7 Rice Starch Diversity - Effects On Structural, Morphological, Thermal, and Physicochemical Properties-A Review

Rice Starch Diversity: Effects on Structural,
Morphological, Thermal, and Physicochemical

PropertiesA Review
Ali Abas Wani, Preeti Singh, Manzoor Ahmad Shah, Ute Schweiggert-Weisz, Khalid Gul, and Idrees Ahmed Wani
Abstract: Rice starch is one of the major cereal starches with novel functional properties. Significant progress has
been made in recent years on the characterization of rice starches separated from different rice cultivars. Studies have
revealed that the molecular structure and functional properties are affected by rice germplasm, isolation procedure,
climate, agronomic conditions, and grain development. Morphological studies (microscopy and particle size analysis)
have reflected significant differences among rice starch granule shapes (polyhedral, irregular) and in granule size (2 to
7 m). Nonwaxy and long-grain rice starches show greater variation in granular size than the waxy starches. Rice starch
granules are smaller than other cereal starches with amylose contents varying from virtually amylose-free in waxy to
about 35% in nonwaxy and long-grain rice starches. Amylose content appears to be the major factor controlling almost
all physicochemical properties of rice starch due to its influence on pasting, gelatinization, retrogradation, syneresis,
and other functional properties. Waxy rice starches have high swelling and solubility parameters, and larger relative
crystallinity values than nonwaxy and long-grain starches. However, nonwaxy rice starches have a higher gelatinization
temperature than the waxy and long-grain starches. The bland taste, nonallergenicity, and smooth, creamy, and spreadable
characteristics of rice starch make it unique and valuable in food and pharmaceutical applications. This review provides
recent information on the variation in the molecular structure and functional properties of different rice starches.
Introduction
Rice (Oryza sativa L.) is a major cereal crop and the staple
food source for half of the world population. Starch is the major component of rice and accounts for more than 80% of the
total constituents. The global rice (paddy) production for the
year 2010 reached 609642285.84 metric tons (FAOSTAT 2012).
Larger rice starch diversity than other cereal grains (maize and
wheat) is important as it allows isolation of rice starch with different functionalities (Vandeputte and Delcour 2004). Increase in
rice production and demand for polished rice has significantly increased the amount of broken rice. Moreover, new rice cultivars
are continuously being released and the total number has exceeded
more than 2000 cultivars around the world (Deepa and others
2008). Diversity in rice cultivars in different regions of the world
is shown in Figure 1. Rice starch is reported as unique, with bland
MS 20120093 Submitted 1/17/2012, Accepted 4/20/2012. Authors Ali Abas
Wani, Shah, and Idrees Ahmed Wani are with Dept. of Food Technology, Islamic
Univ. of Science and Technology, Awantipora, Jammu and Kashmir 192122, India.
Authors Ali Abas Wani, Singh, and Schweiggert-Weisz are with Fraunhofer Inst. of
Process Engineering and Packaging IVV, Freising 85354, Germany. Author Ali Abas
Wani and Singh are also with Chair of Food Packaging Technology, Technical Univ.
of Munich, Freising, Weinstephan 85354, Germany. Author Gul is with Dept. of
Food Engineering and Technology, Sant Longowal Inst. of Engineering and Technology,
Longowal, Punjab 148106, India. Direct inquiries to author Ali Abas Wani/Preeti
Singh (E-mail: ali.abbas.wani@gmail.com or preeti ndri@rediffmail.com)

c 2012 Institute of Food Technologists
doi: 10.1111/j.1541-4337.2012.00193.x
taste, creamy, spreadable, and smooth in texture. These characteristics include hypoallergenicity, digestibility, consumer acceptance,
bland flavor, small granules, white color, increased freeze thaw
stability of pastes, greater acid resistance, and a wide range of amylose:amylopectin ratios (Mitchell 2009; Lawal and others 2011).
These unique properties have increased rice starch demand in the
food and pharmaceutical industries.
Starch occurs naturally as discrete particles, called granules. Rice
starch granules are the smallest known to exist in cereal grains,
with the size reported in the range of 2 to 7 m (Vandeputte and
Delcour 2004). These granules have smooth surface but angular
and polygonal shapes. Starch properties depend on the physical
and chemical characteristics such as mean granule size, granule
size distribution, amylose/amylopectin ratio, and mineral content (Madsen and Christensen 1996; Wani and others 2010). The
complexity of starch biosynthesis results in natural variability in
amylose and amylopectin molecules, which is reflected in the diversity of granule morphology. The variation, notably in granular
size and shape is associated with various functional properties in
different food systems and the possibility of relating granule morphology to manufacturing processes or nutritional qualities (Peterson and Fulcher 2001). The role of amylose and amylopectin
in the gelatinization and pasting properties of rice starch has been
widely studied (Noda and others 2003; Vandeputte and others
2003a, 2003b; Li and others 2008a, 2008b; Wang and others
2010).
Vol. 11, 2012 r Comprehensive Reviews in Food Science and Food Safety 417
Rice starch diversity . . .
Figure 1Biodiversity of world rice production (adapted and modified from Zhao and others 2011).
Amylose is the major factor influencing the physicochemical

properties of rice starch. Upon heating in aqueous solutions, starch
swells irreversibly and its crystalline structure collapses, a phenomenon known as gelatinization. Starch swelling is a property
of amylopectin, whereas amylose has been known to restrict it
(Tester and Morrison 1990a). Gelatinization converts starch into
a physical form that is desirable in many food systems. Starch gels
are, however, thermodynamically unstable and undergo changes
affecting their technological suitability (Lapasin and Pricl 1995).
Upon cooling, starch molecules reassociate in a complex recrystallization process known as retrogradation, which is often associated with water separation from the gel (syneresis) (Yeh and Yeh
1993; Hoover and Manuel 1995). These changes may result in
textural and visual gel deterioration (Thomas and Atwell 1999;
Fredriksson and others 2000). The pasting properties are used in
assessing the suitability of starch as a functional ingredient in food
and other industrial products.
The minor components in starch, which are either at the
surface or inside the starch granules, are lipids and proteins.
Cereal starches contain about 1% lipids and 0.25% proteins
(Baldwin 2001). Nonwaxy rice starches (12.2% to 28.6% amylose) contain 0.9% to 1.3% lipids comprised of 29% to 45%
fatty acids and 48% phospholipids (Azudin and Morrison 1986).
Waxy rice starches (1.0% to 2.3% amylose) contain negligible
amounts of lipids (Azudin and Morrison 1986). Starch proteins
are mostly either storage proteins or biosynthetic or degradative enzymes (Baldwin 2001). Rice storage proteins exist mainly
as protein bodies (PB), such as PB I (mainly prolamin) or
PB II (mainly glutelin) (Resurreccion and others 1993). Biosynthetic or degradative enzymes are most probably entrapped within
the starch granules following starch synthesis (Denyer and others 1995). Besides lipids and proteins, phosphorus is an important
component of rice starch and plays an important role in starch
functional properties, such as paste clarity, viscosity, consistency,
and paste stability. Phosphorus in starch is mainly present in 2
forms, phosphate-monoesters and phospholipids. In nonwaxy rice
starch, phosphorus is primarily in the form of the phospholipids
(0.013% dry basis of phosphate-monoesters and 0.048% for phospholipids), whereas in waxy rice starch, phosphorus is present as
starch phosphate-monoesters (0.003% for phosphate-monoesters
and nondetectable for phospholipids) (Lim and others 1994; Jane
and others 1996). Starch phosphate-monoesters in native starches
are primarily found in amylopectin, and only a trace is found in
amylose. About 80% to 90% phosphate-monoester in waxy rice

starch is on the C6 of glucose units (Jane and others 1996). Other
mineral components of starch which occur in their ionic form,
are calcium, potassium, magnesium, and sodium.
Rice Starch Isolation

Rice starch isolation is different from other starches because
of its unique protein composition. The isolation process consists
mainly of the separation of starch from protein, fiber, and lipid.
Important considerations thereby are avoidance of amylolytic or
mechanical damage to the starch granules, effective deproteinization of the starch, minimization of loss of small granules, and
avoidance of starch gelatinization (Schulman and Kammiovirta
1991). Rice starch isolation is also associated with the entrapment
of small granules in the protein and fine fiber sediments generated during centrifugation (McDonald and others 1991; Schulman and Kammiovirta 1991; Lim and others 1999; Andersson
and others 2001; Xie and Seib 2002). When these sediments are
scraped off and discarded, which is common in laboratory purification methods and in some industrial processes, a severe loss of
small granules occurs (Szczodrak and Pomeranz 1991). To reduce
the entrapment of small granules in the protein layer, researchers
can degrade the protein enzymatically, followed by separation of
the peptides and starch using centrifugation (Radosavljevic and
others 1998; Wang and Wang 2001). These protein digestion
methods produce starches with higher or comparable yields and
reduced starch damage. However, these processes require chromatography to purify the protease and remove any amylase activity
(Radosavljevic and others 1998). Enzymes like hemicellulase and
xylanase have also been used to degrade the polysaccharides present
in the sediments entrapping the starch granules (Wilhelm and others 1998). Lawal and others (2011) reported starch yields of 70.0%
to 73.77% for 5 newly released West African rice cultivars. Wide
ranges of variations in rice starch yield have been observed from
different rice cultivars: 59% to 71.6% (Mohan and others 2005;
Wang and Wang 2004).
Rice protein consists of albumin (5%), globulin (12%), prolamin
(3%), and glutelin (80%), which dissolve in water, salt, ethanol, and
alkali, respectively (Juliano 1985). These proteins are soluble in an
alkaline medium; therefore, alkaline steeping (using 0.2% to 0.5%
NaOH, w/w) has been conventionally used for the isolation of
rice starch, with good recovery and low residual protein content
(Landers and Hamaker 1994; Patindol and others 2003; Sasaki
418 Comprehensive Reviews in Food Science and Food Safety r Vol. 11, 2012

