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Trends in Food Science & Technology 49 (2016) 121e135

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Trends in Food Science & Technology


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Review

Buckwheat starch: Structures, properties, and applications


Fan Zhu
School of Chemical Sciences, University of Auckland, Private Bag 92019, Auckland 1142, New Zealand

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 25 September 2015
Received in revised form
11 November 2015
Accepted 7 December 2015
Available online 23 December 2015

Background: There is increasing interest in utilization of buckwheat for healthy food applications.
Common buckwheat (Fagopyrum esculentum) and tartary buckwheat (Fagopyrum tataricum) are cultivated in Asia, Europe, and Americas for various food formulation and production. Starch, the major
component of the seeds, may account over 70% of the dry weight. Therefore, it is expected that, to a large
extent, the quality of starch determines the quality of buckwheat food products. Furthermore, Buckwheat
starch has great potential for various food and non-food uses due to the unique structural and functional
features.
Scope and approach: This review summarises the current knowledge of chemical composition, chemical
structure of amylose and amylopectin, physical structure of granules, physicochemical properties,
enzyme susceptibility, modications, and uses of buckwheat starch. Suggestions on how to better understand and utilise the starch are provided.
Key ndings and conclusions: Amylose contents of buckwheat starch ranged from 20 to 28%. Starch
granules are most polygonal with size ranging from ~2 to 15 mm and an average diameter of ~6e7 mm.
The polymorph is A-type. The amount of extra-long unit chains of amylopectin (DP > 100) is higher than
that of cereal amylopectins. Low glycaemic index of buckwheat food products could be attributed to the
non-starch components. Buckwheat starch has been used as fat replacer, ingredient for extruded
products, nanocomposite material, and fermentation substrate for alcoholic beverage. It may be
concluded that buckwheat starch can be a unique source of specialty starch for innovative food and nonfood applications.
2016 Elsevier Ltd. All rights reserved.

Keywords:
Buckwheat starch
Composition
Structure
Property
Modication
Use

1. Introduction
Buckwheat belongs to the genus Fagopyrum of the family Polygonaceae (Cai, Corke, & Li, 2004). The most cultivated species
include Fagopyrum esculentum known as common buckwheat and
tartary buckwheat (Fagopyrum tataricum). Tartary buckwheat is
also known as bitter buckwheat due to the bitter taste and high
amount of avonoids present in the kernels. A much less cultivated
species with great local signicance in Asia is Fagopyrum dibotrys
(synonyms Fagopyrum acutatum and Fagopyrum cymosum) which is
known as golden or tall buckwheat (Liu, Li, Zhu, Li, & Shui, 2006a).
Buckwheat has great ecological adaptability. It can grow well in
marginal lands with harsh climatic and soil conditions. In particular, tartary buckwheat can grow at high altitudes even with low
precipitation and low temperature (Cai et al., 2004). Historically,
buckwheat was a popular food crop in Europe and Asia. The

E-mail address: fzhu5@yahoo.com.


http://dx.doi.org/10.1016/j.tifs.2015.12.002
0924-2244/ 2016 Elsevier Ltd. All rights reserved.

production declined greatly in the 20th century. This is due to the


introduction of nitrogen fertilizer and the competition of other
crops such as wheat (Ahmed et al., 2014). In recent years, buckwheat is becoming popular due to its various re-discovered
health benets and as a potential functional food source (Ahmed
et al., 2014). Statistics of Food and Agriculture Organization of the
United Nations (FAO) showed that, during the last two decades, the
world production of buckwheat decreased gradually towards 2010
before a slow increase from 2011 onwards (Fig. 1). The world production quantity of buckwheat reached 2,347,558 tonnes in 2013,
and the top ve producers were Russia, China, Ukraine, France, and
Poland (Supplementary Table 1). In terms of yield, the top 5
countries in 2013 were France (34,786 H g/Ha), Czech (24,000 H g/
Ha), Bhutan (23,608 H g/Ha), Croatia (20,526 H g/Ha), and Bosnia
and Herzegovina (15,434 H g/Ha) (FAOSTAT, 2015).
Buckwheat is becoming a research focus in recent years most
due to the healing and preventative roles in diverse diseases
(Ahmed et al., 2014; Cai et al., 2004; Guo et al., 2013; Li & Zhang,
2001). The proximate composition of major nutrients of

122

F. Zhu / Trends in Food Science & Technology 49 (2016) 121e135

Fig. 1. World production of buckwheat from 1993 to 2013 (FAOSTAT, 2015). Solid black points represent the actual production quantity. Dashed line represents the general trend of
production quantity through the 20 years. Data may include ofcial, semi-ofcial, or estimated data.

buckwheat seeds/our/groats falls within the ranges of the common cereals and pseudocereals (Supplementary Table 2).
Compared with cereals and other pseudocereals, buckwheat appears rather unique in the composition of some functional nutrients. Buckwheat protein is balanced in the amino acid composition
(relatively high lysine content). Buckwheat is relatively high in
dietary bre content. Minor important nutrients include polyunsaturated essential fatty acids (i.e. linoleic acid), minerals such as
Mg and K, vitamins (B, C, and E), D-chiro-inositol, fagopyritols, and
avonoids (e.g., rutin and quercetin) (Li & Zhang, 2001; Wijngaard
& Arendt, 2006). The presence of tannins, phytic acid, and protease
inhibitors lowers the enzyme susceptibility and digestion of starch
(Wijngaard & Arendt, 2006). The above-mentioned factors render
buckwheat various health benets. These include hypocholesterolemic activity, suppression of body fat accumulation, antioxidant
and free radical scavenging activities, anti-hypertension, antiinammation, reducing the occurrence of colon cancer, and so on
(Ahmed et al., 2014; Li & Zhang, 2001; Wijngaard & Arendt, 2006).
In particular, buckwheat can be a major ingredient of gluten-free
nez-Bastida,
food products for people with celiac diseases (Gime
 ski, 2015). Various food products have been
Piskua, & Zielin
developed from buckwheat in the light of the above-mentioned
health benets. These include vinegar, beer and whisky, bread
and steamed bread, breakfast cereals, porridge and soup, noodles
and pasta, pancakes, biscuits and cookies, and tea (Cai et al., 2004;
Hatcher, You, Dexter, Campbell, & Izydorczyk, 2008; Li & Zhang,
2001; Zhang, Gao, Gao, Yin, & Xi, 2011). The majority of these
buckwheat products are commercially available in niche markets
with limited size.
Starch is the major component of buckwheat seeds, and may
amount up to over 70% of the dry weight (Ikeda, Kishida, Kreft, &
Yasumoto, 1997). The properties and structures of starch are critical
for the quality of buckwheat food products (Hatcher et al., 2008;
Ikeda et al., 1997). For example, starch and amylose contents were
highly correlated to the springiness of heated buckwheat dough,
probably due to gelling capacity of amylose and starch (Ikeda et al.,
1997). Understanding the structure and functionality of starch provides a basis for the quality of buckwheat products, and help
commercialize them to a larger scale. Since the pioneering work on
buckwheat starch by Hurusawa and Miyashita (1963, 1964a, 1964b,

1965, 1966) from Japan, a great progress has been made worldwide. This review aims to summarise the present knowledge of
composition, structures, properties, modications, and uses of
buckwheat starch, and to provide future research directions.
2. Isolation
The content of starch in buckwheat our may amount up to 80%
of the dry weight (Hong, Ikeda, Kreft, & Yasumoto, 1996; Ikeda et al.,
1997). Wet-milling process has been used to isolate buckwheat
starch (Zheng, Sosulski, & Tyler, 1998). Basically, dehulled buckwheat groats are steeped overnight in aqueous solution that may
contain small amount of chemicals such as NaHSO3 (0.2%). The
hydrated groats are milled in a high-speed blender (e.g., Waring
blender), and the resulting slurry is screened and washed with
water to remove the brous materials (Zheng et al., 1998). Alternatively, groats are dry-milled into our, and the resulting our is
steeped in aqueous solution that may contain alkaline at a low
concentration. The steeped slurry is further milled in a blender
before passing through mesh. The resulting slurry is centrifuged,
and the protein layer on the top of the sediment is removed. The
starch cake is re-suspended in water. The washing step is repeated
to further remove the protein and other impurity before drying (Li,
Lin, & Corke, 1997). The steeping/washing process may involve
alkaline solution (e.g., 0.1% NaOH) to facilitate the separation of
other components from starch (Acquistucci & Fornal, 1997; Christa,


Soral-Smietana,
& Lewandowicz, 2009; Soral-Smietana,
Fornal, &
Fornal, 1984a; Zheng et al., 1998). It should be noted that differences in isolation method and experimental conditions may result
in differences in starch composition and properties.
3. Chemical composition
Great diversity in the chemical composition of starches from
both common and tartary buckwheat has been observed (Table 1).
Amylose content of buckwheat starches, a major attribute, varied
greatly among different studies. This could be attributed to the
buckwheat genetics and growing conditions (Gao et al., 2016;
Gregori & Kreft, 2012), as well as the measuring method
(Yoshimoto et al., 2004). The genetic and environmental variations

F. Zhu / Trends in Food Science & Technology 49 (2016) 121e135

123

Table 1
Chemical composition of buckwheat starch.
Buckwheat type
Common
Common
Common
Common
Common
Common
Common
Common
Common
Common
Common
Common
Common
Common
Common, tartary
Tartary
Tartary
Tartary
Tartary

