Food Chemistry 388 (2022) 133058

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

Deep eutectic solvent-based ultrasonic-assisted extraction of phenolic

compounds from different potato genotypes: Comparison of free and bound
phenolic profiles and antioxidant activity
Haicui Suo a, Ziting Peng b, Zhiqiang Guo b, Chengjunhong Wu b, Jitao Liu a, Li Wang a,
Juan Xiao b, *, Xiaobo Li a, *
a
Crops Research Institute, Guangdong Academy of Agricultural Sciences/Guangdong Provincial Key Laboratory of Crop Genetic Improvement, Guangzhou 510640,
Guangdong, China
b
State Key Laboratory of Marine Resource Utilization in South China Sea/Engineering Research Center of Utilization of Tropical Polysaccharide Resources, Ministry of
Education/Key Laboratory of Food Nutrition and Functional Food of Hainan Province, College of Food Science and Engineering, Hainan University, Haikou 570228,
China

A R T I C L E I N F O A B S T R A C T

Keywords: Potato phenolics exhibit health-promoting effects. Studies on bound phenolics are scarce. Here, significant dif­
Potato ferences in total phenolic content (TPC), total flavonoid content (TFC) and antioxidant activity in free and bound
Phenolic compound forms were found among 19 potato genotypes. 7 free and 24 bound phenolics were characterized and quantified
Bound form
using ultrahigh-performance liquid chromatograph-mass spectrometry, among which 22 bound phenolics are
Free form
reported for the first time in potato. The number and content of identified free and bound phenolics changed
considerably among the genotypes. Chlorogenic acid, cryptochlorogenic acid and rutin in free form, and benzoic
and caftaric acids in bound form were predominant. Heijingang showed the highest free and total TPC and
antioxidant activity, and the largest number of phenolic compounds, whereas S17-1-1 contained the highest free
and total TFC and Longshu 7 contained the highest bound phenolic content. Cluster analysis segregated the
genotypes into 6 groups. This study provides useful information on benefits of potato in human health.

1. Introduction promoting phenolic compounds in view of its high consumption levels

Potato is the fourth most common staple food after rice, wheat, and
maize, with a worldwide annual output of over 368 million tons. Po­
tatoes play a significant role in human health as a source of key nutri­
ents, including starch, protein, minerals, vitamins, and phytochemicals
(Zaheer & Akhtar, 2016). Various phytochemicals, including phenolic
compounds, are associated with multiple health-promoting effects,
especially with the reduction of the risk of chronic diseases (Catalkaya
et al., 2020). Potato is rich in phenolic compounds, which shown potent
antioxidant, anticancer, anti-inflammatory, and antiproliferative activ­
ities in vitro and in vivo (Akyol, Riciputi, Capanoglu, Caboni, & Verardo,
2016; Kaspar et al., 2011; Madiwale, Reddivari, Holm, & Vanamala,
2011). For this reason, potato is considered an ideal source of health-
(Akyol et al., 2016).
Phenolic compounds usually exist in free and bound forms depend­
ing on their extractability and interaction with plant cell wall compo­
nents (Acosta-Estrada, Gutiérrez-Uribe, & Serna-Saldívar, 2014). Free
phenolics generally exist in vacuoles of plant cells and are absorbed in
small intestine relatively easily, whereas bound phenolics are difficult to
be directly absorbed due to their interaction with cellulose, pectin, and
other polysaccharides (Acosta-Estrada et al., 2014). For these reasons,
the nutritional effects of bound phenolics have been neglected for a long
time. In fact, bound phenolics extracted by hydrolysis exhibit potent
anti-inflammatory and antioxidant abilities in vitro, and have been
implicated in different health benefits (Acosta-Estrada et al., 2014;
Zhang, Zhang, Li, Deng, & Tsao, 2020). Bound phenolics are mainly

Abbreviations: UAE, ultrasonic-assisted extraction; DES, deep eutectic solvent; DES-UAE, ultrasonic-assisted extraction coupled with deep eutectic solvents; TPC,
total phenolic content; TFC, total flavonoid content; GAE, gallic acid equivalent; CE, catechin equivalent; FRAP, ferric-reducing antioxidant power; DW, dry weight;
Fe(II)E, FeSO4 equivalent; UHPLC-MS, ultra-high-performance liquid chromatography-mass spectrometry; MS, mass spectra; PCA, principal component analysis.
* Corresponding authors.
E-mail addresses: xiaojuan209218@163.com (J. Xiao), Lixiaobo1981@163.com (X. Li).