Figure 2Morphology of rice starch as measured by scanning electron microscopy at 2000X (a: SKUAST-5) and at 6000X (SR-1).
and others 2009). It has been reported that the structure of the
starch granule can be damaged when the rice grains are steeped
in 0.2 M aqueous ammonia solution (Chiou and others 2002).
Furthermore, the use of alkali for steeping has been associated
with effluent disposal problems. Environmental concerns and strict
regulations have produced interest among food scientists to find
alternate starch extraction procedures. A physical process, which
employs high-pressure homogenization, was studied for recovering
rice starch and protein fractions by partial mechanical breaking of
the starchprotein matrix (Guraya and James 2002). The residual
protein in the starch yield was 2.7%, which was greater than that of
an alkaline process. Increase in efficiency is preferred for rice starch
isolation, while preserving the native structure of the rice starch
granules and limiting the waste products from the starch separation
process. Alternatively the use of alkaline proteases for rice starch
has been studied by Lumdubwong and Seib (2000). However, this
method has been associated with salt waste. The production of rice
starch by an enzymatic process has reduced the levels of mineral
loads in effluents of rice starch plants (Puchongkavarin and others
2005). Two food-grade enzyme preparations (an alkaline protease,
Alcalase and a neutral protease, Protease N) were found to be more
effective than other proteases for protein removal in the isolation
of rice starch from wet-milled flour (Li and others 2008a, 2008b).
Wang and Wang (2001) found that neutral protease was effective
in assisting rice starch isolation under neutral conditions. This
method was not associated with salt effluent, but the reaction
time was too long to achieve a high starch yield with low residual
protein content. In another study, Wang and Wang (2004) reported
that the use of high-intensity ultrasound, alone or combined with
surfactants (for example, sodium dodecyl sulfate), reduced not only
rice starch isolation time but also was not associated with effluent
disposal problems. Further investigations are required to extract
rice starch with improvements in the existing methods. Specific
concerns will be the minimization/recycling of water required
during the extraction process.
Starch Morphology
Starch occurs naturally as discrete particles, called granules
(Figure 2). Granule size and shape of starch are reported to be primarily affected by the germplasm from which the starch is isolated.
The other factors affecting starch granule morphology include climatic conditions and agronomic practices. Generally, granule size
refers to the average diameter of the starch granule. Granule size
can be determined by various techniques like microscopy (light
microscopy, scanning electron microscopy [SEM]), sieving, elec
trical resistance, laser light scattering, and field flow fractionation

(Lindeboom and others 2004). However, SEM is frequently used
to determine granule size. It also provides a more detailed perspective on granule surface characteristics and granule morphology
(Chmelik 2001). Various studies, using x-ray photoelectron spectroscopy and SEM have revealed that the starch granule surface is
predominantly (90% to 95%) carbohydrate in nature (Oostergetal
and van Bruggen 1993; Calvert 1997).
The granular structure of rice starches varies in shape and size
among different cultivars (Table 1). In rice, several polyhedral small
granules are produced in 1 amyloplast. They form parts of compound granules. Scanning electron micrographs have shown that
starch granules of all rice types are mainly polyhedral in shape.
These granules may also be oval, irregular, angular, or smooth in
shape. Rice starch granules are the smallest known to exist in cereal grains, with a size in the range of 2 to 7 m (Vandeputte and
Delcour 2004). The size of starch granules varies between nonwaxy, waxy, and long-grain rice starches and it also varies from
cultivar to cultivar. Nonwaxy cultivars reportedly show greater
variation than the waxy cultivars. However, the starches extracted
from long-grain rice cultivars show a wide range of granule size
(2 to 7 m) (Hoover and others 1996). Light scattering studies of
starch dispersions have shown that the size and density of an average rice starch granule is 14 m and 1.530 g/cm3 , respectively
(Odeku and Itiola 2007). Starch granule size has been reported
to affect the composition, gelatinization, and pasting properties,
enzyme susceptibility, crystallinity, swelling, and solubility. However, several other factors, including amylose/amylopectin ratio
and molecular weight and granule fine structure, are also influential (Lindeboom and others 2004).
Starch Structure
Starch granules are packed in the form of semicrystalline areas and amorphous regions in an alternating fashion (Figure 3)
(Jenkins and Donald 1994). Treatment with -amylase demonstrates a ringed pattern analogous to tree growth rings (Hoseney
1994). According to French (1984), the number and size of the
growth rings depend on the botanical origin of the starch, and
the semicrystalline growth rings have a thickness in the range
of 120 to 400 nm. Cameron and Donald (1992) suggested that
the amorphous growth ring has the same thickness as that of
the semicrystalline one. The growth rings are approximately 400
nm apart in rice starch as measured by atomic force microscopy
(Dang and Copeland 2003). Like other starches, rice starch is a
copolymer of linear chain (amylose) and branched (amylopectin)

Table 1Diversity in the morphological properties of rice starches.
Type/cultivar
Nonwaxy
TNu67
PR103, PR-106, PR113,
PR-114, IR-8
PR113, PR111, Basmati-370,
IET-16313, IR-64, PR103,
IR08, Bas-386, RYT-2492
ZHONG9B
PUSA44, PR106, PR114
Not specified
Exiang No.1, Honglianyou No. 6, Liangyoupeijiu (Hunan),
Zhongjian No 2, Liangyoupeijiu (Hubei), Heiyouzhan,
98112jing, Tongjin611, Jiyujing, Tianjinxiaozhan
FARO 51, 52, 54, 32 NERICA
Waxy
Not specified
TCW70
SMJ
Long-grain rice
IR64
Shape
Size (m)
Reference
Polyhedral
Polyhedral, round
6.4
2.4 to 5.4
Li and Yeh 2001

Sodhi and Singh 2003
Polyhedral, irregular
1.5 to 5.8
Singh and others 2006b
1.08 to 7.49
3.11 to 7.78
4.16 to 4.48
3 to 8
Yang and others 2006

Raina and others 2007
Zhang and others 2010
Wang and others 2012
1.5 to 6.1
Lawal and others 2011
Polyhedral, angular, oval

Polyhedral
Polyhedral, smooth
Angular, polygonal
Polyhedral with irregular shapes
Polyhedral, smooth
Polyhedral
5.00
5 to 6
5 to 6
Zhang and others 2010

Lu and others 2008
Tatongjai and Lumdubwong 2010
Polyhedral, angular
2 to 8
Hoover and others 1996
Figure 3Starch granular structure: (a) the whole granule, (b) the lamellae, and (c) the polymer chains. Adapted from Waigh and others (1996).
biopolymers. The other minor components in rice starch are lipids

and proteins, and calcium, potassium, magnesium, and sodium in
the ionic form (Vandeputte and Delcour 2004). Starch is classified
as rapidly digestible starch (RDS), slowly digestible starch (SDS),
or resistant starch (RS) (Zhu and others 2011). Variations in amylose and amylopectin ratio and molecular structure are reported to
be greatly affected by genetic, environmental, and agronomic conditions (Lawal and others 2011). These 2 principal components
greatly influence the functional properties of rice starches.
Amylose
Amylose, a linear polymer, is composed almost entirely of
-1,4-linked D-glucopyranosyl units; many amylose molecules
have a few -1,6-linked D-glucopyranose branches, about 0.3%
to 0.5% (Whistler and BeMiller 1997) and at times less than 0.1%
(Ball and others 1996). The location of amylose in a starch granule is still in dispute. Various possible locations have been listed:
(1) amorphous lamellae, (2) amorphous growth ring, or (3) interspersed or cocrystallized with amylopectin molecules (Hoover
and others 2010). Amylose is actually helical. The interior of the
helix contains hydrogen atoms and is therefore hydrophilic, allow-
ing amylose to form a type of clatherate (an inclusion complex

wherein a host molecule entraps a 2nd molecular species as the
guest) complex with free fatty acids, fatty acid components of glycerides, some alcohol, and iodine (Fennema 1985). It has an average
degree of polymerization (DP) value of 800 to 4920, average chain
lengths (CL) of 250 to 670, and -amylolysis limits of 73% to 95%
(Morrison and Karkalas 1990). Rice starch amyloses have DP values of 920 to 1110, CL of 250 to 370, and -amylolysis limits
of 73% to 84%. They are slightly branched with 2 to 5 chains on
average (Takeda and others 1986). Takeda and others (1993) found
ratios of branched to linear rice amylose molecules of 0.22:0.78 by
mole and 0.32:0.68 by weight with DP values of 1180 and 740,
respectively. The branched amylose molecule has been suggested
to have a structure intermediate between that of linear amylose
and amylopectin, frequently referred to as intermediate material
(Takeda and others 1993).
Amylose forms a complex with iodine, changing the color
of amylose to blue-black. This is the basis of commonly used
colorimetric methods or determining the amylose content in
a sample (Juliano and others 1981). Mahmood and others
(2007) attribute the methods widespread use to its economic


advantage and greater throughput per day over other methods
available. The use of delicate reagents such as enzymes is also
not required (Mahmood and others 2007). Yun and Matheson (1990), however, noted a major limitation of the colorimetric method, namely, relying on the color formation of the
starchiodine complex. The amylopectin portion of the starch
also produces a reddish-purple compound when complexed with
iodine (BeMiller and Whistler 1996), which subjects the color
measurements to uncertainties. Amylose standards obtained from
various sources may vary widely in terms of quality, the presence of lipids that could interfere with the assay, and the pH of
the final solution are other possible sources of error (Bhattacharya
2009). Therefore, results from this method could either be lower
or higher than the actual value (Singh and others 2003), and the
value obtained should be termed apparent amylose or amylose equivalent (Bhattacharya 2009). Gibson and others (1997)
developed a method that estimates the amount of the polysaccharide after precipitation with concanavalin-A (Con A), a lectin
that can selectively precipitate amylopectin from starch through
the formation of a complex under defined conditions of pH, temperature, and ionic strength. Yun and Matheson (1990) refined
this method by including an ethanol pretreatment of the starch
sample to extract the lipids, which can also complex with amylose and interfere with colorimetric determinations. The amylose
is then either reacted using phenolsulfuric acid reagent or hydrolyzed enzymatically. The use of phenolsulfuric acid reagent,
however, could yield a higher amylose value, which may be due
to the presence of nonstarchy polysaccharide (Yun and Matheson
1990). Megazyme Intl. Ireland Ltd. (Co. Wicklow, Ireland) has
developed an amylose/amylopectin assay which is based primarily
on the method of Yun and Matheson (1990), but utilized only the
enzymatic hydrolysis.
The amylose content of starch has been reported to vary with
the botanical source of the starch and is affected by the climatic and
soil conditions during grain development (Morrison and others
1984; Yano and others 1985). The variation in the amylose content
among different rice cultivars is reported in Table 2. Typical levels
of amylose in starches are 15% to 25% (Manners 1979). However,
waxy starches are reported to be virtually amylose-free. On the
basis of amylose content, rice starch may be classified as waxy
(0% to 2% amylose), very low (5% to 12% amylose), low (12% to
20% amylose), intermediate (20% to 25% amylose), or high (25%
to 33% amylose) starch (Juliano and others 1981; Yu and others
2012). Wang and others (2010) isolated starches from 10 different
nonwaxy rice cultivars and reported amylose content in the range
18.1% to 31.6%. The amylose content of waxy rice starches ranged
from 0.1% to 3.25% (Zuo and others 2009; Chang and others
2010) and varied among different waxy rice cultivars. The amylose
content of long-grain rice starches ranged from 17.0% to 35.7%
(Puchongkavarin and others 2005; Patindol and others 2007).
The differences in amylose content might be related to cultivar
differences, growing zone and environment. The compositions
of starches can be different, even when all the samples are from
the same rice cultivar. Peisong and others (2004) reported that
the amylose content was in the range of 13.2% to 26.5% for nonwaxy rice starches. The difference might be caused by the different
growing zones and cultivars. On the contrary, rice mutants with
high levels of amylose are known to have amylose content in a
range of 35% to 40% (Juliano 1992). Morrison and others (1993)
reported that in determining amylose contents, the existence of
both lipid-complexed amylose (LAM) and free amylose (FAM)
(major fraction) must be taken into account. LAM may be present

