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Article

LC-MS/MS Screening of Phenolic Compounds in Wild and Cultivated Grapes Vitis amurensis Rupr.

by
Mayya Razgonova
1,2,*,
Alexander Zakharenko
1,3,
Konstantin Pikula
1,
Yury Manakov
3,
Sezai Ercisli
4,
Irina Derbush
1,
Evgeniy Kislin
1,
Ivan Seryodkin
5,
Andrey Sabitov
1,
Tatiana Kalenik
2 and
Kirill Golokhvast
1,2,3,5
1
N.I. Vavilov All-Russian Institute of Plant Genetic Resources, B. Morskaya 42-44, 190000 Saint-Petersburg, Russia
2
Far Eastern Federal University, 10 Ajax Bay, Russky Island, 690922 Vladivostok, Russia
3
Siberian Federal Scientific Centre of Agrobiotechnology, Centralnaya, Presidium, 633501 Krasnoobsk, Russia
4
Department of Horticulture, Agricultural Faculty, Ataturk University, 25240 Erzurum, Turkey
5
Pacific Geographical Institute, Far Eastern Branch of the Russian Academy of Sciences, Radio 7, 690041 Vladivostok, Russia
*
Author to whom correspondence should be addressed.
Molecules 2021, 26(12), 3650; https://doi.org/10.3390/molecules26123650
Submission received: 17 May 2021 / Revised: 10 June 2021 / Accepted: 14 June 2021 / Published: 15 June 2021
(This article belongs to the Special Issue Biochemical Role of Pigments in the Plant Life)
Browse Figure
Versions Notes

Abstract

:
This work represents a comparative metabolomic study of extracts of wild grapes obtained from six different places in the Primorsky and Khabarovsk territories (Far East Russia) and extracts of grapes obtained from the collection of N.I. Vavilov All-Russian Institute of Plant Genetic Resources (St. Petersburg). The metabolome analysis was performed by liquid chromatography in combination with ion trap mass spectrometry. The results showed the presence of 118 compounds in ethanolic extracts of V. amurensis grapes. In addition, several metabolites were newly annotated in V. amurensis. The highest diversity of phenolic compounds was identified in the samples of the V. amurensis grape collected in the vicinity of Vyazemsky (Khabarovsk Territory) and the floodplain of the Arsenyevka River (Primorsky Territory), compared to the other wild samples and cultural grapes obtained in the collection of N.I. Vavilov All-Russian Institute of Plant Genetic Resources.

1. Introduction

The appearance of the first representatives of the Vitaceae family (genus Vitis) dates from the Upper Cretaceous period [1]. Several types of fossil grapes of genus Vitis have been found in different parts of North America [2]. In the Eocene, representatives of the genus Vitis were widespread in Eurasia and the Far North [2]. In the Paleogene, one of the best-preserved species of fossil grapes Vitis sachalinensis Krysht. was found and described in the sediments of the Sakhalin Island, the Russian Far East. These data show that the evolution of the vine in the territory of Russia proceeded from ancient times. Moreover, now wild grapes of the genus Vitis grow in many Russian regions [3,4]. At the same time, there is very little information about the culture of East Asian grapes.
Grape berries contain 65–85% water; 10–33% sugar (glucose and fructose); flofaben; gallic acid; quercetin; oenin; the glycosides monodelphinidin and delphinidin; the acids malic, hydrosilicic, ortho-hydroxybenzoic, phosphoric, tartaric, citric, succinic, formic, pectin, and tannins; salts of potassium; magnesium; calcium; manganese; cobalt; iron vitamins B1, B2, B6, B12, A, C, P, and PP; folic acid; and enzymes. The dominant class of biologically active compounds of fruits and especially grape ridges are flavonoids, in particular complexes of oligomeric proanthocyanidins (condensed tannins), which are polymeric forms of flavonoids from the group of catechins, and their monomeric units, namely catechins and leuсoanthocyanidins [5].
Many studies have been devoted to the biological activity of flavonoids and complexes of oligomeric proanthocyanidins [6,7]. Complexes of oligomeric proanthocyanidins act as traps of free radicals and block the process of lipid peroxidation of biological membranes [8,9]. Their antioxidant activity is many times higher than that of vitamins E and C. They can inhibit the activity of many enzymes (hydrolase, oxidoreductase, kinase, transferase, among others) [10]. Due to the wide spectrum of action, the active compounds of the grapes V. amurensis have a pronounced positive effect on various organs and systems of the body, such as antihypertensive and vasostrengthening effects, as well as antidiabetic, anti-inflammatory, antiallergy, anticarcinogenic, antistress, radioprotective, and antirheumatic effects. Moreover, flavonoids have an anti-Alzheimer’s activity [11,12,13].
This work presents a detailed comparative study of the metabolomic composition of wild V. amurensis grape berry extracts taken from six different locations of the Russian Far East and four cultural specimens of V. amurensis obtained from the collection of N.I. Vavilov All-Russian Institute of Plant Genetic Resources (St. Petersburg). High-performance liquid chromatography (HPLC) in combination with tandem mass spectrometry was used to identify target analytes in the extracts. Previously, the authors carried out metabolomic studies of Far Eastern plant species, such as Schizandra chinensis, Rhodiola rosea, Rhododendron adamsii, and Panax ginseng [14,15].