https://doi.org/10.1016/j.foodchem.2022.133058
Received 7 January 2022; Received in revised form 14 April 2022; Accepted 21 April 2022
Available online 25 April 2022
0308-8146/© 2022 Elsevier Ltd. All rights reserved.
H. Suo et al.
released and are metabolized by microorganisms in the colon, and their
microbial metabolites possess more potent physiological activities
(Duynhovena et al., 2011). The microbial metabolites of phenolic
compounds also play key roles in modulating the intestinal immune
system response and in improving the balance of intestinal bacteria and
the excretion of short chain fatty acids (Zhang et al., 2020). Thus, the
bound phenolics are more sustainable than their free counterparts and
have attracted increasing attention in recently years. In potato, wide
diversity in the free phenolic profile and antioxidant ability among po­
tato genotypes has been reported (Gutiérrez-Quequezana, Vuorinen,
Kallio, & Yang, 2020; Kim, Soh, Bae, & Nam, 2019; Ru, Pang, Gan, Liu, &
Bao, 2019). However, sporadic information is available on bound phe­
nolics, although three bound phenolic acids, including caffeic, ferulic,
and p-coumaric acids, were identified in potatoes by HPLC-DAD
Fig. 1. Photographic images of 19 potato genotypes.
2
Food Chemistry 388 (2022) 133058
(Albishi, John, Al-Khalifa, & Shahidi, 2013; Ru et al., 2019). Besides
these three phenolic acids, those in the bound fraction of potatoes are
not known.
The most common method for extraction of free phenolic compounds
in potato is the solid–liquid extraction, usually with organic solvents
(methanol, acetone, and ethanol) (Kim et al., 2019; Ru et al., 2019),
which are considered environment unfriendly solvents. Compared with
organic solvents, deep eutectic solvents (DESs) are considered as green
and efficient extraction solvents, with several advantages, such as sta­
bility, less volatility, and easy synthesis and degradability (Cunha &
Fernandes, 2018). DESs produced by hydrogen bond interaction be­
tween hydrogen bond acceptors and donors, are a novel type of ionic
liquid analogs (Wu, Li, Chen, Wang, & Lin, 2020). There is no literature
about extracting phenolics from potatos by DESs. Thus, in this study,
H. Suo et al.
eco-friendly DES coupled with ultrasonic-assisted extraction (UAE) was
used to extract free phenolics from 19 potato genotypes with color and
yellow flesh collected from China, and then bound phenolics were
released from the residues by an alkaline hydrolysis method. Moreover,
total phenolic content (TPC), total flavonoid content (TFC), and anti­
oxidant activities were evaluated. Furthermore, phenolic compounds in
free and bound forms were identified and quantified using ultrahigh-
performance liquid chromatograph-mass spectrometry (UHPLC-MS).
This work provides useful information for potato processing and healthy
diet for human.
2. Materials and methods
2.1. Plant materials
Potato genotypes used in present study have wide adaptability with
high yields. They were harvested from Baiyun Experimental Station of
Guangdong Academy of Agricultural Sciences in Guangzhou, Guang­
dong province, China (113◦ 17E′ , 23◦ 8N′ ) in March 2019. They were
divided into two groups: color fleshed group including four genotypes
with purple flesh and three genotypes with red flesh, and yellow fleshed
group including three genotypes with color circle flesh and nine geno­
types with yellow flesh (Fig. 1). Freshly harvested potatoes were peeled,
cut into small pieces (0.5 × 0.5 cm), lyophilized, ground into 40-mesh
size, and kept at − 18 ◦ C.
2.2. Chemicals and reagents
Choline chloride and ethylene glycol were purchased from Aladdin
Biochemical Technology Co., Ltd. (Shanghai, China). Apigenin, hes­
peridin, and rutin for UHPLC-MS were purchased from Qiyun Biotech­
nology (Guangzhou, China) and other phenolic standards for UHPLC-MS
were purchased from Sigma Chemical Co., Ltd. (Shanghai, China).
2.3. Extraction of free and bound phenolic compounds
Free phenolic compounds were extracted according to the previously
described method (Wu et al., 2020). Briefly, choline chloride and tri­
ethylene glycol were mixed in a molar ratio of 1:4 and stirred with a
magnetic stirrer at 80 ◦ C to obtain a homogeneous and transparent
liquid (DES). Potato powder (2 g) was extracted with 20 mL of the
abovementioned DES (30% water content, v/v) at 40 ◦ C with an ultra­
sonic power (320 W, 30 min), and then centrifuged at 10,000 rpm for 10
min. The supernatant served as the free phenolic extract and the pre­
cipitate was used for the extraction of bound phenolics using an alkaline
hydrolysis method (Sun, Chu, Wu, & Liu, 2002).
2.4. Determination of TPC and TFC
TPC was measured by the Folin Ciocalteu colorimetric method
(Adom & Liu, 2002) at 760 nm using an Infinite M200 PRO plate reader
(Tecan Austria GmbH, Grödig, Salzburg-Umgebung, Austria). Gallic acid
was used as the standard for preparing a calibration curve. TPC was
expressed as milligram of gallic acid equivalents per 100 g of potato dry
weight (mg GAE/100 g DW). TFC was determined by colorimetric
method (Adom & Liu, 2002) at 510 nm and expressed as milligram of
(+)-catechin equivalents per 100 g of potato dry weight (mg CE/100 g
DW).
2.5. Identification and quantification of free and bound phenolic
compounds by UHPLC-MS
The free and bound phenolic compounds were detected by UHPLC-
MS following a previously reported method with some modifications
(Xiao et al., 2020). Briefly, the detection was carried out using a UHPLC
tandem with Xevo triple quadrupole mass spectrometer system
3
Food Chemistry 388 (2022) 133058
(Micromass Waters, Milford, MA, USA) with electrospray ionization
source used in both negative and positive ionization modes. An Acquity
UHPLC BEH-C18 column (2.1 mm i.d. × 100 mm length, 1.7 μm pore
size) obtained from Waters (USA) was used for separating the phenolic
compounds. For extraction of free phenolics, the separation procedure
was as follows: 0–3 min, 5% B; 10 min, 25% B; 16 min, 50% B; 20 min,
70% B; 26–30 min, 100% B; and 31–36 min, 5% B, with eluent A (0.25%
formic acid–water) and eluent B (0.25% formic acid–methanol). For
extraction of bound phenolics, the separation procedure was as follows:
0–1 min, 5% B; 8 min, 25% B; 11 min, 60% B; 13–16 min, 100% B; and
16.2–19 min, 5% B, with eluent A (0.25% formic acid–water) and eluent
B (0.25% formic acid–acetonitrile). The identification of compounds
was achieved by multiple-reaction monitoring; after the UHPLC-MS
analysis of all compounds present in the extracts and comparison with
the published MS data, the basic structure of some peaks were deduced,
and further assignation was performed by comparison with the respec­
tive standards using UHPLC-MS. The quantification was achieved by
comparing the calibration curve of respective standards expressed as
microgram per gram of dry weight of potato powder (μg/g DW).
MS data were collected over a mass range of m/z 50–1000. The
constant parameters used were as follows: capillary voltage, 2.0 kV;
cone voltage, 30 V; drying gas (N2) flow, 1000 l/h; and drying gas
temperature, 500 ◦ C.
2.6. Antioxidant activity determination
The antioxidant activity was determined using the total antioxidant
capacity kit with ferric-reducing antioxidant power (FRAP) assay
(Nanjing Jiancheng Bioengineering Institute, Nanjing, Jiangsu, China)
according to the manufacturer’s protocol. The absorbance of the mixed
solution was recorded at 593 nm. The FRAP results were expressed as
millimolar FeSO4 equivalents/gram DW (mM Fe(II)E/g DW).
2.7. Statistical analyses
All data are expressed as means ± standard error derived from
triplicate extractions. The statistical analyses were performed using
ANOVA followed by Duncan’s multiple-range test. A value of p < 0.05
was considered statistically significant. Correlation analysis was con­
ducted using Pearson correlation tests following two-tail tests in SPSS v.
26.0 (SPSS Inc. Chicago, IL, USA). Principal component analysis (PCA)
and cluster analysis were performed using the Origin v. 2021 software.
3. Results and discussion
3.1. TPC and TFC
Significant differences in the free, bound, and total TPC and TFC
among the 19 potato genotypes are shown in Table 1 (p < 0.05). The
free, bound, and total TPC varied from 81.40 to 617.83 mg GAE/100 g
DW, 8.47 to 53.03 mg GAE/100 g DW, and 90.90 to 653.49 mg GAE/
100 g DW, respectively. Heijingang had the highest free and total TPC,
which were 7.59- and 7.19-fold higher than those in Zhongshu 5, having
the lowest free and total TPC. S17-119–2 had the highest level of bound
TPC and Qingshu 9 and Zhongshu 5 had the lowest TPC. The free,
bound, and total TFC varied from 70.61 to 380.83 mg CE/100 g DW,
2.49 to 64.80 mg CE/100 g DW, and 75.56 to 385.11 mg CE/100 g DW,
respectively. S17-119–1 had the highest free and total TFC, which were
5.39- and 5.10-fold higher than the lowest free and total TFC in
Zhongshu 5 (p < 0.05). All-Red had the highest level of bound TPC,
which was 26.02-fold higher that the lowest bound TFC in S17-188–4
and 15A032-49 (p < 0.05). Many studies have reported significant dif­
ferences in free TPC and/or free TFC among different potato genotypes
(Albishi et al., 2013; Deusser, Guignard, Hoffmann, & Evers, 2012;
Gutiérrez-Quequezana et al., 2020; Ru et al., 2019). Sporadic studies
have shown significant differences in bound TPC among different potato
H. Suo et al. Food Chemistry 388 (2022) 133058

Table 1
Free, bound and total TPC, TFC and their proportion of bound in total in 19 potato genotypes.
Genotypes TPC (mg GAE/100 g DW) TFC (mg CE/100 g DW)

Free Bound Total Proportion of bound Free Bound Total Proportion of bound
in total in total

Colour group
Heijingang 617.83 ± 35.67 ± 653.49 ± 26.45 5.46 ± 1.20a 320.56 ± 7.88 ± 0.63f 328.43 ± 2.39 ± 0.13bcd
25.47i 1.2ghi k 8.07j 8.67i
S17-1–1 256.23 ± 35.30 ± 291.53 ± 8.37j 12.07 ± 0.60a 149.44 ± 3.38 ± 152.82 ± 2.21 ± 0.29bc
5.67gh 2.73gh 0.56efg 0.45ab 0.66def
S17-188–4 217.53 ± 10.27 ± 227.80 ± 4.50 ± 0.12a 173.81 ± 2.49 ± 176.31 ± 1.41 ± 0.21ab
9.54f 0.71ab 10.22ghi 1.07 g 0.39a 1.44f
Y16-11 203.11 ± 13.67 ± 216.78 ± 6.30 ± 0.36a 318.33 ± 6.99 ± 325.32 ± 2.15 ± 0.28bc
3.58ef 0.88bcd 3.91fgh 3.46j 0.86ef 2.62i
15A032-49 269.63 ± 9.21 39.50 ± 309.13 ± 7.74j 12.82 ± 0.78b 274.33 ± 2.49 ± 276.83 ± 0.89 ± 0.11a
h 1.46ij 13.86i 0.40a 14.20 h
Y16-14 230.81 ± 10.43 ± 241.25 ± 4.40 ± 0.65a 270.85 ± 4.05 ± 274.90 ± 1.51 ± 0.31ab
17.52 fg 1.16ab 16.86hi 19.11i 0.55bc 18.57 h
All-red 213.38 ± 40.27 ± 253.65 ± 15.95 ± 0.76b 148.89 ± 64.80 ± 213.69 ± 30.28 ± 1.33j
13.92ef 1.27j 14.47i 5.80efg 4.73i 9.01 g
Mean 286.93 ± 26.44 ± 5.36 313.38 ± 8.79 ± 0.02 236.60 ± 13.16 ± 249.76 ± 5.84 ± 0.04
55.88* 58.06* 29.10* 8.64 26.44*

Yellow group
15A029-2 164.69 ± 12.50 ± 177.19 ± 7.30 ± 1.34a 130.22 ± 13.95 ± 144.17 ± 9.70 ± 0.58gh
17.25 cd 1.25abc 16.04cde 6.96de 0.79 g 7.22cde
S17-119–1 163.29 ± 6.44 11.80 ± 175.09 ± 6.78 ± 0.93a 380.83 ± 4.28 ± 385.11 ± 1.11 ± 0.19a
cd 1.43ab 5.56cde 5.77 k 0.62bcd 6.35j
S17-119–2 136.46 ± 53.03 ± 2.02 189.49 ± 28.09 ± 1.88c 141.12 ± 6.52 ± 147.64 ± 5.18 ± 0.81e
7.38bc k 5.37def 11.15ef 0.78ef 10.46de
Longshu 7 217.40 ± 32.90 ± 1.25 250.30 ± 13.14 ± 0.30b 162.5 ± 4.19 13.95 ± 176.45 ± 7.93 ± 0.61 fg
5.03f g 5.99hi fg 0.75 g 3.52f
Yueyin 140.49 ± 17.00 ± 157.49 ± 10.85 ± 0.52a 73.33 ± 8.10 ± 0.64f 81.43 ± 3.76a 9.95 ± 0.91gh
85–38 8.39bc 0.10def 8.45bcd 3.47ab
BY-3 181.50 ± 16.10 ± 197.60 ± 8.25 ± 1.00a 96.75 ± 3.6 ± 0.73b 100.35 ± 3.62 ± 0.75d
12.71de 1.07cde 11.95efg 5.44bc 5.28ab
Xisen 6 115.64 ± 41.20 ± 156.84 ± 26.41 ± 1.09c 206.00 ± 28.13 ± 234.13 ± 12.04 ± 0.84 h
9.32b 0.95j 10.27bcd 10.21 h 0.71 h 10.91 g
Yunshu 304 128.64 ± 20.93 ± 149.58 ± 14.08 ± 1.04b 111.33 ± 27.23 ± 138.56 ± 19.76 ± 1.43i
8.20bc 0.84f 8.02bc 6.96 cd 0.81 h 6.63 cd
Fuxi 132.43 ± 19.43 ± 151.86 ± 12.83 ± 1.21b 161.39 ± 5.93 ± 167.01 ± 3.53 ± 0.17d
6.25bc 1.74ef 6.10bc 6.53 fg 0.53def 7.06ef
Zhongshu 5 81.40 ± 3.52a 9.50 ± 90.90 ± 4.05a 10.44 ± 0.11a 70.61 ± 6.98a 4.76 ± 75.56 ± 7.36a 6.35 ± 0.36ef
0.53ab 0.41bcd
Yanshu 9 145.65 ± 37.33 ± 182.98 ± 20.49 ± 0.62bc 114.00 ± 7.65 ± 121.65 ± 6.20 ± 0.52ef
11.4bc 1.60hij 13.00cdef 11.00 cd 0.42ef 10.59bc
Qingshu 9 122.55 ± 8.47 ± 0.88a 131.02 ± 3.18b 6.50 ± 0.31a 173.61 ± 4.95 ± 178.56 ± 2.96 ± 0.56 cd
3.94b 9.41 g 0.42cde 9.40f
Mean 144.18 ± 23.35 ± 4.14 167.53 ± 11.22 13.76 ± 0.02 151.81 ± 10.74 ± 162.55 ± 7.36 ± 0.02
10.01 23.92 2.48 23.99