in the native starch (Morrison and others 1993), but is possibly

also formed during hydrothermal treatment or gelatinization of the
starch (Biliaderis and others 1986). Amylose content appears to be
the major factor controlling almost all physicochemical properties of rice starch such as turbidity, syneresis, freezethaw stability,
pasting, gelatinization, and retrogradation properties (Wickramasinghe and Noda 2008). Varavinit and others (2003) reported a
positive correlation of gelatinization with amylose content. The
effect of amylose on the rheological property of rice starch paste
has been investigated by Lii and others (1996). They explained
that the amount of leach-out amylose was one of the major factors
influencing the rheological properties of starch during heating.
Amylopectin
Amylopectin, consisting of -1,4-linked D-glucopyranosyl

chains, is highly branched (5% to 6%) with -1,6-bonds (Buleon
and others 1998). It has a DP of 4700 to 12800, CL values of
17 to 24, and -amylolysis limits of 55% to 60% (Morrison and
Karkalas 1990). Individual chains may vary between 10 and 100
glucose units (Manners 1979). Rice starch amylopectins have a
DP of 8200 to 12800, CL of 19 to 23, -amylolysis limits between 49% and 59% (Takeda and others 1987; Wang and others
2010), average external chain lengths (ECL) of 11.3 to 15.8, and
average internal chain lengths (ICL) of 3.2 to 5.7 (Lu and others
1997). Waxy japonica rice starches have the lowest CL (17 to 19)
(Morrison and Karkalas 1990). Takeda and others (2003) reported
that the DP of amylopectins from starches of different botanical
origins is in the range of 9600 to 15900. Moreover, they revealed
the presence of large (DP 13400 to 26500), medium (DP 4400 to
8400), and small (DP 700 to 1200) species.
Both semicrystalline and amorphous growth rings are subdivided into large (20 to 500 nm in dia) and small (25 nm in dia)
spherical blocklets, respectively (Gallant and others 1997). Thus,
1 blocklet in a semicrystalline growth ring contains several amorphous and crystalline lamellae. On average, 2 end-to-end blocklets
would constitute a single semicrystalline growth ring. According
to Dang and Copeland (2003), cross-striations occur within the
growth rings of rice starch which correspond to the blocklets of
amorphous and crystalline lamellae. These blocklets have an average size of 100 nm in dia and are proposed to contain 280 amylopectin side chain clusters. Each semicrystalline growth ring (120
to 400 nm thick) is composed of repeats of alternating amorphous
(2 to 5 nm thick) and crystalline (5 to 6 nm thick) lamellae (French
1984; Cameron and Donald 1992). Independent of the botanical
origin of the starch, repeat distances of amorphous and crystalline
lamellae are about 9 nm (Oostergetel and van Bruggen 1989;
Jenkins and others 1993). Amorphous lamellae contain branch
points of the amylopectin side chains and possibly some amylose,
whereas semicrystalline lamellae are constituted of amylopectin
double helices. Amorphous growth rings contain amylose and
probably less ordered amylopectin (Morrison 1995).
Amylopectin molecules are highly branched, of high molecular
weight and constitute the skeleton of the starch granule (Kossmann
and Lloyd 2000). Peat and others (1956) defined the basic structure
of amylopectin in terms of linear A, B, and C chains. A chains
(outer chains) are attached through their potential reducing end to
B chains. The latter are linked in the same way and carry one or
more A chains. The C chain contains the single reducing group
of the amylopectin molecule and carries other chains. Based on
the A-, B-, C-chain terminology of Peat and others (1956) and
Hizukuri (1986) the cluster model has been refined. Amylopectin
has a polymodal distribution with A (CL 12 to 16) and B chains,

Table 2Diversity in physicochemical properties of starches separated from different rice cultivars.
Type/cultivar
Nonwaxy
PR103, PR-106, PR113,
PR-114, IR-8
PR113, PR111,
Basmati-370,
IET-16313,
IR-64, PR103, IR08,
Bas-386, RYT-2492
PR113, PR103, PR115,
Basmati370,
Basmati386,
IR64
Not specified
AT405, AT306,BG450,
Batapola wee, Martin
Samba, Bandara, Bata
Mawee, Heenati662
Xing indica 24
Exiang No. 1, Honglianyou
No. 6, Heiyouzhan,
98112jing, Jiyjing,
Tianjinxiazhan
PUSA1121
SM, DH, TML
Waxy
Calmochi 101
Not specified
Koganemochi,
Hakuchomochi,
Kantomochi
Not specified
SMJ
TKW1
RD6
SN2
Not specified
W4109, W4111
Calmochi 101
IR29, Malagkit S,
RD4, Tapol
Long-grain
Cocodrie, L205
Not specified
Not specified
Cocodrie, L205
Bolivar, Cheniere, Dixiebelle,
L205, Wells
Lebonnet
Doongara
Amylose (%)
Swelling power (%)
Solubility (%)
Syneresis (%)
Reference
7.83 to 18.86
26.06 to 33.20
0.287 to 0.360
0.04 to 2.41 (48 hrs)
4.10 to 16.40
17.2 to 38.8
0.00 to 1.81 (24 hrs)
5.80 to 12.55
9.7 to 28.3
12.95 to 15.82
7.25 to 8.25

11.9
15.5
3.9
16.0 to 34.6
7.33 to 16.12
Techawipharat and others

2008
Wickramasinghe and Noda
2008
28.5
18.1 to 31.6
16.3 to 30.2
17.0 to 40.0
22.9 to 46.4 (22 hrs)
19.2
16.99 to 38.62
18.3
12.11 to 15.98
10.8
6.28 to 7.06
Sandhu and others 2010

Yu and others 2012
0.80
0.92
26.9
14.9
1.1 to 1.7
Li and others 2008a

2008
Sasaki and others 2009
3.25
2.07
0.10
2.08
1.50
2.0
0.5 to 1.0
1.0
1.2 to 2.4
13.08
0.6 to 8.5
69.16
17.6 to 20.8
35.7
20.0
17.1 to 19.9
17.0 to 21.6
Li and others 2008a, 2008b

Puchongkavarin and others
2005
Shih and others 2007
Park and others 2007b
Patindol and others 2007
17.9
27.0
2.0 (2 wk)
Matalanis and others 2009

Zhou and others 2007
Lin and others 2009

Zuo and others 2009

Tatongjai and Lumdubwong
2010
Chang and others 2010
Noosuk and others 2003
Yu and others 2012
Iturriaga and others 2004
Nakamura and others 2006
namely B1 (CL 20 to 24), B2 (CL 42 to 48), B3 (CL 69 to 75), and

B4 (CL 104 to 140) chains. A and B1 chains form a single cluster,
whereas B2 , B3 and, B4 chains extend into 2, 3, and more than 4
clusters. Hanashiro and others (2002) suggested that C chains are
very similar among botanical sources and range in size from 10
to 130 glucose units, with the majority being around 40 glucose
units (Hanashiro and others 2002). The following composition
was proposed for waxy rice amylopectin: A (CL 13), B1 (CL
22), B2 (CL 42), B3 (CL 69), and B4 (CL 101) (Hizukuri 1986).
Enevoldsen and Juliano (1988) reported waxy and nonwaxy (low
amylose) rice amylopectin to have similar molar ratios of A to B
chains (1.1 to 1.5).
The characteristics of foods containing starch are understood to be

largely by the mass ratio of amylose:amylopectin and the molecular
weight of amylose (Yoo and Jane 2002; El-Khayat and others 2003;
Varavinit and others 2003). The pasting peak viscosity (PV) and
breakdown viscosity of rice and wheat starch were negatively correlated with amylose content (El-Khayat and others 2003; Varavinit
and others 2003). Long-chain-length branches of amylopectin and
intermediate-size branches of amylose produced the greatest synergistic effect on pasting viscosity of reconstituted starch (Jane and
Chen 1992). The role of amylopectin size in starch functionality
has been difficult to determine because of its tendency to form
insoluble aggregates. A key part of the picture of starch functionality includes sound data on the associated molecular structure
of all starch polymers. The fundamental starting point is knowlMolecular Weight
Understanding the relationship of starch functionality to its fun- edge of the molecular weight and size of amylose and amylopectin
damental molecular properties, such as weight-averaged molecu- starch molecules. The molecular weight of polymers is commonly
lar weight and structure, has long been a goal of food scientists. determined by size exclusion chromatography (SEC). However,


this measurement for starch is challenging because calibration
standards are usually necessary. In recent years, high-performance
(HP) SEC instrumentation equipped with both MALLS
(multi-angle laser light scattering) instrumentation and differential refractometer (refractive index, RI) has been used routinely
to determine the molecular weight of polymers without the use
of standards. This technique makes starch molecular weight measurement possible (Aberle and others 1994; Bello-Perez and others
1996). This system has been used to measure average molar mass
molecular weight (Ong and others 1994; Yoo and Jane 2002),
amylose molecular weight (Radosta and others 2001; Roger and
others 2001), and amylopectin molecular weight (Bello-Perez and
others 1998; Yoo and Jane 2002). But to obtain the accurate
molecular weight of amylopectin or amylose by this technique,
the complete dissolution of amylopectin and amylose is necessary.
Dissolving starch is a minimum requirement for the separation and
molecular weight determination of amylopectin and amylose by
HPSEC. Soluble but entangled amylose and amylopectin will lead
to molecular weight values higher than their true values. The limited solubility of starch in neutral aqueous solution makes structural
analysis of starch in aqueous media difficult (Han and Lim 2004).
High temperatures and high pH increase the solubility of many
cereal starches in aqueous solvents, but may result in molecular size
reduction resulting from degradation, depolymerization, or oxidation (Yokoyama and others 1998). Dimethyl sulfoxide (DMSO)
is the most frequently used polar aprotic solvent for SEC analysis
(Jackson 1991).
According to Zhong and others (2006), the SEC analysis of
nonwaxy rice starches should have only 2 peaks, one for amylopectin and the other for amylose. But there was only 1 peak
followed by an unresolved shoulder in the SEC profiles of rice
starch. The poor result could possibly be due to the branched structure of amylopectin. Therefore, starch was physically fractionated
into amylose and amylopectin and molecular weight of both the
polymers was determined separately by HPSEC-MALLS (Zhong
and others 2006) and SEC-MALLS (Park and others 2007a). The
molecular weights of amylopectin and amylose determined by
HPSEC equipped with MALLS and RI detectors showed molecular weights of amylopectin and amylose were 1.48 109 and
3.85 105 , respectively (Bao and others 2004). Zhong and others
(2006) reported the molecular weight of amylopectins and amyloses in the range (4.0 to 5.5) 107 and (3.1 to 3.4) 106 ,
respectively, from different rice cultivars. According to Park and
others (2007a), the average molecular weight values of amylopectin
were 1.10 108 (long grain), 1.81 108 (short/medium grain),
and 2.47 108 (waxy grain); and for amylose were 3.90 105
(long grain) and 3.73 105 for starches extracted from short-/
medium-grain rice cultivars. Park and others (2007a) compared
the molecular weight of the starches and those of the fractionated
components, the molecular weights of amylopectin and amylose
mixtures, and they observed that the molecular weights of the
starches measured by HPSEC-MALLS were lower than the calculated values corresponding to the amylopectin/amylose fractions.
X-Ray Diffraction Studies

