Journal of Cereal Science 39 (2004) 151–165

www.elsevier.com/locate/jnlabr/yjcrs

Review

Starch—composition, fine structure and architecture

Richard F. Tester*, John Karkalas, Xin Qi
Food Research Laboratories, Department of Biological and Biomedical Sciences, Glasgow Caledonian University, Cowcaddens Road, Glasgow G4 0BA, UK
Received 16 October 2003; revised 3 December 2003; accepted 3 December 2003

Abstract
Much has been written over many decades about the structure and properties of starch. As technology develops, the capacity to understand
in more depth the structure of starch granules and how this complex organisation controls functionality develops in parallel. This review puts
the current state of knowledge about starch structure in perspective and integrates aspects of starch composition, interactions, architecture
and functionality.
q 2003 Elsevier Ltd. All rights reserved.
Keywords: Starch; Composition; Amylose; Amylopectin; Architecture; Crystallinity

1. Starch structure outdated relatively quickly. However, such a

Much has been written over the last century concerning
starch structure, properties, biosynthesis and degradation
(Banks and Greenwood, 1975; Blanshard, 1987; Buléon
et al., 1998a; French, 1972, 1984; Galliard and Bowler,
1987; Hoover, 2001; Kent and Evers, 1994; Lineback, 1984,
1986; Morrison and Karkalas, 1990; Tester and Karkalas,
2002; Zobel and Stephen, 1996; Zobel, 1988b, 1992). The
level of analytical sophistication used to understand the
structure of starch and how this defines functional properties
is evident from the developing literature base. Similarly,
molecular biology tools have made it possible to explore, in
depth, the process of starch biosynthesis and to gain a more
complete view of the orchestration of the enzymatic
processes involved. It is recognised that the pace of
development in this field makes a review regarding starch
Abbreviations: ADP, adenosine di-phosphate; AFM, atomic force
microscopy; ATP, adenosine tri-phosphate; 13C CP-MAS/NMR, 13C cross
polarisation-magic angle spinning/nuclear magnetic resonance; CL, chain
length; DP, degree of polymerisation; DPn, degree of polymerisation by
number; DPw, degree of polymerisation by weight; FFA, free fatty acid;
G-1-P, glucose-1-phosphate; G-6-P, glucose-6-phosphate; IBC, iodine
binding capacity; h, viscosity; LPL, lysophospholipid; P, phosphorus; PPi,
pyrophosphate; SANS, small angel neutron scattering; SAXS, small angel
X-ray scattering; SEM, scanning electron microscopy; SGAP, starch
granule associated protein; TEM, transmission electron microscopy; UDP,
uridine di-phosphate; WAXS, wide angle X-ray scattering.
* Corresponding author. Tel.: þ 141-331-8514; fax: þ 141-331-3208.
E-mail address: r.f.tester@gcal.ac.uk (R.F. Tester).
0733-5210/$ - see front matter q 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jcs.2003.12.001
review serves as a point of reference for scientists in this
area and hopefully stimulates further research and
understanding.
Starch biosynthesis is a complex process (Ball, 1995;
Buléon et al., 1998a; Denyer et al., 2001; Emes et al., 2003;
Smith et al., 1997; Tester and Karkalas, 2002). Sucrose
(derived from photosynthesis) is the starting point for
alpha-glucan deposition. In the cell cytosol the sucrose is
converted to uridine diphosphate glucose (UDP-glucose) and
fructose by sucrose synthase, the UDP-glucose being
subsequently converted to glucose-1-phosphate (G-1-P) in
the presence of pyrophosphate (PPi) by UDP-glucose
pyrophosphorylase. This is then itself converted to glu-
cose-6-phosphate (G-6-P) by phosphoglucomutase. The
G-6-P is translocated across the amyloplast (the intra-cellular
organelle responsible for starch biosynthesis in storage
tissues) membrane by specific translocators and is converted
to G-1-P by phosphoglucomutase. There is some evidence
that, in cereals at least, G-1-P may be (a) translocated directly
into the amyloplast or (b) be converted to, and translocated
as, adenosine diphosphate glucose (ADP-glucose) generated
as a consequence of cytosol based adenosine diphosphate
(ADP)-glucose pyrophosphorylase activity in the presence of
adenosine triphosphate (ATP). Using amyloplast located
ADP-glucose pyrophosphorylase, G-1-P within the amylo-
plast is (also) converted to ADP-glucose and provides
glucose residues for amylose and amylopectin biosynthesis.
Starch synthases (of which there are commonly considered to
152 R.F. Tester et al. / Journal of Cereal Science 39 (2004) 151–165

