Starch/Stärke 53 (2001) 211–218 211

Daris Kuakpetoon, Characterization of Different Starches Oxidized by

Ya-Jane Wang
Hypochlorite
Department of Food The effects of starch origin (potato, corn, and rice starches) and hypochlorite level
Science, University of (NaOCl, 0 .8% and 2% w/w) on the structures and physicochemical properties of oxi-
Arkansas, Fayetteville, dized starches were investigated. Carboxyl and carbonyl group contents of oxidized
U.S.A. starches increased with increasing NaOCl level, with potato starch having the highest
and corn starch having the lowest carboxyl groups content at both NaOCl levels. Oxi-
dation generally reduced the pasting temperature and viscosity of native starches as
demonstrated by using a Rapid Visco Analyser. The peak viscosities of oxidized rice
and corn starches were higher than those of their native counterparts at 0.8% NaOCl.
The morphology of starches was not altered and X-ray diffraction patterns of all the
starches remained unchanged after oxidation. Oxidized starch batters exhibited
greater adhesions than did native starch batters, with rice starch batter exhibiting the
greatest adhesion. Carbohydrate profiles by high-performance size-exclusion chro-
matography indicated that both amylopectin and amylose were degraded during oxi-
dation. The level of oxidation was largely dependent on the degree of crystallinity of
starch and the degree of polymerization of amylose, whereas the adhesion property of
oxidized starch was mainly attributed to its granular size and shape.

Keywords: Oxidized starch; Hypochlorite; Carboxyl groups; Carbonyl groups; Adhe-

sion

1 Introduction indicate the level of oxidation, which takes place primarily

Oxidized starch is widely used in industries such as pa-
per, textile, laundry finishing, building material, and food
industries to provide surface sizing and coating property
[1]. Although the main outlets for oxidized starch are in the
paper and textile industries, its applications in the food
industry is increasing because of its low viscosity, high
at the hydroxyl groups of C-2, C-3, and C-6 positions [5].
The factors affecting hypochlorite oxidation include pH,
temperature, hypochlorite concentration, starch molecu-
lar structure, and starch origin [5]. The effects of starch
molecular structure and starch origin on oxidation are still
not well understood despite previous studies [7–11]. One

stability, clarity, film forming and binding properties. Oxi-
dized starch has been applied in foods as coating and
sealing agents in confectionery, as emulsifier [2], as
dough conditioner for bread [3], as gum arabic replacer
[4], and as binding agent in batter application.
Research Paper
study showed that rice starch consumed more hypochlo-
rite but had a lower carboxyl group content and a higher
apparent viscosity compared with corn starch in
hypochlorite-oxidized reactions, possibly because of their
differences in physical and molecular structure [12].

Oxidized starch is produced by reacting starch with a
specified amount of oxidizing reagent under controlled
temperature and pH [5]. Many oxidizing reagents such as
periodate, chromic acid, permanganate, nitrogen dioxide,
and sodium hypochlorite have been used for oxidizing
starch [6]. Among them sodium hypochlorite is the oldest
and most popular commercial oxidant [6]. Hydroxyl
groups on starch molecules are first oxidized to carbonyl
groups and then to carboxyl groups. Therefore, the num-
bers of carboxyl and carbonyl groups on oxidized starch
Correspondence: Ya-Jane Wang, Department of Food Science,
University of Arkansas, Fayetteville, AR 72704, U.S.A. Phone:
+1-501-575-3871; Fax: +1-501-575-6936; e-mail: yjwang@
comp.uark.edu,
This study was designed to investigate the effect of starch
origin and hypochlorite concentration on the physico-
chemical properties of starch. It was studied how the dif-
ferences in granular size, shape and molecular structure
among rice, corn, and potato starches affected the be-
haviors of hypochlorite-oxidized starch.
2 Materials and Methods
2.1 Materials
Three commercial starches were used in this study. Na-
tive unmodified corn starch (C*Gel), rice starch (REMY
DR), and potato starch were obtained from Cerestar USA
(Hammond, IN, USA), A&B Ingredients, Inc. (Fairfield, NJ,
USA), and Avebe America Inc. (Princeton, NJ, USA), re-

