Food Chemistry 335 (2021) 127556

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Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Diverse effects of rutin and quercetin on the pasting, rheological and T

structural properties of Tartary buckwheat starch
⁎ ⁎
Libo Wanga, Lijuan Wanga, Zaigui Lia, , Yanxiang Gaoa, Steve W. Cuic, Tongtong Wangd, Ju Qiub,
a
College of Food Science and Nutritional Engineering, China Agricultural University, P. O. Box 40, No. 17 Qinghuadonglu, Haidian, Beijing 100083, China
b
Institute of Food and Nutrition Development, Ministry of Agriculture and Rural Affaris, Haidian, Beijing 100081, China
c
Guelph Research and Development Centre, Agriculture and Agri-Food Canada, 93 Stone Road West, Guelph, Ontario N1G 5C9, Canada
d
Institute of Quality Standard and Testing Technology for Agri-Products, Chinese Academy of Agricultural Sciences, Key Laboratory of Agro-Food Safety and Quality,
Ministry of Agriculture and Rural Affaris, Beijing 100081, China

A R T I C LE I N FO A B S T R A C T

Keywords: We investigated the interactions of two main phenolics, rutin and quercetin, with starch, the primary component
Starch of Tartary buckwheat. The addition of rutin or quercetin significantly affected the structural and physico-
Rutin chemical properties of the starch, and rutin showed a stronger effect than quercetin, particularly at a dose of 6%
Quercetin (w/w). Rutin better enhanced the aggregation of starch pastes and gel formation than quercetin according to our
Rheological properties
pasting, rheological and thermal property analyses. A scanning electron microscopy analysis of its morphology
Structural analysis
showed that rutin was more easily dispersed in starchy matrix than quercetin and acted as rigid fillers for gels.
The nuclear magnetic resonance results showed different binding sites due to the steric hindrance of the rutin
disaccharide groups (rutinose). These findings provide fundamental information about applying rutin during the
whole grain processing of Tartary buckwheat.

1. Introduction
Tartary buckwheat (Fagopyrum tataricum (L). Gaertn) is an im-
portant whole grain, which plays a key role as staple food in Europe and
Asian (Fabio & Parraga, 2017). Tartary buckwheat is increasingly in
demand due to its nutritional qualities and health benefits, including its
use in the prevention and treatment of many diseases such as diabetes,
inflammation and hypertension (Zhu, 2016). One reason for Tartary
buckwheat’s health benefits is its polyphenols which have been widely
reported to have antidiabetic, antioxidant and anti-inflammatory ac-
tivities (Wu, Johnson, Bornman, Bennett, & Fang, 2017; Wu, Chen, Li, &
Li, 2009). The major polyphenols in Tartary buckwheat flour are fla-
vonoids (6.65–22.74 mg/g, DW), predominantly rutin (6.06–18.67 mg/
g) and quercetin (0.31–2.38 mg/g) (Qin, Wang, Shan, Hou, & Ren,
2010; Zhu, 2016). The rutin and quercetin contents in Tartary buck-
wheat bran are reportedly 541.3 mg/g and 66.3 mg/g, respectively
(Wang, Yang, Qin, Shan, & Ren, 2013). Buckwheat is one of the pseu-
docereal containing the most rutin, which can reach up to 18.67 mg/g
(DW) (Fabjan, Rode, Kosir, Wang, Zhang, & Kreft, 2003; Vollmannova
et al., 2013). Rutin content in the edible parts of Tartary buckwheat is
five- to ten-folds greater than that of common buckwheat (Kim et al.,
2008; Zhang et al., 2012; Zhu, 2016). Accordingly, as a choice of staple
food, Tartary buckwheat is one of the most beneficial sources of rutin,
and it is recommended to increase its daily intake as a whole grain food
due to the benefits of its high flavonoid and other nutrient contents.
Therefore, a study on the interactions between the flavonoids and other
nutrients in Tartary buckwheat will provide a better understanding of
their functional effects and nutritional qualities in the whole grain
system.
Tartary buckwheat is mostly comprised of starch (TBS), which ac-
counts for greater than 70% of its content and plays a key role in the
eating quality of products composed of 100% Tartary buckwheat (Zhu,
2016). The amylose content of TBS has been reported to range from
29.1% to 33.7%, and it is generally higher than that of wheat
(< 25.6%), rice (8.6–24.8%), corn (< 25.9%) and potatoes (< 24.6%)
(Ashwar, Gani, Wani, Shah, Masoodi, & Saxena, 2016; Irani, Razavi,
Abdel-Aal, Hucl, & Patterson, 2019; Karunaratne & Zhu, 2016; Liu, Lv,
Peng, Shan, & Wang, 2015; Liu, Xiao, Shen, Zhang, Wang, & Xie, 2019;
Remya, Jyothi, & Sreekumar, 2018; Wu et al., 2009; Zhang, Sun, Zhang,
Zhu, & Tian, 2015). Starch with high amylose content is commonly
used as a source material to produce resistant starch, which implies that
the conversion of amylose to resistance starch controls postprandial
blood glucose (Chai, Wang, & Zhang, 2013). Dietary phenolics are
known for their ability to modify the physicochemical properties and

⁎
Corresponding authors.
E-mail addresses: lizg@cau.edu.cn (Z. Li), qiuju@caas.cn (J. Qiu).

