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LWT - Food Science and Technology 53 (2013) 176e183

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LWT - Food Science and Technology


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Physico-chemical, thermal and rheological properties of starches isolated from


newly released rice cultivars grown in Indian temperate climates
Ali Abas Wani a, b, c, *, Preeti Singh b, c, *, Manzoor Ahmad Shah a, Idrees Ahmed Wani d, Alexander Gtz b,
Michael Schott b, Christian Zacherl b
a
Department of Food Technology, Islamic University of Science & Technology, Awantipora, Jammu & Kashmir 190 221, India
b
Fraunhofer Institute for Process Engineering & Packaging IVV, 85354 Freising, Germany
c
Chair of Food Packaging Technology, Technical University of Munich, 85350 Freising-Weihenstephan, Germany
d
Department of Food Science & Technology, The University of Kashmir, Hazratbal, Srinagar, Jammu & Kashmir, India

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

Article history: Starches isolated from three newly released rice cultivars were tested for different physico-chemical,
Received 24 July 2012 thermal and rheological properties. The starch granule had either polygonal or irregular shapes with
Received in revised form small particle size mainly falling in the range of 1e10 mm. SR-1 had more polygonal shapes than SKUAST-
17 February 2013
5 and SKUAST-27. SR-1 starch also showed signicantly high (p  0.05) amount of amylose (28.6 g/100 g
Accepted 20 February 2013
starch) which possibly was responsible for high swelling power (25.9 g/100 g starch), solubility (26.4 g/
100 g starch) and syneresis (35.2 g/100 g starch). Thermal properties (To; Tp; Tc) and enthalpy of gela-
Keywords:
tinization (DHgel) also exhibited signicant (p  0.05) differences thereby affecting the stability of
Rice starch
Physico-chemical properties
crystalline structures among the rice starches. SKUAST-5 starch showed the lowest value for To (58.5  C)
Thermal properties but exhibited highest value of DHgel (18.5 J/g). SR-1 starch exhibited slightly higher degree of retrogra-
Rheology dation (83.1 g/100 g starch) than SKUAST-5 (80.2 g/100 g starch) and SKUAST-27 (79.6 g/100 g starch).
Digestibility The ow behavior indicated differences in shear thinning behavior and hysteresis area. All samples
showed high structural recovery indicating their suitable use in high shear processing. SKUAST-27
exhibited high value (42.4 g/100 g starch) of rapidly digestible starch (RDS) than SR-1 (39.8 g/100 g
starch) and SKUAST-5 (39.4 g/100 g starch).
2013 Elsevier Ltd. All rights reserved.

1. Introduction the rice cultivar in terms of physico-chemical properties and


cooking characteristics. Rice starch has several advantages over
Rice (Oryza sativa) is the major cereal crop cultivated in the other starches e.g. hypo-allergenicity, bland avor, small granules,
world and constitutes a staple food for several countries including white color, greater acid resistance, spreadable and relatively good
India, China, Thailand, Philippines etc. In 2010, the total world rice freeze thaw stability of gels (Wani et al., 2012). Additionally it offers
production was estimated as 696324394 tons; India being one of several technological advantages as well as a wide range of
the major producers has a major contribution of about 129349631 amylose: amylopectin ratios (Lawal et al., 2011; Mitchell, 2009).
tons (FAOSTAT, 2012). Diversity in climatic conditions, genetic These unique attributes together with large diversity makes rice as
makeup and consumer preferences have led to natural and trans one of the best starch sources for industry (Vandeputte & Delcour,
genetic evolution of about 2000 thousand rice cultivars (Deepa, 2004). Evolution of rice cultivars has impact on physico-chemical
Singh, & Naidu, 2008; Wani et al., 2012). Diversity in rice cultivars properties of different rice starches as reported by several re-
largely affects their physical properties, composition, cooking searchers (Ahmed, Ramaswamy, Ayad & Ali, 2008; Lawal et al.,
properties and aromatic compounds (Wani et al., 2012). Starch, 2011; Wang, Xie, Xiong, Du, & Liao, 2012). Rice cultivar heteroge-
being the major constituent, mainly determines the acceptability of neity is exploited to produce starches with different techno-
functionalities to meet the demand for novel starches in food,
cosmetic and pharmaceutical applications.
* Corresponding authors. Chair of Food Packaging Technology, Technical Uni-
versity of Munich, 85350 Freising-Weihenstephan, Germany. Tel.: 49 8161 491
Rice starch granules are the smallest known to exist in cereal
194; fax: 49 8161 491 444. grains, having a size in the range of 2e8 mm (Vandeputte & Delcour,
E-mail addresses: ali.abbas.wani@gmail.com, waniabas@gmail.com (A.A. Wani), 2004; Wang et al., 2012). The granules have a smooth surface but
preeti_ndri@rediffmail.com (P. Singh).