2. Results

The metabolome of ten samples of wild and cultural V. amurensis was analyzed and compared. A combination of both ionization modes (positive and negative) in MS full scan mode was applied for the molecular mass determination of the compounds in ethanolic extracts of V. amurensis. Compound identification was performed by comparing the observed m/z values and the fragmentation patterns with the literature. The list of compounds identified in the ethanolic extract of V. amurensis are represented in Table A1. The 118 compounds shown in Table A1 belong to different phenolic families, namely anthocyanidins, flavones, flavonols, flavan-3-ols, flavanones, hydroxycinnamic acids, hydroxybenzoic acids, stilbenes, and tannins.

2.1. Anthocyanidins and Anthocyanins

A total of 18 anthocyanin compounds have been identified in the analyzed samples of V. amurensis (Table 1). The anthocyanins pelargonidin-3-O-glucoside, cyanidin-3-O-glucoside, and petunidin-3-(6-O-coumaroyl) glucoside have already been characterized as a component of Far East V. amurensis [16]. The anthocyanins malvidin-3-O-acetylhexoside, delphinid-3,5-O-diglucoside, malvidin-3-O-rutinoside, malvidin 3-acetyl-5-glucoside, petunidin 3-coumaroylglucoside-5-O-glucoside, and malvidin 3-coumaroylglucoside-5-O-glucoside were only found in the extracts of cultivated V. amurensis (St. Petersburg).

2.2. Other Flavonoid Compounds

A total of 42 flavonoid compounds were identified in analyzed V. amurensis samples (Table 2). The flavonols dihydrokaempferol, kaempferide, mearnsetin, kaempferol-3-O-glucoside, dihydrokaempferol glucoside, isorhamnetin 3-O-rhamnoside, hyperoside, taxifolin-3-O-glucoside, kaempferol 3,7-di-O-glucoside, and quercetin-O-dihexoside have been already characterized as components of Far East V. amurensis.

2.3. Phenolic Acids and Other Compounds

In addition, 22 phenolic acids and 37 other compounds were identified in analyzed V. amurensis samples (Table 3). It should be noted that the coumarins umbelliferone and fraxin; the sterol fucosterol; and the flavanols taxifolin-3-O-glucoside, kaempferol-3,7-di-O-glucoside; hydroxycinnamic acids 3-p-coumaroyl-4-caffeoylquinic acid, and 5-O-(4’-O-p-coumaroyl glucosyl) quinic acid were identified by mass spectrometry only in samples of wild V. amurensis grapes collected from the Pakhtusov Islands and Rikord Island, Peter the Great Bay, Sea of Japan.

3. Discussion

In general, the diversity of phytochemicals identified in wild and cultural grape V. amurensis resulted in the following descending order (number of metabolites in parenthesis): VZK (52) > ART (46) > SPB-2 (39) > SPB-1 (28) > SPB-4 (27) > PAK (25) > RIK (22) > KAL (20) > SPB-3 (19) > ARS (18). The most diverse metabolome was identified in the grapes collected in the vicinity of Vyazemsky, Khabarovsk Territory, which was rich in flavanols and phenolic acids.
The anthocyanins identified in V. amurensis in this study were previously identified and annotated in the vines [17] Solanium nigrum [18], Gaultheria Antarctica [19], and Vitis vinifera [20] and wheat [21]. Our identification of flavonoid compounds agrees with bibliographic data for Echinops [22], Rhodiola rosea [23], Ocimum [24], Alpinia officinarum [25], Brazilian propolis [26], Vitis vinifera [20], Rubus occidentalis [27], C. edulis [28], and Vaccinium macrocarpon [29].
Although wild grapes tend to be more diverse than cultivated varieties [30], this number of anthocyanins in one form is quite rare and more likely to occur in other berries, such as blueberries [31]. We hypothesize that many different anthocyanins are associated with rather low temperatures in summer and monsoon climates. To respond to adverse conditions, various anthocyanins are produced [32]. In addition, V. amurensis have an increased acidity of the fruit, which is also associated with unfavorable growing conditions [33]. As it is known, anthocyanins and many other phenolic compounds participating in the protective processes of plants are more stable in an acidic environment [34].

4. Materials and Methods

4.1. V. amurensis Samples

Ten samples of wild and cultivated grape V. amurensis were selected for the performance of metabolomic study. Six samples of wild V. amurensis were collected from different places in the Primorsky and Khabarovsk territories, Far Eastern Russia (Table 4, Figure 1). Four samples of cultivated V. amurensis, namely SPB-1, SPB-2, SPB-3, and SPB-4, were obtained from the collection of N.I. Vavilov All-Russian Institute of Plant Genetic Resources, St. Petersburg. The grapes were harvested at the end of August and September 2020. Each sample included 100 g of grape berries.

4.2. Chemicals and Reagents

HPLC-grade acetonitrile was purchased from Fisher Scientific (Southborough, UK), and MS-grade formic acid was purchased from Sigma-Aldrich (Steinheim, Germany). Ultra-pure water was obtained with Siemens Ultra-Clear TWF EDI UV UF TM Water Purification System (Siemens, Munich, Germany). All the other chemicals were of analytical grade.

