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Communication

Simultaneous Determination of Steroidal Alkaloids and Polyphenol Group from Eight Varieties of Siberian Solanum tuberosum L. through Tandem Mass Spectrometry

by
Mayya Razgonova
1,2,
Valentina Kulikova
3,
Vera Khodaeva
3,
Lyudmila Bolotova
3,
Timur Baigarashev
3,
Nina Plotnikova
3,
Alexander Zakharenko
3,4 and
Kirill Golokhvast
1,3,4,*
1
N.I. Vavilov All-Russian Institute of Plant Genetic Resources, 190000 Saint-Petersburg, Russia
2
Far Eastern Federal University, 690950 Vladivostok, Russia
3
Siberian Federal Scientific Centre of Agrobiotechnology, Presidium, Russian Academy of Science, 633501 Krasnoobsk, Russia
4
Tomsk State University, 634050 Tomsk, Russia
*
Author to whom correspondence should be addressed.
Agriculture 2023, 13(4), 758; https://doi.org/10.3390/agriculture13040758
Submission received: 5 December 2022 / Revised: 10 March 2023 / Accepted: 16 March 2023 / Published: 24 March 2023
(This article belongs to the Section Agricultural Product Quality and Safety)

Abstract

:
The purpose of this work was a comparative metabolomic study of extracts of from Siberian breeds of the Solanum tuberosum L.: Tuleevsky, Kuznechanka, Memory of Antoshkina, Tomichka, Hybrid 15/F-2-13, Hybrid 22103-10, Hybrid 17-5/6-11, and Sinilga from the collection of Siberian Federal Scientific Centre of Agrobiotechnology of the Russian Academy of Sciences. HPLC was used in combination with ion trap to identify target analytes in extracts of tuber part of a potato. The results showed the presence of 87 target analytes corresponding to S. tuberosum. In addition to the reported metabolites, a number of metabolites were newly annotated in S. tuberosum. There were essential amino acid L-Tryptophan, L-glutamate, L-lysine, Nordenine; flavones Ampelopsin; Chrysoeriol, Diosmetin, Diosmin, Myricetin; flavanones Naringenin and Eriodictyol-7-O-glucoside; dihydrochalcone Phlorizin; oligomeric proanthocyanidin (Epi)afzelechin-(epi)afzelechin; Shikimic acid; Hydroxyphenyllactic acid; Fraxidin; Myristoleic acid; flavan-3-ols Epicatechin, Gallocatechin, Gibberellic acid, etc.