https://doi.org/10.1016/j.foodchem.2020.127556
Received 16 January 2020; Received in revised form 6 July 2020; Accepted 9 July 2020
Available online 18 July 2020
0308-8146/ © 2020 Elsevier Ltd. All rights reserved.
L. Wang, et al.
digestibility of starch. These phenolics include tea catechin (Chai et al.,
2013), simple phenolic acids from different sources other than tea (such
as caffeic acid, gallic acid and ferulic acid) (Li, Pernell, & Ferruzzi,
2018), and flavonoids derived from the lotus leaf (Wang et al., 2018).
Based on the literature, rutin and quercetin can also modify the di-
gestibility and physicochemical properties of starches derived from rice
and maize (Zhang, Yang, Li, & Gao, 2011; Zhu & Wang, 2012). A recent
study on the starch–phenolic interaction in Tartary buckwheat de-
monstrated that rutin and quercetin at low concentrations (0.5, 1.0 and
1.5%, w/w) could facilitate the gelatinization and inhibit the retro-
gradation of TBS (He, Zhang, Liu, Gao, Li, & Wang, 2018). However,
neither the difference between the interactions of quercetin and rutin
with TBS, nor the effects of rutin and quercetin at higher concentrations
are clear enough, which may support crucial developments of Tartary
buckwheat processing. In addition, correlations between the changes in
the physicochemical properties and structural characteristics remain
unclear. As far as we know, limited works have clarified the differences
in the starch–phenolic interactions between rutin and quercetin based
on their structural properties. However, these differences may be cri-
tical for understanding the maintenance of rutin rather than its con-
version to quercetin for improved nutritional and eating qualities
during the whole grain processing of Tartary buckwheat.
The different contents and structures of dietary phenolics could
affect the physicochemical properties of starch. It is vital to investigate
the effects of not only the intrinsic content but also the addition of
increasing amounts of rutin or quercetin in the starch-based Tartary
buckwheat food system. Therefore, in this study, a wide range of
quercetin and rutin concentrations were selected to evaluate their di-
verse effects on TBS, particularly the changes in its rheological prop-
erties and relationship to their structural characteristics. Nuclear
magnetic resonance (NMR) was used to determine the binding sites of
the starch-phenolic complexes. The findings of this study are expected
to stimulate further interest adding phenolics to help develop novel
Tartary-buckwheat-based whole grain foods with improved nutritional
quality.
2. Materials and methods
2.1. Materials
Tartary buckwheat flour (TBF) (cultivar, Yunqiao No. 1) was ob-
tained from Yunnan Zhongjin Special Food Co., Ltd. (Yunnan, China).
Quercetin (97%, w/w) and rutin hydrate (98%, w/w) were purchased
from Shanghai Macklin Biochemical Co., Ltd. (Shanghai, China). A total
starch assay kit was purchased from Megazyme International Ireland,
Ltd. (Bray, Co. Wicklow, Ireland). All the chemicals and solvents pur-
chased from Xilong Chemical Co., Ltd. (Beijing, China) were of analy-
tical grade.
2.2. Isolation of Tartary buckwheat starch
The TBS was isolated from the TBF with an alkaline solution using
the method described by Li, Lin, & Corke (1997) with some modifica-
tions. Specifically, the TBF (100 g) was passed through a 140-mesh
sieve and then mixed with 1000 mL of 0.075 M NaOH at 25 °C. The
mixture was agitated on a rotary shaker (150 rpm) for 10 min at room
temperature to obtain the precipitate which was washed with distilled
water at least 5 times until the supernatant was visibly clear and no
longer yellow. The precipitate was subsequently resuspended in
1000 mL of distilled water and mixed with 100 mL of n-butanol (ana-
lytical grade, ≥99%) at 25 °C to dissolve the amylopectin (Klucinec &
Thompson, 1998). The mixture was agitated on a rotary shaker
(150 rpm) for 1 h and then precipitated for 3 h at 25 °C to remove the
phenolics and to obtain the novel precipitate. The precipitate was re-
suspended in 1000 mL of 100% ethanol for 24 h and washed with the
ethanol three times to remove the n-butanol. Finally, the TBS was dried
2
Food Chemistry 335 (2021) 127556
at 45 °C for 4 h and then passed through a 200-mesh sieve for further
application. The yield of TBS ranged from 55% to 60% (w/w).
2.3. Analysis of chemical composition
The moisture, ash, crude fat, protein (N × 6.25), apparent amylose
and total dietary fiber contents of the TBF and TBS were determined
using AACC Approved Methods 44-19, 08-01, 30-25, 46-11, 61-03 and
32-05, respectively (AACC International, 2002). The total starch con-
tent was determined according to AACC Method 76-13 using the
Megazyme Total Starch kit. The free phenolic in the complex was ex-
tracted according to the method described by Adom & Liu (2002). The
phenolic content was determined according to the Folin–Ciocalteau’s
method (Singleton & Rossi, 1965).
2.4. Preparation of a starch complex with quercetin and rutin
The mixtures of TBS (obtained from Section 2.2) (5.0 g, dry basis)
with phenolics (quercetin and rutin) were prepared in mass ratios of
(starch: phenolic) 10/0, 10/0.1, 10/0.2, 10/0.3, 10/0.6, 10/0.9 and
10/1.2, which corresponded to 0, 1, 2, 3, 6, 9 and 12% (w/w) phenolic
in relation to the mass of the TBS in each sample. Based on the de-
termination of temperature from 75 °C to 95 °C, free phenolics contents
in the complex were lowest at 90 °C, and not significantly different
before and after starch gelatinization. Thus, the mixtures were stirred at
room temperature for 10 min along with 95 mL of distilled water and
heated at 90 °C for 30 min while being constantly stirred at 150 rpm.
The prepared pastes of the TBS, TBS/quercetin (TBSQ) and TBS/rutin
(TBSR) complexes (5%, dry basis) were equilibrated for 1 h.
2.5. Pasting characteristics
The pasting viscosity characteristics of the TBS, TBSQ and TBSR
complexes were measured using a Rapid Visco Analyzer (RVA-4,
Newport Scientific Pty Ltd., Sydney, Australia). TBS (3.0 g, dry basis)
was added to an aluminum canister containing enough distilled water
to bring the total weight to 28.0 g. For the complexes, the relevant
proportions (10/0.1, 10/0.2, 10/0.3, 10/0.6, 10/0.9 and 10/1.2, w/w)
of starch to quercetin (or rutin) with a total weight of 3.0 g (dry basis)
were placed into the aluminum canisters. The samples were maintained
at 50 °C for 1 min. The temperature was increased to 95 °C within
3.7 min, maintained at 95 °C for 2.5 min, cooled to 50 °C within
3.8 min, and finally held at 50 °C for 2 min to develop the final paste
viscosity. The initial speed of the plastic paddle was 960 rpm for the
first 10 s, followed by 160 rpm for the remainder of the assay (Liu et al.,
2015). The experiments of all the samples were performed in triplicate.
2.6. Rheological determination
The rheological properties of all the samples were measured using
an AR1500ex rheometer (TA Instruments, New Castle, DE, USA) ac-
cording to the method described by Qiu, Yadav, Chen, Liu, Tatsumi and
Yin (2015) with minor modifications The prepared TBS, TBSQ and
TBSR (TBS weight on a dry basis, 5%) pastes were equilibrated for 1 h
at room temperature and then loaded onto the rheometer plate (40 mm
in diameter and with a 1000-μm gap) at 25 °C. The apparent viscosity
was monitored as a dependent variable of the shear rate (0.1–10 s−1). A
frequency sweep test was performed with an angular frequency of