be two major classes, ‘granule bound’ and ‘soluble’, with a
number of isoforms of each) add glucose units to the non-
reducing ends of amylose and amylopectin molecules.
Granule bound starch synthase can elongate malto-oligosac-
charides to form amylose and is considered to be responsible
for the synthesis of this polymer. Soluble starch synthase is
considered to be responsible for the synthesis of unit chains
of amylopectin. More recent analysis of starch synthase
families has been discussed by Ball et al. (1998) and makes
this interpretation rather simplistic, although more detailed
discussion is beyond the scope of this review. Starch
branching enzyme creates branching in amylopectin by
linking linear chains (branches) to the growing amylopectin
molecule. A number of mechanisms have been proposed for
the branching of amylopectin and readers are referred to
appropriate publications (above) for details.
Starch granules are synthesised in a broad array of plant
tissues and within many plant species. Variations in granule
size (, 1 – 100 mm in diameter), shape (round, lenticular,
polygonal), size distribution (uni- or bi-modal), association
as individual (simple) or granule clusters (compound) and
composition (a-glucan, lipid, moisture, protein and mineral
content) reflect the botanical origin (Banks and Greenwood,
1975; Blanshard, 1987; Buléon et al., 1998a; Fredriksson
et al., 1998; Gallant and Bouchet, 1986; Galliard and
Bowler, 1987; Kent and Evers, 1994; Lineback, 1984;
Morrison and Karkalas, 1990; Swinkels, 1985; Tester and
Karkalas, 2002; Zobel and Stephen, 1996; Table 1).
Although Nature provides a broad variation of starch
granule dimensions and size distributions, but selection of
plant mutants to provide a broader compositional variation
and more recently, transgenic (transfer gene) technology to
achieve a similar objective but in a more controlled fashion
(Davies et al., 2003). In addition, starches may be
chemically, enzymatically or physically modified to induce
novel characteristics. The structure of starch can be
described in terms of physicochemical properties of the
constituent molecules, compositional variation, interactions
at the molecular level associations of molecular interactions
(architecture) and the macro level of the whole granule
itself. These elements are discussed in detail below.
2. Starch composition and structure of components
Starch granules are composed of two types of alpha-
glucan, amylose and amylopectin, which represent approxi-
mately 98 –99% of the dry weight. The ratio of the two
polysaccharides varies according to the botanical origin of
the starch. The ‘waxy’ starches contain less than 15%
amylose, ‘normal’ 20 –35% and ‘high’ (amylo-) amylose
starches greater than about 40%. The structure of the
alpha-glucans is discussed below in more detail. The
moisture content of air-equilibrated starches ranges from
about 10 –12% (cereal) to about 14 –18% (some roots and
tubers).
Cereal starches contain integral lipids in the form of
lysophospholipids (LPL) and free fatty acids (FFA) which
are positively correlated with the amylose fraction and the
LPL may account for up to , 2% of starch weight (in high
amylose cereal starches). However, the granules may also be
contaminated with surface lipids (Morrison, 1985, 1988,
1995). The contaminants comprise triglycerides, glyco-
lipids, phospholipids and free fatty acids derived from the
amyloplast membrane and non-starch sources. These differ
from integral (internal) lipids, which are composed exclu-
sively of the FFAs and LPL (Morrison, 1985, 1988, 1993,
1995; Morrison and Karkalas, 1990). Starches from the

Table 1
Characteristics of starch granules from different botanical sources

Starch Type Shape Distribution Size (mm)

Barley Cereal Lenticular (A-type), spherical (B-type) Bimodal 15–25, 2–5

Maize (waxy and normal) Cereal Spherical/polyhedral Unimodal 2–30
Amylomaize Cereal Irregular Unimodal 2–30
Millet Cereal Polyhedral Unimodal 4–12
Oat Cereal Polyhedral Unimodal 3–10 (single)
80 (compound)
Pea Legume Rentiform (single) Unimodal 5–10
Potato Tuber Lenticular Unimodal 5–100
Rice Cereal Polyhedral Unimodal 3–8 (single)
150 (compound)
Rye Cereal Lenticular (A-type) Bimodal 10–40
Spherical (B-type) 5–10
Sorghum Cereal Spherical Unimodal 5–20
Tapioca Root Spherical/lenticular Unimodal 5–45
Triticale Cereal Spherical Unimodal 1–30
Sago Cereal Oval Unimodal 20–40
Wheat Cereal Lenticular (A-type) Bimodal 15–35
Spherical (B-type) 2–10

Adapted from Tester and Karkalas (2002).

 R.F. Tester et al. / Journal of Cereal Science 39 (2004) 151–165
Triticeae starches contain almost exclusively LPLs
(-choline, -ethanolamine and -glycerol) while other cereal
starches are rich in FFAs. Part of the amylose fraction within
lipid-containing granules exists as an amylose inclusion
complex where the fatty acid chains occupy a hydrophobic
core located within the single amylose helix. The presence of
these complexes in native starch granules is apparent from
13
C cross polarisation-magic-angle spinning/nuclear mag-
netic resonance (13C CP-MAS/NMR) (Morrison et al.,
1993a –c). The presence of this fraction is also evident
from iodine binding studies where non-defatted amylose
from cereal starches has a lower iodine binding capacity than
the corresponding lipid-extracted material. The amount of
lipid-complexed amylose ranges from , 15 to . 55% of the
amylose fraction in cereal starches, with oat starches being
especially rich in lipids and correspondingly complexed
amylose (Morrison, 1993, 1995).
Purified starches contain , 0.6% protein. In common
with starch lipids, proteins occur on the surface (and include
non-starch derived proteins) and regardless of origin are
embedded within the matrix of granules (regardless of
origin). Both the starch lipids and proteins have the potential
to moderate starch functionality (Appelqvist and Debet,
1997). Collectively, the proteins are referred to as starch
granule associated proteins and may be associated with
lipids on granule surfaces (Baldwin, 2001). In wheat, the
starch surface protein, friabilin, has received much attention
because of its proposed association with grain hardness
(Greenwell and Schofield, 1986; Schofield, 1994; Oda and
Schofield, 1997; Baldwin, 2001; Morris, 2002). Integral
proteins have a higher molecular weight than surface
proteins (, 50 – 150 and , 15 – 30 kDa, respectively)
Fig. 1. Structure of amylose and amylopectin. Adapted from Tester and Karkalas (2002).
153
and include residues of enzymes involved in starch
synthesis, especially starch synthase (Baldwin, 2001).
Starches also contain relatively small quantities (, 0.4%)
of minerals (calcium, magnesium, phosphorus, potassium
and sodium) which are, with the exception of phosphorus, of
little functional significance. The phosphorus is found in
three major forms: phosphate monoesters, phospholipids
and inorganic phosphates (Blennow et al., 1998, 2000a,b,
2002; Kasemsuwan and Jane, 1996). Phosphate monoesters
are selectively bound to specific regions within the
amylopectin molecule (Blennow et al., 1998, 2000a,b,
2002; Kasemsuwan and Jane, 1996). In the Triticeae
starches, the phosphorus content is very close to the
LPL content and there is a relatively small amount of
alpha-glucan phosphate monoesters (Kasemsuwan and
Jane, 1996). Other starches generally contain little phos-
phate, with the exception of potato starch where there is
essentially no lipid. Here, the phosphate monoester content
may exceed 0.1% (Kasemsuwan and Jane, 1996).
More details regarding starch composition may be found
elsewhere (Banks and Greenwood, 1975; Blanshard, 1987;
Buléon et al., 1998a; Fredriksson et al., 1998; Gallant and
Bouchet, 1986; Galliard and Bowler, 1987; Kent and Evers,
1994; Lineback, 1984; Morrison and Karkalas, 1990;
Swinkels, 1985; Tester and Karkalas, 2002; Zobel and
Stephen, 1996).
3. Amylose and amylopectin fine structure
Amylose and amylopectin (Fig. 1) have different
structures and properties which have been discussed
and reviewed by many authors (French, 1972; Banks
154 R.F. Tester et al. / Journal of Cereal Science 39 (2004) 151–165