No. of genotypes
1f
1
1a
3
2
30
1
1
1
5
7
1
1b
5
27 e
3
1
1
1

Amylose content (%)

Method for
quantication

25
25

IA
IC

21.5e25.3
22, 28.5
23.4e29.1
21.3
46.6
25
21.3e26.4
15.6e17.9, 25.7e26.5 c
17.1
3.8e16, 24.3e28.2
25.6e28.6,
34.5e34.5 g
21.1e27.4
22.7e25.7
15.6, 25.5 c
29.1
21.4, 24.5 g

IC
IC
IC
Con A
IC
IC
Con A
IA
IC
IC
IC
IC
IC
IA
IC
IC

Protein (%)

Lipid (%)

Ash (%)

0.4
0.5e0.75
1.04e1.30
0.3, 0.4

0.13
0.1e0.96
0.81e0.98
1.7, 1.8

0.63, 1.47

0.6
0.16

0.05
0.41

0.2
0.1

1.2

0.23

0.94e1.35

0.88e1.06

0.48

0.4

0.9

Reference
Hurusawa & Miyashita, 1965
Kim et al., 1977
Lorenz & Dilsaver, 1982
Li et al., 1997
Acquistucci & Fornal, 1997
Ikeda et al., 1997
Zheng et al., 1998
Qian et al., 1998
Praznik et al., 1999
Qian & Kuhn, 1999b
Yoshimoto et al., 2004
Christa et al., 2009
Gregori & Kreft, 2012
Lu & Baik, 2015
Noda et al., 1998
Li et al., 1997
Yoshimoto et al., 2004
Liu et al., 2015b
Lu & Baik, 2015

IA, iodine-binding amperometric titration-based method; IC, iodine-binding colorimetry-based method; Con A, concanavalin A-precipitation-based method; f, one genotype
harvested in summer and autumn; a, control sample, sample with defatting, and sample after acid hydrolysis (0.1 N HCL for 30 min); b, grain kernels of different plants from
one cultivar were selected and divided into normal amylose and low amylose types. c, 15.6e17.9% and 25.5% are the apparent amylose contents, and 25.7e26.5% and 15.6% are
the actual amylose contents which are from the data of the apparent amylose content subtracted by that of the isolated amylopectin; d, 3.8e16% is for low amylose mutants,
and 24.3e28.2% for normal grains; e, 17 genotypes of common buckwheat and 10 genotypes of tartary buckwheat; g, 21.4e28.6% from samples before defatting and
24.5e34.5% after defatting.

can be compared within the same study. For example, genetic diversity in amylose contents (e.g., 23.4e29.1% for 30 genotypes) was
found in common buckwheat starch (Ikeda et al., 1997). Mutants
with low amylose contents of 3.8e16% were noted (Gregori & Kreft,
2012). Amylose contents of buckwheat starch have been measured
by iodine-binding-based colorimetry and amperometry, and
concanavalin A-precipitation-based methods (Lu & Baik, 2015;
Qian & Kuhn, 1999b; Yoshimoto et al., 2004). Different methods
may give different results for the same sample. For example, the
amylopectin unit chains interact with iodine in solution, giving a
higher estimation of amylose contents of starch (Yoshimoto et al.,
2004). The endogenous lipids in buckwheat starch binding to
amylose gave a lower estimation of amylose contents (Lu & Baik,
2015). Concanavalin A-precipitation based method tends to give
true amylose contents by excluding the inuence of amylopectin
(Gibson, Solah, & McCleary, 1997). Therefore, the quantication
method should be noted when comparing the amylose contents
reported by different studies. In comparative studies, amylose
contents of common buckwheat starch were found similar to those
of tartary buckwheat starch, though only very limited number of
genotypes (1e3) was analysed for the latter (Gao et al., 2016; Li
et al., 1997; Yoshimoto et al., 2004). In general, amylose content
of normal starches from both common and tartary buckwheat
appeared similar to that of normal cereal starches (Gao et al., 2016;
Li et al., 1997). Compared with major cereal starches such as maize
starch, there is a lack of variations in the amylose contents of
buckwheat starch (e.g., lack of high-amylose and waxy genotypes).
Agronomic practice and growing conditions can inuence the
amylose contents of starch, on which there has been little studies
on buckwheat. One report from Japan showed that starch from
buckwheat harvested in summer had similar apparent amylose
content as that of the same genotype harvested in autumn
(Hurusawa & Miyashita, 1965).
Minor components of buckwheat starches include proteins,
lipids, ash, and phosphorus-containing compounds (Acquistucci &
Fornal, 1997; Li et al., 1997; Yoshimoto et al., 2004). Within the
same study, variation in the composition of these minor

components has been observed (Table 1), which may be attributed


to the crop genetics and growing conditions. Between different
studies, the variation appeared much larger than that of the same
study (Acquistucci & Fornal, 1997; Li et al., 1997; Lorenz & Dilsaver,
1982). This could be attributed to the differences in starch isolation
and quantication methods, as well as experimental errors, and to a
lesser extent, the crop genetics. In general, high amounts of the
minor components such as proteins (e.g., >1%) suggest the possibility of reducing their contents in the granules by further purication
(Baldwin,
2001).
Organic
phosphorus-containing
compounds were found either absent or in a small quantity
(0e95 ppm) in buckwheat starches (Yoshimoto et al., 2004).
Neutral lipids accounted for over 80% of the free lipid fraction in
starch. The rest was polar lipids including glycolipids and phos
pholipids (Soral-Smietana,
Fornal, & Fornal, 1984b).
4. Chemical structure
4.1. Starch
Starch was dissolved in DMSO (dimethyl sulfoxide) and analysed by high-performance size-exclusion chromatographyreective index-low angle laser light scattering detection (HPSECRI-LALLS) to reveal the molecular size and structure of common
buckwheat starch (Praznik, Mundigler, Kogler, Pelzl, & Huber,
1999). The weight-average DP (degree of polymerisation) of common buckwheat starch was 94,900 (with a range of 38,000 to
134,000), which was higher than that of amaranth (Amaranthus
cruentus), proso millet (Panicum miliaceum), wheat, and quinoa
starches, and lower than that of waxy maize starch (Praznik et al.,
1999). The sphere equivalent radius of glucan coils was 29 nm
(with a range of 2e40 nm), which was larger than that of wheat
starch. The relative packing density of glucan coils within the
occupied volume of buckwheat starch (3.2) was higher than that of
amaranth (1), proso millet (1.4), wheat (0.5), quinoa (0.9), and waxy
maize (2.9) starches. While this kind of analysis is simple and fast to
gain the structural information of starch, the drawback is that

F. Zhu / Trends in Food Science & Technology 49 (2016) 121e135

124

amylose and amylopectin are not fractionated in the rst place.


Therefore, their respective structures are not readily available.

reects the amount of short chains to that of long chains. Buckwheat amylopectins had lower values than that of rice, maize, and
wheat amylopectins. CL values of buckwheat amylopectins were
23e24 glucosyl residues, which were higher than that of cereal
amylopectins. The longer CL and lower short-to-long chain ratio of
buckwheat amylopectin could be attributed to the higher amounts
of extra-long chains (Hanashiro, Matsugasako, Egashira, & Takeda,
2005; Yoshimoto et al., 2004).
Long unit chains of amylopectin (DP > 100) (LCAP) have been
found most in non-waxy but not in waxy starches, suggesting their
biogenesis is related the granule-bound starch synthase (GBSS)
(Hanashiro et al., 2005). GBSS is responsible for the amylose synthesis. LCAP may impact the physicochemical properties (e.g.,
pasting and gel texture) of starch. In these studies on LCAP,
amylopectin was fractionated from starch by butanol-precipitation
based methods (Hanashiro et al., 2005; Yoshimoto et al., 2004).
Compared with cereal amylopectins, buckwheat amylopectins had
higher amount of LCAP (Yoshimoto et al., 2004). The weight percentages of long unit chains of buckwheat amylopectins (2 genotypes of common buckwheat and 1 genotype of tartary buckwheat)
were 12e13%, higher than that of indica rice (2 genotypes, 7 and
11%), wheat (3.4%), maize (5.6%), and sweetpotato (5.4%)
(Hanashiro et al., 2005). These LCAP were further isolated by precipitation with 1-butanol from isoamylase-debranched amylopectin (Hanashiro et al., 2005). LCAP of buckwheat had higher blue
values and lmax than the others. The number average DP and
number of chains per molecule of buckwheat LCAP ranged from 250
to 330, and 1.2e1.4, respectively. They were rather different from
that of amyloses, and similar to those of starches from other
botanical sources. Molecular size distribution data showed that
LCAP of buckwheat had higher amounts of large molecules,
compared with that of indica rice, wheat, maize, and sweetpotato
(Hanashiro et al., 2005). On molar basis, 6e8% of the LCAP molecules
of buckwheat were branched (resistant to isoamylase hydrolysis),
and their number of chains per molecule ranged from 4 to 6
(Hanashiro et al., 2005). There seemed to be no structural difference of LCAP between common and tartary buckwheat, though only
1 genotype of the latter has been analysed.
The external chains of amylopectin (from the non-reducing ends
to the branches) can be removed by b-amylase to make the b-limit
dextrins. The b-limit values (b-LV(%)) of buckwheat amylopectins,
representing the removed part, ranged from 52 to 56%, which are
similar to that of cereal amylopectins (Yoshimoto et al., 2004). The
internal part of amylopectin (from the reducing end to the branches)
contains the branches which are clustered to form the basic branching
zones termed building blocks (Bertoft, 2013). The composition and
structure of building blocks can be analysed by using a-amylase of
Bacillus amyloliquefaciens (Bertoft, 2013). So far, the building block
structure of buckwheat amylopectin remains unknown.

