Starch/Stärke 61 (2009) 687–695 DOI 10.1002/star.

200900164 687

Yijun Sang Subzero Glass Transition of Waxy Maize Starch

Sajid Alavi
Yong-Cheng Shi Studied by Differential Scanning Calorimetry
Department of A mixture of waxy maize starch and water (1:2, w/w) was heated in a differential scan-
Grain Science & Industry, ning calorimeter (DSC) pan to different temperatures to obtain different degrees of
Kansas State University, gelatinization. Each pan was then quenched to -307C and rescanned, and the subzero
Manhattan, KS, USA
glass transition temperature (Tg0 ) of the content was determined. A three-phase model
of a starch granule—a mobile amorphous phase, a rigid amorphous phase, and a
crystalline phase—was used to interpret results and explain the glass transitions in
starch. Waxy maize starch had an onset gelatinization temperature (To) of 61.57C, peak
temperature (Tp) of 70.37C, and completion temperature (Tc) of 81.77C. The Tg0 was
clearly noted after the starch and water mixture was heated to Tp and Tc, but was small
and barely observable when the mixture was heated up to To and immediately cooled
to -307C. When the starch and water mixture was heated to 557C, which was 67C below
the To, and held for 2 h, a Tg0 was observed. Moreover, Tg0 began to appear and was
observable if the starch and water mixture was heated to 107C below gelatinization
onset temperature (517C) and annealed for 2 h without any gelatinization. Further
holding at -77C showed a clear subzero glass transition of annealed native starch
granules.

Keywords: Differential scanning calorimetry; Glass transition; Granular starch

1 Introduction clearly demonstrated. Slade and Levine [11] reported a

Native granular starch is a partially crystalline polymer [1-
3]. The internal structure of the starch granule consists of
semicrystalline and amorphous growth rings [4]. In the
semicrystalline growth ring, crystalline lamellae from
double helices and amorphous lamellae from branch
points are stacked alternately. A simplified ‘three-micro-
phase’ model has been proposed to explain thermal
behaviors of granular starch [5]. In addition to crystalline
domains, the model incorporates two different amor-
phous regions in a native starch granule: an inter-crystal-
glass transition temperature of -57C for gelatinized wheat
starch (55% water, w/w). Other researchers further inves-
tigated and demonstrated the glass transition of freeze-
concentrated gelatinized starch-water systems contain-
ing other types of starch and/or having different starch
contents [12-19].
In contrast to a gelatinized starch-water system, the glass
transition of a native starch-water system was very diffi-
cult to detect [5, 6, 20-26]. Glass transition of a gelatinized
starch-water system represents the Tg of bulk amorphous

line rigid amorphous region and a mobile amorphous
region [5-7]. A similar multiphase model has been used to
describe synthetic semicrystalline polymers [8-10].
The glass transition temperature (Tg) is an important
property of amorphous polymers. At glass transition
temperature, the amorphous region undergoes a second-
order transition upon heating, changing from an immobi-
lized glassy state to a viscous rubbery state. The glass
transition of a gelatinized starch-water system has been
Correspondence: Yong-Cheng Shi, Department of Grain
Science & Industry, Kansas State University, Manhattan, KS,
66506, USA. Phone: 785-5326771, Fax: 785-532-7010, e-mail:
ycshi@ksu.edu.
Research Paper
starch, which is different from that of native starch. Lim et
al. [15] located subzero glass transition (Tg0 ; -57C) in both
a partially and fully gelatinized potato starch-water sys-
tem (12 – 40% starch) but not in native potato starch so-
lution in the region of -257C to 07C. Amorphous regions of
the native starch granule are physically cross-linked by
crystalline domains. It has been suggested that in syn-
thetic polymers, glass transition of amorphous molecules
restricted by the crystalline phase occurs over a wide
temperature range [27]. There is considerable con-
troversy on the glass transition of a native starch-water
system, partly because of the partial crystalline structure
of native starch granules. Slade and Levine [11] sug-
gested that a glass transition of native wheat and waxy
maize starch in the presence of water (45:55, starch/
water) immediately precedes the nonequilibrium melting

© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.starch-journal.com

688 Y. Sang et al.
transition of crystallite (Tm) by the baseline shift. However,
Noel and Ring [28] suggested that the amorphous regions
of the granules are plasticized at the onset of gelatiniza-
tion. Liu and Lelievre [25] noted that a baseline shift
observed in differential scanning calorimetry (DSC), which
indicated a change in the heat capacity, started at the
same temperature as the gelatinization endotherm com-
menced and continued to increase in size until the gelati-
nization ended, and X-ray data [26] suggest that the initial
specific heat changes in the DSC traces may reflect a
melt rather than a glass transition. Recently, temperature-
modulated DSC has been used to separate glass transi-
tion from melt and to detect glass transition during the
gelatinization process [6, 29]. A stepwise heat capacity
change of native waxy maize starch at the beginning of
gelatinization was revealed by temperature-modulated
DSC, and this glass transition was assigned to the rigid
amorphous region [6]. The mobile amorphous region,
which is less restricted by crystalline domains, was
believed to have a lower Tg than the rigid amorphous
region [5, 22]. However, the glass transition temperature
of the mobile amorphous region has not been clearly
demonstrated.
In this study, in an attempt to detect glass transition of the
mobile amorphous region, we investigated subzero glass
transition of granular waxy maize starch, which contains
only amylopectin, in the presence of excess water without
gelatinizing (melting) starch.
2 Materials and Methods
2.1 Materials
Waxy maize (Amioca) starch was obtained from National
Starch Food Innovation (Bridgewater, NJ, USA). Phos-
phate cross-linked waxy maize starch was prepared
according to the method described by Woo and Seib [30].
Starch (50.0 g, db) was added into water (70.0 g) con-
taining sodium trimetaphosphate (STMP, 0.495 g),
sodium tripolyphosphate (STPP, 0.005 g), and sodium
sulfate (5.0 g) at pH 11.5. The reaction mixture was stirred
at 457C for 3 h, cooled to room temperature and adjusted
to pH 6.5. The starch was washed seven times with dis-
tilled water and dried at 407C overnight. The starch had a
total phosphorus content of 0.034% (dry basis) as meas-
ured by the method described by Smith and Caruso [31].
2.2 DSC measurement
Starch (<10.0 mg) and an appropriate amount of de-
ionized water (1:2, starch/water, w/w) were weighed into a
stainless steel pan, sealed, and equilibrated overnight
© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Starch/Stärke 61 (2009) 687–695
prior to the experiment. A DSC (Q100, TA Instruments,
New Castle, NJ, USA) was used for thermal scan, and an
empty pan was used as a reference.
Gelatinization of waxy maize starch (starch: water, 1:2 w/
w) was determined by cooling the sample to -307C, hold-
ing for 20 min, and scanning at 57C/min to 1207C. Onset
(To), peak (Tp), and completion temperature (Tc), and en-
thalpy (DH) of gelatinization were calculated.
Glass transition was determined by using the first-order
derivative of the heat flow curve, and glass transition
temperature was defined as the peak of the derivative
curve [15, 18, 19, 32].
A mixture of starch and water (1:2, w/w) was also heated
in DSC pans to different temperatures to obtain different
degrees of gelatinization. The starch-water mixture was
heated to a specific temperature (T1) and held for a time
(t1). Each pan was quenched to -307C, held for 20 min,
and rescanned, and its subzero glass transition was
determined. In two additional experiments, the frozen
starch-water mixture was heated to a temperature (T2)
and held for a time (t2) to anneal the starch molecules
(Tab. 1). Gelatinization and glass transition were deter-
mined by scanning at 57C/min to 1207C. Frozen water
was determined by integrating the peak area of ice melt-
ing. Unfrozen water was calculated by (initial water - fro-
zen water). All DSC experiments were done in duplicate.
2.3 Microscopy
The scanned starch sample was loaded on a glass slide
and observed under a 406objective by using an Olympus
BX 51 microscope (Olympus Optical Co. Ltd., Shinjuku-
ku, Tokyo, Japan).
2.4 Statistical analyses
Analysis of variance and least significant difference (LSD)
were calculated on the data of gelatinization by using SAS
9.1 (SAS Institute, Cary, NC, USA).
3 Results and Discussion
3.1 Thermal transition in native and fully
gelatinized waxy corn starch
The native waxy maize starch suspension (1:2, w/w)
showed an endothermic peak due to starch gelatinization
(dotted line in Fig. 1A). Gelatinization started at 61.57C
www.starch-journal.com
Starch/Stärke 61 (2009) 687–695 Subzero Glass Transition of Waxy Maize Starch 689

Tab. 1. Nomenclature of the experimentsa).

