Accepted Manuscript

Buckwheat starch: structures, properties, and applications

Fan Zhu

PII: S0924-2244(15)30117-5
DOI: 10.1016/j.tifs.2015.12.002
Reference: TIFS 1736

To appear in: Trends in Food Science & Technology

Received Date: 25 September 2015

Revised Date: 11 November 2015
Accepted Date: 7 December 2015

Please cite this article as: Zhu, F., Buckwheat starch: structures, properties, and applications, Trends in
Food Science & Technology (2016), doi: 10.1016/j.tifs.2015.12.002.

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 ACCEPTED MANUSCRIPT
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3 Buckwheat starch: structures, properties, and applications

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5 Fan Zhu*

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7School of Chemical Sciences, University of Auckland, Private Bag 92019, Auckland 1142,

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8New Zealand
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9* Correspondence, email: fzhu5@yahoo.com
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12Running head: Buckwheat starch review

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13Abstract

14Background

15There is increasing interest in utilization of buckwheat for healthy food applications.

16Common buckwheat (Fagopyrum esculentum) and tartary buckwheat (F. tataricum) are

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17cultivated in Asia, Europe, and Americas for various food formulation and production. Starch,

18the major component of the seeds, may account over 70% of the dry weight. Therefore, it is

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19expected that, to a large extent, the quality of starch determines the quality of buckwheat food

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20products. Furthermore, Buckwheat starch has great potential for various food and non-food

21uses due to the unique structural and functional features.

22Scope and Approach

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23This review summarises the current knowledge of chemical composition, chemical structure
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24of amylose and amylopectin, physical structure of granules, physicochemical properties,

25enzyme susceptibility, modifications, and uses of buckwheat starch. Suggestions on how to

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26better understand and utilise the starch are provided.

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27Key Findings and Conclusions

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28Amylose contents of buckwheat starch ranged from 20‒28%. Starch granules are most
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29polygonal with size ranging from ~2‒15 µm and an average diameter of ~6‒7 µm. The
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30polymorph is A-type. The amount of extra-long unit chains of amylopectin (DP > 100) is

31higher than that of cereal amylopectins. Low glycaemic index of buckwheat food products

32could be attributed to the non-starch components. Buckwheat starch has been used as fat

33replacer, ingredient for extruded products, nanocomposite material, and fermentation

34substrate for alcoholic beverage. It may be concluded that buckwheat starch can be a unique

35source of specialty starch for innovative food and non-food applications.

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36Keywords: buckwheat starch, composition, structure, property, modification, use

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38Introduction

39Buckwheat belongs to the genus Fagopyrum of the family Polygonaceae (Cai, Corke, & Li,

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402004). The most cultivated species include F. esculentum known as common buckwheat and

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41tartary buckwheat (F. tataricum). Tartary buckwheat is also known as bitter buckwheat due to

42the bitter taste and high amount of flavonoids present in the kernels. A much less cultivated

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43species with great local significance in Asia is F. dibotrys (synonyms F. acutatum and F.

44cymosum) which is known as golden or tall buckwheat (Liu, Li, Zhu, Li, & Shui, 2006a).

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45Buckwheat has great ecological adaptability. It can grow well in marginal lands with harsh
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46climatic and soil conditions. In particular, tartary buckwheat can grow at high altitudes even
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47with low precipitation and low temperature (Cai et al., 2004). Historically, buckwheat was a

48popular food crop in Europe and Asia. The production declined greatly in the 20th century.
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49This is due to the introduction of nitrogen fertilizer and the competition of other crops such as
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50wheat (Ahmed et al., 2014). In recent years, buckwheat is becoming popular due to its

51various “re-discovered” health benefits and as a potential functional food source (Ahmed et
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52al., 2014). Statistics of Food and Agriculture Organization of the United Nations (FAO)
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53showed that, during the last two decades, the world production of buckwheat decreased
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54gradually towards 2010 before a slow increase from 2011 onwards (Fig. 1). The world

55production quantity of buckwheat reached 2,347,558 tonnes in 2013, and the top five

56producers were Russia, China, Ukraine, France, and Poland (Supplementary Table 1). In

57terms of yield, the top 5 countries in 2013 were France (34,786 Hg/Ha), Czech ( 24,000

58Hg/Ha), Bhutan (23,608 Hg/Ha), Croatia (20,526 Hg/Ha), and Bosnia and Herzegovina

59(15,434 Hg/Ha) (FAOSTAT, 2015).

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60Buckwheat is becoming a research focus in recent years most due to the healing and

61preventative roles in diverse diseases (Li & Zhang, 2001; Cai et al., 2004; Guo et al., 2013;

62Ahmed et al., 2014). The proximate composition of major nutrients of buckwheat

63seeds/flour/groats falls within the ranges of the common cereals and pseudocereals

64(Supplementary Table 2). Compared with cereals and other pseudocereals, buckwheat

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65appears rather unique in the composition of some functional nutrients. Buckwheat protein is

66balanced in the amino acid composition (relatively high lysine content). Buckwheat is

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67relatively high in dietary fibre content. Minor important nutrients include polyunsaturated

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68essential fatty acids (i.e. linoleic acid), minerals such as Mg and K, vitamins (B, C, and E), D-

69chiro-inositol, fagopyritols, and flavonoids (e.g., rutin and quercetin) (Li & Zhang, 2001;

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70Wijngaard & Arendt, 2006). The presence of tannins, phytic acid, and protease inhibitors
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71lowers the enzyme susceptibility and digestion of starch (Wijngaard & Arendt, 2006). The

72above-mentioned factors render buckwheat various health benefits. These include

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73hypocholesterolemic activity, suppression of body fat accumulation, antioxidant and free

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74radical scavenging activities, anti-hypertension, anti-inflammation, reducing the occurrence

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75of colon cancer, and so on (Li & Zhang, 2001; Wijngaard & Arendt, 2006; Ahmed et al.,

762014). In particular, buckwheat can be a major ingredient of gluten-free food products for
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77people with celiac diseases (Giménez-Bastida et al., 2015). Various food products have been

78developed from buckwheat in the light of the above-mentioned health impacts. These include
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79vinegar, beer and whisky, bread and steamed bread, breakfast cereals, porridge and soup,
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80noodles and pasta, pancakes, biscuits and cookies, and tea (Zhang et al., 2011; Cai et al.,

812004; Li & Zhang, 2001; Hatcher et al., 2008). The majority of these buckwheat products are

82commercially available in niche markets with limited size.

83Starch is the major component of buckwheat seeds, and may amount up to over 70% of the

84dry weight (Ikeda et al., 1997). The properties and structures of starch are critical for the

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85quality of buckwheat food products (Ikeda et al., 1997; Hatcher et al., 2008). For example,

86starch and amylose contents were highly related to the springiness of heated buckwheat

87dough, probably due to gelling capacity of amylose and starch (Ikeda et al., 1997).

88Understanding the structure and functionality of starch provides a basis for the quality of

89buckwheat products, and help commercialize them to a larger scale. Since the pioneering

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90work on buckwheat starch by Hurusawa and Miyashita (1963, 1964a, 1964b, 1965, 1966)

91from Japan, a great progress has been made worldwide. This review aims to summarise the

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92present knowledge of composition, structures, properties, modifications, and uses of

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93buckwheat starch, and to provide future research directions.

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94
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95Isolation
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96The content of starch in buckwheat flour may amount up to 80% of the dry weight (Hong et

97al., 1996; Ikeda et al., 1997). Wet-milling process has been used to isolate buckwheat starch
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98(Zheng et al., 1998). Basically, dehulled buckwheat groats are steeped overnight in aqueous
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99solution that may contain small amount of chemicals such as NaHSO3 (0.20%). The hydrated

100groats are milled in a high-speed blender (e.g., Waring blender), and the resulting slurry is
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101screened and washed with water to remove the fibrous materials (Zheng et al., 1998).
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102Alternatively, groats are dry-milled into flour, and the resulting flour is steeped in aqueous
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103solution that may contain alkaline at a low concentration. The steeped slurry is further milled

104in a blender before passing through mesh. The resulting slurry is centrifuged, and the protein

105layer on the top of the sediment is removed. The starch cake is re-suspended in water. The

106washing step is repeated to further remove the protein and other impurity before drying (Li et

107al., 1997). The steeping/washing process may involve alkaline solution (e.g., 0.1% NaOH) to

108facilitate the separation of other components from starch (Acquistucci & Fornal, 1997;

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109Christa et al., 2009; Soral-Śmietana et al., 1984a; Zheng et al., 1998). It should be noted that

110differences in isolation method and experimental conditions may result in differences in

111starch composition and properties.

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113Chemical composition

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114Great diversity in the chemical composition of starches from both common and tartary

115buckwheat has been observed (Table 1). Amylose content of buckwheat starches, a major

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116attribute, varied greatly among different studies. This could be attributed to the buckwheat

117genetics and growing conditions (Gregori & Kreft, 2012; Gao et al., 2016), as well as the

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118measuring method (Yoshimoto et al., 2004). The genetic and environmental variations can be
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119compared within the same study. For example, genetic diversity in amylose contents (e.g.,
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12023.4‒29.1% for 30 genotypes) was found in common buckwheat starch (Ikeda et al., 1997).

121Mutants with low amylose contents of 3.8–16% were noted (Gregori & Kreft, 2012).
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122Amylose contents of buckwheat starch have been measured by iodine-binding-based

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123colorimetry and amperometry, and concanavalin A-precipitation-based methods (Yoshimoto

124et al., 2004; Lu and Baik, 2015; Qian & Kuhn, 1999b). Different methods may give different
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125results for the same sample. For example, the amylopectin unit chains interact with iodine in
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126solution, giving a higher estimation of amylose contents of starch (Yoshimoto et al., 2004).
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127The endogenous lipids in buckwheat starch binding to amylose gave a lower estimation of

128amylose contents (Lu and Baik, 2015). Concanavalin A-precipitation based method tends to

129give true amylose contents by excluding the influence of amylopectin (Gibson et al., 1997).