4.2. Amylose
Amylose and amylopectin were fractionated from starches of
common (7 genotypes) and tartary (1 genotype) buckwheat by
precipitation of amylose with 1-butanol and 3-methyl-1-butanol.
The isolated fractions were subjected to structural analysis
(Yoshimoto et al., 2004) (Table 2). The isolated amyloses had
iodine afnity (IA) of 19.3e20.2%, blue values (BV) of 1.36e1.48,
and lmax (wavelength with maximum adsorption) of 645e657 nm.
23e27% (molar basis) of the amyloses was found branched by
treating with b-amylase which is an exo-acting enzyme. The blimit values (b-LV%) ranged from 76 to 82%. Amylose was analysed
by uorescent-labelling/HPSEC method. On molar basis, two types
of molecules peaked at DP 1790 and DP 820, while on the weight
basis, only one type was noted. The molecular size (DP) ranged
from 1020 to 1,380, the numbers of chains per each molecule were
3.1e4.3, and the chain lengths were 280e380 glucosyl residues.
There seems to be little difference in amylose structure between
common and tartary buckwheat starch, though only one genotype
of the latter was analysed. The chemical structure of buckwheat
amyloses was similar to that of wheat and barley (Yoshimoto et al.,
2004).
4.3. Amylopectin
IA, BV, and lmax of amylopectins were 2.21e2.48%, 0.25e0.28,
and 582e583 nm, respectively (Yoshimoto et al., 2004) (Table 2).
Amylopectin was debranched by isoamylase and analysed by
HPSEC-RI with uorescent labelling and high-performance anionexchange
chromatography-pulsed
amperometric
detection
(HPAEC-PAD) (Table 2). Compared with B-type starches, buckwheat
starch (1 genotype) had a higher amount of short unit chains (DP
6e15), a lower amount of long chains (DP 25e60), and shorter
average unit chain length (CL), as revealed by HPAEC-PAD
(Sanderson, Daniels, Donald, Blennow, & Engelsen, 2006). The
molar amounts of fraction a (Fa) were ~63e64% according to the
HPSEC-RI chromatogram. The values are much higher than the
actual amount of A-chain (chains that carry no other chains) of any
type of amylopectins (Bertoft, Piyachomkwan, Chatakanonda, &
Sriroth, 2008) (A-chain as dened by Peat, Whelan, and Thomas
(1952)). Therefore, the fraction a (Fa) is a mixture of both A- and
B-chains, and the molar ratio (Fa Fb1)/(Fb2Fb3) is not equal to
the number of chains per cluster. The correct method for the
quantication of A-chain is through the 4,b-limit dextrins of
amylopectin, in which all the A-chains appear as maltose stubs
(Bertoft et al., 2008). Nevertheless, this ratio ((Fa Fb1)/(Fb2Fb3))

Table 2
Chemical structures of amylose and amylopectin (Yoshimoto et al., 2004).
Buckwheat type

No. of genotypes

IA

BV

lmax

CL

b-LV%

NC

DP

Amylose
Common
Tartary

7
1

19.3e20.2
19.5

1.37e1.48
1.36

645e657
657

280e380
340

76e82
78

3.1e4.3
3.3

1020e1380 a and 1070e1360 b


1120 a and 1230 b

No. of genotypes

IA

BV

lmax

CL

b-LV%

7
1

2.21e2.48
2.42

0.25e0.28
0.26

582e583
584

23e24
24

52e56
55

(Fa Fb1)/
(Fb2Fb3)
7.3
8

Amylopectin
Buckwheat
type
Common
Tartary

Fa

LCAP

63e64
63

12e13
13

a, modied Park-Johnson method; b, uorescent-labelling/HPSEC method; IA, iodine afnity (g/100 g); BV, blue value; lmax, wavelength of maximal absorbance (nm); CL, chain
length by the number of glucosyl residues; b-LV%, b-limit value (%); NC, number of chains; DP, number-average degree of polymerization; Fa, fraction of amylopectin unit
chains with DP of 6e12, Fb1, fraction of amylopectin unit chains with DP of 13e24, Fb2, fraction of amylopectin unit chains with DP of 25e36, Fb3, fraction of amylopectin unit
chains with DP of >37, values are on molar basis; LCAP, long unit chain of amylopectin, weight basis.

F. Zhu / Trends in Food Science & Technology 49 (2016) 121e135

5. Physical structure
5.1. Polymorphism and crystallinity
The adjacent external chains of amylopectin interact with each
other and water to form crystals in the form of double helices
z & Bertoft, 2010). The crystals are systematically arranged to
(Pere
give A- and B-type polymorph of starch. C-type is a blend of A- and
z & Bertoft, 2010). The polymorphism and degree of
B-types (Pere
crystallinity of buckwheat starch have been revealed by wide-angle
X-ray scattering technique (WAXS). Starches of both common and
tartary buckwheat had A-type polymorph (Christa et al., 2009; Gao
et al., 2016; Hurusawa & Miyashita, 1963; Li et al., 2014; Liu et al.,
2015a, 2015b; Lorenz & Dilsaver, 1982; Qian & Kuhn, 1999b;
Zheng et al., 1998; Zhou et al., 2009). The degree of crystallinity
of common buckwheat starch was 24.9% (Zhou et al., 2009), 38.0%
(Li et al., 2014), and 38.31e51.3% (5 genotypes) (Qian & Kuhn,
1999b). The large difference in the degree of crystallinity of starch
between different studies is more likely due to quantication
method, rather than the samples themselves. Therefore, the data
from different studies is impossible to compare. The polymorph
pattern can be affected by the growing conditions. Hurusawa and
Miyashita (1964b) showed that starch from buckwheat harvested
in summer had an A-type polymorph, and that of the same genotype harvested in autumn was Ca-type.
The internal chains of amylopectin are believed to form the
amorphous lamellae in the granules. The crystalline and amorphous lamella alternate with each other to form a ~9 nm repeating
unit, which further forms the semi-crystalline growth ring in the
z & Bertoft, 2010). Small angle X-ray scattering
granules (Pere
(SAXS) has been used to quantify the distance of this repeating unit
in buckwheat starch (Sanderson et al., 2006). SAXS data of buckwheat starch was mathematically modelled (Supplementary Fig. 1).
3 of buckwheat starch (0.01), an indication of how the lamellae
buckle, was much smaller than that of B-type starches (0.2e0.8).
The combined thickness of one crystalline and one amorphous
lamella was 9.3 nm. The differences in the molecular structure of
buckwheat amylopectin, especially the internal and building block
structure, may contribute to the difference in the SAXS results,
which remains to be studied.

125

microscopy (SEM), atomic force microscopy (AFM), and dynamic


light scattering technique (LS) (Table 3). The starch granules have
smooth surface and are most polygonal and less spherical (Fig. 2a)
(Gregori & Kreft, 2012; Hurusawa & Miyashita, 1963; Jane,
Kasemsuwan, Leas, Zobel, & Robyt, 1994; Liu et al., 2015a, 2015b;
Vallons & Arendt, 2009). Some small indentations were seen on
the granule surface, and may be attributed to the amylase activity in
the seeds (Gregori & Kreft, 2012; Lorenz & Dilsaver, 1982). The
diameter of buckwheat starch ranges from ~2 to 15 mm with an
average value of ~6e7 mm (Hurusawa & Miyashita, 1963; Qian,
Rayas-Duarte, & Grant, 1998; Zheng et al., 1998). Therefore, the
granules are more than two times smaller than maize starch
(Neethirajan, Tsukamoto, Kanahara, & Sugiyama, 2012). Compared
with normal starch, starch with low amylose content from mutant
samples (common buckwheat) is most spherical, and tends to be
fragile and get squashed during sample preparation for SEM analysis (Gregori & Kreft, 2012). These granules with low amylose
contents, which easily get cracked open during handling, appeared
to have an empty space in the center as observed by SEM. Granules
of common and tartary buckwheat starches had similar shapes, and
the latter appeared somewhat larger than the former in a
comparative study (Gao et al., 2016).
AFM generates high resolution images by feeling the starch
surface with a sharp probe instead of actual seeing, and the internal structure can be obtained by sectioning the granule with a
microtome (Ridout, Parker, Hedley, Bogracheva, & Morris, 2004;
Zhu, 2015). AFM has been used to visualize the internal granule
structure of common buckwheat starch (Fig. 2b) (Neethirajan et al.,
2012). The edge of the granules is polygonal, and the central hilum
was observed. Amorphous and crystalline growth rings on which
blocklets sit were seen. Growth ring structure becomes less obvious
towards to the central hilum. These observations conrm the
z & Bertoft, 2010).
general structure of any starch granules (Pere
Quantitative AFM analysis of starch (e.g., blocklet size and surface
roughness) may reveal some structural differences between buckwheat and other starches (Zhu, 2015), which may explain the differences in some functional properties as discussed in the
physicochemical property section below.
6. Physicochemical properties

