LWT - Food Science and Technology 59 (2014) 597e604

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LWT - Food Science and Technology

journal homepage: www.elsevier.com/locate/lwt

Phase transition and swelling behaviour of different starch granules

over a wide range of water content
Shujun Wang a, *, Caili Li a, 1, Jinglin Yu b, 1, Les Copeland c, Shuo Wang a
a
Key Laboratory of Food Nutrition and Safety, Ministry of Education of China, College of Food Engineering and Biotechnology, Tianjin University of Science
& Technology, Tianjin 300457, China
b
Research Centre of Modern Analytical Technique, Tianjin University of Science & Technology, Tianjin 300457, China
c
Faculty of Agriculture and Environment, The University of Sydney, NSW 2006, Australia

a r t i c l e i n f o a b s t r a c t

Article history: The relationship between swelling behaviour and thermal transitions of starch was investigated by
Received 25 March 2014 differential scanning calorimetry (DSC) in combination with swelling power of starch. Sodium dodecyl
Received in revised form sulphate (SDS)-treated wheat, waxy maize and potato starches showed increasing swelling power with
30 May 2014
increasing water/starch ratio. In contrast, swelling power of untreated wheat and high-amylose maize
Accepted 10 June 2014
Available online 25 June 2014
starches increased initially with increasing water/starch ratio, and then remained essentially unchanged
above a certain ratio. The main endotherm G of native and SDS-treated wheat starch broadened pro-
gressively with increasing water/starch ratio up to 10:1. SDS-treated wheat, waxy maize and potato
Keywords:
Wheat starch
starches showed a typical endotherm over the whole range of water/starch ratios from 0.33:1 to 25:1, but
Potato starch the maximum enthalpy change occurred at different water/starch ratios. Our results indicate that
Maize starch thermal transition behaviour of starch granules is a very complex process, which involves swelling and
Swelling leaching of starch polymer molecules rather than the dissociation of double helices or melting of
Thermal transition crystallites.
© 2014 Elsevier Ltd. All rights reserved.

1. Introduction hydrothermal processing (Biliaderis, 2009; Goldstein, Nantanga, &

When heated in excess water, starch granules undergo an irre-
versible phase transition, referred to as gelatinization, in which the
highly ordered structure is disrupted. Starch gelatinization has
been broadly defined as the “collapse (disruption) of molecular
orders (breaking of hydrogen bonds) within the starch granule
manifested in irreversible changes in properties such as water
uptake, granular swelling, crystallite melting, unwinding of double
helices, loss of birefringence, starch solubilisation and viscosity
development”(Atwell, 1988; BeMiller, 2011; Biliaderis, 2009). This
definition implies that at least three distinct changes occur during
gelatinization: granule swelling, disruption of ordered structures
(crystalline and molecular) and solubilisation of starch molecules
(Wang & Copeland, 2012a). The extent to which these changes
occur is a major determinant of the functional properties of starch,
including its susceptibility to enzymatic digestion, and depends on
the type of starch and the moisture and heating conditions during
* Corresponding author. Tel.: þ86 60601430; fax: þ86 22 60601332.
E-mail address: sjwang@tust.edu.cn (S. Wang).
1
Equal contribution.
Seetharaman, 2010).
Starch gelatinization has been studied extensively using a vari-
ety of techniques, of which DSC is accepted widely as most suitable
for quantitative and qualitative analyses following pioneering work
of Stevens and Elton (1971) and Donovan (1979). Other techniques
including wide angle X-ray diffraction (WAXD), small angle X-ray
scattering (SAXS), 13C nuclear magnetic resonance (NMR), FTIR, and
microscopy (light microscopy, electron microscopy and trans-
mission microscopy) have also been used directly or in combination
with DSC, to examine multiple aspects of starch gelatinization
simultaneously (Biliaderis, 2009; Ratnayake & Jackson, 2009; Wang
& Copeland, 2013a, 2013b; Derycke et al., 2005; Jenkins & Donald,
1998; Le Bail et al., 1999; Vermeylen et al., 2006a; Vermeylen et al.,
2006b).
Donovan's pioneering work considered the effect of water
content on thermal transitions of starch granules (Donovan, 1979).
He observed a single constant endotherm (called endotherm G)
with potato starch at a water/starch ratio of 1:1.5 or greater, which
was assumed to represent the complete gelatinization of starch
(Donovan, 1979). However, other studies have obtained different
DSC profiles, indicating that Donovan's observations and conclu-
sions for potato starch, which is known to have granules with a

http://dx.doi.org/10.1016/j.lwt.2014.06.028
0023-6438/© 2014 Elsevier Ltd. All rights reserved.
598 S. Wang et al. / LWT - Food Science and Technology 59 (2014) 597e604

typical swelling property, do not apply generally. Increasing 20

18
experimental evidence is showing that the endotherm G at a water/ 18
starch ratio above 1.5 shifts to higher temperature with increasing 16
16
water/starch ratio and does not represent the full gelatinization of
14
e, & Thoen, 2002; Liu, Yu, Xie, Swelling power C