© WILEY-VCH Verlag GmbH, 69451 Weinheim, 2001 0038-9056/2001/0505-0211 $17.50+.50/0

212 Kuakpetoon, Wang
spectively. The moisture and crude protein contents of
starches were determined according to AACC Methods
44-15A, and 46–13 [13], respectively. Sodium hypochlo-
rite containing 6% active chlorine was purchased from J.
T. Baker Chemical Co. (Phillipsburg, NJ, USA). All chem-
icals were ACS grade.
2.2 Oxidation
The oxidation procedure was modified after the method of
Autio et al. [14]. A 40% starch slurry was prepared by
adding deionized water to 450 g starch (dry basis, db) to a
final weight of 1,125 g in a 2-L reaction vessel equipped
with a heating mantle. The starch slurry was maintained
at 35 °C by occasionally turning off the mantle heating
power and the pH was adjusted to 9.5 with 2 N NaOH.
Sodium hypochlorite, 60 g (0.8 g Cl/100 g starch, 0.8%
w/w) or 150 g (2 g Cl/100 g starch, 2% w/w), was slowly
added in the starch slurry in 30 min while maintaining the
pH at 9.5 with 2 N H2SO4. After the addition of NaOCl, the
pH of the slurry was maintained at 9.5 with 2 N NaOH for
an additional 50 min. The slurry was then adjusted to pH
7.0 with 2 N H2SO4, filtered through suction (Whatman fil-
ter #4), washed with deionized water and dried in an oven
at 40 °C for 48 h. In order to prevent rice starch from
swelling, Na2SO4 (35%, dry starch basis) was added to
the rice starch slurry before the reaction. This variation
was based on preliminary results. Oxidized rice starch
slurry was centrifuged (15 min at 9,800 × g)) because of
the difficulty in filtration, and the top yellowish layer was
discarded.
2.3 Carboxyl group content analysis
The carboxyl group content of oxidized starch was deter-
mined according to the modified procedure of Chatto-
padhyay et al. [4]. About 2 g of a starch sample was mixed
with 25 mL of 0.1 N HCI, and the slurry was stirred occa-
sionally for 30 min with a magnetic stirrer. The slurry was
then vacuum filtered through a 150-mL medium porosity
fritted glass funnel and washed with 400 mL of distilled
water. The starch cake was then carefully transferred to a
500-mL beaker, and the volume was adjusted to 300 mL
with distilled water. The starch slurry was heated in a boil-
ing water bath with continuous stirring for 15 min to en-
sure complete gelatinization. The hot starch dispersion
was then adjusted to 450 mL with distilled water and titrat-
ed to pH 8.3 with standardized 0.01 N NaOH. A blank test
was performed with unmodified starch.
Carboxyl group content was calculated as follows:
milliequivalents of acidity/100 g starch =
[(Sample-Blank) mL × Normality of NaOH × 100]/
Sample weight (dry basis) in g
Starch/Stärke 53 (2001) 211–218
Percentage of carboxyl content =
[milliequivalents of acidity/100 g starch] × 0.045
2.4 Carbonyl group content analysis
The carbonyl group content was determined by following
the titrimetric method of Smith [15]. Four grams of a
starch sample was suspended in 100 mL distilled water in
a 500-mL flask. The suspension was gelatinized in a boil-
ing water bath for 20 min, cooled to 40 °C, adjusted to pH
3.2 with 0.1 N HCl, and 15 mL of hydroxylamine reagent
was added. The flask was stoppered and placed in a
40 °C water bath for 4 h with slow stirring. The excess hy-
droxylamine was determined by rapidly titrating the reac-
tion mixture to pH 3.2 with standardized 0.1 N HCl. A
blank determination with only hydroxylamine reagent was
performed in the same manner. The hydroxylamine
reagent was prepared by first dissolving 25 g hydroxyl-
amine hydrochloride in 100 mL of 0.5 N NaOH before the
final volume was adjusted to 500 mL with distilled water.
Carbonyl group content was calculated as follows:
Percentage of carbonyl content =
[(Blank-Sample) mL × Acid normality × 0.028 × 100]/
Sample weight (dry basis) in g
2.5 Pasting properties of starches
The pasting properties of native and oxidized starches
(10%, w/w) were determined according to the AACC
method 61-02 [13] with a Rapid Visco Analyser (RVA-4
Series, Newport Scientific Pty, Ltd, Warriewood, NSW,
Australia).
2.6 Scanning electron microscopy (SEM)
The scanning electron micrographs were taken with a
Hitachi S-2300 scanning electron microscope (Tokyo,
Japan) at an accelerating voltage of 25 kV. Starch gran-
ules were sprinkled onto double-backed cellophane tape
attached to a stub before coating with gold-palladium.
2.7 Adhesion of starch batter
The adhesive property of starch batter was determined by
using a TA.XT2i Texture Analyzer (Texture Technologies,
Scarsdale, NY). Starch batter (45%, starch dry basis) was
prepared by adding distilled water to 81 g (db) of starch
and 0.9 g guar gum to a final weight of 180.9 g in a
250-mL beaker. Guar gum was added to prevent starch
from settling. Each starch batter was poured into six alu-