0.1–10 rad/s at 0.1% strain (which was within the linear viscoelastic
region as determined from the stain sweep tests). Prior to each ex-
periment, the edge of the sample was covered with a thin layer of si-
licone oil to prevent moisture from evaporating.
2.7. Differential scanning calorimetry (DSC)
The thermal properties of all the samples were measured using a
L. Wang, et al.
differential scanning calorimeter (DSC) (Shimadzu, TA-60 WS, Tokyo,
Japan) according to the method described by Zhu & Wang (2012) with
minor modifications. The starch was mixed with quercetin (or rutin) at
different ratios (10/0.1, 10/0.2, 10/0.3, 10/0.6, 10/0.9 and 10/1.2, w/
w) for a total weight of 3.0 mg (dry basis). The powdered starch sam-
ples or mixtures (3.0 mg, dry basis) were prepared with 9 μL of distilled
water in hermetically sealed aluminum pans and then maintained at
room temperature for 24 h to equilibrate the moisture content. The
prepared pan was heated from 25 to 130 °C for the gelatinization test.
The gelatinized samples were maintained at 4 °C for 7 days before being
rescanned from 25 to 130 °C for the retrogradation test. The scanning
was performed at a rate of 10 °C/min, and an empty aluminum pan was
used as the control. The onset, peak and conclusion temperatures (To,
Tp and Tc), and the melting enthalpy (ΔH) were recorded. The experi-
ments were performed in triplicate.
2.8. Texture profile analysis (TPA)
The textural properties of all the samples were measured using a TA-
XT2i Texture Analyzer (Stable Micro Systems, UK) by performing tex-
ture profile analysis (TPA) according to the method described by
Bourne (1978) with minor modifications. The starch (or complex)
pastes (TBS weight on a dry basis, 10%) were prepared as described in
Section 2.4. The prepared gel samples were stored at 4 °C for 24 h and
then cut into test cubes with an edge length of 10 mm each. The
samples were compressed twice to 25% of their original height using a
cylindrical probe with a diameter of 20.0 mm (P/20a). The test speed
and trigger force were 1 mm/s and 0.5 N, respectively. All the samples
were treated in triplicate, and their textural parameters, including their
hardness, adhesiveness, cohesiveness, springiness and gumminess, were
calculated. The experiments were performed in triplicate.
2.9. Scanning electron microscopy (SEM)
The microstructures of quercetin, rutin and the freeze-dried TBS,
TBSQ and TBSR gels were analyzed using a scanning electron micro-
scope (S-3400 N, Hitachi Ltd., Tokyo, Japan). The freeze-dried gels
were divided into small pieces (5 mm × 5 mm) with a blade and at-
tached to the sample holders. All the samples were gold-coated and
observed using an electron beam with an acceleration voltage of 10 kV.
2.10. X-ray diffraction (XRD)
The recrystallization outcomes for all the powder samples (passed
through a 100-mesh sieve) were measured using an X-ray dif-
fractometer (Rigaku, RAPID-S, Rigaku Denki Co., Ltd., Japan) ac-
cording to the method described by Wang et al. (2018) with minor
modifications. The diffractometer was operated at 40 kV and 200 mA
with Cu Kα radiation (λ = 0.154 nm). All the diffraction patterns were
measured by scanning from 4° to 40° in 2θ angles at a rate of 4°/min
and a step size of 0.02°. Two independent measurements were per-
formed for each sample.
2.11. Fourier transform infrared (FT-IR) spectroscopy
The starch (or complex) pastes were freeze-dried and then crushed
by mortar and pestle. The spectral data for the TBS, quercetin, rutin and
dry gelatinized TBS, TBSQ and TBSR powders were determined using
an FT-IR spectrometer (Spectrum 100, Perkin Elmer Co., USA). All the
samples were pressed into conventional KBr (chromatographic grade)
pellets (2 mg sample/200 mg KBr) and tested within a wavelength
range of 4000–400 cm−1 (Zhang et al., 2011). All the samples were
successively scanned 16 times. The mean of the spectra was obtained
using Thermo Scientific OMNIC version software.
3
Food Chemistry 335 (2021) 127556
2.12. Nuclear magnetic resonance (NMR)
The freeze-dried samples were dissolved in DMSO‑d6 (J&K
Scientific Ltd.) with a concentration of 50 mM (0.4 mL) and then in-
cubated at 37 °C for 30 min. The 1H NMR and nuclear Overhauser
enhancement spectroscopy (NOESY) spectra of the quercetin, rutin and
gelatinized TBS, TBSQ and TBSR were recorded at 298 K using a Bruker
Avance III 400-MHz spectrometer equipped with a 5-mm probe (Bruker
Technologies, Germany). The mixing time was 0.8 s. The obtained data
were processed using TopSpin and MestReNova software packages
(Bruker Biospin GmbH) (Xie et al., 2019).
2.13. Statistical analysis
An analysis of variance (ANOVA) was used to measure significant
differences with SPSS Version 16.0 software (IBM software, Chicago,
USA). Significant differences (p < 0.05) were determined using the
Duncan’s procedure.
3. Results
3.1. Chemical composition and phenolic content
The chemical compositions of TBF and TBS were shown in
Supplemental Table S1. The contents of starch and amylose in the TBS
(dry basis) were 93.68% and 41.53%, respectively, which were much
higher than that of TBF. The remainder composition of TBS included
~7.10% moisture, ~1.74% protein (N × 6.25), ~0.25% ash, ~0.15%
crude fat and ~2.32% total dietary fiber. In addition, no phenolics were
detected in TBS. However, the contents of free phenolic in the 3% TBSQ
and 6% TBSR were ~29.08% and ~25.32%, respectively
(Supplemental Fig. 1).
3.2. Pasting properties
The pasting properties of TBS were found to be significantly affected
by the presence of quercetin and rutin (Table 1). The peak viscosity
(PV), through viscosity (TV) and final viscosity (FV) of the TBSQ were
significantly decreased as the quercetin concentration increased from
3% to 12%. There were no significant differences in the values obtained
for 1% and 2%. The breakdown viscosity (BV) and setback viscosity
(SV) were clearly decreased from 1% to 6% due to the addition of
quercetin and remained relatively stable from 6% to 9%. The peak time
(PeT) and pasting temperature (PaT) of the TBS were not significantly
affected by the addition of quercetin. In the TBSR complexes, the PV,
TV and BV values showed similar decreasing trends with rutin additions
from 1% to 12%, and there were also no significant differences in the
values between 1% and 2%. However, the FV value was increased
suddenly at 6% of the rutin concentration, while the SV value showed a
similar increasing trend after rutin addition and reached a maximum at
6%. Furthermore, the PeT values of the TBSR complexes were increased
linearly with the higher rutin concentrations, indicating a smooth curve
up to the PV. It was worth noting that there seemed to be no significant
differences in the pasting properties when the content of phenolic was
1% or 2%, although the values were reduced. In addition, increases in
the rutin concentration were found to contribute to a lower PV value in
comparison with the quercetin at doses ranging from 1% to 12%
(P < 0.01).
3.3. Rheological properties
The apparent viscosities of the TBSQ and TBSR were found to be
greatly dependent on the shear rates and they exhibited a gradually
decreasing tendency, suggesting that all the samples showed non-
Newtonian behavior (Fig. 1A and B). As shown in Fig. 1A, the apparent
viscosities of all the TBSQ complexes were lower than that of the
L. Wang, et al. Food Chemistry 335 (2021) 127556