130Therefore, the quantification method should be noted when comparing the amylose contents

131reported by different studies. In comparative studies, amylose contents of common

132buckwheat starch were found similar to those of tartary buckwheat starch, though only very

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133limited number of genotypes (1‒3) was analysed for the latter (Gao et al., 2016; Yoshimoto et

134al., 2004; Li et al., 1997). In general, amylose content of normal starches from both common

135and tartary buckwheat appeared similar to that of normal cereal starches (Gao et al., 2016; Li

136et al., 1997). Compared with major cereal starches such as maize starch, there is a lack of

137variations in the amylose contents of buckwheat starch (e.g., lack of high-amylose and waxy

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138genotypes). Agronomic practice and growing conditions can influence the amylose contents

139of starch, on which there has been little studies on buckwheat. One report from Japan showed

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140that starch from buckwheat harvested in summer had similar apparent amylose content as that

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141of the same genotype harvested in autumn (Hurusawa and Miyashita, 1965).

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142Minor components of buckwheat starches include proteins, lipids, ash, and phosphorus-
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143containing compounds (Yoshimoto et al., 2004; Li et al., 1997; Acquistucci & Fornal, 1997).

144Within the same study, variation in the composition of these minor components has been
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145observed (Table 1), which may be attributed to the crop genetics and growing conditions.

146Between different studies, the variation appeared much larger than that of the same study (Li
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147et al., 1997; Acquistucci & Fornal, 1997; Lorenz & Dilsaver, 1982). This could be attributed
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148to differences in the starch isolation and quantification methods, as well as experimental
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149errors, and to a lesser extent, the crop genetics. In general, high amounts of the minor

150components such as proteins (e.g., >1%) suggest the possibility of reducing their contents in
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151the granules by further purification (Baldwin, 2001). Organic phosphorus-containing

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152compounds were found either absent or in a small quantity (0‒95 ppm) in buckwheat starches

153(Yoshimoto et al., 2004). Neutral lipids accounted for over 80% of the free lipid fraction in

154starch. The rest was polar lipids including glycolipids and phospholipids (Soral-Śmietana et

155al., 1984b).

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157Chemical structure

158Starch

159Starch was dissolved in DMSO (dimethyl sulfoxide) and analysed by high-performance size-

160exclusion chromatography-reflective index-low angle laser light scattering detection

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161(HPSEC-RI-LALLS) to reveal the molecular size and structure of common buckwheat starch

162(Praznik et al., 1999). The weight-average DP (degree of polymerisation) of common

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163buckwheat starch was 94,900 (with a range of 38,000 to 134,000), which was higher than that

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164of amaranth (Amaranthus cruentus), proso millet (Panicum miliaceum), wheat, and quinoa

165starches, and lower than that of waxy maize starch (Praznik et al., 1999). The sphere

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166equivalent radius of glucan coils was 29 nm (with a range of 2 to 40 nm), which was larger
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167than that of wheat starch. The relative packing density of glucan coils within the occupied

168volume of buckwheat starch (3.2) was higher than that of amaranth (1), proso millet (1.4),
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169wheat (0.5), quinoa (0.9), and waxy maize (2.9) starches. While this kind of analysis is simple
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170and fast to gain the structural information of starch, the drawback is that amylose and
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171amylopectin are not fractionated in the first place. Therefore, their respective structures are

172not readily available.

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173Amylose
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174Amylose and amylopectin were fractionated from starches of common (7 genotypes) and
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175tartary (1 genotype) buckwheat by precipitation of amylose with 1-butanol and 3-methyl-1-

176butanol. The isolated fractions were subjected to structural analysis (Yoshimoto et al., 2004)

177(Table 2). The isolated amyloses had iodine affinity (IA) of 19.3‒20.2%, blue values (BV) of

1781.36‒1.48, and max (wavelength with maximum adsorption) of 645‒657 nm. 23–27% (molar

179basis) of the amyloses was found branched by treating with β-amylase which is an exo-acting

180enzyme. The β-limit values (β-LV%) ranged from 76‒82%. Amylose was analysed by

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181fluorescent-labelling/HPSEC method. On molar basis, two types of molecules peaked at DP

1821790 and DP 820, while on the weight basis, only one type was noted. The molecular size

183(DP) ranged from 1,020 to 1,380, the numbers of chains per each molecule were 3.1‒4.3, and

184the chain lengths were 280‒380 glucosyl residues. There seems to be little difference in

185amylose structure between common and tartary buckwheat starch, though only one genotype

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186of the latter was analysed. The chemical structure of buckwheat amyloses was similar to that

187of wheat and barley (Yoshimoto et al., 2004).

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188Amylopectin

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189IA, BV, and λmax of amylopectins were 2.21‒2.48%, 0.25‒0.28, and 582‒583 nm, respectively

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190(Yoshimoto et al., 2004) (Table 2). Amylopectin was debranched by isoamylase and analysed
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191by HPSEC-RI with fluorescent labelling and high-performance anion-exchange

192chromatography-pulsed amperometric detection (HPAEC-PAD) (Table 2). Compared with B-

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193type starches, buckwheat starch (1 genotype) had a higher amount of short unit chains (DP 6‒
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19415), a lower amount of long chains (DP 25–60), and shorter average unit chain length (CL),
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195as revealed by HPAEC-PAD (Sanderson et al., 2006). The molar amounts of fraction a (Fa)

196were ~63‒64% according to the HPSEC-RI chromatogram. The values are much higher than
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197the actual amount of A-chain (chains that carry no other chains) of any type of amylopectins

198(Bertoft et al., 2008) (A-chain as defined by Peat et al (1952)). Therefore, the fraction a (Fa)
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199is a mixture of both A- and B-chains, and the molar ratio (Fa+Fb1)/(Fb2+Fb3) is not equal to
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200the number of chains per cluster. The correct method for the quantification of A-chain is

201through the φ,β-limit dextrins of amylopectin, in which all the A-chains appear as maltose

202stubs (Bertoft et al., 2008). Nevertheless, this ratio ((Fa+Fb1)/(Fb2+Fb3)) reflects the amount

203of short chains to that of long chains. Buckwheat amylopectins had lower values than that of

204rice, maize, and wheat amylopectins. CL values of buckwheat amylopectins were 23‒24

205glucosyl residues, which were higher than that of cereal amylopectins. The longer CL and

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206lower short-to-long chain ratio of buckwheat amylopectin could be attributed to the higher

207amounts of extra-long chains (Hanashiro et al., 2005; Yoshimoto et al., 2004).

208Long unit chains of amylopectin (DP > 100) (LCAP) have been found most in non-waxy but

209not in waxy starches, suggesting their biogenesis is related the granule-bound starch synthase

210(GBSS) (Hanashiro et al., 2005). GBSS is responsible for the amylose synthesis. LC AP may

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211impact the physicochemical properties (e.g., pasting and gel texture) of starch. In these

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212studies on LCAP, amylopectin was fractionated from starch by butanol-precipitation based

213methods (Hanashiro et al., 2005; Yoshimoto et al., 2004). Compared with cereal

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214amylopectins, buckwheat amylopectins had higher amount of LCAP (Yoshimoto et al., 2004).

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215The weight percentages of long unit chains of buckwheat amylopectins (2 genotypes of
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216common buckwheat and 1 genotype of tartary buckwheat) were 12‒13%, higher than that of

217indica rice (2 genotypes, 7 and 11%), wheat (3.4%), maize (5.6%), and sweetpotato (5.4%)
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218(Hanashiro et al., 2005). These LCAP were further isolated by precipitation with 1-butanol

219from isoamylase-debranched amylopectin (Hanashiro et al., 2005). LCAP of buckwheat had

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220higher blue values and max than the others. The number average DP and number of chains
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221per molecule of buckwheat LCAP ranged from 250‒330, and 1.2‒1.4, respectively. They were
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222rather different from that of amyloses, and similar to those of starches from other botanical

223sources. Molecular size distribution data showed that LC AP of buckwheat had higher amounts
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224of large molecules, compared with that of indica rice, wheat, maize, and sweetpotato
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225(Hanashiro et al., 2005). On molar basis, 6‒8% of the LCAP molecules of buckwheat were

226branched (resistant to isoamylase hydrolysis), and their number of chains per molecule

227ranged from 4‒6 (Hanashiro et al., 2005). There seemed to be no structural difference of LC AP

228between common and tartary buckwheat, though only 1 genotype of the latter has been

229analysed.

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230The external chains of amylopectin (from the non-reducing ends to the branches) can be

231removed by β-amylase to make the β-limit dextrins. The β-limit values (β-LV(%)) of

232buckwheat amylopectins, representing the removed part, ranged from 52‒56%, which are

233similar to that of cereal amylopectins. The internal part of amylopectin (from the reducing

234end to the branches) contains the branches which are clustered to form the basic branching

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235zones termed “building blocks” (Bertoft, 2013). The composition and structure of building

236blocks can be analysed by using α-amylase of Bacillus amyloliquefaciens (Bertoft, 2013). So

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237far, the building block structure of buckwheat amylopectin remains unknown.

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239Physical structure

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240Polymorphism and crystallinity
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241The adjacent external chains of amylopectin interact with each other and water to form

242crystals in the form of double helices (Peréz & Bertoft, 2010). The crystals are systematically
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243arranged to give A- and B-type polymorph of starch. C-type is a blend of A- and B-types
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244(Peréz & Bertoft, 2010). The polymorphism and degree of crystallinity of buckwheat starch
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245have been revealed by wide-angle X-ray scattering technique (WAXS). Starches of both

246common and tartary buckwheat had A-type polymorph (Lorenz & Dilsaver, 1982; Christa et
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247al., 2009; Zhou et al., 2009; Hurusawa & Miyashita, 1963; Qian & Kuhn, 1999b; Li et al.,
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2482014; Zheng et al., 1998; Liu et al., 2015a and 2015b; Gao et al., 2016). The degree of

249crystallinity of common buckwheat starch was 24.9% (Zhou et al., 2009), 38.0% (Li et al.,

2502014), and 38.31‒51.3% (5 genotypes) (Qian & Kuhn, 1999b). The large difference in the

251degree of crystallinity of starch between different studies is more likely due to quantification

252method, rather than the samples themselves. Therefore, the data from different studies is

253impossible to compare. The polymorph pattern can be affected by the growing conditions.

