Artigo amido revisão

Starch/Stärke 2014, 66, 1–16 DOI 10.1002/star.201300238 1
REVIEW
Production, structure, physicochemical and functional properties
of maize, cassava, wheat, potato and rice starches
Jasmien Waterschoot, Sara V. Gomand, Ellen Fierens and Jan A. Delcour
Laboratory of Food Chemistry and Biochemistry, Leuven Food Science and Nutrition Research Centre (LFoRCe), KU Leuven,
Leuven, Belgium
In 2012, the world production of starch was 75 million tons. Maize, cassava, wheat and potato are
the main botanical origins for starch production with only minor quantities of rice and other
starches being produced. These starches are either used by industry as such or following some
conversion. When selecting and developing starches for specific purposes, it is important to
consider the differences between starches of varying botanical origin. Here, an overview is given
of the production, structure, composition, morphology, swelling, gelatinisation, pasting and
retrogradation, paste firmness and clarity and freeze–thaw stability of maize, cassava, wheat,
potato and rice starches. Differences in properties are largely defined by differences in amylose
and amylopectin structures and contents, granular organisation, presence of lipids, proteins and
minerals and starch granule size.
Received: October 3, 2013
Revised: January 21, 2014
Accepted: January 23, 2014
Keywords:
Gelatinisation / Production / Retrogradation / Starch / Structure
1 Introduction
Starch is an important source of carbohydrates in the human
diet. In addition, it is a versatile and widely used additive in
the food, paper, chemical and pharmaceutical industries.
Worldwide, 75 million tons of starch were produced in 2012
(http://www.zuckerforschung.at/) and marketed as native,
physically or chemically modified starch but also as liquid
and solid sweeteners. This paper gives an overview of the
production, chemical composition, structure and functional
properties of maize, cassava, wheat, potato and rice starches.
2 Starch production and uses
Of the above mentioned world starch production more than
half was produced in the United States. In the European
Union, 10 million tons were produced (http://www.zuck-erforschung.
at/).World production is estimated to increase to
about 85 million tons by 2015. The most important botanical
origins for producing starches are maize, cassava, wheat and
potato, respectively. Table 1 shows the estimated 2015
production for each starch. Almost 80% of the starch
production is from maize. In the USA, mainly maize starch is
produced, although (very) small amounts of wheat, potato and
rice starches are also manufactured [1]. In Europe, in addition
to maize (47%) and wheat starch (39%), also potato starch
(14%) and a very small amount of rice starch (<0.5%) are
produced [2] (http://www.aaf-eu.org/). Cassava starch is
mainly produced in Southeast Asia and Brazil [3]. Only a
small fraction (7% for maize, 4% for cassava, 0.9% for wheat
and potato and 0.007% for rice) of the raw material crops
are used for starch production.
In applications, starch is mainly used as starch derived
sweeteners and as native and modified starches. In 2011,
in the European Union, 57% of the produced starch was
converted to sweeteners, 23% was used as native starch
and 20% was modified (http://www.aaf-eu.org/). Important
starch derived sweeteners are glucose (syrups), (high)
fructose (syrups), and the polyols mannitol, sorbitol and
maltitol. Maltodextrins and oligosaccharide syrups are also
produced [1, 4]. Native starch is used because of its thickening
and gelling capacities. However, for a number of applications,
properties of native starches fail to meet process or product
requirements. This is why starches are also chemically or
Correspondence: Jasmien Waterschoot, Laboratory of Food
Chemistry and Biochemistry, Leuven Food Science and Nutrition
Research Centre (LFoRCe), KU Leuven, Kasteelpark Arenberg 20,
B-3001 Leuven, Belgium
E-mail: jasmien.waterschoot@biw.kuleuven.be
Fax: þ32-16-32-19-97
2014 WILEY-VCH Verlag GmbH Co. KGaA, Weinheim www.starch-journal.com

2 J. Waterschoot et al. Starch/Stärke 2014, 66, 1–16
physically modified. Cross-linking and substitution are
common modifications for starches used in food production.
Cross-linking of starch improves its acid, heat and shear
stability, while the introduction of bulky substituents on the
starch chains reduces retrogradation [5]. The EU exports
approximately 10% of its produced starch and starch
derivatives. Of the remaining 90%, 62% is used by the food
industry, 1%is used for feed and 37% is used by the non-food
industry (http://www.aaf-eu.org/). Major non-food starch
applications are in the paper and board, pharmaceutical (e.g.
tablet formulations, encapsulating agents), cosmetics, chem-ical
(e.g. adhesives, starch-based plastics) and textile indus-tries.
Modifications to meet requirements for non-food
applications include oxidation, cationisation, copolymerisa-tion,
hydrolysis and substitution [6].
3 Starch production processes
Starch production processes and their associated costs
depend on the botanical origin of the starch. Isolation of
starch from cassava and potato tubers is relatively simple
due to their tissue structure and their relatively low protein
and fat contents [7, 8]. Isolation of cereal starches is more
difficult as higher levels of these components need to be
removed [2, 9, 10].