4.3. Fractional Maceration

Fractional maceration with ethyl alcohol was applied to obtain highly concentrated extracts of V. amurensis. Each sample of V. amurensis was divided into three parts and consistently infused. The infusion time of each part of the extractant was seven days.

4.4. Liquid Chromatography

The separation of multicomponent mixtures was performed by a Shimadzu LC-20 Prominence HPLC (Shimadzu, Kyoto, Japan) equipped with a UV detector and a Shodex ODP-40 4E reverse-phase column (4.6 × 250 mm, particle size 4 µm). The gradient elution program with two mobile phases (A, deionized water; B, acetonitrile with formic acid 0.1% v/v) was as follows: 0.01–2 min, 100% B; 2–50 min, 100–0% B; control washing 50–60 min, 0% B. The entire HPLC analysis was done with an SPD-20A detector at wavelengths of 230 and 330 nm; the temperature corresponded to 40 °C. The injection volume was 10 µL.

4.5. Mass Spectrometry

MS analysis was performed on an ion trap amaZon SL (Bruker Daltonics, Bremen, Germany). Four-stage ion separation (MS/MS mode) was implemented. All the chemical profiles of the samples were obtained by the HPLC–ESI–MS/MS method. The working parameters were as follows: ionization source temperature 50 °C, gas flow 4 L/min, nebulizer gas (atomizer) 7.3 psi, capillary voltage 4500 V, endplate bend voltage 1500 V, fragmentary voltage 280 V, and collision energy 60 eV. The ion trap was used in the scan range of 100–1.700 m/z for MS and MS/MS. The capture rate was one spectrum/s for MS and two spectrum/s for MS/MS. The mass spectra were recorded in negative and positive ion mode. Data collection was controlled by Hystar DataAnalisys 4.1 software (Bruker Daltonics, Bremen, Germany). All the measurements were performed in triplicate.

Author Contributions

Conceptualization, M.R. and A.Z.; methodology, M.R. and I.D. resources, S.E., E.K., I.S., and A.S.; investigation, M.R.; data curation, K.P.; writing—original draft preparation, M.R.; writing—review and editing, A.Z. and K.P.; supervision, K.G. and T.K.; project administration, Y.M.; funding acquisition, K.G. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Conflicts of Interest

The authors declare no conflict of interest.

