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Preparation of granular cold-water-soluble corn starch by surface

modification with poly(ethylene glycol)
Article in Starch - Starke · October 2011
DOI: 10.1002/star.201100033

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Starch/Sta¨rke 2011, 63, 625–631 DOI 10.1002/star.201100033 625

RESEARCH ARTICLE

Preparation of granular cold-water-soluble corn starch by

surface modification with poly(ethylene glycol)
Jiwen Wang, Wentao Zhai and Wenge Zheng

Ningbo Key Laboratory of Polymer Materials, Ningbo Institute of Material Technology and Engineering (NIMTE),
Chinese Academy of Sciences, Ningbo, Zhejinag Province, P. R. China

The main target of this study is to synthesize one kind of granular cold-water-soluble (GCWS) Received: March 1, 2011
starch by grafting poly(ethylene glycol) (PEG) segments onto the surface of native starch Revised: April 11, 2011
granules. It is found that the grafting process could introduce long PEG chains onto the granule Accepted: April 11, 2011
surface, resulting in the presence of special micropits on the granule surface, as characterized
by SEM. The cold water solution test verified that the resultant PEG-grafted corn starches
exhibited excellent cold-water-solubility. The XRD analysis and further polar optical micrograph
(POM) observation indicated that the crystallites structure inside the PEG-grafted corn starches
was fully preserved, since no gelatinization process was involved. The present study provides a
new train of thought that we can adjust the physiochemical proper-ties of starch granules with
proper surface modification.

Keywords:
Crystallinity / Granular cold-water-soluble / Morphology / Surface-grafting

1 Introduction medium and the resultant gelatinized starch was dried in

Considerable efforts have been devoted to the preparation
and investigation of granular cold-water-soluble (GCWS)
starches, which gained wide application such as ingre-
dients of non-toxic insecticide [1], encapsulation, and con-
trolled release of drugs [2], gelling and thickening agent in
food systems [3], and so on.
Several methods have been successfully developed to
prepare GCWS starches, involving in the alternation of the
physical and chemical characteristics. In an early patent,
Pitchon et al. [4] reported a multi-fluid spray-drying method
to fabricate the GCWS starches, where the aqueous of
starch slurry was atomized and gelatinized in an enclosed
chamber and steam was interjected as the heating
Correspondence: Dr. Wenge Zheng, Ningbo Key Laboratory of
Polymer Materials, Ningbo Institute of Material Technology and
Engineering (NIMTE), Chinese Academy of Sciences, Ningbo,
Zhejinag Province 315201, P. R. China. E-mail:
wgzheng@nimte.ac.cn
Fax: þ86-574-86685186
Abbreviations: CWS, cold-water-solubility; EG, ethylene glycol;
GCWS, granular cold-water-soluble; MA, Maleic anhydride;
PEG, poly(ethylene glycol); POM, polar optical micrograph.
the spray drying tower. Later, the GCWS starches were
also prepared by heating native starch in aqueous mono-
hydric alcohol under elevated pressure [5], or in
polyhydric alcohol at atmospheric pressure [6–7].
Alcoholic-alkaline method [8–9] is the most popular
method to prepare GCWS starches. With this method,
native starch is treated with a mixture of ethanol and
alkali. The product is neutral-ized with hydrochloric acid
and washed with alcohol before drying. Except these
treatments, mechanical activation such as cryo-milling
activation has also been carried out to improve the cold-
water-solubility (CWS) of the starch granules [10].
The crystallites structure of native starch is usually
disrupted during the preparation of GCWS starches [11],
leading to the presence of fragmental particle struc-ture.
During the preparation process, the native starch granules
normally undergo degradation, hydrolyzation, and
gelatinization, which disrupt the original crystalline and
ordered structure in starch granules, characterized by the
apparent change in XRD patterns and the loss of bire-
fringence under polarized light microscope [12]. Specifically,
researchers observed that the typical A-, B-, and C-type
double-helix crystalline structure of native starches was
converted to a V-type single helix crystalline arrangement