3.1 Maize starch
Maize starch is commercially isolated by a wet milling
procedure. First, contaminating material is removed from the
bulk mass, after which the maize is steeped in water
containing a low level of sulphur dioxide for typically 24–40 h
at 48–52°C to soften the kernels and to obtain optimal milling
and separation of the maize components during the wet
milling phase. During steeping, the kernels absorb water and
sulphur dioxide [10]. The latter induces protein swelling and
dispersion because it cleaves inter- and intramolecular
disulphide bonds and thus reduces the average MW and
increases the solubility of the proteins [11]. During steeping,
lactic acid bacteria develop and produce lactic acid from the
available sugars. This causes a drop in pH to 4–5 which is
optimal for separation of the maize protein from starch. In
addition, lactic acid bacteria hydrolyse some highMWsoluble
protein [10]. An important side effect of the steeping process
is annealing of the starch granules, which changes their
structural properties and increases the gelatinisation temper-ature
[12]. After steeping, and wet milling, the germ is
removed and starch and protein are separated from non-starch
polysaccharides by sieving. After dietary fibre removal,
starch is separated from protein by centrifugation or
sedimentation and flash dried [10].
3.2 Cassava starch
Cassava roots are cleaned, peeled and pulverised into a pulpy
slurry. Starch is then isolated at ambient temperature.
The roots contain very small levels of protein (1%) and
impurities, which can all be removed by decantation. Non-starch
polysaccharides are removed by passing the slurry
through extractors with coarse and fine screens to remove
both large and smaller molecules. The slurry is then
dewatered by centrifugation and flash dried. A small level
of sulphur dioxide can be added to the process water to
control bacterial growth and facilitate the process [13].
3.3 Wheat starch
Wheat is dry milled to separate bran and germ from the
endosperm which is recovered as flour. Different processes
are used to separate starch and gluten proteins from wheat
flour, i.e. dough-ball, batter, dough-batter and high pressure
disintegration processes [9]. Van Der Borght et al. [14]
extensively reviewed the main processes. In these processes,
flour is mixed with different amounts of water to induce
gluten agglomeration or even gluten network formation. The
dough-ball and dough-batter process are carried out at
ambient temperature, while for the other processes warm
water (30–50°C) is usually used [9, 14, 15]. After formation
of batter or dough, starch and gluten can be separated based
on their difference in density (by centrifugation, in hydro-cyclones)
or particle size (by sieving) [9, 14, 15]. The starch
is then further purified with the use of hydrocyclones or
separators and decanters and dried [9].
Table 1. Production of starches of different botanical origins
Maize starch Cassava starch Wheat starch Potato starch Rice starch
Estimated world starch production 2015
(million tons/year)
64.6 10.2 6.0 3.4 0.05
World production raw material 2011
(million tons/year) (www.faostat.fao.org)
880 250 704 374 723
Main production countries USA, Japan, China,
South Korea [3]
Thailand, Indonesia,
Brazil, China [3]
France, Germany,
USA, China [3]
Netherlands, Germany,
France, China [2]
Belgium [2],
Thailand, Italy

Starch/Stärke 2014, 66, 1–16 3
3.4 Potato starch
Potatoes are ground to obtain a mixture of starch granules,
broken cell walls and the ‘potato juice’, a solution containing
proteins, amino acids, sugars and salts. Starch granules and
non-starch polysaccharides are separated from the juice by
centrifugation. Starch and large non-starch polysaccharides
are then separated by sieving. However, some smaller non-starch
polysaccharides and some proteins remain present in
the starch fraction. The remaining non-starch polysacchar-ides
can be removed by centrifugation based on the density
difference between these polysaccharides and starch. The
soluble protein is removed in a multi-stage, countercurrent
flow system. After this, water is removed with rotating
vacuum drum filters and flash drying [3].
3.5 Rice starch
Rice starch is traditionally isolated by an alkaline procedure.
Broken rice, a by-product of the conversion of brown rice into
white rice in a process referred to as milling, is steeped in a
0.3–0.5% sodium hydroxide solution for 12–24 h at 20–50°C.
As mentioned above, annealing of the starch granules may
occur at the higher process temperatures. In rice, protein and
starch are strongly associated. Sodium hydroxide solubilises
the rice protein and facilitates the isolation of starch during
subsequent wet milling of the kernels. After wet milling,
starch is kept in suspension to allow further solubilisation of
proteins. Non-starch polysaccharides are removed by filtra-tion
and the slurry is washed to remove the proteins,
neutralised and dried [2, 16].
4 Chemical composition of starch granules
Starch mainly consists of two polymers of a-D-glucose units
linked by a-1,4 and a-1,6 bonds. These are the nearly linear
amylose (AM) and highly branched amylopectin (AP). In
addition, starch contains minor constituents (lipids, proteins
and minerals) of which the levels vary with the botanical
origin (Table 2). Tuber and root starches [e.g. potato (0.1%)
and cassava starch (0.2%)] usually contain less lipid than
cereal starches (0.6–1.4%) [17, 18]. Lipid content is positively
correlated with AM content, i.e. most AM free starches
Figure 1. Structure of glucose-6-phosphate in an a-(1,4) bound
glucose chain.
contain negligible lipid levels [18]. Wheat starch contains a
high level of LPLs and some glycolipids, whereas lipids of
maize and rice starches consist of FFA and LPLs [18]. The
endogenous lipids reduce swelling and leaching of carbo-hydrates
during heating of starch in excess water by the
formation of AM lipid complexes [19–21]. In general, protein
(0.1–0.5%) and ash (0.1–0.3%) contents of starch are very
low [22–26]. Potato starch contains a relatively high level of
phosphorus (0.09%) in the form of phosphate monoesters
that are primarily covalently bound to AP [27]. The phosphate
is mainly ester linked at the C-6 (61%) (see Fig. 1) and C-3
(38%) positions, with only 1% linked at the C-2 position [28].
