Starch: Structure, Property, and Determination
Y Ai and Jl Jane, Iowa State University, Ames, IA, USA
ã 2016 Elsevier Ltd. All rights reserved.
Introduction
Starch is the second largest biomass produced on Earth, next to
cellulose, and is synthesized in amyloplasts of higher plants for
energy storage. Starch is a major energy source for human and
animal diets and an important raw material for industrial
applications. Starch granules consist of highly branched glucan,
amylopectin, and, a primarily linear glucan, amylose. The
amylopectin and amylose molecules are aligned radially in
the semicrystalline starch granule. Native starch granules have
specific densities around 1.5 g cm
3. Because of the large den-
sity, the granular starch can be readily isolated from grains,
tubers, roots, and stems by gravity using a wet milling process.
The granular structure of starch also facilitates its chemical
modifications, which can be washed to remove residues and
by-products. Consequently, starch is produced as an economi-
cal commodity for food and industrial applications. Major
markets of starch are in the corn syrup, paper, textile, food,
and bioethanol industries.
The semicrystalline starch granules are not dispersible in
water at ambient temperatures. After starch is cooked above its
gelatinization temperature, the starch loses its crystalline struc-
ture and can then be dispersed to a paste in excess water with
continuous heating and stirring. Depending on the composition
and structure of starch, such as amylopectin branch chain length,
and contents of amylose, lipids, and phosphate monoester deriv-
atives, starch displays different properties. Chemical and physi-
cal structures of starch in food determine the enzymatic digestive
rate of the starch after the food is ingested, which is reflected as
the glycemic response. Prolonged consumption of starchy food
with large glycemic index is known to cause insulin resistance,
type-2 diabetes, obesity, and other metabolic syndrome. Ingest-
ing of resistant starch (RS) that cannot be hydrolyzed by
enzymes in the small intestine and is then passed to the colon,
however, reduces the glycemic response and facilitates
the growth of microbiota in the colon. Fermentation of the RS
in the colon by microbiota can produce short-chain fatty acids to
maintain colon health and prevent colon cancer.
This article aims to provide an overview on the composition
and structures of starch molecules, morphology and internal
structures of starch granules, functional properties of starch,
and methods used to determine these characteristics. Other
relevant publications, which provide in-depth discussions of
the subjects covered in this article, are listed in section ‘Further
Reading’ for information on starch structures and properties.
Composition, Structures, and Analysis of Starch
Molecules
Normal starch consists of about 70–80% amylopectin and
20–30% amylose, waxy starch consists of mostly amylopectin
and 0–8% amylose, and high-amylose starch consists of
Encyclopedia of Food and Health http://dx.doi.org/10.1016/B978-0-12-384947-2.00657-7
40–90% amylose. In addition to amylose and amylopectin,
most cereal normal starches also contain lipids, including
phospholipids, which have significant impacts on the pasting,
gelling, and digestive properties of the starch. Many tuber and
root starches and some cereal starches have phosphate mono-
ester derivatives. Some starches, such as high-amylose maize
starch and sugary-2 starch, contain intermediate component
that has branched molecules, however, with smaller molecular
weights and longer branch chain lengths than amylopectin.
Sugary-1 starch consists of phytoglycogen, a water-soluble glu-
can with a highly branched structure and substantially shorter
branch chains. Structures of these components are discussed in
the following sections.
Amylose
Amylose is a primarily linear molecule, consisting of mainly a-
1–4 linked D-glucopyranose with a few a-1–6 branches. The
molecular weight of amylose varies from degree of polymeri-
zation (DP) 500 in high-amylose maize starch to more than
DP 6000 in potato starch. The number of branches increases
with the molecular size of amylose.
The a-1–4 glycosidic bonds of amylose chains render a
flexible random-coil conformation to the molecule. The pres-
ence of hydrophobic hydrocarbon groups and hydrophilic
hydroxyl groups on the anhydroglucose units (AGU) prompts
two adjacent amylose chains in the aqueous dispersion to fold
together and form double-helical crystallites, resulting in the
hydrocarbon groups of the AGU folded inside of the double
helix, away from the aqueous medium to reach a lower energy
state. This crystallization process of dispersed starch molecules
taking place during storage of cooked starch is known as retro-
gradation. The retrograded amylose displays the B-type x-ray
diffraction pattern (polymorph), having the amylose double
helices packed in a hexagonal unit cell.
Amylose can also form single-helical complexes with many
chemicals (complexing agents) that consist of a hydrophobic
moiety, such as alcohols and fatty acids. The amylose single-