2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.starch-journal.com

626 J. Wang et al. Starch/Sta¨rke 2011, 63, 625–631

or an amorphous structure [13–15]. Mechanical activation
usually leads to cracking of starch granules, resulting in
apparently decreased particle size, and the fragmental
structure on SEM observation [16]. On the other hand, it is
also observed that starch granules may swell during the
gelatinization process, which results in an apparently
increased particle size of the starch granules and the dis-
ruption of crystallites structure [12, 17].
In this paper, poly(ethylene glycol) (PEG), a common
water soluble polymer was chemically grafted onto the
surface of corn starch granules via a two-step esterification
process. Results of investigations of PEG-grafted corn
starches are presented, including particle size analysis,
1 esterification process, which is illustrated in Fig. 1. MA was
CWS, H NMR analysis, XRD, polarized light observation,
and scanning electron microscopy (SEM). Excellent CWS
was successfully vested to corn starch without disturbing
the natural granular structure and inner crystalline. Thus a
novel routine for producing GCWS starch was developed.
This resulted in completely different properties when com-
pared to common GCWS starches prepared by spray-
drying, drum-drying, alcoholic-alkaline, and mechanical
activation methods. The results could serve as a starting
point for the development of low-cost and energy-saving
GCWS starch products and lead to further research on
dissolving kinetics and solution dispersibility and stability of
surface-modified starches.
300 g corn starch powder was added into the flask. The
agitation was kept for another 2 h, during which the
water absorbed in starch granules and produced during
chemical reaction was removed by azeotropic distillation
with toluene. The reaction system was cooled to room
tempera-ture and washed in alcohol to remove toluene,
residual anhydride, and unbonded PEG. The product
was filtered then and the solid was vacuum dried and
preserved air tightly for further characterization. The corn
starch grafted with PEG2000, PEG4000, and PEG6000
were labeled as P2000St, P4000St, and P6000St,
respectively, through out this work.
The PEG-grafted starches were prepared via a two-step
used as the coupling agent and was bonded on the
terminals of PEG molecules firstly. The carboxyl groups
were introduced on PEG molecules, therefore the end-
capped PEG polymers can be chemically connected with
the abundant hydroxyl groups on starch polymer chains in

2 Material and methods

2.1 Materials

Corn starch of edible grade was purchased form Zhucheng

Xingmao Corn Development Co., Ltd. The Maleic anhy-
dride (MA) was supplied by Aladdin Reagent Database Inc.,
and it was white needle-like crystalline at room temperature.
Three types of commercial available PEG, PEG2000,
PEG4000, and PEG6000, with average MW of 2000, 4000,
and 6000, respectively, were also pur-chased from Aladdin
Reagent Database Inc. Toluene was provided by
Sinopharm Chemical Reagent Co., Ltd. All these chemical
reagents were analytically pure and used as received.

2.2 Preparation of the PEG-grafted starch

The PEG-grafted starches were prepared in a three-necked

flask equipped with an oil-and-water separator, a silicone
oil-bath and a mechanical agitator. Two hundred grams of
PEG and MA were melted at 1308C. The molar ratio of MA
to PEG was 2:1. One hundred and fifty milliliters of toluene
was added to reduce the thickness and agitation was Figure 1. Preparation of PEG-grafted corn starch: (a)
applied for homogeneously intermix of the reagents for 2 h. End-capped reaction of PEG and MA; (b) Hypothetical
Then reaction temperature was set to 1508C and reaction of end-capped PEG and starch.

2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.starch-journal.com

 Starch/Sta¨rke 2011, 63, 625–631 627

the second step. It is important to be noticed that the

starch granules were not dissolved or gelatinized during
the graft-ing process, so the grafting reaction occurred
only at the surface layer of starch granules.

2.3 Particle morphology characterizations

The 1H NMR spectra of native and surface-grafted

corn starch was obtained using a Bruker AVANCE III 400
MHz spectrometer. The samples were dissolved in
deuterated DMSO for analysis.
The particle size distribution of native and PEG-
grafted corn starches was determined using an S3500-
special Microtrac Particle Size Analyzer. Starch particles
were dispersed in absolute ethanol using an Ultrasonic
Crasher (SCIENTZ-IID, Ningbo Scientz Biotechnology
Co., Ltd.) before analyses.
Scanning electron micrographs (SEM) of all samples
were obtained with a HITACHI S-4800 field emission SEM.
Before observation, starch samples were extracted with
absolute alcohol for 24 h. Residual particles were dried at
708C in vacuum to constant mass. Starch samples
were sprinkled on conductive tape fixed on an aluminum
stub. The samples were coated with Au using a HITACHI
E-1045 ion sputter.