Table 1
Pasting properties of Tartary buckwheat starch in the presence of quercetin or rutin.
Polyphenol content PV (cP) TV (cP) BV (cP) FV (cP) SV (cP) PeT (min) PaT (°C)
(%)

TBS
0 5365.00 ± 23.90Fg 3114.33 ± 26.08Ee 2250.67 ± 12.90Cg 5687.33 ± 30.01Ef 2573.00 ± 11.00BCb 4.05 ± 0.04Bab 71.28 ± 0.49Ac

TBSQ
1 4840.67 ± 35.02E 3165.00 ± 67.67E 1675.67 ± 102.57B 5768.67 ± 35.50E 2603.67 ± 97.50C 3.95 ± 0.04A 70.75 ± 0.52A
2 4784.33 ± 82.28E 3219.33 ± 48.22E 1565.00 ± 40.26B 5707.33 ± 73.87E 2488.00 ± 31.43BC 3.93 ± 0.00A 70.77 ± 0.45A
3 4523.50 ± 86.97D 2992.00 ± 100.41D 1531.50 ± 187.38B 5452.00 ± 11.31D 2460.00 ± 111.72B 3.90 ± 0.04A 70.58 ± 0.60A
6 4001.00 ± 47.62C 2771.33 ± 76.01C 1229.67 ± 35.23A 4926.67 ± 49.66C 2155.33 ± 29.94A 3.93 ± 0.07A 70.97 ± 0.03A
9 3731.00 ± 12.73B 2556.00 ± 74.95B 1175.00 ± 62.23A 4639.50 ± 10.61B 2083.50 ± 64.35A 3.94 ± 0.09A 71.00 ± 0.07A
12 3380.00 ± 25.51A 2211.33 ± 24.83A 1168.67 ± 24.83A 4273.67 ± 17.39A 2062.33 ± 41.10A 3.89 ± 0.03A 70.75 ± 0.52A

TBSR
1 4455.67 ± 0.58f 2738.67 ± 60.04d 1717.00 ± 60.62f 5609.67 ± 14.43e 2871.00 ± 74.48 cd 3.93 ± 0.00a 70.17 ± 0.03a
2 4143.67 ± 32.53e 2711.00 ± 60.70 cd 1432.67 ± 35.53e 5564.67 ± 19.50de 2853.67 ± 44.43 cd 4.13 ± 0.12b 70.45 ± 0.52ab
3 3865.67 ± 68.53d 2601.33 ± 98.56bc 1264.33 ± 31.47d 5430.33 ± 55.19c 2829.00 ± 84.15c 4.42 ± 0.10c 70.43 ± 0.41ab
6 3419.33 ± 28.36c 2555.00 ± 77.13b 864.33 ± 88.22c 5531.33 ± 31.01d 2976.33 ± 102.49d 4.80 ± 0.00d 70.70 ± 0.48abc
9 3087.00 ± 19.97b 2386.33 ± 51.25a 700.67 ± 54.86b 4931.00 ± 26.51b 2544.67 ± 75.64b 5.02 ± 0.08e 70.75 ± 0.52abc
12 2930.00 ± 26.89a 2391.00 ± 50.09a 539.00 ± 23.58a 4533.67 ± 9.87a 2142.67 ± 57.55a 5.13 ± 0.07e 71.02 ± 0.10bc

TBS, Tartary buckwheat starch; TBSQ, TBS-quercetin complex; TBSR, TBS-rutin complex; PV: Pasting viscosity, TV: Trough viscosity, BV: Breakdown viscosity, FV:
Final viscosity, SV: Setback viscosity, PeT: Peak time, PaT: Pasting temperature. All values are averages ± SD of three runs. The different letters in the same column
are significantly different. The uppercase and lowercase superscripts represent significant differences in TBSQ and TBSR, respectively (P < 0.05).