0023-6438/$ e see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.lwt.2013.02.020
A.A. Wani et al. / LWT - Food Science and Technology 53 (2013) 176e183 177

angular, irregular and polygonal shapes. The complexity of starch was determined with a moisture analyzer (MA 100, Sartorius
biosynthesis results in natural variability in amylose and amylo- AG, Gottingen Germany). Apparent amylose content was deter-
pectin molecules, which is reected in diversity of granule mined according to the method of Hoover and Ratnayake
morphology. Starch properties depend on the physical and chem- (2002).
ical characteristics such as mean granule size, granule size distri-
bution, amylose/amylopectin ratio and mineral content (Madsen & 2.3.2. Morphological properties
Christensen, 1996). The role of amylose and amylopectin in the Starch granule size distribution was determined with a laser
gelatinization and pasting properties of rice starch has been widely diffraction particle size analyzer (Malvern S Mastersizer, Malvern
studied (Li, Shoemaker, Ma, Kim, & Zhong, 2008). Instruments Limited, UK). Dry starch sample (0.1 g, dry weight
Starch sources with desirable physico-chemical properties (syn- basis) was mixed with 200 ml of HPLC-grade water, and the sus-
eresis, turbidity, freeze thaw stability) are continuously explored by pension was agitated at a slow speed using a magnetic stirrer for 1 h
the scientists in hopes that chemical modications can be avoided at 20  C. The starch suspension was then lled into the small vol-
(Correja, Nunes, & Beirao-da-Costa, 2012). Therefore, the character- ume sample dispersion unit of the Mastersizer to obtain an
ization of different starches is of great importance to select the starch obscuration level of around 20%. Refractive indices of 1.530 and
for product specic end use. Rice starch is also used in some food 1.330 were used for the starch and liquid phases, respectively, while
products due to its desirable rheological properties. To understand the the starch granule absorption was 0.1 (Nayouf, Loisel, & Doublier,
rheological properties, Rapid visco analyser and stress controlled 2003).
rheometer are commonly used to study the pasting properties, ow For scanning electron microscopy, the dry starch granules were
behavior and dynamic rheological properties (Lin, Xiao, Zhao, Li, & Yu, placed on an adhesive tape attached to a circular aluminum spec-
2009; Wani et al., 2012). These properties are reported to be affected imen stub and then coated vertically with gold. The samples were
by amylose, lipid contents and by branch chain length distribution of examined at 5 kV using a scanning electron microscope (ABT-55 ISI
amylopectin. The rheological properties of starch pastes or gels may be Abt, Akashi Beam Technology Corporation, Tokyo Japan).
investigated as ow behavior, viscoelasticity, mechanical spectra,
creep, and gel strength (Ahmed et al., 2008; Lawal et al., 2011). The 2.3.3. Swelling power (g/100 g H2O) and solubility (g/100 ml H2O)
most frequently measured ow behavior index of rice starch disper- Swelling power and solubility of starch suspension was deter-
sions in steady ow can be carried out during gelatinization or on a mined according to the methods of Wang et al. (2010).
gelatinized paste. Power law and HerschelleBulkely models are
frequently used to describe the ow behavior of rice starches. These 2.3.4. Syneresis
models give information on the ow behavior index (n) and the Syneresis was determined by slight modications to the
consistency coefcient (K) and yield stress (so) of starch suspensions. methods of Lan et al. (2010). Starch dispersions (6.0 g/100 ml H2O)
The values of n, K, and so are dependent on starch type, starch con- were heated in a Rapid Visco Analyser at 95  C for 30 min with
centration, and temperature. The gelatinized starch pastes preheated constant stirring at 75 rpm. The paste was allowed to cool at room
to temperatures of about 90  C are reported to exhibit shear-thinning temperature; the water loss was weighed and added back to the
(pseudoplastic) behavior with values of n considerably less than 1.0. sample. The samples were stored for 24 h at 22  C and then
Lawal et al. (2011) reported the shear thinning behavior of 5 different equilibrated at 30  C in a water bath. Syneresis was measured as
rice starches from West Africa. water release (g/100 g starch) after centrifugation (3000 rpm;
The objectives of the present work were to study the physico- 20 min).
chemical, thermal, rheological properties of the starch for newly
released rice cultivars. 2.4. Thermal properties

