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Effects of heat-moisture treatment reaction conditions on the

physicochemical and structural properties of maize starch: Moisture and
length of heating

Article in Food Chemistry · April 2015

DOI: 10.1016/j.foodchem.2014.11.021 · Source: PubMed

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 Food Chemistry 173 (2015) 1125–1132

Contents lists available at ScienceDirect

Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Effects of heat–moisture treatment reaction conditions on the

physicochemical and structural properties of maize starch: Moisture
and length of heating
Zhongquan Sui a, Tianming Yao a, Yue Zhao a, Xiaoting Ye a, Xiangli Kong b,⇑, Lianzhong Ai c,⇑
a
Department of Food Science and Engineering, Key Lab of Urban Agriculture (South), Bor S. Luh Food Safety Research Center, School of Agriculture and Biology,
Shanghai Jiao Tong University, Shanghai 200240, China
b
Institute of Nuclear Agricultural Science, College of Agriculture and Biotechnology, Zhejiang University, Hangzhou 310029, China
c
School of Medical Instrument and Food Engineering, University of Shanghai for Science and Technology, Shanghai 200093, China

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

Article history: Changes in the properties of normal maize starch (NMS) and waxy maize starch (WMS) after heat–mois-
Received 2 June 2014 ture treatment (HMT) under various reaction conditions were investigated. NMS and WMS were adjusted
Received in revised form 8 October 2014 to moisture levels of 20%, 25% and 30% and heated at 100 °C for 2, 4, 8 and 16 h. The results showed that
Accepted 3 November 2014
moisture content was the most important factor in determining pasting properties for NMS, whereas the
Available online 8 November 2014
heating length was more important for WMS. Swelling power decreased in NMS but increased in WMS,
and while the solubility index decreased for both samples, the changes were largely determined by
Keywords:
moisture content. The gelatinisation temperatures of both samples increased with increasing moisture
Maize starch
HMT
content but remained unchanged with increasing heating length. The Fourier transform infrared
Moisture content (FT-IR) absorbance ratio was affected to different extents by the moisture levels but remained constant
Length of heating with increasing the heating length. The X-ray intensities increased but relative crystallinity decreased to
a greater extent with increasing moisture content. This study showed that the levels of moisture content
and length of heating had significant impacts on the structural and physicochemical properties of normal
and waxy maize starches but to different extents.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction (<35% slurry in water) and a relatively high temperature (80–

140 °C) above its glass transition temperature but below the
Starch is a biopolymer with unique physical and chemical char- temperature when gelatinisation occurs (Jacobs & Delcour, 1998;
acteristics that make it different from other carbohydrates. Most Hoover, 2010). HMT-mediated changes of starch properties are
starch granules consist of a mixture of two major polymers, amylose often found in products with starch in intact granular form. HMT
and amylopectin. Generally, native starches have some shortcom- decreases starch solubility, swelling power, amylose leaching and
ings such as low resistance to acid and shear stress, low heating peak viscosity, and increases the pasting temperature (Chung,
stability, and high tendency towards syneresis and retrogradation Liu, & Hoover, 2009; Gunaratne & Corke, 2007; Pinto et al., 2012;
(Jacobs & Delcour, 1998). Chemical modification of starch is com- Sui, Shah, & BeMiller, 2011; Varatharajan et al., 2011). The extent
monly performed in the food industry before its use as an ingredient of the changes in these physicochemical characteristics is mainly
to provide better behavioural characteristics (BeMiller, 2007, chap. influenced by the alteration of the semi-crystalline supramolecular
6). Recently, there has been intense active research and interest in structure in starch granules (Ambigaipalan, Hoover, Donner, & Liu,
the area of physical modifications of starch to develop environmen- 2014; Gunaratne & Hoover, 2002). Hoover and Manuel (1996)
tally friendly ‘‘clean label’’ food products (Puncha-arnon & Uttapap, suggested that HMT resulted in structural changes within both
2013; Wongsagonsup, Varavinit, & BeMiller, 2008). amorphous region and crystalline region to different degrees. The
Heat moisture treatment (HMT) is a hydrothermal treatment greatest changes were proposed to occur in the amorphous region
technique that heats starch granules at low levels of moisture through facilitating the chain associations in cereal, tuber and
legume starches (Hoover & Vasanthan, 1994; Jacobs & Delcour,
⇑ Corresponding authors. Tel.: +86 571 86971932; fax: +86 571 86971421 1998; Vermeylen, Goderis, & Delcour, 2006).
(X. Kong). Tel.: +86 21 55897302 (L. Ai). It is difficult to define the properties of HMT starches in a con-
E-mail addresses: [email protected] (X. Kong), [email protected] (L. Ai). sistent way because the reaction conditions are diverse, including

http://dx.doi.org/10.1016/j.foodchem.2014.11.021
0308-8146/Ó 2014 Elsevier Ltd. All rights reserved.
1126 Z. Sui et al. / Food Chemistry 173 (2015) 1125–1132