Appendix A

Table
Table A1. The list of compounds identified in ethanolic extracts of V. amurensis.
Table A1. The list of compounds identified in ethanolic extracts of V. amurensis.
No.Identified CompoundMolecular FormulaCalculated MassPrecursor Ion, m/zFragment Ions, m/zReferences
[M–H]–[M+H]+
Anthocyanins
1. Cyanidin 3,5-O-diglucosideC27H31O16611.5335 611287; 449; 269; 231; 199; 161; 231; 213; 189; 175; 147[35,36]
2. Cyanidin-3-O-glucosideC21H21O11449.3848 449287; 206; 143[19,20,35,37,38]
3. Delphinidin 3-O-glucosideC21H21O12+465.3905 465303; 257; 229; 201; 165; 239; 213; 173; 145; 117[19,20,21,39]
4. Delphinidin-3,5-O-diglucosideC27H30O17626.5169 627465; 303; 257; 153; 229; 155[18,40]
5. Malvidin 3,5-O-diglucosideC32H31O15655.5795 655493; 331; 315; 179; 313[17,20,21]
6. Malvidin 3-(6-O-acetyl) glucosideC25H27O13535.478 537331; 299; 261; 243; 211; 154; 111[20,39]
7. Malvidin 3-(6-O-coumaroyl) glucosideC32H31O14639.5801 639331; 315; 299; 270; 242; 179; 150; 287; 213[20,39,40]
8. Malvidin 3-coumaroylglucoside-5-O-glucosideC35H45O21801.7192 801639; 493; 331; 315; 287; 270; 242; 300[39]
9. Malvidin 3-O-acetyl hexosideC25H27O14535.479 537331; 305; 261; 207; 185; 255; 229; 211[17]
10. Malvidin 3-O-glucosideC23H25O12493.4374 493331; 315; 179[20,39,40]
11. Pelargonidin-3-O-glucoside (callistephin)C21H21O10433.3854 433414; 271; 172; 226; 116[35,39,41]
12. Peonidin-3,5-О-diglucoside [Peonin; Peonidin 3-glucoside-5-glucoside]C28H33O16625.5520 625301; 463; 286; 258[21,39,40]
13. Peonidin-3-O-glucosideC22H23O11 +463.4114 463301; 286; 268; 258; 230; 202; 174; 121[20,39,41]
14. Petunidin 3-(6-O-coumaroyl) glucosideC31H29O14625.553 625317; 302; 274; 218[20,39,40]
15. Petunidin 3-coumaroylglucoside-5-O-glucosideC34H43O21787.6926 787625; 479; 317; 301; 246; 302; 274; 228[39,40]
16. Petunidin 3-galactosideC22H23O12+479.4108 479317; 302; 273[19,20,21,39]
17. Petunidin 3,5-diglucosideC28H33O17641.5514 641317; 479; 420; 257; 302; 274; 228[39,40]
Flavonols
18. DihydrokaempferolC15H12O6288.2522 289271; 199; 127; 243; 189; 118[22,42]
19. Dihydrokaempferol glucosideC21H22O11450.3928449 287; 227; 269; 225; 149[27]
20. Dihydroquercetin (taxifolin; taxifoliol)C15H12O7304.2516 305259; 149; 199; 241; 159; 171[20,43,44]
21. Herbacetin [3,5,7,8-tetrahydroxy-2-(4-hydro- xyphenyl)-4H-chromen-4-one]C15H10O7302.2357301 179; 273; 121; 151[24,45]
22. Hyperoside (quercetin 3-O-galactoside; hyperin)C21H20O12464.3763463 301; 179; 257; 255; 147[43,46,47,48]
23. Isorhamnetin [isorhamnetol; quercetin 3’-methyl ether; 3-methylquercetin]C16H12O7316.2623 317299; 270; 230; 207;177; 165;147; 123; 147; 123; 119[49,50]
24. Isorhamnetin 3-O-glucosideC22H22O12478.4029 479317; 301; 257; 274; 228; 150[20,47,51]
25. Isorhamnetin 3-O-rhamonosideC22H22O11462.4035461 315; 152; 219[28,49]
26. KaempferideC16H12O6300.2629 301283; 265; 239; 211; 185; 133; 151[20,24,26]
27. KaempferolC15H10O6286.2363 287269; 227; 153[20,24,50]
28. Kaempferol diglycosideC27H30O16610.5175 611449; 287; 229; 165; 213; 111[52,53]
29. Kaempferol glycosideC21H20O11448.3769 449287; 269; 217[20,47]
30. MearnsetinC16H12O8332.2617 333318; 301; 273; 245; 193; 165; 139; 289; 271; 219; 153; 136[49]
31. MyricetinC15H10O8318.2351317 273; 191; 255; 229; 205; 187; 163; 125; 227[20,28,54]
32. Myricetin-3-O-galactosideC21H20O13480.3757479 299; 153; 271; 243; 171[47,48,55]
33. QuercetinC15H10O7302.2357 303285; 163; 267; 159; 239[20,24,37,43]
34. Quercetin 3-O-glucoside [Isoquercitrin; Hirsutrin]C21H20O12464.3763 465303; 285; 257; 229; 201; 150; 155[20,27,47,56]
35. Quercetin-3-O-glucuronideC21H18O13478.3598477 301; 179; 273; 151[39,47,57]