Values are means ± standard error of three determinations. Values with no common letters in each column are significantly different (p < 0.05).* Values between
groups are significantly different(p < 0.05).

genotypes (Albishi et al., 2013; Ru et al., 2019). The purple flesh potato
had a significantly higher free, bound, and total TPC, as well as higher
total anthocyanin content than that in yellow flesh potato (Albishi et al.,
2013). Red and purple potato flesh had a significantly higher free,
bound, and total TPC than that in white and yellow potato flesh (Ru
et al., 2019). In present study, the mean of free and total TPC and TFC
from seven color fleshed genotypes were 1.99- and 1.87-fold and 1.56-
and 1.54-fold higher than that in 12 yellow fleshed genotypes, respec­
tively. These results are consistent with those of the previous studies
(Albishi et al., 2013; Deusser et al., 2012; Ru et al., 2019). However, no
significant differences in the mean of bound TPC and TFC were found
between color and yellow fleshed genotypes. In colored fleshed geno­
types, bound TPC in Heijingang, S17-1–1, 15A032-49, and All-Red
ranged from 35.30 to 40.27 mg GAE/100 g DW, and that in the other
three colored genotypes was nearly 10.27 mg GAE/100 g DW. In yellow
fleshed genotypes, bound TPC in S17-119–2, Longshu 7, Xisen 6, and
Yanshu 9 ranged from 32.90 to 53.03 mg GAE/100 g DW, and that in the
other eight ranged from 8.47 to 20.93 mg GAE/100 g DW. Bound TFC in
All-Red (colored fleshed genotype), and Xisen 6 and Yunshu 304 (yellow
fleshed genotypes) ranged from 27.23 to 64.80 mg CE/100 g DW, and
that in the other genotypes ranged from 2.49 to 13.95 mg CE/100 g DW.
These results indicate that bound TPC and TFC may be affected by the
flesh color and other related traits of potato (Gutiérrez-Quequezana
et al., 2020; Jin et al., 2009).
Extraction method has an important role in the rate of extraction of
phenolics (Akyol et al., 2016). Traditional organic solvents, with or
without assisted extraction technology, are generally used for extracting
free phenolics from potatoes (Albishi et al., 2013; Gutiérrez-Quequezana
et al., 2020; Ru et al., 2019). DESs are a new type of green solvents,
having the advantages of easy synthesis and a wide range of polarity
(Cunha & Fernandes, 2018). DES has been reported to have great ad­
vantages in obtaining large amount of phenolics from plants (Wang
et al., 2021; Wu et al., 2020; Zhu, Zhang, Li, Liu, & Wang, 2020). We are
reporting the extraction of free phenolics from potatoes using DES-UAE
for the first time. Previously, extraction of potato genotypes, Heijingang
and Zhongshu 5, using 80% methanol yielded 73.6 and 11.84 mg GAE/
100 g DW free TPC, respectively (Ru et al., 2019). In the present study,
free TPC in Heijingang and Zhongshu 5 was 8.39- and 6.88-fold higher,

4
H. Suo et al. Food Chemistry 388 (2022) 133058

respectively, than that extracted using 80% methanol by Ru et al.
(2019).
Phenolics in foods, including fruits, vegetables, and cereals, exist in
free and bound forms. The proportion of bound TPC in total TPC is
different among foods. In fruits, this proportion ranges from 6.5% to
76.21%, with an average of 29.28% (Acosta-Estrada et al., 2014; Sun
et al., 2002). Similar results were observed for vegetables; bound TPC
comprised an average of 23.8% of the total TPC, within the range of
9.7%–37.6% (Chu, Sun, Wu, & Liu, 2002). In corn, wheat, and rice,
bound TPC comprised approximately 85%, 75%, and 62% of the total
TPC, respectively (Adom & Liu, 2002). Bound TPC in brown rice com­
prises approximately 88% of total TPC (Zhou, Robards, Helliwell, &
Blanchard, 2004), whereas that in barley, including the black, blue, and
yellow varieties, ranged from 54.6% to 88.9% of total TPC (Abdel-Aal,
Choo, Dhillon, & Rabalski, 2012). Chu et al. (2002) reported that bound
TPC in potato (Solanum tuberosum) comprises 39.9% of total TPC.
Russet, yellow, and purple potato varieties have a proportion of bound
TPC to total TPC of 15.79%, 21.95%, and 36.76% (Albishi et al., 2013).

Table 2
Free and bound phenolics compounds in 19 potato genotypes identified by UHPLC-MS.
Phenolic Peak Retention λmax Tentative Model Parents Fragment ions Reference Form
Classes no. time (min) (nm) assignment ions

Hydroxycinnamic 1 2.91 295, Chlorogenic acid – 353.2 191.0 (Ieri et al., 2011; Ivanescu F, B
acid 327 et al., 2010; Mattonai
et al., 2016)
2 8.75 243, Cryptochlorogenic – 353.2 191.0, 179.2 Ieri et al., 2011 F, B
315 acid
3 4.29 270, p-coumaric acid – 163.1 119.0, 91.0 Mattonai et al., 2016; F, B
307 Lambert et al., 2015
4 12.33 320 Caftaric acid – 311.0 179.0, 149.0, 135.0 (Lambert et al., 2015) F, B
5 5.91 241, Neochlorogenic acid – 353.2 191.0, 179.2 Ieri et al., 2011 F
322
6 8.58 299, Caffeic acid – 179.0 135.0, 79.0 (Ivanescu et al., 2010) F
323
7 5.10 244, Sinapic acid – 223 193.0, 149.0, 121.0 (Mattonai et al., 2016) B
323
8 4.98 299, Ferulic acid – 193.0 178.0, 149.0, 134.0 (Ivanescu et al., 2010) B
323

Benzoic acid 9 0.83 271 Gallic acid – 168.9 125.0, 97.0 (Mattonai et al., 2016) B
10 1.65 260, Protocatechuic acid – 152.9 109.0, 80.9 (Lambert et al., 2015) B
295
11 2.43 255 Gentisic acid – 153.0 108.7 ) B
12 2.32 260, 4-hydroxybenzoic – 137.0 93.0 (Arivalagan et al., 2018) B
294 acid
13 3.01 259, Vanillic acid + 169.0 125.0, 93.0 (Lambert et al., 2015) B
291
14 5.75 275 Benzoic Acid + 123.1 79.0 (Caravaca, Carretero, B
Gutiérrez, & Caboni, 2011
15 4.01 275 Vanillin + 153.0 138.0, 125.0, 93.0 (Flamini et al., 2007) B
Flavanol 16 13.05 255, Rutin – 609.0 301.1, 270.9, 178.7 (Caravaca et al., 2011; F
355 Mattonai et al., 2016)
Flavonol 17 3.69 280 Catechin – 289.1 137.1 (Arivalagan et al., 2018) B
18 5.32 248 Daidzein – 253.1 208.0, 131.9, 91.0 (Gardana & Simonetti, B
2016)
19 8.39 255, Quercetin – 301.0 179.0, 151.0 (Ivanescu et al., 2010) B
347
20 8.25 275, Ellagic acid – 301.1 258.1, 229.1 (Fischer et al., 2011) B
367
21 9.60 251, Myricetin – 317.0 179.0, 151.0 (Mattonai et al., 2016) B
375
Flavone 22 9.80 276 Baicalein + 271.0 122.9 (Li, Zhang, Lin, & Zuo, B
2011)
23 13.23 267, Apigenin + 271.0 227.0, 151.0 (Ivanescu et al., 2010) B
339
Flavanone 24 6.84 283, Hesperidin – 609.0 301.0 (Mattonai et al., 2016) B
327
25 10.46 287, Naringenin – 271.0 151.0, 107.0 (Mattonai et al., 2016) B
327
26 10.69 270, Isovitexin – 431.0 280.9, 253.0 (Pereira et al., 2005) B
350
Stilbene 27 13.43 280, Trans-resveratrol + 229.0 135.0, 107.1 (Lambert et al., 2015) B
306
9.39 unknown + 625.3 519.0, 530.9,375.1,257.2 B
9.41 unknown – 933.3 882.8,577.0,473.2,285.0 B
10.56 unknown – 725.3 695.4,595.2,494.7,430.9,270.9 B
10.73 unknown – 370.9 325.0,286.8,237.3, 207.1 B
10.95 unknown + 494.9 473.0, 372.9, 315.2, 286.1 B
9.09 unknown – 852.6 372.7,293.0 B
12.53 unknown + 932.7 493.3, 394.7,292.6 F
16.84 unknown + 855.4 718.7, 456.8, 300.5 F
20.73 unknown + 863.2 827.2,761.2,697.2,474.7,332.6 F
12.83 unknown – 692.6 308.5 F

B, bound; F, free.