Starch structure is described in terms of amorphous and
semicrystalline growth rings (Figure 4). The amorphous region contains mainly amylose and less ordered amylopectin
(Morrison 1995). Every semicrystalline region is composed of
repeats of alternating amorphous and crystalline lamellae, which
consist of branch points of amylopectin side chains and amylopectin double helices, respectively (French 1984). The amount

of crystallinity within starch granules can be determined by different techniques, but x-ray diffraction is most widely used to study
starch structure. The parallel chains occasionally have crystalline
arrangements in the local regions of submicroscopic size that makes
x-ray diffraction a suitable approach to study starch (Dunder and
others 2009). Wide-angle x-ray scattering and small-angle x-ray
scattering are used in parallel to reveal the complex ultra-structure
of the granule and quantification of crystallinity and polymorphic
forms or crystalline laminates, respectively (Tester 1997).
As mentioned earlier, starch crystallinity is primarily determined
with a wide-angled x-ray diffractometer. X-ray determinations of
crystallinity include determinations of absolute and relative
crystallinity. The former differentiates between the amorphous
and crystalline components (integrated area) of the x-ray diffractogram. The latter relies on calculating the proportion of crystallinity within starch granules, using as references materials with
0% and 100% crystallinity. The 0% reference, representing fully
amorphous material (such as freeze-dried gelatinized material),
and the 100% reference usually generated by extensive acid hydrolysis of starch in which all the amorphous (but not crystalline)
material has been eroded (Tester and others 2004). Starches can
be designated as A, B, and C type on the basis of x-ray diffraction patterns. The differences between A-type and B-type starches
arise from water content and the manner in which these pairs are
packed in the crystals (Imberty and others 1991). The lattice of
B-type starch has a large void in which numerous water molecules
can be accommodated. This void is not present in A-type starch.
Rice starch (cereal starch) exhibits the A-type pattern.
Native rice starches (waxy and normal) displayed A-type diffraction patterns to Vandeputte and others (2003a). The x-ray diffractograms of native nonwaxy rice starches showed typical A-type
diffraction patterns with strong reflection at 15 and 23 , and
the degree of crystallinity of the rice starch was 21.69% (Mohan
and others 2005). The x-ray diffraction patterns of rice (japonica) starch also showed an A-type x-ray diffraction pattern with a
crystallinity of 36.1% (Bao and others 2004). Waxy rice starches
had larger relative crystallinity values than normal starches. Absolute and free amylose contents are reported to be negatively
correlated with relative crystallinity. Crystallinity was also influenced by amylopectin CL distribution. According to Iturriaga
and others (2004), the x-ray diffraction spectra of starch from
the 7 rice cultivars studied showed an A-type pattern typical of
cereal starches. The relative crystallinity in waxy genotypes was
found to be higher (48%) than that corresponding to the nonwaxy ones (37% to 40%). It is widely accepted that the amylopectin is the predominant crystalline component in granules,
with the short-branched chains forming local organizations compatible with cluster models (Imberty and others 1991). However,
no significant differences in crystallinity were found among the
nonwaxy varieties with different amylose:amylopectin ratios. Ong
and Blanshard (1995) reported similar relative crystallinities for
different nonwaxy rice starch varieties. The extent of crystallinity
seemed to be closely related with the gelatinization temperatures
(Yang and others 2006). The spectrum of rice starch shows definite diffraction peaks that presumably reflect the crystalline region
in the starch. The A-type rice starch with characteristic diffraction
peaks at 14.0 , 16.9 , 17.6 , and 22.9 is most susceptible to enzymatic hydrolysis (Han and others 2007; Martinez and others 2007).
According to Singh and others (2007a, 2007b), x-ray diffractions
of rice starches from various nonwaxy rice cultivars showed the
typical A-pattern. These rice starches showed strong reflections
at 2 = 15.1 , 17.2 , 18.1 , and 23.2 . An additional peak at
Figure 4The range of elastic neutron scattering techniques, corresponding size range, and complementary methods shown in relation to the
hierarchical structure of starch (adapted from Lopez-Rubio and Gilbert 2009).
2 = 20.0 was observed for Basmati-386, which was attributed

to amyloselipid complexes by Zobel and others (1988). Higher
peak intensities indicate greater crystallinity, while the weakest xray patterns, as well as the lowest peak intensities, indicate low
granule crystallinity. Yu and others (2012) reported that x-ray
diffractions of rice starches showed typical A-pattern and strong
reflections at 2 = 15 , 17.5 (nonwaxy), and 23.16 (waxy).
Amylose does not appear to have any significant effect on crystallinity in normal and waxy starches (which may be virtually free
of amylose), both of which display strong birefringence (Morrison
and Karkalas 1990; Zobel 1992; Kent and Evers 1994; Hoover
2001; Tester and Karkalas 2002). Singh and others (2007a, 2007b)
attributed the differences in crystallinity in different rice starches
to differences in proportions of amylose, short side-chain and long
side-chain amylopectin. Tester and others 2000 reported that in
high-amylose starches, the amylose may contribute significantly to
the crystallinity. The exact nature of the crystalline polymorphs
may be different (Matveev and others 2001). However, in the case
of amylopectin-rich starches it is understood that the origin of
crystallinity is due to the intertwining of the outer chains of amylopectin (exterior or external chains, representing A and B1 types)
in the form of double helices. These associate together to form
ordered regions or crystalline lamellae. Adjacent double helices
give rise to regular 3-dimensional geometrical patterns. Such an
array of atoms, molecules, or groups of molecules, according to the
rules of crystallography, will interact with electromagnetic waves
of short wavelength (x-rays) to give a characteristic diffraction
pattern (Tester and others 2004).
Starch Gelatinisation
Gelatinization, an endothermic process, results in the disruption of molecular order within the starch granules. Double helical and crystalline structures are disrupted in starches during
gelatinization. Increase in temperature causes the crystallites to
break apart, and then to undergo hydration resulting in several
changes such as granular swelling, native crystalline melting, loss of
birefringence, and starch solubilization (Atwell and others 1988).
Gelatinization, or molecular disordering, is not a simple granular
order-to-disorder transition; it is more complex. Understanding

of the gelatinization mechanism has evolved simulatneously with
the knowledge of granular structure (Blazek and Gilbert 2011).
Gelatinization is a 2-step process, first starch granules swell due
to breakage of hydrogen bonds in the amorphous portions of the
starch. In the next event, water acts as a plasticizer, which results in
hydration and swelling of the amorphous regions. Slade and Levine
(1988) reported that for gelatinization to occur, the amorphous
regions of starch must first melt or undergo glass transition. Last,
polymer molecules, particularly those of amylose, leach out of the
granules resulting in increased viscosity (Biliaderis 1991; Eerlingen
and Delcour 1995; BeMiller 2007). Gelatinization is an important
functional property of starches that varies with respect to their
composition (such as amylose-to-amylopectin ratio, phosphorus,
lipids, proteins, and enzymes), the molecular structure of amylopectin (unit CL, extent of branching, molecular weight) granule
architecture (crystalline-to-amorphous ratio), granule morphology, and granule size distribution (Tester 1997; Hoover and others
2010).
Although several analytical methods exist, differential scanning calorimetry (DSC) has emerged as the preffered method
of choice for the measurement of starch gelatinization (Nakazawa
and others 1984; Shiotsubo and Takahashi 1984; Wickramasinghe
and Noda 2008; Acquistucci and others 2009; Wani and others 2010). The other methods include x-ray diffraction (IAnson
and others 1988; Zobel and others 1988), nuclear magnetic resonance (NMR) (Chinachoti and others 1991) and use of the
rapid visco-analyzer. Thermal properties typically reported using
DSC include gelatinization onset (T o ), peak (T p ), and conclusion (T c ) temperatures, peak hight index (PHI), gentinization
range (R), and enthalpy (H g ). It measures 1st-order (melting)
and 2nd-order (glass transition) transition temperatures and heat
flow changes in polymeric materials and gives information on
orderdisorder phenomena of starch granules (Biliaderis and others 1986). In the DSC curve of starch at intermediate water levels,
3 endothermic transitions are usually observed. The first 2 endotherms correspond to the disorganization of starch crystallites
(Biliaderis and others 1986), or gelatinization, wherein glass