36. Quercetin-O-dihexosideC27H30O17626.5179 627303; 257; 150; 229[51,58]
37. Rutin (quercetin 3-O-rutinoside)C27H30O16610.5175 611303; 229; 257[27,35,37,56]
38. Taxifolin-3-O-glucosideC21H22O12466.3922 467449; 303; 188; 287; 132; 260[20]
Flavones
39. Apigenin [5,7-dixydroxy-2-(40hydroxyphenyl)-4H-chromen-4-one]C15H10O5270.2369 271253; 181; 137[56,59,60]
40. LuteolinC15H10O6286.2363 287271; 225; 175; 158[43,56,59,60]
41. Diosmetin [luteolin 4’-methyl ether; salinigricoflavonol]C16H12O6300.2629 301286; 258; 229; 184; 153; 124[61,62,63]
42. Cirsimaritin [scrophulein; 4’,5-dihydroxy-6,7-dimethoxyflavone; 7-methylcapillarisin]C17H14O6314.2895313 298; 247; 151; 270[24]
43. NevadensinC18H16O7344.3154343 328; 259; 313; 269[24,63]
44. SyringetinC17H14O8346.2883345 330; 315; 246; 151; 287; 271; 203; 183; 163[28]
45. Pentahydroxy trimethoxy flavoneC18H16O10392.3136 393378; 347; 317; 284; 246; 206; 349; 321; 284; 193; 322; 304;282; 196; 154[28]
46. Apigenin diglycosideC21H20O10432.3775 433414; 287; 186; 241; 158[20,56,64,65]
47. Vitexin [apigenin 8-C-glucoside]C21H20O10432.3775431 249; 221; 192[57,66,67]
48. Luteolin diglycosideC21H20O11448.3769 449287; 213; 137; 185[20,55,56,66,68]
49. Isovitexin 6”-O-deoxyhexoside [apigenin 6-C-glucoside 6”-O-deoxyhexoside]C27H30O14578.5187 579415; 297; 177; 397; 344; 362[66]
50. Vitexin glucosideC27H30O15594.5181 595415; 353; 283; 265; 176[66]
51. Apigenin glucosideC29H32O15620.5554 621561; 547; 461; 533; 461; 433[66]
Flavan-3-ols
52. Catechin [D-catechol]C15H14O6290.2681289 245; 205; 203; 188[43,49,55,57]
53. EpicatechinC15H14O6290.2681 291272; 175; 130; 157; 140[20,49,55]
54. Gallocatechin [+(-)gallocatechin]C15H14O7306.2675305 179; 125[20,28,43,44]
55. Catechin gallateC22H18O10442.3723441 289; 169; 245; 205; 203[20,56]
Flavanones
56. Naringenin [Naringetol; Naringenine]C15H12O5272.5228 273227; 155; 209; 139[20,43,49]
57. Hesperitin [Hesperetin]C16H14O6302.2788301 257; 151; 228; 189[20,43,68]
58. Eriodictyol-7-O-glucoside [Pyracanthoside; miscanthoside]C21H22O11450.3928449 269; 207; 251; 165[48,65,68]
59. Hexahydroxyflavanone hexosideC21H22O13482.3916 483437; 359; 263; 231; 298; 255; 225; 155[28]
Hydroxybenzoic acids
60. 4-hydroxybenzoic acidC7H6O3138.1207 139121[20,69,70]
61. Protocatechuic acidC7H6O4154.1201 155127[20,28,55]
62. Gallic acidC7H6O5170.1195 171126[20,54,55]
63. Syringic acid [benzoic acid; cedar acid]C9H10O5198.1727 199154; 140; 111; 140; 123; 125[20,55,71]
64. Ellagic acid [benzoaric acid; elagostasine]C14H6O8302.1926 303172; 158; 144; 127; 116[27,41,44]
65. Salvianolic acid FC17H14O6314.2895 315269; 243; 213;185; 144; 207; 181; 153; 179; 161; 133[69]
66. Dihydroxybenzoyl-hexosideC13H16O9316.2607315 153; 253; 151; 184[66]
67. Salvianolic acid GC18H12O7340.2837 341323; 295; 255; 195; 159; 305[63,72]
68. Salvianolic acid DC20H18O10418.3509417 373; 329; 287; 209[69,73]
Hydroxycinnamic acids
69. p-Coumaric acidC9H8O3164.16 165146; 119[20,46,55,73]
70. Sinapic acid [trans-sinapic acid]C11H12O5224.2100 225179; 153; 115; 133; 115[20,37,55,74]
71. Caffeoylmalic acidC13H12O8296.2296295 133; 179; 148; 119; 115[28]
72. Coutaric acid [trans-p-Coumaroyltartaric acid]C13H12O8296.2296295 163; 119[20]
73. Caftaric acid [cis-caftaric acid; 2-caffeoyl-L-tartaric acid; caffeoyl tartaric acid}C13H12O9312.23311 149; 221; 131[20,38,64,69]
74. Fertaric acid [fertarate]C14H14O9326.2556325 193; 149; 134[20]
75. p-Coumaric acid-O-hexoside [trans-p-coumaric acid 4-glucoside]C15H18O8326.2986325 193; 163; 119[28,57,75]
76. 1-caffeoyl-beta-D-glucose [caffeic acid-glucoside]C15H18O9342.298341 179; 161; 135[20,66]