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254Hurusawa and Miyashita (1964b) showed that starch from buckwheat harvested in summer

255had an A-type polymorph, and that of the same genotype harvested in autumn was Ca-type.

256The internal chains of amylopectin are believed to form the amorphous lamellae in the

257granules. The crystalline and amorphous lamella alternate with each other to form a ~9 nm

258repeating unit, which further forms the semi-crystalline growth ring in the granules (Peréz &

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259Bertoft, 2010). Small angle X-ray scattering (SAXS) has been used to quantify the distance of

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260this repeating unit in buckwheat starch (Sanderson et al., 2006). SAXS data of buckwheat

261starch was mathematically modelled (Supplementary Fig. 1). ɛ of buckwheat starch (0.01), an

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262indication of how the lamellae buckle, was much smaller than that of B-type starches (0.2‒

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2630.8). The combined thickness of one crystalline and one amorphous lamella was 9.3 nm. The
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264differences in the molecular structure of buckwheat amylopectin, especially the internal and

265building block structure, may contribute to the difference in the SAXS results, which remains
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266to be studied.
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267
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268Granule morphology
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269The granule shape and dimension of buckwheat starch have been probed by light microscopy

270(LM), scanning electron microscopy (SEM), atomic force microscopy (AFM), and dynamic
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271light scattering technique (LS) (Table 3). The starch granules have smooth surface and are
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272most polygonal and less spherical (Fig. 2a) (Vallons & Arendt, 2009; Hurusawa & Miyashita,

2731963; Jane et al., 1994; Gregori & Kreft, 2012; Liu et al., 2015a and 2015b). Some small

274indentations were seen on the granule surface, and may be attributed to the amylase activity

275in the seeds (Lorenz & Dilsaver, 1982; Gregori & Kreft, 2012). The diameter of buckwheat

276starch ranges from ~2‒15 µm with an average value of ~6‒7 µm (Hurusawa & Miyashita,

2771963; Qian et al., 1998; Zheng et al., 1998). Therefore, the granules are more than two times

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278smaller than maize starch (Neethirajan et al., 2012). Compared with normal starch, starch

279with low amylose content from mutant samples (common buckwheat) is most spherical, and

280tends to be fragile and get squashed during sample preparation for SEM analysis (Gregori &

281Kreft, 2012). These granules with low amylose contents, which easily get cracked open

282during handling, appeared to have an empty space in the center as observed by SEM.

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283Granules of common and tartary buckwheat starches had similar shapes, and the latter

284appeared somewhat larger than the former in a comparative study (Gao et al., 2016).

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285AFM generates high resolution images by ‘feeling’ the starch surface with a sharp probe

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286instead of actual “seeing”, and the internal structure can be obtained by sectioning the granule

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287with a microtome (Ridout et al., 2004; Zhu, 2015). AFM has been used to visualize the
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288internal granule structure of common buckwheat starch (Fig. 2b) (Neethirajan et al., 2012).

289The edge of the granules is polygonal, and the central hilum was observed. Amorphous and
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290crystalline growth rings on which blocklets sit were seen. Growth ring structure becomes less

291obvious towards to the central hilum. These observations confirm the general structure of any
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292starch granules (Peréz & Bertoft, 2010). Quantitative AFM analysis of starch (e.g., blocklet
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293size and surface roughness) may reveal some structural differences between buckwheat and
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294other starches (Zhu, 2015), which may explain the differences in some functional properties

295as discussed in the physicochemical property section below.

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296
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297Physicochemical properties

298Swelling and solubility

299Various studies reported the swelling power, swelling volume, solubility, and amylose

300leaching of buckwheat starch in a wide range of temperature (60‒92.5 oC) (Table 4). The

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301difference in swelling power and solubility obtained from the same temperature among

302different studies appeared rather large, as compared with the difference between genotypes of

303the same study (Liu et al., 2015b; Li et al., 2014; Acquistucci & Fornal, 1997; Lu and Baik,

3042015). This may be more attributed to the differences in the experimental conditions, rather

305than the buckwheat genetics. For example, the speed and time of centrifugation, used for the

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306formation of sediment and supernatant phases after heating, differed from each other in

307various studies (e.g., 2,000 × g for 10 min (Acquistucci & Fornal, 1997), 3,000 rpm for 15

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308min (Liu et al., 2015a and 2015b), and 700 × g for 15 min (Lorenz & Dilsaver, 1982)).

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309Therefore, it is rather inaccurate to compare data from different studies. Within the same

310study, diversity in swelling and solubilization behaviours of buckwheat starch has been

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311observed (Lu and Baik, 2015; Li et al., 1997). It appears that starches of common and tartary
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312buckwheat were similar in swelling behaviour (swelling volume) (3 genotypes each) (Li et

313al., 1997), and the former had somewhat higher solubility than the latter (2 genotypes each)
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314(Gao et al., 2016). More buckwheat genotypes should be employed systematically to reveal if
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315the swelling and solubility of starch are species-specific.

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316Swelling and solubilization of buckwheat starch have been compared with other starches
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317(Kim et al., 1977). Compared with wheat and rye starches, common buckwheat starch started

318swelling at a higher temperature with higher swelling power (Kim et al., 1977). This is
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319supported by another study that common buckwheat starch started swelling at a higher
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320temperature, and had higher swelling power and lower solubility, as compared with wheat

321starch (Acquistucci & Fornal, 1997), but in contrast with one study that buckwheat starch had

322lower swelling power and solubility than wheat and maize starches when temperature was

323over 75°C (Qian et al., 1998). Compared with maize and potato starches (1 genotype each),

324tartary and common buckwheat starches (2 genotypes each) had much lower solubility (70‒

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32590 oC), and tartary buckwheat starches had somewhat lower solubility than common

326buckwheat starches (Gao et al., 2016).

327The differences in the results of swelling and solubility within buckwheat starches and among

328different types of starches may be attributed to the differences in the starch structure and

329composition (Srichuwong and Jane, 2007). For example, higher contents of amylose and

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330amylose-lipid inclusion complex in buckwheat starch reinforced the internal granules and

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331restricted the swelling and leaching (Qian et al., 1998). Structural basis for these

332discrepancies among various studies remains to be explored.

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333Gelatinization measured by Kofler hot-stage microscopy and differential scanning

334calorimetry

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335Gelatinization of buckwheat starch has been analysed by Kofler hot-stage microscopy
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336(KHSM) and differential scanning calorimetry (DSC) (Table 5). Apart from the gelatinization

337temperatures (onset temperature (To), peak temperature (Tp), conclusion temperature (Tc)),
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338KHSM can visualize the gelatinization process while the DSC can obtain the enthalpy change
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339(ΔH). Hot-stage microscopic study on buckwheat starch at an extremely low concentration

340showed that granules started to swell at 65 oC, and continued to swell up to 92.5 oC, while
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341keeping the granular shape (Hurusawa and Miyashita, 1966). KHSM and DSC methods differ
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342in the experimental conditions, and tend to give different results for the same sample (Hari,
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343Garg, & Garg, 1989). Scanning rate of DSC analysis may affect the results (Liu and Lelièvre,

3441991). 5 oC/min and 10 oC/min were used to analyse buckwheat starches in different studies

345(Yoshimoto et al., 2004; Li et al., 1997). Water content may also influence the gelatinization

346behaviours of starch (Zhou et al., 2009). Decreasing water content (e.g., less than 50%)

347resulted in incomplete gelatinization when the heating temperature was lower than 100 oC

348(Eliasson, 1980). In some of the reports with sufficient amount of water for complete

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349gelatinization (Zhou et al., 2009; Vallons & Arendt, 2009; Qian & Kuhn, 1999a), ΔH of

350buckwheat starch appeared much lower (e.g., 2.4 J/g) than that of some other reports and also

351cereals (Li et al., 1997; Eliasson, 1980). Thus, these results were excluded in this review. This

352may be attributed to the DSC system that was not properly calibrated, the starch samples that

353were severely damaged in the first instance, and to a less likelihood, the genetics of the

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354buckwheat variety. Diversity in gelatinization behaviours of buckwheat starch has been

355observed (Noda et al., 1998; Yoshimoto et al., 2004; Lu and Baik, 2015). For example, Tp and

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356ΔH of starches from 27 buckwheat genotypes (both common and tartary buckwheat) ranged

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357from 57.2–66.7 oC and from 9.4–13.9 J/g, respectively, though the difference between

358common and tartary buckwheat starches was not analysed (Noda et al., 1998). There appears

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359to be little difference in the DSC parameters between common and tartary buckwheat starches
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360in comparative studies (Li et al., 1997; Gao et al., 2016). Amylose content had little

361correlations with gelatinization profile, while the unit chain length distribution of
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362amylopectin was highly correlated with To, Tp, and ΔH (Noda et al., 1998). The amounts of
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363unit chains of DP 7‒11 and DP 12‒17 were negatively and positively correlated to To, Tp, and
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364ΔH, respectively (Noda et al., 1998). Unit chains with DP 7−11 may be too short to from

365double helices, and they tend to cause defects in the crystals (which may be most composed
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366of chains with DP 12‒17) (Srichuwong and Jane, 2007).

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367Gelatinization of buckwheat starch has been compared with that of other starches in the same
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368study (Zheng et al., 1998; Qian et al., 1998; Gao et al., 2016). Compared with maize and

369wheat starches, starch of common buckwheat had a wider gelatinization temperature range

370(Qian et al., 1998). This suggests that buckwheat starch is more structurally heterogeneous

371than the other two, and may result from milling process or genetics. Compared with rice and

372maize starches (1 genotype for each), common buckwheat starch (1 genotype) had lower To

373and Tp, and higher ΔH (Zheng et al., 1998). To, Tp, and Tc of common and tartary buckwheat

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374starches (2 genotypes each) were lower than those of maize starches and higher than those of

375potato starch (1 genotype each). Both had lower ΔH than maize and potato starches (Gao et

376al., 2016). Buckwheat starches (common and tartary buckwheat) had higher Tp and Tc than

377wheat starch (Li et al., 1997; Qian et al., 1998). The gelatinization of starch is influenced by

378interactive factors including granule morphology, amylose content, molecular structures of

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379amylopectin and amylose, and minor-component contents, in which buckwheat starch differs

380from other starches (Srichuwong and Jane, 2007).