1. Introduction

Extensive genetic diversity exists among potato germplasm, which includes around 200 wild species found in extremely varied habitats throughout the Americas [1]. However, only a small portion of this genetic diversity has been incorporated into modern cultivars, resulting in a narrow genetic pool. Consequently, wild species are a largely untapped resource that likely contain many novel genes useful for trait enhancement of domesticated potatoes. Relatively little is known about the extent of metabolite diversity present among potato germplasm. Metabolomics holds promise toward understanding metabolite abundance and diversity in plants. GC-MS and HPLC MS/MS metabolic profiling of a few potato cultivars has been shown to be an effective tool [2,3,4,5].
Preliminary LC-MS analysis of the seven genotypes in this study suggested glycoalkaloids were a large source of metabolite diversity. Glycoalkaloids are plant metabolites containing an oligosaccharide, a C27 steroid and a heterocyclic nitrogen component. Solanine and chaconine are thought to comprise upward of 90% of the total glycoalkaloid complement of domesticated potatoes, with chaconine often more abundant than solanine [6].
The glycoalkaloid biosynthetic pathway is not fully delineated, even for the major potato glycoalkaloids, solanine and chaconine. Glycoalkaloids, derived from the mevalonate path-way via cholesterol, occur throughout the tuber but are primarily synthesized in the phelloderm [7]. Surprisingly little has been elucidated about the genes and enzymology involved in conversion of cholesterol into the various glycoalkaloids. Identification of glycoalkaloid biosynthesis genes has enabled transgenic approaches to decrease potato glycoalkaloid content, because glycoalkaloids are typically regarded as antinutritive compounds capable of causing vomiting and other ill effects if ingested in high enough amounts [8]. Potatoes overexpressing a soybean sterol methyltransferase exhibited decreased amounts of both cholesterol and glycoalkaloids [9].
Initial LC-MS screening suggested that among the hundreds of compounds detected in tubers, glycoalkaloid composition was particularly diverse. Potato glycoalkaloids can be divided into two general classes, those with solanidane or spirosolane aglycones, and this study focused on solanidine or solanidane-like glycoalkaloids [10]. Therefore, tandem mass spectrometry was used in this study for comparative small molecule profiling of eight potato varieties cultivated in the Siberian Federal Scientific Center of Agrobiotechnology of Russian Academy of Sciences.
Selection of Siberian potatoes is carried out in the conditions of a sharply continental climate of the West Siberian region of the Russian Federation and is carried out in the following areas:
Early ripeness, varieties of early and mid-early ripeness groups, because the growing season is 90–100 days;
Resistance to the most common fungal and viral diseases inherent in the region—late blight (Phytophthora infestans (Mont.) de Bary), Alternaria blight (Alternaria solani (Ell.Et Matr) Sor), Fusarium blight (Fusarium oxysporum Schlecht.), Rhizoctonia blight (Rhizoctonia solani J.G. Kühn) and viruses;
Stably high productivity;
High consumer and culinary qualities;
Suitability for mechanized cultivation;
Keeping quality of tubers during storage.

2. Materials and Methods

2.1. Materials

The object of the study was the eight varieties of Siberian S. tuberosum of breeding varieties obtained as a result of many years of research from the collection of Siberian Federal Scientific Centre of Agrobiotechnology (Krasnoobsk) of Russian Academia of Science. There were varieties: Tuleevsky, Kuznechanka, Memory of Antoshkina, Tomichka, Hybrid 15/F-2-13, Hybrid 22103-10, Hybrid 17-5/6-11, Sinilga. The varieties of studied potatoes from Siberian Federal Scientific Centre of Agrobiotechnology are presented on the Table 1.
The potato tubers were harvested at the end of September 2021. All samples morphologically corresponded to the pharmacopoeial standards of the State Pharmacopoeia of the Russian Federation [11].

2.2. Chemicals and Reagents

HPLC-grade acetonitrile C2H3N was used as a mobile phase for HPLC process (Fisher Scientific, Southborough, UK), MS-grade formic acid CH2O2 used for liquid chromatography process (Sigma-Aldrich, Steinheim, Germany).
Ultrapure water was produced using SIEMENS ULTRA clear equipment (SIEMENS water technologies, Germany), all reagents used in chemical research were also of analytical purity.

2.3. Fractional Maceration

Fractional maceration technique was applied to obtain highly concentrated extracts [12]. Maceration for small scale extraction usually consists of several steps. Grinding plant materials (500 g of tuber part of a potato) to very small particles (3 × 3 mm) is used to increase the surface area for proper mixing with the solvent. Also, during the maceration process, an appropriate solvent is added to the extraction vessel (methyl alcohol of reagent grade).
Next, the liquid is filtered and the remaining pomace, which is the solid residue of this extraction process, is squeezed out to extract a large amount of occluded solutions. The resulting filtered and squeezed liquid is also later mixed and filtered from impurities.
The solid–solvent ratio was 1:20. The infusion of each part of the extractant lasted 7 days at room temperature.