5.2. Granule morphology

6.1. Swelling and solubility

The granule shape and dimension of buckwheat starch have


been probed by light microscopy (LM), scanning electron

Various studies reported the swelling power, swelling volume,


solubility, and amylose leaching of buckwheat starch in a wide

Table 3
Morphology of buckwheat starch granules.
Buckwheat type

Measuring method

Size (mm)

Shape

Reference

Common
Common
Common
n.a.
Common
Common
Common
Common
Common
Common
Common

LM
LM
SEM
SEM
LM
SEM, LM
SEM
SEM
SEM
SEM, AFM, LS
SEM

5e15
411, (average, 7.8)
5e10
2e7
214, (average, 6.5)
2.9e9.3, (average, 5.8)
2e6
2e9
2e19
48 a, 3e6 b

Hurusawa & Miyashita, 1963


Kim et al., 1977
Lorenz & Dilsaver, 1982
Jane et al., 1994
Acquistucci & Fornal, 1997
Zheng et al., 1998
Qian et al., 1998
Qian & Kuhn, 1999b
Christa et al., 2009
Neethirajan et al., 2012
Gregori & Kreft, 2012

Common
Tartary
Tartary

SEM
SEM
SEM

4e10
2e10
3e14

Polygonal and eclipsed


Polygonal
Round or polygonal with some indentations on surface
Polygonal
Polygonal
Polygonal
Polygonal, round
Polygonal, spherical, oval
Polygonal and irregular with a few being spherical
Polygonal, hilum in the granule center
Polygonal for normal samples, spherical for low
amylose samples with pinpricks on surface
Polygonal
Polygonal, oval, spherical with smooth surface
Polygonal

Li et al., 2014
Liu et al., 2015b
Gao et al., 2016

LM, light microscopy; SEM, scanning electron microscopy; AFM, atomic force microscopy; LS, light scattering technique; n.a., not available; a, size for normal samples, b, size
for samples with low amylose contents.

126

F. Zhu / Trends in Food Science & Technology 49 (2016) 121e135

Fig. 2. a. SEM images of common buckwheat starch after high pressure (left) and thermal (right) treatments (Vallons & Arendt, 2009). b. AFM imaging of internal granule structure
of buckwheat (F. esculentum) starch using intermittent contact mode. (a) Error-signal image and (c) corresponding topography image; (b) growth ring structure; (d) blocklet
structure; H, hilum (Neethirajan et al., 2012).

F. Zhu / Trends in Food Science & Technology 49 (2016) 121e135

range of temperature (60e92.5  C) (Table 4). The difference in


swelling power and solubility obtained from the same temperature
among different studies appeared rather large, as compared with
the difference between genotypes of the same study (Acquistucci &
Fornal, 1997; Li et al., 2014; Liu, Lv, Peng, Shan, & Wang, 2015b; Lu &
Baik, 2015). This may be more attributed to the differences in the
experimental conditions, rather than the buckwheat genetics. For
example, the speed and time of centrifugation, used for the formation of sediment and supernatant phases after heating, differed
from each other in various studies (e.g., 2000  g for 10 min
(Acquistucci & Fornal, 1997), 3000 rpm for 15 min (Liu et al., 2015a,
2015b), and 700  g for 15 min (Lorenz & Dilsaver, 1982)). Therefore, it is rather inaccurate to compare data from different studies.
Within the same study, diversity in swelling and solubilization
behaviours of buckwheat starch has been observed (Li et al., 1997;
Lu & Baik, 2015). It appears that starches of common and tartary
buckwheat were similar in swelling behaviour (swelling volume) (3
genotypes each) (Li et al., 1997), and the former had somewhat
higher solubility than the latter (2 genotypes each) (Gao et al.,
2016). More buckwheat genotypes should be employed systematically to reveal if the swelling and solubility of starch are speciesspecic.
Swelling and solubilization of buckwheat starch have been
compared with other starches (Kim, Hahn, Kwon, & DAppolonia,
1977). Compared with wheat and rye starches, common buckwheat starch started swelling at a higher temperature with higher
swelling power (Kim et al., 1977). This is supported by another
study that common buckwheat starch started swelling at a higher
temperature, and had higher swelling power and lower solubility,
as compared with wheat starch (Acquistucci & Fornal, 1997), but in
contrast with one study that buckwheat starch had lower swelling
power and solubility than wheat and maize starches when temperature was over 75  C (Qian et al., 1998). Compared with maize
and potato starches (1 genotype each), tartary and common buckwheat starches (2 genotypes each) had much lower solubility
(70e90  C), and tartary buckwheat starches had somewhat lower
solubility than common buckwheat starches (Gao et al., 2016).
The differences in the results of swelling and solubility within
buckwheat starches and among different types of starches may be
attributed to the differences in the starch structure and composition (Srichuwong & Jane, 2007). For example, higher contents of

127

amylose and amylose-lipid inclusion complex in buckwheat starch


reinforced the internal granules and restricted the swelling and
leaching (Qian et al., 1998). Structural basis for these discrepancies
among various studies remains to be explored.
6.2. Gelatinization measured by Koer hot-stage microscopy and
differential scanning calorimetry
Gelatinization of buckwheat starch has been analysed by Koer
hot-stage microscopy (KHSM) and differential scanning calorimetry (DSC) (Table 5). Apart from the gelatinization temperatures
(onset temperature (To), peak temperature (Tp), conclusion temperature (Tc)), KHSM can visualize the gelatinization process while
the DSC can obtain the enthalpy change (DH). Hot-stage microscopic study on buckwheat starch at an extremely low concentration showed that granules started to swell at 65  C, and continued
to swell up to 92.5  C, while keeping the granular shape (Hurusawa
& Miyashita, 1966). KHSM and DSC methods differ in the experimental conditions, and tend to give different results for the same
sample (Hari, Garg, & Garg, 1989). Scanning rate of DSC analysis
vre, 1991). 5  C/min and 10  C/min
may affect the results (Liu & Lelie
were used to analyse buckwheat starches in different studies (Li
et al., 1997; Yoshimoto et al., 2004). Water content may also inuence the gelatinization behaviours of starch (Zhou et al., 2009).
Decreasing water content (e.g., less than 50%) resulted in incomplete gelatinization when the heating temperature was lower than
100  C (Eliasson, 1980). In some of the reports with sufcient
amount of water for complete gelatinization (Qian & Kuhn, 1999a;
Vallons & Arendt, 2009; Zhou et al., 2009), DH of buckwheat starch
appeared much lower (e.g., 2.4 J/g) than that of some other reports
and also cereals (Eliasson, 1980; Li et al., 1997). Thus, these results
were excluded in this review. This may be attributed to the DSC
system that was not properly calibrated, the starch samples that
were severely damaged in the rst instance, and to a less likelihood,
the genetics of the buckwheat variety. Diversity in gelatinization
behaviours of buckwheat starch has been observed (Lu & Baik,
2015; Noda et al., 1998; Yoshimoto et al., 2004). For example, Tp
and DH of starches from 27 buckwheat genotypes (both common
and tartary buckwheat) ranged from 57.2 to 66.7  C and from 9.4 to
13.9 J/g, respectively, though the difference between common and
tartary buckwheat starches was not analysed (Noda et al., 1998).

Table 4
Swelling and solubility of buckwheat starch.
Buckwheat type

Common
Common
Common
Common
Common
Common
Common
Common
Common
Common
Tartary
Tartary
Tartary
Tartary
Tartary

No. of genotypes

Parameters

Temperatures ( C)
60

70
9.33
7.53e9.05
1.92e2.27
9.6, 10.3
1.5, 2.7
17.29
7.08

1
1a
1
2
2
1
1
5
5
5

SP
SP
S
SP
S
SP
S
SP
S
AML

2.95
2.33e2.54
0.45e0.50
4.4, 5.3
0.6, 0.9
5.35
3.94

2
1
1
2
1
1
1

S
SP
S
S
SP
S
AML

1.7,2.8
4.12
2.83
0.9, 1.1

5.7,5.9
10.66
7.44
4.2, 4.6

Reference
80

13.5, 18.5
4.5, 6.0
27.3
10.09

10.9
11.45
14.68
7.7, 9.5

90
22.88
10.65e11.04

Kim et al., 1977


Lorenz & Dilsaver, 1982

22.9, 25.5
9.2, 10
34.2
24.44
22.4e24.9 (92.5)
4.1e5.9 (92.5)
94.5e146.1 b
3.7e5.3 c
11.2, 12.1
13.02
20.57
9.9, 10.4
19.6 (92.5)
5.3 (92.5)
86.4 b, 4 c

Acquistucci & Fornal, 1997


Li et al., 2014
Lu & Baik, 2015

Gao et al., 2016


Liu et al., 2015b
Gao et al., 2016
Lu & Baik, 2015

SP, swelling power; S, solubility (%); AML, amylose leaching; gure in the parenthesis denotes the actual temperature used; a, control sample, defatted sample, and sample
with acid hydrolysis (0.1 N HCl for 30 min); b, amylose leached (mg) from 100 g of starch (db); c, amylose leached (mg) per gram of apparent amylose (db).