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381The endogenous lipids in buckwheat starch form V-type inclusion complexes with amylose

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382which have been analysed by DSC (Lu and Baik, 2015; Qian et al., 1998). ΔH of melting of

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383amylose-lipid inclusion complexes in buckwheat starch (6 genotypes) ranged from 0.9‒1.8
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384J/g (Lu and Baik, 2015). ΔH of re-melting these amylose-lipid inclusion complexes ranged

385from 1‒1.7 J/g (Lu and Baik, 2015). Amylose-lipid inclusion complexes of common
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386buckwheat starch (1 genotype) had To of 70.8 oC, Tp of 84.6 oC, Tc of 99.7 oC, and ΔH of 2.0

387J/g, respectively (Qian et al., 1998). Compared with that of maize and wheat starches, the
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388melting temperatures of inclusion complexes were lower and the ΔH was higher. The
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389difference in the thermal properties of amylose-lipid inclusion complexes between buckwheat

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390starch and others could be due to the difference in the content and structure of amylose and

391lipids.
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392
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393Pasting

394Pasting properties of buckwheat starches have been analysed by Rapid Visco-Analyzer

395(RVA), Brabender Viscoamylography (BVA), Brabender Amylograph (BA), and Brabender

396Micro Visco-Amylo-Graph (MVAG) at various starch concentrations (5.5‒11%) (Table 6). It

397is impossible to compare the results from different studies employing different instruments

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398and starch concentrations. For example, gelatinization of buckwheat starch (5 genotypes) was

399studied by DSC, BVA, and RVA (Qian & Kuhn, 1999a). Comparison between the results of

400BVA and RVA on the same samples revealed little correlations (Qian & Kuhn, 1999a). It is

401also noted that gelatinization temperatures of buckwheat starch measured by DSC were lower

402than those of BVA and RVA, and may be attributed to the increasing pressure generated

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403during heating in the sealed DSC crucibles (Qian & Kuhn, 1999a). The different aspects of

404gelatinization measured by various methods may differentially reflect various aspects of

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405granule structure. Within the same study, diversity in pasting properties has been observed

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406(Yoshimoto et al., 2004; Lu and Baik, 2015). For example, PV of buckwheat starch from 7

407genotypes ranged from 226‒261 RVU (Yoshimoto et al., 2004). Differences in pasting pattern

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408between common and tartary buckwheat starches have been observed (Li et al., 1997; Gao et
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409al., 2016). One study (2 genotypes for each species) showed that common buckwheat starch

410had lower PV than tartary buckwheat starch, while the other study (3 genotypes for each
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411species) observed the opposite pattern (Li et al., 1997). This may be attributed to the crop
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412genetics and growing conditions. Indeed, another study showed that pasting properties were
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413affected by the growth environment (Hurusawa and Miyashita, 1964b). Starch from

414buckwheat harvested in summer had a lower pasting temperature by 3 oC and a higher peak
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415viscosity (PV) than that of the same genotype harvested in autumn (Hurusawa and Miyashita,

4161964b).
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417Pasting of buckwheat starch has been compared with that of other starches and showed

418differences (Gao et al., 2016; Li et al., 1997; Zheng et al., 1998; Acquistucci & Fornal, 1997;

419Praznik et al., 1999; Qian et al., 1998). Compared with wheat starch, buckwheat starch had

420higher PV (Acquistucci & Fornal, 1997; Li et al., 1997; Praznik et al., 1999). Pasting

421viscosity of both common and tartary buckwheat starches (2 genotypes) was lower than that

422of potato, and higher than that of maize starch (1 genotype each) (Gao et al., 2016). Both

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423buckwheat starches had higher breakdown (BD) than maize and potato starches, higher

424setback (SB) than maize starch but lower than potato starch. In another comparison study

425(Praznik et al., 1999), common buckwheat starch had higher final viscosity than amaranth,

426proso millet, wheat, quinoa, and waxy maize starches. Different starches differ in their

427chemical composition and structures which affect the pasting properties (Srichuwong and

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428Jane, 2007). For example, defatting may have a great influence on pasting properties

429(Hurusawa & Miyashita, 1964a). Buckwheat amylopectin contains relatively high amount of

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430extra-long unit chains. These long unit chains were negatively correlated to BD of rice starch

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431paste (Han & Hamaker, 2001). Indeed, buckwheat starches (6 genotypes) had lower BD than

432wheat starch (Li et al., 1997). However, another study showed that buckwheat starches (4

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433genotypes) had higher BD than maize and potato starches (Gao et al., 2016). Other factors
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434such as amylose content, presence of minor components, and granule structure may

435contribute to this discrepancy (Srichuwong and Jane, 2007). Molecular weight of starch
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436appeared not determinative in pasting properties (Praznik et al., 1999).

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437
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438Retrogradation
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439Upon cooling, the disordered amylose and amylopectin of the gelatinized starch re-associate
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440to re-gain a degree of order. This process, termed retrogradation, can be reflected by various
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441physicochemical properties of the resulting retrograded starch, and probed by diverse

442experiments with different techniques (Wang et al., 2015). The initial retrogradation is most

443attributed to the re-association of amylose, and the long-term retrogradation is due to the

444recrystallization of amylopectin side chains (Wang et al., 2015). Factors affecting

445retrogradation of starch include composition and structures of starch components, thermal

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446processing conditions, water content, and temperature (Wang et al., 2015). Diverse aspects of

447retrogradation of buckwheat starch has been probed as follows:

448

449Freeze-thaw stability and syneresis

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450The retrogradation of starch leads to the formation of new crystals, resulting in reduced water

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451holding capacity and syneresis. The gelatinized starch undergoes freeze/cool-thaw cycles in

452some processing scenarios. Common buckwheat starch had better freeze-thaw (‒7 oC/30 oC)

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453stability than amaranth, proso millet, wheat, quinoa, and waxy maize starches (Praznik et al.,

4541999). Buckwheat starch gel had less syneresis than maize and wheat starch gels, even

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455though the former had higher amylose content which is positively linked to syneresis (Qian et
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456al., 1998; Srichuwong et al., 2012). Another study on buckwheat starch gels from 6 genotypes
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457confirmed that syneresis was positively related to amylose content and also resistant starch

458content of cooked groats (Lu and Baik, 2015). Comparative study showed that common
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459buckwheat starch had denser packing of glucan coils than the other starches (Praznik et al.,
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4601999). This may explain the better water holding capacity of buckwheat starch within the

461packing matrix.
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462
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463Re-crystallization
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464Retrogradation behaviour of buckwheat starch at 21 oC for 6 days was modelled by Avrami

465equation. The result suggested that the re-crystallization of amylopectin is instantaneous

466nucleation followed by rod-like growth of crystals (Kim et al., 1977). Diversity in starch

467retrogradation, measured by DSC has been observed. Retrograded buckwheat starches (6

468genotypes) had To of 39.3‒41.5 oC, Tp of 49.2‒51.2 oC, Tc of 59.2‒60.9 oC, and ΔH of 4.6‒5.6

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469J/g (Lu and Baik, 2015). Buckwheat starch had a lower retrogradation than wheat and maize

470starches at ‒12 oC and 25 oC (Qian et al., 1998).

471

472Starch paste turbidity

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473Pasted starch (2%) was stored at 4 oC up to 15 days and diversity in turbidity development

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474has been observed (6 genotypes) (Lu and Baik, 2015). Turbidity was positively linked to

475amylose and resistant starch contents of starch.

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476

477Gel textural properties

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478Pasted starch was stored at 4 oC for 1 day and the textural properties of the resulting gel
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479showed great diversity (6 genotypes) (Lu and Baik, 2015). Hardness, cohesiveness, and

480springiness were positively linked to amylose and resistant starch contents of cooked groats.
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481Pasted starch was stored at room temperature for 1 day. Compared with wheat starch gel,
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482buckwheat starch gels (3 genotypes of common buckwheat and 3 genotypes of tartary

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483buckwheat) had considerably higher hardness (Li et al., 1997). Shearing of 1000 s–1 was

484applied on starch gels for 5 min (Praznik et al., 1999). Buckwheat starch gel had a lower
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485stability against shearing than amaranth, quinoa, and wheat starch gels. When the pH was
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486lowered to 3, the stability of buckwheat starch gel was lower than that of quinoa and millet

487starches, and higher than amaranth, wheat, and waxy maize starches (Praznik et al., 1999).

488The stability against shearing was suggested to be determined by higher amounts of shorter

489chains of starch, but not by the molecular weight of starch (Praznik et al., 1999).

490

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491Enzyme susceptibility and digestion

492Enzyme susceptibility of buckwheat starch has been compared with other starches

493(Acquistucci & Fornal, 1997; Qian et al., 1998). Native common buckwheat starch (1

494genotype) had higher susceptibility to porcine pancreatic α-amylase than normal wheat and

495maize starches (1 genotype each) (Qian et al., 1998). This was attributed to the smaller

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496granule size, also higher amylose content (thus higher portion of amorphous region in the

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497granules). Compared with wheat starch (1 genotype), common buckwheat starch (2

498genotypes) had higher content of rapidly digestible starch (RDS) (41 and 46% for buckwheat

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499and 34% for wheat) and lower content of slowly digestible starch (SDS) (46 and 49% for

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500buckwheat and 58% for wheat) (Acquistucci & Fornal, 1997).
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501Enzyme susceptibility of starch in various buckwheat food products (flour, groats, and bread)

502has been studied (Wolter et al., 2013; Lu and Baik, 2015; Acquistucci & Fornal, 1997). A
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503comparison study on the in vitro starch digestibility and predicted glycaemic index showed
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504that gluten-free bread of buckwheat had lower digestion than quinoa and white wheat bread,
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505but higher than oat, sorghum, and teff gluten-free breads (Wolter et al., 2013). Apart from

506non-starch factors such as dietary fiber and lipids, characteristics of starch determined the in
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507vitro digestibility of these breads. Gelatinization temperatures of buckwheat starch are lower

508than that of sorghum and teff, and higher than that of quinoa and wheat. The granule size is
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509larger than that of quinoa. Amylose content is also higher than that of quinoa, facilitating the
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510formation of amylose-lipid inclusion complexes which are resistant to enzyme hydrolysis

511(Wolter et al., 2013). Diversity in resistant starch (RS) content of cooked buckwheat groats

512has been observed (1.6‒3.8 g/100g), and the RS content was correlated to various

513physicochemical characteristics of isolated starch (Lu and Baik, 2015). RS was positively

514correlated to amylose content, starch paste turbidity, and gel hardness, while being negatively

515correlated to pasting temperature and peak viscosity, and To and Tp of the melting of

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516retrograded starch (Lu and Baik, 2015). Indeed, retrograded starch (type 3 RS) is much

517determined by the re-association and re-ordering of amylose component (Sajilata et al.,

5182006).