minum dishes (5 cm diameter × 2 cm height) until the top
level of the batter was 0.7 cm below the dish rim. The bat-
ter was compressed at a speed of pre-test 5.0 mm/s, test
1.0 mm/s, and post-test 5.0 mm/s to a distance of 5 mm
Starch/Stärke 53 (2001) 211–218 Characterization of Different Starches Oxidized by Hypochloride
with a cylindrical probe (2.54 cm diameter × 2.50 cm
height). The adhesion of the starch batter was defined as
the work (g · s) required to lift the probe from the starch
batter and calculated from the area under the texture pro-
file.
2.8 X-ray diffraction
The X-ray patterns of starches were obtained with a cop-
per anode X-ray tube using a Philips Analytical diffrac-
tometer (Philips, Almelo, The Netherlands). The diffrac-
tometer was operated at 27 mA and 50 kV. The scanning
region of the diffraction angle (2 θ ) was from 5° to 45° at
0.1° step size with a count time of 2 s. The starch samples
were equilibrated in a 100% RH chamber for 24 h at room
temperature.
2.9 Characterization of starch structures
The carbohydrate profiles of native and oxidized starch-
es were obtained by a high-performance size-exclusion
chromatography (HPSEC) system (Waters Corporate,
Milford, MA) according to the method of Kasemsuwan et
al. [16] with modification [17].
The chain-length distribution of amylopectin was charac-
terized by high-performance anion-exchange chromato-
graphy equipped with a pulsed amperometric detector
(HPAEC-PAD) according to the method of Kasemsuwan
et al. [16] with minor modifications. The HPAEC-PAD
(Dionex DX500) system consisted of the following com-
ponents: GP50 gradient pump, LC20-1 chromatography
organizer, ED40 electrochemical detector, 4 × 50-mm
CarboPac PA1 guard column, 4 × 250-mm CarboPac PA1
analytical column, and AS40 automated sampler. Defat-
ted starch (20 mg) was mixed with 3.2 mL deionized water
and gelatinized in a boiling water bath for 1 h. After cool-
ing to room temperature, 30 µL of isoamylase (activity
3,100 enzyme units, Hayashibara Biochemical Laborato-
ries Inc. Okayama, Japan) and 0.4 mL of acetate buffer
(pH 3.5) were added to the starch sample, and the mix-
ture was incubated at 40 °C for 48 h. The enzyme was in-
activated in a boiling water bath for 20 min, and the buffer
was removed from the starch mixture through adsorption
Tab. 1. Carboxyl and carbonyl group contents of oxidized starches.
0.8% NaOCl
Starch Carboxyl content [%] Carbonyl content [%]
Potato 0.21a1
Corn 0.05c
Rice 0.07b
1 Values in the same column followed by the same letter are not significantly different at the 95% confidence level.
213
onto IONAC mixed bed exchange resin (JT Baker) for
7 min. The mixture was filtered through a 0.5 µm filter and
placed into sample vials prior to injection.
2.10 Experimental design and statistical
analyses
A 3 × 2 completely randomized design (CRD) structure (3
starch types and 2 hypochlorite levels) was used. Each
combination was performed in duplicate. The data were
statistically analyzed by the SAS program [18]. General
linear model procedure (GLM) was conducted to identify
differences among data. All significant differences were
reported at the 95% confidence interval.
3 Results and Discussion
3.1 Carboxyl and carbonyl groups contents
The carboxyl and carbonyl groups contents of oxidized
starches are listed in Tab. 1. Both carboxyl and carbonyl
contents of oxidized starch increased as hypochlorite
concentration increased, which agree with previous re-
ports [12, 19–20]. There was no significant difference in
carbonyl content for different starches at the same
hypochlorite concentration. In contrast, carboxyl contents
varied significantly according to starch types. Potato
starch had the highest carboxyl content, whereas corn
starch had the lowest at both hypochlorite concentrations.
The present results differed from those by Hebeish and
coworkers [12], in which oxidized corn starch had a high-
er carboxyl content than oxidized rice starch. This dis-
crepancy might be ascribed to the different pHs employed
in oxidation (pH 7 versus 9.5).
In an oxidation reaction, NaOCl will first oxidize protein
before attacking hydroxyl groups on starch molecules [1,
5]. Therefore, there will be less residual NaOCl to oxidize
starch if a starch sample has a higher protein content, re-
sulting in a lower carboxyl content. Although the protein
contents in potato, corn, and rice starches were signifi-
cantly different, 0.04%, 0.33%, and 0.19%, respectively,
these differences alone cannot completely explain the dif-
ferences of these starches in carboxyl content. All oxi-
dized starches were expected to have similar increases in
2% NaOCl
Carboxyl content [%] Carbonyl content [%]
0.03a 0.39a 0.07a
0.03a 0.14c 0.06a
0.03a 0.24b 0.06a
214 Kuakpetoon, Wang Starch/Stärke 53 (2001) 211–218