2.4 Cold-water-solubility

The CWS% was calculated as is shown in Eq. (1):

w1 2
CWS% ¼ 100%
w0
The method described by Eastman and Moore [5] was
slightly modified to determine the CWS. The native and PEG-
grafted corn starches were dried in a vacuum oven under
1108C for 4 h and 0.2 g (w 0) of each dry sample were
weighed and put in 50 mL centrifugal tube. Twenty milliliters
of distilled water was added and the centrifugal tubes were
kept in 208C for 2 h for the samples to dissolve sufficiently.
The solution of PEG-grafted starch and undis-solved
substances were separated in a table top refriger-ated
centrifuge (Z36HK, Hermle Labortechnik GmbH) at a rotation
rate of 3100 rpm for 15 min. Ten milliliters of clear solution of
each tube was transferred to watch tube, which was weighed
and labeled in advance. After 4 h of vacuum drying under
1108C, the gaining in weight of each watch tube was
recorded as w1.

2.5 Crystallites structure characterizations

The birefringent images of native and PEG-grafted corn

starches were observed with an Olympus BX51 polarized
light microscope and starch particles were dispersed in
ethylene glycol (EG).

2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

 The XRD studies of native and PEG grafted starch
powders were carried out using a Bruker AXS D8
Advance Diffractometer. Starch samples were scanned
with 2u from 3 to 508. The voltage and the current were
40 kV and 40 mA, respectively.

3 Results and discussion

1
3.1 H NMR analysis

The 1H NMR resonance signals of the protons on the

alkylene groups of grafted MA molecules can be used to
characterize the graft ratio qualitatively. The 1H NMR
spectra of native and PEG-grafted corn starches was
shown in Fig. 2. Since there are no alkylene groups on
the starch polymer chains, no signals can be observed
on the 1H NMR spectra of native corn starch between
the chemical shift of 6 and 7 ppm.
In Fig. 2, weak signals between chemical shift 6 and 7
ppm can be recognized on the 1H NMR spectra of
sample P2000St. These are the resonance signals of
protons connecting to the sp2 hybridized carbon in MA
molecules that chemically bonded onto starch.
It is illustrated by Fig. 3 that three different chemical
potentials of alkylene protons existed on starch-g-PEG
polymer. The resonance signals of H a and Hb was spin-
splitted into doublets by each other. Thus five resonance
signals were observed, which proved that the PEG seg-
ments were successfully grafted onto the starch granules.
(1) The resonance signals on the spectra of sample P4000St
and P6000St are even weaker and unrecognizable, indi-
cating that the grafting ratio decreased while larger PEG
molecules were used. This may be caused by the steric

Figure 2. 1H NMR spectra of native and PEG-grafted

corn starches.