519Processing of buckwheat may affect the enzyme susceptibility of starch (Table 7). Groats

520were subjected to autoclaving (120 oC for 1h) and cooling (to room temperature) cycles

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521(Skrabanja & Kreft, 1998). This processing increased the resistant starch content and little

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522affected the slowly digestible fraction. Hydrothermal treatment gave a 5.5% of type 3

523resistant starch which was indigestible in rats. Groats dry-heated at 110 °C had less amount of

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524rapidly digestible starch than hydrothermally treated samples (Skrabanja et al., 1998).

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525Roasting at 160 oC for 30 min decreased the enzyme susceptibility of starch (Christa et al.,
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5262009). By varying the experimental conditions of hydrothermal processing, a reduced rate of

527enzyme susceptibility of buckwheat products could be obtained (Skrabanja et al., 1998).

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528These physical processing techniques can be feasibly applied to everyday cooking for

529nutritional practice.
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530Difference in the enzyme susceptibility between buckwheat starch and buckwheat food

531products has been observed (Acquistucci & Fornal, 1997; Takahama & Hirota, 2011). For
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532example, in comparison with wheat flour, buckwheat flour had similar amount of RDS and

533higher or lower SDS, while the starches showed a different pattern as discussed above
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534(Acquistucci & Fornal, 1997). The enzyme susceptibility of boiled buckwheat noodles was
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535compared with that of white wheat bread, boiled wheat noodles, and boiled buckwheat groats

536(Kreft & Skrabanja, 2002). Boiled buckwheat groats had the lowest enzyme susceptibility

537and highest resistant starch content, followed by boiled buckwheat noodles, boiled wheat

538noodles, and white wheat bread. This suggests that the other factors physically and

539chemically affect enzyme susceptibility of starch in the food matrix (Singh et al., 2010).

540Lipids (e.g., fatty acids), proteins, epicatechin-dimethylgallate, dietary fiber, rutin, phytic

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541acid, protease inhibitors, and tannins present in the buckwheat flour interact with starch

542and/or α-amylase, and make the starch less available to the enzyme hydrolysis (Wolter et al.,

5432013; Kreft & Skrabanja, 2002; Takahama & Hirota, 2011; Wijngaard & Arendt, 2006).

544Furthermore, the bile salts (e.g., cholate and taurocholate) in the intestine may interact with

545starch to reduce the starch digestion (Takahama & Hirota, 2011). The relatively low glycemic

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546profile of buckwheat has been confirmed in clinical model in vivo (Skrabanja et al., 2001)

547(Fig. 3). In vitro and in vivo (human) starch digestion analysis showed that boiled buckwheat

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548groats and bread containing buckwheat flour had lower enzyme susceptibility and in vivo

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549glycemic index than white bread (Skrabanja et al., 2001). Buckwheat groats also gave higher

550post-meal satiety than breads (Skrabanja et al., 2001). This suggests the importance of food

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551matrix structure in satiating capacity, and confirms the role of whole grain buckwheat in
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552glycaemic and weight management.
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553
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554Modifications
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555Native buckwheat starch has been treated physically and chemically to alter the

556physicochemical properties and structures of starch (Table 7).

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557Physical modifications
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558Heat-moisture treatment (HMT) of starch decreased the solubility and swelling, PV of

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559pasting, hardness and adhesiveness of gel, increased the degree of crystallinity, gelatinization

560temperatures, and slowly digestible starch content, without affecting the polymorph pattern

561(Liu et al., 2015b). Microwave assisted hydrothermal treatment and roasting also gave similar

562results (Zondag, 2003; Christa et al., 2009). Moisture content had a great influence on the

563outcome of the hydrothermal treatments (Liu et al., 2015a and 2015b; Zondag, 2003). For

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564example, increasing moisture content of starch from 20–35% decreased swelling power and

565solubility, PV, BD, SB, and FV (final viscosity) of pasting, decreased ΔH of gelatinization,

566and increased the water absorption capacity, gelatinization temperature range, degree of

567crystallinity, and resistant starch content (Liu et al., 2015a and 2015b). These observations

568agreed with the previous reports on other types of starch (Hoover, 2010). Similar to HMT,

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569annealing (starch to water ratio at 1:4, 50 oC for 24 h) of common buckwheat starch had no

570effect on granular polymorphism, increased gelatinization temperatures and resistant starch

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571content, decreased swelling and water solubility, PV, BD, SB, and FV of pasting, and ΔH of

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572gelatinization (Liu et al., 2015a). Hydrothermal treatments facilitate the re-alignment and re-

573association of chain segments with certain degree of mobility in the granules, without

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574disrupting the ordered crystalline structure (Hoover, 2010). Common buckwheat starch in
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575water (25%, w/w) was treated with high pressure from 200 to 600 MPa (Fig. 2a). Starch

576gelatinization occurred between 300 to 500 MPa. Compared with heat-induced gelatinization,
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577high pressure-induced gelatinization retained the granule shape and gave the resulting gel
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578stronger texture (Vallons & Arendt, 2009). Common buckwheat starch has been subjected to
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579ball-milling (Li et al., 2014). Ball-milling most disrupted the granule and destroyed the

580crystallinity as revealed by thermal and pasting analysis. Maltese cross pattern of granules
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581was partially retained (Li et al., 2014). Pre-gelatinization of common buckwheat starch with

582drum drying for cold water soluble starch production increased the swelling power and
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583solubility of starch, and PV of pasting, and decreased the degree of crystallinity (Li et al.,
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5842014).

585Buckwheat starch has been blended with non-starch polysaccharides (hydrocolloids) and

586mucilage to obtain novel physicochemical properties (Liu et al., 2006b; Cho et al., 2009;

587Choi and Chang, 2012). Addition of yellow mustard mucilage increased PV of pasting, G'

588(storage modulus) and G'' (loss modulus) of dynamic oscillatory rheology, hardness and

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589adhesiveness of gel, and the temperature range of gelatinization, while decreasing the

590syneresis (Liu et al., 2006b). Addition of galactomannans (guar gum, tara gum, and locust

591bean gum) gave synergy in apparent viscosity, consistency index, yield stress, dynamic

592moduli, and complex viscosity with buckwheat starch (Choi and Chang, 2012). An

593antagonistic effect in viscosity of buckwheat starch and fucoidan blends was seen when the

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594concentration of fucoidan was less than 0.5%. When the concentration of fucoidan became

595higher than 0.5%, G' of dynamic rheology kept increasing with the ratio (Cho et al., 2009). It

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596was suggested that phase separation between starch and fucoidan might occur when there are

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597enough solids. This may lead to the increasing interactions among fucoidan molecules and

598also starch chains, resulting in the formation of three-dimensional networks (Cho et al.,

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5992009). A systematic review showed that the pasting and gelling properties of starch and
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600hydrocolloid mixtures, as well as the mechanisms of interactions, are dependent on the types

601of starch and hydrocolloids, the concentration of the solids, and the preparation methods of
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602the composite gels (BeMiller, 2011).

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603Chemical modifications
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604Buckwheat starch has been acetylated (Zheng et al., 1998), acid hydrolysed (Qian et al.,
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6051998; Neethirajan et al., 2012), and treated in alkaline-ethanol mixture (Li et al., 2014).

606Acetylation decreased gelatinization temperatures and retrogradation, and increased water

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607solubility and cold storage stability of the gel (Zheng et al., 1998). The spherical
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608nanocrystals, 120‒200 nm long and 4‒30 nm in diameter, were produced in H2SO4 solution

609(3.16 M) at 40 oC for 5 days (Neethirajan et al., 2012). Compared with wheat and maize

610starches, buckwheat starch was more susceptible to acid hydrolysis (HCl solution (2.2N), 35

611oC, up to 24h) (Qian et al., 1998). This may be attributed to higher surface area and more

612amorphous region (e.g., higher amylose content) in the granules (Qian et al., 1998). Cold

613water soluble starch with increased transmittance of gel and decreased crystallinity was

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614produced by treating starch in NaOH-ethanol solution at 70 oC. The resulting starch retained

615the granule shape and Maltese cross pattern, and had reduced pasting viscosity and ΔH of

616gelatinization (Li et al., 2014). All the outcomes of these chemical modifications agreed with

617previous reports of modifications on other types of starches (Wurzburg, 1986).

618

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619Uses

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620There have been limited uses of buckwheat starches for food and industrial applications even

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621at the laboratory level (Table 8).

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622Common buckwheat starch has been used in pie fillings, and showed consistency that was
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623comparable to wheat, millet, and triticale starches. However, when used in cake production,

624the baking performance was inferior, compared with wheat starch, as revealed by sensory
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625evaluation (Lorenz & Dilsaver, 1982). When used as an ingredient with milk protein for

626extruded products, the products had lower enzyme susceptibility of starch than that of pure
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627buckwheat starch (Śmietana et al., 1988). The small size of buckwheat starch, similar to lipid
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628micelles, suggests potential use as fat replacers (Gregori & Kreft, 2012). A patent described
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629that buckwheat starch can be fat replacers in an oil-and-water emulsion to give smooth

630organoleptic taste, due to the size and shape of buckwheat starch granules (Singer, 1994).
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631Buckwheat starch may be modified with octenyl succinic anhydride (OSA) to enhance the
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632hydrophobicity. The OSA modified starch, with relatively small granule size, may be used as

633emulsifiers to stabilise Pickering emulsions (Timgren, Rayner, Sjöö, & Dejmek, 2011).