2. Material & methods Thermal properties of rice starches in the presence of water
(1:3) were measured using a differential scanning calorimeter
2.1. Materials (DSC Q2000, TA Instruments, New Castle, DE USA). Starch (3.5 mg,
db) was weighed into an aluminum pan (Tzero hermetic pan and
Three newly released rice cultivars grown in Indian temperate lid, TA Instruments, New Castle, DE USA) and mixed with 2.05 mg
climates were harvested in October 2010 and were procured form H2O to equilibrated to moisture. The sample pan was sealed,
the Regional Rice Research Station, Sher-e-Kashmir University of equilibrated at room temperature for 6 h and then heated from 20
Agricultural Sciences and Technology, Shalimar, Srinagar, J&K, India. to 120  C at a heating rate of 10  C/min. The samples were placed
All the reagents used in the study were obtained from Sigmae in a refrigerator at 5  C for 5 days and the measurements were
Aldrich, St. Louis, USA. repeated for retrogradation studies. The instrument was calibrated
with Indium and Zinc, while an empty sealed pan was used as a
2.2. Starch isolation reference.

The paddy grains were dehusked using a McGill sample sheller 2.5. Pasting properties
(Rapisco, Brookshire, TX, USA) followed by 5% polishing with Mc
Gill mill No. 2 polisher (Rapisco, Brookshire, TX, USA). The polished The pasting properties were determined with a rapid visco
rice was milled in a laboratory mill (LM120, Perten Instruments, analyser (RVA 4500, Perten Instruments, Kungens, Sweden). Starch,
Hgersten, Sweden). The starch was extracted following the alkali 3.5 g dry basis was weighed into an aluminum canister and then
extraction method of Lawal et al., 2011. mixed with 25 g H2O. The starch pasting was completed in a 13 min
programmed cycle. The cycle started with the starch stirring
2.3. Physico-chemical properties (950 rpm, 10 sec) at 50  C for 1 min. This was followed by heating
the suspension from 50 to 95  C at 6  C/min and then held at 95  C
2.3.1. Chemical composition for 1.5 min, cooled to 50  C and held for 2 min. The values of pasting
Ash, crude ber, crude protein, and fat were determined ac- temperature, peak viscosity, hot paste and cool viscosity were
cording to the methods of AACC (2001). The moisture content recorded and reported as average of three samples.
178 A.A. Wani et al. / LWT - Food Science and Technology 53 (2013) 176e183