T1[7C] t1 [min] T2 [7C] t2 [min]

Native starch N/A N/A N/A N/A

Fully gelatinized 120 0 N/A N/A
Preheated to
Tp 71 0 N/A N/A
To 61 0 N/A N/A
(To – 6)7C 55 0 N/A N/A
(To – 6)7C and hold for 120 min 55 120 N/A N/A
(To – 6)7C and hold plus annealing at -77C 55 120 -7 30
(To – 10)7C and hold for 120 min 51 120 N/A N/A
(To – 10)7C and hold plus annealing at -77C 51 120 -7 30

a) The starch-water mixture (1;2, w/w) was heated to a specific temperature (T1) and held for a time (t1), cooled to -307C,
then heated to a temperature (T2) and held for a time (t2). The gelatinization and glass transition were then determined by
scanning at 57C/min to 1207C.

(To), peaked at 70.37C (Tp), and completed at 81.77C (Tc)
with an enthalpy of 16.0 J/g (Tab. 2). No clear glass tran-
sition was evident for native starch in the range from
-257C to -37C when the starch was not preheated (Fig. 1A).
In agreement with previous studies [11-13, 15-19], the
rescanning of gelatinized waxy maize starch (starch/
water =1:2, w/w) showed a peak at -6.77C in the first
derivative curve (solid line in Fig. 1B), indicating a glass
transition of gelatinized bulk amorphous starch. No melt-
ing peak was observed in the second scan, indicating a
complete gelatinization of starch in the first scan.
The phosphate cross-linked waxy maize starch had
gelatinization properties similar to that of native waxy
maize starch. Gelatinization started at 62.87C (To),
peaked at 70.57C (Tp), and was completed at 80.77C (Tc)
with an enthalpy of 16.4 J/g. Other researchers [16, 30]
reported a significant increase of gelatinization tempera-
ture of STMP/STPP cross-linked starches. However, the
cross-linked starch prepared in the present study had a
cross-linking density 10 times lower than those reported
[16, 30].
The gelatinized phosphate cross-linked waxy maize
starch showed a higher glass transition temperature
(-5.57C) than the gelatinized native waxy maize starch
(-6.77C). The bulky phosphate groups or cross-links be-
tween starch chains may decrease chain mobility and
increase Tg [16]. In addition, after it was pre-scanned to
1207C, native waxy maize starch was gelatinized and
fragmented (Fig. 2A), whereas cross-linked starch
retained its granule shape (Fig. 2B) despite the full gelati-
nization (no birefringence). Cross-linking created perma-
nent covalent bonds between starch molecules. It is
interesting to note that those swollen, non-crystalline
cross-linked starch granules were not molecularly dis-
persed (Fig. 2B) but showed a clear subzero Tg. In con-
trast, no clear subzero Tg was observed in native starch
granules (Fig. 1A) [11]. Crystallites, acting as physical
cross-linkers in native starch granules, have been sug-
gested to elevate the Tg of the amorphous regions [11, 23,
24]. In addition, each amylopectin molecule may be par-
tially crystalline [1] and each may manifest a distinctive Tg
[11]. Glass transition temperatures of starch amorphous
regions may also depend on proximity to the crystal as
well as molecular weights and local moisture distribution.
As a result, a range of non-ordered structural domains
may exist in granular starch and spread the glass transi-
tion over a broad range of temperature, making it difficulty
to be detected by DSC [22].
3.2 Glass transition of the starch-water mixture
pre-scanned to gelatinization onset
temperature and beyond
A trace of glass transition was observed when the waxy
maize starch solution was pre-scanned to gelatinization
onset temperature and then quenched (Fig. 3A). Pre-
scanning to onset temperature partially destroyed the
starch crystal, showing a smaller gelatinization enthalpy
than native starch (15.2 vs. 16.0 J/g, Tab. 2). After the
starch was gelatinized more by pre-scanning to gelatini-
zation peak (Fig. 3B) or complete temperature (Fig. 3C),
glass transitions were clearly observed at –6.07C.
3.3 Glass transition of the starch-water mixture
pre-scanned to 67C below gelatinization
onset temperature
No glass transition was observed in the range from -257C
to -37C after the starch solution was pre-scanned to 557C,

© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.starch-journal.com

690 Y. Sang et al. Starch/Stärke 61 (2009) 687–695

Fig. 1. DSC thermograms of

a native waxy corn starch-
water system (1/2, w/w)
showing: (A) starch gelatini-
zation in the first scan from
-307C to 1207C at 57C/min;
(B) glass transition by re-
scanning the gelatinized
sample from -307C to 1207C
at 57C/min.

67C below gelatinization onset temperature. Gelatiniza-
tion temperatures and enthalpy were not changed com-
pared with native starch solution (Tab. 2).
However, after the starch-water mixture was held at 67C
below gelatinization onset temperature for 2 h, the first
derivative curve indicated a glass transition temperature
of -6.27C (Fig. 4A). After this starch solution was held at
67C below To and further held at -77C for 30 min, the first
derivative curve had a clear peak showing a glass transi-
tion at -3.87C (Fig. 4B). However, holding the starch sam-
ple at 67C below gelatinization onset temperature for 2 h
slightly decreased gelatinization enthalpy (15.0 J/g vs.
16.0 J/g; Tab. 2), indicating that water was able to at least
partially plasticize the amorphous phase and melt part of
the crystallites in starch granules. The partial gelatiniza-
tion of the starch complicated the interpretation of sub-
zero glass transition. Starch solution pre-treated at a
lower temperature was further studied, and results of that
experiment are presented in the next section.

© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.starch-journal.com

Starch/Stärke 61 (2009) 687–695 Subzero Glass Transition of Waxy Maize Starch 691

Fig. 2. Microscopy of DSC preheated to 1207C (A) native

waxy maize starch and (B) cross-linked waxy maize
starch.

3.4 Glass transition of the starch solution pre-

scanned to 107C below gelatinization onset
temperature

Holding the native starch-water system (1:2, w/w) at 517C

for 2 h showed an annealing effect, increasing gelatiniza-
tion onset temperature from 61.57C to 63.47C and
decreasing the gelatinization temperature range (Tab. 2).
It is generally believed that annealing can take place only
at a temperature higher than Tg when the polymer is in the
mobile rubbery state. This result indicated an existence of
Tg less than 517C in the native starch-water system [7, 20,
33].
A glass transition was indicated at about -7.57 to -5.07C
after the starch sample was held at 107C below gelatini-
zation onset temperature for 2 h (Fig. 5A). After further
annealing the partially heated starch-water mixture at
-77C for 30 min, the glass transition temperature increased
to -4.07C and became more evident (Fig. 5B). Gelatiniza-
tion enthalpy was not changed after the starch solution
Fig. 3. DSC thermograms of a native waxy corn starch-
water system (1/2, w/w) after being preheated to (A)
gelatinization onset, (B) peak, and (C) complete tempera-
ture.
was held at 107C below gelatinization onset temperature
for 2 h (Tab. 2). These results indicated that subzero glass
transition temperature could be detected directly without
the gelatinization of starch. We attribute this subzero Tg to
the mobile amorphous regions.
In a previous study [6], we suggested that the rigid amor-
phous region corresponded to the interlamellar non-
crystalline regions close to crystallites and had a glass
transition temperature of 627C for waxy maize starch

© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.starch-journal.com

692 Y. Sang et al. Starch/Stärke 61 (2009) 687–695

Fig. 4. DSC thermograms of

a native waxy corn starch-
water system (1/2, w/w) after
being (A) preheated to 67C
below onset temperature
and held for 2 h and (B) pre-
scanned to 67C below onset
temperature and held for 2 h
then held at -77C for 30 min.