helical complex, also known as an inclusion complex, has the
hydrophobic moiety of the complexing agent located inside the
hydrophobic cavity of the helix. Depending on the cross-sectional
diameter of the complexing agent, amylose can form single heli-
ces of different sizes, including six, seven, and eight AGU/turn, to
accommodate the diameters linear complexing agents (e.g.,
n-butyl alcohol), branched complexing agents, (e.g., isobutyl
alcohol), and bulky ones (e.g., a-naphthol), respectively. The
x-ray diffraction pattern of the amylose single-helical complexes
is known as the V pattern.
Amylopectin
Amylopectin consists of a-1–4 linked D-glucopyranose linear
chains that are connected by a-1–6 branch linkages, about 5%.
165
166 Starch: Structure, Property, and Determination
The molecule is highly branched and has a molecular size
about DP 106. Branch chains of amylopectin molecules can
be categorized into three groups: the A chain, with its reducing
end attached to a B or C chain but not carrying any other
chains; the B chain, not only having the reducing end attached
to another B or C chain but also carrying other A or B chains;
and the C chain, being the only chain of the molecule carrying
a reducing end (Figure 1). The A chains are generally short and
extend within one cluster. The B chains have different chain
lengths, which can extend through one cluster (B1 chain), two
clusters (B2 chain), three clusters (B3 chain), or more clusters.
The branch chain-length distribution of amylopectin varies
with the botanical origin of the starch, which determines the
polymorphic form of the crystalline structure and the gelatini-
zation, pasting, and retrogradation property of the starch. Spe-
cific properties of starch will be discussed in section ‘Properties
of Starch.’
Branch chains of amylopectin are arranged in clusters,
which are evidenced by wormlike cluster structures remaining
after exhaustive acid hydrolysis of granular waxy maize starch
at room temperature, as viewed using transmission electron
microscopy. The wormlike cluster is attributed to the crystal-
line structure of outer chains of amylopectin molecules. The
amorphous structure of the waxy maize starch, mainly consist-
ing of branch linkages, is hydrolyzed during the acid
hydrolysis.
Starches that consist of amylopectin with larger propor-
tions of long branch chains (e.g., B2 and B3 chains), such as
potato, high-amylose maize, and ae waxy maize starches,
display the B-type x-ray pattern. Starches that consist of amy-
lopectin with more short branch chains of A and B1 chains,
such as maize, wheat, taro, barley, and rice starches, display
the A-type x-ray diffraction pattern, having a monoclinic unit-
cell packing.
Extra-long branch chains are present in amylopectin of
many cereal normal starches, such as normal wheat, rice,
A B2
A
A
B1 B1
B1
A
B1
C. L. =
12-16
C. L. = 27-28
Figure 1 A proposed cluster model of amylopectin with A( ), B1( ), B2( ), and B3( ) chains. The chain carrying the reducing end (Ø) is the C chain.
–, a-1–4 glucan chain; !, a-1–6 linkage; C.L., chain length. Reprinted from Hizukuri, S. (1986). Polymodal distribution of the chain lengths of
amylopectins, and its significance. Carbohydrate Research 147(2), 342–347.
barley, and maize starches, but are not found in cereal waxy
starch and potato starch. The extra-long branch chains have
amylose-like structures. For example, the extra-long chains of
wheat amylopectin have DP  720, which contribute to larger
blue values and iodine affinities of the amylopectin of normal
wheat starch than that of the waxy wheat starch. The concen-
tration of the extra-long branch chains of wheat amylopectin is
positively correlated to the dosage of the waxy gene encoding
granular-bound starch synthase that is primarily responsible
for amylose biosynthesis.
Intermediate Component and Phytoglycogen
Intermediate component is found in starch of many mutants,
including maize ae mutant and sugary-2 mutant. The interme-
diate component has a branched structure, but its molecular
weight is similar to amylose and its branch chain length is
longer than amylopectin. After the starch is fractionated using
a complexing agent, such as n-butyl alcohol, to complex and
precipitate the amylose, the intermediate component remains
in the supernatant with amylopectin. Gel permeation chro-
matograms of the mixture collected from the supernatant
show that amylopectin is eluted first at the void volume and
the intermediate component is eluted later. High-amylose
maize starch consists of up to 52% intermediate component.
The intermediate component together with amylose of the
high-amylose starch forms double-helical crystallites, resulting
in a conclusion gelatinization temperature (Tc) up to 130.0  C.
Consequently, the starch remains semicrystalline after cooking
and has a large RS content (up to 40%).
Phytoglycogen is another water-soluble glucan, which is
found in rice and maize sugary-1 mutants that are deficient in
the starch-debranching enzyme. Phytoglycogen has a smaller
molecular weight and shorter branch chain length than amy-
lopectin. The branch chains of the phytoglycogen display a
Ø
B3
B2