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628 J. Wang et al.
Figure 3. Illustration of hydrogen atoms of three different
chemical potentials.
hindrance and relatively less terminal hydroxyl groups of
relatively larger PEG molecule.
3.2 Cold-water-solubility
The CWS of native and PEG-grafted starches in this
study is shown in Table 1. Native corn starch is insoluble
in cold water as expected, with the negligible CWS% of
only 0.4%. By surface grafting with water soluble PEG
segments, excellent CWS is gained. There is little
difference between the CWS% of P2000St and P4000St
(91.6 and 92.4%, respectively). However, the CWS% of
sample PEG6000St decreased to 52.3%. This may be
due to the lower grafting ratio proved by 1H NMR
analysis and the difference in granule surface
morphology, which will be discussed at the latter
sections of this paper.
3.3 Particle size analysis
Previous work has proven that the granule size and
shape of prepared GCWS starches get changed during
physiochemical treatment. The starch granules cracked
under external force during mechanical acti-vation such
as milling or ultrasonic disintegration, which resulted in
the decrease in granule size and fracture in granule
shape. On the other hand, the alcoholic-alkaline treated
GCWS starch granules expanded in size and
deformation can be observed in granule morphology.
Table 1. Average particle size and CWS of native and
PEG-grafted corn starches
Average particle
Sample size (mm) CWS (%)
Corn starch 12.7 0.4
P2000St 12.9 91.6
P4000St 11.7 92.4
P6000St 11.2 52.3
2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Starch/Sta¨rke 2011, 63, 625–631
The particle size of native and PEG-grafted corn
starches is shown in Table 1. The native corn starch has
an average primary particle diameter of 12.7 mm. It can
be seen that the surface-grafting process brought no
pronounced change to starch particle size, although the
diameter of PEG-grafted starches decreased slightly
(from 12.9 to 11.2 mm).
3.4 Crystallite structure characterization
The insolubility of native starch in cold water can be
traced to the double helix conformation of the starch
polymer chains, which are strongly ordered in crystal
arrays that give the A-, B-, and C-type XRD patterns of
native starches. It has been reported that a V-type XRD
pattern was displayed by GCWS starches prepared by
treating the starch–aqueous alcohol suspension under
high temperature [14–15]. The starch crystalline
structure is converted to a single helix crystalline
arrangement that is soluble in cold water. Amorphous X-
ray pattern were presented by GCWS starches prepared
via mechanical activation, alcoholic-alkaline treatment,
and spray-drying, indicating that a random arrangement
of polymer chains is formed.
The XRD patterns of native and PEG-grafted corn
starches are shown in Fig. 4. Native corn starch is a
semi crystalline material and five diffraction peaks of
typical A-type starch at 15.0, 17.2, 18.0, 20.1, and 23.28
were observed, just as was described by Waigh et al.
[18]. Some change can be observed at the XRD curves
of PEG-grafted starch samples. The peaks at 17.2 and
18.08 began to coincide and the weak diffraction peak at
20.18 became even faint. However, the crystalline
Figure 4. X-ray patterns of native and PEG-grafted corn
starches.
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Starch/Sta¨rke 2011, 63, 625–631
degree and type showed tiny changes for all samples,
indicating that the grafting of PEG molecules occurred
only at the outer amorphous layer of starch granules.
The inner spherulite structure remained unchanged
during the grafting process.
Various studies have shown a loss of refringence with
prepared GCWS starch [12]. It has been reported that
internal fragmentation was exhibited by the GCWS
starches prepared via alcoholic-alkaline treatment, which
clearly indicates the swelling and shrinkage in that
region of the granule [8]. However, in this study, a cross
shaped shadow was observed under polarized light for
both the native and PEG-grafted starch granules, as is
shown in Fig. 5. It can be easily comprehend that the
toluene and PEG used during surface-grafting process
cannot penetrate the polysaccharide chains of native
starch granules. Since no swell or gelatinization process
was involved during the preparation, all starch particles
remained their original size and inner crystalline struc-
ture. This conclusion can also be proved by the small
angle XRD results.
Figure 5. Polarized light micrographs of native and PEG-grafted corn starches: Corn starch (a); P2000St (b); P4000St
(c), and P6000St (d). Magnification 500 for all samples.
2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
629
3.5 Surface morphology observation
The SEM micrographs provided the following results as
shown in Fig. 6. The surface of native corn starch granules
is quite smooth and compact, with some natural small holes
scattered on it (Fig. 6a and e). Although little changes were
observed in the particle size and shape, the grafting of PEG
molecules brought significant changes to the morphology of
starch granule surface. Special micropits was observed on
the surface of sample P2000St and P4000St (Fig. 6b, c, f,
and g). The outer layer of the granules became loose and
porous and this structure is commonly observed on the
surface of polymer materials after grafting modification. The
micropits disap-peared on sample P6000St (Fig. 6d and h),
unsteadily micro-cracks were observed. This may restrict
the per-meability of water molecules and therefore lead to
the decrease of CWS of sample P6000St. The variation in
the surface morphology in PEG-grafted starch granules may
be due to the difference in grafting ratio of PEG segments,
1
which was characterized by H NMR analysis.
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630 J. Wang et al.
4 Conclusions
A novel routine for producing GCWS starch was developed
by grafting water-soluble PEG segments onto the surface of
starch granules, where excellent CWS (over 90%) can be
achieved. The starch granules were heated with toluene
and all the water was removed during the grafting reaction.
Therefore no swelling, gelatinization, or hydrolysis was
involved during the preparation of GCWS starch. The
granule size and shape, type, and degree of crystallinity and
birefringence of native corn starch granules were fully
preserved. SEM pictures revealed a loose and porous outer
layer with special micropits structure on it, indicating that the
PEG segments were grafted at the outer layer
2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Starch/Sta¨rke 2011, 63, 625–631
Figure 6. Scanning electron micro-
graphs of native and PEG-grafted corn
starches: Corn starch (10 000 ) (a);
P2000St (10 000 ) (b); P4000St (10
000 ) (c); P6000St (10 000 ) (d); Corn
starch (50 000 ) (e); P2000St (50 000 )
(f); P4000St (50 000 ) (g) and P6000St
(50 000 ) (h).
of native starch granules. The effect of MW of PEG on
grafting ratio, surface morphology, and CWS was also
explored in this paper.
This research has been funded by China National
Key Technology R&D Project (2007BAE42B05).
The authors have declared no conflict of interest.
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