transitions of water-plasticized amorphous portions and then
nonequilibrium melting of the microcrystallites of the partially
crystalline amylopectin occur (Slade and others 1996). The 3rd
endotherm, which occurs at higher temperature, relates to the
melting of complexes formed by amylose and native lipids (Biliaderis and others 1986). Crystallite quality and the overall crystallinity of the starch are measured by the peak temperature (T p )
and the enthalpy of gelatinization (H g ), respectively (Tester and
Morrison 1990a). Onset temperature (T o ) and conclusion temperature (T c ) determine the boundaries of the different phases in
a semicrystalline material like starch (Biliaderis and others 1986).
Noda and others (1996) postulated that DSC parameters (T o ,
T p , T c , and H g ) are influenced by the molecular architecture
of the crystalline region of starch, which corresponds to the distribution of short-chain amylopectin (DP 6 to 11) and not by
the proportion of the crystalline region which corresponds to the
amylose content. Cooke and Gidley (1992) have shown that the
H g values of gelatinization primarily reflect more the loss of
double helices than the loss of crystallinity. However, Tester and
Morrison (1990a) postulated that H g reflects the overall crystallinity (quantity and amount of starch crystallites) of amylopectin.
Tester (1997) suggested that the extent of the crystalline perfection
is reflected in the gelatinization temperature. Starch reportedly exhibits lower T o , T p , and T c , but higher H g , compared to the
flour prepared from the sample (Teo and others 2000; Wang and
others 2002). This reportedly is due to the heat-moisture treatment
during starch preparation.
DSC results of starches separated from different rice cultivars
are summarized in Table 3. The transition temperatures (T o ,
T p , and T c ), enthalpies of gelatinization (H g ), temperature
range (T) among different rice cultivars varies significantly resulting in different physicochemical properties of these starches.
For nonwaxy rice starches the values of T o range from 53.3 C
(Wang and others 2010) to 75.9 C (Wickramasinghe and Noda
2008); T p from 61.8 C (Wang and others 2010) to 80.0 C
(Wickramasinghe and Noda 2008); T c from 70.9 C to 85.4 C
(Wang and others 2010); H g from 3.7 J/g (Singh and others
2007a, 2007b) to 19.2 J/g (Vandeputtee and others 2003a); and
T from 7.43 C (Sodhi and Singh 2003) to 21.1 C (Wang and
others 2010). In the case of waxy rice starches the values of T o
range from 5.5 C (Lin and others 2008) to 63.0 C (Lin 2007);
T p from 1.6 C (Lin and others 2008) to 75.8 C (Sasaki and
others 2009); T c from 4.9 C (Lin and others 2008) to 88.3 C
(Sasaki and others 2009); H g from 3.4 J/g (Lin and others 2008)
to 16.7 J/g (Sasaki and others 2009); and T from 1.6 C (Lin
and others 2008) to 24.0 C (Li and others 2009). For long-grain
rice starches the values of T o range from 50.9 C (Shih and others
2007) to 77.0 C (Patindol and others 2007); T p from 62.3 C
(Shih and others 2007) to 80.8 C (Patindol and others 2007); T c
from 72.1 C (Li and others 2009) to 89.6 C (Puchongkavarin
and others 2005); H g from 10.3 J/g (Zhou and others 2007)
to 14.4 J/g (Patindol and others 2007); and T from 8.7 C
(Li and others 2008a) to 21.6 C (Puchongkavarin and others
2005). Vandeputte and others (2003a) reported that waxy rice
starches have lower T p values than normal rice starches. Amylose content (absolute and free amylose content) did not affect
the transition temperatures of waxy rice starches. Higher levels of
long amylopectin chains delay gelatinization, whereas short amylopectin chains (DP 6 to 9) facilitate it (Vandeputte and others
(2003a). The differences in T o , T p , T c , and H g in starches
from different rice cultivars may be attributed to differences in
amylose content, granular structure, molecular weight, and amy
lose/amylopectin ratio (Chung and others 2011). The variation

in T o , T p , T c , H g , and T in starches from different cultivars might be due to differences in amounts of longer chains in
amylopectins. These longer chains require a higher temperature
to dissociate completely than that required for shorter double helices (Yamin and others 1999). Raina and others (2007) reported
that a small variation in amylose contents has no significant effect
on thermal properties as compared to the higher amylose content. According to Singh and others (2007a, 2007b), Basmati-386
exhibited 2 endotherms during heating, one for melting of crystallites and the other for melting of amylose-lipid complexes. The
complexes have been reported to be present in some native cereal
starches (Morrison and others 1993) and more are formed during heating (LeBail and others 1999). Double-helical and crystalline structures are disrupted in starches during gelatinization.
This orderdisorder phase transition is due to the melting of crystals, which has been illustrated by DSC endotherms in the range
of 60 to 85 C for various native starches (Jacobs and others 1995).
The variation in T o , H g , and T in starches from different
cultivars might be due to differences in proportion of amylose,
fraction I, long sidechains, and short sidechains of amylopectin.
Noda and others (1998) postulated that gelatinization temperature
is influenced by the molecular structure of the crystalline region
which corresponds to the distribution of amylopectin short chains
(DP6 to 11). The variation in gelatinization temperatures might
be due to differences in the amounts of longer chains in amylopectin. These longer chains require a higher temperature to
dissociate completely than that required for shorter double helices
(Yamin and others 1999). The high T o values of Liangyoupeijiu
(Hubei) and Liangyoupeijiu (Hunan) starch suggests the presence
of crystallites of varying stability within the crystalline domains of
their granules (Hoover and others 1997). Thermal properties are
controlled in part by the molecular structure of amylopectin (unit
CL, extent of branching, molecular weight, interaction and/or supermolecular interaction of molecular chains, and polydispersity),
starch composition (amylose content), and granule architecture
(crystalline to amorphous content) (Tester 1997; Bao and others
2004).
Retrogradation
Retrogradation causes starch gels to become less soluble during cooling due to recrystallization of starch molecules (BeMiller
and Whistler 1996). It is basically a crystallization process arising from a strong tendency for hydrogen bond formation between
hydroxyl groups on adjacent starch molecules. In simple terms, retrogradation of gelatinized starch materials involves formation and
subsequent aggregation of double helices of amylose and amylopectin chains, thus governing elasticity, firmness, and textural
staling of all starch-containing systems (Atwell and others 1988).
The changes leading to retrogradation restrict starch functional
properties making starch less desirable for various food products.
Several factors have different responsible roles for starch retrogradation. Amylose content plays a significant role. Amylose retrogradation occurs on cooling and very short-term-aging
(Biliaderis and Zawistowiski 1990). As described, the retrogradation depends on the amylose content in the sample, the amount
that is free and uncomplexed with lipids, and its molecular weight
distribution. Amylose content bestows critical influences on the
elastic property of freshly retrograded starch dispersions (Lii and
others 1996) and on hardness of freshly cooked rice (Champagne
and others 1999). Retrogradation due to amylose is favored at
lower starch concentration (Orford and others 1987) and results

Table 3Diversity in thermal properties of starches separated from different rice cultivars.
Type/cultivar
Nonwaxy
TNu67
IR42, IR48, IR24, IR5,
IR2071, Thaibonnet,
Puntal, PSBRc18, Pelde,
Century Patna231
PR103, PR-106, PR113,
PR-114, IR-8
Not specified
PR113, PR111,
Basmati-370,
IET-16313,
IR-64, PR103, IR08,
Bas-386, RYT-2492
PR113, PR103, PR115,
Basmati370,
Basmati386,
IR64
Not specified
AT405, AT306, BG450,
Mawee, Heenati662
Basmati, Pachchaperumal,
Selenio, Perla, Baldo,
Roma,
Arborio
Not specified
Exiang No. 1, Honglianyou
No. 6, Heiyouzhan,
98112jing, Jiyjing,
Tianjinxiazhan
Arborio, Calrose, Glutinous
Waxy
Thai glutinous I, Thai
glutinous II,
Sanpathong,
Black rice, IR65
Not specified
TCW70
TCW70
Koganemochi,
Hakuchomochi,
Kantomochi
SMJ
RD6
CM 101
Not specified
Calmochi 101
Long-grain
Lebonnet
Doongara
RL-100
Not specified
Cocodrie
Not specified
Cocodrie, L205
Bolivar, Cheniere,
Dixiebelle, L205, Wells
Long grain
T o ( C)
T p ( C)
T c ( C)
Hg (J/g)
57.7
56.6 to 75.6
65.1
62.8 to 78.5
71.0 to 83.3
11.5
7.7 to 19.2
16.8 to 19.8
Li and Yeh 2001

Vandeputtee and others
2003a
66.0 to 67.3
69.74 to 71.94
74.08 to 78.04
8.16 to 11.80
7.43 to 10.78
73.45
77.77
83.52
15.07
10.07
61.1 to 74.47
66.6 to 79.21
71.93 to 84.49
8.09 to 13.81
7.85 to 10.89
Thirathumthavorn and
Charoenrein 2005
65.17 to 68.92
60.8 to 71.8
70.15 to 71.84
65.7 to 75.9
73.66 to 76.86
72.2 to 82.4
13.24 to 14.98
3.7 to 5.1
8.2 to 9.8

71.64
64.1 to 75.9
76.38
69.4 to 80.0
83.50
11.74
12.0 to 17.3
11.86
57.8 to 71.5
66.61 to 79.20
11.03 to 17.04
72.3
76.4
80.2
12.5
7.9
53.3 to 71.0
61.8 to 76.0
70.9 to 85.4
7.2 to 11.8
9.2 to 21.1
Banchathanakij and
Suphantharika 2009
58.5 to 60.0
68.2 to 68.9
79.4 to 80.5
13.1 to 15.4
19.4 to 22.0
Chung and others 2011
57.9 to 59.6
65.2 to 65.8
75.5 to 75.8
16.3 to 17.7
18.4 to 19.6
Vandeputtee and others

2003a
58.9
63.0
5.5
41.6 to 61.6
67.1
70.7
1.6
56.9 to 75.8
82.5
4.9
76.7 to 88.3
15.7
14.5
3.4
12.6 to 16.7
19.5
-1.6
Jacquier and others 2006

Chang and Lin 2007
Lin and others 2008
Sasaki and others 2009
61.58
67.72
74.26
16.53
62.68
56.2
59.9
56.25
69.00
63.5
66.6
62.6
75.21
80.2
84.1
83.95
13.95
13.2
10.1
12.8
24.0
70.0
71.3
66.6
68.0
74.7
76.6
73.1
79.3
81.1
80.6
89.6
13.7
10.3
12.4
13.2
11.1
9.3
21.6
63.4
50.9
61.8 to 67.7
73.4 to 77.0
67.2
62.3
67.9 to 71.9
78.0 to 80.8
72.1
76.8
75.4 to 83.4
83.1 to 86.1
11.7
10.4
10.9 to 13.7
13.3 to 14.4
8.7
Matalanis and others 2009

Wang and Wang 2004
Puchongkavarin and others
2005
Li and others 2009
Patindol and others 2007
67.8
74.3
84.7
13.5
16.9
Reference
Deetae and others 2008

2008
Acquistucci and others 2009
Tatongjai and Lumdubwong

2010
Li and others 2009
T o = Onset gelatinization temperature; T p = Peak onset gelatinization temperature; T c = conclusion gelatinization temperature; Hg = gelatinization enthalpy; R = gelatinization temperature range.
in a material very resistant to enzymatic hydrolysis. On the other

hand, amylopectin retrogradation occurs slowly during aging and
requires several weeks or months of storage for equilibrium (Biliaderis and Zawistowiski, 1990; Lai and others 2000), and the
degree of retrogradation depends on the CL distribution of amylopectin (Philpot and others 2006). Amylopectin tends to have
additional effects on the extent of retrogradation of starches (Yaun
and others 1993) or on the hardness of short-term staled cooked
rice through the proportion of extra long and long B chains