The presence of phosphate monoesters in potato starch has
large consequences for its swelling behaviour. Negatively
charged phosphate groups cause repulsion between adjacent
AP chains and allow rapid hydration and large swelling of the
granule [27]. Phosphorus in cereal starches (0.01–0.07%) is
mainly present in the form of phospholipids [26, 29].
5 Amylose and amylopectin
The AM content of normal starches varies between 14 and
29% [30–36]. Table 3 shows AM contents of potato, cassava,
wheat, maize and rice starches. The AM content of rice
starches varies from 0 to 40% [30, 37]. Variations in AM
content can be produced through cross-breeding, mutagene-sis
or transgenic breeding [38]. AM free starches are called
‘waxy’ and exist for maize, cassava, wheat, potato and rice
starches [30, 31, 39–45]. Starches with a high AM content
(30%) are also available. For maize, starches with an
AM content ranging from 50 to 90% are commercially
Table 2. Composition of starches of different botanical origins
Lipids (%) 0.6–0.8 [18, 26] 0.2 [17] 0.8–1.2 [18] 0.1 [17, 26] 0.6–1.4 [18]
Proteins (%) 0.4 [22, 26] 0.3 [23] 0.2–0.3 [22, 24] 0.1 [22, 26] 0.1–0.5 [25]
Ash (%) 0.1 [22, 26] 0.3 [23] 0.2 [22] 0.3 [22], 0.2 [26] 0.1 [25]
Phosphorus (%) 0.02 [29], 0.01 [26] 0.01 [29] 0.05 [29] 0.09 [29], 0.06 [26] 0.07 [29]
Lipid, protein, ash and phosphorus contents are shown as % of total dry weight.

Table 3. Contents and structural properties of amylose (AM) and amylopectin (AP) and degree of crystallinity of starches of different
available [44, 46]. Also for potato starch an AM content from
56 to 92% was obtained [31, 47–49], while the highest AM
content obtained so far for wheat (74%) [50] and rice
(56%) [51] is lower. Mutants with only slightly higher AM
contents than those of their regular counterparts have been
developed for wheat (31–56%) [41, 47, 52–54], cassava (28–
36%) [39, 55] and potato (27–37%) starches [31].
In essence, AM is a linear polymer. It contains hardly any
a-1,6 branch points (1%) [56]. AP is highly branched, with
5–6% a-1,6 linkages [18]. A starch characteristic is its DP, i.e.
the number of glucose units in the polysaccharide. Average
degrees of polymerisation can be calculated based on the
number or on the weight of the molecules. The number
average DP (DPn) and the weight average DP (DPw) are given
by formulas (1) and (2):
DPn ¼
P1
1 DPiðmi=MiÞ
P1
1
ðmi=MiÞ
ð1Þ
DPw ¼
P1
P1 DPimi 1
1 mi
ð2Þ
withmi the mass concentration andMi theMWof chains with
a DP¼i [57]. DPw is always higher than DPn, except for a
monodisperse polymer, in which case DPn equals DPw [58].
Table 3 lists DPn of AM and AP of the different starches. DPn
ofAMvaries from 570 to 8025 [59–65], while DPn of AP varies
from 4700 to 18 000 [62, 63, 66–68]. DPn values of potato and
botanical origins
AM content (%) 23 [34],
28 [32]
18–24 [33],
18 [31, 34]
25 [35],
26 [32, 34]
19–22 [31],
17 [34],
23 [32],
25–27 [35]
17–21 [32],
21 [34],
14–29 [30],
16–19 [36],
4–16 [37]
DPn
a) of AM 960 [61],
830 [63]
2660 [59],
3642 [60]
570 [59]
3827 [60],
1290 [61],
830–1570 [62],
1200–1500 [67]
4920 [59],
8025 [60]
920–1110 [64],
847–1118 [65]
DPn of AP 5100 [63],
15 900 [66]
– 5000–9400 [62],
13 000–18 000 [67]
11 200 [66] 4700–12 800 [68],
8200–10 900 [66]
Number of AM
molecules per g
starch 1017
9–10 2–3 3–11 1–2 6–9
Number of AP
molecules per g
starch 1017
2–6 – 2–6 3 2–4
CLb) of AM 335 [61],
340 [63]
340 [59] 250–320 [67],
135–255 [62],
270 [61],
300 [59]
670 [59] 230–370 [64]
CL of AP 28 [70],
24 [34],
20–21 [63],
20 [72, 75]
26 [70],
28 [34],
18–19 [73],
19 [72]
25 [70],
23 [34],
19–20 [67],
19–21 [62],
19 [72],
23 [69]
34 [70],
29 [34],
31 [71],
23 [72]
25–28 [70],
23 [34],
17–18 [73],
19–22 [68],
18–19 [72]
Average number of
chains per molecule
of AM
2.9 [61],
2.4 [63]
7.8 [59] 4.4–5.2 [67],
5.5–6.5 [62],
4.8 [61],
1.9 [59]
7.3 [59] 2.5–4.3 [64]
Average number of chains
per molecule of AP
240 [63] – 660–920
(based on [67])
500 (based on
[72] and [66])
220–700 [74]
Degree of crystallinity
as determined with
X-ray diffraction (%)
27 [86],
40 [85]
24 [86],
38 [85]
20 [86],
36 [85]
24 [86],
28 [85]
38 [85]
a) DPn, number degree of polymerisation
b) CL, average chain length

cassava AM are higher than those of maize, wheat and rice
AM. Based on DPn and the contents of AM and AP, the
number of AM and AP molecules per mass unit of starch can
be calculated. It can be estimated from data in Table 3 that a
given mass of regular starch contains more AM molecules
than AP molecules (except for potato starch), which is due to
their lower DPn.