and Greenwood, 1975; Lineback, 1984, 1986; Swinkels,

Wheat

1290
19.9

270
4.8
1985; Gallant and Bouchet, 1986; Blanshard, 1987; Galliard

82

73
and Bowler, 1987; Morrison and Karkalas, 1990; Kent and
Water chestnut

Evers, 1994; Seib, 1994; Zobel and Stephen, 1996; Buléon

160–8090 et al., 1998a; Fredriksson et al., 1998; Tester and Karkalas,
2002). Amylose is a relatively long, linear a-glucan
4210
20.2

5.76
800

420
containing around 99% (1 ! 4)-a- and (1 ! 6)-a- linkages

1.9
95

89
and differs in size and structure depending on botanical
580–22400

origin. Amylose has a molecular weight of approximately

Tapioca

1 £ 105 –1 £ 106 (Mua and Jackson, 1997; Buléon et al.,

6680
2660
20.0

2.51
384

340

1998a; Biliaderis, 1998), a degree of polymerisation (DP)

7.8
75

58
7

by number (DPn) of 324– 4920 with around 9 –20 branch

Sweet potato

points equivalent to 3 –11 chains per molecule (Hizukuri

840–19100

et al., 1981; Hizukuri, 1993; Morrison and Karkalas, 1990;

Mua and Jackson, 1997; Takeda et al., 1987; Wang and
5430
4100
20.2

1.31
324

380
73

11
30

White, 1994; Yashushi, et al., 2002; Yoshimoto, et al.,

6

2000). Each chain contains approximately 200 –700 glucose

2750–3320
210– 12900
20.0–21.1

920– 1110
2.64–3.39

residues (Morrison and Karkalas, 1990; Tester and Karka-

180– 216

250– 370
2.5– 4.3
73– 84

las, 2002) equivalent to a molecular weight of 32,400 –

None
Rice

69

113,400 (Morrison and Karkalas, 1990). Examples of

amylose structural elements are presented in Table 2.
840 –21800

Amylopectin (Fig. 1, Table 3) is a much larger molecule

than amylose with a molecular weight of 1 £ 107 –1 £ 109
Potato

6360
4920
20.5

1.29
384

670
7.3
80

(Biliaderis, 1998; Buléon et al., 1998a; Morrison and

3

Karkalas, 1990; Mua and Jackson, 1997) and a heavily

Nagaimo yam

branched structure built from about 95% (1 ! 4)-a- and 5%

800–20000

(1 ! 6)-a- linkages. The DPn is typically within the range

9600– 15,900 but comprises three major species with DPn
6300
2000
19.9

3.15
525
3.8
86

71

13,400 – 26,500, 4400 –8400 and 700 – 2100 (Takeda et al.,

2

2003). In common with amylose, the molecular size, shape,

390–13100

structure and polydispersity of the molecule varies with

Maize

botanical origin. Unlike amylose, however, there is great

2550
20.0

2.66
169

960

305
3.1
84

52

additional variation with respect to the unit chain lengths

and branching patterns. Amylopectin unit chains are
360–18900

relatively short compared to amylose molecules with a

broad distribution profile. They are typically , 18– 25 units
Trace
5010
2310
20.0

2.17
Lily

312

475
4.9

long on average (Hizukuri, 1985, 1986, 1988, 1993;

89

61

Morrison and Karkalas, 1990; Mua and Jackson, 1997;

480 –12300

Takeda et al., 2003; Wang and White, 1994; Table 3)

although the range is extended (19 –31) if high-amylose
Kuzu

3220
1540
20.0

2.09
228

320
4.8

starches are also included (Jane et al., 1999). The individual

76

47
10

chains can be specifically classified in terms of their lengths

440–14900

(chain lengths, CL) and consequently position within starch

Adapted from Morrison and Karkalas (1990).
Chestnut

granules (Hizukuri, 1985, 1986). The A and B1 chains (see

Properties of amylose from different sources

4020
1690
19.9

2.38
242

375

Fig. 2) are the most external (exterior) and form double

4.6
86

66
10

helices (and crystallites) within the native granules. Their

Iodine binding capacity (g 100 g21)

CL is typically , 12– 24 depending on genetic origin

½h at 22.5 8C in M KOH (ml g21)

(Franco et al., 2002; Hizukuri, 1985, 1993; Li et al., 2001;

Unbranched amylose (mol%)

Mua and Jackson, 1997) and starches with ‘A-type’

beta-amylolysis limit (%)

crystallinity, (most cereals, See Section 6) having shorter

chain lengths on average than ‘B-type’ starches (like
potato). With the exterior chains of amylopectin (A- and
Chain number

B1) comprising a range from CL 12 – 24 as previous

DPw (range)
DPw (mean)
DPn (mean)

P (mg g21)

mentioned, the A-type chains are typically CL 12 –16 and

DPw/DPn
Property
Table 2

B1 CL 20 – 24 (Hizukuri, 1985, 1986, 1988, 1993).