(Ramesh and others 1999; Lai and others 2001). Recrystallization and retrogradation of amylopectin are dominant at a higher
concentration of solids (Orford and others 1987) and the polymer
formed is more loosely bound than retrograded amylose (Englyst
and others 1992) and, hence, is highly susceptible to amylolysis.
The retrogradation properties can be measured by DSC
(Qi and others 2003; Vandeputte and others 2003b; Lawal and


others 2011; Chung and others 2011), rheological properties,
(Vandeputte and others 2003b), and NMR (Yao and others 2003;
Qi and others 2003). Methods to study retrogradation of starch
have been reviewed by Karim and others (2000). Recrystallization
of amylopectin branched chains has been reported to occur in a less
ordered manner in stored starch gels than in native starches. This
explains the occurrence of amylopectin retrogradation endotherms
at a temperature range below that for gelatinization (Ward and others 1994). Enthalpy of retrogradation (H R ) for starches separated
from different rice cultivars ranged from 2.61 to 3.71 J/g. The
differences in the H R among the various rice starches suggest
differences in tendencies toward retrogradation. The retrogradation (percent) ranged from 61.9% to 86.6% (Lawal and others
2011) The differences in H r of different starches may be due
to differences in amylose-amylopectin ratios, granular structures,
and phosphate esters (Hizukuri and others 1983; Kasemsuwan and
others 1995; Hizukuri 1996). The amylopectin and intermediate
materials play a significant role in starch retrogradation during refrigerated storage. The intermediate materials with longer chains Figure 5Typical starch pasting curve showing pasting parameters
than amylopectin may also form longer double helices during reas- measured with Rapid Visco Analyzer or Visco amylograph.
sociation under refrigerated storage conditions (Yamin and others
1999).
granules. Breakdown is a measure of the ease of disrupting swollen
Pasting/Rheological Properties
starch granules and suggests the degree of stability during cooking
Heating of starch continuously in excess of water with stirring (Adebowale and Lawal 2003). Minimum viscosity, also called hot
causes the granules to swell and burst due to breakage of the native paste viscosity, holding strength, or trough, marks the end of the
starch structure. Then the amylose leaches out and the granules holding stage at the maximum temperature of the RVA test. The
disintegrate resulting in the formation of a viscous material called cooling stage begins and viscosity again rises (setback) which is
paste (BeMiller 2007). Pasting occurs after or simultaneously with caused by retrogradation of starch, particularly amylose. Setback is
gelatinization. Pasting properties of starch are important indicators an indicator of final product texture and is linked to syneresis or
of how the starch will behave during processing and, starch is gen- weeping during freezethaw cycles. Viscosity normally stabilizes
erally regarded as the most important constituent of rice in terms at a final viscosity or cold paste viscosity, which is related to the
of cooking quality and functionality. The pasting properties of capacity of starch to form a viscous paste or gel after cooking and
starch are used in determining the suitability of starch in different cooling (Newport Scientific 1998). Other components naturally
foods and other allied products. The most important pasting char- present in the starchy material or additives interact with starch
acteristic of granular starch dispersion is its viscosity. High paste and influence pasting behavior (Newport Scientific 1998). The
viscosity suggests suitability as a thickening agent in foods and as a presence of proteins with disulfide linkages has been reported to
finishing agent in the textile and paper industries.
confer shear strength and gelatinized paste rigidity to rice starch
The pasting characteristics of starch are determined either us- (Hamaker and Griffin 1993; Xie and others 2008).
ing a Brabender Visco Amylograph or a Rapid Visco Analyzer
Pasting parameters of rice starches are summarized in Table 4.
(RVA) (Wickramasinghe and Noda 2008; Tukomane and Var- The pasting temperature for nonwaxy rice starches ranges from
avinit 2008; Lin and others 2009). Rotational rheometers (Park 63.80 C (Raina and others 2007) to 95.10 C (Banchathanakij
and others 2007b; Li and others 2008a, 2008b) or other viscome- and Suphantharika 2009); PV from 45.8 RVU (Banchathanakij
ters, which record the viscosity continuously with respect to tem- and Suphantharika 2009) to 5512.0 RVU (Raina and others
perature changes, are also used to measure the pasting properties. 2007); breakdown viscosity from 3.3 RVU (Banchathanakij and
RVA is used to determine pasting properties, namely PV, final vis- Suphantharika 2009) to 3187.0 RVU (Raina and others 2007);
cosity, setback viscosity, breakdown viscosity, pasting temperature, final viscosity from 55.9 RVU (Banchathanakij and Suphantharika
and peak time. Figure 5 shows a typical pasting curve with pasting 2009) to 454.8 RVU (Lin and others 2009); and setback viscosity
parameters as measured by RVA/Visco Amylograph. In the RVA from 55.6 (Lin and others 2009) to 4999.0 RVU (Raina and othtest, starch is mixed with water and allowed to rapidly hydrate ers 2007). For waxy rice starch pasting temperature ranges from
on heating, held constant for a specific time, and then cooled to 69.0 C (Lu and others 2008) to 69.1 C (Techawipharat and othmeasure the pasting properties of the starch. As heating contin- ers 2008); PV from 76.0 RVU (Park and others 2007b) to 471.2
ues, an increase in viscosity can be observed by swelling of starch RVU (Noosuk and others 2003); breakdown viscosity from 25.5
granules, which reflects the process of pasting. The temperature RVU (Park and others 2007b) to 228.2 RVU (Noosuk and othat the onset of viscosity increase is termed pasting temperature. ers 2003); final viscosity from 79.5 RVU (Park and others 2007b)
Viscosity increases with continued heating until the rate of gran- to 182.5 RVU (Lu and others 2008); and setback viscosity from
ule swelling equals the rate of granule collapse, which is referred 14.1 RVU (Techawipharat and others 2008) to 30.0 RVU (Noosuk
to as the peak viscosity (PV). PV reflects the swelling extent or and others 2003). For long-grain rice starch PV ranges from 42.0
water-binding capacity of starch and often correlates with final RVU (Park and others 2007b) to 369.0 RVU (Wang and Wang
product quality since the swollen and collapsed granules relate to 2004); breakdown viscosity from 9.5 RVU (Park and others 2007b)
the texture of cooked starch. Once PV is achieved, a drop in vis- to 145.02 RVU (Wang and Wang 2004); final viscosity from 60.0
cosity, or breakdown, is observed as a result of disintegration of RVU (Li and others 2008a, 2008b; Park and others 2007b) to


Table 4Diversity in pasting properties of starches separated from different rice cultivars.
Type/cultivar
Nonwaxy
PR113, PR111,
Basmati-370,
IET-16313,
IR-64, PR103, IR08,
Bas-386, RYT-2492
AT405, AT306, BG450,
Mawee, Heenati662
Not specified
Not specified
Xing indica 24
Arborio, Calrose, Glutinous
FARO 51, 52, 54, 32,
NERICA
Waxy
Not specified
Calmochi 101
RD6
Calmochi 101
TCW70
Long-grain
Cocodrie, L205
RL-100
Cocodrie, L205
Doongara
Long grain
Pasting
Peak
temperature ( C) viscosity (RVU)
Breakdown
viscosity (RVU)
Final
Setback
viscosity (RVU) viscosity (RVU)
Reference
71.55 to 79.90
83.6 to 201.0
124.6 to 277.2
56.2 to 146.8
63.80 to 67.05
73.5 to 84.0
4994 to 5512
218 to 458
2918 to 3187
146 to 380
177 to 433
4128 to 4999
99 to 285

2008
67.0
243.0
94.4
169.3
20.7
95.1
45.8
3.3
55.9
12.5
82.3
64.4 to 70.8
85.6 to 87.2
510.4
454 to 543.7
147.6 to 209.2
347.2
214.1 to 328.56
23.8 to 65.7
454.8
255 to 365.5
182.7 to 273.5
55.6
39.8 to 154.1
58.8 to 122.4

2008
Banchathanakij and
Suphantharika 2009
Lin and others 2009
Lawal and others 2011
69.1
141.4
66.0
89.5
14.1
69.0
86.0
471.2
76.0
34.0
228.2
25.5
70.92
80.0
79.5
182.5
27.0
30.0
29.0
16.67
76.6
48.0 to 72.0
369.0
42.0 to 64.0
153.0
319.3
18.0 to 25.0
145.0
9.0 to 14.0
93.8
151.9
60.0 to 109.0
304.0
60.0 to 103.0
128.7
389.4
30.0 to 61.0
80.0
30.0 to 54.0
24.4
221.9

2008
Li and others 2008a
Lu and others 2008
Li and others 2008a
Wang and Wang 2004
RVU = rapid visco unit.
304.0 RVU (Wang and Wang 2004); and setback viscosity from
30.0 RVU (Li and others 2008a, 2008b; Park and others 2007b)
to 80.0 RVU (Wang and Wang 2004).
The increase in viscosity with temperature may be attributed
to removal of water from the exuded amylose by the granules
as they swell (Ghiasi and others 1982). Final viscosity increases
upon cooling, which may be due to the aggregation of the amylose molecules (Miles and others 1985a,1985b). Setback value is
the recovery of viscosity during cooling the heated starch suspension. High setback of starches may be due to the amount and
the molecular weight of the amylose leached from the granules
and the remnants of the gelatinized starch (Loh 1992). Pasting
properties of starch have been reported to be affected by amylose and lipid contents and by branch chainlength distribution of
amylopectin. The small variation in the amylose contents had no
significant effect on pasting (Raina and others 2007). Han and
Hamaker (2000) observed that almost all amylose in the granule
is leached out at the level of PV. Thus, the influence of amylose
on the breakdown would be very low, even though the PV could
be affected by both amylose and amylopectin (Han and Hamaker
2001). Amylopectin contributes to swelling of starch granules and
pasting, while amylose and lipids inhibit the swelling (Tester and
Morrison 1990a). Also, the amylopectin chainlength and amylose
molecular size produce synergistic effects on the viscosity of starch
pastes (Jane and Chen 1992).
The other major techniques to measure starch rheology include rotational viscometers (viscosity) to modern stress-controlled
rheometers (dynamic properties). The rheological measurements
for rice starch include flow behavior, viscoelastic properties, mechanical properties, recovery measurements, gel strength, gelatinisation kinetics, and so on (Ahmed and others 2008; Lawal and
others 2011). The most frequently measured flow behavior in-
dex of rice starch dispersions in steady flow can be carried out