5
H. Suo et al.
Ru et al. (2019) reported that the proportion of bound TPC to total TPC
was different among 14 potato varieties, ranging from 10.59% to
39.41%, and the average was not significantly different among white,
yellow, red, and purple varieties. In this study, the proportion of bound
TPC to total TPC was significantly different among the 19 genotypes,
ranging from 4.40% to 28.09%, and the average was not significantly
different between yellow and color fleshed potato genotypes. Impor­
tantly, Heijingang showed a proportion of 20.8% in the study by Ru et al.
(2019), whereas it was 5.5% in the present study. The difference may be
because of the harvest location and period, which influence the accu­
mulation of phenolic compounds due to the synthesis of different
quantities and/or types of phenolics (Deusser et al., 2012; Ieri, Inno­
centi, Andrenelli, Vecchio, & Mulinacci, 2011; Reddivari, Hale, &
Miller, 2007), as well as because of the difference in the methods of
extraction of free and bound phenolics.
3.2. Identification of phenolic compounds
In this study, 7 free form (including 6 hydroxycinnamic acid and
derivatives and 1 flavonol) and 24 bound form (including 7 benzoic acid
and derivatives, 6 hydroxycinnamic acid and derivatives, 5 flavonols, 3
flavanones, 2 flavones, and 1 stilbene) phenolic compounds were iden­
tified (Table 2). It is the first time that bound phenolics have identified
from potatoes by UHPLC-MS.
Eight hydroxycinnamic acid and derivatives were identified. Four of
them (chlorogenic, cryptochlorogenic, p-coumaric, and caftaric acids)
were found in both free and bound fractions. Moreover, neochlorogenic
and caffeic acids were found in the free fraction, whereas sinapic and
ferulic acids were found in the bound fraction. Chlorogenic acid (peak
1), which is the esterified product of quinic and caffeic acids, exists in
three main isomeric forms, viz., chlorogenic (5-O-caffeoylquinic acid),
neochlorogenic (3-O-caffeoylquinic acid), and cryptochlorogenic (4-O-
caffeoylquinic acid) acids (Ieri et al., 2011; Ivanescu, Vlase, Corciova, &
Lazar, 2010; Mattonai, Parri, Querci, Degano, & Ribechini, 2016). They
displayed the same precursor ion [M − H]− at m/z 353.2 and the same
product ions at m/z 191.0 [quinic acid − H]− and 179.2 [caffeic acid −
H]− , with different retention times. p-coumaric, sinapic, and ferulic
acids displayed the parent ions [M − H]− at m/z 163.1, 193.0, and
223.0, and product ions at m/z 119.0 [M− H− CO2]− , 91.0
[M− H− CO2− C2H4]− (peak 3), 193.0 [M− H− CH3− CH3]− , 149.0
[M− H− CH3− CH3− CO2]− (peak 7), 178.0 [M− H− CH3]− , and 149.0
[M− H− CO2]− (peak 8), respectively (Ivanescu et al., 2010; Lambert
et al., 2015; Mattonai et al., 2016). In accordance with a previously
published report, peak 4 was assigned as caftaric acid, indicated by the
parent ion [M − H]− at m/z 311.0 and tartrate fragment at m/z 149.0
(Lambert et al., 2015). Caffeic acid (peak 6) was observed as a depro­
tonated ion [M − H]− at m/z 179.0, with product ions at m/z 135.0
[M− H− CO2]– and 79.0 corresponding to the loss of the
–CH– – CHCOOH and –OH groups (Ivanescu et al., 2010).
Seven benzoic acid and derivatives in the bound fraction were
identified. Peaks 9–14 in the bound fraction at m/z 168.9, 152.9, 153.0,
137.0, 169.0, and 123.1, with their product ions at m/z 125.0, 109.0,
108.7, 93.0, 125.0, and 79.0 due to a loss of CO2, respectively, were
tentatively identified as gallic, protocatechuic, gentisic, 4-hydroxyben­
zoic, vanillic, and benzoic acids, respectively (Arivalagan et al., 2018;
Gómez-Caravaca, Segura-Carretero, Fernández-Gutiérrez, & Caboni,
2011; Ivanescu et al., 2010; Lambert et al., 2015; Mattonai et al., 2016).
Peak 15, with m/z 153.0, showed methyl and methanol losses, and CO
loss as principal fragmentation, and it was tentatively assigned as
vanillin (Flamini, Vedova, Cancian, Panighel, & De Rosso, 2007).
One flavanol (rutin) in the free fraction and five flavonols (catechin,
daidzein, quercetin, ellagic acid, and myricetin) in the bound fraction
were identified. Rutin was distinguished by the deprotonated ion [M −
H]− at m/z 609.0 and the quercetin fragment (m/z 301.1) (Gómez-
Caravaca et al., 2011; Mattonai et al., 2016). Peak 17 was tentatively
identified as catechin ([M − H]− ion at m/z 289.1) by virtue of retro
6
Food Chemistry 388 (2022) 133058
Diel–Alder fragmentation ([M − H − 152]− ) (Arivalagan et al., 2018).
Quercetin and myricetin were observed as deprotonated ions [M − H]–
at m/z 301.0 and 317.0, respectively, and the same product ions at m/z
179.0 and 151.0, which are typical retro Diel–Alder fragmentations of
flavanols. Daidzein was distinguished by the deprotonated ion [M − H]−
at m/z 253.1 and its fragment at m/z 91.0, in accordance with a previous
study (Gardana & Simonetti, 2016). Peak 20 showed [M − H]− at m/z
301.1, with fragments at m/z 258.1 and 229.1, which was consistent
with the reported fragments of ellagic acid (Fischer, Carle, & Kammerer,
2011).
Two flavones (baicalein and apigenin) were found in the bound
fraction by their same protonated ion [M + H]+ at m/z 271.0, and
product ions at m/z 122.9 for baicalein and m/z 227.0 and 151.0 for
apigenin as reported by Li, Zhang, Lin, & Zuo (2010) and Ivanescu et al.
(2010), respectively. Three flavanones (hesperidin, naringenin, and
isovitexin) in the bound fraction were identified. Hesperidin was
observed as a deprotonated molecule [M − H]− ion at m/z 609.0 and its
fragments at m/z 301.0 (aglycone hesperitin), corresponding to the loss
of glycoside (Mattonai et al., 2016). Naringenin was distinguished by a
deprotonated ion [M − H]− at m/z 271.0 and its fragments m/z 151.0
and 107.0, as reported by Mattonai et al. (2016). Isovitexin was char­
acterized by the deprotonated molecule [M − H]− ion at m/z 431.0, and
its fragments at m/z 280.9, corresponding to the fragment [M − H −
150]− and m/z 253.0 [M − H − 150 − CO]− , as reported by Pereira,
Yariwake, and Mccullagh (2005). Additionally, trans-resveratrol was
characterized by the protonated ion [M + H]+ at m/z 229.0, and its
product ions at m/z 135.0 corresponding to the loss of a phenol group
and m/z 107.1, corresponding to the formation of a hydroxytropylium
ion (Lambert et al., 2015).
Among the seven free phenolic compounds identified in our study,
five—rutin, and chlorogenic, cryptochlorogenic, neochlorogenic, and
caffeic acids—have been assigned both by HPLC–UV and UHPLC-MS
(Deusser et al., 2012; Ieri et al., 2011; Kim et al., 2019; Rytel et al.,
2014). p-coumaric acid has been identified with HPLC in many studies
(Albishi et al., 2013; Deusser et al., 2012; Rytel et al., 2014), and has
been identified with UHPLC-MS for the first time in the present study.
Moreover, caftaric acid has been identified with UHPLC-MS for the first
time in potatos in the present study. Besides flavonoids and phenolic
acids, anthocyanins were also identified in the free fraction of pig­
mented potato cultivars (Ieri et al., 2011; Ru et al., 2019). In the present
study, 6 phenolic acids and 1 flavonoids were found in the free fraction
of colored flesh potatoes, without anthocyanins. Anthocyanins were
easily extracted by acidic organic aqueous mixtures (Ieri et al., 2011; Ru
et al., 2019), whereas flavonoids and phenolic acids were easily and
efficiently extracted by DES coupled with UAE (Wang et al., 2021; Wu
et al., 2020; Zhu et al., 2020). Additionally, there are still some unknown
peaks, which need to be identified in a future study.
Sporadic information is available on bound phenolics, although
three of them, namely caffeic, ferulic, and p-coumaric acids, were
identified in potatoes using HPLC-DAD (Albishi et al., 2013; Ru et al.,
2019). However, 24 bound phenolic compounds were assigned using
UHPLC-MS for the first time in this study. Among them, bound ferulic
and p-coumaric acids were identified in potatoes (Albishi et al., 2013; Ru
et al., 2019). Importantly, 22 bound phenolic compounds including 11
phenolic acids (gallic, protocatechuic, gentisic, 4-hydroxybenzoic,
vanillic, benzoic, chlorogenic, cryptochlorogenic, caftaric and sinapic
acids, and vanillin), 10 flavonoids (catechin, daidzein, quercetin, ellagic
acid, myricetin, hesperidin, naringenin, isovitexin, baicalein, and api­
genin,) and 1 stilbene (trans-resveratrol) were firstly identified in po­
tatoes. Among these phenolics, gallic, protocatechuic, chlorogenic acid,
cryptochlorogenic acid, vanillic acid, catechin, vanillin, and quercetin
were found in free fraction of potato (Shakya & Navarre, 2006; Ru et al.,
2019; Deußer et al., 2012; Makori, Mu, & Sun, 2022). In sweet potato