the botanical source, moisture content, temperature, length of 2.5. Determination of thermal properties
treatment, heat resource and cooling process. Moisture and tem-
perature are the most extensively studied of these conditions The starch sample (2 mg, db) was mixed with distilled water to
(Vermeylen et al., 2006; Varatharajan et al., 2011; Jiranuntakul, obtain a total weight of 6 mg (1:3 w/w) in an aluminium pan. The
Puttanlek, Rungsardthong, Puncha-arnon, & Uttapap, 2012; pan was hermetically sealed and equilibrated at room temperature
Ambigaipalan et al., 2014). However, there is limited information for at least 2 h before testing. Samples were scanned from 20 °C to
on comparison of the effects of moisture content and heating 120 °C at a heating rate of 10 °C/min. A sealed empty pan was used
length on the properties of maize starch during HMT. Therefore, as a reference, and indium was used for temperature calibration.
the objective of this study was to investigate the effect of moisture Triplicate tests were performed on each sample.
level and heating length on the physicochemical and structural
properties of normal and waxy maize starch during HMT. 2.6. Fourier transform infrared spectroscopy (FT-IR)

The Fourier transform infrared (FT-IR) spectra of the samples

2. Materials and methods
were recorded by a Nicolet Nexus 670 FT-IR spectrometer with a
Smart iTR diamond ATR accessory (Thermo Scientific, Pittsburgh,
2.1. Materials
PA) ranging from 800 1 to 1200 cm 1. The spectra were recorded
at a resolution of 4 cm 1 by averages of 128 scans. Intensity
Normal maize starch (NMS) and waxy maize starch (WMS)
measurements were estimated from the deconvoluted spectra
were obtained from Gaofeng Starch Technology Company Limited
according to the method of Chung, Liu, et al. (2009).
(Suzhou, China). The amylose contents of the NMS and WMS
samples were 18.4% and 0.1%, respectively. All chemicals and sol-
vents were analytical grade. 2.7. X-Ray diffraction

X-ray diffraction (XRD) analyses of starches were performed

2.2. Heat–moisture treatment using a D8 Advance diffractometer (Bruker-AXS, Karlsruhe, Ger-
many) equipped with a goniometer at 30 mA (tube current) and
Heat–moisture treatment was performed according to a labora- 30 kV (target voltage). The scanning range of the diffraction angle
tory protocol (Sui et al., 2011). The moisture content of the NMS (2h) was from 5° to 35°, and the scanning speed was 1°/min
and WMS samples was 12.2% and 11.3%, respectively. The starch at room temperature. The relative crystallinity was estimated
samples (20 g, db) were weighed and placed into screw-capped according to the method previously described by Komiya and
glass containers. Small amounts of distilled water were slowly Nara (1986).
added to the containers with frequent stirring until the moisture
level of the total mixture reached 20%, 25% and 30%. After thorough
2.8. Statistical analysis
mixing, the glass containers were sealed and equilibrated at 4 °C
for at least three days. Samples were then heated at 100 °C for 2,
Differences between the functional properties of samples before
4, 8, 16 h in a hot-air oven. After HMT, the samples were dried at
and after hydrothermal treatment were established using analysis
40 °C overnight to a constant weight. All samples were ground in
of variance (ANOVA). Duncan’s multiple range tests (p < 0.05) were
a mortar and pestle and passed through a 0.4 mm sieve.
carried out to analyse their differences. Statistical analysis was per-
formed using SPSS 17.0 for windows (SPSS Inc., Chicago, IL, USA).
2.3. Swelling power and solubility index
3. Results and discussion
The swelling power and solubility index of normal and waxy
maize starch were analysed according to a previously described
3.1. Swelling power and solubility index
procedure with minor modifications (Li & Yeh, 2001). Briefly,
samples (1.0 g) were mixed with 40 mL of distilled water in
The swelling power (SP) and solubility index (SOL) of NMS and
50-mL centrifuge tubes. The mixture was kept at 90 °C for
WMS were determined at 90 °C before and after HMT and are pre-
30 min to ambient temperature and centrifuged at 1000g for
sented in Table 1. The swelling behaviour is apparently a property
20 min. The swelling power is expressed as the ratio of the weight
of amylopectin, i.e., chain length distribution, branching pattern
of wet sedimented gel to its dry weight. The solubility was
and the molecular weight of amylopectin (Sasaki & Matsuki,
estimated by drying the supernatant to a constant weight at
1998; Tester & Morrison, 1990a, 1990b). It is well known that
110 °C in a hot-air oven. Values are represented as the percentage
the amylose and/or amylopectin molecules can diffuse out of the
of dried solid weight based on the weight of dry starch.
starch granules during gelatinisation. As expected, the native and
HMT WMS exhibited higher SP and SOL than the NMS samples.
2.4. Determination of pasting properties Native and HMT WMS were less rigid and more easily ruptured
in addition to being swollen and massively overcrowded, resulting
The pasting and paste properties of the starches were deter- in the majority of fragments leached from the aggregated WMS
mined using a Rapid Viso-Analyzer (RVA) (Newport Scientific, granules being large and composed of amylopectin molecules
Warriewood, Australia). Starch samples and distilled water were (Tester & Morrison, 1990a). Native and HMT NMS granules, in con-
mixed in an aluminium sample canister to obtain a 10% concentra- trast, exhibited less swelling and tended to retrograde easily and
tion (w/w) starch suspension (2.8 g, db in a 28 g total). The slurry form firm gels, so the main fragments leached from the aggregated
was manually stirred using a plastic paddle for at least 1 min NMS granules were small and composed of amylose (Doublier,
before RVA loading to avoid the formation of lumps. The following Llamas, & Le Meur, 1987).
heating and cooling cycle program (13 min) was used (Sui, Huber, HMT generally resulted in a slight decrease in the SP and SOL of
& BeMiller, 2013): initial heating at 50 °C for 60 s, increasing from all NMS products with the exception of SOL at 30% moisture con-
50 °C to 95 °C at 0.22 °C/s within 222 s, holding at 95 °C for 150 s, tent, which remained more or less constant (Table 1). When NMS
then decreasing to a final temperature of 50 °C and held for 120 s. underwent HMT at the same moisture levels, the values were
 Z. Sui et al. / Food Chemistry 173 (2015) 1125–1132 1127