F. Zhu / Trends in Food Science & Technology 49 (2016) 121e135

128

Table 5
Gelatinization properties of buckwheat starch by DSC and KHSM.
Buckwheat
type

No. of
genotypes

Technique

Common
Common
Common
Common
Common
Common
Common
Common
Common
Common
Common
Common
Common, tartary
Tartary
Tartary
Tartary
Tartary
Tartary

1
1a
3
1
1
5
7
1b
1
1
5
2
27c
3
1
1
1
2

KHSM
KHSM
DSC
DSC
DSC
DSC
DSC
DSC
DSC
DSC
DSC
DSC
DSC
DSC
DSC
DSC
DSC
DSC

Starch: water
ratio (w:w)

4:13
1:2.28
11:42
1:11.5 to 1:2.5
1:2
1:3 to 3.5:1
1:3
1:4
1:2
1:2
3:7
4:13
1:2
1:3.5
1:2
1:2

Scanning rate
( C/min)

10
10
10
10
5
5
5
10
10
10
10
10
5
10
10
10

To ( C)

Tp ( C)

61
61e62.5
57.8e62.4
61.1
62.7
58.6e64.1
59.5e64.1
52.4e64.3
60
61.2
58.6e60.2
62.5, 63
51.5e62.3
62.8e64.3
61
73.5
63.1
61.6, 62.4

68e70
66.3e68.8
68.4
69
64.8e69.6
63.7e68.4
63.3e67.6
65.6
66.1
61.5e64.3
66.7, 66.8
57.2e66.7
68.8e70.8
64.1
78
67
66.2, 66.3

Tc ( C)
65
74e76
77.3e79.2
80.8
80.9
70.8e80.8
81.7e85.8
72.9e78.4
71.8
75.2
70e73
71.6, 72.1
79.9e81.3
81.7
83.9
75
69.1, 71.3

DH (J/g)

9.1e10
10
12.7
14.5e15

9.0
14e15.3
7.8, 8.3
9.4e13.9
9.7e11.0
14.7
19.8
14.1
7.5

Reference
Kim et al., 1977
Lorenz & Dilsaver, 1982
Li et al., 1997
Qian et al., 1998
Zheng et al., 1998
Qian & Kuhn, 1999a and 1999b
Yoshimoto et al., 2004
Zhou et al., 2009
Vallons & Arendt, 2009
Li et al., 2014
Lu & Baik, 2015
Gao et al., 2016
Noda et al., 1998
Li et al., 1997
Yoshimoto et al., 2004
Liu et al., 2015b
Lu & Baik, 2015
Gao et al., 2016

DSC, differential scanning calorimetry; KHSM, Koer hot-stage microscopy; To, onset temperature; Tp, peak temperature; Tc, conclusion temperature; DH, enthalpy change; a,
control sample, sample with defatting, and sample with acid hydrolysis (0.1 N HCl for 30 min); b, a range of moisture content; c, 17 genotypes of common buckwheat and 10
genotypes of tartary buckwheat.

There appears to be little difference in the DSC parameters between


common and tartary buckwheat starches in comparative studies
(Gao et al., 2016; Li et al., 1997). Amylose content had little correlations with gelatinization prole, while the unit chain length
distribution of amylopectin was highly correlated with To, Tp, and
DH (Noda et al., 1998). The amounts of unit chains of DP 7e11 and
DP 12e17 were negatively and positively correlated to, Tp, and DH,
respectively (Noda et al., 1998). Unit chains with DP 7e11 may be
too short to from double helices, and they tend to cause defects in
the crystals (which may be most composed of chains with DP
12e17) (Srichuwong and Jane, 2007).
Gelatinization of buckwheat starch has been compared with
that of other starches in the same study (Gao et al., 2016; Qian et al.,
1998; Zheng et al., 1998). Compared with maize and wheat
starches, starch of common buckwheat had a wider gelatinization
temperature range (Qian et al., 1998). This suggests that buckwheat
starch is more structurally heterogeneous than the other two, and
may result from milling process or genetics. Compared with rice
and maize starches (1 genotype for each), common buckwheat
starch (1 genotype) had lower To and Tp, and higher DH (Zheng
et al., 1998). To, Tp, and Tc of common and tartary buckwheat
starches (2 genotypes each) were lower than those of maize
starches and higher than those of potato starch (1 genotype each).
Both had lower DH than maize and potato starches (Gao et al.,
2016). Buckwheat starches (common and tartary buckwheat) had
higher Tp and Tc than wheat starch (Li et al., 1997; Qian et al., 1998).
The gelatinization of starch is inuenced by interactive factors
including granule morphology, amylose content, molecular structures of amylopectin and amylose, and minor-component contents,
in which buckwheat starch differs from other starches (Srichuwong
and Jane, 2007).
The endogenous lipids in buckwheat starch form V-type inclusion complexes with amylose which have been analysed by DSC (Lu
& Baik, 2015; Qian et al., 1998). DH of melting of amylose-lipid inclusion complexes in buckwheat starch (6 genotypes) ranged from
0.9 to 1.8 J/g (Lu & Baik, 2015). DH of re-melting these amylose-lipid
inclusion complexes ranged from 1 to 1.7 J/g (Lu & Baik, 2015).
Amylose-lipid inclusion complexes of common buckwheat starch
(1 genotype) had To of 70.8  C, Tp of 84.6  C, Tc of 99.7  C, and DH of
2.0 J/g, respectively (Qian et al., 1998). Compared with that of maize
and wheat starches, the melting temperatures of inclusion

complexes were lower and the DH was higher. The difference in the
thermal properties of amylose-lipid inclusion complexes between
buckwheat starch and others could be due to the difference in the
content and structure of amylose and lipids.
6.3. Pasting
Pasting properties of buckwheat starches have been analysed by
Rapid Visco-Analyser (RVA), Brabender Viscoamylography (BVA),
Brabender Amylograph (BA), and Brabender Micro Visco-AmyloGraph (MVAG) at various starch concentrations (5.5e11%)
(Table 6). It is impossible to compare the results from different
studies employing different instruments and starch concentrations.
For example, gelatinization of buckwheat starch (5 genotypes) was
studied by DSC, BVA, and RVA (Qian & Kuhn, 1999a). Comparison
between the results of BVA and RVA on the same samples revealed
little correlations (Qian & Kuhn, 1999a). It is also noted that gelatinization temperatures of buckwheat starch measured by DSC
were lower than those of BVA and RVA, and may be attributed to
the increasing pressure generated during heating in the sealed DSC
crucibles (Qian & Kuhn, 1999a). The different aspects of gelatinization measured by various methods may differentially reect
various aspects of granule structure. Within the same study, diversity in pasting properties has been observed (Lu & Baik, 2015;
Yoshimoto et al., 2004). For example, PV of buckwheat starch
from 7 genotypes ranged from 226 to 261 RVU (Yoshimoto et al.,
2004). Differences in pasting pattern between common and tartary buckwheat starches have been observed (Gao et al., 2016; Li
et al., 1997). One study (2 genotypes for each species) showed
that common buckwheat starch had lower PV than tartary buckwheat starch, while the other study (3 genotypes for each species)
observed the opposite pattern (Li et al., 1997). This may be attributed to the crop genetics and growing conditions. Indeed, another
study showed that pasting properties were affected by the growth
environment (Hurusawa & Miyashita, 1964b). Starch from buckwheat harvested in summer had a lower pasting temperature by
3  C and a higher peak viscosity (PV) than that of the same genotype harvested in autumn (Hurusawa & Miyashita, 1964b).
Pasting of buckwheat starch has been compared with that of other
starches and showed differences (Acquistucci & Fornal, 1997; Gao
et al., 2016; Li et al., 1997; Praznik et al., 1999; Qian et al., 1998;

F. Zhu / Trends in Food Science & Technology 49 (2016) 121e135

129

Table 6
Pasting properties of buckwheat starch.
Buckwheat type

No. of genotypes

Instrument

Starch concentration (%)

PV

BD

SB

Common
Common
Common
Common
Common
Common
Common
Common
Common
Common
Common
Common
Tartary
Tartary
Tartary
Tartary

1
5
2
7
1
2
5
1
n.a.
1
1
5
1
1
2
1

RVA
RVA a
RVA a
RVA
RVA a
BVA
BVA
BVA
BA
BA
BA
MVAG
RVA
RVA a
RVA a
MVAG

6
8
8
9
11
5.5 b
8
10
8
9
7
8
9
10.7
8
8

148
2280e3098
1629, 1685
226e261
4589
540, 790
800e1000
1740
680e1020
1170

48
139e487
315, 412
37e98
2418

164
1348e1620
737, 743
180e226
1816

40100

560e1070

1304e1382
242
3803
2121, 1928
1154

162e247
67
1612
652, 825
188

PT
71e80
63.8, 63.9
68.6e71.0
68.8
58, 55
75e84
64.3e67.7
64.5

620
531e575
223
2017
803, 954
564

67.5e69.2
68.5
62.8
62.8, 63.2
75.5

Reference
Qian et al., 1998
Qian & Kuhn, 1999a
Gao et al., 2016
Yoshimoto et al., 2004
Li et al., 2014
Acquistucci & Fornal, 1997
Qian & Kuhn, 1999a and 1999b
Praznik et al., 1999
Hurusawa & Miyashita, 1964a
Kim et al., 1977
Zheng et al., 1998
Lu & Baik, 2015
Yoshimoto et al., 2004
Liu et al., 2015b
Gao et al., 2016
Lu & Baik, 2015

RVA, Rapid Visco-Analyser; BVA, Brabender viscoamylography; BA, Brabender Amylograph; MVAG, Brabender Micro Visco-Amylo-Graph; PV, peak viscosity; BD, breakdown;
SB, setback; PT ( C), pasting temperature where viscosity takes off; the units of PV, BD, and SB for RVA, BA, and MVAG are RVU, BU, and BU, respectively, except for where
specied; a, viscosity unit is cP; b, mixture of starch (25 g), carboxymethylcellulose (3.5 g), and water (420 g).