77. 5-O-(4’-O-p-coumaroyl glucosyl) quinic acidC22H28O13500.4499 501339; 277; 203[56]
78. 3-p-coumaroyl-4-caffeoylquinic acidC25H24O11500.4515 501355; 483; 181; 225; 281; 193; 120; 133[76]
79. Coumaric acid derivativeC30H30O7502.5550 503457; 411; 382; 339; 293; 409; 391; 367; 323; 293; 233; 205[57]
80. Di-O-caffeoylquinic acidC25H24O12516.4509 517355; 339; 202[58,66,76]
81. Caffeic acid-O-(sinapoyl-O-hexoside)C26H30O14566.5080 567405; 520; 249; 234[57,77]
Other compounds
82. Malic acidC4H6O5134.0874133 115[57,69,78]
83. Tartaric acidC4H6O6150.0900149 131[78,79]
84. UmbelliferoneC9H6O3162.1421161 115[20,28,54]
85. Shikimic acidC7H10O5174.1513 175112[28,78]
86. Indole-3-carboxylic acidC10H9NO2175.1840 176130[75]
87. Esculetin [Cichorigenin; Aesculetin]C9H6O4178.1415 179133; 115[20]
88. Citric acidC6H8O7192.1235191 111; 173; 143; 127[57,59,79]
89. Quinic acidC7H12O6192.1666191 111; 173[20,28,57,59]
90. Dihydroferulic acidC10H12O4196.1999195 159; 129; 113; 122[28,80,81]
91. Ethyl gallateC9H10O5198.1727197 169; 125[45]
92. L-Tryptophan [tryptophan; (S)-tryptophan]C11H12N2O2204.2252 205188; 146; 170; 118[41,66]
93. Myristoleic acid [cis-9-tetradecanoic acid]C14H26O2226.3550 227209; 181; 155; 199; 181; 127[28]
94. Resveratrol [trans-resveratrol; stilbentriol]C14H12O3228.2433 229142; 184; 114[28,43]
95. Linolenic acid (alpha-linolenic acid; linolenate)C18H30O2278.4296 279260; 176; 120[62,74]
96. 9-oxo-10E,12Z-octadecanoic acid [9-oxo-ODE]C18H30O3294.4290 295249; 165; 220; 125[62,82]
97. Nonadecadienoic acidC19H34O2294.4721 295278; 250; 211; 172; 204; 181; 176[28]
98. Protocatechuic acid-O-hexosideC13H16O9316.2607315 153; 298; 151[57,69,75]
99. Bilobalide [(-)-Bilobalide]C15H18O8326.2986325 183; 261; 119; 183[46,50,75]
100. 3,7-dimethylquercetinC17H14O7330.2889 331314; 297; 255; 228; 203; 146; 267; 227; 203; 186; 164; 134[75]
101. Galloyl glucose [beta-glucogallin; 1-O-galloyl-beta-D-glucose]C13H16O10332.2601331 313; 195; 166[41]
102. Gallic acid hexosideC13H16O10332.2601331 271; 169; 125[83]
103. Erucic acid (cis-13-docosenoic acid)C22H42O2338.5677 339132; 293[65]
104. Esculin [aesculin; esculoside; polichrome]C15H16O9340.2821339 177; 293; 131[20,28,56]
105. Palmatine [berbericinine; Burasaine]C21H22NO4352.4037 353335; 235; 317; 235; 137[84]
106. Hexose-hexose-N-acetylC14H25NO10367.3490366 186; 142[85]
107. Fraxin (fraxetin-8-O-glucoside)C16H18O10370.3081 371208; 352; 135[20]
108. 1-O-sinapoyl-beta-D-glucoseC17H22O10386.3576 387205; 130[20]
109. Polydatin [piceid; trans-piceid]C20H22O8390.3839389 227; 343; 184; 143[27,43]
110. Fucosterol [fucostein; trans-24-ethylidenecholesterol]C29H48O412.6908 413395; 355; 271; 194; 119; 297; 199; 268; 187[28]
111. Stigmasterol [stigmasterin; beta-stigmasterol]C29H48O412.6908 413301; 259; 189; 171[28,86,87]
112. Phlorizin [phloridzin; phlorizoside; floridzin: phlorrhizin; phloretin 2’-glucoside; phloretin-O-hexoside]C21H24O10436.4093 437397; 217; 377[20,27,46,49,57]
113. Oleanoic acidC30H48O3456.7003 457439; 411; 365; 337; 293; 248; 205; 364; 309; 219; 319; 301; 279; 247; 232[24,76]
114. Ursolic acidC30H48O3456.7003 457411; 393; 365; 337; 279; 247; 292; 247; 219; 205[63,76,86]
115. Anmurcoic acidC30H46O5486.6922 487469; 427; 397; 367; 325; 307; 304; 261; 279[76]
116. Dimethylellagic acid hexoseC22H20O13492.3864 493331; 299; 270; 242; 179; 150; 225[41]
117. Procyanidin A-type dimerC30H24O12576.501 577425; 397; 373; 287; 245; 181; 245; 218; 189; 123[20,55,57]
118. Cyclopassifloic acid glucosideC37H62O12698.8810 699537; 347; 271; 259; 185[66]