The average chain length (CL) of AM varies from 135 to
670 glucose units per chain. The CL of potato AM is 670
glucose units while that of the other starches ranges from 135
to 370 glucose units [59, 61–64, 67]. Because of the highly
branched nature of AP, its CL (17–34 glucose units) is much
smaller than that of AM. Potato and cassava AP have a slightly
higher CL than AP of the cereal starches [34, 62, 63, 67–75].
AP of high AM starches has a similar or higher CL than AP of
the regular counterparts. In addition, these starches contain
some material with DPs and branching patterns intermediate
between those of AM and AP [46, 47, 76–79]. The average
number of chains per molecule can be calculated from DPn
and CL and is much smaller for AM (1.9–7.8) than for AP
(220–920) [59, 61–64, 66, 67, 72, 74].
With regard to determination of starch molecular size, it is
important to note that the analytical results depend on the
procedure used. Molecular size determinations require
complete dissolution of the starch polymers, with removal
of non-starch components that interfere with the analysis and
without starch loss or degradation during the procedure.
These requirements are challenging, so when interpreting
results, caution should be taken when comparing results
obtained by different procedures [80, 81].
6 Different levels of starch granule
organisation
Plants synthesise starch in a granular form. Starting from the
hilum, starch is deposited in alternating amorphous and semi-crystalline
concentric growth rings [16]. The semi-crystalline
growth rings consist of amorphous and crystalline lamellae.
AP is largely responsible for the crystalline character of starch.
Side chains of AP form double helices which are ordered in
clusters. The crystalline lamellae contain the double helices,
while the amorphous lamellae contain the AP branch points,
which connect the double helices [82]. The amorphous growth
rings consist of AMand less ordered AP [16]. AM and AP are
not present in separate regions, but highly intermingled in
the granule [83, 84]. The degree of crystallinity is usually
determined with X-ray diffraction [18]. It varies from 20 to
40% depending on the botanical origin (Table 3) [85, 86].
The packing of AP double helices can give rise to different
crystal structures or polymorphic forms. Cereal starch
crystals are generally packed according to the A-type packing.
Such packing is more dense than the B-type packing of e.g.
potato starch and high AM maize starches. Cassava starch
contains A-type or C-type crystals (a mixture of A- and B-type
crystals) [85, 87, 88]. In A-type starches, crystals are packed in
a monoclinic unit cell (a¼2.124 nm, b¼1.172 nm, c¼1.069
nm and g¼123.5°) with eight water molecules, whereas in
B-type starches, crystals are packed in a hexagonal unit cell
(a¼b¼1.85nm and c¼1.04 nm) with 36 water molecules
(see Fig. 2). Besides A- and B-type crystals, a third polymorph
exists, i.e. V-type crystals. In this polymorph, AM single
helices form inclusion complexes with e.g. iodine, alcohols
or fatty acids [18].
7 Morphology of the starch granule
The size and shape of starch granules (Table 4) depend on
the botanical origin and vary widely. Figure 3 shows the
granular morphology of potato, cassava, wheat, maize and
rice starches. Potato starch has very large, round or oval
granules (10–100mm), while rice starch has very small,
polygonal granules (3–8mm) [32, 89, 90]. Cassava starch has
round or truncated granules while maize starch granules are
polygonal. Both starches have granules with somewhat
similar dimensions (5–20mm for maize starch and 3–32 mm
for cassava starch) [31–33, 89]. While the shape and size of
waxy maize starch granules resemble those of regular maize
starch granules, high AM maize starches contain, in addition
to the normal polygonal granules, a number of filamentous
elongated granules [89, 91]. Wheat starch has a bimodal size
distribution, with small, round B granules (2–10mm) and
large, lenticular (20–32mm) A granules [32, 89, 92, 93].
Figure 2. Monoclinic unit cell of A-type crystals and hexagonal unit
cell of B-type crystals. Projection of the structure is in the ab plane.
Reprinted from International Journal of Biological Macromolecules,
23, Buléon, A., Colonna, P., Planchot, V. and Ball, S., Starch
granules: structure and biosynthesis, 85–112, Copyright (1998),
with permission from Elsevier.