Swelling power (g/g)

starch granules (Cruz-Orea, Pitsi, Jame 14

Starch solubility (%)

& Chen, 2006; Randzio, Flis-Kabulska, & Grolier, 2002; Tananu- 12 12
Starch solubility
wong & Reid, 2004; Wang & Copeland, 2012a, 2012b). In addition
10 10
to water content, the surface proteins and lipids were shown to
influence the swelling behaviour and thermal properties of starch 8 8
granules (Debet & Gidley, 2006; Wang et al., 2014). Sodium dodecyl 6
6 B
sulphate (SDS) solution has been proven to remove proteins and
4
lipids from surface of starch granules sufficiently (Debet & Gidley, 4
2006). 2
2 A
In a previous study (Wang & Copeland, 2012a), we investigated
0
the effect of water content on the thermal transitions of pea starch 0
granules over a wide range of water/starch ratios. The endothermic

0.33:1
0.5:1
0.67:1
1:1
1.33:1
1.67:1
2:1
3:1
4:1
5:1
7.5:1
10:1
15:1
20:1
25:1
30:1
--
transition of pea starch granules was proposed to reflect the
swelling behaviour of starch during DSC heating, and not complete Water/starch ratio (%)
gelatinization. The present study is aimed at determining how
generally this relationship between DSC thermal transitions and Fig. 1. Effect of water/starch ratio (40 mg of starch was used) on swelling power and
swelling behaviour, as observed for pea starch, applies, thereby solubility of wheat starch granules. The zones marked A, B and C correspond to the
stages of swelling discussed in the text, namely A: limited swelling without leaching;
increasing our understanding of what the DSC endothermic tran-
B: incomplete swelling with some leaching; C: complete swelling with continuous
sitions for starch actually represent. To this end, the swelling power leaching.
and DSC profiles of wheat starch, waxy maize starch, potato starch
and high-amylose maize starch were investigated over a wide
range of water/starch ratios (from 0.33:1 to 25:1 or 30:1). To our centrifuged at 13, 000  g for 10 min. When a supernatant was
knowledge, this is the first study to investigate the thermal tran- obtained, it was transferred carefully to a glass evaporating dish,
sitions of different starches over such a wide range of water/starch evaporated to dryness on a steam bath, and dried further for 24 h at
ratios. 80  C. SDS-treated wheat starch, potato starch and waxy maize
starch formed a soft gel, making it difficult to separate a clear su-
2. Materials and methods pernatant even after centrifugation. For these starches, the starch
solubility was considered to be zero. The sedimented, swollen
2.1. Materials granules and dried soluble fraction were weighed to determine
swelling power (g H2O absorbed/g dry starch) and solubility (% of
Wheat, potato, and waxy maize starches were obtained from dry starch) using the following formulae:
commercial sources, with amylose content of 27%, 25% and 3%,
respectively. High-amylose maize starch (85% amylose) was ob- Solubility; S ¼ ½weight of solubles=
tained from the National Starch and Chemical Company (Shanghai,  ½dry weight of original starch
China). The starches were used without further purification. To
investigate the influence of surface proteins and lipids on starch
swelling and thermal transition, wheat starch was treated with 2% Swelling power; SP ¼ ½weight of swollen granules=
sodium dodecyl sulphate (SDS) solution at room temperature for  ½dry weight of original starch
24 h to remove surface proteins and lipids (Debet & Gidley, 2006).
All other chemicals were analytic grade from SigmaeAldrich
Chemical Corporation (Shanghai, China).
40 1.0

2.2. Sample preparation 35

0.8
30 Swelling power
To understand the swelling behaviour of starches during the
Swelling power (g/g)

Starch solubility (%)

DSC heating, the water:starch ratios used in the DSC measurements Starch solubility
25
were largely consistent with those used in the swelling power test, 0.6

which can be seen in Figs. 1e5. For direct comparison of the effect of 20
water/starch ratio on swelling power and DSC thermal transition, 0.4
15
the water/starch ratio used in Figures of DSC thermal transition
parameters was adjusted correspondingly. 10
0.2
2.3. Swelling power and starch solubility 5