CL

Amylopectin molecules from high amylose starches contain

Table 3
Properties of amylopectin molecules from different botanical sources

Property Chestnut Kuzu Maize Potato Rice Sweet potato

R.F. Tester et al. / Journal of Cereal Science 39 (2004) 151–165

Japonica Indica Waxy (jap.) Normal ML fraction Tapioca Water chestnut

Iodine binding capacity (g 100 g21) 0.51 0 1.25 0.39–0.87 1.62– 2.57 0.38– 0.44 0.83–1.04 0.41
[h] at 22.5 8C in M KOH (ml g21) 176 160 168 224 134– 137 150– 170 175–193 187–200
beta-amylolysis (%) 55 57 60 55 58– 59 56– 59 55–56 57–58 57 59
DPn (103) 10.2 8.2– 12.8 4.7– 5.8 12.6
CL (average) 22.5 20.4–21.1 22 22.0–23.9 19– 20 21– 22 17.5– 18.3 20.8– 22.4 21.4–22.9 21.2 22
P (total) (mg g21) 61 158 15–27 604 8–13 11– 29 117–135 120–121 44
P (gluc-6-PO4) (mg g21) 43 121 3–5 8–13 9–28 95–115 100–102 24
Component chains
DPn
B4 119 104 101 115 130
F1 140 91 136 120– 180 85– 130 77–162 210
B3 70 75 69 69 65
F2 64 51 47 41– 44 42– 44 69–70 77
B2 42 48 42 42 43
F3 43 16 18 16– 17 16– 17 44–45 46
B1 20 24 22 21 19
F4 15 15 15
A 13 16 13 12 10
A:B molar ratio 0.89 0.79 2.2 0.89 0.82

Adapted from Morrison and Karkalas (1990).

155
156 R.F. Tester et al. / Journal of Cereal Science 39 (2004) 151–165
Fig. 2. Schematic representation of a section of amylopectin indicating the branching pattern of unit (1 ! 4)-a-chains (A, B1 –B3) joined together by (1 ! 6)-
a- linkages (branch points). Adapted from Hizukuri (1986).
relatively high proportions of very long chains (Yoshimoto
et al., 2000).
With respect to the structure of amylopectin (Fig. 2), the
A-chains of amylopectin are (1 ! 6)-a- linked by B-chains
which in turn can be linked to other B-chains or the
‘backbone’ of the amylopectin molecule, the single C-chain.
Depending on the CL and correspondingly the number of
(radial) clusters traversed within the native granule, B-
chains are referred to as B1 – B4 (one to four clusters).
Typical CLs for A, B1 –B4 chains for different starches
(after debranching with isoamylase) are 12– 16, 20 – 24,
42 –48, 69– 75 and 101 –119, respectively (BelloPerez et al.,
1996; Hizukuri, 1986, 1988; Mua and Jackson, 1997; Wang
and White, 1994). The ratio of A- to B-chains depends on
the starch source and is typically of the order of , 1:1 to
. 2:1 on a molar basis or , 0.5:1 to . 1:1 on a weight basis
(Morrison and Karkalas, 1990; Tester and Karkalas, 2002).
4. Intermediate material and phytoglycogen
According to some authors certain starches (such as high
amylose maize, oat and pea) contain an a-glucan with an
intermediate molecular weight between that of amylose and
amylopectin (Banks and Greenwood, 1975; Baba and Arai,
1984; Colonna and Mercier, 1984; Paton, 1979; Wang and
White, 1994). However, other investigators (Tester and
Karkalas, 1996) have disputed that intermediate material
exists (especially in oats) as a discrete fraction. Certain
maize and rice mutants (sugary 1, su1) contain a soluble
alpha-glucan which is similar to animal glycogen and for
this reason has been termed phytoglycogen for this reason
(Ball et al., 1996; Wong et al., 2003).
5. Interactions within starch granules
Both amylose chains and exterior chains of amylopectin
can form double helices which may in turn associate to
form crystalline domains. In most starches these are
confined to the amylopectin component. Early work by
Wu and Sarko (1978a,b) subsequently confirmed
subsequently confirmed by Rao et al. (1998) showed that
crystalline amylose double helices (A- and B-type poly-
morphs, see Section 6) with single helix pitch lengths of
2.1 nm (equivalent to double helical pitch of 1.05 nm) with
six glucose residues per single helix pitch. Although these
early studies suggested that the double helices were right-
handed, parallel helices, subsequent work showed they
may be left-handed (Oostergetel and van Bruggen, 1993),
anti-parallel and left-handed (Eisenhaber and Schultz,
1992), but most probably, parallel and left-handed (Imberty
et al., 1987, 1988a,b, 1991; Imberty and Pérez, 1988;
Gidley, 1989). In contradiction to these observations,
certain authors have proposed that although V-type
amylose complexes (below) may be left-handed, the
double helices (A- or B-type polymorphs) may be right-
handed (Veregin et al., 1987a).
For pure malto-oligosaccharides and amylolytic enzyme
resistant starches, the minimum CL required to form double
helices is 10, although shorter chains may form helical
structures if longer chains are present (Gidley and Bulpin,
1987; Gidley et al., 1995). The relatively short exterior
chains of cereal starch amylopectin molecules (CL 14– 20,
or , 20) favour the formation of A-type crystalline
polymorphs (of double helices), with the longer exterior
chains of tuber starches (CL 16– 22, or . 22) favouring the
formation of B-type polymorphs (Cheetham and Tao,
1998a; Gérard et al., 2000; Gidley and Bulpin, 1987;
Gidley, 1987; Hizukuri et al., 1983; Hizukuri, 1985, 1993;
Jane et al., 1997; Rao, 1998; Whittam et al., 1990) as
discussed below. The presence of helical structures within
starch granules (and solubilised/dispersed glucans) has been
extensively researched by 13C nuclear magnetic resonance
(13C NMR) and in particular 13C cross polarisation-magic
angle spinning/nuclear magnetic resonance (13C CP-MAS/
NMR) and 13C-single pulse magic angle spinning (13C SP/
MAS) which reveals the presence of, or capacity to form:
(i) double helical amylopectin (Bogracheva et al., 2001;
Cheetham and Tao, 1998b; Cooke and Gidley, 1992;
Gidley and Bociek, 1985; Gidley and Cooke, 1991;
Jacobs et al., 1997; Marchessault et al., 1985; Morgan
et al., 1995; Morrison et al., 1994; Paris et al., 1999,
 R.F. Tester et al. / Journal of Cereal Science 39 (2004) 151–165 157