Table 4. Morphological properties of granules of starches of different botanical origins
Shape Round, polygonal [32, 89] Round, truncated [31] Round, lenticular [32, 89] Round, oval [89] Polygonal [32, 89]
Diameter, range (mm) 5–20 [89] 3–32 [33] A: 20–35 B: 2–10 [32] 10–110 [31] 3–8 [32, 89]
Volume mean diameter (mm) 15 [32] 17–18 [31] A: 21–23 B: 6–7 [92, 93] 48–60 [31] 6 [90]
Number mean diameter (mm) (own data) 13 11 A: 17 B: 3 29 2
Number of granules per g starch 108 6 10 A: 2 B: 80 0.5 1600
Specific surface area (m2/kg) 270 220 A: 180 B: 670 75 670
Average granule diameters can be calculated based on the
number of granules or on their volume (or weight). Number
mean diameter (D [1,0]) and volume mean diameter (D [4,3])
can be calculated with formulas (3) and (4),
D½1; 0 ¼
P
n1
di
n
ð3Þ
D½4; 3 ¼
P
n1
d4i
P
n1
d3i
ð4Þ
where di is the diameter of particle i and n is the total number
of particles. Based on the number mean diameter, the
number of granules per gram starch can be determined. This
allows estimating that a given weight of rice starch contains
about 3000 times more granules than a same given weight of
potato starch. The specific surface area, i.e. the total surface
area per unit of volume, of rice starch is about ten times that
of potato starch. The values for specific surface area in Table 4
are probably an underestimation, as the presence of channels
and pores on the granule surface is not included in the
calculation. However, to the best of our knowledge, no
information is available on this. Especially cereal starches
contain pores [94, 95], while for potato and cassava starches
also depressions and protrusions on the granule surface
have been observed [96].
8 Gelatinisation properties
Heating starch in excess water (1:2 starch:water) above a
certain temperature, the ‘gelatinisation temperature’, dis-rupts
the molecular order of the granules and melts the
crystallites [97]. When relatively less water (1:2 starch:water)
is available, gelatinisation is partly postponed to higher
temperatures [16]. Table 5 lists gelatinisation onset (To), peak
(Tp) and conclusion (Tc) temperatures and melting enthalpies
(DH) of the different starches in excess water. DH represents
the amount of energy needed to melt all the crystals [16].
Wheat starch has the lowest gelatinisation temperature,
followed by potato, cassava and maize starches [22, 25, 26, 30,
31, 34, 71, 98–106]. Rice starches show a high variation in
gelatinisation temperature, which is at least partly due to the
high variation of AM content in regular rice starches [25, 30,
Figure 3. SEM pictures of maize (a), cassava (b), wheat (c), potato (d) and rice (e) starches (own data). Bars represent 10mm.

Table 5. Gelatinisation properties of starches of different botanical origins in excess water measured with DSC
Reference Starch-to-water ratio To (°C)a) TP (°C)b) Tc (°C)c) TcTo (°C) DH (J/g)d)
Maize starch [22, 26, 34] 1:3 64–67 68–71 72–75 8–11 11–12
[98] 3:7 63 67 72 9 9
[103] 1:4 67 71 – – 12
[104] 1:9 66 71 – – 12
Cassava starch [31, 34] 1:3 55–64 61–68 71–74 10–16 15–19
[98] 3:7 60 65 75 15 11
[103] 1:4 64–66 68–70 – – 11–14
[104] 1:9 65 71 – – 13
Wheat starch [22, 34, 100] 1:3 53–62 61–65 64–69 7–12 9–12
[98, 105, 108] 3:7 48–57 54–62 58–68 9–11 7–15
[103] 1:4 60 65 – – 10
Potato starch [22, 26, 31, 34, 71] 1:3 58–63 61–68 68–73 8–11 15–24
[98, 99, 101, 102] 3:7 57–66 61–70 67–75 7–12 12–18
[103] 1:4 62 65 – – 17
[104] 1:9 59 64 – – 17
Rice starch [34] 1:3 70 76 80 10 13
[37] 3:7 61–76 67–79 72–85 8–13 8–14
[25] 3:11 51–70 58–74 64–79 9–13 8–12
[104] 1:9 58 65 – – 12
[30] 1:2 57–76 63–79 71–83 8–19 17–20
34, 37, 104]. For a single starch granule, loss of molecular
order typically takes place over a very small temperature range
(1°C) [107], while gelatinisation occurs over a wider interval
for a population of granules. The gelatinisation temperature
range of starches mostly varies from 8 to 12°C [22, 25, 26, 30,
31, 34, 37, 71, 98–105, 108], although some exceptions with a
larger temperature range have also been described [30, 31,
98]. DH of potato starch is slightly higher than that of the
other starches. Wheat and maize starches have a low DH [22,
25, 26, 30, 31, 34, 37, 71, 98–105, 108].
The gelatinisation temperature is a measure of crystal
quality, while DH is a measure of both crystal quality and
quantity [109]. The presence of a relatively high amount
of short AP chains (DP14) reduces the gelatinisation
temperature, while a relatively high amount of longer chains
leads to an increased gelatinisation temperature [30, 31, 105].
According to Gidley and Bulpin [110], a chain DP of at least 10
is needed to form double helices. Consequently, starches with
a relatively high level of short AP chains have lower crystalline
order, which leads to a lower gelatinisation temperature.
Relatively high amounts of longer chains may be responsible
for both better stabilisation of the crystal structure over a
longer distance as well as for a higher gelatinisation
temperature [31]. Although CL of potato AP (23–34) is
higher than CL of the other starches (17–28) (Table 3), its
gelatinisation temperature is relatively low (To¼57–66°C)
(Table 5), probably because of the presence of phosphate
monoesters and the more open crystal structure of B-type
than of A-type starches [26, 34, 88]. The importance of the AP
chain length for gelatinisation temperature is expressed by
the Gibbs–Thomson Eq. (5) for lamellar crystallites

m 1 2g
Tm ¼ T0
DHlc
ð5Þ
This equation relates the melting temperature (Tm) to the
average crystalline layer thickness (lc), the melting tempera-ture
of an ideal crystal with an infinite crystal size (T0
m), the
lamellar surface free energy (g) and DH. Longer AP chains
lead to increased lc and thus also Tm. A high Tm is obtained
when branch chain lengths are relatively long (high lc) and
when crystal quality is high (low g and high DH) [111].