single-modal chain-length distribution, which is different from
the bimodal distribution of amylopectin.
Lipids and Phospholipids
Lipids and phospholipids are mainly found in cereal starches.
Cereal normal starch contains up to 1% lipids, and the lipid
content is positively correlated with the amylose content of
starch. Starches of different botanical origins consist of differ-
ent species of lipids. For example, normal maize starch consists
of mainly free fatty acids, triglycerides, and little phospho-
lipids; normal rice starch contains substantial amount of phos-
pholipids and some free fatty acids; and wheat, barley, rye, and
triticale starches consist of exclusively phospholipids. Substan-
tial amount of amylose in normal starch is found in helical
complexes with lipids, which were revealed by using solid 13C
cross polarization/magic angle spinning NMR. Cereal waxy
starches contain little lipids, whereas high-amylose starches
contain substantially more lipids. Root and tuber starches
contain very little lipids and no detectable phospholipids.
Free fatty acids, monoglycerides, diglycerides, and phos-
pholipids are good complexing agents with amylose and long
branch chains of amylopectin. Differential scanning calorimet-
ric (DSC) thermograms show dissociation peaks of the
amylose–lipid complex (ALC) at 90  C or higher. Unlike the
retrogradation of starch, which is a slow process and normally
takes days for the double helices to develop, the ALC formation
is an instant reaction. The dissociation peak of the ALC reap-
pears upon an immediate rescan of the starch sample using a
DSC. The ALC present in native starch is amorphous (type 1),
which does not give a V-type x-ray diffraction pattern and
displays a dissociation peak at a lower temperature
(90–100  C). After cooking, the ALC is reorganized to a lamel-
lar, semicrystalline structure (type 2), which displays a V-type
x-ray diffraction pattern and shows a higher dissociation tem-
perature (100–125  C).
Phosphate Monoester Derivatives
Phosphate monoester derivatives are covalently attached to the
amylopectin of potato starch and are also found in many other
tuber and root starches. The phosphate groups carry negative
charges, which repel one another and, thus, reduce the gelati-
nization and pasting temperatures and increase the viscosity
and clarity of the starch paste. In the presence of salt, the
viscosity of the potato starch paste reduces significantly
because the negative charges of the phosphate are masked by
cations of the salt.
Traditionally, phospholipid and phosphate monoester
derivative contents of starch are analyzed by measuring the
total phosphorus content after dry ashing of the starch. The
method, however, relies on a complete removal of phospho-
lipids by solvent extraction, which is difficult to achieve except
by using a 90% dimethyl sulfoxide solution. 31P-NMR spec-
troscopy has been demonstrated to give unambiguous results
for qualitative and quantitative analyses of phospholipid and
phosphate monoester contents of starch. Phospholipids,
being phosphate diesters, have chemical shifts at 0–1 ppm,
whereas phosphate monoesters have chemical shifts at
4–5 ppm at pH 8. Quantitative results can be obtained when
Starch: Structure, Property, and Determination 167
adequate acquisition times are programmed to allow spin
relaxation.
Structures of Starch Granules
Morphology of Starch Granules
Morphologies of starch granules isolated from different botan-
ical sources and different organs of the plant are different.
Images of some starch granules viewed using scanning electron
microscopy are shown in Figure 2. Shapes of starch granules
include spherical, oval, disk, polygonal, elongated, kidney, and
lobe shapes. Starch isolated from leaves has flat and small
granules. Starch from wheat, barley, and rye kernels in the
triticale family displays bimodal granule-size distributions,
the large disk-shaped A-granules, and the small spherical
B-granules (Figure 2(g)). Rice and oat have compound starch,
resulting from multiple granules being synthesized within a
single amyloplast. High-amylose starch from maize and other
sources consists of elongated starch granules, and some gran-
ule displays a rod shape that is 3 mm in diameter and 30 mm in
length (Figure 3(A)). Diameters of common starch granules
vary from submicrons to more than 100 mm. For example, the
diameters of potato starch are 15–75 mm, wheat starch
A-granules 18–33 mm and B-granules 2–5 mm, maize starch
5–20 mm, rice starch 3–8 mm, and amaranth starch 0.5–2 mm.
When viewed under a polarized light microscope, starch
granules display birefringence, known as Maltese cross, which
reflects the radial arrangement of starch molecules in the starch
granule (Figure 2). The center of the Maltese cross, the hilum,
is where the biosynthesis of the starch granule initiates. The
hilum is not necessarily at the geometric center of the granule;
some can be located close to one end of the granule, reflecting
the initiating site of the starch biosynthesis (Figure 2(c), 2(f),
and 2(h)). Elongated starch granules of high-amylose maize
starch (Figure 3) display multiple hila and several Maltese
crosses overlapping in a single granule (Figure 3(C) and
3(D)). Confocal laser scanning micrographs also show multi-
ple granules in a single elongated granule (Figure 3(B)). Trans-
mission electron micrographs of developing endosperm tissue
reveal that the biosynthesis of the elongated granules is a result
of an interaction between amylose molecules of adjacent starch
granules initiated in the same amyloplast. The small granules
are fused together and continuously synthesized to one
elongated granule.
Internal Structures of Starch Granules
Starch of the A-type polymorph consists of amylopectin with
large proportions of short branch chains, whereas that of the B-
type polymorph consists of amylopectin with more long
branch chains that extend through two or more clusters. Starch
of the C-type polymorph has amylopectin with a combination
of the A- and B-type structures. Because of the large proportion
of short branch chains of the A-type polymorphic starch, the
short double helices of the branch chains are arranged to a
closely packed monoclinic unit cell, resulting in a porous
internal structure (Figure 4(a1) and 4(b1)). On the contrary,
the B-type starch granules, consisting of more B2 and B3 chains
that extend through multiple clusters (Figure 1), maintain a
168 Starch: Structure, Property, and Determination