2001; Qi et al., 2003; Tamaki et al., 1998; Tester et al., Table 4

1998, 1999, 2000; Veregin and Fyfe, 1985; Veregin Proportion of double helical material in starches of different botanical
origins
et al., 1986, 1987a,b; Yusuph et al., 2003),
(ii) spacer regions between the helices and branching/ Native starch Amount of double Authors
structural conformations (Falk et al., 1996; Gidley, helical amylopectin (%)
1985; Gidley and Bociek, 1988a,b; Morgan et al.,
1995; Tamaki et al., 1998), Maize, amylo 38 Gidley and Bociek, 1985
Maize, amylo 38 (with possibly some Tester et al., 2000
(iii) double helical amylose/alpha-glucan (Gidley and
amylose and amylose–
Bulpin, 1987; Gidley, 1988; Gidley and Bociek, amylopectin double
1988a; Gidley, 1989; Paris et al., 1999, 2001; Shi helices)
et al., 1998; Tester et al., 2000; Veregin et al., 1987a), Maize, normal 43 Cooke and Gidley, 1992
(iv) single helical material/amorphous-amylopectin Maize, normal 42 Gidley and Bociek, 1985
Maize, normal 38 Bogracheva et al., 2001
(Bogracheva et al., 2001; Cheetham and Tao, 1998b;
Maize, waxy 48 Cooke and Gidley, 1992
Gidley and Bociek, 1985; Gidley and Bociek, 1988a; Maize, waxy 53 Gidley and Bociek, 1985
Morgan et al., 1995; Paris et al., 1999, 2001), Maize, waxy 36–50 (depending on Paris et al., 1999
(v) single helical material/amorphous-amylose conditioning)
(Bogracheva et al., 2001; Cheetham and Tao, 1998b; Maize, waxy 48 Bogracheva et al., 2001
Pea 41–48 (includes Bogracheva et al., 2001
Gidley and Bociek, 1985, 1988a; Gidley, 1988, 1989;
mutants)
Morgan et al., 1995; Paris et al., 1999, 2001), Potato 40 Cooke and Gidley, 1992
(vi) amylopectin – amylose helices/co-complexes (Tester Potato 50 Gidley and Bociek, 1985
et al., 2000), Potato 64 Yusuph et al., 2003
(vii) amylose– lipid V-type inclusion complexes (Cheetham Potato 29–38 (depending on Paris et al., 1999
conditioning)
and Tao, 1998b; Gidley and Bociek, 1988a; Jacobs
Potato 48–55 Tester et al., 1999
et al., 1997; Morrison et al., 1993a – c; Morgan et al., Potato 48 Bogracheva et al., 2001
1995; Veregin et al., 1987a). Potato, waxy 52 Bogracheva et al., 2001
Rice 49 Gidley and Bociek, 1985
The proportions of double helices within native Rice 63 Qi et al., 2003
starch granules reported by various authors are presented Tapioca 44 Cooke and Gidley, 1992
Wheat 39 Cooke and Gidley, 1992
in Table 4. Note the variability in double helical content Wheat 46 Morrison et al., 1994
between starches of different botanical origins and within a Wheat 32 Bogracheva et al., 2001
given species. This variation may in part reflect difficulties
with respect to integrating the NMR spectra. Importantly,
not all of the amylopectin fraction in starches forms double of the presence of amylopectin. Indeed, certain authors
helices—as can been seen from Table 4. If all amylopectin propose that amylose disrupts amylopectin crystallite
were capable of forming double helices normal starches formation (Cheetham and Tao, 1998b). The formation of
would contain , 70% and waxy starches . , 95%. How- amylose lipid complexes in vitro is outside the scope of this
ever, this is simplistic since it is necessary to differentiate review and readers are referred to Snape et al., (1998).
between exterior chains that have the capacity to form
However, it is important to note that the lipid fraction within
double helices and non-helical forming regions within
starch granules is insufficient to saturate the amylose
amylopectin. In a recent paper (Qi et al., 2003) the
fraction and hence form fully saturated amylose –lipid
proportion of double helices as a fraction of the short
complexes. Hence, amylose is referred to as free-amylose
chains of amylopectin was calculated. These data show that
(FAM) or lipid complexed amylase (LAM) which may be
in fact . 80% of these chains can form double helices in rice
differentiated by iodine binding, NMR and synchrotron
starches.
Amylose does, as previously discussed, form part of most X-ray diffraction (Cheetham and Tao, 1998b; Czucha-
starches (even ‘very-waxy’ starches contain some amylose). jowska et al., 1998; Hoover, and Ratnayake, 2002; Hoover
Although amylopectin is the predominant crystalline et al., 2003; Le Bail et al., 1999; Li et al., 2001; Morrison,
component in starch (Veregin et al., 1986), where amylose 1985, 1988, 1989, 1992, 1993, 1995; Morrison and
may be considered as a diluent to amylopectin (Tester and Karkalas, 1990; Morrison et al., 1993a – c, 1994; Tester
Morrison, 1990a,b, 1992) there is NMR evidence that in and Morrison, 1992; Tester and Karkalas, 1996, 2002;
high amylose starches, amylose forms double helices (and Tester et al., 2000; Yuryev et al., 1998) and these forms may
potentially crystalline arrays) (Shi et al., 1998; Tester et al., have specific locations within starch granules (Morgan et al.,
2000). 1995). It has been reported that all of the lipid in native
The tendency for amylose molecules to aggregate, starches is complexed with some of the amylose, (as
especially around DP 100 (Gidley and Bulpin, 1989; previously mentioned), where 12.5% of the complex
Pfannemüller et al., 1971), is limited in starches because represents lipid (Morrison et al., 1993c). More recent data
158 R.F. Tester et al. / Journal of Cereal Science 39 (2004) 151–165
(Kiseleva et al., 2003), however, suggest that not all of the
lipid may be complexed.
6. Double helical arrays and crystallinity
As discussed above, starch alpha-glucans (mostly
exterior chains of amylopectin) form double helices.
These form more or less ordered arrays where the ordered
structures are crystalline entities. The traditional view was
that cereal starches generate A-type X-ray diffraction
patterns, tuber and high amylose starches, B-type, and
legume, root and some fruit and stem starches, C-type,
although it is now believed that C-type starch diffraction
patterns represent a combination of A- and B-type
polymorphs (Banks and Greenwood, 1975; Sarko and Wu,
1978; French, 1984; Veregin et al., 1986; Blanshard, 1987;
Gidley and Bulpin, 1987; Zobel, 1988a,b, 1992; Gernat
et al., 1990; Imberty et al., 1991; Cairns et al., 1997;
Biliaderis, 1998; Buléon et al., 1998a,b; McPherson and
Jane, 1999; Sevenou et al., 2002). The A- and B-type
polymorphic structures are represented schematically in
Fig. 3.
The double helices within the two polymorphic forms are
essentially identical with respect to helical structure
(Gidley, 1987; Imberty et al., 1991). However, the packing
of these double helices within the A-type polymorphic
(crystalline) structure is relatively compact with a low water
content, whilst the B-type polymorph has a more open
structure containing a hydrated helical core (Fig. 3).
Ordering of starch granules may vary from the hilum
(centre) to the periphery (Sevenou et al., 2002). Certain pea
mutants show different proportions of A- and B-type
polymorphs within the starch granule and serve as useful
models to understand the development of the different
polymorphs (Bogracheva et al., 1999; Hedley et al., 2002).
Indeed, the centres of pea starch granules are rich in B-type
whilst peripheral regions are rich in A-type polymorphs
(Bogracheva et al., 1998). There is a transition from A- to
Fig. 3. A- and B-type polymorphs of amylose. Adapted from Wu and Sarko (1978b).
B-type polymorphic forms within maize starch granules
accompanying a decrease in crystallinity but increase in
apparent amylose content (Cheetham and Tao, 1998a).
Interesting work has recently been done on starch
extracted from Chlamydomonas reinhardtii wild type and
mutant variants. Starches produced by strains containing no
defective starch synthases together with mutants carrying a
faulty granule bound starch synthase (GBSS) gene exhibited
A-type diffraction patterns with a high degree of crystal-
linity (Buléon et al., 1997). Strains with a mutant defective
soluble starch synthase (SSSII) gene formed B-type starch
with a low degree of crystallinity. Mutants exhibiting only
SSSI expression exhibited a hybrid (A þ B or C-type)
starch. Crystallites synthesised by GBSSI induce the
formation of B-type crystallites (Wattebled et al., 2002).
Certain pea mutations favour the formation of A- or B-type
polymorphs (Bogracheva et al., 1995).
7. Relative versus absolute crystallinity
The amount of crystallinity within starch granules has
been determined by a number of authors as presented in
Table 5. The table reflects variation identified by different
groups using different samples and different techniques.
Readers should also note that X-ray determinations of
crystallinity, although not discussed separately above,
include determinations of ‘absolute’ and ‘relative’ crystal-
linity (Blanshard, 1987; Buléon et al., 1998a; Tester and
Karkalas, 2002). The former differentiates between the
amorphous and crystalline component (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
(e.g. freeze-dried gelatinised material) with the ‘100%’
reference usually being generated by extensive acid
hydrolysis of starch in which all the amorphous (but not
crystalline) material has been eroded.
 R.F. Tester et al. / Journal of Cereal Science 39 (2004) 151–165 159