0 0.0
Swelling power and solubility of starch were determined in
triplicate according to the method described elsewhere (Wang &
0.33:1
0.5:1
0.67:1
1:1
1.33:1
1.67:1
2:1
3:1
4:1
5:1
7.5:1
10:1
15:1
20:1
25:1
30:1
--

Copeland, 2012c) as follows. Exactly 40 mg (wet basis) of starch

were weighed into a 2 ml screw cap plastic test tube and water was
Water/starch ratio (w/w)
added. After the lid was screwed on tightly, the starch-water
mixtures were heated in a water bath at 92.5  C for 30 min with Fig. 2. Effect of water/starch ratio on swelling power and starch solubility of SDS-
regular shaking. The samples were cooled at 20  C for 3 min and treated wheat starch.
 S. Wang et al. / LWT - Food Science and Technology 59 (2014) 597e604 599

-2 2.4. Differential scanning calorimetry

a Native wheat starch
3:1
-4 Thermal transition measurements of starch were made over a
3:1.5
wide range of water content using a Modulated Differential Scan-
Endothermic heat flow

3:2
-6
3:3 ning Calorimeter MDSC 2920 instrument (TA Instruments Inc.,
3:4
Delaware, USA) equipped with a thermal analysis data station and
-8
3:5 data recording software. Exactly 3 mg of starch were weighed into
-10 3:6
40 mL aluminium pans. Different amounts of distilled water were
Endo
3:9 added to the starch in the DSC pans with a microsyringe. For
-12 Exo samples with low water content (water/starch ratios of 1:3 and
3:12
1:2), a pin was used to mix gently starch with water. When larger
3:15
-14 volumes of water were added, care was taken to ensure that the
3:22.5
3:30 starch granules were completely immersed in the water by gentle
-16 shaking. The pans were sealed and reweighed to determine the
2:30
amount of water added. The sealed pans were allowed to stand
-18
1:25 overnight at room temperature before DSC analysis. An empty pan
-20
was used as a reference. The pans were heated from 30 to 120  C at
50 60 70 80 90 100 110 120 a scanning rate of 10  C/min. The instrument was calibrated using
o indium as a standard. The analysis was done in duplicate, and the
Temperature ( C) precision of water addition based on the weight of the sealed pans
80 before heating was estimated to be ±0.5%.
Start temperature The Universal Analysis 2000 software was used to analyse the
b main endotherm of the DSC traces for start (Ts), peak (Tp) and end
Peak temperature
75
End temperature (Te) temperatures and enthalpy change (DH). The start and
Transition temperature ( o C)

conclusion temperatures were defined, respectively, as the point at

70
which the DSC trace first starts and finally ceases to deviate from a
flat baseline. The peak temperature was defined as the point of
maximum endothermic heat flow relative to the baseline. The DH
65 was defined as the area under the line drawn from the start tem-
perature to the end temperature.

60
2.5. Statistical analysis

55 All analyses were replicated at least twice and mean values and
standard deviation values are reported. Analysis of variance (one-
way ANOVA) by Duncan's test (p < 0.05) were conducted using the
50 SPSS 10.0 Statistical Software Program (SPSS Inc. Chicago, IL, USA).
0.33:1

0.5:1

0.67:1

1:1

1.33:1

1.67:1

2:1

3:1

4:1

5:1

7.5:1

10:1

3. Results
Water/starch ratio (w/w)
3.1. Effect of water content on swelling power and solubility of
14
wheat starch
c
12 Swelling power of native wheat starch increased from 1.5 g/g at
a water/starch ratio of 0.33:1 to 16.7 g/g at a water/starch ratio of
10 15:1, above which swelling power decreased slightly (Fig. 1). No
Enthalpy change J/g

supernatant was obtained on centrifugation when the water/starch

8 ratio was below 10:1, indicating that all of the water added was
absorbed into the swollen granules and remained inside the starch
6 gel. At a water/starch ratio of 10:1, a supernatant was obtained after
centrifugation, even though the swelling power of starch had not
reached a maximum (Fig. 1). The amount of wheat starch solubi-
4
lized (i.e., leached out of the swollen granules into the supernatant)
at a water/starch ratio of 10:1 was 1.2%. The solubility of wheat
2
starch increased to a value of 13.1% at a water/starch ratio of 30:1
(Fig. 1).
0 In comparison, SDS-treated wheat starch displayed a quite
different swelling power curve (Fig. 2). Swelling power increased
continuously with increasing water content up to a value of 34.6 g/g
0.33:1