Tab. 2. Gelatinization characteristics of native and pre-treated waxy corn starcha)

Native and pre-treated waxy corn starch To [7C] Tp [7C] Tc [7C] DH [J/g]

Native starch 61.5 a 70.3 a 81.7 a 16.0 c

Fully gelatinized - - - -
Preheated to
Tp 70.3 d 75.1 c 81.3 a 6.36 a
To 62.0 a 70.7 80.8 a 15.2 b
(To – 6)7C 61.4 a 70.6 a 81.2 a 16.5 c
(To – 6)7C and hold for 120 min 66.2 c 71.7 b 80.5 a 15.1 b
(To – 6)7C and hold plus annealing at -77C 66.2 c 71.7 b 81.1 a 15.0 b
(To – 10)7C and hold for 120 min 63.4 b 70.4 a 81.7 a 16.4 c
(To – 10)7C and hold plus annealing at -77C 63.0 b 70.1 a 80.8 a 16.4 c
LSD (a = 0.05) 0.54 1.0 1.5 0.74

a) The ratio of starch to water was 1:2 (w/w). Values followed by the same letter in the same column are not significantly
different.

© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.starch-journal.com

Starch/Stärke 61 (2009) 687–695 Subzero Glass Transition of Waxy Maize Starch 693

Fig. 5. DSC thermograms of

a native waxy corn starch-
water system (1/2, w/w) after
being (A) preheated to 107C
below onset temperature
and held for 2 h and (B) pre-
heated to 107C below onset
temperature and held for 2 h
then held at -77C for 30 min.

(75% water). Motion of a rigid amorphous polymer is
strongly restricted by the crystalline domain. The mobile
amorphous phase in the starch granule mainly corre-
sponds to the amorphous growth rings. Glass transition
temperatures of mobile amorphous regions might be a
distribution rather than a single value [11, 22, 24]. Different
mobile amorphous regions may have different Tg accord-
ing to the different motion restriction brought to them by
the surrounding crystals. Holding starch and water mix-
ture at 517C, 107C below onset gelatinization tempera-
ture, for 2 h may change these mobile amorphous
regions, which had a distribution of Tg, from a glass state
into a rubbery state. Starch granule structure does not
restrict the water absorption of starch. The maximal mo-
lecular limit to enter a native starch granule was 1000 Da
[34]. Water molecules entered into granules in a matter of
seconds [35]. With the high water mobility at 517C, mobile
amorphous regions were plasticized by water molecules
and showed a single Tg of -67C.
Annealing, or holding the starch-water mixture at -77C,
which was slightly above the onset of Tg, provided
enough molecular mobility to freeze more unfrozen water
into ice (Tab. 3). It has been reported that starch granules

© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.starch-journal.com

694 Y. Sang et al.
Tab. 3. Amount of unfrozen water in waxy maize starch
and water (1/2, w/w) mixtures.
Unfrozen water
[g/g starch]
Native starch 0.45 6 0.01
Fully gelatinized 0.56 6 0.05
(Tp – 10)7C and hold 0.41 6 0.02
plus annealing at -77C
contained 0.25–0.40 g unfrozen water per gram of starch [36
and references therein]. In the present study, the unfrozen
water content (0.56 g /g of starch) in fully gelatinized system
was higher than that in the native starch (0.45 g/g of starch;
Tab. 3). However, the unfrozen water content in gelatinized
starch decreased to 0.41 g /g of starch (29% water) after
annealing (Tab. 3). As the amount of plasticizer (unfrozen
water) decreased, glass transition temperature increased.
These results also support the finding of Tananuwong and
Reid [19], who reported that annealing at a temperature
around subzero glass transition temperature could give a
more clear glass transition peak in the derivative curve.
The ‘three-microphase’ model indicated that the
sequence of thermal transitions of granular starch
in water would be Tg (mobile amorphous) , Tg (rigid amorphous)
, Tm (rigid crystalline) [5, 22]. Based on the present and a
previous study [6[, we suggest the following sequence
when granular starch is heated in water: Tg (mobile amorphous)
, Tg (rigid amorphous) < Tm (rigid crystalline).
4 Conclusions
Subzero glass transition was observed in annealed gran-
ular waxy maize starch without gelatinization. The small
but observable transition was attributed to the part of the
mobile phase in granular starch. This study supports the
proposed concept that there are two types of amorphous
phase in granular starch: rigid and mobile. The glass
transition of the mobile amorphous phase in granular
starch extends over a broad range of temperatures before
gelatinization and is not easily pinpointed by conventional
DSC, but part of the transition can be observed below
zero in excess water. The rigid amorphous phase begins
to become mobile when temperature is high enough to
melt the crystals in granular starch [6].
Acknowledgement
This is contribution no. 09-252-J from Kansas Agricultural
Experiment Station, Kansas State University, Manhattan,
KS, USA.
© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Starch/Stärke 61 (2009) 687–695
References
[1] D. French: Organization of starch granules, in Starch Chem-
istry and Technology (Ed. R.L. Whisler, J.N. BeMiller, E.F.
Paschall), Academic Press, New York, 1984.
[2] H. F. Zobel: Molecules of granules: a comprehensive starch
review. Starch/Stärke 1988, 40, 44–50.
[3] T. A. Waigh, M. J., Gidley, B. U. Komanshek, A. M. Donald:
The phase transformations in starch during gelatinization: a
liquid crystalline approach. Carbohydr. Res. 2000, 328(2),
165–176.
[4] T. A. Waigh, A. M. Donald, F. Jeidelbach, C. Riekel, M. J.
Gidley: Analysis of the native structure of starch granules
with small angle X-ray microfocus scattering. Biopolymers
1999, 19, 91–105.
[5] C. G. Biliaderis, C. M. Page, T. J. Maurice, B. O. Juliano:
Thermal characterization of rice starched: a polymeric
approach to phase transitions of granular starch. J. Agric.
Food Chem. 1986, 34, 6–14.
[6] Y. Liu, Y.-C. Shi: Phase and state transitions in granular
starches studied by dynamic differential scanning calo-
rimetry. Starch/Stärke 2006, 58, 433–442.
[7] Y.-C. Shi: Two- and multi-step annealing of cereal starches in
relation to gelatinization. J. Agric. Food Chem. 2008, 56,
1097–1104.
[8] S. Z. D. Cheng, Z. Q. Wu, B. Wunderlich: Glass transition
and melting behavior of poly(thio-1,4-phenylene). Macro-
molecules 1987, 20, 2802–2810.
[9] P. Hou, P. Cebe: Effects of thermal history on the rigid amor-
phous phase in poly(phenylene sulfide). Colloid. Polym. Sci.
1992, 270, 840–852.
[10] R. K. Krishnaswamy, D.S. Kalika: Dynamic mechanical
relaxation properties of poly(ether ketone). Polymer 1994,
35, 1157–1165.
[11] L. Slade, H. Levine: Non-equilibrium melting of native gran-
ular starch: Part I. Temperature location of the glass transi-
tion associated with gelatinization of A-type cereal starches.
Carbohydr. Polym. 1988, 8, 183–208.
[12] R.-M. Huang, W.-H Chang, Y.-H. Chang, C.-Y. Lii: Phase