Table 5
Proportion of crystalline material in starches of different botanical origins

Native starch Technique Amount of crystalline References

amylopectin (%)

Maize X-ray diffraction Cheetham and Tao, 1998a

0% Amylose 42
28% Amylose 30
40% Amylose 22
56% Amylose 20
65% Amylose 18
84% Amylose 17
Maize X-ray diffraction 43 Cooke and Gidley, 1992
Maize, waxy 48
Potato 40
Tapioca 44
Wheat 39
Potato X-ray diffraction 26 Yusuph et al., 2003
Maize, waxy X-ray diffraction 37– 43 Paris et al., 1999
Potato 23– 53 (both dependent only
extent of conditioning)
Wheat X-ray diffraction 36 Morrison et al., 1994
Rice X-ray diffraction 47– 51 Qi et al., 2003
Oat X-ray diffraction 28– 37 Hoover et al., 2003
Lentils X-ray diffraction Hoover and Ratnayake, 2002
Black bean 17– 22
Chick pea 18
Lentil 19
Navy bean 20– 21
Smooth pea 20
Pinto bean 25– 26
Pea X-ray diffraction Bogracheva et al., 1999; Hedley et al., 2002
Wild type 20
r Mutant 19
rb Mutant 27
rug3-a Mutant 17
rug4-b Mutant 23
rug5-b Mutant 20
lam-a 22
Barley (includes fractions) X-ray diffraction 22– 27 Tang et al., 2001
Barley, normal X-ray diffraction 20– 24 Tang et al., 2002
Barley, waxy 33– 37
Maize Moisture regain 45 Nara, 1978
Potato 32
Sweet potato 42
Maize X-ray diffraction 39 Nara et al., 1978
Potato 25
Tapioca 38
Sweet potato 37
Rice 38
Wheat 36
Maize, amylo Deuterium ex 25 Morsi and Sterling, 1966
Maize, amylo X-ray diffraction 24
Potato Deuterium ex 24
Potato X-ray diffraction 28