Zheng et al., 1998). Compared with wheat starch, buckwheat starch


had higher PV (Acquistucci & Fornal,1997; Li et al.,1997; Praznik et al.,
1999). Pasting viscosity of both common and tartary buckwheat
starches (2 genotypes) was lower than that of potato, and higher than
that of maize starch (1 genotype each) (Gao et al., 2016). Both buckwheat starches had higher breakdown (BD) than maize and potato
starches, higher setback (SB) than maize starch but lower than potato
starch. In another comparison study (Praznik et al., 1999), common
buckwheat starch had higher nal viscosity than amaranth, proso
millet, wheat, quinoa, and waxy maize starches. Different starches
differ in their chemical composition and structures which affect the
pasting properties (Srichuwong and Jane, 2007). For example,
defatting mayhave a greatinuence onpasting properties (Hurusawa
& Miyashita,1964a). Buckwheat amylopectin contains relatively high
amount of extra-long unit chains. These long unit chains were
negatively correlated to BD of rice starch paste (Han & Hamaker,
2001). Indeed, buckwheat starches (6 genotypes) had lower BD
than wheat starch (Li et al., 1997). However, another study showed
that buckwheat starches (4 genotypes) had higher BD than maize and
potato starches (Gao et al., 2016). Other factors such as amylose
content, presence of minor components, and granule structure may
contribute to this discrepancy (Srichuwong and Jane, 2007). Molecular weight of starch appeared not determinative in pasting properties (Praznik et al., 1999).
6.4. Retrogradation
Upon cooling, the disordered amylose and amylopectin of the
gelatinized starch re-associate to re-gain a degree of order. This
process, termed retrogradation, can be reected by various physicochemical properties of the resulting retrograded starch, and
probed by diverse experiments with different techniques (Wang, Li,
Copeland, Niu, & Wang, 2015). The initial retrogradation is most
attributed to the re-association of amylose, and the long-term
retrogradation is due to the recrystallization of amylopectin side
chains (Wang et al., 2015). Factors affecting retrogradation of starch
include composition and structures of starch components, thermal
processing conditions, water content, and temperature (Wang
et al., 2015). Diverse aspects of retrogradation of buckwheat
starch has been probed as follows:
6.4.1. Freeze-thaw stability and syneresis
The retrogradation of starch leads to the formation of new

crystals, resulting in reduced water holding capacity and syneresis.


The gelatinized starch undergoes freeze/coolethaw cycles in some
processing scenarios. Common buckwheat starch had better freezethaw (7  C/30  C) stability than amaranth, proso millet, wheat,
quinoa, and waxy maize starches (Praznik et al., 1999). Buckwheat
starch gel had less syneresis than maize and wheat starch gels, even
though the former had higher amylose content which is positively
linked to syneresis (Qian et al., 1998; Srichuwong, Isono, Jiang,
Mishima, & Hisamatsu, 2012). Another study on buckwheat
starch gels from 6 genotypes conrmed that syneresis was positively correlated to amylose content and also resistant starch content of cooked groats (Lu & Baik, 2015). Comparative study showed
that common buckwheat starch had denser packing of glucan coils
than the other starches (Praznik et al., 1999). This may explain the
better water holding capacity of buckwheat starch within the
packing matrix.
6.4.2. Re-crystallization
Retrogradation behaviour of buckwheat starch at 21  C for 6
days was modelled by Avrami equation. The result suggested that
the re-crystallization of amylopectin is instantaneous nucleation
followed by rod-like growth of crystals (Kim et al., 1977). Diversity
in starch retrogradation measured by DSC has been observed.
Retrograded buckwheat starches (6 genotypes) had To of
39.3e41.5  C, Tp of 49.2e51.2  C, Tc of 59.2e60.9  C, and DH of
4.6e5.6 J/g (Lu & Baik, 2015). Buckwheat starch had a lower
retrogradation than wheat and maize starches at 12  C and 25  C
(Qian et al., 1998).
6.4.3. Starch paste turbidity
Pasted starch (2%) was stored at 4  C up to 15 days and diversity
in turbidity development has been observed (6 genotypes) (Lu &
Baik, 2015). Turbidity was positively linked to amylose and resistant starch contents of starch.
6.4.4. Gel textural properties
Pasted starch was stored at 4  C for 1 day and the textural
properties of the resulting gel showed great diversity (6 genotypes)
(Lu & Baik, 2015). Hardness, cohesiveness, and springiness were
positively linked to amylose and resistant starch contents of cooked
groats.

130

F. Zhu / Trends in Food Science & Technology 49 (2016) 121e135

Pasted starch was stored at room temperature for 1 day.


Compared with wheat starch gel, buckwheat starch gels (3 genotypes of common buckwheat and 3 genotypes of tartary buckwheat) had considerably higher hardness (Li et al., 1997). Shearing
of 1000 s1 was applied on starch gels for 5 min (Praznik et al.,
1999). Buckwheat starch gel had a lower stability against
shearing than amaranth, quinoa, and wheat starch gels. When the
pH was lowered to 3, the stability of buckwheat starch gel was
lower than that of quinoa and millet starches, and higher than
amaranth, wheat, and waxy maize starches (Praznik et al., 1999).
The stability against shearing was suggested to be determined by
higher amounts of shorter chains of starch, but not by the molecular weight of starch (Praznik et al., 1999).
6.5. Enzyme susceptibility and digestion
Enzyme susceptibility of buckwheat starch has been compared
with other starches (Acquistucci & Fornal, 1997; Qian et al., 1998).
Native common buckwheat starch (1 genotype) had higher susceptibility to porcine pancreatic a-amylase than normal wheat and
maize starches (1 genotype each) (Qian et al., 1998). This was
attributed to the smaller granule size, also higher amylose content
(thus higher portion of amorphous region in the granules).
Compared with wheat starch (1 genotype), common buckwheat
starch (2 genotypes) had higher content of rapidly digestible starch
(RDS) (41 and 46% for buckwheat and 34% for wheat) and lower
content of slowly digestible starch (SDS) (46 and 49% for buckwheat
and 58% for wheat) (Acquistucci & Fornal, 1997).
Enzyme susceptibility of starch in various buckwheat food
products (our, groats, and bread) has been studied (Acquistucci &
Fornal, 1997; Lu & Baik, 2015; Wolter, Hager, Zannini, & Arendt,
2013). A comparison study on the in vitro starch digestibility and
predicted glycaemic index showed that gluten-free bread of buckwheat had lower digestion than quinoa and white wheat bread, but
higher than oat, sorghum, and teff gluten-free breads (Wolter et al.,
2013). Apart from non-starch factors such as dietary bre and
lipids, characteristics of starch determined the in vitro digestibility
of these breads. Gelatinization temperatures of buckwheat starch
are lower than that of sorghum and teff, and higher than that of
quinoa and wheat. The granule size is larger than that of quinoa.
Amylose content is also higher than that of quinoa, facilitating the
formation of amylose-lipid inclusion complexes which are resistant
to enzyme hydrolysis (Wolter et al., 2013). Diversity in resistant
starch (RS) content of cooked buckwheat groats has been observed
(1.6e3.8 g/100 g), and the RS content was correlated to various
physicochemical characteristics of isolated starch (Lu & Baik, 2015).
RS was positively correlated to amylose content, starch paste
turbidity, and gel hardness, while being negatively correlated to
pasting temperature and peak viscosity, and To and Tp of the
melting of retrograded starch (Lu & Baik, 2015). Indeed, retrograded starch (type 3 RS) is much determined by the re-association
and re-ordering of amylose component (Sajilata, Singhal, &
Kulkarni, 2006).
Processing of buckwheat may affect the enzyme susceptibility of
starch (Table 7). Groats were subjected to autoclaving (120  C for
1 h) and cooling (to room temperature) cycles (Skrabanja & Kreft,
1998). This processing increased the resistant starch content and
little affected the slowly digestible fraction. Hydrothermal treatment gave a 5.5% of type 3 resistant starch which was indigestible
in rats. Groats dry-heated at 110  C had less amount of rapidly
digestible starch than hydrothermally treated samples (Skrabanja,
Laerke, & Kreft, 1998). Roasting at 160  C for 30 min decreased
the enzyme susceptibility of starch (Christa et al., 2009). By varying
the experimental conditions of hydrothermal processing, a reduced
rate of enzyme susceptibility of buckwheat products could be