Figure 2 Scanning electron microscopy (SEM) and polarized light microscopy (insets) images of native starch granules from various botanical
sources: (a) taro; (b) chestnut; (c) ginger; (d) manioc; (e) maize; (f) green banana; (g) wheat; (h) potato. Scale bars in all images: 20 mm. Reprinted from
Pérez, S. and Bertoft, E. (2010). The molecular structures of starch components and their contribution to the architecture of starch granules: a
comprehensive review. Starch-Starke 62, 389–420.

homogeneous internal structure (Figure 4(a2) and 4(b2)). The
porous structure of the A-type polymorphic maize starch gran-
ules was first revealed using a nitrogen gas surface adsorption
method, which has later been confirmed using a surface-
gelatinized technique, and confocal laser scanning microscopy
(Figure 4). The porous structure of the A-type starch granules
prompts greater susceptibility of the granule to chemical pen-
etration and enzymatic hydrolysis. The A-type starches, such as
sorghum and maize starch, display pinholes on the surface of
the starch granule, which are open ends of serpentine-like
channels likely hydrolyzed by amylases and penetrating into
the granule.
Relative locations of amylose and amylopectin molecules in
the starch granule have been studied using chemical cross-
linking reactions. Results of the cross-linked starch granules
show that amylose molecules are primarily cross-linked to
amylopectin molecules, an evidence that amylose is inter-
spersed among amylopectin molecules. Amylose is more con-
centrated at the periphery of the granule than at the hilum as
revealed by using the surface gelatinization of starch granules
with saturated neutral salt solutions, such as LiCl and CaCl2.
This result is consistent with the fact that the amylose content
of starch increases with increased size of the starch granule.
The large concentration of amylose at the periphery of
starch granules renders a hard shell on the surface of normal
starch granules, making it difficult for enzymatic hydrolysis.
The hard shell is sometimes misinterpreted as a membrane. But
it is known that starch chains on the surface of the starch
granule can be elongated with the addition of ADP–glucose,
which excludes the presence of a membrane on the surface of
the granule. The apparent shell on the surface of starch gran-
ules, therefore, can be attributed to tightly associated amylose
and amylopectin molecules. It is well known that amylose
produces tough films.
Properties of Starch
Starch has versatile properties and applications. It can be used
in a granular form for an anticaking agent or facial/baby
 Starch: Structure, Property, and Determination 169

Figure 3 (A) Scanning electron microscopy (SEM) image of high-amylose maize starch. Arrows indicate elongated starch granules. Scale bar: 20 mm.
(B) Confocal laser scanning microscopy images of high-amylose maize starch stained by using 8-aminopyrene-1, 3, 6-trisulfonic acid (APTS): (a)
spherical granule with bright color around one hilum; (b–g) elongated granules with multiple hila differing in intensity of fluorescence. Scale bar: 10 mm.
Phase contrast (C) and polarized (D) light microscopy images of high-amylose maize starch. Arrows indicate multiple Maltese crosses overlapping
in one granule. (B) Reprinted from Jiang, H., et al. (2010). Formation of elongated starch granules in high-amylose maize. Carbohydrate Polymers 80(2),
533–538. (C) and (D) Reprinted from Jiang, H., et al. (2010). Variations in starch physicochemical properties from a generation-means analysis
study using amylomaize V and VII parents. Journal of Agricultural and Food Chemistry 58(9), 5633–5639.

