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Graduate School of Life Sciences and Biotechnology, Korea University, Seoul 136-701, Republic of Korea
Washington State University, Department of Crop & Soil Sciences, Pullman, WA 99164-6420, USA
c
Department of Food Science & Technology and Carbohydrate Bioproduct Research Center, Sejong University, 98 Gunja-Dong, Gwangjin-Gu, Seoul 143-747, Republic of Korea
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 1 June 2009
Received in revised form
10 September 2009
Accepted 22 September 2009
Gelatinized waxy and normal corn starches at various concentrations (2050%) in water were stored
under temperature cycles of 4 C and 30 C (each for 1 day) up to 7 cycles or at a constant temperature of
4 C for 14 days to investigate the effects of temperature cycling on the retrogradation of both starches.
Compared to starches stored only at 4 C, both starches stored under the 4/30 C temperature cycles
exhibited smaller melting enthalpy for retrogradation (DHr), higher onset temperature (To), and lower
melting temperature range (Tr) regardless of the starch concentration tested. Fewer crystallites might be
formed under the temperature cycles compared to the isothermal storage, but the crystallites formed
under temperature cycling appeared more homogeneous than those under the isothermal storage. The
effect of starch content on the retrogradation was greater when the starch gels were stored under cycled
temperatures. The reduction in DHr and the increase in conclusion temperature (Tc) by retrogradation
under 4/30 C temperature cycles became more apparent when the starch concentration was lower (20 or
30%). Degree of retrogradation based on melting enthalpy was greater in normal corn starch than in waxy
corn starch when starch content was low.
2009 Elsevier Ltd. All rights reserved.
Keywords:
Temperature cycling
Retrogradation
Corn starch
1. Introduction
The starch granule, commonly composed of both amylose and
amylopectin, is semicrystalline. The crystalline regions in granules
appear in clusters of branched amylopectin chains. Amylose,
mainly linear starch chains, is largely amorphous and randomly
distributed between amylopectin clusters (Bemiller, 2007). When
the starch granule is heated in the presence of water, the semicrystalline structure in granules transforms to an amorphous form;
this process is termed gelatinization. Gelatinized starch, however,
tends to re-associate in an ordered crystalline structure during
storage, which is termed retrogradation (Yuan et al., 1993).
As the retrogradation of starch affects the acceptability and shelf
life of starchy food, its control in rate and degree has been
substantially studied by food scientists. Starch retrogradation
occurs in three phases: nucleation, i.e. formation of critical nuclei;
propagation, i.e. growth of crystals from the nuclei formed; and
maturation, i.e. crystal perfection or continuous slow growth. The
58
2. Experimental
2.1. Materials
2.4. Statistical analysis
Waxy and normal corn starches were gifts from Samyang Genex
Company (Seoul, Korea). The moisture content of waxy corn starch
was 13.2% and that of normal corn starch was 12.6%, determined by
Normal
Waxy
20%
(14.4J/g)
30%
(14.5J/g)
20%
(16.4J/g)
30%
(17.6J/g)
40%
(14.7J/g)
40%
(18.5J/g)
50%
(15.0J/g)
50%
(19.6J/g)
M2
M1
0.1m W
20
40
G
60
80
M1
100
Temperature (C)
0.1m W
120
20
G
40
60
80
100
120
Temperature (C)
Fig. 1. DSC gelatinization thermograms of waxy and normal corn starches at various concentrations in water. Data in brackets are values of melting enthalpy for gelatinization (DHg).
Each value is the mean of triplicate measurements.
59
Normal
Waxy
2d
2d
20%
14d
20%
14d
2d
2d
30%
14d
14d
2d
30%
2d
40%
14d
14d
40%
2d
50%
2d
14d
50%
14d
0 .1 m W
20
30
0 .1 m W
40
50
60
70
20
80
30
Temperature (C)
40
50
60
70
80
Temperature (C)
Waxy
Normal
1cycle
1cycle
20%
Endothermic Heat Flow
7cycles
1cycle
20%
7cycles
30%
1cycle
7cycles
30%
1cycle
7cycles
40%
1cycle
7cycles
40%
7cycles
1cycle
50%
1cycle
7cycles
50%
7cycles
0.1mW
20
30
0.1mW
40
50
60
70
80
Temperature (C)
20
30
40
50
60
70
80
Temperature (C)
Fig. 2. (A) DSC thermograms of waxy and normal corn starches retrograded at 4 C for 2 and 14 days at various starch concentrations; (B) DSC thermograms of waxy and normal
corn starches retrograded for 1 and 7 temperature cycles of 4 C for 1 day and 30 C for 1 day at various starch concentrations.
60
Waxy
Waxy
Normal
Normal
70
60
50
40
30
20
80
70
60
50
40
30
20
2
10
12
14
Temperature Cycles
Fig. 3. Onset temperature (To) (open symbol) and the conclusion temperature (Tc) (solid symbol) of waxy (upper) and normal (lower) corn starches at various concentrations: 20%
(square), 30% (round), 40% (up triangle) and 50% (diamond). Starches were retrograded at 4 C for 14 days (left) or under the temperature cycles of 4 C for 1 day and 30 C for 1 day
up to 7 cycles (right).
by reorganization (crystallite perfection) and nal melting of perfected crystallites in a DSC scan. Since starch crystallite perfection is
a slow process, it is less likely to occur in a short time, such as
during the DSC scan. Garcia et al. (1997) used SEM and TEM to
observe the structural changes of cassava starch granules during
gelatinization and illustrated that a competition of granules for
water during heating would take place when the starch concentration was high. In other words, the presence of the two endotherms (G and M1) indicates heterogeneity in water distribution
during starch gelatinization. Starch may solubilise in different
manners when its moisture content is changed. After gelatinization, the heterogeneous distribution of water as well as some water
limitation among the starch molecules might inuence the rate and
degree of starch retrogradation too.