634Buckwheat starch has also been suggested as fermentation substrate for the production of

635beer-like alcoholic beverage (Kusano et al., 1999). Indeed, buckwheat beer is a commercial

636product. Nanocrystals, produced by acid hydrolysis of buckwheat starch, has been

637incorporated in starch films (Neethirajan et al., 2012). The resulting films had lower water

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638penetration and a 3-stage transition of moisture adsorption (Neethirajan et al., 2012). The

639small granules of buckwheat starch may also be suitable as ingredients for cosmetics and as

640fillers in bio-composite.

641The limited uses of buckwheat starch is probably due to abundant and cheap supply of other

642starches such as maize and potato starches. Another reason is the limited exploitation of

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643buckwheat starch for various possible applications. The unique chemical composition,

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644structures, and properties of buckwheat starch should grant it a special place in some food

645and non-food applications. To be able to increase the potential uses of buckwheat starch, a

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646wide range of diversity in properties and structures should be explored by natural (e.g.,

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647genetic resource evaluation) and artificial (e.g., physical and chemical modifications) means.
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648
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649Conclusions

650The conclusions on buckwheat starch according to the majority of literature are:

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651(1) The amylose contents are similar to that of normal cereals (ca. 20‒28%); (2) starch

652granules are most polygonal, and the size ranges from ~2‒15 µm with an average value of
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653~6‒7 µm; (3) A-type polymorph; (4) amylopectin chemical structure of starches from

654common and tartary buckwheat is similar, and may be due to limited genotypes analysed; (4)
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655the amount of extra-long chains of amylopectin (DP > 100) is more than those of cereal
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656amylopectins; (5) low glycemic index of buckwheat food products may be attributed to the

657non-starch components and food matrix effects.

658Methods for evaluation of starch structures and properties should be standardized to

659maximize the communal research efforts. Genetic resource of starches from common

660buckwheat and especially from tartary buckwheat should be further explored. So far, there is

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661no report on starches from other buckwheat species such as F. dibotrys. Structural basis for

662physicochemical properties of buckwheat starches or between buckwheat and other starch

663types should be better explored in comparative studies. The roles of amylose and amylopectin

664in the physicochemical properties can be better studied. More types of physical and chemical

665modifications can be conducted to widen the variations in the structures and properties of the

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666starch. Comprehensive approaches on composition-structure-property-modification-use

667relationships, rather than just focusing on one aspect, should be employed to maximize the

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668possible utilization of buckwheat starch.

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669

670References

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674Ahmed, A., Khalid, N., Ahmad, A., Abbasi, N. A., Latif, M. S. Z., & Randhawa, M. A.
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675(2014). Phytochemicals and biofunctional properties of buckwheat: a review. Journal of

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676Agricultural Science, 152, 349–369.

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678Starch/Stärke, 53, 475–503.

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 Diverse aspects of buckwheat starch is comprehensively reviewed

 Starch structure-property relationships are explored

 How buckwheat starch can be better utilised is suggested

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Dear Prof. Yada,

Thank you for the feedback regarding the submitted article (TIFS_2015_136). The referees'
comments were constructive, and I believe by implementing the comments in the revised

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manuscript the paper is much improved. I have addressed all of the referees' comments and
below have outlined in detail how each of the points has been addressed.

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Sincerely,

Fan Zhu (Dr)

Lecturer
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Food Science and Nutrition Programme
School of Chemical Sciences
University of Auckland
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Auckland, New Zealand

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-Reviewer #1

Comments to the Author

The review manuscript entitled “Buckwheat starch: Structure, properties and applications” is

good. It is substantial in content including many important properties. The English is good,

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but there are some sentences not necessory. It needs some major revisions that are highlighted

in the attached file.

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Response: I thank the useful comments from the reviewer which greatly improved the

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manuscript.

1. Many of the references were reported more than 10 year ago. And I can not find the

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reference reported by Cai, Corke, & Li (2004), please revise it.
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Response: This reference is added now. Cai, Corke, & Li (2004). Buckwheat. In C.W.
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Wrigley, H. Corke, and C.E. Walker (Eds.), Encyclopedia of Grain Science, (pp 120‒128).

Elsevier, Oxford.
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2. In line 41, I advise to add a bracket on F.tataricum. The authors should add a reference to
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support the description about the F. Dibotrys in line 43.

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Response: A bracket is added li line 41. Also, a reference is added in line 43. Liu, G., Li, M.,
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Zhu, Q., Li, Y., & Shui, S. (2006a). The research advance on resource plant Fagopyrum

dibotrys. Chinese Agricultural Science Bulletin, 22, 380−389.

3. The format of the reference in line 45 is different from the one in line 39. Are there two

references reported by Cai. Et al ?

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Response: They are the same reference and is added now.

4. The references using in line 59 are a little bit old. I suggest to read some papers from Guo

Xudan et al to understand the function of healing and preventing chronic diseases of

buckwheat.

PT
Response: Now a new reference suggested by the reviewer is added. Also, another updated

reference from just last year is added.

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[1] Xu-Dan Guo, Dong-Yan Zhang, Xue-Jiao Gao, John Parry, Kang Liu, Bao-Lin Liu, Min

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Wang. Quercetin and quercetin-3-O-glucuronide are equally effective in ameliorating

endothelial insulin resistance through inhibition of reactive oxygen species-associated

U
inflammation. 2013. Molecular Nutrition & Food Research.
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[2] Xu-Dan Guo, Chun-Sen Wu, Yu-Jie Ma, John Parry, Yuan-Yuan Xu, Hang Liu, Min

Wang. 2012. Comparison of milling fractions of tartary buckwheat for their phenolics and
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antioxidant properties. Food Research International, 49: 53-59 .

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[3] Xu-Dan Guo, Min Wang, Jin-Ming Gao, Xin-Wei Shi. 2012. Bio-guided fraction of

antioxidant activity of ethanol extract from tartary buckwheat bran. Cereal Chemistry, 89
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(6):311-315.

[4]Xu-Dan Guo, Yu-Jie Ma, John Parry, Jin-Ming Gao, Liang-Li Yu and Min Wang. 2011.

Phenolics content and antioxidant activity of tartary buckwheat from different locations.

Molecules, 16: 9850-9867.

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5.In line 81-84, authors wanted to express the properties of starch are critical for the quality

of products, but these are not clear. The reader can not understand the critical roles of the

starch.

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Response: An explanation is added that this is due to starch gelation property.

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6. Change the word “normal” to “common” in line 130.

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Response: This is actually normal (a word usually used) as opposed to mutants (waxy and

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high amylose genotypes).
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7. Advise to delete the sentence in line 145-147, which is not related to this paper closely.

And it may be the speculation by the authors.

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Response: This is actually well reviewed previously, and a reference (Baldwin, 2001) is
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added now to support this.

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8. I am not sure that the meaning of “max” in line 172. Please make it clear.
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AC

Response: This is max. The system is not showing it after converting MSWord file to PDF

online. Hopefully, this will be resolved in the production stage.

9. The authors should add a reference to support the statement in line 238.

Response: the paper (Peréz & Bertoft, 2010) (an excellent review) is added.

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10. The SEM can not observe the inner structure of the starch granules. So how the authors

know that low amylose contents are related to the empty space in the granule center in line

276-277.

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Response: These granules get cracked easily. Now, the whole sentence is revised to be

clearer.

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11. The “Swelling” section is not good. It just the simple exerpt. There needs some

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summarisations. The references citing in this part are limited, and most of them were

published more than 10 years ago.

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Response: Now the whole section is re-arranged with more information added.
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12. The example in line 328-330 is not appropriate. It makes the context more confused.
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Meanwhile, this example does not show the functions of these two methods clearly.
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Response: The sentence is modified. Also, a relevant reference is added now.

Hari, P. K., Garg, S. and Garg, S. K. (1989), Gelatinization of Starch and Modified Starch.
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Starch/Stärke, 41: 88–91.

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AC

13. Change “7 to 11” to 7-11 in line 353. Make it consistent with obove pattern.

Response: This is corrected now.

14. Please refine the “Pasting” section. Limit the comparation between the different

technology. The main point is to show the pasting properties of buckwheat starches.

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Response: The comparison between different methods is a pre-requisite to better understand

the pasting of buckwheat starch and correctly interpret data. This point is added in the

conclusion part.

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15. The “Retrogradation” part does not show any statement of buckwheat starch

16. The “Re-crystallization” part should be combined with “ Retrogradation” part. I

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mean they can write together.

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17. Delete the “Starch paste turbidity”. It has no extensive meaning because of just one

reference.

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18. The Gel textural properties is not good enough. Limited references can not make is clear.

The authors can read the artical reported by Ma Yujie that show the textural properties of
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buckwheat noodles.
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[5]Ma Y J, Guo X D, Liu H, Xu B N, Wang M. 2013. Cooking, textural, sensorial and

antioxidant properties of common and tartary buckwheat noodles. Food Science and
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Biotechnology, 22(1): 153~159

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Response: Actually they (including Starch paste turbidity and gelling) are together. This part

is solely focusing on the starch properties rather than product property. Please refer to the font

style of the title (as required by the Journal). “Retrogradation” includes diverse aspects. Also,

a sentence is added as “Diverse aspects of retrogradation of buckwheat starch has been

probed as follows:”

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19. Consider to delete the sentence in line 497-498.

Response: The sentence is re-arranged.

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20. In the physical modification part, author can add the artical reported by Liu et al (2015,

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Carbohydrate Polymers) that does the physical modification on the common buckwheat

starch.

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[6] Hang Liu, Xudan Guo, Wuxia Li, Xiaofang Wang, Manman lv, Qiang Peng, Min
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Wang∗.Changes in physicochemical properties and in vitro digestibility of common

buckwheat starch by heat-moisture treatment and annealing. Carbohydrate Polymers 2015,

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132: 237–244.
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Response: this reference is added and incorporated into the manuscript.

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-Reviewer #2
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- The author has clearly reviewed all aspect of buckwheat starch in detail. I recommend to

make a separate list of abbreviations, since there are lot of abbreviations that are not clearly

indicated. Moreover, try to reduce information in supplementary text. Please correct all

references according to the instructions.