powder, a dispersed paste for thickening or sizing agents, a
hydrogel structure for puddings or bread, and a crystalline
structure (retrograded amylose) for RS (type 3) to improve
health. These broad applications are the results of the transfor-
mation of starch from semicrystalline granules, to amorphous
structures by losing the native crystalline order (gelatiniza-
tion), to a paste after absorbing water and developing viscosity,
to a gel after network formation, and to RS after recrystalliza-
tion (Figure 5). The transformation and properties of starch
are discussed in the following sections.
Starch Gelatinization
Native starch granules can absorb about 30% (w/w) moisture,
when steeped in water at an ambient temperature. The water is
distributed in the amorphous region of starch granules. When
starch is heated to a specific temperature in the presence of
water (two times or more), it loses the crystalline structure and
the Maltese cross and becomes transparent. This thermal tran-
sition is known as gelatinization, and the temperature at which
starch loses the crystalline structure is the gelatinization tem-
perature. Gelatinization temperatures of selected A-, B-, and C-
type polymorphic starch varieties are shown in Table 1. The
gelatinization temperature is a characteristic property of each
starch, and it is, in general, positively correlated with the
branch chain length of the amylopectin. Phosphate monoester
derivatives of starch, however, reduce the gelatinization tem-
perature. For example, potato starch displays a much lower
onset gelatinization temperature (To ¼ 58.2  C) than the nor-
mal maize and rice starches (64.1  C and 70.3  C, respec-
tively), despite the fact that potato amylopectin has much
longer branch chains than the normal maize and rice starches.
This is a result of a high concentration (0.08%) of the phos-
phate derivatives of the potato starch. The repulsion between
negative charges of the phosphate groups destabilizes the
double-helical structure of potato starch and decreases the
gelatinization temperature.
Starch gelatinization temperature can be determined by
observing the loss of Maltese cross using a light microscope
equipped with a polarizer and a hot stage, measuring the trans-
parency of a starch suspension during heating, or using a DSC.
The DSC can measure both the temperature and enthalpy
change of starch gelatinization, which is an endothermic reac-
tion. To obtain a consistent gelatinization temperature of starch,
it needs to have at least two times (w/w) water. Without suffi-
cient water, starch is gelatinized at a higher temperature with a
broader temperature range. Without the presence of water or
other plasticizers, starch will not gelatinize by heat but will be
thermally decomposed at a temperature above 250  C.
DSC thermograms of cereal normal starch show an addi-
tional thermal transition peak at temperatures above 90  C,
corresponding to the dissociation of ALC. Dissociation
170 Starch: Structure, Property, and Determination

Figure 4 (a) Scanning electron microscopy (SEM) image of surface-gelatinized normal maize starch (1) and potato starch (2). The granules have about
65% surface starch removed. (b) Confocal laser scanning microscopy images of normal maize starch (1) and potato starch (2). Reprinted from Jane,
J. (2006). Current understanding on starch granule structures. Journal of Applied Glycoscience 53, 205–213.

Swelling
Heating
Starch Swollen Gelatinized
granules granules starch
Temp. > Tc
Shrinking
Heating and
shearing
Storage Cooling
Retrograded Starch Starch
starch gel paste
Heating
Figure 5 Transformation of starch structures.

temperature of the ALC, in general, increases with increasing
chain length of the fatty acid and decreases with an increasing
number of double bonds. Among the unsaturated fatty acids,
the fatty acids with trans-double bonds form ALC with a higher
dissociation temperature than those with cis-double bonds.
Starch gelatinization can also be achieved by using chemi-
cal solutions, such as aqueous alkaline solutions (e.g., NaOH
and KOH), dimethyl sulfoxide, and various neutral salt solu-
tions (e.g., KI, KSCN, CaCl2, and LiCl). Aqueous solutions of
NaOH and KOH (0.5 M or higher) and dimethyl sulfoxide
(90%) are commonly used to gelatinize and disperse starch.
A concentrated sodium sulfate solution, however, can be used
to increase the gelatinization temperature of starch.
Pasting Property
When gelatinized starch is continuously heated in excess water
with shearing, starch granules swell to develop viscosity and
some starch molecules are dispersed in the aqueous medium
(Figure 5). The viscosity development in this process is known
 Starch: Structure, Property, and Determination 171

Table 1 Gelatinization properties of starches with different polymorphic structures analyzed using differential scanning calorimetry

Type To ( C)a Tp ( C) Tc ( C) Range ( C) DH (J g
1)

A-type starch
Normal maize 64.1  0.2 69.4  0.1 74.9  0.6 10.8 12.3  0.0
Waxy maize 64.2  0.2 69.2  0.0 74.6  0.4 10.4 15.4  0.0
du Waxy maize 66.1  0.5 74.2  0.4 80.5  0.2 14.4 15.6  0.2
Normal rice 70.3  0.2 76.2  0.0 80.2  0.0 9.9 13.2  0.6
Waxy rice 56.9  0.3 63.2  0.3 70.3  0.7 13.4 15.4  0.2
Sweet rice 58.6  0.2 64.7  0.0 71.4  0.5 12.8 13.4  0.6
Wheat 57.1  0.3 61.6  0.2 66.2  0.3 9.1 10.7  0.2
Barley 56.3  0.0 59.5  0.0 62.9  0.1 6.6 10.0  0.3
Waxy amaranth 66.7  0.2 70.2  0.2 75.2  0.4 8.5 16.3  0.2
Cattail millet 67.1  0.0 71.7  0.0 75.6  0.0 8.5 14.4  0.3
Mung bean 60.0  0.4 65.3  0.4 71.5  0.4 11.5 11.4  0.5
Chinese taro 67.3  0.1 72.9  0.1 79.8  0.2 12.5 15.0  0.5
Tapioca 64.3  0.1 68.3  0.2 74.4  0.1 10.1 14.7  0.7
B-type starch
ae Waxy maize 71.5  0.2 81.0  1.7 97.2  0.8 25.7 22.0  0.3
Amylomaize V 71.0  0.4 81.3  0.4 112.6  1.2 41.6 19.5  1.5
Amylomaize VII 70.6  0.3 N.D.b 129.4  2.0 58.8 16.2  0.8
Potato 58.2  0.1 62.6  0.1 67.7  0.1 9.5 15.8  1.2
Green leaf canna 59.3  0.3 65.4  0.4 80.3  0.3 21.0 15.5  0.4
C-type starch
Lotus root 60.6  0.0 66.2  0.0 71.1  0.2 10.5 13.5  0.1
Green banana 68.6  0.2 72.0  0.2 76.1  0.4 7.5 17.2  0.1
Water chestnut 58.7  0.5 70.1  0.1 82.8  0.2 24.1 13.6  0.5
a
To, onset temperature; Tp, peak temperature; Tc, conclusion temperature; Tc
To, range of gelatinization; DH, enthalpy change.
b
Not detectable.
Source: Jane, J., et al. (1999). Effects of amylopectin branch chain length and amylose content on the gelatinization and pasting properties of starch. Cereal Chemistry 76(5), 629–637.