2.4. Liquid Chromatography

Shimadzu LC-20 Prominence HPLC (Shimadzu, Kyoto, Japan) equipped with a UV sensor and C18 silica reverse phase column, 4.6 × 150 mm, particle size: 2.7 μm (Ascentis Express C18, Supelco, Sigma-Aldrich Tokyo, Japan) used to do high performance liquid chromatography analysis. The gradient elution program with two mobile phases (H2O, deionized water; C2H3N, acetonitrile with formic acid CH2O2 0.1% v/v) was as follows: 0–2 min, 0% C2H3N; 2–50 min, 0–100% C2H3N; control washing 50–60 min 100% C2H3N. Formic acid in this case was used as a mobile phase component in high performance liquid chromatography analysis to separate hydrophobic macromolecules such as peptides, proteins and more complex structures. The entire HPLC analysis was performed with a UV–vis detector SPD- 20A (Shimadzu, Kyoto, Japan) at a wavelength of 230 nm for identification compounds; the temperature was 50 °C, and the total flow rate 0.25 mL min−1. The injection volume was 10  μL. In this study, liquid chromatography was combined into one analytical unit with a mass spectrometric ion trap for the identification of chemical compounds.

2.5. Mass Spectrometry

MS analysis was performed on an ion trap amaZon SL (Bruker Daltoniks, Bremen, Germany) equipped with an ESI source in negative ion mode. The optimized parameters were obtained as follows: ionization source temperature: 70 °C, gas flow: 4 l/min, nebulizer gas (atomizer): 7.3 psi, capillary voltage: 4500 V, end plate bend voltage: 1500 V, fragmentary: 280 V, collision energy: 60 eV. An ion trap was used in the scan range m/z 100 −1.700 for MS and four-stage ion separation mode (MS/MS mode). Data collection was controlled by Windows software for Bruker Daltoniks. All experiments were repeated four times.

3. Results

Eight of the extracts of tuber part of a potato have been selected. All of them have a rich bioactive composition, characterized by a large presence of a complex of flavonoids, steroidal alkaloids, phenolic amines, oxylipins, etc. There were eight extracts from Siberian S. tuberosum L.: Tuleevsky, Kuznechanka, Memory of Antoshkina, Tomichka, Hybrid 15/F-2-13, Hybrid 22103-10, Hybrid 17-5/6-11, and Sinilga from the collection of Siberian Federal Scientific Centre of Agrobiotechnology of the Russian Academy of Science.
High accuracy mass spectrometric data were recorded on an ion trap amaZon SL BRUKER DALTONIKS equipped with an ESI source in the mode of negative-positive ions. The combination of both ionization modes (positive and negative) in MS full scan mode gave extra certainly to the molecular mass determination (Figure 1). The positive and negative ion modes provide the highest sensitivity and results in limited fragmentation, making it most suited to infer the molecular mass of the separated polyphenols, especially in cases where concentration is low. By comparing the m/z values, the RT and the fragmentation patterns with the MS2 spectral data taken from the literature or to search the data bases (MS2T, MassBank, HMDB). A unifying system table was compiled of the molecular masses of the target analytes isolated from the MeOH-extract of S. tuberosum for ease of identification (Appendix A Table A1). The 87 target analytes shown in Table 1 belong to different polyphenolic families: flavones, flavonols, flavan-3-ols, flavanones, hydroxycinnamic acids, hydroxybenzoic acids, stilbenes, tannins and belong to glycoalkaloids.
In addition to the reported metabolites, a number of metabolites were newly annotated in Siberian S. tuberosum L. There were essential amino acid L-Tryptophan; stilbene Oxyresveratrol; flavones Chrysoeriol, Diosmetin, Diosmin, Myricetin, Ampelopsin; dihydrochalcone Phlorizin; Shikimic acid; Hydroxyphenyllactic acid; Fraxidin; Myristoleic acid; flavanone Naringenin; flavan-3-ols Epicatechin, Gallocatechin, Gibberellic acid, etc.
The total ion chromatogram of tandem mass spectrometry of the S. tuberosum L. (variety Hybrid 15/F-2-13) sample is represented on Figure 1. Purple line—base peek chromatogram of positive ion signal intensity; red line—base peek chromatogram of negative ion signal intensity; light green line—total intensity of positive ions; brown line—total intensity of negative ions; blue line—UV chromatogram (wavelength 230 ηm); black line—UV chromatogram (wavelength 330 ηm). The obtained mass spectrometric data make it possible to compile a detailed table of the presence of identified compounds in different varieties of the Siberian S. tuberosum, which further makes it possible to construct comparative Venn diagrams. (Appendix A Table A2).