roots, flavonoids (quercetin, myricetin), phenolic acids (gallic, chloro­
genic acid, cryptochlorogenic, isochlorogenic), and others phenolics
were also found (Ghasemzadeh et al., 2016; Oki et al., 2006). Benzoic, 4-
H. Suo et al.
hydroxybenzoic, gentisic, sinapic, and ellagic acids, hesperidin, apige­
nin, the isomer of isovitexin (vitexin), naringenin, and trans-resveratrol
were detected in cereal grains, such as rice and oat (Goufo et al., 2014;
Liu et al., 2017; Orzechowski, Ostaszewski, Jank, & Berwid, 2002;
Prabakaran et al., 2018; Shah, Masoodi, Gani, Ul Ashraf, & Ashwar,
2022; Shumoy & Raes, 2016; Ti et al., 2014; Xiao et al., 2020). Baicalein
and daidzein, as well as gallic, chlorogenic, 4-hydroxybenzoic, syringic,
and ferulic acids, and quercetin were found in beans (Yu et al., 2016).
Grape wines have been reported to be rich in caftaric acid (Lambert
et al., 2015).
3.3. Quantification of phenolic compounds
The number and content of individual phenolic compounds in free
and bound forms from 19 potato genotypes changed considerably
(Table 3). Potato genotypes contains 11–23 kinds of phenolic com­
pounds, including phenolic acids, flavonoids, and stilbenes, which are
3–6 free phenolic compounds and 7–18 bound phenolic compounds.
Heijingang contains the largest number of phenolic compounds (5 free
and 18 bound). Potatoes contain approximately 4–10 free phenolic acids
and flavonoids, identified using HPLC or HPLC-MS (Albishi et al., 2013;
Deusser et al., 2012; Ru et al., 2019), as well as approximately 6–11
anthocyanins in colored-flesh potato (Ieri et al., 2011; Ru et al., 2019).
There were no significant differences in the number of free, bound, and
total phenolic compounds between yellow and colored-flesh potatoes in
this study.
Chlorogenic acid is the dominant free phenolic compound (Deusser
et al., 2012; Navarre, Shakya, Holden, & Kumar, 2010; Ru et al., 2019;
Rytel et al., 2014), which was also observed in this study. Among free
phenolics, chlorogenic acid was found in all the potato genotypes and
accounted for 39.30%–85.03% of free phenolic content in 17 genotypes.
Moreover, chlorogenic acid isomers were also found in all the genotypes,
and cryptochlorogenic acid constituted 2.65%–21.52% of the free
phenolic content. Chlorogenic acid and isomers accounted for 43.54%–
100.00% of the free phenolic content in 18 potato genotypes besides Yun
304, in which they accounted for 20.31% of the content. Caftaric acid
accounted for 69.56% of the free phenolic content in Yun 304.
Furthermore, rutin was found in 16 potato genotypes, accounting for
1.73%–54.53% of the free phenolic content, and was identified as the
predominant free phenolic compound in S17-1–1, S17-188–4, 15A032-
49, and 15A029-2, with the percentage contribution of 41.39%–
54.52% to the free phenolic content. These results are similar to the
former reports that chlorogenic acid is the dominant free phenolic
compound followed by rutin (Blessington et al., 2010; Navarre et al.,
2010).
Bound phenolic acids, including caffeic, ferulic, and p-coumar­
ic acids, were identified in potatoes using HPLC-DAD (Albishi et al.,
2013; Ru et al., 2019), among which caffeic acid was the major bound
phenolic acid, accounting for 50.01%–74.25% of the bound phenolic
content in four potato varieties (Ru et al., 2019). In this study, the
content of benzoic acid was the highest, ranging from 227.01 to
1831.84 μg/g DW. Benzoic acid was detected in 12 potato genotypes and
accounted for 32.24%, 40.34%, and 52.80%–91.69% of the bound
phenolic content in 15A032-49, Longshu 7, and the other 10 genotypes.
Caftaric acid was detected in 17 genotypes, with its content ranging
from 7.01 to 940.77 μg/g DW, and its percentage contribution to the
bound phenolic content ranging from 1.00% to 44.32%; it accounted for
24.20%–44.32% of the bound phenolic content in Qingshu 9, BY-3, Y16-
11, Y16-14, and Longshu 7. However, in our study, caffeic acid was only
detected in free form.
The phenolic content ranged from 201.8 to 5463.645 μg/g DW for
the free form, with the percentage contribution to the total phenolic
content ranging from 12.78% to 99.31%, and from 26.35 to 3187.00 μg/
g DW for the bound form, with the percentage contribution to the total
phenolic content ranging from 0.69% to 76.08%. In 8 genotypes,
including 2 color and 6 yellow flesh genotypes, the bound phenolic
7
Food Chemistry 388 (2022) 133058
content was 1.53- to 6.82-fold higher than the free phenolic content,
whereas in 10 genotypes, including five color and five yellow, the free
phenolic content was 2.46- to 143.29-fold higher than the bound
phenolic content. The genotype S17-1–1 had the highest free and total
phenolic content (p < 0.05). Longshu 7 contained the highest bound
phenolic content (p < 0.05).
Free phenolic compounds in potatoes are mostly substituted phenolic
acids in white and yellow flesh genotypes, and mostly substituted fla­
vonoids and anthocyanins in red and purple flesh genotypes (Gutiérrez-
Quequezana et al., 2020; Ieri et al., 2011; Kim et al., 2019; Ru et al.,
2019). In this study, the proportion of phenolic acid content to phenolic
content ranged from 45.57% to 47.91% among S17-1–1, S17-188–4, and
15A029-2 and from 58.61% to 100% among the other genotypes in free
form, whereas it ranged from 63.27% to 100% in 17 potato genotypes
besides 15A032-49 (43.80%) and Yun 304 (14.22%) in bound form. The
proportion of phenolic acid number to phenolic number ranged from
80.00% to 100.00% for all the genotypes in free form, and from 60.00%
to 100.00% for all the genotypes in bound form. These results indicate
that phenolic acids are the predominant phenolic compounds in both
free and bound forms in most potato genotypes. Many studies have re­
ported that the extraction methods play a crucial role in the phenolic
profile because of the principle of “the substances are more likely to
dissolve in the solvent with the similar polarity to them” (Wu et al.,
2020). Six phenolic acids and one flavonoid were found in the free
fraction of colored-flesh potatoes, without anthocyanins, in this study.
Anthocyanins were easily extracted by acidic organic aqueous mixtures
(Ieri et al., 2011; Ru et al., 2019), whereas flavonoids and phenolic acids
were easily and efficiently extracted by DES coupled with UAE (Wu
et al., 2020). Thus, the difference in the free phenolic profile between
our study and previous studies may be caused by the extraction methods
used.
3.4. Correlation between free, bound, total TPC, and TFC and
antioxidant activity
The free, bound, and total antioxidant capacity and their percentage
contributions to the total antioxidant capacity in the 19 potato geno­
types are presented in Table 4. The free FRAP values ranged from 2.03 to
4.59 mM Fe(II)E/g DW, with the percentage contributions to the total
ranging from 46.9% to 89.8%. The bound FRAP values ranging from
0.38 to 2.31 mM Fe(II)E/g DW, with the percentage contributions to the
total ranging from 10.2% to 47.0%. The average level of FRAP antiox­
idant activity in the bound fraction was lower than that in the free
fraction in both color and yellow fleshed genotypes, which is in accor­
dance with previous studies (Albishi et al., 2013; Ru et al., 2019).
Moreover, the average levels of free and total antioxidant capacity in
color fleshed potato genotypes were 1.33– and 1.15-fold higher than
that in the yellow ones, which corroborates with previous studies
(Albishi et al., 2013; Reddivari et al., 2007; Ru et al., 2019). Heijingang
showed the highest total antioxidant capacity, 15A032-49 and S17-
188–4 showed the highest free antioxidant capacity, and Xiseng 6
showed the highest bound antioxidant capacity.
Previous studies have shown significant correlations between free
and bound or total TPC and antioxidant activity although different as­
says were used (Albishi et al., 2013; Kim et al., 2019). Similar results
were found in our study. According to the correlation coefficient,
analyzed using Pearson correlation test, the free and total TPC showed a
significantly positive correlation with the free FRAP (p < 0.01) and the
total FRAP (p < 0.05). In addition, the free and total TFC were positively
correlated with the free FRAP (p < 0.05) (Table 5).
3.5. Correlation among the content of individual phenolic compounds,
TPC, and TFC and antioxidant activity
As shown in Supplementary Table 1, the correlation coefficients
among the content of individual phenolic compounds to the free, bound,
 H. Suo et al.
Table 3
The contents of free and bound phenolic compounds in 19 potato genotypes.
Phenolics Form content (μg/g DW)