Table 2 Pasting properties of starches measured using a Rapid Visco Analyzer with 8% (dry starch basis) starch content

Viscosity (RVU)

Starch Pasting temperature ( C) Peak Hot paste Final Setback

Normal maize 82.0 152 95 169 74

Waxy maize 69.5 205 84 100 16
du Waxy maize 75.7 109 77 99 22
ae Waxy maize 83.2 162 150 190 40
Waxy rice 64.1 205 84 100 16
Sweet rice 64.6 219 100 128 28
Normal rice 79.9 113 96 160 64
Wheat 88.6 104 75 154 79
Barley 91.2 88 58 116 58
Waxy amaranth 70.2 125 75 86 11
Cattail millet 74.2 201 80 208 128
Chinese taro 73.1 171 88 161 73
Tapioca 67.6 173 61 107 46
Lotus root 67.4 307 84 138 54
Potato 63.5 702 165 231 66
Mung bean 73.8 186 161 363 202
Green banana 74.0 250 194 272 78
Water chestnut 74.3 61 16 27 11

RVU, rapid visco unit.

Source: Jane, J., et al. (1999). Effects of amylopectin branch chain length and amylose content on the gelatinization and pasting properties of starch. Cereal Chemistry 76(5), 629–637.

as the pasting property. Pasting property of starch is very
important for many applications of starch, such as for thicken-
ing agents and sizing agents, and different starch varieties
display different viscosities and pasting temperatures. Pasting
property of starch is commonly measured using an
amylograph, such as Brabender amylograph, and Rapid Visco
Analyzer (RVA).
Pasting properties of common starches analyzed using an
RVA are summarized in Table 2. Amylopectin is primarily
responsible for the swelling power of starch granules and
172 Starch: Structure, Property, and Determination
viscosity. Amylose molecules, particularly with the presence of
lipids, tend to restrict the swelling of granules. Consequently,
normal maize starch that has 29.4% amylose and around 1%
lipids shows a higher pasting temperature (82.0  C) and a
lower peak viscosity (152 rapid visco units, RVU) than its
waxy counterpart (0% amylose, 69.5  C and 205 RVU, respec-
tively). Amylose molecules, however, are responsible for
increasing the setback viscosity upon cooling of the starch
paste, resulting from the network formation between amylose
and amylopectin molecules. For example, normal maize starch
has a setback viscosity of 74 RVU, which is larger than the waxy
maize starch, 16 RVU.
ALC formed in starch granules renders entanglements
between amylose and amylopectin molecules and restricts the
swelling of granules during cooking. Consequently, it increases
the pasting temperatures, decreases the pasting viscosities, and
results in an opaque appearance of the starch paste. Among all
the cereal normal starches, wheat and barley starches display
the highest pasting temperatures and the lowest peak viscosi-
ties (Table 2) because both have high concentrations of phos-
pholipids, which are readily available for the complex
formation. After removal of endogenous lipids using deter-
gents (e.g., sodium dodecyl sulfate), wheat starch shows a
pasting temperature and peak viscosity similar to tapioca
starch. In contrast, potato starch has a remarkably low pasting
temperature (63.5  C) and great peak viscosity (702 RVU)
(Table 2), resulting from its large content of phosphate mono-
ester derivatives. Repulsion between the negative charges of the
phosphate monoester groups enhances the swelling of starch
granules and increases the peak viscosity and clarity of the
paste. The large granule size of the potato starch with a diam-
eter up to 75 mm (Figure 2) also contributes to the great peak
viscosity.
Gel Formation
After cooling and storing a paste of 5–15% starch, swollen
starch granules in the paste fill up the volume, deform one
another, adhered by amylose leached out from the swollen
granules, and hold the shape of the mold to form a gel
(Figure 5). To maintain the volume of swollen starch granules,
amylose and amylopectin molecules must interact with one
another to form a network to hold water in the swollen gran-
ules. Cereal normal starches, such as normal maize, wheat, and
rice starches, are known to retain rigid swollen granules and
form strong gels. Waxy starch, normal potato starch, and tap-
ioca starch tend to freely swell and disperse after cooking
because of the lack of amylose or lipids to facilitate stable
interactions between amylose and amylopectin in the granules.
Consequently, those starches cannot form gels. After being
thoroughly mixed with lipids, including soy lecithin, oleic
acid, and linoleic acid, before cooking, the mixtures of tapioca
starch and lipid can develop gels. This result suggests that
the formation of ALC facilitates molecular interactions in the