Branch chain length can also influence DH. Starches with
higher CL (e.g. potato starch) appear to have a higher DH[34].
DH is also correlated with crystallinity, i.e. a higher degree of
crystallinity (e.g. waxy starches) leads to a higher DH [26, 31,
34, 105]. Furthermore, the presence of lipids in cereal
starches might also explain the difference in DH between
potato and cereal starches. The exothermic formation of AM
lipid complexes can occur simultaneously with gelatinisation,
thereby lowering the measured DH [22].
9 Swelling power and solubility
At roomtemperature, starch granules can absorb up to 30% of
their weight in excess water without swelling noticeably [112].
a) To, gelatinisation onset temperature;
b) Tp, gelatinisation peak temperature,
c) Tc, gelatinisation conclusion temperature;
d) DH, gelatinisation enthalpy.

Table 6. Swelling power and solubility of starches of different botanical origins
Reference Starch concentration (%) Temperature (°C) Swelling power (g/g) Solubility (%)
Maize starch [103] 0.5 84 16 –
[115] 1.0 95 23 17
[122] 2.0 95 11 18
Cassava starch [103] 0.5 84 40–60 –
[114] 0.3 90 50 13
Wheat starch [103] 0.5 84 40 –
[105] 2.0 90 13–25 –
[122] 2.0 95 9 20
Potato starch [103] 0.5 84 168 –
[116] – 90 26–49 3–37
[114] 0.3 90 60–130 12–17
[115] 1.0 95 91 12
Rice starch [117] 1.0 95 25–45 13–32
[37] 2.0 90 17–39 –
However, during heating, starch granules absorb much
more water and swell. At higher temperatures, part of
the polysaccharides go into solution and leach out of the
granules [113]. Table 6 lists the swelling powers and
solubilities of the different starches. The former are the
amounts of water a starch can absorb per gram starch at a
certain temperature and at a certain starch concentration,
while the solubilities represent the percentages of leached AM
and AP at this temperature.
Potato starch has a much higher swelling power than
other starches [103, 114–116]. As mentioned above, this is
largely due to its negatively charged phosphate monoesters.
The swelling power of cassava starch is also higher than that
of the cereal starches [37, 103, 105, 114, 115, 117]. Granule
swelling is mainly attributed to AP and is inhibited by
AM [118]. As a result, waxy starches have a higher swelling
power than their AM containing counterparts [34, 114, 117,
118]. Removal of endogenous starch lipids reduces formation
of AM lipid complexes and increases the swelling power of
wheat and maize starches but not up to the level of swelling
that characterises tuber starches [21, 118]. The impact of
exogenous lipids on swelling of starch granules depends on
the type of lipid added and the temperature [19, 119–121]. The
absence of AM lipid complexes in potato and cassava starches
also contributes to their extensive swelling power [34, 114].
Starch solubility, determined at temperatures from 84 to
95°C, varies from 3 to 37%, with values for most starches
between 10 and 20% (Table 6) [103, 105, 114–117, 122]. Both
AM and AP leach out of granules of regular starches, while
evidently only AP leaches from waxy starches. Usually, in
excess water, AM leaching starts at relatively low temper-atures
(70°C), while AP only leaches out at higher
temperatures (90°C). This has been observed for potato
and cassava [114], rice [117], maize [123] and wheat [21, 119,
123] starches.
10 Pasting properties
Pasting can be described as a term encompassing the events
that occur after gelatinisation in a starch suspension, i.e.
further swelling of the granules, leaching of polysaccharides,
increase in viscosity and formation of an AM gel network [97].
Changes in viscosity depend on the concentration of the
starch suspension and can be measured with a Rapid Visco
Analyser or a Viscoamylograph. Figure 4 shows typical
pasting profiles for maize, cassava, wheat, potato and rice
starches (own data). The pasting temperature is that at which
an onset in viscosity rise can be observed. Table 7 lists pasting
temperatures, and peak and cold paste viscosities of the
different starches. While the term peak viscosity speaks for
itself, cold paste viscosity is that measured at the end of the
Figure 4. Pasting profiles of 8.0% suspensions of potato, cassava,
maize, rice and wheat starches in water measured with a rapid visco
analyser. The following temperature-time profile was used at a
stirring speed of 160 rpm: 1 min at 50°C, heating from 50 to 95°C
in 9 min, 10 min at 95°C, cooling from 95 to 50°C in 15 min,
10 min at 50°C (own data).

heating and cooling cycle. Potato and cassava starches have
lower pasting temperatures than cereal starches. Due to the
high level of negatively charged phosphate groups in potato
starch, viscosity development starts at lower temperatures.
Potato starch reaches a very high peak viscosity. The peak
viscosities of cereal starches are rather low because of their
lower swelling power [34, 37, 105, 116, 124, 125]. Waxy
starches reach higher peak viscosities than their AM
containing counterparts due to their higher swelling
power [117]. It is of note that starches with a high swelling
power are more sensitive to granule breakdown at high
temperatures than those with a lower swelling power. Pasting
profiles of potato starch show a large breakdown during the
holding phase at 95°C [114, 124].Waxy starches also have low
thermal stability and quickly disintegrate during pasting at
high temperatures [22].