0.5:1

0.67:1

1:1

1.33:1

1.67:1

2:1

3:1

4:1

5:1

7.5:1

10:1

15:1

Water/starch ratio (w/w)

w); b. Effect of water/starch ratio (the ratio was modified for comparison with that for
swelling power test) on DSC transition temperatures of wheat starch; c. Effect of water/
Fig. 3. a: Effect of water/starch ratio (3 mg of starch was used) on DSC thermograms of
starch ratio (the ratio was modified for comparison with that for swelling power test)
wheat starch (the numbers under each line represent the actual water/starch ratio (w/
on DSC enthalpy changes of wheat starch.
600 S. Wang et al. / LWT - Food Science and Technology 59 (2014) 597e604

-2 at a water/starch ratio 30:1, at which point it had not reached a

a potato starch
plateau, unlike untreated wheat starch as shown in Fig. 1. A theo-
3:1
-4 3:1.5 retical value for swelling power of starch can be calculated from the
3:2 weight of starch plus added water divided by the dry weight of the
Endothermic heat flow

3:3 G M1
-6 starch (Wang & Copeland, 2012a). At a water/starch ratio of 30:1,
3:4
the actual swelling power of SDS-treated starch was slightly less
3:5
-8 than the theoretical value. No supernatant was obtained on
3:6
centrifugation of the swollen granules after heating and cooling,
3:9
-10 indicating that no starch was leached out of the SDS-treated starch
3:12
3:15 granules.
-12 3:22.5
Potato starch and waxy maize starch presented similar swelling
3:30 power curves as that of SDS-treated wheat starch (not shown). The
2:30 swelling power of both potato and waxy maize starches starch
-14
increased with increasing water/starch ratio without reaching a
1:25 plateau, and no supernatant was obtained after centrifugation of
-16
the swollen granules, indicative of the strong binding of water by
50 60 70 80 90 100 110 120 the swollen granules. The measured swelling power was close to
o
the calculated theoretical value (22.9 g/g and 23.3 g/g, respectively,
Temperatrue ( C)
for potato starch at a water/starch ratio of 20:1).
85 The swelling trend of high-amylose maize starch resembled that
Start temperature b of untreated wheat starch (data not shown). Swelling power
Peak temperature
80 increased to a maximum of 4.4 g/g at a water/starch ratio of 3:1,
End temperature
above which swelling power decreased slightly to a plateau value of
Transition temperature ( o C)

4.0 g/g above a water/starch ratio of 10:1. Below a water/starch ratio

75
of 3:1, no starch was leached out of the swollen granules after
centrifugation, but starch solubility increased to a maximum value
70 of 5.8% at a water/starch ratio of 10:1.

65 3.2. Thermal transitions of starch at different water/starch ratios

DSC thermograms of native wheat starch are shown in Fig. 3a,

60
with the effect of different water/starch ratios on transition tem-
peratures and enthalpy change shown in Fig. 3b and c, respectively.
55 A well-defined endothermic transition (endotherm G) was
observed between 50 and 85  C for water/starch ratios below 15:1.
50 At greater water/starch ratios, the initial endothermic trend
seemed to flatten out at the maximum heat flow (Fig. 3a). A second
0.33:1
0.5:1
0.67:1
1:1
1.33:1
1.67:1
2:1
3:1
4:1
5:1
7.5:1
10:1
15:1
25:1

shallow endotherm occurring at about 90e100  C was also

observed, which appeared to overlap with a subsequent exothermic
Water/starch ratio (w/w) transition (Fig. 3a).
25 With increasing water/starch ratios, endotherm G shifted to a
c higher temperature, as shown by a gradual increase in the peak (Tp)
and end (Te) temperatures. In contrast, the start temperature (Ts) of
20 endotherm G remained essentially unchanged across the entire
range of water/starch ratios (Fig. 4c). Tp and Te of endotherm G
Enthalp change (J/g)

increased from 61.8 to 65.1  C, and from 66.8 to 73.3  C, respec-

15
tively, whereas the enthalpy change of endotherm G increased
gradually from 1.3 to 13.4 J/g with increasing water/starch ratio up
10
to 10:1. When the water/starch ratio was above 10:1, the endo-
therm G flattened out from the maximum heat flow, making
identification of Tc of endotherm G extremely difficult.
5 DSC thermograms of SDS-treated wheat starch were similar to
those shown for native wheat starch. Tp and Te increased from 62.4
to 65.8  C and from 65.8 to 71.1  C, respectively, as the water/starch
0 ratio increased up to 15:1 (results not shown). The enthalpy change
increased from 1.4 (water/starch ratio of 0.33:1) to 12.5 J/g as the
water/starch ratio increased up to 10:1, and then decreased to
0.33:1