during gelatinization or on a gelatinized paste. Power law and
HerschellBulkely models are frequently used to describe the flow
behavior of rice starches. These models give information on the
flow behavior index (n) and the consistency coefficient (K) and
Yeild stress ( o ) of starch suspensions. The values of n, K, and
o are dependent on starch type, starch concentration, and temperature. The gelatinized starch pastes preheated to temperatures
of about 90 C are generally reported to exhibit shear-thinning
(pseudoplastic) behavior with values of n considerably less than
1.0. Lawal and others (2011) reported the shear thinning behavior of 5 different rice starches from West Africa. Differences in
the shear thinning behavior could be observed between different
rice starches. Amylose content was reported be the responsible
factor for variation in the viscosity values. Other studies have revealed that the flow behavior is affected by temperature, starch
concentration, density, amylose CL, extraction conditions, granule size, and so on (Karim and others 2008; Ahmed and others
2008).
Small amplitude oscillatory shear measurements have been used
for soft materials to elucidate their structural insight. Wang and
others 2010 reported that during earlier stages of heating rice starch
suspensions increases the storage modulus (G) while storage modulus (G) was relatively slow. These values reached a maximum
and then decreased with further heating. The initial increase in G
has been attributed to the starch granule swelling and the formation of a 3-dimensional gel network (Hsu and others 2000; Wang
and others 2010). Singh and others (2011) reported that the initial rise in the moduli for different rice starches separated Indian
rice cultivars were in the range of 66.75 to 81.07 C. The decrease in the values of storage and loss moduli (Gmax and Gmax )
may be attributed to starch gel breakdown due to disentaglement


of the amylopectin molecules in the swollen particles. Wang and
others (2010) reported that the differences in dynamic properties
of 10 rice starches are due to variation in amylose contents, variety, the branch CL, and distribution of amylopectin. Lawal and
others (2011) performed oscillatory shear tests of rice starches and
reported that they have weak elastic behavior. Such behavior has
been classified as Type III by different researchers (Hyun and others 2002; Sim and others 2003). Type III behavior is exhibited
by disperse systems and weak polymeric gels where polymeric interchain association posses several constraints to incipient flow of
the relevant structural units. The rheological data are increasingly
being used to correlate the rheological properties with the molecular structure and the thermal properties of different starches. The
rheological data provide information on the processing of starch
into different food products and starch based laminates and films.
Physicochemical Properties of Rice Starch

Physicochemical characteristics of rice starches largely depend
on the rice cultivar, environment, and agronomic and extraction conditions. The physicochemical characteristics of different
rice starches are shown in Table 2. Most of the thermophysical
properties are dictated by the amylose content. In turn, amylose
content varies with growth and environment conditions of the
starch source.
Studies have shown that there are significant changes in the
structural and thermophysical properties of various starches when
subjected to annealing. There is structural change within the
amorphous and crystalline domains of starch granules (Tester and
others 2000; Lan and others 2008). The changes in amorphous
and crystalline domains, in turn, influence granular swelling, amylose leaching, pasting properties, gelatinization, and susceptibility
toward enzymes and acid. The changes to physicochemical properties of normal, waxy, and high-amylose starches on annealing are
influenced by changes to amylose conformation (helix to coil), enhanced interaction between starch chains, increase in crystalline
perfection, decrease in the proportion of small B-type granules,
and by the native starch structure (crystalline defects, amylose concentration, amylopectin CL, distribution degree of association between starch chains within the amorphous, and crystalline domains
of the granule) (Lan and others 2008).
Zhu and others (2011) investigated that there was a positive
corelation between amylose content and resistant starch (RS). The
portion of starch that is not digested in the small intestines is RS.
Less of the starch is converted to glucose when RS is ingested.
This has a potential impact on diabetes and energy intake, provides
fermentable carbohydrates to colon bacteria, there is production
of short-chain fatty acids also that have direct health benefits to
the colon and also play other physiological roles (Bird and others 2009). With an increasing level of amylose, RS content also
increases, except for low-amylose rice (Zhu and others 2011).
Light Transmittance (Percent)

Light transmittance provides the information on the behavior
of starch paste when the light passes through it (Sandhu and others
2007). Higher light transmittance implies a more transparent paste.
The light transmittance of starch paste is a function of the amount
of swollen starch granules in the paste, which refract light (Singh
and others 2006a, 2006b). Singh and others (2006a, 2006b) reported light transmittance by measuring the transmittance of starch
pastes (1%) from different indica rice cultivars. Measurements carried out every 24 h by transmittance at 640 nm against a water
blank showed decrease in light transmittance during storage from

0 h (3.0% to 5.8%) of 1.6% to 4.2% after 144 h. The presence

of phospholipids produces opaque starch pastes and solutions with
low light transmittances (Jane and others 1996). The difference in
the light transmittance values may be due to the variation in the
amount of swollen granule remnants in the starches that refract
light to different extent and thus give the distorted images (Craig
and others 1989).
Swelling Power and Solubility

When starch is heated in excess water the crystalline structure is disrupted due to the breakage of hydrogen bonds, and
water molecules become linked by hydrogen bonding to the exposed hydroxyl groups of amylose and amylopectin. This causes
an increase in granule swelling and solubility. Swelling power and
solubility can be used to assess the extent of interaction between
starch chains and within the amorphous and crystalline domains
of the starch granule (Ratnayake and others 2002). Starch swelling
occurs concomitantly with loss of birefringence and precedes solubilization (Singh and others 2004). The extent of this interaction is thought to be influenced by a samples amylose content, amylose and amylopectin structure, degree of granulation,
starch components, and other factors. According to Tester and
Morrison (1990a), amyloselipid complexes inhibit swelling, and
the swelling behavior of cereal starch is primarily related to amylopectin structure and amylose acts as a diluent. Vandeputte and
others (2003a) have reported that swelling power is a function of
temperature for waxy and normal rice starches. The swelling of
normal rice starch is a 2-step event. In the first swelling step, at a
temperature between 55 and 85 C, amylose does not influence
the swelling of normal rice starches, whereas the relative amounts
of short amylopectin chain (DP 6 to 9) increase swelling at 55
and 65 C. Only in the 2nd swelling step (at temperatures between 95 and 125 C), amylose decreases swelling power. In the
first swelling step, granule swelling is influenced by the short amylopectin chains, whereas in the 2nd step, it is influenced by amylose
leaching. Lee and Osman (1991) reported that swelling power of
starch depends on the capacity of starch molecules to hold water
by hydrogen bonding; when the hydrogen bonds between starch
molecules are broken after complete gelatinization they are replaced by hydrogen bonds of water. The amylose content and the
proportion of outside-chains of amylopectin were thought to be
the major factors stabilizing the gel structure to retain water (Tang
and others 2005). The distribution of amylose in a starch granule
was shown not to be uniform (Seguchi and others 2003), which
also affects the swelling power of starch. It was explained that the
starch granules mainly contained amylose and amylopectin and
during gelatinization some amylose molecules leaked out; however, the quantity of amylose that leaked out was related to the
channels and molecule structure or to hydrogen bonding. The
distribution of amylose and amylopectin in starch granules also
influences the solubility of starch. Amylose played a role in the
maintenance of the structure of starch granules and was concentrated in the central region of the granules in a study by Seguchi
and others (2003). Therefore, the higher the amylose content, the
more compact the starch granule and the starch is more difficult
to overflow outside the granules and thus lowers solubility values.
The swelling power and solubility of rice starches from all
the 3 types of rice starches are shown in the Table 4. The
swelling power for nonwaxy rice starches ranged from 7.33%
(Wickramasinghe and Noda 2008) to 38.8% (Singh and others
2006a, 2006b). According to Sodhi and Singh (2003), the cultivar
with the lowest amylose content has the highest swelling power

and the lowest solubility, whereas the sample with the greatest
amylose content has the lowest swelling power. Lii and others
(1995) also reported a higher swelling power for rice with lower
amylose content. The differences in swelling power and solubility
among different cultivars may be attributed to the differences in
amylose content, viscosity patterns, and weak internal organization resulting from negatively charged phosphate groups within
the rice starch granules (Jane and others 1996). Techawipharat and
others (2008) determined the swelling power of different waxy and
normal rice starches and observed that swelling power of waxy rice
starch (26.9%) was higher than those of normal rice starch (15.5%).
Lii and others (1996) observed that waxy rice starch granules were
less firm and tended to disintegrate easily when swollen and extensively overcrowded. In contrast, normal rice starch granules were
more rigid, with less swelling, and not easily ruptured. Generally, the amount of exudate from normal rice starch granules was
small, suggesting that the main component leached from the granules was amylose (Mandala and Bayas 2004), whereas the amount
of exudate from waxy rice starch granules was large and consisted
of amylopectin molecules (Tester and Morrison 1990b). The solubility of nonwaxy rice starches ranged from 0.287% (Sodhi and
Singh 2003) to 40.0% (Wang and others 2010) and in the case of
waxy rice starch solubility ranged from 0.6% (Chang and others
2010) to 69.16% (Yu and others 2012).
Syneresis
As cooked, cooled starch gel ages it contracts causing water
loss and shrinkage. This is known as syneresis or weeping. Starch
suspensions (5%) were heated at 90 C for 30 min followed by
rapid cooling to room temperature. The syneresis of gels prepared
from starches separated from different rice cultivars was measured
as amount of water released from the gels during storage (up to
168 h) at 4 C (Sodhi and Singh 2003; Singh and others 2006a,
2006b). Syneresis increased with length in storage duration for
various nonwaxy (indica) rice cultivars (Sodhi and Singh 2003).
The increase in percentage syneresis during storage has been attributed to the interaction between leached amylose and amylopectin chains, which leads to the development of junction zones,
which reflect or scatter a significant amount of light (Perera and
Hoover 1999). Amylose aggregation and crystallization have been
reported to be completed within the first few hours of storage,
while amylopectin aggregation and crystallization occurs during
later stages (Miles and others 1985a,1985b).
Syneresis of starches is an undesired property for the use of
starch in both the food and nonfood industries. It is also an index
for degree of starch retrogradation at low temperature. Singh and
others (2006a, 2006b) had reported low syneresis values in the
range of 0.00% to 1.81% for various indica rice starches stored
at 4 C for 24 h. According to Sodhi and Singh (2003), the
syneresis ranged from 0.04% to 2.41% for nonwaxy (indica) rice
starches stored at 4 C for 48 h. The syneresis values indicated that
temperatures below freezing point are against recommending the
storage of frozen starch paste (Wang and others 2010).
FreezeThaw Stability
Freezing a starch gel normally leads to the formation of ice
crystals and the concentration of starch in the unfrozen phase.
Upon thawing, water is easily expressed from the network, giving
rise to the phenomenon known as syneresis. The ability of a starch
gel to withstand this phenomenon during freezethaw cycling
(freezethaw stability) enhances its potential use in frozen food
products (Baker and Rayas-Duarte 1998). The level of syneresis
is inversely proportional to the freezethaw stability of a starch