control (TBS) (P < 0.05), while no significant differences were ob-
served among the various concentrations. Similar results were observed
in the TBSR complexes at low rutin concentrations from 1% to 3%.
However, their apparent viscosities were significantly higher than those
of the other concentrations when the rutin addition reached 6% (as well
as reaching the highest shear rate) and then decreased again when the
dose increased from 9% to 12% (Fig. 1B). The results of the angular
frequency sweep tests on the TBSQ and TBSR pastes were shown in
Fig. 1C–F. Both the storage modulus (G′) and lost modulus (G″) were
gradually increased with the increasing angular frequency, with no
crossover observed between these two moduli. All the G′ values were an
order of magnitude greater than G″ within the measured frequency
range, and both moduli showed a great dependence on the frequency.
The presence of quercetin (ranging from 1% to 12%) caused a decrease
in the G′ and G″ during the TBSQ pastes compared to that of the TBS
(Fig. 1C and E). However, both the G′ and G″ of the TBSR pastes
reached maximum levels when 6% rutin was added, and their shear rate
was also much higher than that of the other concentrations (Fig. 1D and
F).
3.4. Thermal properties
The effects of quercetin and rutin on the gelatinization and retro-
gradation characteristics of TBS were shown in Supplemental Table S2.
The ΔH for the gelatinization process of TBS was decreased significantly
with the increase in quercetin and rutin concentrations from 2% to
12%, and there were no significant differences in the values of TBSQ
between 1% and 2%. The addition of quercetin had little effect on the
onset temperature (To), while compared with TBS, the peak (Tp) and
conclusion temperatures (Tc) were decreased significantly in the pre-
sence of quercetin (P < 0.05). Compared with TBS, the Tp, Tc and To
values of the gelatinized TBSR complexes were all decreased with
added rutin, regardless of its concentration. Furthermore, the To, Tp and
Tc values of the TBSR complexes were lower than those found in the
TBSQ complexes (P < 0.05). Compared with gelatinization, retro-
gradation led to lower melting temperatures (To, Tp and Tc) and ΔH
values (P < 0.05) for the TBS, TBSQ and TBSR, and the ΔH values
were negatively correlated with the quercetin and rutin concentrations.
3.5. Gel texture analysis
In comparison to the control (TBS), the hardness, adhesiveness and
gumminess of the TBSQ and TBSR were decreased significantly due to
the additions of quercetin and rutin, independent of their concentra-
tions (Supplemental Table S3). The cohesiveness of the TBSQ was
higher than that of the TBS following the addition of quercetin, in-
dependent of its concentration. However, in the TBSR, the cohesiveness
was decreased (but still higher than TBS) when the rutin concentration
was lower, between 1% and 3%. Then, the cohesiveness was increased
significantly again at higher concentrations between 6% and 12%,
reaching a maximum at 6%.
3.6. SEM analysis
The SEM micrographs showed that the quercetin exhibited rod-
shaped particles in the dozens of microns, while the rutin presented
irregular solid particles with some fine particles attached to the surface
(Fig. 2A and B). The TBS granules exhibited a compact structure, which
was composed of a large number of random starch particles smaller
than 10 µm (Fig. 2C). In addition, all the gel samples displayed three-
dimensional honeycomb network structures, and the porous portions
indicated excellent swelling capacities. However, compared with gela-
tinized starch (Fig. 2D), when the concentration of the quercetin or
rutin was higher than 2% or 6%, respectively, it was clearly observed to
be embedded in the starchy matrix of the TBSQ and TBSR gel pore walls
(Fig. 2E1–E6, F1–F6).
3.7. Recrystallization
The XRD patterns of the TBS, quercetin, rutin, TBSQ and TBSR were
shown in Fig. 3. The native TBS showed a typical A-type crystallinity
pattern with strong peaks at 2θ of 15.03°, 17.00°, 17.95° and 22.94°,
while the gelatinized TBS showed an amorphous pattern with broad
peaks (Fig. 3A). Quercetin and rutin exhibited characteristic diffraction
peaks at 2θ equal to 6.07°, 10.60°, 12.29°, 15.66°, 16.00°, 23.69°, and
27.18° and 5.08°, 7.09°, 10.31°, 14.30°, 14.80°, 15.54°, 16.62°, 20.32°,
21.98°, 26.09°, and 26.67°, respectively. An amorphous pattern with
broad peaks occurred in both the TBSQ and TBSR, and crystalline peaks
for quercetin and rutin were also observed (Fig. 3B and C). Moreover,
the crystalline peak intensities also showed a corresponding increase
with the addition of quercetin and rutin, particularly at 10.60°, 12.29°,
15.66°, 23.69°, and 27.18° in the TBSQ and 7.09°, 10.31°, 14.30°,
14.80°, 16.62°, 21.98°, and 26.43° in the TBSR.

4
L. Wang, et al. Food Chemistry 335 (2021) 127556

Fig. 1. Effects of the quercetin (A) and rutin (B) concentration on the apparent viscosity of TBS pastes at 25 °C. The variation in the G′ and G″ with the angular
frequency at 25 °C for 5% TBS pastes with quercetin (C, E) or rutin (D, F) addition. G′ (storage modulus), G″ (loss modulus).

5
L. Wang, et al. Food Chemistry 335 (2021) 127556

Fig. 2. SEM images for quercetin (A), rutin (B), TBS powders (C), gelatinized TBS (D), TBSQ (E1-E6) and TBSR (F1-F6) gels (fracture surface). The addition of
quercetin (or rutin) were 1% (E1, F1), 2% (E2, F2), 3% (E3, F3), 6% (E4, F4), 9% (E5, F5) and 12% (E6, F6), respectively.