carboxyl content when hypochlorite was increased from

0.8% to 2%, assuming protein had been completely oxi-
dized by 0.8% NaOCl as evidenced by the presence of
carboxyl groups. Nevertheless, the percentage increase
in carboxyl content of oxidized potato, corn, and rice
starches were 86, 180, and 243%, respectively, indicating
factors other than protein content may play more impor-
tant roles in determining oxidation level.

3.2 Pasting properties of starches

The pasting profiles of oxidized starches analyzed with a
Rapid Visco Analyser are shown in Fig. 1. The pasting
temperatures of all oxidized starches decreased as
hypochlorite concentration increased. Potato starch
showed the least change in pasting temperature before
and after oxidation compared with rice and corn starches.
Oxidized corn and rice starches exhibited higher peak vis-
cosities than their nonoxidized counterparts at 0.8% NaO-
Cl concentration. Farley and Hixon [21] also observed a
similar phenomenon during the initial phase of alkaline-
catalyzed oxidation by electrolysis. The decrease in past-
ing temperature and increase in peak viscosity suggests
that oxidized starch granules were easier to swell and
swelled to a greater extent because the association
forces between molecules in native starch were weak-
ened by electrical repulsion of carboxyl groups, and thus
more water was allowed to penetrate into the granules
[22]. Fig. 1. Rapid Visco Analyser pasting curves of unmodified
and hypochlorite-oxidized starches.
The viscosities of 2% NaOCl-oxidized starches were low-
er than those of the non-oxidized starches, which agrees
with previous reports [11–12, 23]. The decrease in viscos- shown). It was apparent that the levels of hypochlorite
ity was caused by partial cleavage of the glucosidic link- used in this study did not cause any significant changes in
ages from extensive oxidation, resulting in a decrease in starch morphology.
molecular weight of starch molecules [24]. This partially
degraded network was not resistant to shear and could
not maintain the integrity of starch granule and thereby 3.4 Adhesion of starch batter
produced a lower viscosity. The oxidized potato starch
had a lower peak viscosity than the native one at both The adhesion properties of native and hypochlorite-oxi-
NaOCl concentrations, implying that potato starch was dized starch batters are summarized in Tab. 2. Rice
more susceptible to oxidative cleavage than the other two starch batters had the greatest adhesion, whereas corn
starches as supported by its higher carboxyl contents. starch batters had the smallest at both oxidation levels.
The proposed factors that could contribute to these differ-
As the hypochlorite concentration increased, the degree ences include contact area and carboxyl group content.
of starch set-back decreased (Fig. 1). Wurzburg [5] pro- Harnby et al. [25] calculated the bond strength between
posed that retrogradation of oxidized starch paste was two dissimilar spheres and concluded that bonding force
hindered by the bulky carboxyl group on the starch mole- was dependent on particle size, shape, and surface
cule. Carbonyl groups may have a minor role in prevent- roughness, which directly relate to contact area. In gener-
ing starch from retrogradation. al, smaller, flatter, and rougher particles give rise to a
greater contact area and stronger bonding. The contact
area in this study referred to the area where hydrogen
3.3 Scanning electron microscopy
bonding occurred between starch granule and water. The
The appearance of oxidized starches resembled the ap- rice starch granule was polygonal and smaller in shape
pearance of non-oxidized starches (micrographs not with a rougher surface compared with corn and potato
Starch/Stärke 53 (2001) 211–218 Characterization of Different Starches Oxidized by Hypochloride 215