Table 1
RVA pasting parameters, swelling power and solubility index of native and HMT normal and waxy maize starches.A,B

Treatment Pasting parameters Swelling power (g/g) Solubility (%)

Moisture content (%) Heating length (h) Peak viscosity (RVU) Breakdown (RVU) Final viscosity (RVU) Setback (RVU)
NMS 0 220 ± 0a 130 ± 1a 266 ± 2a 137 ± 3a 7.7 ± 0.3a 2.6 ± 0.3a
20 2 190 ± 2b 47 ± 4b 263 ± 2a 120 ± 4b 6.8 ± 0.1b 1.1 ± 0.0e
4 190 ± 7b 42 ± 3c 260 ± 7a 111 ± 2b 6.4 ± 0.1cde 1.5 ± 0.0cd
8 193 ± 7b 41 ± 4c 263 ± 14a 110 ± 11b 6.5 ± 0.2bcd 1.6 ± 0.0cb
16 194 ± 2b 38 ± 2c 256 ± 1a 100 ± 1c 6.6 ± 0.1bc 1.1 ± 0.0e
25 2 162 ± 1c 31 ± 1d 210 ± 2b 79 ± 2d 6.8 ± 0.3b 1.8 ± 0.0b
4 156 ± 3cd 24 ± 0e 200 ± 4bc 68 ± 1e 6.7 ± 0.2bc 1.6 ± 0.0bcd
8 146 ± 2de 22 ± 1ef 186 ± 1cd 62 ± 1e 6.4 ± 0.4cd 1.3 ± 0.0de
16 143 ± 9e 15 ± 1hg 176 ± 14d 48 ± 7f 5.9 ± 0.1f 1.7 ± 0.0bc
30 2 114 ± 3f 17 ± 0fg 132 ± 3e 35 ± 0g 6.0 ± 0.1f 2.4 ± 0.0a
4 110 ± 1fg 12 ± 5hi 129 ± 5ef 31 ± 1g 6.0 ± 0.2ef 2.7 ± 0.0a
8 100 ± 7g 7 ± 3i 113 ± 10fg 20 ± 6h 6.0 ± 0.1f 2.5 ± 0.0a
16 88 ± 12h 1.9 ± 2j 101 ± 14g 15 ± 4h 6.0 ± 0.1def 2.6 ± 0.0a
WMS 0 317 ± 0a 92 ± 2f 113 ± 4a 22 ± 1a 3.9 ± 0.0h 41.9 ± 0.7a
20 2 216 ± 3c 123 ± 2bc 114 ± 4a 21 ± 1a 6.5 ± 0.0d 11.7 ± 0.7b
4 198 ± 2d 111 ± 2d 105 ± 0b 17 ± 1bc 6.3 ± 0.1de 10.5 ± 0.9b
8 156 ± 6f 91 ± 2f 778 ± 2e 13 ± 1d 6.1 ± 0.1e 10.0 ± 2.0b
16 85 ± 13h 56 ± 9h 42 ± 4g 13 ± 0d 5.7 ± 0.0f 6.7 ± 1.3c
25 2 215 ± 0c 121 ± 2c 112 ± 2a 18 ± 0b 6.9 ± 0.3c 6.9 ± 0.3c
4 182 ± 2e 103 ± 1de 94 ± 1c 15 ± 0c 6.4 ± 0.0d 5.8 ± 0.9cd
8 135 ± 2g 75 ± 2g 75 ± 1e 15 ± 0c 5.3 ± 0.1g 4.2 ± 0.7d
16 67 ± 8i 40 ± 5i 37 ± 4h 10 ± 1e 5.7 ± 0.1f 4.0 ± 0.0d
30 2 253 ± 5b 154 ± 6a 116 ± 3a 17 ± 2bc 7.8 ± 0.0a 5.7 ± 0.0cd
4 202 ± 4d 130 ± 5b 88 ± 0d 15 ± 1c 7.4 ± 0.1b 4.9 ± 0.0cd
8 151 ± 2f 101 ± 1e 67 ± 1f 16 ± 0bc 8.0 ± 0.1a 4.3 ± 0.0d
16 75 ± 0hi 52 ± 3h 34 ± 3h 10 ± 0e 6.8 ± 0.1c 5.6 ± 0.0cd
A
All data represent the mean of triplicates.
B
Values in each column with the different superscript are significantly different (p < 0.05).