obtained (Skrabanja et al., 1998). These physical processing techniques can be feasibly applied to everyday cooking for nutritional
practice.
Difference in the enzyme susceptibility between buckwheat
starch and buckwheat food products has been observed
(Acquistucci & Fornal, 1997; Takahama & Hirota, 2011). For
example, in comparison with wheat our, buckwheat our had
similar amount of RDS and higher or lower SDS, while the starches
showed a different pattern as discussed above (Acquistucci &
Fornal, 1997). The enzyme susceptibility of boiled buckwheat
noodles was compared with that of white wheat bread, boiled
wheat noodles, and boiled buckwheat groats (Kreft & Skrabanja,
2002). Boiled buckwheat groats had the lowest enzyme susceptibility and highest resistant starch content, followed by boiled
buckwheat noodles, boiled wheat noodles, and white wheat bread.
This suggests that the other factors physically and chemically affect
enzyme susceptibility of starch in the food matrix (Singh, Dartois, &
Kaur, 2010). Lipids (e.g., fatty acids), proteins, epicatechindimethylgallate, dietary bre, rutin, phytic acid, protease inhibitors, and tannins present in the buckwheat our interact with
starch and/or a-amylase, and make the starch less available to the
enzyme hydrolysis (Kreft & Skrabanja, 2002; Takahama & Hirota,
2010; Wijngaard & Arendt, 2006; Wolter et al., 2013). Furthermore, the bile salts (e.g., cholate and taurocholate) in the intestine
may interact with starch to reduce the starch digestion (Takahama
& Hirota, 2011). The relatively low glycemic prole of buckwheat
has been conrmed in clinical model in vivo (Skrabanja, Elmsthl,
rck, 2001) (Fig. 3). In vitro and in vivo (human) starch
Kreft, & Bjo
digestion analysis showed that boiled buckwheat groats and bread
containing buckwheat our had lower enzyme susceptibility and
in vivo glycemic index than white bread (Skrabanja et al., 2001).
Buckwheat groats also gave higher post-meal satiety than breads
(Skrabanja et al., 2001). This suggests the importance of food matrix
structure in satiating capacity, and conrms the role of whole grain
buckwheat in glycaemic and weight management.
7. Modications
Native buckwheat starch has been treated physically and
chemically to alter the physicochemical properties and structures
of starch (Table 7).
7.1. Physical modications
Heat-moisture treatment (HMT) of starch decreased the solubility and swelling, PV of pasting, hardness and adhesiveness of gel,
increased the degree of crystallinity, gelatinization temperatures,
and slowly digestible starch content, without affecting the polymorph pattern (Liu et al., 2015b). Microwave-assisted hydrothermal treatment and roasting also gave similar results (Christa et al.,
2009; Zondag, 2003). Moisture content had a great inuence on the
outcome of the hydrothermal treatments (Liu et al., 2015a and
2015b; Zondag, 2003). For example, increasing moisture content of
starch from 20 to 35% decreased swelling power and solubility, PV,
BD, SB, and FV (nal viscosity) of pasting, decreased DH of gelatinization, and increased the water absorption capacity, gelatinization temperature range, degree of crystallinity, and resistant starch
content (Liu et al., 2015a, 2015b). These observations agreed with
the previous reports on other types of starch (Hoover, 2010). Similar
to HMT, annealing (starch to water ratio at 1:4, 50  C for 24 h) of
common buckwheat starch had no effect on granular polymorphism, increased gelatinization temperatures and resistant
starch content, decreased swelling and water solubility, PV, BD, SB,
and FV of pasting, and DH of gelatinization (Liu et al., 2015a). Hydrothermal treatments facilitate the re-alignment and re-

F. Zhu / Trends in Food Science & Technology 49 (2016) 121e135

131

Table 7
Modications of buckwheat starch.
Modication type
Physical
Roasting

Buckwheat
type

Major ndings

References

Common

Starch with a moisture content of 14.5% was roasted at 160  C for 30 min.
Infrared spectra and polymorphism of starch were not affected. Swelling power
and solubility was decreased. Breaking and conglomerates of granules were
formed. Roasting decreased the glucose releasing from starch by enzymes
Starch suspension (25% solid content) was treated with a range of high pressure
(200e600 MPa). Gelatinisation of starch occurred between 300 and 500 MPa.
High pressure-induced gelatinization much better retained the granule shape,
compared with heat-induced gelatinization (Fig. 2a). This resulted in a stronger
gel from the former as revealed by rheological analysis
Starch with a moisture content of 22% was heated up to 150  C with or without

pressure, and the processing steps were detailed (Fornal, Soral-Smietana,
&
Fornal, 1981). Hydrothermal treatments decreased the pasting viscosity,
increased the swelling power and solubility of starch. Pressure (588,400 Pa)
induced gelatinization and disrupted the granules as revealed by scanning
electron microscopy
Groats were autoclaved at 120  C for 1 h before cooling to room temperature
(~25  C). Two more autoclaving/cooling cycles were applied. More autoclaving/
cooling cycles increased the retrograded starch content, and had little effect on
the content of slowly digestible starch fraction
Hydrothermally treated buckwheat samples (including groats) had 5.5% of total
starch content as retrograded starch (resistant starch type 3), which was
correlated to undigested starch fraction in rats in vivo. There was much less
rapidly digestible starch fraction in raw groats and groats dry-heated to 110  C
than hydrothermally treated samples. Compared with white bread, groats
hydrothermally treated in traditional way (cooking before dehusking followed
by warm-air drying) had less amount of rapidly digestible starch by 11%
Starch with moisture contents of 32.3%, 40%, and 44.4% were microwave-heated
below the gelatinization temperature. Microwave heating had little effect on
polymorph pattern and decreased the amylose leaching of starch when the
initial moisture contents were 40% and 44.4%. Microwaving increased
gelatinization temperatures of starch when the moisture content was 44.4%
Starch with a moisture content of 20e35% was treated at 110  C for 16 h. HMT of
starch decreased solubility and swelling power, peak viscosity of pasting, gel
hardness and adhesiveness, increased the gelatinization temperature, relative
crystallinity, and slowly digestible starch content, and had no effect on
polymorphism
Starch with a moisture content of 80% was heated at 50  C for 24 h. Annealing of
starch decreased solubility and swelling power, peak and nal viscosities of
pasting, increased the gelatinization temperature, relative crystallinity, and
resistant starch content, and had no effect on polymorph type
Ball-milling up to 8 h at low moisture content (6%) destroyed the crystallinity of
starch, decreased the pasting viscosity, and disrupted the granules, while
maintaining the Maltese cross pattern. DSC analysis showed no endothermic
peak of the milled starch
Pre-gelatinization increased the swelling power and solubility of starch, and
peak viscosity of pasting, while decreasing the degree of crystallinity

Christa et al., 2009

High pressure
treatment

Common

Hydrothermal
treatments

Common

Autoclaving
and cooling

Common

Hydrothermal
treatments

Common

Microwave assisted
Hydrothermal
treatment

Common

Heat moisture
treatment
(HMT)

Tartary and
common

Annealing

Common

Ball-milling

Common

Pre-gelatinization
by drum drying
Blending with other
ingredients
Blending with yellow
mustard mucilage

Common

n.a.

Blending with
Fucoidan

Common

Blending with
galactomannans

Common

Chemical
Acetylation

Common

Acid hydrolysis

Common

Mucilage addition increased peak viscosity of pasting, G0 and G00 during


frequency sweep of dynamic rheology, hardness, adhesiveness, and chewiness
of gel, and gelatinization temperature range of buckwheat starch. Mucilage
decreased the syneresis of starch gel
Fucoidan from brown seaweeds was mixed with buckwheat starch at various
ratios (fucoidan to starch 1:2 to 0:3 for a total solid concentration of 3%, 1:5 to
0:6 for a total solid concentration of 6%). Steady and dynamic shear rheological
studies showed that when the ratio of fucoidan was less than 0.5%, an
antagonistic interaction in viscosity was observed. When the ratio of fucoidan
was more than 0.5%, viscosity kept increasing with the increasing ratio
Galactomannans including guar gum, tara gum, and locust bean gum were
mixed with buckwheat starch (gum to starch ratio 1:9, total carbohydrate
concentration 5%). Steady shear and dynamic rheological studies revealed
synergism between starch and galactomannans. The apparent viscosity,
consistency index, yield stress, dynamic moduli, and complex viscosity of the
mixtures were higher than those of the individual starch
Acetylation decreased gelatinization and pasting temperatures, setback of
pasting, and increased the swelling power, water solubility, and cold storage
stability of starch gel
Starch was hydrolysed in HCl solution (2.2 N) at 35  C up to 24 days. Buckwheat
starch was more susceptible to acid hydrolysis than wheat and maize starches
under the same condition

Vallons & Arendt, 2009


Soral-Smietana
et al.,
1984a

Skrabanja & Kreft, 1998

Skrabanja et al., 1998

Zondag, 2003

Liu et al., 2015a and


2015b

Liu et al., 2015a

Li et al., 2014

Li et al., 2014

Liu et al., 2006b

Cho et al., 2009

Choi & Chang, 2012

Zheng et al., 1998

Qian et al., 1998

(continued on next page)

F. Zhu / Trends in Food Science & Technology 49 (2016) 121e135

132
Table 7 (continued )
Modication type

Buckwheat
type

Major ndings

References

Acid hydrolysis

Common

Neethirajan et al.,
2012

Alkaline treatment
in ethanol

Common

Starch was hydrolysed in concentrated H2SO4 solution (3.16 M) at 40  C for 5


days to produce nanocrystals. The nanocrystals were spherical and were 120
e200 nm long and 4e30 nm in diameter
Starch was treated in solution of NaOH and ethanol mixture at 70  C to produce
cold water soluble starch with much enhanced transmittance of gel. NaOHethanol treatment greatly decreased the degree of crystallinity of starch while
maintaining the granule shape and Maltese cross pattern, signicantly
increased the water solubility without much altering the swelling power, and
reduced the pasting viscosity and the DH of gelatinization without affecting the
temperatures of gelatinization