0.5:1

0.67:1

1:1

1.33:1

1.67:1

2:1

3:1

4:1

5:1

7.5:1

10:1

15:1

25:1

10.2 J/g at a water/starch ratio of 15:1. A weak endothermic tran-

sition was still observed at a water/starch ratio of 25:1, although Tc
Water/starch ratio (w/w)
was not identified clearly.
Fig. 4. a: Effect of water/starch ratio on DSC thermograms of potato starch (the Potato starch showed a typical endothermic transition over the
numbers under each line represent the actual water/starch ratios); b: Effect of water/ wide range of water/starch ratios from 0.33:1 to 25:1 (Fig. 4a). At
starch ratio (the ratio was modified for comparison with that for swelling power test) water/starch ratios of 0.33:1 and 0.5:1, the endothermic transition
on DSC transition temperatures of potato starch; c: Effect of water/starch ratio (the
was small, and at water/starch ratios of 0.67:1 and 1:1, a shoulder
ratio was modified for comparison with that for swelling power test) on DSC enthalpy
changes of potato starch. on the high-temperature side of endotherm G developed, which
 S. Wang et al. / LWT - Food Science and Technology 59 (2014) 597e604 601

was termed endotherm M1. Similar to SDS-treated wheat starch,

-2 a Waxy maize starch potato starch also showed a typical endotherm G transition at a
3:1 water/starch ratio of 25:1. At water/starch ratios greater than
-4 3:2 1.33:1, the system showed a characteristic endothermic transition
Endothermic heat flow

3:3
with well-defined Ts, Tp and Te values. Tp increased from 65.1 to
-6 3:4
68.0  C as the water/starch ratio increased up to 10:1. Tc increased
3:5
-8
gradually from 66.2 to 71.0  C as the water/starch ratio was
3:6
3:9
increased from 0.33:1 to 1:1, followed by a sharp increase to 77.8  C
G M1
-10 at a water/starch ratio of 1.33:1. At higher water/starch ratio, Tc did
3:12
not vary greatly until the water/starch ratio was 10:1, above which
3:15
-12 3:22.5
Tc decreased slightly. The enthalpy change increased from 1.0 to
3:30 17.0 J/g as the water/starch ratio increased up to 1.33:1. Above this
-14 2:30
ratio, the enthalpy remained essentially unchanged till the water/
starch ratio of 10:1, above which there was a slight decrease (Fig. 4b
1:25
-16 and c).
Typical endothermic transitions occurring between 50 and 80  C
-18 were observed for waxy maize starch at all of the water/starch
50 60 70 80 90 100 110 120 ratios measured, although at the lowest water/starch ratio endo-
o
Temperature ( C) therm G was small (Fig. 5a). Ts was not greatly affected by the water/
95 starch ratio. With water/starch ratio increasing, the peak of endo-
Start temperature thermic transition shifted slowly to higher temperature. Tp
b
90 Peak temperature increased from 70 to 73.4  C as the water/starch ratio increased
End temperature from 0.67:1 to 25:1. Te increased from 72.6 to 83.1  C as the water/
85
Transition temperature ( C)

starch ratio increased from 0.67:1 to 2:1 and did not change
o

80 significantly at higher ratios. The enthalpy change increased

sharply from 1.0 to 16.3 J/g at a water/starch ratio of 2:1 and then
75 did not change greatly at higher water/starch ratios (Fig. 5b and c).
Similar to potato starch, waxy maize starch also showed a biphasic
70
transition at certain water/starch ratios and a typical endothermic
65 transition at a water/starch ratio of 25:1.
No distinct endothermic transitions were observed over the
60 entire range of water/starch ratios for high-amylose starch. A broad
endothermic trend was observed, which was appeared to be fol-
55
lowed by an exothermic transition occurring at 100e120  C (data
50 not shown).
0.33:1

0.67:1

1:1

1.33:1

1.67:1

2:1

3:1

4:1

5:1

7.5:1

10:1

15:1

25:1

4. Discussion
Water/starch ratio (w/w)
The present study has sought to increase our understanding of
20
the starch gelatinization processes that DSC thermograms repre-
18
c sent and thereby advance our knowledge of the mechanism of
starch gelatinization. This is the first study to investigate swelling
16
power and solubility of water/starch systems over a wide range of
14 water/starch ratios for wheat, waxy maize, potato and high-
Enthalpy change (J/g)

amylose starches at fixed temperature (92.5  C). DSC thermal

12
transitions of the starches over the same wide range of water/starch
10 ratios were also recorded. The swelling power and starch solubility
of starch granules were measured at the same water/starch ratios
8
as were thermal transitions, with the aim of relating the swelling
6 behaviour of granules to thermal transitions.
4
4.1. Effect of water content on swelling power and starch solubility
2