unchanged or changed slightly as the length of heating increased, 3.2. Pasting properties
indicating that the SP and SOL of HMT NMS were reduced equiva-
lently as a function of the length of heating. When NMS underwent The pasting properties of native and HMT maize starches deter-
HMT at a constant length of heating, the extent of SP and SOL mined by RVA are presented in Table 1 and Fig. 1. Pasting properties
reduction at all moisture levels of HMT NMS was in the following are supposed to provide information on intermolecular bonding
order: N20%  N25% > N30% and N30% > N25%  N20% for SP and between densely packed starch granules and the rigidity of swollen
SOL, respectively. Hoover and Manuel (1996) proposed that starch granules during the heating process (Vandeputte, Derycke,
development of starch chain interactions and dissociation of a Geeroms, & Delcour, 2003). All HMT starches exhibited significantly
few double helices during HMT could restrict starch swelling lower peak viscosities, final viscosities, breakdown and setback than
behaviour. Wongsagonsup et al. (2008) found that HMT produced native starches (Table 1). The paste and pasting properties of HMT
slightly crosslinks within amorphous regions of starch granules. In products were affected to different degrees by various reaction con-
this study, the results indicated that HMT conducted at higher ditions. When the length of heating was constant, the extent of the
moisture levels enhanced the mobility of amylose chains and decrease in peak viscosity and final viscosity of NMS as a function of
decreased the available hydroxyl groups for hydration due to the moisture content during HMT was more pronounced than that of
greater extent of interaction within AM–AP and/or AP–AP chains WMS (Fig. 1a and b). When the peak viscosity and final viscosity
for NMS. Consistent with previously reports, granular swelling and for NMS treated at 20%, 25%, 30% moisture content for 16 h were
solubility were reduced during HMT of sorghum starches (Sun, compared to those of native starch, they were found to be 0.88,
Han, Wang, & Xiong, 2014), wheat and potato starches (Gunaratne, 0.65, 0.40, and 0.96, 0.66, 0.38 times, respectively, whereas when
Kong, & Corke, 2010) and pinhao starches (Pinto et al., 2012). WMS was conducted at same conditions, they were 0.27, 0.21,
HMT greatly increased the SP but decreased the SOL of all WMS 0.24, and 0.37, 0.33, 0.30 times, respectively.
products. When WMS was treated at the same level of moisture, When the moisture level was constant, the extent of the change
both the SP and SOL tended to decrease slightly as the length of in the WMS peak viscosity and final viscosity as a function of the
heating increased. Cooke and Gidley (1992) suggested that the length of heating were more pronounced than those of NMS
forces keeping the starch granule integrated are primarily at amy- (Fig. 1a and b). When the WMS peak viscosity and final viscosity
lopectin double helices. It was previously reported that starch after 2, 4, 8 and 16 h at 30% was compared to those of native starch,
swelling and structural stability were weakened due to the unrav- they were found to be 0.80, 0.64, 0.48, 0.24, and 1.03, 0.78, 0.59,
elling of double helices during HMT (Varatharajan et al., 2011). 0.30 times, respectively. When NMS was subjected to the same
When WMS was subjected to a constant length of heating, the conditions, they were 0.52, 0.50, 0.46, 0.46, and 0.50, 0.48, 0.43,
extent of SP increase at all moisture levels of HMT WMS was in 0.38 times, respectively. The thermal energy imparted to the
the order W30% > W25%  W20%, whereas the SOL gradually outmost short chain (A chains) of densely packed amylopectin in
decreased in the order W30% < W25% < W20%. This implies that the presence of limited water during HMT, leads to the disruption
HMT conducted at higher moisture levels impedes WMS amylo- of hydrogen bonds and/or the breaking of covalent linkages of
pectin molecules from leaching out of the fragile granules for double helices (Chung, Hoover, & Liu, 2009; Jiranuntakul et al.,
WMS. 2012; Khunae, Tran, & Sirivongpaisal, 2007). As the length of
1128 Z. Sui et al. / Food Chemistry 173 (2015) 1125–1132