2.6. Rheological properties starch), fat (0.4e0.5 g/100 g starch), and ash contents from 0.27 to
0.29 g/100 g starch (Table 1). These parameters did not show any
Starch dispersions (6 g/100 ml H2O) were heated at 95  C for signicant differences between the three starch samples. The low
30 min in a Rapid Visco Analyser (RVA 4500, Perten Instruments, protein, fat and ash contents indicate that these starches were
Australia). The water lost during heating was restored to the formed extremely pure and the residual protein was completely removed
gel/paste and thoroughly mixed before rheological measurements during alkali steeping. The apparent amylose content of the rice
at 25  C. Prior to measurements, the paste was allowed to cool at starches was in the range of 22.3e28.6 g/100 g starch. SR-1 had
ambient temperatures for 1 h.The measurements were carried out signicantly (p  0.05) higher amount of amylose as compared to
on a controlled stress rheometer (MCR 301, Anton Par, Graz, SKUAST-5 and SKUAST-27 starches (Table 1). Differences in the
Austria) using a parallel plate geometry (PP25/TG, Anton Par, Graz, amylose content of rice starches have been reported being inu-
Austria) with serrated surfaces (diameter: 25 mm, gap: 1 mm). enced by climatic and agronomic conditions, cultivar, starch isola-
Temperature was controlled by a peltier element, holding the tion procedures and analytical methods (Lawal et al., 2011; Wang
temperature constant at 25  C for all experiments. et al., 2010).
The swelling power and solubility showed signicant (p  0.05)
2.6.1. Continuous shear experiments differences between different rice starches. Swelling power was in
Flow properties were determined by registering the shear stress the range of 23.5e27.4 g/100 g H2O whereas solubility was in the
(s) over the applied shear rate (g). The shear rate was increased range of 22.3e26.4 g/100 ml H2O (Table 1). Ratnayake, Hoover,
from 0.4 to 700 s1 in 4 min, held constant at 700 s1 for 2 min, and Warkentin (2002) concluded that the solubility is primarily
followed by a decrease down to a shear rate of 0.4 s1 in 4 min. inuenced by the amylose content while amylopectin inuences
The experimental data was tted with HerscheleBulkley model the swelling power. Lipid-amylose complexes, starch chains in-
(Eq. 1) teractions within amorphous and crystalline domains, amylose and
s s0 K g_ n (1) amylopectin ratio, molecular weight and relative distribution of
amylose and amylopectin are reported to affect the swelling power
Hereby s is the shear stress (Pa), s0 is the yield stress (Pa), K is the and solubility of starch (Wani, Sogi, Wani, Gill, & Shivhare, 2010).
consistency index (Pa sn), and n is the ow behavior index. Syneresis of different starch samples was in the range of 30.2e
35.2 g/100 g H2O. The increase in syneresis during storage is due
2.6.2. Oscillation experiments to the interaction between leached out amylose and amylopectin
Three different oscillatory experiments were carried out to chains leading to junction zones formation. This in turn shrinks
analyze the viscoelastic properties. The viscoelastic range was the starch gel and releases the water on storage (Hermansson &
determined through stress sweep tests at constant frequency of Svegmark., 1996). Structural differences (degree of polymerization
1 Hz with a logarithmic increase of shear stress from 1 to 1000 Pa in of amylose, amylopectin chain length, proportion of short chains)
40 steps as reported in the literature. between starches may also be responsible for the differences in
Frequency sweep tests at constant stress were carried out to syneresis values.
obtain mechanical spectra. Frequency was logarithmically
decreased from 100 to 0.01 Hz in 25 steps and a constant shear 3.2. Morphological properties
stress of 1 Pa. The appropriate shear stress was chosen after
analyzing the LVE-range results as the applied shear stress was in Starch granules form temperate rice cultivars showed bimodal
the LVE-range of all investigated samples. Structural recovery tests size distributions as shown in Fig. 1. The granule size ranged from
were carried out according to the procedures of Lawal et al. (2011). >1 mm to 18 mm for different rice starches. Signicant (p  0.05)
variations in the particle size distributions of rice starches were
2.7. Starch digestibility observed among different starches. The rst distribution showed
the particle in the range of 0.2e2 mm while the second major size
The amounts of RDS, SDS and RS were measured by Approved distribution (80%) was in the range of 2e18 mm (Fig. 2). Scanning
Method 32e40 (AACC, 2000) as modied by Chung, Lim, and Lim electron microscopy studies showed that the rice starch granules
(2008). had polyhedral or irregular shapes with size in the range of 1.9e
6.8 mm. Rice starches grown in tropical climates have shown
2.8. Statistical analysis polyhedral, round or irregular shapes (Sodhi & Singh, 2003). Rice
starch has small size with polyhedral or irregular shapes (Lawal
Experiments were carried out in triplicate, so the reported data et al., 2011; Zhang, Zhao, & Xiong, 2010). Starch biosynthesis re-
are the mean values. Rheological measurements under continue sults in natural variability in amylose and amylopectin molecules,
shear stress as well as investigations for mechanical spectra and
recovery tests were carried out in duplicate, due to the high
reproducibility of rheological measurements. An analysis of vari- Table 1
Physico-chemical properties of rice starches (n 3).
ance with signicance level (p  0.05) was done and Duncans test
was applied to determine differences between means using the Parameter (g/100gstarch) Rice cultivar
commercial statistical package (SPSS, 10.2 Inc., USA). The rheolog- SR-1 SKUAST-5 SKUAST-27
ical data were analyzed with commercial software (Rheo plus, Moisture 7.2a  0.1 7.4a  0.2 7.3a  0.2
Anton Par Graz Austria). Protein 0.4a  0.0 0.3a  0.0 0.4a  0.0
Fat 0.5a  0.3 0.4a  0.2 0.4a  0.2
Ash 0.29a  0.01 0.28a  0.01 0.27a  0.01
3. Results & discussion
Amylose 28.6c  0.2 22.3a  0.73 23.9b  0.31
Swelling power 25.9b  0.2 23.5a  0.4 27.4c  0.2
3.1. Physico-chemical properties Solubility 26.4c  0.3 24.1b  0.3 22.3a  0.4
Syneresis 35.2c  0.5 30.2a  0.4 33.4b  0.6
The compositional analysis of different rice starches showed a Values expressed are mean  standard deviation.
moisture content of 7.2e7.4 g/100 g starch, protein (0.3e0.4 g/100 g Means in the rows with different superscript are signicantly different at p  0.05.
A.A. Wani et al. / LWT - Food Science and Technology 53 (2013) 176e183 179

which may be responsible for granule diversity. The other factors


responsible may include climate, agronomic conditions processing
etc. (Wani et al., 2012). The variation in granule size distribution
and shape is reported to be associated with functional properties in
different food systems (Peterson & Fulcher, 2001).