3.2. DSC thermogram for retrogradation
Waxy and normal corn starches retrograded at a constant
temperature of 4 C exhibited broad endotherms at all concentrations tested (Fig. 2A). The shapes of these retrogradation endotherms varied as a function of starch concentration. After storage
for 2 days, the main peak was observed at about 55 C for 20% waxy
corn starch, moving to a higher temperature as starch concentration increased. A lower-temperature shoulder was apparent for
waxy corn starch of 40% and 50% concentration. After further
storage to 14 days, the major peak after the rst 2 days storage was
61
45
Waxy
Waxy
Normal
Normal
40
35
30
25
20
15
10
5
45
40
35
30
25
20
15
10
5
2
10
12
14
Temperature Cycles
Fig. 4. Melting temperature range (Tr) of retrograded waxy (upper) and normal (lower) corn starches at various concentrations: 20% (-), 30% (C), 40% (:) and 50% (A). Starches
were retrograded at 4 C for 14 days (left) or under the temperature cycles of 4 C for 1 day and 30 C for 1 day up to 7 cycles (right). Starch of 30% concentration retrograded at 4 C
(B) was included for comparison.
Tc values of both waxy and normal corn starches were little affected
(no difference at p < 0.05) by storage time, whereas the To
increased: from 28.3 to 33.2 C (p < 0.05) in 40% waxy corn starch
and from 26.1 to 32.6 C (p < 0.05) in 40% normal corn starch during
14 days storage at 4 C.
When both waxy and normal corn starches were stored under
the 4/30 C temperature cycling, To values were higher by 1819 C
compared with To values at constant 4 C, regardless of the starch
concentration studied. Silverio et al. (2000) reported that To was
only controlled by propagation temperature, regardless of the type
of the starch. Storage at 30 C during the propagation step might
melt some unstable crystallites formed at 4 C, which accounted for
the To increase under 4/30 C temperature cycles (Baik et al., 1997;
Durrani and Donald, 1995; Elfstrand et al., 2004; Park et al., 2009;
Silverio et al., 2000). The remaining crystallites could be melted at
higher temperatures. Tc values of both waxy and normal starches at
20% and 30% concentration increased by about 4 C and 2 C after 14
days, respectively, whereas those at 40% and 50% concentration
were relatively unchanged compared with the Tc values at constant
4 C. The greater To but relatively similar Tc under temperature cycled
storage compared to those stored at 4 C resulted in much smaller Tr
values. The crystallites formed under the 4/30 C temperature cycled
storage were more uniform and heat stable than those formed at
a constant 4 C. The stability of the crystallites of both waxy and
normal corn starches was more improved at lower concentration, as
indicated by a large increase in Tc. However, the crystallites of both
62
Waxy
Waxy
16
14
12
10
8
6
4
2
0
18
Normal
Normal
16
14
12
10
8
6
4
2
0
0
10
12
14
Temperature Cycles
Fig. 5. The melting enthalpy for retrogradation (DHr) of waxy (upper) and normal (lower) corn starches at various concentrations: 20% (-), 30% (C), 40% (:) and 50% (A). Starches
were retrograded at 4 C for 14 days (left) or under the temperature cycles of 4 C for 1 day and 30 C for 1 day up to 7 cycles (right). Starch of 30% concentration retrograded at 4 C
(B) was included for comparison.
14.5 J/g with cycled temperature storage (p < 0.05). The DHr values
of 20% and 50% normal corn starches dropped from 9.0 J/g to 6.4 J/g
(p < 0.05) and from 9.4 J/g to 9.0 J/g (no signicant difference at
p < 0.05), respectively, by storing starch under the cycled temperature rather than constant 4 C. As discussed previously, the crystallites formed at a lower starch concentration under 4 C were
more homogeneous but less stable. The stable crystallites formed at
lower concentration of starch after storage at 4 C could be due to
the melting of more unstable crystallites during the subsequent
storage at 30 C. This melting resulted in a signicant decrease in
DHr, whereas the crystallites were further perfected under a propagation temperature of 30 C, as indicated by the higher To and Tc.
The crystallites formed in low concentrations revealed a greater
degree of annealing under 4/30 C temperature cycles. These results
were consistent with those reported by Ward et al. (1994), who
found that 25% amylopectin showed smaller DHr but higher To than
40% amylopectin when both were nucleated at 1 C and then
propagated at 23 C.
DHr to DHg (Baik et al., 1997; Jane et al., 1999; Vandeputte et al.,
2003; Varavinit et al., 2003; Ward et al., 1994). When starch
gelatinized at a concentration greater than 30% was retrograded at
constant 4 C, DR of normal corn starch was lower than that of waxy
100
20%
90
80
70
70
60
60
50
50
40
40
30
30
20
20
10
10
30%
90
80
0
2
10
12
14
100
10
12
14
100
40%
90
50%
90
80
80
70
70
60
60
50
50
40
40
30
30
20
20
10
10
0
2
10
12
14
10
12
14
100
20%
90
63
30%
90
80
80
70
70
60
60
50
50
40
40
30
30
20
20
10
10
0
0
1
100
100
40%
90
80
80
70
70
60
60
50
50
40
40
30
30
20
20
10
10
50%
90
0
1
Temperature Cycles
Temperature Cycles
Fig. 6. The degree of retrogradation (DR) for waxy (blank) and normal (lled) corn starches at various concentrations. Starches were retrograded at 4 C for 14 days (upper) or under
the temperature cycles of 4 C for 1 day and 30 C for 1 day up to 7 cycles (lower).
64
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