Fig. 1. Effect of heating length on the pasting and thermal properties of native and HMT normal and waxy maize starches at different levels of moisture content. (a) Peak
viscosity of normal and waxy maize starches conducted at 100 °C for 2, 4, 8, 16 h. (b) Final viscosity of normal and waxy maize starches conducted at 100 °C for 2, 4, 8, 16 h. (c)
Onset gelatinisation temperature of normal and waxy maize starches conducted at 100 °C for 2, 4, 8, 16 h. (d) Peak gelatinisation temperature of normal and waxy maize
starches conducted at 100 °C for 2, 4, 8, 16 h. (e) Conclusion gelatinisation temperature of normal and waxy maize starches conducted at 100 °C for 2, 4, 8, 16 h. NMS and
WMS 20%, 25%, 30% represent normal and waxy maize starches heating at 20%, 25%, 30% moisture levels, respectively.

heating increased, intra- and inter-molecular hydrogen bonds Gidley, Komanshek, and Donald (2000) found that the amorphous
in starch granules were further disrupted (Vermeylen et al., regions could be plasticised from a glassy state into a rubbery state
2006). in the presence of water even at room temperature. Jacobs and
Numerous studies have found that the physicochemical proper- Delcour (1998) suggested that changes occurred in amorphous
ties of starches during HMT were mainly dependent on the degree regions during hydrothermal treatment due to an increase in the
of moisture content and starch botanical source (Hoover, 2010; degree of order rather than an increase in degree of crystallinity,
Zavareze & Dias, 2011). Surprisingly, WMS HMT conducted at a leading to higher rigidity of starch granular structure in amorphous
constant length of heating resulted in a little or no significant regions that would disrupt the organised crystalline structure of
decrease in the pasting or paste properties as a function of mois- starch granules. In this study, the results showed that moisture
ture content. This evidence was attributed to the lack of amylose content was an important factor in determining the pasting prop-
in WMS granules, which are the main component of amorphous erties for NMS, while it was not significant for WMS, suggesting
regions in normal maize starch granules (Jane, Xu, Radosavljevic, that the pasting properties of amylose-containing starch correlated
& Seib, 1992; Saibene & Seetharaman, 2010). Water acts as a plas- with moisture levels, while those of amylose-free starch were
ticiser for starch granules during the heating process. Waigh, correlated with heating length.
 Z. Sui et al. / Food Chemistry 173 (2015) 1125–1132 1129

3.3. Thermal properties for starches treated for 2, 4, 8, 16 h at 30% were as follows: for
NMS, 0.55, 0.66, 0.63, 0.56 times, respectively, and for WMS,
The gelatinisation temperatures (To, Tp, Tc), gelatinisation tem- 0.64, 0.56, 0.73, 0.78 times, respectively, indicating that less energy
perature range (Tc To) and enthalpy of gelatinisation (DH) of was required during gelatinisation at higher levels of moisture. The
native and HMT starches are shown in Table 2. The gelatinisation greater increase in Tp and decrease in DH as a function of moisture
temperatures (To, Tp, Tc) of all HMT products were higher than content could be attributed to a higher number of effective cross-
those of the native starches, indicating that more ordered crystals links in the amorphous region and disrupted hydrogen bonds in
may have formed during treatment (Fig. 1c–e). Similar increases in the crystalline region. Therefore, it can be concluded that the level
gelatinisation temperatures during HMT have been observed for of moisture content of the starch was a greater determinant of
potato (Varatharajan et al., 2011), pulse (Ambigaipalan et al., thermal properties than the length of heating.
2014) and pinhao starches (Pinto et al., 2012).
The value of Tp has been shown to be a reflection of starch gran-
ule structural stability and resistance to gelatinisation (Barichello, 3.4. ATR-FTIR spectroscopy and X-ray diffraction
Yada, Coffin, & Stanley, 1990). When the length of heating was
constant, the extent of the increase in Tp for HMT NMS and HMT The ATR-FTIR spectrum and X-ray diffractograms of native and
WMS as a function of moisture content followed the order NMS HMT starches at 20%, 25% and 30% moisture content for 16 h are
20% < NMS 25% < NMS 30% and WMS 20% < WMS 25%  WMS illustrated in Figs. 2 and 3. The spectrum and diffractograms of
30%, respectively (Fig. 1d). This result is in good agreement with starches subjected to other reaction conditions exhibited similar
the peak viscosity and final viscosity of the corresponding samples trends (Fig. 2). The ATR-FTIR is used as a short-range probe,
(Table 1), indicating that greater starch chain mobility at high whereas the X-ray diffractogram is considered a long-range probe.
moisture levels may enhance starch granule stability through The ATR-FTIR technique has been shown to illustrate changes in
interactions between AM–AP and AP–AP chains. The ranges of the starch molecular structure near the granule surface because
gelatinisation temperature (Tc To) represent the crystallite the IR beam only reaches 2 lm into the starch granule. The ATR-
heterogeneity within starch granules. The Tc To values of all FTIR spectrum of starch displayed stretched bands in the region
HMT products were broader than those of native starches, indicat- 861 cm 1, indicating the presence of COC stretching bands
ing that HMT increased the degree of crystallite heterogeneity. and CH deformation. The peaks at 1077, 1047, 1022, 994, and
The enthalpy of gelatinisation (DH) has been shown to reflect 928 cm 1 were ascribed to the presence of COH bending and
the amount of unravelling of double helices during gelatinisation CH2-related modes. The peaks at 1150, 1124 and 1103 cm 1 were
and represents the disorder of double helices (Cooke & Gidley, assigned to CO and CC stretching with some COH contributions
1992; Gunaratne & Hoover, 2002). Comparing the values for DH (Cael, Koenig, & Blackwell, 1975). No significant differences in
of starches treated at 20%, 25%, and 30% moisture content for the spectrum pattern were observed between the native and
16 h with those of the native starches, the following results were HMT starches (Fig. 2). Similar observations have been reported
observed: for NMS, 1.0, 0.91, 0.56 times, respectively, and for for potato, pea and lentil starches (Varatharajan et al., 2011;
WMS, 1.15, 0.98, 0.78 times, respectively. Similar comparisons Chung, Hoover, et al., 2009).