6
L. Wang, et al.
Fig. 3. XRD (A, B and C) patterns and FT-IR (D) spectra of quercetin, rutin, TBS and GTBS, TBSQ and TBSR. TBS, Tartary buckwheat starch; GTBS, gelatinized Tartary
buckwheat starch; TBSR, TBS-rutin complex; TBSQ, TBS-quercetin complex; R, rutin; and Q, quercetin.
3.8. FT-IR analysis
The FT-IR spectra showed a broad absorption peak at 3300 cm−1,
suggesting the stretching of the –OH groups of starch or phenolics
(Fig. 3D). The absorption peak at 2930 cm−1 was related to the CeH
stretching vibration of starch or rutin, and the band at 1650 cm−1 was
attributed to the CeOeO stretching vibration in a carbohydrate group.
The band at 1340 cm−1 for the native TBS was ascribed to OeCeH,
CeCeH and CeOeH. The absorption peaks at 1080, 1010 and
930 cm−1 described the stretching of the CeOeC groups and α-1,4-
glycosidic linkages in the starch. Compared with the native TBS, the
disappearance of the absorption peaks at 1520 cm−1 in the gelatinized
TBS could be related to the rearrangement of the starch molecules
during the heating process. The characteristic peak of either quercetin
or rutin indicated a C]O stretching vibration at 1665 cm−1, and the
peaks at 1610, 1560 and 1510 cm−1 were attributed to benzene ring
bond stretching. Compared with the gelatinized TBS, new characteristic
absorption peaks of the TBSQ and TBSR appeared at 1610, 1560, 1510,
1450, 1370, 1320, 1260 and 1210 cm−1, corresponding to the presence
of quercetin and rutin. There were no new characteristic peaks in either
the TBSQ or TBSR, indicating that no new covalent bonds were formed.
3.9. NMR analysis
As shown in Fig. 4A, the 1H NMR spectrum of the quercetin dis-
played proton signals at δ = 12.49, 10.77, 9.58, and 9.35 ppm, which
were attributable to the 5-OH, 7-OH, 3-OH, 4′-OH and 3′-OH, respec-
tively. Proton signals at δ = 7.68, 7.54, 6.88, 6.40 and 6.19 ppm were
related to 2′-H, 6′-H and 5′-H of ring B and 8-H and 6-H of ring A,
respectively. Regarding the 1H NMR spectrum of rutin, the proton
7
Food Chemistry 335 (2021) 127556
signals from 9.0 to 12.6 ppm, 6.1 to 7.8 ppm, and 3.0 to 5.5 ppm and
1.12 ppm were related to the hydrogens of the hydroxyl group (on the
benzene ring), benzene ring, oxygen atom and carbon atom, respec-
tively (Fig. 4B). Regarding the gelatinized TBS, the most prominent
signals in the region of from 3.5 to 5.9 ppm were correlated to their
respective protons of the anhydroglucose units (3.4–4.0 ppm) and the
equatorial protons of the anhydroglucose units (5.0–5.6 ppm) of starch.
The proton signal at 5.53 ppm was related to 1-β-H of starch. All the
TBSQ and TBSR complex spectra showed partial proton signals of starch
(3.5–5.9 ppm) and phenolics (6.0–12.6 ppm) (Fig. 4A and B). Moreover,
the NOESY spectrum of the TBSQ complex in DMSO‑d6 showed the
correlations of the 5-OH, 4′-OH and 3′-OH groups in the quercetin to
the –OH and –H of the TBS, and the weak correlations of the 8-H and 6-
H in the quercetin to the –OH and -H of the TBS (Fig. 4C). Moderate
NOE correlations between the 5-OH, 2′-H, 6′-H and 5′-H groups of the
rutin and the –OH and -H of the TBS were observed in the spectra for
the TBSR complex (Fig. 4D). These results indicated that the binding
sites of the quercetin and rutin were different. Moreover, rutin and
quercetin were associated with starch molecules primarily by CeH and
OeH, respectively (Fig. 5).
4. Discussion
The primary purpose of this study was to investigate the effects of
quercetin and rutin on the physicochemical properties of starch in
Tartary buckwheat. Furthermore, this study explored the differences in
the interactions of starch with quercetin and rutin at high concentra-
tions.
Firstly, the pasting property results showed that quercetin and rutin
could decrease the swelling power of the TBS granules, as indicated by
L. Wang, et al.
Fig. 4. 1H NMR spectra of quercetin, rutin, gelatinized TBS, TBSQ (A) and TBSR (B). The NOESY spectra of TBSQ (C) and TBSR (D) in DMSO-D6 was recorded at
400 MHz NMR at 25 °C.
the lower PV, TV and PaT values (Table 1). Since quercetin and rutin
were slightly soluble in water, they could prevent the contact of the
starch granules from interacting with amylose or amylopectin leached.
This allowed more amylose to remain in the discontinuous phase
(swollen granules and granule fragments) rather than moving into the
continuous phase (dissolved and partially dissolved starch polymer
molecules and hydrocolloid molecules), which would restrict the
swelling power of the starch granules (Qiu et al., 2015). Secondly,
quercetin and rutin caused less impedance during starch gelatinization,
thereby maintaining the stability of starch pastes against shear force
and heating, as evident by the lower BV values (Liu et al., 2019; Ma,
Pan, Xie, Li, Zhang, & Chen, 2019). Thirdly, the different effects of
quercetin and rutin on the pasting properties showed that the BV value
of TBSR was significantly lower than that of TBSQ, particularly at doses
greater than 6% (P < 0.01), suggesting that rutin enhances starch
paste stability. Moreover, rutin promoted the increase in the SV and FV
values at 6% dose while quercetin did not, providing further evidence
that rutin could enhance the aggregation of starch pastes and, thus,
form highly viscous pastes or gels of starch during cooling after heating.
During the retrogradation process, starch molecules could interact with
each other through a strong hydrogen bond and form a rigid structure
in amorphous regions (Wu et al., 2009). The swollen starch granules
could release both amylose and amylopectin chains allowing the phe-
nolics to interact with them via polyhydroxy structures (Fig. 5). These
interactions might be attributed to hydrogen bonds or hydrophobic
interactions, which could interfere with the native starch molecules, re-
ordering the amylose matrix, and thus affecting in the changes of SV
8
Food Chemistry 335 (2021) 127556
and FV values. The free phenolic in the complex could represent the
insoluble quercetin or rutin (Supplemental Fig. 1). Quercetin was found
to dissolve slightly in starchy matrix, and its precipitated crystals fur-
ther diluted the starchy matrix, thus leading to less frequent interac-
tions between starch molecules and a decrease in the viscosity or fric-
tion of starch pastes as a result of the reduction in the SV and FV (Chai
et al., 2013; Karunaratne & Zhu, 2016). However, rutin showed the
opposite effects on the SV and FV at a dose of 6%, which might be
related to its different solubility and distributivity in the starchy matrix
(Supplemental Fig. 1). The better solubility of rutin than quercetin
might be attributed to the disaccharide groups (rutinose) present in
rutin (Fig. 5). The better distributivity might be due to the different
crystals’ size or structure of rutin, although the rutin at dose of 6% also
presented precipitated crystals in starch matrix. Furthermore, this result
indicated the possible influence of differences in the molecular struc-
tures of rutin and quercetin on their physicochemical properties of the
complexes within starch.