Heijingang S17-1–1 S17- Y16-11 15A032- Y16-14 All-red 15A029- S17- S17- Longshu Yueyin BY-3 Xisen 6 Yun 304 Fuxi Zhongshu Yanshu 9 Qingshu
188–4 49 2 119–1 119–2 7 85–38 5 9

chlorogenic acid F 456.00 ± 2176.68 440.00 168.96 793.04 340.68 406.72 555.8 ± 203.56 913.28 302.75 1713.08 773.04 612.12 346.68 414.28 281.56 ± 730.6 ± 157.2 ±
13.54f ± 22.45 ± ± ± 32.21j ± ± 18.36 g ± ± 21.45 ± 16.45c ± 35.69 ± 35.21j ± 26.87 ± ± 14.35c 11.25i 12.69a
m 19.65ef 14.69ab 19.32d 21.54e 6.12b k l h 25.69d 31.25e
B nd 1.36 ± 0.83 ± nd nd 1.11 ± nd nd nd nd nd nd nd nd nd nd nd 2.67 ± nd
0.64ab 0.05a 0.51ab 0.54b
cryptochlorogenic F 90.23 ± 392.68 292.21 29.07 326.65 54.04 75.76 ± 37.17 ± 30.40 351.47 64.25 ± 400.01 276.01 140.67 93.47 ± 201.55 109.89 ± 143.39 ± 43.45 ±
acid 5.78ef ± 21.05 l ± 9.24i ± 2.70a ± 8.51j ± 5.75de 4.69ab ± ± 5.96 k 4.63 cd ± 6.93 l ± 9.24i ± 4.67 g 4.85ef ± 10.61 7.74f 5.94 g 2.66abc
3.46bcd 2.89ab h
B 32.39 ± 4.69 ± 4.53 ± 10.13 19.17 ± 5.52 ± 8.13 ± 10.21 ± 6.64 ± 23.03 ± 13.14 ± 15.63 ± 4.59 ± 9.37 ± nd 11.65 ± 5.39 ± 19.44 ± 5.36 ±
0.76 k 0.71a 0.57a ± 0.48i 0.64ab 0.59 cd 0.59ef 0.58bc 0.55j 0.69 g 0.76 h 0.64a 0.53de 0.50 fg 0.35ab 0.36i 0.46ab
0.51ef
p-coumaric acid F nd 0.48 ± nd nd 3.51 ± nd nd nd nd 3.45 ± nd nd nd 4.4 ± nd nd nd nd nd
0.17a 0.77b 0.64b 0.90b
B 47.31 ± 5.33 ± 9.85 ± 8.64 ± 12.49 ± 14.76 6.11 ± 10.57 ± 2.59 ± 22.35 ± 2.91 ± 2.27 ± nd nd 1.61 ± 1.64 ± nd 1.75 ± 2.71 ±
5.51f 0.73b 0.54 cd 0.67bcd 0.81de ± 0.51bc 0.91 cd 0.74a 0.81e 0.63a 0.78a 0.38a 0.31a 0.41a 0.72a
0.66de
caftaric acid F nd nd nd nd nd nd nd nd nd nd nd nd nd nd 1530.93 nd nd nd nd
± 0.81
B 72.05 ± 7.01 ± nd 25.67 26.09 ± 21.92 21.55 ± 25.61 ± 23.19 45.96 ± 940.77 38.51 ± 24.12 ± 25.33 ± nd 38.15 ± 25.25 ± 26.88 ± 26.11 ±
5.20d 0.91a ± 0.47b 1.30b ± 0.58b 0.93b 1.30b ± 1.75c ± 5.20e 4.96c 0.49b 0.76b 5.31c 0.69b 0.86b 0.93b
0.61b
neochlorogenic F 2.43 ± 22.16 ± 8.65 ± 0.92 ± 17.95 ± 3.44 ± 13.77 ± 17.57 ± 1.28 ± 18.11 ± 1.67 ± 18.56 ± 13.01 ± 7.57 ± 6.77 ± 7.92 ± 3.73 ± 8.89 ± 1.23 ±
acid 0.48ab 0.61 g 0.70d 0.29a 0.66f 0.70b 0.55e 0.40f 0.46a 0.63f 0. 51a 0.65f 0.62e 0.59 cd 0.62c 0.61 cd 0.67b 0.76d 0.43a
8

caffeic acid F 9.76 ± 25.45 ± 32.80 ± 8.63 ± 41.43 ± 3.6 ± 78.41 ± 39.97 ± nd nd 5.75 ± 7.87 ± nd 19.79 ± 11.61 ± nd 15.84 ± 9.47 ± nd
0.60 cd 0.69 g 0.61 h 0.68c 0.71i 0.06a 2.93j 2.92hi 0.67b 0.61c 0.62f 0.64d 0.63e 0.55 cd
sinapic acid B 6.60 ± nd nd 10.25 nd 10.57 24.73 ± 8.92 ± 3.67 ± 25.69 ± 15.77 ± 29.40 ± 4.13 ± 23.05 ± 13.29 ± 26.21 ± 9.85 ± 35.00 ± 5.56 ±
0.56b ± 0.57c ± 0.63 2.42f 0.67c 0.52a 1.02f 0.58e 0.57 fg 0.70a 0.57f 0.47de 1.05f 0.53c 0.56 g 0.52ab
cd
ferulic acid B 3.29 ± 3.03 ± 6.20 ± 6.73 ± 9.87 ± 9.84 ± 21.67 ± 7.71 ± 6.63 ± 14.96 ± 37.92 ± 52.79 ± 7.93 ± 4.96 ± 25.40 ± 5.40 ± 1.63 ± 3.86 ± 3.49 ±
0.57b 0.58b 0.57ef 0.52efg 0.60 g 0.62 g 0.72i 0.88 fg 0.50efg 0.62 h 1.15jk 2.44 k 0.58 fg 0.93cde 0.93ij 0.52def 0.39a 0.74bcd 0.54bc
gallic acid B 0.45 ± nd nd nd nd nd 8.23 ± nd nd 2.31 ± nd nd nd nd 1.81 ± nd nd 1.89 ± nd
0.05a 0.14c 0.12b 0.10ab 0.10ab
protocatechuic B nd 1.55 ± nd nd 2.80 ± nd nd 1.76 ± nd 2.83 ± nd nd 1.06 ± nd nd nd nd nd nd
acid 0.65a 0.63a 0.61a 0.63a 0.55a
gentisic acid B 16.49 ± 2.65 ± 1.88 ± nd nd 4.60 ± 2.52 ± nd nd nd nd 5.83 ± 2.29 ± nd 4.37 ± 3.31 ± 1.92 ± 10.51 ± nd
0.77d 0.70a 0.65a 0.85ab 0.52a 0.73b 0.51a 0.51ab 0.49ab 0.65a 0.66c
4-hydroxybenzoic B 13.61 ± 3.73 ± 2.24 ± nd nd 3.71 ± 23.24 ± 6.81 ± nd nd nd 8.08 ± 2.83 ± nd 4.12 ± 6.05 ± 1.76 ± 3.83 ± 3.79 ±
acid 1.05e 0.72ab 0.67ab 0.56ab 0.46f 0.98d 0.60d 0.64ab 0.55bc 0.56 cd 0.73a 0.68ab 0.65ab
vanillic acid B 3.73 ± nd 0.40 ± nd nd 0.44 ± 4.65 ± nd 1.75 ± nd nd 5.28 ± nd nd nd nd 2.00 ± nd nd
0.60b 0.14a 0.05a 0.66b 0.55a 0.62b 0.57a
benzoic Acid B 804.11 ± nd nd nd 263.00 nd 1145.19 360.79 340.48 1619.79 1285.89 1011.82 nd 1745.46 nd 1386.02 227.34 ± 1831.84 nd