Table 2
Gelatinisation transition parameters of native and HMT normal and waxy maize starches.A,B

Moisture content (%) Heating length (h) To (°C)C Tp (°C)C Tc (°C)C Tc To (°C)C DH (J/g)C
i d g g
NMS 0 65.8 ± 0.1 70.5 ± 0.1 74.3 ± 0.2 8.5 ± 0.2 12.5 ± 0.2a
20 2 67.3 ± 0.2h 72.3 ± 0.3cd 81.9 ± 0.6f 14.6 ± 0.6ef 12.2 ± 0.3ab
4 68.2 ± 0.2gh 73.2 ± 0.1c 83.4 ± 0.5e 15.3 ± 0.5de 11.7 ± 0.2abc
8 69.1 ± 0.2fg 73.9 ± 0.3bc 83.2 ± 0.6e 14.1 ± 0.5f 12.1 ± 0.5ab
16 68.5 ± 0.0g 73.4 ± 0.1bc 83.7 ± 0.3e 15.3 ± 0.3cde 12.5 ± 0.3a
25 2 68.4 ± 0.2g 78.6 ± 0.2a 83.1 ± 0.3e 14.8 ± 0.1def 10.3 ± 0.4bc
4 69.6 ± 0.2ef 79.3 ± 2.4a 84.8 ± 0.2d 15.2 ± 0.1def 10.7 ± 0.38abc
8 70.3 ± 0.0de 79.4 ± 3.7a 86.0 ± 0.3c 16.4 ± 0.4abc 9.9 ± 0.8cd
16 70.8 ± 0.1cd 79.5 ± 0.5a 87.2 ± 0.4bc 16.4 ± 0.4ab 11.3 ± 0.5abc
30 2 70.0 ± 0.2def 80.4 ± 0.1a 87.1 ± 0.3bv 17.2 ± 0.1a 6.9 ± 0.0e
4 72.0 ± 1.3c 80.6 ± 1.0a 88.0 ± 1.9b 16.4 ± 0.8ab 8.2 ± 3.1de
8 74.0 ± 0.3a 80.3 ± 1.3a 89.7 ± 0.4a 15.8 ± 0.5bcd 7.9 ± 2.6e
16 72.78 ± 1.8b 80.5 ± 2.6a 89.6 ± 0.9a 16.8 ± 2.3ab 7.1 ± 0.6e
WMS 0 65.0 ± 0.13g 70.9 ± 0.1h 76.1 ± 0.5h 11.2 ± 0.4g 13.4 ± 0.0c
20 2 66.4 ± 0.1f 72.5 ± 0.3g 84.9 ± 0.5g 18.5 ± 0.6a 14.5 ± 0.9b
4 67.2 ± 0.2e 73.5 ± 0.1f 85.1 ± 0.7fg 17.9 ± 0.6a 16.1 ± 0.8a
8 67.8 ± 0.6e 73.8 ± 0.7f 85.7 ± 0.5ef 17.9 ± 0.9a 14.9 ± 0.4b
16 68.6 ± 0.8d 74.5 ± 0.7e 86.1 ± 0.7de 17.6 ± 1.1ab 15.4 ± 0.6ab
25 2 68.8 ± 0.1d 80.5 ± 0.1d 85.2 ± 0.3fg 16.4 ± 0.3cd 11.7 ± 0.7e
4 71.0 ± 0.3c 81.1 ± 0.2c 86.8 ± 0.4cd 15.8 ± 0.5cde 12.0 ± 0.4e
8 70.7 ± 0.2c 82.1 ± 0.2b 87.5 ± 0.1bc 16.8 ± 0.2bc 12.3 ± 0.3de
16 71.8 ± 0.7b 82.6 ± 0.5a 88.1 ± 0.7ab 16.3 ± 1.2cd 13.2 ± 1.2cd
30 2 70.8 ± 1.5c 81.0 ± 0.3c 86.1 ± 0.5de 15.3 ± 1.6de 8.6 ± 1.0g
4 73.3 ± 0.2a 82.7 ± 0.3a 88.6 ± 0.6a 15.3 ± 0.4de 7.5 ± 0.1h
8 73.4 ± 0.2a 81.1 ± 0.3c 88.0 ± 0.3c 13.6 ± 0.5f 9.8 ± 1.0f
16 73.9 ± 0.1a 82.4 ± 0.0ab 88.5 ± 0.2a 14.7 ± 0.2ef 10.4 ± 0.2f
A
All data represent the mean of triplicates.
B
Values in each column with the different superscript are significantly different (p < 0.05).
C
To, onset gelatinisation temperature; Tp, peak gelatinisation temperature; Tc, conclusion gelatinisation temperature; Tc To, gelatinisation temperature range; DH,
enthalpy.
1130 Z. Sui et al. / Food Chemistry 173 (2015) 1125–1132