If you put one paragraph indicating emulsifying properties of buckwheat starch, its greater. It

will increase the worth of this review.

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Response: I thank the kind comments from the reviewer. I carefully denoted the

abbreviations when appearing for the first time in the text. Less tables and figures are

supplementary now. The journal only allows limited numbers of tables and figures. So some

of them are with supplementary materials.

Potential uses of modified buckwheat starch for emulsifying has been suggested with a new

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reference added.

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Table 1 Chemical composition of buckwheat starch

Buckwheat type No. of Amylose Method for Protein (%) Lipid (%) Ash (%) Reference
genotypes content (%) quantification

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Common 1f 25 IA Hurusawa & Miyashita, 1965
Common 1 25 IC 0.4 0.13 Kim et al., 1977

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Common 1a 0.5‒0.75 0.1‒0.96 Lorenz & Dilsaver, 1982
Common 3 21.5‒25.3 IC 1.04‒1.30 0.81‒0.98 Li et al., 1997
Common 2 22, 28.5 IC 0.3, 0.4 1.7, 1.8 0.63, 1.47 Acquistucci & Fornal, 1997

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Common 30 23.4‒29.1 IC Ikeda et al., 1997
Common 1 21.3 Con A 0.6 0.05 0.2 Zheng et al., 1998
Common 1 46.6 IC 0.16 0.41 0.1 Qian et al., 1998

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Common 1 25 IC Praznik et al., 1999

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Common 5 21.3‒26.4 Con A Qian & Kuhn,1999b
Common 7 15.6‒17.9, IA Yoshimoto et al., 2004
25.7‒26.5 c

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Common 1 17.1 IC 1.2 0.23 Christa et al., 2009
Common 1b 3.8–16, 24.3– IC Gregori & Kreft, 2012

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28.2

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Common 5 25.6‒28.6, IC Lu & Baik, 2015
34.5‒34.5 g
Common, 27 e 21.1–27.4 IC Noda et al., 1998
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Tartary 3 22.7‒25.7 IC 0.94‒1.35 0.88‒1.06 Li et al., 1997
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Tartary 1 15.6, 25.5 c IA Yoshimoto et al., 2004

Tartary 1 29.1 IC 0.48 0.4 0.9 Liu et al., 2015b
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Tartary 1 21.4, 24.5 g IC 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 with 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, 15.6‒17.9% and 25.5% are the apparent amylose contents, and 25.7‒26.5% and 15.6% are the actual amylose contents which are from the data

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of the apparent amylose content subtracted by that of the isolated amylopectin; d, 3.8–16% is for low amylose mutants, and 24.3–28.2% for
normal grains; e, 17 genotypes of common buckwheat and 10 genotypes of tartary buckwheat; g, 21.4‒28.6% from samples before defatting and
24.5‒34.5% after defatting

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

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Amylose

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Buckwheat No. of IA BV max CL β-LV% NC DP
type genotypes

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Common 7 19.3‒20.2 1.37‒1.48 645‒657 280‒380 76‒82 3.1‒4.3 1,020‒1,380 a and 1,070‒1,360 b
Tartary 1 19.5 1.36 657 340 78 3.3 1,120 a and 1,230 b

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Amylopectin
Buckwheat No. of IA BV max CL β-LV% (Fa+Fb1)/ Fa LCAP

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type genotypes (Fb2+Fb3)
Common 7 2.21‒2.48 0.25‒0.28 582‒583 23‒24 52‒56 7.3 63‒64 12‒13
Tartary 1 2.42 0.26 584 24 55 8 63 13

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a, modified Park-Johnson method; b, fluorescent-labelling/HPSEC method; IA, iodine affinity (g/100g); BV, blue value; max, wavelength of

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maximal absorbance (nm); CL, chain length by the number of glucosyl residues; β-LV%, β-limit value (%); NC, number of chains; DP, number-
average degree of polymerization; Fa, fraction of amylopectin unit chains with DP of 6‒12, Fb1, fraction of amylopectin unit chains with DP of
13‒24, Fb2, fraction of amylopectin unit chains with DP of 25‒36, Fb3, fraction of amylopectin unit chains with DP of > 37, values are on molar
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basis; LCAP, long unit chain of amylopectin, weight basis
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Table 3 Morphology of buckwheat starch granules

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Buckwheat Measuring Size (µm) Shape Reference
type method
Common LM 5‒15 Polygonal and eclipsed Hurusawa & Miyashita, 1963

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Common LM 4‒11, (average, 7.8) Polygonal Kim et al., 1977
Common SEM Round or polygonal with some indentations on surface Lorenz & Dilsaver, 1982

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n.a. SEM 5‒10 Polygonal Jane et al., 1994
Common LM 2‒7 Polygonal Acquistucci & Fornal, 1997
Common SEM, LM 2‒14, (average, 6.5) Polygonal Zheng et al., 1998

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Common SEM 2.9–9.3, (average, 5.8) Polygonal, round Qian et al., 1998

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Common SEM 2–6 Polygonal, spherical, oval Qian & Kuhn,1999b
Common SEM 2‒9 Polygonal and irregular with a few being spherical Christa et al., 2009
Common SEM, AFM, LS 2‒19 Polygonal, hilum in the granule center Neethirajan et al., 2012

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Common SEM 4‒8 a, 3‒6 b Polygonal for normal samples, spherical for low Gregori & Kreft, 2012
amylose samples with pinpricks on surface

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Common SEM 4‒10 Polygonal Li et al., 2014
Tartary SEM 2‒10 Polygonal, oval, spherical with smooth surface Liu et al., 2015b
Tartary SEM 3–14 Polygonal
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LM, light microscopy; SEM, scanning electron microscopy; AFM, atomic force microscopy; LS, light scattering technique; n.a., not available; a,
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size for normal samples, b, size for samples with low amylose contents
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Table 4 Swelling and solubility of buckwheat starch

Buckwheat No. of Parameters Temperatures (oC) Reference

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type genotypes
60 70 80 90

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Common 1 SP 2.95 9.33 22.88 Kim et al., 1977
Common 1a SP 2.33‒2.54 7.53‒9.05 10.65‒11.04 Lorenz & Dilsaver, 1982
Common 1 S 0.45‒0.50 1.92‒2.27

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Common 2 SP 4.4, 5.3 9.6, 10.3 13.5, 18.5 22.9, 25.5 Acquistucci & Fornal, 1997

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Common 2 S 0.6, 0.9 1.5, 2.7 4.5, 6.0 9.2, 10
Common 1 SP 5.35 17.29 27.3 34.2 Li et al., 2014
1 S 3.94 7.08 10.09 24.44

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Common 5 SP 22.4‒24.9 (92.5) Lu & Baik, 2015
Common 5 S 4.1‒5.9 (92.5)

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Common 5 AML 94.5‒146.1 b
3.7‒5.3 c

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Common 2 S 1.7,2.8 5.7,5.9 10.9 11.2, 12.1 Gao et al., 2016
Tartary 1 SP 4.12 10.66 11.45 13.02 Liu et al., 2015
1 S 2.83 7.44 14.68 20.57
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Tartary 2 S 0.9, 1.1 4.2, 4.6 7.7, 9.5 9.9, 10.4 Gao et al., 2016
Tartary 1 SP 19.6 (92.5) Lu & Baik, 2015
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Tartary 1 S 5.3 (92.5)

Tartary 1 AML 86.4 b, 4 c
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SP, swelling power; S, solubility (%); AML, amylose leaching; figure 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)

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Table 5 Gelatinization properties of buckwheat starch by DSC and KHSM

Buckwheat No. of Technique Starch: water Scanning rate To (oC) Tp (oC) Tc (oC) ΔH (J/g) Reference
type genotypes ratio (w:w) (oC/min)

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Common 1 KHSM 61 65 Kim et al., 1977
Common 1a KHSM 61‒62.5 68‒70 74‒76 Lorenz & Dilsaver, 1982

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Common 3 DSC 4:13 10 57.8‒62.4 66.3‒68.8 77.3‒79.2 9.1‒10 Li et al., 1997
Common 1 DSC 1:2.28 10 61.1 68.4 80.8 10 Qian et al., 1998
Common 1 DSC 11:42 10 62.7 69 80.9 12.7 Zheng et al., 1998

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Common 5 DSC 1:11.5 to 1:2.5 10 58.6‒64.1 64.8‒69.6 70.8‒80.8 Qian & Kuhn, 1999a and
1999b

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Common 7 DSC 1:2 5 59.5‒64.1 63.7‒68.4 81.7‒85.8 14.5‒15 Yoshimoto et al., 2004
Common 1b DSC 1:3 to 3.5:1 5 52.4‒64.3 63.3‒ 67.6 72.9‒78.4 Zhou et al., 2009

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Common 1 DSC 1:3 5 60 65.6 71.8 Vallons & Arendt, 2009
Common 1 DSC 1:4 10 61.2 66.1 75.2 9.0 Li et al., 2014
Common 5 DSC 1:2 10 58.6‒60.2 61.5‒64.3 70‒73 14‒15.3 Lu & Baik, 2015

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Common 2 DSC 1:2 10 62.5, 63 66.7, 66.8 71.6, 72.1 7.8, 8.3 Gao et al., 2016
Common, 27c DSC 3:7 10 51.5–62.3 57.2–66.7 9.4–13.9 Noda et al., 1998

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Tartary 3 DSC 4:13 10 62.8‒64.3 68.8‒70.8 79.9‒81.3 9.7‒11.0 Li et al., 1997
Tartary 1 DSC 1:2 5 61 64.1 81.7 14.7 Yoshimoto et al., 2004
Tartary 1 DSC 1:3.5 10 73.5 78 83.9 19.8 Liu et al., 2015b
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Tartary 1 DSC 1:2 10 63.1 67 75 14.1 Lu & Baik, 2015
Tartary 2 DSC 1:2 10 61.6, 62.4 66.2, 66.3 69.1, 71.3 7.5 Gao et al., 2016
DSC, differential scanning calorimetry; KHSM, Kofler hot-stage microscopy; To, onset temperature; Tp, peak temperature; Tc, conclusion
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temperature; ΔH, enthalpy change; a, control sample, sample with defatting, and sample with acid hydrolysis (0.1 N HCl for 30 min); b, a range
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Table 6 Pasting properties of buckwheat starch