During cooling of a starch suspension, viscosity
increases as the leached AM forms a gel network [126].
Cold paste viscosities of regular wheat, maize and rice
starches are at least as high as their peak viscosities, while
cold paste viscosities of potato and cassava starches
aremuch lower than their peak viscosities due to significant
granule breakdown [34, 105, 116, 124, 125]. After some
hours, AM forms stable crystalline structures, which are
acid resistant and have a melting temperature of about
150 °C [16, 126]. AMcrystallisation is largely responsible for
Table 7. Pasting properties of starches of different botanical origins
Reference Starch concentration (%) Pasting temperature (°C) Peak viscosity (mPa s) Cold paste viscosity (mPa s)
Maize starch [124] 8 82 2100 2000
[34] 8 82 1800 2000
Cassava starch [124] 8 67 2300 1400
[34] 8 68 2100 1300
Wheat starch [34] 8 89 1250 1850
[125] 9 – 2100 2950
[105] 11 82–90 2250–3400 2600–4000
Potato starch [124] 8 67 9500 3400
[34] 8 64 8400 2750
[116] 11 65–70 4100–7200 2300–3400
Rice starch [124] 8 71 2500 2050
[34] 8 80 1350 1900
[37] 6 72–80 1000–2400 1500–3500
Table 8. Retrogradation properties of starches of different botanical origins measured with DSC
Reference Starch-to-water ratio Storage conditions [time (days)/temperature (°C)] DH (J/g)a)
Maize starch [34] 1:3 7/4 5.8
[98] 3:7 7/22 3.0
Cassava starch [114] 1:3 28/20 No retrogradation detected
[34] 1:3 7/4 3.7
[98] 3:7 7/22 No retrogradation detected
Wheat starch [34] 1:3 7/4 3.6
[98] 3:7 7/22 2.0
[105] 3:7 7/4 0.7–3.0
[108] 3:7 28/5 10.1–10.6
Potato starch [114] 1:3 7/20 2.8–7.0
[114] 1:3 28/20 6.3–9.9
[34] 1:3 7/4 7.5
[98] 3:7 7/22 4.2
[99] 3:7 14/4 6.4–8.6
Rice starch [34] 1:3 7/4 5.3
[140] 1:2 28/RTb) 1.4–3.1, 7.8–11.6
[140] 1:2 28/6 5.7–11.1
a) DH, melting enthalpy of retrograded amylopectin;
b) RT, room temperature.

the initial firmness of a starch gel, while AP retrogradation
(cf. infra) is responsible for the long-term changes in gel
firmness [127].
11 Amylopectin retrogradation
Retrogradation is the process of crystallisation of AP
molecules in a starch paste [16]. The term retrogradation,
which means ‘to go back’, is here only used for AP and not
for AM, as strictly speaking only AP molecules can go back
to a crystalline entity [16]. AP crystals are acid labile and
melt at 50–60°C [87]. Table 8 shows the melting enthalpies
of retrograded amylopectin. The extent of retrogradation
highly depends on the storage time and temperature, starch
concentration and starch structural properties [45, 128].
It consists of three steps: nucleation, propagation and
maturation. Nucleation occurs faster at a relatively low
temperature, close to the Tg of the starch, while propagation
and maturation occur faster at a temperature close to the
melting temperature [129]. Besides storage temperature,
also the starch-to-water ratio has an important effect on
retrogradation. Water content should neither be too high
(80%) nor too low (30%) to allow retrogradation [130].
Evidently, AP structure also impacts retrogradation. Short
AP chains (DP 6–9) are less susceptible to retrogradation
than chains with DP 14–24 [114, 131]. Asmentioned earlier,
at least a DP of 10 is needed for forming double
helices [110]. This could explain the higher extent of
retrogradation of potato starch than of cereal starches under
the same conditions (Table 8) [35, 132]. During storage of
starch gels, interactions or even co-crystallisation with AM
can occur, especially when the AM content is relatively
high [133–136].
12 Starch functionality
12.1 Paste firmness
As mentioned above, due to AM crystallisation (short-term)
and AP retrogradation (long-term), firmness of starch gels
increases with time [115, 127]. This is an important aspect of
starch functionality in food products. Gel firmness can be
measured by compressing a gel by a certain percentage. It
depends on starch concentration, storage time and tempera-ture
[137]. Table 9 lists the firmness of gels of maize, cassava,
wheat, potato and rice starches. As different starch concen-trations
and storage conditions are used, it is difficult to
compare results. When comparing firmness values obtained
under the same conditions, maize, wheat and potato starches
show similar firmness values which are higher than that of
a cassava starch gel [138, 139]. This could be due to the
relatively low AM content of cassava starch and the large loss
of granular integrity in the gel [139]. Rice starch gels have a
broad range of firmness values (0.09–7N) [140]. AM content
is positively correlated with gel firmness. Waxy starch gels
have only a low firmness as a result of their poor gel network
formation [140]. In contrast, lipid content is negatively
correlated with gel firmness. The formation of AM lipid
complexes reduces the amount of AM available for network
formation [122, 141, 142].
12.2 Paste clarity
Another important characteristic in many starch applications
in food systems is paste clarity. The presence of relatively
short chains of AM or AP adds to opacity in food products.