Fig. 2. (a) Deconvoluted ATR-IR spectra of native and HMT normal maize starches Fig. 3. (a) X-ray diffractograms of native and HMT normal maize starches
conducted at 20%, 25%, 30% moisture levels for 16 h. (b) Deconvoluted ATR-IR conducted at 20%, 25%, 30% moisture levels for 16 h. (b) X-ray diffractograms of
spectra of native and HMT waxy maize starches conducted at 20%, 25%, 30% native and HMT waxy maize starches conducted at 20%, 25%, 30% moisture levels
moisture levels for 16 h. NMS and WMS 20%, 25%, 30% represent normal and waxy for 16 h. NMS and WMS 20%, 25%, 30% represent normal and waxy maize starches
maize starches heating at 20%, 25%, 30% moisture levels, respectively. heating at 20%, 25%, 30% moisture levels, respectively.

The IR band regions at 1048 1 and 1016 cm 1 have been shown doublet-centered diffraction peak at 2h values of 17.2°, 18.1° and
to be related to the crystalline and amorphous starch structures, two single peaks at 2h values of 15.1° and 23.2°, known as the
respectively. The ratio of the intensity at 1048–1016 cm 1 repre- A-type diffraction pattern (Fig. 3). Increasing levels of moisture
sents the ratio of ordered crystalline starch granule regions to and/or length of heating increased the peak intensity for all HMT
amorphous regions (van Soest, Tournois, de Wit, & Vliegenthart, starches but did not alter the inherent diffraction pattern of native
1995). The ratio of 1048–1016 cm 1 intensity for native and HMT starches. Hoover and his co-authors (Hoover & Vasanthan, 1994;
starches is depicted in Table 3. HMT produced various effects on Gunaratne & Hoover, 2002) found that the X-ray pattern of B-type
the 1048–1016 cm 1 intensity ratio, i.e., at different levels of mois- tuber starches could be altered to A-type starches by HMT,
ture content, it increased (20% M.C.), had no effect (25% M.C.), or whereas the X-ray pattern of A-type cereal starches remained
decreased (30% M.C.) compared to native starch, whereas the unchanged. The X-ray intensities of the strongest peaks at 17.2°
length of heating had no effect. It appears that sufficient water increased 3.98–4.50 times and 3.45–4.11 times, respectively, for
enhanced the formation of hydrogen bonds between AM–AM and HMT NMS and WMS compared to untreated controls. Changes in
AM–AP starch chains, which is consistent with the pasting and the X-ray intensities in cereal starches (A-type) during HMT have
thermal properties results. Chemical modification of starch with been suggested to be a result of moisture and thermal energy
rapidly reacting reagents occurs primarily on starch granule sur- causing a strengthening of the association of the adjacent double
faces and starch channels, i.e., crosslinking with phosphoryl chlo- helices and, consequently, an increased amount of direct hydrogen
ride and esterification with acetic anhydride (Sui et al., 2013). bonds (Zavareze & Dias, 2011).
Structural changes at the molecular level near the surfaces of The relative crystallinity of native and HMT WMS was higher
starch granules during HMT determined by ATR-FTIR could provide than that of untreated and treated NMS. According to
more information for the field of physical and chemical modifica- Wongsagonsup et al. (2008), the crystallinity of starch is influenced
tion of starch. by (1) amylopectin chain-length distribution, (2) double helix
The intensity of X-ray diffractograms and relative crystallinity orientation in crystalline regions, (3) weight ratio of amylopectin
(RC) of native and HMT starches are presented in Table 3. The short chains, and (4) crystallite size. The amylopectin of maize
X-ray pattern of all native and HMT starches exhibited a strong starch had a higher proportion of short chains (DP 6-12) than other
 Z. Sui et al. / Food Chemistry 173 (2015) 1125–1132 1131

Table 3
Peak intensity, relative crystallinity and short range molecular order of native and HMT normal and waxy maize starches.