3.3. Thermal properties

Thermal properties of rice starches from three rice cultivars


grown in Indian temperate climates are presented in (Table 2). The
SKUAST-5 starch gave the lowest values for To (58.5  C) and Tp
(65.0  C), while highest values for To (61.8  C) and Tp (71.5  C) were
observed for SKUAST-27. SKUAST-5 starch showed highest values
for Tc (89.7) and DHgel (18.5 J/g), while SKUAST-27 gave the lowest
lowest value for Tc (82.6) and SR1 starch gave the lowest value for
DHgel (10.7 J/g). These values are in agreement with the reports on
ten rice starches reported by Wang et al., 2010. However, these
values are lower than rice starches extracted from four West Afri-
can cultivars (Lawal et al., 2011). The signicantly (p  0.05) high
Fig. 1. Particle size distribution of starches separated from SR-1 ( ), SKUAST-5 ( ), &
SKUAST-27 ( ) rice cultivars (n 3).
value of DHgel of SKUAST-5 may be due to the second endothermic
curve suggesting the role of amylose-lipid complexes. Enthalpy of
gelatinization (DHgel) gives an overall measure of crystallinity
(quality and quantity) and is used as an indicator of the degree of

Fig. 2. Scanning electron microscopy rice starch at a magnication of 1820X (A, B, C) And 6000X (a, b, c) (SR-1, A, a), SKUAST-5 (B, b), & SKUAST-27 (C, c).
180 A.A. Wani et al. / LWT - Food Science and Technology 53 (2013) 176e183

Table 2
Thermal properties of starches from different rice cultivars: Transition temperatures (To; Tp; Tc), enthalpy of gelatinization (DHgel), DHR5 enthalpy of retrogradation (n 2).

Cultivar Gelatinization (0 day scan) Retrogradation (5th day scan)

To ( C) Tp ( C) Tc ( C) DHgel (J/g) To ( C) Tp ( C) Tc ( C) DHR5 (J/g) RT (g/100 g starch)


SR-1 60.4b  0.6 70.9b  0.2 87.1b  0.3 10.7a  0.5 55.2c  0.1 69.8b  0.6 80.6a  0.8 8.3b  0.3 83.1
SKUAST-5 58.5a  0.3 65.0a  0.3 89.7c  0.2 18.5b  0.6 44.7a  0.4 64.5a  0.3 79.1a  0.5 7.6a  0.1 80.2
SKUAST-27 61.8c  0.4 71.5b  0.4 82.6a  0.4 11.0c  0.8 53.9b  0.2 70.3b  0.3 79.8a  0.2 9.1c  0.7 79.6

To-Onset temperature; Tp-peak temperature; Tc-conclusion temperature; DHgel-enthalpy of gelatinization; DHR5-Enthalpy of retrogradation after 5 days of storage.
Means in the columns with different superscript are signicantly different at p  0.05.