While for a range of products including sauces, dressings and
puddings this is not a problem, products such as fruit fillings
Table 9. Firmness of gels of starches of different botanical origins
Reference Starch content (%) Storage conditions [time (days)/temperature (°C)] Compressed proportion of gel (%) Gel firmness (N)
Maize starch [138] 8 1/RTa) 40 0.64
[138] 8 7/4 40 1.03
[139] 6 1/4 33 0.93
[141] 6 0.2/25 11 0.04
[141] 6 1/4 11 0.05
Cassava starch [138] 8 1/RTa) 40 Not measurable
[138] 8 7/4 40 0.35
[139] 6 1/4 33 0.19
Wheat starch [138] 8 1/RTa) 40 0.69
[138] 8 7/4 40 0.70
[125] 9 1/4 Not reported 0.50
Potato starch [138] 8 1/RTa) 40 0.56
[138] 8 7/4 40 0.71
Rice starch [140] 8 2/6 10 0.09–4.17
[140] 8 14/6 10 0.12–7.05
a) RT, room temperature.

Starch/Stärke 2014, 66, 1–16 11
and jellies require the starch pastes to be of high clarity [143].
Paste clarity can be determined by measuring the light
transmittance (at 650 nm) of a 1.0% starch paste. Potato
starch (42–96% light transmittance) has the highest
paste clarity, followed by cassava starch (51–81% light
transmittance) and the cereal starches (13–62% light
transmittance) [144–148]. The clarity of waxy cereal starch
gels is better than that of their AM containing counter-parts
[144–146]. The very high paste clarity of potato starch
gels is caused by the absence of granule remnants in the
gel (cf. high swelling power and high granular break-down)
[144]. Pastes of cassava and waxy starches also
show few granule remnants. However, more interactions
between leached material lead to a higher opacity of these
gels. The low clarity of pastes of regular cereal starches
is caused by swollen granule remnants [144] and by the
presence of AM lipid complexes [149]. During storage
of starch gels, their paste clarity decreases as more and
more association of AM and/or AP molecules takes
place [146, 150].
12.3 Freeze–thaw stability
Freeze–thaw stability is an important quality aspect of starch
gels. When a starch gel undergoes repeated freezing and
thawing cycles, it releases water. The gel is then said to
undergo syneresis. The extent of syneresis is a measure for its
freeze–thaw stability [128, 151]. During freezing, phase
separation takes place as ice crystals are formed. As a result,
starch is concentrated in the unfrozen matrix. During
thawing of the gel, association of AM and AP takes place in
the more concentrated zones. As a result, increasingly
insoluble aggregates are formed. Ice crystals melt and the
water is not reabsorbed by the starch gel. A sponge like
structure develops and the melted water readily separates
from the gel [152].
Different factors have an influence on the freeze–thaw
stability. These include the freezing rate, the botanical origin
of the starch and its AM content, the starch concentration, the
number of freeze–thaw cycles and the sample prepara-tion
[128, 153]. The freezing rate is an important factor
affecting syneresis. Slow freezing favours formation of large
ice crystals which disrupt the gel structure to a larger extent
than small ice crystals [128, 152, 154]. Slow freezing also leads
to maximal ice formation and AM self-association which
result in significant structure loss and syneresis. The latter is
positively correlated with AM content [153]. Native, AM
containing starches have very low freeze–thaw stability.
Syneresis readings after several freeze–thaw cycles for maize
starch (47–79%) [153, 155, 156], cassava starch (50–67%) [153,
155], wheat starch (44–68%) [153, 155, 156] and potato starch
(60–76%) [153, 155, 157] are very high. Rice starch shows a
broad range of syneresis values (7–75%) [153, 155, 158, 159].
Waxy starches are intrinsically more stable than AM
containing starches, although they can also undergo strong
textural changes during freeze–thaw cycles [151, 155]. Waxy
rice starch has a very good freeze–thaw stability. A relatively
high proportion of AP side chains with DP 6–12, which is the
case for waxy rice starch, is believed to be at the basis of a
reduced extent of syneresis [153, 157]. In contrast, syneresis
of waxy maize starch gels is comparable to that of gels from
regular maize starch [153, 155]. For different waxy maize
starches, no correlation was observed between syneresis and
retrogradation enthalpy as measured with DSC. Syneresis
values were already maximal, when little, if any, double helical
order was present. This indicates that the early stages of
AM and/or AP association (before the formation of real
crystal structures) already cause syneresis due to network
formation [160].
The presence of lipids in cereal starches may also
contribute to a relatively high freeze–thaw stability. Granular
swelling and leaching of AM are reduced in the presence of
lipids. As a result, starch molecules remain close to each
other in the granules. This facilitates their reassociation and
in this way it may contribute to a low freeze–thaw
stability [153].
In conclusion, there are significant differences in
structural, physicochemical and functional properties of
starches of different botanical origins. Starch is widely used
by the food and non-food industry in a broad range of
products. The overview of starch properties provided in this
review can be of assistance when developing starches for
specific purposes. The botanical origin of the used starch has
a great impact on final product properties. Within a botanical
origin, in some instances the starch AM content is a major
determinant of its properties and starch should therefore be
selected with great care.
The authors gratefully acknowledge Flanders’ FOOD (Brus-sels,
Belgium) and the Methusalem programme ‘Food for the
future’ (KU Leuven) for financial support. J.A.D. is W.K. Kellogg
Chair in Cereal Science and Nutrition at the KU Leuven.
The authors have declared no conflict of interest.
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