Moisture content (%) Heating length (h) Intensity(CPS)A RCB (%) Ratio (1048/1016 cm 1 C
)
15.1° 17.2° 18.1° 23.2°
NMS 0 488 466 468 391 30.48 0.544
20 2 1925 2006 2003 1652 16.26 0.562
4 1952 2060 2083 1577 16.82 0.578
8 1896 1974 2005 1540 16.06 0.556
16 2023 2096 2142 1673 16.58 0.566
25 2 1930 2002 1987 1590 16.57 0.539
4 1927 2001 2065 1559 15.78 0.544
8 1904 1894 1888 1522 15.58 0.546
16 1805 1907 1878 1543 14.41 0.534
30 2 1789 1857 1828 1453 12.71 0.499
4 1826 1901 1896 1498 12.24 0.508
8 1811 1898 1876 1497 12.01 0.484
16 1907 1940 1869 1425 13.15 0.527
WMS 0 561 542 589 505 41.28 0.576
20 2 2017 2017 1930 1530 16.40 0.607
4 2113 2111 2037 1594 18.31 0.609
8 2089 2111 2030 1672 19.21 0.602
16 2124 2227 2111 1693 18.36 0.589
25 2 1949 2007 1900 1509 16.70 0.570
4 2006 2080 1917 1602 17.65 0.576
8 2090 2112 2009 1614 18.77 0.575
16 2036 2064 2069 1611 18.68 0.573
30 2 1855 1889 1910 1444 15.55 0.550
4 1963 2017 1944 1519 17.63 0.537
8 1848 1868 1836 1401 14.81 0.542
16 1938 1955 1876 1480 17.64 0.533
A
Counts per second.
B
Relative crystallinity.
C 1 1
Ratio of the ordered crystalline (1048 cm ) to amorphous regions (1016 cm ).

starches, i.e., lentil and pea starches. With regard to this study, (FT-IR) absorbance bands than the length of heating for both
the amount of short chains (DP 6-9) of WMS amylopectin is 1.8 samples. The decrease in the pasting properties of NMS was more
times higher than that of NMS amylopectin, leading to greater pronounced with increased in moisture content, while that of
rearrangement of starch chains and less susceptibility to pancre- WMS was more pronounced with heating length. The increase in
atic a-amylase (Jane et al., 1992; Chung, Liu, et al., 2009). X-ray intensities and decrease in relative crystallinity after HMT
When NMS was treated at 20%, 25%, or 30% moisture for 16 h, the suggests that structural changes mainly occur in amorphous
relative crystallinity was found to be 0.53, 0.46, and 0.42 times of regions due to enhanced starch chain mobility for NMS, while
native starch, respectively, whereas when WMS was treated under changes in WMS mainly occur in crystalline regions due to disorga-
the same conditions, the relative crystallinity was 0.46, 0.47, and nisation of the amylopectin double helices.
0.44 times of native starch, respectively. The same values for This study provides new evidence that, in addition to being
starches treated for 2, 4, 8, 16 h at 30% moisture were as follows: more highly derivatised than amylopectin after chemical modifica-
for NMS, 0.40, 0.39, 0.38, 0.42 times, respectively, and for WMS, tion of starch (BeMiller, 2007, chap. 6), amylose plays an essential
0.39, 0.44, 0.37, 0.44 times, respectively, indicating disruption of role in physical modifications of starch by annealing and HMT.
amylopectin crystallites. Structural changes in starch granules are Importantly, the rearrangement of amylose is associated with the
strongly influenced by starch-chain mobility (Varatharajan et al., presence of water molecules, which might serve as plasticisers,
2011). In conjunction with the pasting and thermal properties, the leading to higher rigidity of starch granular structure in amorphous
results suggested that the main structural changes in NMS primarily regions that may disrupt the organised crystalline structure of the
occur in amorphous regions, including the disruption of hydrogen starch granule.
bonding between AM–AP and/or AP–AP chains and the rearrange- Although a large body of evidence indicates that moisture levels
ment of AM–AM and/or AM–AP chains. In contrast, the main struc- and botanical resources are the determinant factors in HMT condi-
tural changes in WMS primarily occur in crystalline regions, tions (Hoover, 2010; Zavareze & Dias, 2011), the concept that
including the disorganisation of the amylopectin double helices moisture content is the only determinant external reaction factor
and hydrogen-bonding interactions within adjacent helices. has been challenged. In the present study, we provided evidence
indicating that moisture content and heating length both affected
4. Conclusion the properties of maize starches to a large extent. This study
provides information for the field of starch modification.
HMT altered the pasting properties, gelatinisation behaviour
and crystalline characteristics of NMS and WMS to different Acknowledgements
degrees at different levels of moisture content and length of
heating. The moisture content resulted in greater changes in the This research was financially supported by the National Natural
swelling power, water solubility index, gelatinisation temperature, Science Foundation of China (Grant Nos. 31301419; 31101225)
enthalpy of gelatinisation and the Fourier transform infrared and SJTU starting fund for young faculty (Grant No. AF1500013).
1132 Z. Sui et al. / Food Chemistry 173 (2015) 1125–1132

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