Review
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
122
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
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
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
124
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
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.
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
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
Common
Tartary
Tartary
SEM
SEM
SEM
4e10
2e10
3e14
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
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).
127
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
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
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).
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.
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;
129
Table 6
Pasting properties of buckwheat starch.
Buckwheat type
No. of genotypes
Instrument
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).
130
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-
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
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
Soral-Smietana
et al.,
1984a
Zondag, 2003
Li et al., 2014
Li et al., 2014
132
Table 7 (continued )
Modication type
Buckwheat
type
Major ndings
References
Acid hydrolysis
Common
Neethirajan et al.,
2012
Alkaline treatment
in ethanol
Common
Li et al., 2014
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).
133
Table 8
Uses of buckwheat starch.
Uses
Buckwheat type
Form
Major ndings
Reference
Common
As ingredient for
nanocomposite lms
Common
Nanocrystal
As fermentation substrate
for producing beer-like
alcoholic beverage
Tartary
Native
n.a.
Native
Cream substitute
n.a.
Native and
cross-linked
Smietana
et al., 1988
Singer, 1994
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