starch granules, which restrict the swelling and maintain
the integrity of swollen granules for the gel development.
Potato starch granules with a prior heat-and-moisture treat-
ment or chemical cross-linking can also develop a gel. Starch
gels are formed by storing starch pastes at a refrigeration
temperature for a selected period of time, and gel strength
can be measured using a texture analyzer.
Starch Retrogradation/Syneresis
After prolonged storage, amorphous starch molecules in the
aqueous medium form double-helical crystalline structures
and lose their water-binding capacity (Figure 5). This process
is known as starch retrogradation, as shown in staled bread and
syneresis of gravy. The rate of starch retrogradation can be
increased by increasing the concentration of starch in the
paste, storing the starch paste at 0–5  C, increasing amylose
(linear molecule) content, having chain length of DP 80–100,
and increasing the branch chain length of amylopectin. Cereal
normal starch in a paste or a gel tends to retrograde faster than
tuber and root starches because of the limited swelling of starch
granules. Molecules of cereal normal starch are located in close
proximity within the swollen granules, which facilitate the
retrogradation.
Chemical derivatives of starch, such as acetyl and hydro-
xypropyl groups, retard starch retrogradation. When the starch
paste or gel is stored below the glass-transition temperature
(Tg), the starch retrogradation is retarded because of the lack of
molecular mobility. Addition of complexing agents, such as
monoglycerides, to bread making can reduce the retrograda-
tion rate of the bread because of the single-helical complex
formed with the monoglycerides. When the hydrophobic sides
of starch molecules are bound with the complexing agent, it
retards the double-helical formation.
Starch Digestibility
Starch, a major energy source, can be hydrolyzed by amylolytic
enzymes to generate glucose to support lives of plants, animals,
and humans. Starch granules have semicrystalline structures
and are less readily hydrolyzed by enzymes. After starch is
gelatinized and becomes amorphous, starch molecules can be
hydrolyzed quickly.
The enzymatic digestive rate of granular starch is determined
by factors including polymorphism/amylopectin structure,
amylose content, and size of starch granules. Starch granules
with the A-type polymorphs (e.g., normal wheat, rice, and maize
starches) are hydrolyzed much faster than those of the B-type
(e.g., potato and high-amylose maize starches). Starch with the
C-type polymorph (e.g., green banana starch) displays a hydro-
lysis rate in between (Figure 6). The greater hydrolysis rate of the
A-type starch is attributed to the large proportions of short
branch chains of the amylopectin (DP 6–12) and the porous
structure of the granule (Figure 4). For starch granules with the
same type of polymorph, the enzymatic hydrolysis rate
decreases with increased amylose content; for example, waxy
starches are hydrolyzed fast, whereas high-amylose barley starch
and mung bean starch are hydrolyzed more slowly (Figure 6).
This could be the result of amylose restricting the swelling of the
starch granules and concentrating at the periphery to form a
hard shell, which reduces the accessibility of starch granules to
enzymatic hydrolysis. Small-granule starches, such as amaranth
and rice starches, are more susceptible to enzymatic hydrolysis
(Figure 6) because they have a larger relative surface area.
 Starch: Structure, Property, and Determination 173

120 A A
A
A
100 A
A
Hydrolysis% at 24 h

A
80 A
A
A
A
60 C C
A A C
A A
40 A
C

20 C C B B B
B B B

0
Amaranth
Waxyrice
Sweetrice
Oat
Waxycom
Barley
Chinesetaro
Tapioca
Wheat
Normalrice
Cattailmillet
Lotus root
Yam
Normal
Glacier

Sweetpotato
H-A G barley
Mungbean
H-A H barley

chestnut
G banana
Ginkgo
H-A maize 7
Waxypotato
Ae W maize
Potato

G L canna
H-A maize V
barley
maize

Water
Figure 6 Percentages enzymatic hydrolysis of starches with different polymorphic structures. Porcine pancreatic a-amylase (120 U/20 mg starch
in 9 ml phosphate buffer, pH 6.9) was used to hydrolyze starch at 37  C for 24 h. The percentage enzymatic hydrolysis was determined by measuring
the total carbohydrate content in the supernatant using a phenol–sulfuric acid method. The letter above each bar indicates the x-ray diffraction
pattern of the starch. Reprinted from Jane, J., Aol, Z., Duvick, S. A., Wiklund, M., Yoo, S. -H., Wong, K. -S., and Gardner C. (2003). Structures of
amylopectin and starch granules: how are they synthesized? Journal of Applied Glycoscience 50, 167–172.