Differences were also observed in the rheological properties in that
the apparent viscosities, G′ and G″ reached their maximum levels when
the rutin was increased to 6%, while the added quercetin had no such
effect (Fig. 1). Similarly, further determinations of the different con-
centrations from 4% to 8% TBSQ and TBSR showed that G′ and G″ only
increased when the rutin concentration ranged from 5% to 7%
(Supplemental Fig. 2). It has been suggested that dissolved rutin and its
precipitated crystals might have an antagonistic effect on gel formation
(Karunaratne & Zhu, 2016). In this current study, when the rutin con-
tent was less than 5%, the amount of rutin dissolved in the starchy
L. Wang, et al.
Fig. 5. Schematic illustration of the chemical structure of starch-phenolic complexes. TBS, Tartary buckwheat starch; Q, quercetin; R, rutin; TBSR, TBS-rutin
complex; TBSQ, TBS-quercetin complex; cyan circle, hydrogen bonding site; red circle, –OeH proton; magenta circle, –CeH proton; large circle, strong correlation of
binding site; and small circle, weak correlation of binding site. (For interpretation of the references to colour in this figure legend, the reader is referred to the web
version of this article.)
matrix was not sufficient to promote the gelation of starch pastes with a
high G′ value. A rutin content of 6% appeared to achieve an optimal
balance. The direct interaction of dissolved rutin with the amylose
promoted the formation of linear fragment of amylopectin in the starch.
In addition, the precipitated rutin microcrystals acted as rigid fillers in
the continuous starchy matrix and contributed to the increase in the
solid parts of the systems (Fig. 5). However, the presence of precipitated
rutin at a concentration of greater than 7% began to dilute the starch
pastes, causing structural disruption in the gel, thus exerting the same
influence as the quercetin. These findings were consistent with previous
results reported by Zhu & Wang (2012) that the addition of rutin gen-
erally increased the G′ value of rice starch in a dose-dependent manner,
while an excessive rutin content caused the disruption of the amylose-
lipid inclusion complex.
The stronger ability of rutin compared to that of quercetin to pro-
mote the gelation of TBS was further supported by the following
thermal and gel texture analysis results. The reduction of To, Tp, Tc and
ΔH values indicated that rutin and quercetin could reduce the gelati-
nization temperature and energy, and the lowering effect of TBSR was
much stronger than that of the TBSQ, particularly at 6% (P < 0.01).
Thus, rutin could more readily promote starch gelatinization than
quercetin (Supplemental Table S2). This result was consistent with the
lower BV values of the TBSR from the pasting properties analysis, fur-
ther showing its ability to enhance the starch pastes’ stability (Table 1).
Moreover, the lower melting temperature and ΔH of the retrograded
starch (could be due to weaker starch crystallinity in comparison to
native TBS), together with the reduction in hardness, adhesiveness and
gumminess in the complex gels, indicated that the presence of quercetin
and rutin inhibited TBS retrogradation (Supplemental Table S3). The
inhibitory levels of quercetin and rutin were ranged from 11.5% to
27.1% and 26.8% to 49.8%, respectively, based on the ΔH values in
retrogradation. Similar results have found in studies of caffeic acid
(Igoumenidis, Zoumpoulakis, & Karathanos, 2018) and tea polyphenols
(Zhang et al., 2015), which inhibited rice or wheat starch retro-
gradation. Although no differences were observed in the hardness,
adhesiveness and gumminess trends between the rutin and quercetin,
probably because the starch component in the system was structurally
9
Food Chemistry 335 (2021) 127556
responsible for the gel texture (Zhu & Wang, 2012). The enhanced TBSR
cohesiveness was found to be significantly higher than that of the TBSQ
at 6% (P < 0.01), supporting the stronger internal bond of the gels
induced by the rutin. This difference in the effects on the pasting,
rheological and thermal properties and gel texture profiles might be
primarily attributed to the different molecular structures of quercetin
and rutin, which had one quercetin and one rutinose moiety (Fig. 4B),
correspondingly resulting in the different solubility and interactions
with TBS.
The subsequent SEM observations showed various morphological
characteristics and provided evidence of the different solubility of rutin
and quercetin and their interactions with the TBS (Fig. 2). Rutin was
more effectively dissolved and distributed in the starchy matrix of the
TBSR than quercetin, thus maintaining the integrity of the three-di-
mensional network structure of the TBSR gels (Fig. 5). Unlike the rod-
shaped particles of quercetin (Fig. 2A), rutin particles were irregular
and small (Fig. 2B), thus providing a larger specific surface area in
water to achieve a higher solubility (~90 μg/mL) (Huang et al., 2017)
compared to that of quercetin (0.17–10.28 μg/mL) (Chen & Yao, 2017).
This phenomenon contributed to rutin’s superior promotion of starch
gel formation at a concentration of 6% compared to that of quercetin
(Fig. 2E4, F4), similar to the aforementioned findings for the pasting,
rheological and thermal properties. However, at higher concentrations,
quercetin crystals were clearly observed in the TBSQ, which were ir-
regularly distributed in the gel wall and seriously restricted starch ag-
gregation (Fig. 2E5, E6). In contrast, the smaller rutin particles were
more uniformly distributed in the gel wall and only slightly restricted
the starch aggregation (Fig. 2F5, F6). These findings confirm that, when
the phenolic concentration was greater than 6%, the precipitated par-
ticles disturbed the ordered arrangement of starch molecules and re-
stricted gel formation. However, rutin created less disturbance than
that of quercetin.
The different effects of the rutin and quercetin molecules on their
interactions with the TBS were characterized by XRD, FTIR and NMR.
As shown in the XRD results for recrystallization, neither the TBSQ nor
TBSR appeared to show the characteristic V-type crystalline peaks at
20° (Fig. 3), although the apparent amylose content of the TBS was
L. Wang, et al.
equal to 41.53% (Supplemental Table S1). This result was further
supported by the FTIR results, in which no new characteristic peaks
appeared in the TBSQ or TBSR, and no new covalent bonds were formed
(Fig. 3D). This observation was because of the cavity size of the TBS
amylose helical structure, which was not sufficiently large for the for-
mation of the V-type complex with its bulky molecules given the hy-
drophobicity of quercetin or rutin (Zhu, 2015). Starch was able to in-
teract with phenolics through hydrogen bond formation or hydrophobic
interactions (Igoumenidis et al., 2018). However, the effect of the ru-
tinose presence in promoting the binding between starch and rutin
through hydrogen bonds was not clear and was therefore analyzed by
NMR in the subsequent experiment (Fig. 4).
The spatial interactions between the starch and phenolics were ex-
