between chitosan and oxidized starch.
The angular frequency (ω) dependence of the viscoelastic
properties of the blends is shown in Fig. 5. An increase in ω causes
a significant increase in G and G . For the CS blend, G is higher
than G , indicating that the blend is predominantly non-elastic and
its rheological behavior is typical of a ‘weak gel’. However, for CSGE
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and CSOX blends in the frequency range considered a crossover
wileyonlinelibrary.com/journal/pi
 www.soci.org MM Horn, VCA Martins, AMG Plepis

Figure 3. Moduli G and G as a function of angular frequency. S: G (
), G Figure 5. Moduli G and G as a function of ω for corn starch/chitosan
(); SGE: G (•), G (◦); SOX: G (), G (). blends. CS: G (
), G (); CSGE: G (•), G (◦); CSOX: G (), G ().

Table 1. G and G values for starch and blends

Oscillatory Temperature
tests Frequency tests tests

G (Pa) G (Pa) G (Pa) G (Pa) G (Pa) G (Pa)

S 0.63 0.92 5.29 × 10−5 1.32 × 10−3 0.18 0.10

CS 0.36 1.70 4.12 × 10−3 0.04 0.27 1.63
SEG 6.31 4.01 6.54 × 10−4 1.05 × 10−3 0.42 0.32
CSGE 12.02 9.36 1.29 1.64 71.26 29.43
SOX 11.46 8.89 0.83 1.35 77.83 8.97
CSOX 74.87 13.50 72.25 3.90 93.19 30.96

Figure 6. Strain as function of η∗ for corn starch/chitosan blends at 25 ◦ C:

CS (
); CSGE (•); CSOX ().

Figure 7 shows the temperature dependence of G and G for

all blends. For the CS blend, the curve shows that with an increase
of temperature, a crossover of the moduli occurs (at 66.7 ◦ C) and
G then becomes higher than G , thus indicating that an elastic
gel network has been formed. For the CSGE and CSOX blends
the sol–gel transformation does not occur with an increase of
temperature.
The effect of temperature on apparent viscosity at a specified
shear rate can be described by an Arrhenius relationship:


Figure 4. Moduli G and G as a function of temperature. Chitosan: G (
), Ea
G (); SOX: G (•), G (◦); CSOX: G (), G (). η = A exp (1)
RT

where Ea is the activation energy for viscous flow and A is a constant.

occurs at ω = 0.02 and 0.04 rad s−1 , respectively, suggesting the
occurrence of a sol–gel process.
Figure 6 shows the dependence of complex viscosity (η∗ ) on
strain (%). The variation of η∗ according to the starch chemical
modification can be explained by the fact that for CSGE and
CSOX the interaction between chitosan and starch is stronger due
the increased interconnected network extension. In all the cases,
η∗ decreases with increasing strain, indicating a shear-thinning
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Values of Ea for the viscous behavior of corn starch/chitosan blends
were determined from the slopes of plots of ln η versus 1/T (Fig. 8).
In the range between 25 and 75 ◦ C, for CSGE and CSOX blends, Ea
values are −0.47 and −0.97 kJ mol−1 , respectively, i.e. for CSGE Ea
is twice that for CSOX. For the CS blend the curve shows a quite
different behavior, with two distinct slopes and with calculated Ea
values of −9.63 kJ mol−1 (25–50 ◦ C) and 0.20 kJ mol−1 (50–75 ◦ C).
Starch modification affects significantly the rheological be-

behavior. havior of the gels. The gelatinization is characterized by the

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c 2011 Society of Chemical Industry Polym Int 2011; 60: 920–923
Effect of starch modification on starch blend rheology
Figure 7. Moduli G and G as a function of temperature for corn
starch/chitosan blends. CS: G (
), G (); CSGE: G (•), G (◦); CSOX:
G (), G ().
Figure 8. Viscosity dependence on temperature for corn starch/chitosan
blends: CS (
); CSGE (•); CSOX ().
disorganization of crystalline granule arrangement in excess wa-
ter, the presence of which promotes the breaking down of the
intermolecular bonds of starch molecules. This allows an increase
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c 2011 Society of Chemical Industry
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in hydrogen bond interactions between starch hydroxyl groups
and chitosan amino groups. The dialdehyde groups formed after
starch oxidation interact with amino groups of chitosan and this
interaction is stronger than the previous one since the moduli are
higher for all tests performed.
CONCLUSIONS
A three-dimensional network is obtained when starch molecules
are changed by gelatinization and oxidation treatments. Both
modifications probably promote an increase in starch/chitosan
interactions as well as an increase in solvation. The CS blend
shows a sol–gel transition at 66.7 ◦ C, and its rheological behavior
is typical of a ‘weak gel’. The calculated activation energy shows
that, for CSGE, Ea is twice as high as that for CSOX, suggesting that
interactions are stronger when gelatinized starch is used.
ACKNOWLEDGEMENT
MMH gratefully acknowledges the financial support of Conselho
Nacional de Pesquisa (CNPq).
REFERENCES
1 Arvanitoyannis I, Nakayama A and Aiba A, Carbohydr Polym 36:105
(1998).
2 Wang Q, Zhang N, Hu X, Yang J and Du Y, Eur J Pharm Biopharm 66:398
(2007).
3 Rinaudo M, Polym Int 57:397 (2008).
4 Moura MJ, Figueiredo MM and Gil MH, Biomacromolecules 8:3823
(2007).
5 Tomasik P and Schilling CH, Adv Carbohydr Chem Biochem 59:175
(2004).
6 Wilhelm HM, Sierakowski MR, Reicher F, Wypych F and Souza GP,
Polym Int 54:814 (2005).
7 Hoffmann B, Volkmer E, Kokott A, Weber M, Hamisch S, Schieker M,
et al, J Mater Chem 17:4028 (2007).
8 Para A and Karolczyk-Kostuch S, Carbohydr Polym 50:151 (2002).
9 Tang R, Du Y and Fan L, J Polym Sci Polym Phys 41:993 (2003).
10 Yu D, Xiao S, Tong C, Chen L and Liu X, Chin Sci Bull 52:2913 (2007).
11 Horn MM, Martins VCA and Plepis AMG, Carbohydr Polym 77:239
(2009).
12 Kurita K, Tomita K, Tada T, Ishii S, Nishimura S and Shimoda K, J Polym
Sci Polym Chem 31:485 (1993).
13 Liu F, Qin B, He L and Song R, Carbohydr Polym 78:146 (2009).
923
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