0
Native wheat starch granules absorbed all the added water on
heating to 92.5  C, and no starch polymer molecules were leached
from the swollen granules after centrifugation when the water/
0.33:1

0.67:1

1:1

1.33:1

1.67:1

2:1

3:1

4:1

5:1

7.5:1

10:1

15:1

25:1

--

starch ratio was less than 10:1. Hence, under these conditions,
swelling of native wheat starch was incomplete. Starch polymer
Water/starch ratio (w/w) molecules started to leach out of the swollen granules at a water/
starch ratio of 10:1, even though granule swelling had not reached a
Fig. 5. a: Effect of water/starch ratio on DSC thermograms of waxy maize starch (the
maximum value. At a water/starch ratio of 15:1, starch granules
numbers under each line represent the actual water/starch ratios); b: Effect of water/
starch ratio (the ratio was modified for comparison with that for swelling power test) were swollen to their maximum extent under the conditions and
on DSC transition temperatures of waxy maize starch; c: Effect of water/starch ratio starch polymer molecules were leached in increasing amounts
(the ratio was modified for comparison with that for swelling power test) on DSC from the swollen granules. Starch polymer molecules continued to
enthalpy changes of waxy maize starch.
leach out of the granules as the water/starch ratio increased,
602 S. Wang et al. / LWT - Food Science and Technology 59 (2014) 597e604
whereas swelling power decreased slightly. Thus, swelling behav-
iour of wheat starch can be divided into three different stages
which occur progressively as the water/starch ratio increases:
limited swelling at low water/starch ratio (stage A), incomplete
swelling with starch leaching at high water/starch ratio (stage B),
and complete swelling with continuous starch leaching in excess
water (stage C) (Fig. 1). The swelling profile of wheat starch was
comparable with that of pea starch granules (Wang & Copeland,
2012a).
In comparison, swelling power of SDS-treated wheat starch did
not reach a limiting value as water/starch ratios were increased up
to 30:1. The measured swelling power of SDS-treated starch was
comparable to the theoretical values, consistent with starch poly-
mer molecules not being leached during the swelling power test.
No differences in swelling power and starch solubility were
observed between native wheat and SDS-treated starches at water/
starch ratios below 7.5:1, as the swelling of starch granules was
incomplete in both cases. However, as the water/starch ratio
increased, SDS-treated starch held more water, resulting in higher
swelling power and lower starch solubility. The increased swelling
capability of SDS-treated starch was assumed to be associated with
the removal of surface proteins and lipids, which are considered to
inhibit swelling of most cereal starches (Chan, Bhat, & Karim, 2010;
Debet & Gidley, 2006; Tester & Morrison, 1990).
The swelling power profiles of potato and waxy maize starches,
which were similar to that of SDS-treated wheat starch, did not
reach a limiting value at a water/starch ratio of 30:1. No leaching of
starch polymer molecules occurred over the whole range of water/
starch ratios, and the measured swelling power of these starches
was close to the theoretical value. Potato starch and waxy starch are
known to have very high swelling capacity. The high swelling po-
wer of potato starch has been proposed to be related to repulsion
between phosphate groups weakening the bonding within the
crystalline domain, thereby increasing potential for swelling
(Galliard & Bowler, 1987), whereas for waxy starch high swelling
power has been attributed to the high content of amylopectin,
which is assumed to absorb and hold more water within its three-
dimensional branched structure than the linear amylose (Wang,
Sharp, & Copeland, 2011).
In contrast to the other starches, high-amylose maize starch had
much lower swelling power, as has been reported for high-amylose
starches generally (Case et al., 1998; Liu, Ramsden, & Corke, 1997;
Shi, Capitani, Trzasko, & Jeffcoat, 1998). The lower swelling power
of high-amylose starch is considered to be associated with the
lower content of amylopectin and the presence of amyloseelipid
complexes (Tester & Morrison, 1990). The gelatinization tempera-
ture of high-amylose starches is generally higher than for other
starches (Carciofi et al., 2012; Li, Jiang, Campbell, Blanco, & Jane,
2008; Naguleswaran, Vasanthan, Hoover, & Bressler, 2013; Shi
et al., 1998; Wei et al., 2011). High-amylose starches begin to
swell below 100  C, but temperatures greater than 130  C are
required to fully disperse these starches due to the greater
involvement of amylose molecules in the crystalline regions than in
other starches (Shi et al., 1998). Hence, it is possible that at the
temperature used in the present experiments (92.5  C), the peak
swelling power value, which was observed at a water/starch ratio of
3:1, did not represent granules that had swollen completely.
4.2. Effect of water content on thermal transition behaviour of
starches
The thermograms of native wheat starch showed that endo-