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Molecules 26 03650 g001 550
Figure 1. Region of wild V. amurensis grape collection.
Figure 1. Region of wild V. amurensis grape collection.
Molecules 26 03650 g001
Table
Table 1. Anthocyanins identified in the ethanolic extracts of V. amurensis.
Table 1. Anthocyanins identified in the ethanolic extracts of V. amurensis.
No.Identified CompoundARSARTKALPAKRIKVZKSPB-1SPB-2SPB-3SPB-4
1. Cyanidin 3,5-O-diglucoside + ++++
2. Cyanidin-3-O-glucoside [Cyanidin 3-O-beta-D-glucoside] +
3. Delphinidin 3-O-glucoside + +
4. Delphinidin-3,5-O-diglucoside +
5. Malvidin 3-(6-O-acetyl) glucoside++ +
6. Malvidin 3-(6-O-coumaroyl) glucoside + +
7. Malvidin 3-(6’-p-caffeoylglucoside)+++ + ++
8. Malvidin 3,5-diglucoside + +++++++
9. Malvidin 3-coumaroylglucoside-5-O-glucoside +
10. Malvidin 3-O-acetyl hexoside +
11. Malvidin 3-O-glucoside ++ ++++++
12. Pelargonidin-3-O-glucoside (callistephin) +
13. Peonidin-3,5-О-diglucoside [peonin; peonidin 3-glucoside-5-glucoside] + +++++
14. Peonidin-3-O-glucoside +++
15. Petunidin 3-(6-O-coumaroyl) glucoside +
16. Petunidin 3-coumaroylglucoside-5-O-glucoside +
17. Petunidin 3-O-glucoside-5-O-glucoside [Petunidin 3,5-di-O-beta-D-glucoside] ++ + ++
18. Petunidin-3-O-glucoside +
Total number21051387866
ARS, wild V. amurensis sample obtained from floodplain of the Arsenyevka River (Primorsky Territory); ART, wild V. amurensis sample obtained from the vicinity of Artem (Primorsky Territory); KAL, wild V. amurensis sample obtained from the vicinity of Kalinovka (Primorsky Territory); PAK, wild V. amurensis sample obtained from the Pakhtusov Islands (Sea of Japan); RIK, wild V. amurensis sample obtained from Rikord Island (Sea of Japan); VZK, wild V. amurensis sample obtained from the vicinity of Vyazemsky (Khabarovsk Territory); SPB-1, SPB-2, SPB-3, and SPB-4, samples of cultivated V. amurensis provided by N.I. Vavilov All-Russian Institute of Plant Genetic Resources (St. Petersburg).
Table
Table 2. Other flavonoid compounds identified in the ethanolic extracts of V. amurensis.
Table 2. Other flavonoid compounds identified in the ethanolic extracts of V. amurensis.
No.Identified CompoundARSARTKALPAKRIKVZKSPB-1SPB-2SPB-3SPB-4
Flavonols
1. Quercetin-3-O-glucuronide++++++ +++
2. Kaempferol+++ ++ +
3. Quercetin + +++ +
4. Isorhamnetin [Isorhamnetol; Quercetin 3’-Methyl ether] + ++ +
5. Isorhamnetin 3-O-glucoside ++++
6. Myricetin-3-O-galactoside + + ++
7. Quercetin 3-O-glucoside [Isoquercitrin; Hirsutrin] + + + +
8. Myricetin ++ +
9. Dihydrokaempferol + +
10. Dihydroquercetin (Taxifolin; Taxifoliol) + +
11. Hyperoside (Quercetin 3-O-galactoside; Hyperin)+ +
12. Kaempferol diglycoside ++
13. Kaempferol glycoside+ +
14. Dihydrokaempferol glucoside+
15. Herbacetin +
16. Isorhamnetin 3-O-rhamonoside +
17. Kaempferide +
18. Mearnsetin +
19. Quercetin-O-dihexoside +
20. Rutin (Quercetin 3-O-rutinoside) +
21. Taxifolin-3-O-glucoside +
Total number:3921483624
Flavones
22. Apigenin++++ + +
23. Syringetin + +++
24. Luteolin diglycoside +++
25. Nevadensin + +
26. Vitexin 2”-O-glucoside [Apigenin 8-C-glucoside 2”-O-glucoside] + +
27. Luteolin +
28. Diosmetin [Luteolin 4’-Methyl Ether; Salinigricoflavonol] +
29. Pentahydroxy trimethoxy flavone +
30. Apigenin diglycoside +
31. Vitexin [ Apigenin 8-C-Glucoside] +
32. Vitexin glucoside+
33. Apigenin glucoside +
Total number:2322132423
Dimethoxyflavone
34. Cirsimaritin [Scrophulein; 4’,5-dihydroxy-6,7-dimethoxyflavone; 7-methylcapillarisin] +
Flavan-3-ols
35. Catechin [D-Catechol] + +++++++
36. Epicatechin + +
37. Gallocatechin [+(-)Gallocatechin] +
38. Catechin gallate +
Total number:0202121211
Flavanones
39. Naringenin [Naringetol; Naringenine] +++
40. Eriodictyol-7-O-glucoside [Pyracanthoside; Miscanthoside] + +
41. Hesperitin [Hesperetin] +
42. Hexahydroxyflavanone hexoside +
Total number:0102120001
ARS, wild V. amurensis sample obtained from floodplain of the Arsenyevka River (Primorsky Territory); ART, wild V. amurensis sample obtained from the vicinity of Artem (Primorsky Territory); KAL, wild V. amurensis sample obtained from the vicinity of Kalinovka (Primorsky Territory); PAK, wild V. amurensis sample obtained from the Pakhtusov Islands (Sea of Japan); RIK, wild V. amurensis sample obtained from Rikord Island (Sea of Japan); VZK, wild V. amurensis sample obtained from the vicinity of Vyazemsky (Khabarovsk Territory); SPB-1, SPB-2, SPB-3, and SPB-4, samples of cultivated V. amurensis provided by N.I. Vavilov All-Russian Institute of Plant Genetic Resources (St. Petersburg).
Table
Table 3. Phenolic acids and other compounds identified in the ethanolic extracts of V. amurensis.
Table 3. Phenolic acids and other compounds identified in the ethanolic extracts of V. amurensis.
No.Identified CompoundARSARTKALPAKRIKVZKSPB-1SPB-2SPB-3SPB-4
Hydroxybenzoic acids
1. Salvianolic acid D + + + + +
2. Salvianolic acid G+ + +
3. Ellagic acid [Benzoaric acid; Elagostasine] + +