Food Chemistry 388 (2022) 133058

2.31e ± 2.33b ± 3.17 g ± 1.93d ± 5.79c ± 6.64j ± 11.03 ± 5.77f ± 6.96 k ± 6.43i 5.95a ± 6.33 l
h
vanillin B 64.71 ± 7.42 ± 0.41 ± 17.65 23.87 ± 18.12 40.16 ± 14.48 ± 8.79 ± 48.13 ± 50.88 ± 43.20 ± 11.68 ± 41.84 ± 21.05 ± 24.21 ± 10.67 ± 58.07 ± 7.93 ±
4.63i 5.25b 0.08a ± 2.11f ± 3.59 g 0.39de 0.92bc 5.63gh 5.95ghi 5.62 g 0.71 cd 5.20 g 1.73f 2.39f 0.54c 4.61hi 0.570b
0.61ef 1.14ef
Phenolic acid F 4 5 4 4 5 4 4 4 4 5 4 4 4 5 5 4 4 4 3
number B 11 9 8 6 7 10 11 9 8 9 7 10 8 7 6 9 9 11 7
F 558.41 ± 2617.46 773.67 207.57 574.67 650.52 1286.31 374.42 784.55 1989.44 411.00 ± 892.35 ± 201.88
6.36c ± 16.90 l ± 10.30e ± 7.91a ± 9.27c ± 9.26d ± 12.15i ± 8.59b ± 14.32e ± 15.42j 1.00b 8.70f ± 9.28a
(continued on next page)
 Table 3 (continued )

H. Suo et al.
Phenolics Form content (μg/g DW)

Heijingang S17-1–1 S17- Y16-11 15A032- Y16-14 All-red 15A029- S17- S17- Longshu Yueyin BY-3 Xisen 6 Yun 304 Fuxi Zhongshu Yanshu 9 Qingshu
188–4 49 2 119–1 119–2 7 85–38 5 9

Phenolic acid 1182.57 401.76 235.24 2139.52 1062.07 623.75

content ± 17.71 ± ± ± 18.09 ± 18.16 ±
h 10.82b 3.32a k g 28.98d
B 1064.75 36.77 ± 26.35 ± 79.08 357.29 90.59 1306.17 446.87 393.72 1804.92 2347.23 1214.81 58.63 ± 1850.01 71.65 ± 1502.64 285.15 ± 1995.73 54.95 ±
± 6.93i 3.59ab 3.67a ± 6.05 ± 7.35f ± 6.89d ± 9.30 k ± 8.92 h ± 7.29 ± 14.23 ± 7.38p ± 9.17j 8.93bc ± 6.24n 4.70 cd ± 11.81 l 8.33e ± 9.05o 6.59bc
cd g m
rutin F 47.07 ± 2846.21 927.97 nd 835.28 12.19 74.45 ± 751.11 4.15 ± 581.76 92.77 ± 1332.27 347.08 349.72 211.59 362.19 19.57 ± 350.39 ± nd
4.04b ± 8.74 k ± 4.36i ± 5.91 h ± 1.17a 3.49c ± 5.88 g 0.57a ± 10.40f 5.33c ± 5.78j ± 8.15e ± 5.78e ± ± 6.40e 2.02a 5.49e
15.13d
catechin B nd nd nd nd 52.23 ± nd nd nd nd nd nd nd nd nd nd nd nd nd nd
2.44
daidzein B nd nd nd nd 17.21 ± nd nd nd nd nd nd nd nd nd nd nd nd nd nd
1.62
quercetin B 16.99 ± 1.76 ± nd nd nd nd nd 2.65 ± 3.03 ± 22.24 ± nd nd 10.48 ± nd 6.85 ± 9.03 ± nd nd nd
0.81d 0.60a 0.51a 0.55a 0.64e 0.76c 0.53b 0.58c
ellagic acid B 14.79 ± nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd
1.97
myricetin B 6.04 ± nd nd nd nd nd nd nd nd nd nd 3.80 ± nd nd nd nd nd nd nd
1.24b 0.17a
baicalein B 6.43 ± nd nd 7.87 ± 12.20 ± nd 29.16 ± nd nd 136.79 nd nd nd 21.69 ± nd nd 9.46 ± 9.06 ± 3.96 ±
0.50b 0.60bc 0.66d 0.65f ± 2.44 g 0.66e 0.79c 0.68c 0.61a
apigenin B nd nd nd nd nd nd nd nd nd nd nd 22.18 ± nd nd nd nd nd nd nd
1.73
hesperidin B 213.39 ± nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd
4.49
9

naringenin B 144.72 ± nd nd nd 376.77 nd 608.32 nd 177.24 57.04 ± 840.37 nd nd 657.12 97.84 ± nd 135.97 ± 150.24 ± nd
2.68c ± 6.61e ± 4.63f ± 0.65a ± 11.55 ± 6.21 g 3.20b 9.87c 5.84c
6.74d h
isovitexin B 34.43 ± nd nd nd nd nd 8.04 ± nd nd nd nd nd nd nd 31.30 ± nd nd nd nd
1.40b 0.59a 4.05b
Flavonoids F 1 1 1 0 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0
number B 7 1 0 1 4 0 3 1 2 3 1 2 1 2 3 1 2 2 1
flavonoids content F 47.07 ± 2846.21 927.97 0 835.28 12.19 74.45 ± 751.11 4.15 ± 581.76 92.77 ± 1332.27 347.08 349.72 211.59 362.19 19.57 ± 350.39 ± 0
4.04b ± 8.74 k ± 4.36i ± 5.91 h ± 1.17a 3.49c ± 5.88 g 0.57a ± 10.40f 5.33c ± 5.78j ± 8.15e ± 5.78e ± ± 6.40e 2.02a 5.49e
15.13d
B 436.79 ± 1.76 ± 0 7.87 ± 458.41 0 645.52 2.65 ± 180.27 216.07 840.37 25.98 ± 10.48 ± 678.81 135.98 9.03 ± 145.43 ± 159.3 ± 3.96 ±
5.36 g 0.60a 0.60ab ± 5.36 h ± 5.17i 0.51a ± ± 7.40f ± 11.55 5.23b 0.76ab ± 6.82j ± 7.44c 0.58ab 10.65 cd 6.17d 0.61a
7.07e k
trans-resveratrol B nd nd nd nd nd nd 112.64 nd nd nd nd 6.49 ± nd nd 296.38 nd nd nd nd
± 6.91b 0.59a ± 4.63c
Phenolics number F 5 6 5 4 6 5 5 5 5 6 5 5 5 6 6 5 5 5 3
B 18 10 8 7 11 10 15 10 10 12 8 13 9 9 10 10 11 13 8
T 23 16 13 11 17 15 20 15 15 18 13 18 14 15 16 15 16 18 11
phenolic content F 605.48 ± 5463.67 1701.64 207.57 2017.85 413.95 649.12 1401.63 239.39 1868.07 467.19 3471.79 1409.15 1134.27 2201.02 985.93 430.57 ± 1242.73 201.88

Food Chemistry 388 (2022) 133058

8.64d ± 25.14o ± 12.97j ± 7.91a ± 11.10 ± ± ± 9.95i ± ± 15.91 ± 9.04c ± ± 21.11i ± 14.21 ± 6.70 ± 25.67f 11.05bc ± 11.79 h ± 9.27a
(28.7*) (99.3) (98.5) (70.4) l (71.2) 10.93b 11.07e (75.7) 3.38a k (48.0) (12.8) 18.25n (95.3) g (31.0) m (81.4) (39.5) (50.0) (36.6) (77.4)
(82.0) (23.9) (29.4) (73.6)
B 1501.54 38.53 26.35 ± 86.95 815.69 90.59 2064.33 449.52 573.98 2021.00 3187.60 1247.28 69.11 ± 2528.83 504.01 1511.67 430.58 ± 2155.026 58.91 ±
± 12.28i ±3.84ab 3.67a ± 5.44c ± 10.88 ± 6.89c ± 18.49 ± 8.87d ± ± 21.62j ± ± 12.44 8.75bc ± 12.95 ± ± 12.04i 15.99d ± 15.15 l 7.20abc
(71.3) (0.7) (1.5) (29.6) g (28.8) (18.0) k (76.1) (24.3) 14.35f (51.9) 18.89n h (26.4) (4.7) m (69.0) 16.73e (60.5) (50.0) (63.4) (22.6)
(70.5) (87.2) (18.6)
T 2107.02 5502.21 1727.99 294.52 2835.54 504.54 2713.45 1851.15 813.37 3889.05 3654.79 4719.07 1478.25 3663.09 2705.04 2497.60 861.15 ± 3397.76 260.79
± 19.55 g ± 28.20o ± ± 4.53a ± 20.96j ± ± 23.18i ± 15.96f ± ± 33.82 ± 24.11 l ± ± ± 20.81 ± 10.12i ± 24.05 25.98c ± 24.27 k ± 2.87a
15.54e 12.57b 16.25c m 29.32n 12.44d l h