transition of rice starch and flour gels. Cereal Chem. 1994,
71, 202–207.
[13] Y. J. Wang, J. Jane: Correlation between glass transition
temperature and starch retrogradation in the presence of
sugar and maotodextrins. Cereal Chem. 1994, 71(6), 527–
531.
[14] Y. Vodovots, P. Chinachoti: Glass-rubbery transition and
recrystallization during aging of wheat starch gels. J. Agric.
Food Chem. 1998, 46, 446–453.
[15] M. H. Lim, H. Wu, D. S. Reid: The effect of starch gelatini-
zation and solute concentrations on Tg0 of starch model
system. J. Sci. Food Agric. 2000, 80, 1757–1762.
[16] P. Chantakanonda, S. Varavinit, P. Chinachoti: Relationship
of gelatinization and recrystallization of cross-linked rice to
glass transition temperature. Cereal Chem. 2000, 77, 315–
319.
[17] J. K. Jang, S. H. Lee, S. C. Cho, Y. R. Pyun: Effect of sucrose
on glass transition, gelatinization, and retrogradation of
wheat starch. Cereal Chem. 2001, 78, 186–192.
[18] H. J. Chung, E. J. Lee, S. T. Lim: Comparison in glass tran-
sition and enthalpy relaxation between native and gelati-
nized rice starches. Carbohydr. Polym. 2002, 48, 287–298.
[19] K. Tananuwong, D. S. Reid: Differential scanning calorimetry
study of glass transition in frozen starch gels. J. Agric. Food
Chem. 2004, 52, 4308–4317.
[20] D. A. Yost, R. C. Hoseney: Annealing and glass transition of
starch. Starch/Stärke 1986, 38, 289–292.
www.starch-journal.com
Starch/Stärke 61 (2009) 687–695
[21] K. J. Zelenznak, R. C. Hoseney: The glass transition in
starch. Cereal Chem. 1987, 64, 121–124.
[22] C. G. Biliaderis: Non-equilibrium phase transitions of aque-
ous starch systems, in Water Relationships in Food. (Eds. H.
Levine, L. Slade) Plenum Publishing Corp., New York, 1991,
251–273.
[23] T. J. Maurice, L. Slade, R. R. Sirett, C. M. Page: Poly-
saccharide–water interactions – thermal behavior of rice
starch, in Properties of Water in Food (Eds. D. Simatos, J. L.
Multon) Martinus Nijhoff Publishers, Dordrecht, Nether-
lands, 1985, pp. 211–217.
[24] L. Slade, H. Levine: Recent advances in starch retro-
gradation, in Recent Developments in Industrial Poly-
saccharides (Eds. S. S. Stivala, V. Crescenzi, I. C. M. Dea)
Dordon and Breach Science, New York, 1987.
[25] H. Liu, J. Lelievre: A differential scanning calorimetry study
of glass and melting transitions in starch suspensions and
gels. Carbohydr. Res. 1991, 219, 23–32.
[26] H. Liu, J. Lelievre, W. Ayoung-Chee: A study of starch gela-
tinization using differential scanning calorimetry, X-ray, and
birefringence measurements. Carbohydr. Res., 1991, 210,
79–87.
[27] B. Wunderlich: Thermal Analysis. Boston, Academic Press,
1990.
[28] T. R. Noel, S. G. Ring: A study of the heat capacity of starch/
water mixtures. Carbohydr. Res. 1992, 227, 203–213.
© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Subzero Glass Transition of Waxy Maize Starch 695
[29] I. Tan, C. C. Wee, P. A. Sopade, P. J. Halley: Investigation of
the starch gelatinization phenomena in water-glycerol sys-
tem: application of modulated temperature differential
scanning calorimetry. Carbohydr. Polym. 2004, 58, 191–204.
[30] K. Woo, P. A. Seib: Cross-linked resistant starch: preparation
and properties. Cereal Chem. 2002, 79(6), 819–825.
[31] R. J. Smith, J. Caruso: Determination of phosphorus, Meth-
ods in Carbohydr. Chem. 1964, 4, 42–46.
[32] R. F. Tester, S. J. J. Debon, J. J. Karkalas: Annealing of
wheat starch. J. Cereal Sci. 1998, 28, 259–272.
[33] H. Levine, L. Slade: A polymer physicochemical approach to
the study of commercial starch hydrolysis products (SHPs).
Carbohydr. Polym. 1986, 6, 213–244.
[34] S. A. Brown, D. French: Specific adsorption of starch oligo-
saccharides on the gel phase of starch granules. Carbohydr.
Res. 1977, 59, 203–212.
[35] J. M. V. Blanshard: Physiochemical aspects of starch gela-
tinization, in Polysaccharides in Food (Eds. J. M. V. Blan-
shard, J. R. Mitchell), Butterworths, London, 1979.
[36] A. C. Eliasson, M. Gudmundsson: Starch: physicochemical
and functional aspects, in Carbohydrates in Food (Ed. A. C.
Eliasson), Marcel Dekker Inc., New York, 1996.
(Received: April 10, 2009)
(Revised: July 10, 2009)
(Accepted: August 8, 2009)
www.starch-journal.com