8. Semi-crystalline structure and relationship with
growth rings
When viewed under the polarising microscope, native
starch granules show a dark birefringence cross (‘Maltese
cross’) which is characteristic of crystalline substances
whose index of refraction varies depending on
the direction that a light ray travels through the
substance. Furthermore, the insertion of a gypsum plate
(first order red selenite plate) in the light path of the
polarising microscope results in the appearance of four
opposite-sited blue and yellow quadrants; this is a typical
pattern of ‘spherulites’ composed of radially orientated
crystallites. The analogy originates from samples of
160 R.F. Tester et al. / Journal of Cereal Science 39 (2004) 151–165
obsidian (volcanic glass), which contain embedded
spherical clusters of radially arranged needle-like crys-
tals. Spherulites are also formed in some synthetic
organic polymers under certain conditions.
The microcrystalline nature of starch granules has been
the subject of numerous studies and a prolific list of
publications is available dating back to the early 1930s. The
subject area has been critically discussed by Banks and
Greenwood (1975) and reviewed by others (Blanshard,
1987; Buléon et al., 1998a; French, 1972, 1984; Galliard
and Bowler, 1987; Hoover, 2001; Kent and Evers, 1994;
Lineback, 1984, 1986; Morrison and Karkalas, 1990; Tester
and Karkalas, 2002; Zobel, 1988b, 1992; Zobel and
Stephen, 1996). Early attempts to relate crystallinity to the
molecular composition of the starch granule focussed on the
disposition of amylopectin molecules, whose branches are
envisaged as radiating from the hilum (the centre of growth)
towards the periphery of the granule. A model proposed by
A. Meyer as early as 1895 had a characteristic ‘trichitic’
(hair-like) structure (French, 1972). 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 (Banks
and Greenwood, 1975; Blanshard, 1987; Buléon et al.,
1998a; French, 1972, 1984; Galliard and Bowler, 1987;
Hoover, 2001; Kent and Evers, 1994; Lineback, 1984, 1986;
Morrison and Karkalas, 1990; Tester and Karkalas, 2002;
Zobel, 1988b, 1992; Zobel and Stephen, 1996). In high
amylose starches, however, the amylose may contribute
significantly to the crystallinity (Banks and Greenwood,
1975; Tester et al., 2000) although the exact nature of the
crystalline polymorphs may be different (Matveev et al.,
2001).
For 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 type) in the form of double
helices. These associate together to form ordered regions
or ‘crystalline lamellae’ (Fig. 4, see also previous
sections). Adjacent double helices give rise to regular
three-dimensional geometrical patterns. Such an array of
Fig. 4. Diagrammatic representation of the lamellar structure of a starch granule according to Donald et al. (1997). (A) Stacks of microcrystalline lamellae
separated by amorphous growth rings. (B) Magnified view of the amorphous and crystalline regions. (C) Double helical structures formed by adjacent chains of
amylopectin give rise to crystalline lamellae. Branching points constitute the amorphous regions.
atoms, molecules, or group of molecules, according to the
rules of crystallography, will interact with electromagnetic
waves of short wavelength (X-ray) to give a characteristic
diffraction pattern. This intertwining of adjacent branches
of amylopectin and the formation of helical structures was
originally proposed by French (1972) who also pro-
pounded the cluster (or racemose) hypothesis for the
structure of amylopectin. This hypothesis is now widely
accepted in principle and forms the basis of more
elaborate models (below).
X-ray analysis of starch granules is complemented by
scanning electron microscopy and by transmission electron
microscopy. More recently atomic force microscopy has
become an important tool for structural studies. However,
most useful information about the ordered arrangement of
alpha-glucan molecules is provided by X-ray diffraction
and related techniques. These techniques have reached a
high level of sophistication and modern instruments can
probe deeply into the starch granule and provide detailed
information. Wide angle X-ray scattering and small angle
X-ray scattering are used in parallel to reveal the complex
ultrastructure of the granule and quantification of crystal-
linity and polymorphic forms or crystalline laminates,
respectively (Tester, 1997). Small angle neutron scattering
is also used to understand architectural aspects of the starch
granules and complements the X-ray techniques. The use of
these techniques for this purpose and related broader
understanding of starch crystallinity has been discussed
extensively (Banks and Greenwood, 1975; Biliaderis, 1998;
Blanshard, 1987; Bogracheva et al., 1998, 1999, 2001;
Buléon, 1998a,b; Cameron and Donald, 1992; Cairns et al.,
1997; Cheetham and Tao, 1998a,b; Cooke and Gidley,
1992; Donald et al., 1997, 2001; Donald, 2001; French,
1972, 1974; Gallant and Bouchet, 1986; Galliard and
Bowler, 1987; Gérard et al., 2000; Gernat et al., 1990;
Gidley, 1987; Hedley et al., 2002; Imberty and Perez, 1988;
Imberty et al., 1987, 1988a,b, 1991; Jenkins et al., 1993;
McPherson and Jane, 1999; Sarko and Wu, 1978; Seib,
1994; Tester and Karkalas, 2002; Waigh et al., 1996, 1999,
2000a; Wu and Sarko, 1978a,b; Zobel, 1988a,b, 1992; Zobel
and Stephen, 1996; Table 5).
 R.F. Tester et al. / Journal of Cereal Science 39 (2004) 151–165
Starch granules (especially potato) viewed under the
optical microscope have a characteristic layered structure,
due to the so-called ‘growth rings’ (Gallant et al., 1997;
Smith, 1999; Baker et al., 2001; Donald, 2001; Donald et al.,
2001; Ridout et al., 2002; Li et al., 2003; Pilling and Smith,
2003). This feature is the result of multiple concentric shells
(or lamellae) of increasing diameter extending from the
hilum towards the surface of granules (like the layers of an
onion). These growth rings represent (periodical) diurnal
deposition of starch as originally defined by French (French,
1972; Kainuma and French, 1972; Robin et al., 1974),
usually based on data generated by acid or amylase
treatment of granules. Further, studies of growth rings