amined using 1H NMR and NOESY. The increase in the half-width peak
values (corresponding to the reciprocal of the transverse relaxation
time) of the protons on the benzene ring and 5-OH showed that the
phenolics were strongly attached to the starch (Fig. 4A and B). No
significant chemical shifts were observed in the proton signals, neither
in the 5-OH and aromatic peaks of the phenolics nor in the –CH and
–CH2 peaks (~3.6 ppm) of the starch (Igoumenidis et al., 2018). The
proton signal intensities from 9.3 to 10.8 ppm for the phenolics were
clearly decreased, indicating that 7-OH, 3-OH, 4′–OH and 3′–OH of the
quercetin and 7-OH, 4′–OH and 3′–OH of the rutin might be the asso-
ciated positions (Liu, Wang, Yong, Kan, Zhang, & Jin, 2018). Therefore,
to explain these different binding positions and obtain more detailed
insights into the actions of quercetin and rutin at the binding sites to the
TBS, NOESY experiments were performed (Fig. 4C and D). The NOESY
spectrum is a feasible tool for detecting the spatial distance between
molecules (Mw < 1000 Da, or greater than 2000 Da) (Sedaghat Doost,
Akbari, Stevens, Setiowati, & Van der Meeren, 2019; Xie et al., 2019)
and identifying the signals generated by protons that are spatially ad-
jacent to each other but not covalently bonded (Hakkinen & Abbott,
2019). The results showed that the difference in the binding sites be-
tween quercetin (4′–OH, 3′–OH, 8-H and 6-H groups) and rutin (2′-H,
6′-H and 5′-H groups) might be a result of the steric hindrance of the
disaccharide groups (rutinose) of the rutin molecule, which restricted
the binding of hydrogen between the benzene ring and starch molecule,
thus reducing the degree of starch binding. Interestingly, the stronger
NOE correlations of the TBSQ than the TBSR implied stronger inter-
actions between quercetin and starch, which did not support the
stronger promotion of rutin in TBS gelation, as in the aforementioned
results for the viscosity, rheological and structural properties. It was,
therefore, necessary to consider that the NOE correlation could not
distinguish the overlaps in the proton signals between rutinose and
starch which explained the complicated interactions in the TBSR
complex. In addition, it has been reported that non-starch poly-
saccharides (with polyhydroxy structures) could interact with potato
starch through hydrogen and noncovalent bonding (Ren et al., 2020). It
was speculated that the structural group of the rutinose in rutin might
also interact with starch through hydrogen bonding, thereby affecting
the TBSR properties. Compared with the structural group of quercetin
in rutin, the rutinose group in rutin was likely to obtain better disper-
sion and present excellent mechanical properties for the TBSR, although
weak correlations were observed on the benzene ring with the quercetin
group in rutin compared to those of quercetin itself. Furthermore, the
minimal NOE correlations of the TBSR mixture (composed of the direct
mixing of pasted TBS with rutin that was different from the TBSR
complex in the text) in the NOESY spectrum showed that the heat
treatment induced the rearrangement of starch molecules and the un-
folding of molecular chains. These phenomena, in turn, supported the
effective binding of the phenolics to the starch molecules through hy-
drogen bonds (Supplemental Fig. 3). According to these findings, the
possible binding schematic chemical structures in the TBSQ and TBSR
complexes were deduced (Fig. 5).
As shown in Fig. 5, quercetin interacted with TBS mainly by OeH
but when its hydroxyl position bonds to rutinose groups (became rutin),
10
Food Chemistry 335 (2021) 127556
the interaction with TBS changes to CeH. The structural group of ru-
tinose was mainly contributed to better distribution of rutin in a starchy
matrix compared to quercetin, and thus showed an excellent ability to
alter the physicochemical properties of TBSR. These alterations in-
cluded enhancing the aggregation of starch pastes to promote gel for-
mation based on the higher SV and FV values of the pasting property
results, strengthening the TBS gel via the presence of linear fragments
of amylopectin in the starch according to the higher apparent viscosities
and G′ and G″ values, and producing a softer but more compact struc-
ture in the TBS gel on the basis of the textural profile results. The SEM
morphology clearly showed the better solubility and distribution of
rutin compared to those of quercetin in the starchy matrix, as well as
the better starch granular aggregation and gel integrity. Both the XRD
and FTIR results indicated the interaction of phenolics with starch via
noncovalent bond, and the NMR results further confirmed the forma-
tion of hydrogen bonds. The difference in the binding sites between
quercetin and rutin observed in the NOE spectra was closely associated
with the steric hindrance of the disaccharide groups (rutinose) in the
rutin molecule.
5. Conclusions
The present study has shown that quercetin and rutin addition was
able to restrict the swelling power of starch granules, inhibit the ret-
rogradation of TBS, and alter the strength and structure of the gel.
These variations were closely associated with their concentrations. This
study demonstrated for the first time that rutin more effectively pro-
moted TBS gelation than quercetin, and an appropriate concentration of
added rutin was 6% (w/w). Our hypothesis was verified that the steric
hindrance of the disaccharide groups (rutinose) bonding to quercetin
group actually led to the difference in the solubility and distributivity
between rutin and quercetin, and subsequently resulted in the different
physicochemical properties of the TBSR from TBSQ. Overall, an ap-
propriate addition of rutin has been confirmed to significantly promote
TBS gel formation, providing a feasible and potential application for the
development of whole grain food composed of Tartary buckwheat. The
difference in the physiological function involved with starch digestion
in vitro and in vivo between rutin and quercetin still needs to be clar-
ified in the further studies.
CRediT authorship contribution statement
Libo Wang: Conceptualization, Methodology, Software,
Investigation, Writing - original draft. Lijuan Wang: Validation, Formal
analysis, Visualization, Software. Zaigui Li: Resources, Writing - review
& editing, Supervision, Project administration, Funding acquisition.
Yanxiang Gao: Resources, Supervision. Steve W. Cui: Writing - review
& editing. Tongtong Wang: Software, Formal analysis. Ju Qiu:
Resources, Writing - review & editing, Supervision, Project adminis-
tration, Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
The work was kindly funded by the Earmarked Fund for China
Agriculture Research System (grant No. CARS-07-E-4) and the Scientific
Research Staring Foundation for the Returned Overseas Chinese
Scholars from the Ministry of Education of China (grant No. [2015]
311).
L. Wang, et al.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.foodchem.2020.127556.
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