loss of molecular order within the granule during gelatinization 2009) to 66.13 Pa s (Raina et al., 2007); break-down viscosity
(Hoover & Vasanthan, 1994; Wani et al., 2010). Lower value of DHgel from 0.039 Pa s (Banchathanakij & Suphantharika, 2009) to 3.82
suggests a lower degree of organization in, or a lower stability of, (Raina et al., 2007); nal viscosity from 5.59 Pa s (Banchathanakij &
the crystals (Chitotelli & Meste, 2002). The other factors affecting Suphantharika, 2009) to 6.67 Pa s (Lin et al., 2009); and setback
the thermal properties of starches may include starch granule size, viscosity from 6.67 Pa s (Lin et al., 2009) to 5.60 Pa s (Raina et al.,
phosphorus content, granule shape, amylopectin chain length, and 2007). Physico-chemical characteristics such as amylose content,
crystalline regions of different stability and/or size (Wang et al., phosphorus content and granule size distribution are the main
2010; Wani et al., 2012). Starch retrogradation as measured by determinants of the pasting and rheological properties of rice and
DSC on 5th day of storage at 4  C showed signicant (p  0.05) other starches (Lawal et al., 2011; Wani et al., 2010, 2012).
reduction in the To, Tp, Tc and DHgel parameters. The percentage
retrogradation was in the range of 79.6e83.1 g/100 g starch. SR-1 3.5. Rheological properties
starch showed signicantly (p  0.05) higher value of retrograda-
tion (83.179.6 g/100 g starch) as compared to SKUAST-5 (80.2 3.5.1. Continuous shear
79.6 g/100g starch) and SKUAST-27 (79.6 g/100 g starch) starches. The ow curves of the three different rich starch pastes,
Similar ndings on retrogradation behavior (61.9e86.6 g/100 g showing the changes in viscosity over a wide range of applied shear
starch) have been reported for ve West African cultivars (Lawal stress, are presented in Fig. 3. The plotted curves are the results out
et al., 2011). Retrogradation or recrystallization behavior is re- of the tted HerscheleBulkely model and the values are presented
ported to be a time temperature dependent process which is in Table 4. The yield stress (so) (8.8e14.1 Pa), consistency index K
mainly inuenced by several factors including amylose, lipids, (1.05e1.73 Pa sn) and ow behavior index (n) of starch gels was in
amylose/amylopectin chain length etc. (Lawal et al., 2011; Sasak, the range of 0.63e0.67. The ascending curve for SKUAST-5 starch
Kohyama, Suzuki, Okamoto, Noel, & Ring, 2009). had a signicantly (p  0.05) higher value for yield stress (so) than
the other starches. Irrespective of the sample type, decrease in
3.4. Pasting properties viscosity was observed with increased shear rates which indicated
non-Newtonian behavior. The ow behavior index of n < 1 showed
The pasting properties of the rice starches are presented in that the gel structure is broken down by the applied shear stress
Table 3. Pasting temperature of three starches was in the range of which indicates their shear-thinning behavior (Chan et al., 2011).
75.8e77.6  C while the peak viscosity varied from 5.51 to 7.75 Pa s. The results (Fig. 3) clearly show that both ascending and
Heating of starch granules in aqueous solution results in loss of descending curves exhibited shear-thinning behavior as the
crystalline zones and increase in starch surface area. The increase downward curve also reected concave shape which is typical to
in viscosity is primarily due to granule swelling. Hot paste pseudoplastic materials. The ow curves also exhibited differences
viscosity is reported to be affected by the amylose leaching, in hysteresis pattern among the three starches. For comparison and
amyloseelipid complex formation, granule swelling etc. (Lu, characterization of thixotropy, the coefcient of thixotropic
Chen, & Lii, 1997). Trough viscosity showed values ranging from breakdown (Kd) was estimated. Therefore we used Eq. (2), pro-
2.51 to 5.94 Pa s while the breakdown viscosity values were in the posed by Dokic, Dapcevic, Krstonosi
c, Doki
c, and HadnaCev (2010).
range of 1.45e2.71 Pa s. The nal viscosity was in the range of 6.57e
9.39 Pa s respectively for SR-1 and SKUAST-5 starches. Setback
viscosity as noted was reported in the range of 3.45e3.56 Pa s with
the peak time lasting from 5.5 to 6.3 min. The pasting temperature
for rice starches range from 63.80  C (Raina, Singh, Bawa, & Saxena,
2007) to 95.10  C (Banchathanakij & Suphantharika, 2009);
peak viscosity from 0.54 Pa s (Banchathanakij & Suphantharika,

Table 3
Pasting properties of rice starches from cultivars grown in Indian temperate climates
(n 3).

Parameter SR-1 SKUAST-5 SKUAST-27


Peak viscosity (Pa s) 5.51a 7.39b 7.75c
Trough viscosity (Pa s) 2.51a 5.94c 5.04b
Breakdown viscosity (Pa s) 2.51b 1.45a 2.71c
Final viscosity (Pa s) 6.57a 9.39c 8.60b
Setback viscosity (Pa s) 3.56b 3.45a 3.56b
Peak time (min) 5.5a 6.3b 6.1b
Pasting temperature ( C) 76.7ab 75.8a 77.6b
Fig. 3. Flow curves of starch pastes (6% d.b) extracted from newly released rice cul-
Means in the rows with different superscript are signicantly different at p  0.05. tivars SR-1 ( ), SKUAST-5 ( ), & SKUAST-27 ( ) measured at 25  0.1  C (n 3).
A.A. Wani et al. / LWT - Food Science and Technology 53 (2013) 176e183 181

Table 4
Parameters of starches from rice cultivars, grown in Indian tempered climate, ob-
tained from ow measurements after 1 h (n 3).