therm G shifted to a higher temperature and that Tp, Tc and DH
increased gradually with increasing water/starch ratio up to 10:1. At
water/starch ratios greater than 2:1, Tp and Tc have been reported to
increase with increasing water content (Cruz-Orea et al., 2002;
Fukuoka, Ohta, & Watanable, 2002; Liu et al., 2006; Randzio
et al., 2002; Tananuwong & Reid, 2004; Wang & Copeland,
2012a; Wong & Lelievre, 1982). Similarly, the DH of endotherm G
has also been reported to increase with increasing water/starch
ratio for wheat starch (Randzio et al., 2002; Tananuwong & Reid,
2004), rice starch (Biliaderis, Page, Maurice, & Juliano, 1986),
legume starches (Wang & Copeland, 2012a) and maize starch (Liu
et al., 2006). At higher water/starch ratios, endotherm G flattened
out at the point of maximum heat flow and did not have a clearly
identified end point. Endotherm G has been proposed to represent
water absorption and swelling by starch granules, with the end
point corresponding to the completion of these processes under the
particular experimental conditions (Wang & Copeland, 2012a).
We propose that the change from a well-defined sharp endo-
therm G to a broadening thermogram without clearly defined
features represents the transition from granules absorbing water
and swelling to swelling of granules accompanied by leaching of
starch polymer molecules, considered to be predominantly
amylose. Accordingly, at a water/starch ratio of 2:1, swelling of
wheat starch granules is incomplete and endotherm G reflects the
partial swelling behaviour of starch granules rather than full gela-
tinization. This interpretation is substantiated by previous findings
that not all crystalline and lamellar structures are disrupted at the
end of this so-called gelatinization endotherm (Jenkins & Donald,
1998; Vermeylen et al., 2006a).
The thermograms of SDS-treated wheat starch were generally
similar to those of native wheat starch, with similar Ts, Tp and DH
changes over the wide range of water/starch ratios, although SDS-
treated starch had lower Te values. However, unlike native wheat
starch, the endotherm was still clearly defined at water/starch ra-
tios of 15:1 and 25:1, when the starch granules had not reached
maximum swelling and there was no leaching of starch polymer
molecules. This finding supports the proposal that endotherm G
represents the completion of water absorption and granule
swelling. SDS-treated starch displayed a more rapid and greater
swelling tendency as seen from decreased pasting temperature and
increased peak viscosity in RVA profiles (data not shown), and from
the swelling power data presented in this paper. The faster
completion of granule swelling was consistent with the lower Te
compared to native wheat starch at the same water/starch ratios.
DSC enthalpy change of starch reflects the loss of ordered structure
(double helices/crystallites) of granules (Cooke & Gidley, 1992), and
the similarity in DH for native and SDS-treated wheat starches is
consistent with SDS treatment not significantly affecting the crys-
talline structure of starch granules (data not shown). For SDS-
treated starch, the greater swelling tendency at a given water/
starch ratio implies comparatively more disruption of ordered
structures, which would tend to increase enthalpy change. On the
other hand, decreased Te indicates the end-point of granule
swelling reached under the water-limited conditions, occurred at a
lower temperature, which may cause less disruption to ordered
structure in the granules (for example, some of the more stable
helical regions are not affected at the lower temperature). The
balance between these two scenarios could result in the little or no
net change in enthalpy, as was observed.
The thermograms of potato and waxy maize starches had
several features in common. Firstly, both starches presented a weak
shoulder on the high-temperature side of endotherm G at low
water/starch ratios, as has been observed with other starches
(Donovan, 1979), although not in this and some previous studies
(Biliaderis et al., 1986; Fredriksson, Silvrio, Andersson, Eliasson, &
Aman, 1998; Patel & Seetharaman, 2010; Wang & Copeland,
2012a). Secondly, both starches reached the maximum enthalpy
change at low water/starch ratios (1.33:1 for potato starch and 2:1
 S. Wang et al. / LWT - Food Science and Technology 59 (2014) 597e604
for waxy maize starch), when both starches had swollen to only a
limited extent. Similar results were also reported for potato starch
(Cruz-Orea et al., 2002; Donovan, 1979) and waxy maize starch (Liu
et al., 2006), although potato and waxy maize starch had higher
maximum swelling power and greater maximum enthalpy changes
than other starches. Swelling power of potato and waxy maize
starch increased with increasing water/starch ratio up to 30:1, but
the enthalpy change did not follow this trend, and hence did not
correlate with the swelling of granules. The reason for this obser-
vation is unclear and needs to be investigated further. Finally,
similar to SDS-treated wheat starch, potato and waxy maize