Tab. 2. Adhesion of unmodified and oxidized starch bat-

ters.
Adhesion [g · s]
Starch Unmodified 0.8% NaOCl 2% NaOCl
Potato 218.8b1 278.7b 328.3b
Corn 100.2c 107.80c 128.5c
Rice 548.6a 1044.7a 931.1a
1 Values in the same column followed by the same letter are not
significantly different at the 95% confidence level.

granule, therefore, it had a higher contact area and exhib-

ited a greater adhesion. The contact area concept, how-
ever, cannot explain the adhesion results of oxidized corn
and potato starch batters. A higher carboxyl group content
and the presence of ionizable phosphate groups in potato
starch may contribute to its greater adhesion than corn
starch.

Oxidized potato and rice starch batters exhibited signifi-

cantly greater adhesion than their native counterparts.
This increase was attributed to additional hydrogen bond-
ing from carboxyl groups formed by oxidation. The pres-
ence of 0.07% carboxyl content in 0.8% NaOCl-oxidized
rice starch doubled the adhesion compared with non-oxi-
dized rice starch but additional carboxyl groups from 2%
oxidized rice starch did not result in further increase in
adhesion. It is not clear why no difference was noted
between unmodified and oxidized corn starch batters.
The present results suggest that starch granular size and
shape were more important than carboxyl groups in de-
termining its adhesion property.
3.5 X-ray diffraction
The X-ray diffraction patterns of native and oxidized
starches are depicted in Fig. 2. Oxidation did not result in
any significant changes in the degree of crystallinity of
starch because of no change in the upper diffraction peak
areas, implying that oxidation took place mainly in the
amorphous region. These results support the results of
Morton and Solarek [24], indicating no change in the bire-
fringence of oxidized starch granules and the occurrence
of oxidation mainly in the amorphous region.
It is proposed that the level of starch oxidation in terms of
carboxyl group content was strongly related to their de-
grees of crystallinity. Potato starch is classified as B form
starch and has a lower degree of crystallinity and more
amorphous area than corn and rice starches of A-form ori-
gin [26–27]. Therefore more NaOCl was assumed to en-
ter the amorphous region of potato starch for reaction to
take place, resulting in a significantly higher carboxyl
Fig. 2. X-ray diffraction patterns of unmodified and
hypochlorite-oxidized starches.
group content (Tab. 1). The degree of crystallinity, instead
of granule size and shape, of starch is considered to be a
main determinant in the amount of oxidation.
3.6 Characterization of starch structures
The normalized HPSEC chromatograms of unmodified
and oxidized starches are presented in Fig. 3. Each
starch profile can be divided into two major fractions:
Fraction I (Fr. I) and Fraction II (Fr. II). Fr. I which eluted at
the first 16 min, consisted of high molecular-weight carbo-
hydrates, mainly amylopectin (AP). Fr. II, which eluted af-
ter 16 min, was composed of low molecular-weight carbo-
hydrates, mainly amylose. Fr. I of corn starch was de-
graded the most (46%) among 0.8% NaOCl-oxidized
starches; Fr. I of potato starch was degraded the most
(59%) among 2% NaOCl-oxidized starches; Fr. I of rice
starch was degraded the least at both NaOCl concentra-
tions. The amylopectin fraction of starch degraded signifi-
cantly during oxidation, however, there was no clear rela-
tion between the amount of oxidation and the degree of
amylopectin degradation.
The normalized HPSEC chromatograms of isoamylase-