Cultivar Flow properties as measured with HerscheleBulkely model

s0 [Pa]a,b Ka,b na,b Kdc sDC [Pa]d


SR-1 8.8 1.73 0.66 0.112 55.5
SKAUST-5 14.1 1.16 0.63 0.170 85.1
SKUAST-27 8.8 1.05 0.67 0.209 95.3

Model-ttings for mechanical spectra

Power-Law model with G00 prefactor Power Law model

G00 KG n K n
SR-1 77.36 0.08 1.45 5.59 0.40
SKAUST-5 111.97 0.02 1.80 5.58 0.39
SKUAST-27 124.74 0.82 0.83 5.59 0.40

LVR parameters

G0 G00 G0 /G00 tan(d) sY [Pa] sF [Pa] sY/sF


SR-1 42.2 7.8 5.4 0.185 5.3 14.6 0.361
SKAUST-5 80.9 8.9 9.1 0.133 9.9 26.2 0.379
SKUAST-27 97.8 12.4 7.9 0.125 11.9 35.8 0.332 Fig. 4. Oscillatory sweep tests of rice starch pastes (6% db.) measured as function of
a 2 storage modulus (G0 ) SR-1 ( ), SKUAST-5 ( ), & SKUAST-27 ( ) and loss modulus (G00 )
Regression coefcient R > 0.99.
b SR-1 ( ), SKUAST-5 ( ), & SKUAST-27 ( ) after 1 h storage at 25  0.1  C (n 3).
Parameters obtained by tting the descending curve by the HerscheleBulkley
equation.
c
Coefcient of thixotropic breakdown.
d
Starting point of the descending curve modied after Doki c, Dap
cevi
c,
coefcients of thixotropic breakdown (Kd) and higher G0 /G00 ratios.
Krstonosi
c et al. (2010).
Similar results for tan (d) were obtained in our work but not for G0 /
G00 ratios.
Mechanical Spectra showed a slight increase of G0 with increase
Aup  Adown in angular frequency (u) (Fig. 5). The results indicated that the G0
Kd (2)
Aup was dependent on u but prevailed over G00 along the whole
investigated range. In case of an ideal gel with an entirely elastic
In this equation, Aup is the integrated area under the ascending
behavior, G0 is expected to be independent of frequency and much
curve and Adown the area under the descending curve. The differ-
higher than G00 (G0 >> G00 ) (Tzoumaki, Moschakis, Kiosseoglou, &
ence between both curves AupeAdown is named as hysteresis area
Biliaderis, 2011). The mechanical spectra indicated that SR-1 and
AHys. Kd-values for the investigated starches signicantly (p > 0.05)
SKUAST-5 have weaker gel structures compared to SKUAST-27.
varied from 0.112 (SR-1) to 0.209 (SKUAST-27). As described by
SKUAST-27 exhibited a nearly perfect gel structure that was
Dokic et al. (2010), Kd is measure for the required energy to destroy
weakly dependent on u. The power law was tted to the data but
the system structure, what in this case is the breakdown of the
the obtained values could not explain the estimated values
paste or gel structure. The results indicated that SR-1 has the
(R < 0.8). By addition of a mathematical prefactor designated as G00 ,
highest structural strength, further validated by the consistency
we obtained a t with a total regression of R > 0.99, leading to the
index K. The higher K value indicates high structural strength,
following Eq. (3):
resulting in a less thixotropic behavior. By correlating this with the
previously obtained data, it is possible the see a correlation be-
tween the amylose content and the Kd-values. It appears that a high G0 G00 KG un G (3)
amylose content leads to increased system strength as well as in- This factor was required in the equation because the curves
crease in syneresis and swelling power Lawal et al., 2011). Similar showed different x-axis shifts. SKUAST-27 had the highest values
results were reported by Doki c et al. (2010) and Karim et al. (2008).

3.5.2. Oscillatory shear


Oscillatory rheological measurements were performed to mea-
sure the viscoelastic properties (Fig. 4). Loss modulus (G00 ) was
lower than storage modulus (G0 ) in the low stress region, however
further increase in the stress sharply increased the loss modulus
values. We observed that the yield stress values (sY) have strong
relationship with the G0 values as well as with the ow point (sF).
The ow point is dened as the intersection of G0 and G00 (G0 G00 ).
This behavior (Type III) is reported for weak polymeric gels, where
particle concentration and attractive forces or inter-chain associa-
tions pose severe constrains to incipient ow of the relevant
structural units e.g. particles, ocks or gel microdomains (Hyun,
Kim, Ahn, & Lee, 2002; Lawal et al., 2011; Sim, Ahn, & Lee, 2003).
It can be seen that the obtained results correlate with the shear
stress at the starting points of the descending curves of continues
shear experiments named as sDC. Hereby, higher values for sDC Fig. 5. Mechanical spectra of starch pastes (6% d.b). Storage modulus (G0 ) is repre-
result in higher G0 , sY and sF-values. Doki
c et al. (2010) postulated sented as (SR-1 ( ), SKUAST-5 ( ), & SKUAST-27 ( ) and loss modulus (G") as (SR-1 ( ),
that lower loss tangent (tan (d) values correlate with higher SKUAST-5 ( ), & SKUAST-27 ( ) for starch gels (6%), Tmeas 25  C  0.1  C (n 3).
182 A.A. Wani et al. / LWT - Food Science and Technology 53 (2013) 176e183