starches both showed a clearly defined endotherm even at a water/
starch ratio of 25:1, when the all the water added was absorbed and
granule swelling occurred without leaching of starch polymer
molecules. Again, this is consistent with our hypothesis that
endotherm G reflects the water absorption and swelling of starch
granules.
The thermogram of high-amylose maize starch displayed an
endothermic trend over the whole range of water/starch ratios
rather than a typical endotherm, indicating that gelatinization of
high-amylose maize starch was limited at both low and high water/
starch ratios. As high-amylose starch requires high temperature for
complete gelatinization, the lack of a well-defined endotherm may
reflect limited swelling of granules at low water/starch ratios, and
swelling of granules with partial leaching of starch molecules at
high water/starch ratios.
4.3. Nature of overlapping endothermic and exothermic transitions
in DSC thermograms
Overlapping endothermic and exothermic transitions were
observed for all the starch-water systems, although the effect was
weak at some water/starch ratios. Similar observations have been
reported in other studies and have been attributed to the dissoci-
ation, melting and subsequent recrystallization of amyloseelipid
complexes (Derycke et al., 2005; Le Bail et al., 1999). While this
could apply to cereal starches, it is less likely to apply to tuber,
legume starches, and especially waxy starches, all of which contain
very small amounts of lipid. In a previous study, these overlapping
transitions were attributed to a phase transition of water from
vapour to liquid (Wang & Copeland, 2012a; 2012b). We now pro-
pose that this occurs by the following mechanism. Firstly, water is
absorbed into the granules causing them to swell and giving rise to
endotherm G. With increasing temperature, the liquid water mol-
ecules redistribute in the swollen granules, concomitant with
ongoing melting of residual crystallites, before the water molecules
vaporise and escape from the starch gel. The condensation of water
droplets on the inside of the pan lids results in the DSC exothermic
transition.
5. Conclusions
In this study, the effect of water/starch ratio on swelling
behaviour and DSC thermal transition of starch granules was
investigated. Swelling behaviour of starch granules as a function of
water/starch ratio at 92.5  C can be divided into three categories:
limited to complete swelling with partial leaching of starch poly-
mer molecules (as observed for wheat and pea starches), swelling
without leaching of starch polymer molecules (waxy maize and
potato starches), and limited swelling with some leaching of starch
polymer molecules (high-amylose starch). The endothermic tran-
sition over a wide range of water/starch ratio reflects different as-
pects of the swelling behaviour of starch granules during DSC
heating. For wheat and pea starches, the endotherm G reflects the
change from limited swelling to maximum swelling with partial
603
leaching of starch polymer molecules. For potato and waxy starches
with very high swelling power, the endotherm G only reflects
swelling of starch granules. However, the swelling behaviour of
high-amylose starch during DSC heating is not as easily
characterized.
Based on the results of the present study and previous work
(Wang & Copeland, 2012a), we propose that endotherm G in DSC
profiles of commonly used starch/water systems represents the
energy change mainly associated with water absorption and
granule swelling. As most DSC measurements are made at low
water/starch ratios (2:1 or 3:1), the extent to which endotherm G
represents starch gelatinization will depend on how gelatinization
is defined. If gelatinization includes solubilisation of starch poly-
mers, endotherm G obtained at water/starch ratios below which
starch polymers begin to leach out of granules will not represent
complete gelatinization. If gelatinization is defined as the complete
disruption of granular structure, a clearly defined endotherm G
would indicate this has occurred even though swelling of the
granules is incomplete and no starch polymer molecules have
leached out. As the endotherm obtained at a water/starch ratio of
2:1 does not represent the complete gelatinization of most starch
granules, the enthalpy change under these conditions does not
totally relate to the quantity or quality of starch crystalline struc-
ture. The relationships between the loss of ordered structure and
swelling behaviour of starch granules during thermal transition
need to be studied further to better understand the extent to which
the energy absorbed is for the unwinding of amylopectin helices, or
for the swelling of starch granules.
Acknowledgements
SW gratefully acknowledges the financial support from the
National Natural Science Foundation of China (31371720) and the
Natural Science Foundation of Tianjin (13JCYBJC38100). SW also
greatly appreciates the financial support of Haihe River Scholar
Program (000050401) from Tianjin University of Science &
Technology.
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