The digestive rate of starch in a diet is measured as the cellulosic materials and protein matrix also reduces its
glycemic response, which determines the blood glucose con- susceptibility to enzymatic hydrolysis.
centration. A consistently high blood glucose concentration
can cause insulin resistance and type-2 diabetes. The enzymatic
hydrolysis rate of starch in a diet is determined by factors
See also: Amaranth; Bananas and Plantains; Barley; Beer:
including the presence of retrograded starch, chemical deriva-
Fermentation; Biofilms; Biscuits, Cookies, and Crackers: Chemistry and
tives of the starch, formation of ALC, and presence of cellulosic
Manufacture; Bread: Chemistry of Baking; Browning: Non-enzymatic
materials and the protein matrix. Retrograded starch is resistant
browning; Carbohydrate: Digestion, Absorption and Metabolism;
to enzymatic hydrolysis. Chemically modified starch (e.g.,
Cassava: The Nature and Uses; Cereals: Dietary Importance; Cereals:
cross-linked and octenyl succinic starch) is less hydrolyzable.
Types and Composition; Chapatis and Related Products; Chilled
Lamellar crystallites of ALC are protected from enzymatic
Foods: Effects on Shelf-life and Sensory Quality; Cooking: Domestic
hydrolysis. The ALC can also restrict the swelling of gelatinized
Techniques; Fatty Acids: Fatty Acids; Fructose and High-Fructose Corn
starch and reduce the enzymatic hydrolysis rate of the starch.
Syrup; Glucose: Metabolism and Regulation; Legumes in the Diet;
Type 5 resistant starch (RS5) is made by complexing high-
Maize; Microscopy: Light Microscopy and Histochemical Methods;
amylose maize starch with free fatty acids. After human sub-
Millets; Pasta: Manufacture and Composition; Phospholipids:
jects were fed with bread made with 60% of the RS5, it signif-
Properties and Occurrence; Potatoes and Related Crops; Pulsed
icantly reduced postprandial glucose concentration (55%) and
Electric Fields; Rice: Types and Composition; Sorghum: A Novel and
the insulin response (43%) compared with 100% for human
Healthy Food; Starch: Modified Starches; Starch: Sources and
subjects fed with white bread.
Processing; Starch; Tortillas; Triacylglycerols: Structures and
DSC thermograms and x-ray diffraction studies show no
Properties; Wheat: Grain Structure of Wheat and Wheat-based
complex formation between amylose and triglycerides, a major
Products.
component of lipids in foods. Enzymatic hydrolyses of
normal- and high-amylose starch cooked with corn oil
(triglycerides), however, show substantial decreases in the
hydrolysis rate of the starch. The effect is not observed with Further Reading
waxy maize starch. 13C-NMR spectra confirm the formation of
BeMiller J and Whistler R (2009) Starch: chemistry and technology, 3rd ed. New York:
the amylose helical complex between amylose and corn oil. Academic Press.
Cooking rice with corn oil to prepare fried rice and rice pilaf Eliasson A-C (2004) Starch in food: structure, function and applications. New York:
decreases the starch hydrolysis rate. Surrounding of starch by CRC Press.
174 Starch: Structure, Property, and Determination
Eliasson A-C and Gudmundsson M (2006) Starch: physicochemical and functional
aspects. In: Eliasson A-C (ed.) Carbohydrates in food, 3rd ed., pp. 391–469.
New York: CRC Press.
Hizukuri S, Abe J, and Hanashiro I (2006) Starch: analytical aspects. In: Eliasson A-C
(ed.) Carbohydrates in food, 3rd ed., pp. 305–390. New York: CRC Press.
Jane J, Aol Z, Duvick SA, Wiklund M, Yoo S-H, Wong K-S, and Gardner C (2003)
Structures of amylopectin and starch granules: how are they synthesized? Journal of
Applied Glycoscience 50: 167–172.
Jane J (2006) Current understanding on starch granule structures. Journal of Applied
Glycoscience 53: 205–213.
Jane J (2007a) Structure of starch granules. Journal of Applied Glycoscience
54: 31–36.
Jane J (2007b) Carbohydrates: basic concepts. In: Hui YH (ed.) Food chemistry:
principles and applications, 2nd ed. West Sacramento: Science Technology,
pp. 4-1–4-21.
Morrison WR (1995) Starch lipids and how they relate to starch granule structure and
functionality. Cereal Foods World 40: 437–446.
Putseys JA, Lamberts L, and Delcour JA (2010) Amylose-inclusion complexes: formation,
identity and physico-chemical properties. Journal of Cereal Science 51: 238–247.
Robyt J (2008) Starch: structure, properties, chemistry and enzymology. In: Fraser-
Reid BO, Tatsuta K, and Thiem J (eds.) Glycoscience: chemistry and chemical
biology, pp. 1437–1472. Berlin: Springer-Verlag.
Shi Y-C and Maningat CC (2013) Resistant starch: sources, applications and health
benefits. Hoboken, NJ: Wiley-Blackwell.