for G00 and KG and the lowest for nG While SR-1 showed the lowest Table 5
values for G00 and KG and the highest for nG Thereby G00 seemed to Digestibility of rice starches separated from Indian temperate rice cultivars (n 3).

correlate with the results of the LVE-range as well as ow in- Rice cultivar RDS (%) SDS (%) RS (%)
vestigations. Gels with higher gel strengths and longer LVE-ranges SR-1 39.8a  0.8 57.8a  0.5 0.4b  0.0
showed higher G00 values than gels with lower strengths and SKUAST-5 39.4a  0.3 58.3b  0.5 0.3b  0.0
shorter LVE-ranges. We also observed that gel curves (mechanical SKUAST-27 42.4b  0.5 57.5a  0.6 0.1a  0.0
spectra) with lower K values had an earlier ascend. This assumption Values expressed are mean  standard deviation.
can be used to describe the point of structure breakup. The values Means in the rows with different superscript are signicantly different at p  0.05.
for G00 showed similar results and the three different curves
exhibited similar pattern (Table 4).
rate of hydrolysis. These types of starches may not be benecial for
Data on structural recovery tests showed differences in the re-
diabetic persons due to their high glycemic indices.
covery behavior of different starches (Fig. 6). SKUAST-27, the starch
with the highest structured system showed the highest changes by
applying constant shear rates. SKUAST-5 and SR-1 showed similar 4. Conclusions
patterns with the least structured system for SR-1 starch. The re-
sults indicated that the rice starches had high recovery values after The present study deals with the physicochemical, thermal, and
applying high shear rates, which is different from the results pre- rheological properties and digestibility of rice starches separated
sented by (Lawal et al., 2011). Although differences in recovery from three rice cultivars grown in temperate climates. The results
could be observed between different rice starches, they exhibited indicated that these starches had differences in physico-chemical
extremely high structural recovery, which is a good indicator for properties possibly due to variation in granular size and shape
processing these starches under high shear conditions for different and amylose-and amylopectin ratios. The thermal properties indi-
food and allied applications. cated that these starches have differences in gelation and retro-
gradation properties. All the samples exhibited good pasting
properties making them suitable for different food formulations.
3.6. Starch digestibility The results showed that the Herschel-Bulkely model could be tted
to ow curves while the mechanical spectra can be described by a
In vitro starch digestibility measured as rapidly digestible starch modication of this model. The high structural recovery of these
(RDS), slowly digestible starch (SDS), and resistant starch (RS) is starches makes them suitable for high shear applications. The
presented in (Table 5). Starch digestibility is reported to be affected starches exhibited high values for rapidly and slowly digestible
by several factors such as amylose/amylopectin ratio, granule size, starch indicating that they can rapidly increase the blood plasma
amylose-lipid complexes, and molecular structure of amylopectin glucose levels in diabetic people.
(Chung et al., 2008; Chung, Liu, Lee, & Wei, 2011; Srichuwong &
Jane, 2007). Rice starch of SR-1, SKUAST-5, & SKUAST-27 showed
extremely high values of RDS (40.5e42.4 79.6 g/100 g starch) and Acknowledgments
SDS (57.3e59.3 79.6 g/100 g starch) while the RS values were less
than 0.5 79.6 g/100 g starch. These results indicated that rice cul- We are thankful to Regional Rice Research Station, Khudwani
tivars, grown in temperate climates, had a high digestibility. Similar (SKUAST-Shalimar) for providing us the paddy. We also thank Ms.
results were also reported by other research groups (Chung et al., Isabel Muranyi of Department of Process Engineering, Fraunhofer
2011). Snow and ODea (1981) reported that the high digestibility Institute IVV Freising for her help in doing scanning electron mi-
of rice starch is primarily related to smaller starch granular size, croscopy of starch samples.
which results in an increased surface area. This increased surface
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