Buckwheat No. of genotypes Instrument Starch PV BD SB PT Reference

type concentration (%)

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Common 1 RVA 6 148 48 164 Qian et al., 1998
Common 5 RVA a 8 2280‒3098 139‒487 1348‒1620 71‒80 Qian & Kuhn, 1999a

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Common 2 RVA a 8 1629, 1685 315, 412 737, 743 63.8, 63.9 Gao et al., 2016
Common 7 RVA 9 226‒261 37‒98 180‒226 68.6‒71.0 Yoshimoto et al., 2004
Common 1 RVA a 11 4589 2418 1816 68.8 Li et al., 2014

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Common 2 BVA 5.5 b 540, 790 58, 55 Acquistucci & Fornal, 1997
Common 5 BVA 8 800‒1000 -40‒100 560‒1070 75‒84 Qian & Kuhn, 1999a and

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Common 1 BVA 10 1740 Praznik et al., 1999

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Common n.a. BA 8 680‒1020 64.3‒67.7 Hurusawa & Miyashita,
1964a

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Common 1 BA 9 1170 64.5 Kim et al., 1977
Common 1 BA 7 620 Zheng et al., 1998
Common 5 MVAG 8 1304‒1382 162‒247 531‒575 67.5‒69.2 Lu & Baik, 2015

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Tartary 1 RVA 9 242 67 223 68.5 Yoshimoto et al., 2004

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Tartary 1 RVA a 10.7 3803 1612 2017 62.8 Liu et al., 2015b
Tartary 2 RVA a 8 2121, 1928 652, 825 803, 954 62.8, 63.2 Gao et al., 2016
Tartary 1 MVAG 8 1154 188 564 75.5 Lu & Baik, 2015
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RVA, Rapid Visco-Analyzer; BVA, Brabender viscoamylography; BA, Brabender Amylograph; MVAG, Brabender Micro Visco-Amylo-Graph;
PV, peak viscosity; BD, breakdown; SB, setback; PT (oC), pasting temperature where viscosity takes off; the units of PV, BD, and SB for RVA,
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BA, and MVAG are RVU, BU, and BU, respectively, except for where specified; a, viscosity unit is cP; b, mixture of starch (25 g),
carboxymethylcellulose (3.5 g), and water (420 g)
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Table 7 Modifications of buckwheat starch

Modification type Buckwheat Major findings References

type

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Physical
Roasting Common Starch with a moisture content of 14.5% was roasted at 160 oC for 30 min. Infrared spectra and polymorphism Christa et al.,

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of starch were not affected. Swelling power and solubility was decreased. Breaking and conglomerates of 2009
granules were formed. Roasting decreased the glucose releasing from starch by enzymes

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High pressure Common Starch suspension (25% solid content) was treated with a range of high pressure (200–600 MPa). Vallons & Arendt,
treatment Gelatinisation of starch occurred between 300 and 500 MPa. High pressure-induced gelatinization much better 2009
retained the granule shape, compared with heat-induced gelatinization (Fig. 2a). This resulted in a stronger gel

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Hydrothermal Common Starch with a moisture content of 22% was heated up to 150 oC with or without pressure, and the processing Soral-Śmietana et
treatments steps were detailed (Fornal et al., 1981). Hydrothermal treatments decreased the pasting viscosity, increased al., 1984a
the swelling power and solubility of starch. Pressure (588,400 Pa) induced gelatinization and disrupted the

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granules as revealed by scanning electron microscopy
Autoclaving and Common Groats were autoclaved at 120 °C for 1 h before cooling to room temperature (~25 oC). Two more Skrabanja &

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cooling autoclaving/cooling cycles were applied. More autoclaving/cooling cycles increased the retrograded starch Kreft, 1998

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content, and had little effect on the content of slowly digestible starch fraction
Hydrothermal Common Hydrothermally treated buckwheat samples (including groats) had 5.5% of total starch content as retrograded Skrabanja et al.,
treatments starch (resistant starch type 3), which was correlated to undigested starch fraction in rats in vivo. There was 1998
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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
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dehusking followed by warm-air drying) had less amount of rapidly digestible starch by 11%
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Microwave Common Starch with moisture contents of 32.3%, 40%, and 44.4% were microwave-heated below the gelatinization Zondag, 2003
assisted temperature. Microwave heating had little effect on polymorph pattern and decreased the amylose leaching of
Hydrothermal starch when the initial moisture contents were 40% and 44.4%. Microwaving increased gelatinization
treatment temperatures of starch when the moisture content was 44.4%

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Heat moisture Tartary and Starch with a moisture content of 20–35% was treated at 110 °C for 16 h. HMT of starch decreased solubility Liu et al., 2015a
treatment (HMT) common and swelling power, peak viscosity of pasting, gel hardness and adhesiveness, increased the gelatinization and 2015b
temperature, relative crystallinity, and slowly digestible starch content, and had no effect on polymorphism
Annealing Common Starch with a moisture content of 80% was heated at 50 oC for 24 h. Annealing of starch decreased solubility Liu et al., 2015a

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and swelling power, peak and final viscosities of pasting, increased the gelatinization temperature, relative
crystallinity, and resistant starch content, and had no effect on polymorph type

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Ball-milling Common Ball-milling up to 8 h at low moisture content (6%) destroyed the crystallinity of starch, decreased the pasting Li et al., 2014
viscosity, and disrupted the granules, while maintaining the Maltese cross pattern. DSC analysis showed no

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endothermic peak of the milled starch
Pre-gelatinization Common Pre-gelatinization increased the swelling power and solubility of starch, and peak viscosity of pasting, while Li et al., 2014
by drum drying decreasing the degree of crystallinity

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Blending with Ball-milling disrupted the granules and destroyed the crystallinity as revealed by thermal and pasting analysis

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other ingredients (Li et al., 2014). However, Maltese cross pattern of granules was partially retained
Blending with n.a. Mucilage addition increased peak viscosity of pasting, G' and G'' during frequency sweep of dynamic Liu et al., 2006b

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yellow mustard rheology, hardness, adhesiveness, and chewiness of gel, and gelatinization temperature range of buckwheat
mucilage starch. Mucilage decreased the syneresis of starch gel
Blending with Common Fucoidan from brown seaweeds was mixed with buckwheat starch at various ratios (fucoidan to starch 1:2 to Cho et al., 2009

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Fucoidan 0:3 for a total solid concentration of 3%, 1:5 to 0:6 for a total solid concentration of 6%). Steady and dynamic

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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
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increasing with the increasing ratio
Blending with Common Galactomannans including guar gum, tara gum, and locust bean gum were mixed with buckwheat starch (gum Choi and Chang,
galactomannans to starch ratio 1:9, total carbohydrate concentration 5%). Steady shear and dynamic rheological studies 2012
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revealed synergism between starch and galactomannans. The apparent viscosity, consistency index, yield
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stress, dynamic moduli, and complex viscosity of the mixtures were higher than those of the individual starch
Chemical
Acetylation Common Acetylation decreased gelatinization and pasting temperatures, setback of pasting, and increased the swelling Zheng et al., 1998
power, water solubility, and cold storage stability of starch gel

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Acid hydrolysis Common Starch was hydrolysed in HCl solution (2.2 N) at 35 oC up to 24 days. Buckwheat starch was more susceptible Qian et al., 1998
to acid hydrolysis than wheat and maize starches under the same condition
Acid hydrolysis Common Starch was hydrolysed in concentrated H2SO4 solution (3.16 M) at 40 oC for 5 days to produce nanocrystals. Neethirajan et al.,
The nanocrystals were spherical and were 120‒200 nm long and 4‒30 nm in diameter 2012

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Alkaline Common Starch was treated in solution of NaOH and ethanol mixture at 70 oC to produce cold water soluble starch with Li et al., 2014
treatment in much enhanced transmittance of gel. NaOH-ethanol treatment greatly decreased the degree of crystallinity of

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ethanol starch while maintaining the granule shape and Maltese cross pattern, significantly increased the water
solubility without much altering the swelling power, and reduced the pasting viscosity and the ΔH of

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gelatinization without affecting the temperatures of gelatinization
n.a., not available

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Table 8 Uses of buckwheat starch

Uses Species Form Major findings Reference

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As ingredients for Common Native For cake production, the baking performance of buckwheat starch was unsatisfactory Lorenz &

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cake and pie fillings (defatted and according to sensory evaluation, as compared with wheat starch. For pie filling, buckwheat Dilsaver, 1982
non-defatted) starch produced initial consistency comparable to wheat, millet, and triticale starches
As ingredient for Common Nanocrystal Starch/nanocrystal/glycerol composite film had a 3-stage transition of moisture adsorption as Neethirajan et
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nanocomposite films revealed by sorption isotherms. Under a constant water activity, increasing the nanoparticle al., 2012
concentration decreased the water adsorption of films
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As fermentation Tartary Native α-Amylase, β-amylase, and amyloglucosidase were used to hydrolyse the starch, and the Kusano et al.,
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substrate for
producing beer-like
alcoholic beverage
As ingredient for n.a.
extruded products
structural changes of granules were monitored by scanning electron microscopy. α-Amylase 1999
hydrolysed both the inner and outer layers of granules. β-Amylase and amyloglucosidase
hydrolysed the inner part of granules
Native Milk protein (25%) and buckwheat starch mixture was extruded. The milk protein addition Śmietana et al.,
decreased the enzyme susceptibility of starch 1988

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Cream substitute n.a. Native and The patent described the use of buckwheat starch as effective fat replacer to impart the smooth Singer, 1994
cross-linked organoleptic character of an oil-and-water emulsion
n.a., not available

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Figure captions

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 official, semi-official, or
estimated data

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Fig 2a. SEM images of common buckwheat starch after high pressure (left) and thermal
(right) treatments (Vallons & Arendt, 2009)

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Fig. 2b. 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)

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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,

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Fig. 3.

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• Diverse aspects of buckwheat starch is comprehensively reviewed

• Starch structure-property relationships are explored

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How buckwheat starch can be better utilised is suggested

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