Li et al., 2014

n.a., not available.

association of chain segments with certain degree of mobility in the


granules, without disrupting the ordered crystalline structure
(Hoover, 2010). Common buckwheat starch in water (25%, w/w)
was treated with high pressure from 200 to 600 MPa (Fig. 2a).
Starch gelatinization occurred between 300 and 500 MPa.
Compared with heat-induced gelatinization, high pressureinduced gelatinization retained the granule shape and gave the
resulting gel stronger texture (Vallons & Arendt, 2009). Common
buckwheat starch has been subjected to ball-milling (Li et al., 2014).
Ball-milling most disrupted the granule and destroyed the crystallinity as revealed by thermal and pasting analysis. Maltese cross
pattern of granules was partially retained (Li et al., 2014). Pregelatinization of common buckwheat starch with drum drying for
cold water soluble starch production increased the swelling power
and solubility of starch, and PV of pasting, and decreased the degree
of crystallinity (Li et al., 2014).
Buckwheat starch has been blended with non-starch polysaccharides (hydrocolloids) and mucilage to obtain novel physicochemical properties (Cho, Choi, & You, 2009; Choi & Chang, 2012;
Liu, Eskin, & Cui, 2006b). Addition of yellow mustard mucilage

increased PV of pasting, G' (storage modulus) and G'' (loss modulus)


of dynamic oscillatory rheology, hardness and adhesiveness of gel,
and the temperature range of gelatinization, while decreasing the
syneresis (Liu et al., 2006b). Addition of galactomannans (guar gum,
tara gum, and locust bean gum) gave synergy in apparent viscosity,
consistency index, yield stress, dynamic moduli, and complex viscosity with buckwheat starch (Choi & Chang, 2012). An antagonistic
effect in viscosity of buckwheat starch and fucoidan blends was seen
when the concentration of fucoidan was less than 0.5%. When the
concentration of fucoidan became higher than 0.5%, G0 of dynamic
rheology kept increasing with the ratio (Cho et al., 2009). It was
suggested that phase separation between starch and fucoidan might
occur when there are enough solids. This may lead to the increasing
interactions among fucoidan molecules and also starch chains,
resulting in the formation of three-dimensional networks (Cho et al.,
2009). A systematic review showed that the pasting and gelling
properties of starch and hydrocolloid mixtures, as well as the
mechanisms of interactions, are dependent on the types of starch
and hydrocolloids, the concentration of the solids, and the preparation methods of the composite gels (BeMiller, 2011).

Fig. 3. Postprandial blood glucose responses in healthy humans (nine women and one man, average age of 33) following ingestion of breakfast meals; WWB, white wheat bread;
BWG, buckwheat groats (Skrabanja et al., 2001).

F. Zhu / Trends in Food Science & Technology 49 (2016) 121e135

133

Table 8
Uses of buckwheat starch.
Uses

Buckwheat type

Form

Major ndings

Reference

As ingredients for cake


and pie llings

Common

Native (defatted and


non-defatted)

Lorenz & Dilsaver, 1982

As ingredient for
nanocomposite lms

Common

Nanocrystal

As fermentation substrate
for producing beer-like
alcoholic beverage

Tartary

Native

As ingredient for extruded


products

n.a.

Native

Cream substitute

n.a.

Native and
cross-linked

For cake production, the baking


performance of buckwheat starch
was unsatisfactory according to
sensory evaluation, as compared
with wheat starch. For pie lling,
buckwheat starch produced initial
consistency comparable to wheat,
millet, and triticale starches
Starch/nanocrystal/glycerol
composite lm had a 3-stage
transition of moisture adsorption as
revealed by sorption isotherms.
Under a constant water activity,
increasing the nanoparticle
concentration decreased the water
adsorption of lms
a-Amylase, b-amylase, and
amyloglucosidase were used to
hydrolyse the starch, and the
structural changes of granules were
monitored by scanning electron
microscopy. a-Amylase hydrolysed
both the inner and outer layers of
granules. b-Amylase and
amyloglucosidase hydrolysed the
inner part of granules
Milk protein (25%) and buckwheat
starch mixture was extruded. The
milk protein addition decreased the
enzyme susceptibility of starch
The patent described the use of
buckwheat starch as effective fat
replacer to impart the smooth
organoleptic character of an oiland-water emulsion

Neethirajan et al., 2012

Kusano et al., 1999


Smietana
et al., 1988

Singer, 1994

n.a., not available.

7.2. Chemical modications


Buckwheat starch has been acetylated (Zheng et al., 1998), acid
hydrolysed (Neethirajan et al., 2012; Qian et al., 1998), and treated
in alkaline-ethanol mixture (Li et al., 2014). Acetylation decreased
gelatinization temperatures and retrogradation, and increased
water solubility and cold storage stability of the gel (Zheng et al.,
1998). The spherical nanocrystals, 120e200 nm long and
4e30 nm in diameter, were produced in H2SO4 solution (3.16 M) at
40  C for 5 days (Neethirajan et al., 2012). Compared with wheat
and maize starches, buckwheat starch was more susceptible to acid
hydrolysis (HCl solution (2.2N), 35  C, up to 24 h) (Qian et al., 1998).
This may be attributed to higher surface area and more amorphous
region (e.g., higher amylose content) in the granules (Qian et al.,
1998). Cold water soluble starch with increased transmittance of
gel and decreased crystallinity was produced by treating starch in
NaOH-ethanol solution at 70  C. The resulting starch retained the
granule shape and Maltese cross pattern, and had reduced pasting
viscosity and DH of gelatinization (Li et al., 2014). All the outcomes
of these chemical modications agreed with previous reports of
modications on other types of starches (Wurzburg, 1986).
8. Uses
There have been limited uses of buckwheat starches for food
and industrial applications even at the laboratory level (Table 8).
Common buckwheat starch has been used in pie llings, and
showed consistency that was comparable to wheat, millet, and
triticale starches. However, when used in cake production, the
baking performance was inferior, compared with wheat starch, as

revealed by sensory evaluation (Lorenz & Dilsaver, 1982). When


used as an ingredient with milk protein for extruded products, the
products had lower enzyme susceptibility of starch than that of

pure buckwheat starch (Smietana,
Fornal, Szpendowski, & Soral
Smietana,
1988). The small size of buckwheat starch, similar to
lipid micelles, suggests potential use as fat replacers (Gregori &
Kreft, 2012). A patent described that buckwheat starch can be fat
replacers in an oil-and-water emulsion to give smooth organoleptic
taste, due to the size and shape of buckwheat starch granules
(Singer, 1994). Buckwheat starch may be modied with octenyl
succinic anhydride (OSA) to enhance the hydrophobicity. The OSA
modied starch, with relatively small granule size, may be used as
o
,
emulsiers to stabilise Pickering emulsions (Timgren, Rayner, Sjo
& Dejmek, 2011). Buckwheat starch has also been suggested as
fermentation substrate for the production of beer-like alcoholic
beverage (Kusano, Izumita, Inui, & Chiue, 1999). Indeed, buckwheat
beer is a commercial product. Nanocrystals, produced by acid hydrolysis of buckwheat starch, has been incorporated in starch lms
(Neethirajan et al., 2012). The resulting lms had lower water
penetration and a 3-stage transition of moisture adsorption
(Neethirajan et al., 2012). The small granules of buckwheat starch
may also be suitable as ingredients for cosmetics and as llers in
bio-composite.
The limited uses of buckwheat starch is probably due to abundant and cheap supply of other starches such as maize and potato
starches. Another reason is the limited exploitation of buckwheat
starch for various possible applications. The unique chemical
composition, structures, and properties of buckwheat starch should
grant it a special place in some food and non-food applications. To
be able to increase the potential uses of buckwheat starch, a wide

134

F. Zhu / Trends in Food Science & Technology 49 (2016) 121e135

range of diversity in properties and structures should be explored


by natural (e.g., genetic resource evaluation) and articial (e.g.,
physical and chemical modications) means.
9. Conclusions
The conclusions on buckwheat starch according to the majority
of literature are:
(1) The amylose contents are similar to that of normal cereals
(ca. 20e28%); (2) starch granules are most polygonal, and the size
ranges from ~2 to 15 mm with an average value of ~6e7 mm; (3) Atype polymorph; (4) amylopectin chemical structure of starches
from common and tartary buckwheat is similar, and may be due to
limited genotypes analysed; (4) the amount of extra-long chains of
amylopectin (DP > 100) is higher than those of cereal amylopectins;
(5) low glycemic index of buckwheat food products may be
attributed to the non-starch components and food matrix effects.
Methods for evaluation of starch structures and properties
should be standardized to maximize the communal research efforts. Genetic resource of starches from common buckwheat and
especially from tartary buckwheat should be further explored. So
far, there is no report on starches from other buckwheat species
such as F. dibotrys. Structural basis for physicochemical properties
of buckwheat starches or between buckwheat and other starch
types should be better explored in comparative studies. The roles of
amylose and amylopectin in the physicochemical properties can be
better studied. More types of physical and chemical modications
can be conducted to widen the variations in the structures and
properties of the starch. Comprehensive approaches on
composition-structure-property-modication-use
relationships,
rather than just focussing on one aspect, should be employed to
maximize the possible utilization of buckwheat starch.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.tifs.2015.12.002.
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