gel.
Freezethaw stabilities of native rice was determined with 25 g
starch paste (8%) in centrifugal tubes, allowed to cool to 30 C
followed by freezing at 14 C for 22 h. They were subjected to
5 freezethaw cycles, each time thawed at 30 C in a water bath for
1 h. Rice starch showed the highest percent syneresis in the 1st
cycle and then syneresis gradually decreased to the 5th cycle, decreasing of percent syneresis from cycle 1 to cycle 5 of 28.86%,
22.26%, 10.61%, 1.25%, and 1.31%, respectively (Deetae and others 2008). Rice starches showed decreases in percent syneresis from
cycle 1 to cycle 5, which was not the normal freezethaw stability property. The water separation or percent syneresis of any
starch paste should increase with an increase of freezethaw cycling
(Varavinit and others 2000). Native rice starch with rather high
amylose showed a high percent syneresis for the first freezethaw
cycle, but surprisingly low syneresis after the 2nd cycle, where it
appeared to have good freezethaw stability (Varavinit and others 2002). However, it was found that during these cycles the
amylose rice starch gel had changed from a smooth gel to a roughtextured porous gel (rough surface) with a sponge-like structure
that allowed it to reabsorb the separated water; thus syneresis was
reduced, unless this rough-textured gel was pressed to squeeze out
the absorbed water. This retrogradation phenomenon occurred
when the rice starch gel was frozen and ice crystals spread within
the gel. Upon subsequent thawing at a lower temperature (30 C),
the ice crystals melted and a rough-textured with relatively high
porosity was obtained. In the 1st freezing cycle, only a small quantity of the rough porous gel was formed and it was not enough to
form a spongy structure and a high syneresis value was observed.
From the 2nd to the 5th cycle, the quantity of rough-textured gel
accumulated sufficiently to form a sponge-like structure (Deetae
and others 2008).
Rice Starch Applications

Commercial native rice starch finds applications as cosmetic
dusting powder, laundry stiffening agent, paper and photographic
paper powder, sugar coating in confectionary products, soups,
noodles, and thickener and excipient for pharmaceutical tablets
(Singh and others 2006a, 2006b). Rice starch granules being very
small in size provide a texture perception similar to that of fat
and have a low glycemic index (Champagne 1996). Rice starch
acts as a carrier and offers time-release and protection of flavors
from oxidation (Zhao and Whistler 1994). Starch is an attractive raw material for edible packaging because of its low cost,
renewability, and biodegradability (Guilbert 2000). Furthermore,
it is abundant, nonallergenic, and possesses good mechanical and
barrier properties that may allow for wider food applications (Gujska and others 1994; Rindlav-Westling and others 1998; Pagella
and others 2002). It is used in various fermentation processes to
produce different compounds with high specificity and purity.
Lactic acid was synthesized by the fermentation of rice starch using microorganisms, and it was found to be of high optical purity
(Fukushima and others 2004). Starches as a group are the cheapest
and most important polysaccharides and are therefore used in a
variety of food and industrial applications (Ellis and others 1998).
Starch is one of the most important and abundant food ingredients of staple foods such as in bread and noodle manufacture
(Funami and others 2005), as well as adhesion, binding, clouding,
dusting, film-formation, foam strengthening, antistaling, gelling,
glazing, moisture retention, stabilizing, texturizing, and thickening
applications (Whistler and BeMiller 1997).


Starches are generally regarded as the most important constituents of cereals in terms of pasting behavior, gelatinization,
retrogradation, and other functional attributes which influence
product quality (Hagenimana and Ding 2005). In the worldwide
market for industrial starches, corn accounts for over 90% of the
total starch production, followed by potatoes and wheat. In the
Asian market the most used starch as a food additive is rice starch.
The availability of corn to the Indian starch industry is decreasing,
day by day, because of its increased demand being involved in the
production of breakfast cereals and snacks. Broken rice, which
is cheaper than corn and is available in abundance, can be used
in the production of starch (Sodhi and Singh 2003). Rice starch
exhibits a number of unique characteristics and can be a better
substitute of corn starch in a number of food applications (Juliano
1984). Rice starch, in its gelatinized form, has a bland taste and
is smooth, creamy, and spreadable, which makes it a good custard
starch. Rice starch granules are of the same size as homogenized
fat globules, therefore, they provide a texture perception similar to that of fat. Rice starch with high amylose content has a
low glycemic index (Champagne 1996). It is the ratio of amylose to amylopectin and the fine structure of these polymers that
give native starches its distinctive properties (Alberle and others
1994). Starch granules are used as flavor carriers. Using appropriate methods, small starch granules may be mixed with gelatin
or water-soluble polysaccharides and then spray-dried forming a
globular mass. These spherical aggregates of starch granules contain open porous spaces that can be filled and used to transport
materials such as flavors, essences, and other compounds. Spherical aggregate carriers potentially offer time-release and protection
of these flavors from oxidation (Zhao and Whistler 1994).
Interest in biodegradable packaging is increasing because it consists of natural materials, which do not contribute to environmental pollution (Ahvenainen and others 1997; Webb-Jenkins 2002).
These films and coatings may be applied on a food or between heterogeneous food components to prevent mass transfer phenomena that could deteriorate the quality of food (Guilbert 2000).
Starch is an attractive raw material for edible packaging because
of its low cost, renewability, and biodegradability (Guilbert 2000).
Furthermore, it is abundant, nonallergenic, and possesses good
mechanical and barrier properties that may allow for wide food
applications (Gujska and others 1994; Rindlav-Westling and others
1998; Pagella and others 2002). High-amylose starch is a very useful film-forming material because of its strong gelation properties
and helical linear polymer structure (Juliano 1985). Starch can be
used as a starting material for the production of various chemicals;
for example, D-lactic acid was synthesized by the fermentation of
rice starch using microorganisms (Lactobacillus delbrueckii and Sporolactobacillus inulinus) and it was found to be of high optical purity
(Fukushima and others 2004).
Summary and Conclusion

Starch is the major component of rice grain comprising about
90% of total weight of polished rice grains. Rice starch is commonly isolated by alkaline extraction, but this method produces a
highly loaded alkaline effluent. Enzymes and other physical methods can be used to isolate starch with high purity and without any
objectionable effluent. Rice starch is composed mainly of amylose
and amylopectin. Starch occurs as discrete, semicrystalline granules. The rice starch granule is one of the smallest starch granules
(2 to 7 m). Starch is insoluble in cold water, but when heated
in the presence of water starch granules swell and soluble components leach out. The phase transition of starch granule is an

orderdisorder transition and includes the phenomena of gelatinization and retrogradation. Gelatinization involves melting of
crystallites, loss of birefringence, and starch solubilization. Retrogradation of gelatinized starch materials involves formation and
subsequent aggregation of double helices of amylose and amylopectin chains. Pasting encompasses the changes that occur after
gelatinization upon further heating leading to increased swelling
of granules, leaching of molecular components from grains, and
disruption of granules. Rice starch isolated from different rice cultivars has different morphological, physicochemical, thermal, and
pasting properties. The differences may be due to several factors
such as compositional, environmental, varietal, and genetic. The
ratio of amylose and amylopectin and the branching properties of
the amylopectin molecules of rice stanch can affect its properties.
Rice starch finds its applications in both the food and nonfood industries. It is used as a thickening or gelling agent, a sugar coating
in confectionary products, excipient for pharmaceutical tablets,
fat replacer due to its small size, and as a component of allergyfree products. The nonfood applications include cosmetic dusting
powder, laundry stiffening agent, and paper and photographic
powder.
Rice starches, because of their uniform granules (shape, size, and
size distribution) and the vast varietal diversity, offer an excellent
model to study the effect of composition and physical characteristics on the properties of starches. A growing trend for ingesting less
fatty foods has led to the development of starch-based fat replacers, and rice starch, due to its small size, provides the same texture
as that imparted to foods by fat. High fat intake often leads to
obesity and cardiovascular disease. Starch-based films and plastics
(bioplastics) have generated much interest recently. Starch-based
coating provides many benefits, including cost-effectiveness due
to low use level, good flavor release, compatibility with a wide
range of processes, and friendly labeling. Small starch granules
are able to combine into interesting and potentially useful porous
spheres when spray-dried with small amounts of bonding agents.
The spherical aggregates contain open spaces in the form of interconnecting cavities that provide extensive porosity capable of
being filled and used to transport material within the spheres. A
need exists in the food industry for containment of flavor essences
and other components in a manner that will provide for oxidative
protection and for controlled release over a defined period of time.
The encapsulation method using spheres of bound starch granules
offers a low-cost, food-grade package that can be produced by
normal processing methods.
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Rice Starch Diversity: Effects on Structural,

Morphological, Thermal, and Physicochemical

Rice starch diversity . . .

Amylose is the major factor influencing the physicochemical

amylose. About 80% to 90% phosphate-monoester in waxy rice

Rice Starch Isolation

Rice starch diversity . . .

trical resistance, laser light scattering, and field flow fractionation

Rice starch diversity . . .

Li and Yeh 2001

Singh and others 2006b

Yang and others 2006

Lawal and others 2011

Polyhedral, angular, oval

Zhang and others 2010

Hoover and others 1996

biopolymers. The other minor components in rice starch are lipids

ing amylose to form a type of clatherate (an inclusion complex

Rice starch diversity . . .

in the native starch (Morrison and others 1993), but is possibly

Amylopectin, consisting of -1,4-linked D-glucopyranosyl

Rice starch diversity . . .

Swelling power (%)

0.04 to 2.41 (48 hrs)

Sodhi and Singh 2003

0.00 to 1.81 (24 hrs)

Singh and others 2006b

Raina and others 2006

Techawipharat and others

22.9 to 46.4 (22 hrs)

Sandhu and others 2010

Li and others 2008a

Li and others 2008a, 2008b

Matalanis and others 2009

Lin and others 2009

Zuo and others 2009

namely B1 (CL 20 to 24), B2 (CL 42 to 48), B3 (CL 69 to 75), and

The characteristics of foods containing starch are understood to be

Rice starch diversity . . .

X-Ray Diffraction Studies

Rice starch diversity . . .

2 = 20.0 was observed for Basmati-386, which was attributed

order-to-disorder transition; it is more complex. Understanding

Rice starch diversity . . .

lose/amylopectin ratio (Chung and others 2011). The variation

Rice starch diversity . . .

Li and Yeh 2001

Sodhi and Singh 2003

Raina and others 2007

Chung and others 2011

Vandeputtee and others

Jacquier and others 2006

Matalanis and others 2009

Chung and others 2011

Deetae and others 2008

Tatongjai and Lumdubwong

in a material very resistant to enzymatic hydrolysis. On the other

rice through the proportion of extra long and long B chains

Rice starch diversity . . .

Rice starch diversity . . .

Singh and others 2006b

Raina and others 2007

Techawipharat and others