4. 4-Hydroxybenzoic acid +
5. Protocatechuic acid +
6. Gallic acid +
7. Syringic acid [Benzoic acid; Cedar acid] +
8. Salvianolic acid F +
9. Dihydroxybenzoyl-hexoside +
Total number:1101062311
Hydroxycinnamic acids
10. Caftaric acid [cis-caftaric acid; 2-caffeoyl-L-tartaric acid; caffeoyl tartaric acid}+ ++++ +++
11. Di-O-caffeoylquinic acid + ++
12. Sinapic acid [trans-Sinapic acid] + +
13. Coutaric acid [Trans-p-Coumaroyltartaric acid] + +
14. Fertaric acid [Fertarate] + +
15. p-Coumaric acid-O-hexoside [Trans-p-Coumaric acid 4-glucoside] + +
16. Caffeic acid-O-(sinapoyl-O-hexoside) ++
17. p-Coumaric acid +
18. Caffeoylmalic acid +
19. 1-Caffeoyl-beta-D-glucose [Caffeic acid-glucoside] +
20. 5-O-(4’-O-p-coumaroyl glucosyl) quinic acid +
21. 3-p-coumaroyl-4-caffeoylquinic acid +
22. Coumaric acid derivative +
Total number:0103221104
Other compounds
23. Ethyl gallate++++ +++++
24. Malic acid++ +++++
25. Hexose-hexose-N-acetyl++ ++++
26. Citric acid ++ +++
27. Quinic acid + ++++
28. Galloyl glucose [Beta-Glucogallin; 1-O-Galloyl-Beta-D-Glucose] ++ + + +
29. L-Tryptophan [Tryptophan; (S)-Tryptophan] ++ ++
30. Cyclopassifloic acid glucoside++ ++
31. Indole-3-carboxylic acid + ++
32. Myristoleic acid [Cis-9-Tetradecanoic acid] + + +
33. Resveratrol [trans-Resveratrol; Stilbentriol]+++
34. Protocatechuic acid-O-hexoside + + +
35. Palmatine [Berbericinine; Burasaine] ++ +
36. Polydatin [Piceid; trans-Piceid] + + +
37. Procyanidin A-type dimer + ++
38. Shikimic acid + +
39. Esculetin [Cichorigenin; Aesculetin] + +
40. 9-oxo-10E,12Z-octadecanoic acid [9-Oxo-ODE] + +
41. Gallic acid hexoside + +
42. Esculin [Aesculin; Esculoside; Polichrome] + +
43. 1-O-Sinapoyl-beta-D-glucose + +
44. Stigmasterol [Stigmasterin; Beta-Stigmasterol]+ +
45. Oleanoic acid + +
46. Tartaric acid +
47. Umbelliferone +
48. Dihydroferulic acid +
49. Linolenic acid (Alpha-Linolenic acid; Linolenate) +
50. Nonadecadienoic acid +
51. Bilobalide [ (-)-Bilobalide] +
52. 3,7 -Dimethylquercetin +
53. Erucic acid (Cis-13-Docosenoic acid) +
54. Fraxin (Fraxetin-8-O-glucoside) +
55. Fucosterol [Fucostein; Trans-24-Ethylidenecholesterol] +
56. Phlorizin [Phloridzin; Phlorizoside; Floridzin: phlorrhizin; Phloretin 2’-Glucoside; Phloretin-O-hexoside]+
57. Ursolic acid +
58. Anmurcoic acid +
59. Dimethylellagic acid hexose +
Total number715711717111155
ARS, wild V. amurensis sample obtained from floodplain of the Arsenyevka River (Primorsky Territory); ART, wild V. amurensis sample obtained from the vicinity of Artem (Primorsky Territory); KAL, wild V. amurensis sample obtained from the vicinity of Kalinovka (Primorsky Territory); PAK, wild V. amurensis sample obtained from the Pakhtusov Islands (Sea of Japan); RIK, wild V. amurensis sample obtained from Rikord Island (Sea of Japan); VZK, wild V. amurensis sample obtained from the vicinity of Vyazemsky (Khabarovsk Territory); SPB-1, SPB-2, SPB-3, and SPB-4, samples of cultivated V. amurensis provided by N.I. Vavilov All-Russian Institute of Plant Genetic Resources (St. Petersburg).
Table
Table 4. Locations of wild V. amurensis grape collection.
Table 4. Locations of wild V. amurensis grape collection.
Code Name of the SampleLocationGeographical ValuesSoil Type
ARSFloodplain of the Arsenyevka River, Primorsky TerritoryN. 44°52′18″, E 133°35′12″brown grey bleached soils
ARTThe vicinity of Artem, Primorsky TerritoryN 43°21′34″, E 132°11′19″yellow-brown soil
KALThe vicinity of Kalinovka, Primorsky TerritoryN 43°07′27″, E 133°12′30″layered floodplains
PAKThe Pakhtusov Islands, Peter the Great Bay, Sea of JapanN 42°53′57″, E 131°38′45″yellow-brown soil
RIKRikord Island, Peter the Great Bay, Sea of JapanN 42°52′54″, E 131°40′06″yellow-brown earth soils
VZKThe vicinity of Vyazemsky, Khabarovsk TerritoryN 47°32′15″, E 134°45′20″podzolic brown forest heavy loamy soils
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Razgonova, M.; Zakharenko, A.; Pikula, K.; Manakov, Y.; Ercisli, S.; Derbush, I.; Kislin, E.; Seryodkin, I.; Sabitov, A.; Kalenik, T.; et al. LC-MS/MS Screening of Phenolic Compounds in Wild and Cultivated Grapes Vitis amurensis Rupr. Molecules 2021, 26, 3650. https://doi.org/10.3390/molecules26123650

AMA Style

Razgonova M, Zakharenko A, Pikula K, Manakov Y, Ercisli S, Derbush I, Kislin E, Seryodkin I, Sabitov A, Kalenik T, et al. LC-MS/MS Screening of Phenolic Compounds in Wild and Cultivated Grapes Vitis amurensis Rupr. Molecules. 2021; 26(12):3650. https://doi.org/10.3390/molecules26123650

Chicago/Turabian Style

Razgonova, Mayya, Alexander Zakharenko, Konstantin Pikula, Yury Manakov, Sezai Ercisli, Irina Derbush, Evgeniy Kislin, Ivan Seryodkin, Andrey Sabitov, Tatiana Kalenik, and et al. 2021. "LC-MS/MS Screening of Phenolic Compounds in Wild and Cultivated Grapes Vitis amurensis Rupr." Molecules 26, no. 12: 3650. https://doi.org/10.3390/molecules26123650

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