debranched unmodified and oxidized starches are shown
in Fig. 4. Each chromatogram can be divided into three
216 Kuakpetoon, Wang
Fig. 3. Normalized high-performance size-exclusion chro-
matograms of unmodified and hypochlorite-oxidized
starches.
fractions. Fr. I, which eluted first, consisted of amylose
molecules; Fr. II consisted of long B chains of AP; Fraction
III (Fr. III) consisted of short B chains and A chains of AP.
Within Fr. I, the larger molecular-weight (MW) amylose
molecules (shorter retention time) of potato starch de-
graded the most to smaller MW amylose molecules
(longer retention time) after oxidation, suggesting that the
amylose fraction in potato starch was more prone to
breaking glucosidic linkages compared with amyloses of
corn and rice starches. The high susceptibility of potato
amylose to oxidation may be possibly caused by its sig-
nificantly higher degree of polymerization (DP) of 4,700
compared with ~ 1000 of corn and rice amylose [28]. As
amylose is largely distributed in the amorphous region
where oxidation takes place, amylose with a high DP has
more chances to be oxidized. The Fr. II of potato starch
and Fr. III of rice starch increased significantly after 2%
NaOCl oxidation, suggesting that more degradation from
oxidation took place in the Fr. I of potato starch and Fr. II
of rice starch.
The chain-length distributions of AP from isoamylase-de-
branched unmodified and oxidized starches by HPAEC-
Starch/Stärke 53 (2001) 211–218
Fig. 4. Normalized high-performance size-exclusion chro-
matograms of isoamylase-debranched unmodified and
hypochlorite-oxidized starches.
PAD are summarized in Tab. 3. The AP fractions are
grouped into four chain types and corresponding DP ac-
cording to Hanashiro et al. [29]. The percentage of A
chain remained mostly unchanged for all starches after
oxidation. The percentage of B1 chain decreased but B2
chain increased after 0.8% NaOCl oxidation. Further
changes in percentage of chains varied according to
starch origin. These results suggest the occurrence of ox-
idation in the amorphous region and possible involvement
of AP long chains in oxidation [30, 31].
4 Conclusion
The differences in physicochemical properties among ox-
idized potato, corn, and rice starches were attributed to
their differences in granular size and shape and molecu-
lar structure. Oxidation occurred mainly in the amorphous
region and oxidation level in terms of carboxyl group con-
tent was largely dependent on the degree of crystallinity
and the degree of polymerization of amylose. The pasting
property of oxidized starch was affected by carboxyl
groups and the adhesion property was more related to the
granular size and shape of oxidized starch.
Starch/Stärke 53 (2001) 211–218 Characterization of Different Starches Oxidized by Hypochloride 217

Tab. 3. Chain-length distribution of amylopectins of isoamylase-debranched native and hypochlorite-oxidized starches

fractionated by high-performance anion-exchange chromatography equipped with a pulsed amperometric detector.
% Distribution
Starch DP Range Chain type Unmodified 0.8% NaOCl 2% NaOCl
Potato 6–12 A 21.9 22.2 22.5
13–24 B1 54.4 49.6 54.3
25–36 B2 17.7 20.9 17.1
37–54 B3 + long chains 6.1 7.4 6.1

Corn 6–12 A 23.5 21.4 21.9

13–24 B1 52.7 50.2 52.6
25–36 B2 16.8 20.9 20.3
37–54 B3 + long chains 7.0 7.5 5.2

Rice 6–12 A 24.0 24.3 23.7

13–24 B1 53.1 49.4 48.8
25–36 B2 15.1 18.3 21.3
37–54 B3 + long chains 7.7 8.1 6.2

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(Received: January 23, 2001)