Values are means ± standard error of three determinations. Values with no common letters in each column are significantly different (p < 0.05). nd, not detected. * Values in parentheses indicate percentage contribution
to the total. In forms, F,B, and T represented free, bound and total forms.
H. Suo et al. Food Chemistry 388 (2022) 133058

and total TPC, TFC, FRAP reveal the possible contribution of the indi­ Table 4
vidual phenolic compounds to these parameters. Among the free frac­ Antioxidant activity of free and bound extracts of potatos and the percentage
tion in all the potato genotypes, the content of none of the free phenolic contribution of each fraction to total.
compounds was positively correlated with free and total TPC and TFC Genotypes FRAP (mM Fe(II)E/g DW)
and FRAP value, whereas free p-coumaric acid content was positively Free Bound Total
correlated with total TPC, TFC, and FRAP value for the colored and
Heijingang 4.01 ± 0.10hi (68.5) 1.84 ± 0.05de (31.5) 5.85 ± 0.51 g
yellow flesh potatoes. Free p-coumaric acid content was reported to be
S17-1–1 3.76 ± 0.04gh (75.2) 1.24 ± 0.33bcd 5.00 ± 0.35ef
positively correlated with free TPC and antioxidant activity among 14 (24.8)
potato genotypes, including colored, white, and yellow flesh potatoes S17-188–4 4.23 ± 0.04i (88.1) 0.57 ± 0.19ab (11.9) 4.80 ± 0.07e
(Ru et al., 2019). Y16-11 4.59 ± 0.07j (80.8) 1.09 ± 0.15abc(19.2) 5.68 ± 0.89 fg
Among all the potato genotypes, the content of cryptochlorogenic 15A032-49 4.22 ± 0.14i (88.7) 0.54 ± 0.18ab (11.3) 4.76 ± 0.32e
Y16-14 2.75 ± 0.27de (77.9) 0.78 ± 0.25ab (22.1) 3.53 ±
acid, vanillin, benzoic acid, baicalein, and naringenin had positive 0.56abcd
correlation with bound TPC, the content of cryptochlorogenic acid, p- All-red 2.36 ± 0.01bc (83.1) 0.48 ± 0.11a (16.9) 2.84 ± 0.11a
coumaric acid, gentisic acid, hesperidin, ellagic acid, and isovitexin had Mean 3.70 ± 0.31* 0.94 ± 0.19 4.64 ± 0.41
positive correlation with total TPC, the content of gallic acid, 4-hydrox­ 15A029-2 2.03 ± 0.09a (53.0) 1.8 ± 0.51de(47.0) 3.83 ± 0.39 cd
S17-119–1 2.72 ± 0.06de (87.5) 0.39 ± 0.14a (12.5) 3.11 ± 0.11abc
ybenzoic acid, naringenin, and trans-resveratrol were positively corre­
S17-119–2 3.62 ± 0.12 g (74.8) 1.22 ± 0.14bcd 4.84 ± 0.14e
lated with bound TFC, and that of p-coumaric acid, hesperidin, and (25.2)
ellagic acid had positive correlation with the total FRAP value. In the Longshu 7 2.53 ± 0.03cde 0.67 ± 0.09ab (20.9) 3.20 ± 0.08abc
colored flesh potatoes, the content of cryptochlorogenic acid, p-cou­ (79.1)
maric acid, caftaric acid, gentisic acid, vanillin, hesperidin, ellagic acid, Yueyin 85–38 2.67 ± 0.07de (64.1) 1.50 ± 0.24 cd (35.9) 4.18 ± 0.21de
BY-3 2.78 ± 0.10e (77.7) 0.80 ± 0.13ab (22.3) 3.59 ±
quercetin, myricetin, and isovitexin was positively correlated with total 0.22abcd
TPC, the content of sinapic acid, ferulic acid, gallic acid, 4-hydroxyben­ Xisen 6 2.04 ± 0.04a (46.9) 2.31 ± 0.34e (53.1) 4.35 ± 0.37de
zoic acid, benzoic acid, vanillic acid, baicalein, naringenin, and trans- Yunshu 304 2.47 ± 0.10 cd (58.6) 1.75 ± 0.16cde 4.23 ± 0.24de
resveratrol was positively correlated with bound TFC, the content of (41.4)
Fuxi 2.11 ± 0.01ab (72.8) 0.79 ± 0.22ab (27.2) 2.90 ± 0.23ab
caftaric acid was positively correlated with total TFC, the content of
Zhongshu 5 3.19 ± 0.05f (52.5) 0.54 ± 0.24ab (47.5) 3.73 ± 0.13bcd
gentisic acid, hesperidin, ellagic acid, quercetin, myricetin was posi­ Yanshu 9 3.87 ± 0.07gh (89.8) 0.44 ± 0.12a (10.2) 4.31 ± 0.19de
tively correlated with the bound FRAP value, and that of ferulic acid was Qingshu 9 3.30 ± 0.06f (89.6) 0.38 ± 0.06a (10.4) 3.67 ±
positively correlated with the total FRAP value. Bound caffeic and p- 0.05abcd
coumaric acids had positive correlation with bound TPC and antioxidant Mean 2.78 ± 0.18 1.25 ± 0.24 4.03 ± 0.25

activity among four red and purple fleshed potatoes (Ru et al., 2019). In
the yellow flesh potatoes, the content of cryptochlorogenic, sinapic, and
benzoic acids, and vanillin was only positively correlated with bound
TPC, the content of gallic acid and baicalein was positively correlated
with both bound TPC and the total FRAP value, the caftaric acid content
was positively correlated with total TPC, and the content of isovitexin
and trans-resveratrol was positively correlated with bound TFC.
3.6. PCA and cluster analysis
PCA was used to investigate the variations in phenolic profiles
among different potato genotypes and to identify a potential phenolic
profile fingerprint for the genotypes. Principal components 1 and 2 (PC1
and PC2, respectively) explained 16.4% and 21.5% of the total variance
in the data presented in Table 3, respectively (Supplementary Fig. 1).
Potato genotypes in the same taxon generally had similar phenolic
composition and content, probably reflecting similarities in the phenolic
profiles. The potato genotypes (15A029-2, 15A032-49, Xisen 6, S17-1–1,
and BY-3) in the upper left of the PCA had similar composition and
content of phenolics, especially of free neochlorogenic, chlorogenic,
caffeic, cryptochlorogenic, and p-coumaric acids and rutin (a, b, c, d, e,
and j) and of bound chlorogenic acid, daidzein, catechin, and proto­
catechuic acid (A, O, N, and H). In contrast, potato genotypes (Hei­
jingang and All-red) in the lower right part had similar bound caftaric
acid, gentisic acid, hesperidin, ellagic acid, isovitexin, and trans-
resveratrol content (D, I, P, Q, V, and X). Moreover, cluster analysis
was used to find similarities in free, bound, and total TPC, TFC, FRAP,
bound/total ratio for TPC and TFC, and phenolic profiles in the 19 po­
tato genotypes. On the cluster analysis map, the 19 potato genotypes
were mainly divided into six groups (marked by different colored lines in
Supplementary Fig. 2). Phenolic profiles depend on phenolic metabo­
lites pathways (Acosta-Estrada et al., 2014). Thus, potato genotypes in
the same groups may have similar phenolic metabolites pathways,
whereas there are significant differences in phenolic metabolites path­
ways among these 6 groups.
Values are means ± standard error of three determinations. aValues with no
common letters in each column are significantly different (p < 0.05). * Values in
parentheses indicate percentage contribution to the total.
4. Conclusion
Significant differences in TPC, TFC, and antioxidant activity in the
free and bound fractions of the 19 potato genotypes with different flesh
colors were found. The free TPC and TFC were significantly higher than
the bound TPC and TFC in all genotypes. The mean of free and total TPC
and TFC from colored flesh genotypes was higher than those from yellow
fleshed genotypes. The free and total TPC were strongly positively
correlated with antioxidant activity of the free and total fractions. 11 to
23 phenolic compounds were found in the potato genotypes. Rutin,
chlorogenic acid and cryptochlorogenic acid in free form, and benzoic
and caftaric acids in bound form were identified as the dominant
phenolic compounds. The genotype Heijingang has the highest free and
total TPC and antioxidant activity, and largest number of phenolic
compounds, indicating that it is an ideal potato genotype for human
consumption. Cluster analysis divided 19 potato genotypes into six
groups. These results provide useful information for potato processing.
Funding
This work was supported by the Key-Area Research and Develop­
ment Program of Guangdong Province (2020B020219002) and the
National Natural Science Foundation of China (31960483).
CRediT authorship contribution statement
Haicui Suo: Investigation, Conceptualization, Data curation,
Writing – original draft. Ziting Peng: Software, Formal analysis. Zhi­
qiang Guo: Data curation, Writing – review & editing, Formal analysis.
Chengjunhong Wu: Methodology, Writing – original draft. Jitao Liu:
Methodology, Validation. Li Wang: Validation. Juan Xiao: Supervision,
Writing – review & editing, Funding acquisition. Xiaobo Li: Funding

10
H. Suo et al. Food Chemistry 388 (2022) 133058

Table 5
Pearson correlation coefficients among the free, bound and total TPC, TFC and antioxidant activity.
TPC TFC FRAP

Free Bound Total Free Bound Total Free Bound Total

TPC Free 1
Bound 0.239 1
Total 0.993** 0.349** 1
TFC Free 0.580** 0.066 0.568** 1
Bound − 0.099 0.783** 0.002 − 0.169 1
Total 0.567** 0.233 0.575** 0.978** 0.04 1
FRAP Free 0.391** 0.112 0.391** 0.292* 0.038 0.304* 1
Bound − 0.012 − 0.02 − 0.014 − 0.256 − 0.149 − 0.291* − 0.176 1
Total 0.307* 0.073 0.305* 0.043 − 0.081 0.27 0.674** 0.608** 1
**
*and indicate significance at p < 0.05 and p < 0.01, respectively.

acquisition, Project administration, Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.foodchem.2022.133058.
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