have resulted in a number of developments with respect to
the understanding of starch structure (below). Particularly
relevant in this respect is the eloquent work of Donald and
co-workers that has led to the modern view of the starch
granule (Donald et al., 1997; Fig. 4). The early work of
French provided an internal model of starch granules where
there is radial growth of amylopectin with 16 clusters per
growth ring and growth rings 120– 400 nm thick. The
double helices forming the subgrowth ring crystalline
lamellae represent , 5 nm thick regions (repeats) inter-
spersed with amorphous branch regions , 2 nm long.
Different crystalline polymorphs (A- and B-type) may be
accommodated in this model (Fig. 4).
The modern view regarding internal dimensions within
starch granule is largely due to the work of Donald and her
collaborators (Cameron and Donald, 1992; Donald, 2001;
Donald et al., 1997, 2001; Jenkins et al., 1993; Waigh et al.,
1996, 1999, 2000a,b). The quantification of dimensions
representing crystalline and amorphous lamellae, growth
rings and ‘blocklet’ type units within granules has, however,
evolved over many years. This has been reviewed in detail
elsewhere (Tester and Karkalas, 2002) and readers are
referred to this review for more details.
When hydrated starch is viewed with small angle X-ray
scattering, a peak is seen at a value of q of 0.063Å21. This
peak is attributed to the alternating crystalline and
amorphous lamellae of amylopectin and is not observed in
dry starch (Cameron and Donald, 1992). The same authors
concluded that wheat starch granules consist of stacks of
infinite lamellae embedded in a medium of specified
electron density. The lamellar repeat distance was found
to be 8.85 nm and some 16 such lamellae form the dense
material of a growth ring with a thickness of about 140 nm.
It is noteworthy that starch granules are far from being
perfect crystals. At best they consist of crystalline and
amorphous regions and the degree of crystallinity, as
discussed earlier (Table 5), is in the range 17 – 51%
depending on their origin and the methods used with an
average of about 35%. Furthermore, there is an optimum
moisture content (about 27%) at which maximum crystal-
linity is observed, while a minimum of 8% water is
necessary for the starch to give a diffraction pattern (Imberty
and Perez, 1988). This important observation is consistent
161
with the notion that water acts as a plasticiser originally
proposed by French (1984). This relative ‘fluidity’ of the
crystalline domains of starch granules has led to a ‘liquid
crystalline’ model for starch (Waigh et al., 1996) based on
data from small angle neutron scattering. This concept was
applied to explain the phenomenon of gelatinisation (Waigh
et al., 2000a).
A chiral side-chain liquid-crystalline polymeric model of
starch was developed from data obtained by the new
technique of scanning microfocus X-ray diffraction used in
the study of the double helix orientation and tilt of the
lamellae (Waigh et al., 2000b). These authors postulate a
self-assembly mechanism for the orientation of amylopectin
double helices in the presence of plasticiser (water). This
orientation is disturbed on dehydration of the granule. The
lamellae give rise to flat 9 nm reflections which are tilted on
average at an angle of 17.258 to the local fibre axis. A model
for helical lamellae has been proposed as being the product
of the chiral, side-chain, liquid-crystalline structure in
amylopectin in the presence of chiral bending forces
(Waigh et al., 1999). The use of scattering techniques in
the study of the internal structure of starch granules and the
plasticisation and self-assembly of amylopectin double
helices in granular starch have been recently reviewed
(Donald et al., 2001; Donald, 2001).
According to the Cameron and Donald (1992) model,
starch granules contain relatively broad radial growth rings
comprising semi-crystalline shells (about 140 nm thick)
separated by broad amorphous zones of at least the same
thickness. In this model the semi-crystalline growth rings
themselves (140 nm) contain 16 radiating clusters of
amylopectin exterior chains (A and B1) with the actual
length of the registered double helices about 6.65 nm
(equivalent to the crystalline lamellae) interspersed within
amorphous lamellae of about 2.2 nm (amylopectin (1 ! 6)-
a-branch points) (Fig. 4).
9. The complete picture with respect to starch structure
The literature does not provide answers to many
questions regarding starch architecture (that is how the
component parts interact to provide the three dimensional
structure). The location of amylose with respect to the
amylopectin in the granule is uncertain, as is the role of lipid
in cereal starches and the origin of phosphoester formation
(especially in potato starch). Why there is a distribution of
granules of different sizes is a matter of much debate but
there is little understanding of the reasons for this variation.
These questions are further complicated by lack of under-
standing of how the biosynthetic processes define archi-
tecture as opposed to simply components of starch
granules—although the partition between amylose and
amylopectin biosynthesis itself is still a mystery. These
challenges will undoubtedly be met in the near future. To do
this we will need to develop more sophisticated techniques
162 R.F. Tester et al. / Journal of Cereal Science 39 (2004) 151–165
to understand the developing starch granules with input
from biotechnologists and molecular biologists who are able
to modify the enzymes involved in the biosynthetic process.
10. Overview
The starch granule is a very complex structure. The
complexity is built around variations in the composition
(alpha-glucan, moisture, lipid, protein and phosphorylated
residues) and structure of the components. Over and above
this, there is an additional level of variation, which reflects
the way in which amorphous and crystalline elements are
associated. There is still much to learn about the complex-
ities of starch granules although considerable knowledge
gained over the last century led to new views regarding this
important component of many food and non-food products.
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