4. Discussion

The results presented in Table A2 (Appendix A) clearly show that the variety Hybrid 22103-10 provided the highest polyphenol content, the variety Memory of Antoshkina, Hybrid 15/F-2-13, and Hybrid 17-5/6-11 provided the lowest polyphenol content. In turn, analyzing Table A2 (Appendix A), the highest content of steroidal alkaloids was shown by potato tubers of the variety Hybrid 22103-10, and the lowest content was shown by the varieties Hybrid 15/F-2-13, Hybrid 17-5/6-11, and Tomichka.
The results of studies for all bioactive substances, identified from MeOH extracts of S. tuberosum are presented in the Venn diagram (Figure 2).
The detailed interpretation of the identified compounds in potato varieties is presented in Table 2. Also in this table, repeated matches for identified substances in different varieties of potatoes are well traced.
The results of studies for all steroidal alkaloids are presented in the Venn diagram (Figure 3).
The detailed interpretation of the identified steroidal alkaloids in potato varieties is presented in Table 3.
The applied LC gradient of acetonitrile in water permitted to resolve all steroid alkaloid glycosides N° 70–87 (Appendix A Table A2) during reasonable short time.
Monitoring the elution profile of the compounds N° 70–87 was much more easier from single ion chromatograms of protonated molecules [M + H]+, than in total ion chromatogram (Figure 4, Figure 5, Figure 6 and Figure 7). The resolution of the particular peaks of steroid alkaloid glycosides was satisfactory in the applied LC gradient and identification of the compounds on the basis of the registered mass spectra was unambiguous. In the extracts α-chaconine and α-solanine were identified as major glycoalkaloid components, their peaks were easily recognized in the total ion current (Figure 4, Figure 5, Figure 6 and Figure 7).
Figure 4 shows an example of decoding the spectrum of the steroidal alkaloid α-solanine from an ion chromatogram obtained by tandem mass spectrometry. The [M + H]+ ion produces four product ions at m/z 398.26, m/z 560.33, m/z 706.32, and at m/z 851.39 (Figure 4). A fragment ion at m/z 398.26 gives rise to three daughter ions at m/z 327.22, m/z 253.19, and m/z 157.04. A fragment ion at m/z 327.22 gives rise to three daughter ions at m/z 312.27, m/z 204.13, and m/z 150.13. This compound is identified in scientific articles as α-solanine, for example in S. tuberosum [8,13,14,15].
Figure 5 shows an example of decoding the spectrum of the steroidal alkaloid α-chaconine from an ion chromatogram obtained by tandem mass spectrometry. The [M + H]+ ion produces three product ions at m/z 706.4, m/z 560.36, and at m/z 398.32 (Figure 5). A fragment ion at m/z 706.4 gives rise to two daughter ions at m/z 560.32, and m/z 398.3. A fragment ion at m/z 560.32 gives rise to three daughter ions at m/z 398.24, m/z 269.18, and m/z 183.24. This compound is identified in scientific articles as α-chaconine, for example in S. tuberosum [8,13,14,15].
In the mass spectra [M + H]+ ions at m/z 868 and 884 were observed. Four additional peaks of triglycosides described by us, as glycosidic conjugates of dehydrosolanidine were also identified, their protonated molecular ions [M + H]+ were detected at m/z 850 and m/z 866, respectively (Figure 5, Figure 6 and Figure 7).
In the mass spectra of all triglycosides [M + H]+ ions and fragments were observed, formed after consecutive cleavage of glycosidic bonds between sugars and sugar and aglycone. In the first step of the fragmentation pathway of studied compounds (Figure 4, Figure 5, Figure 6 and Figure 7) cleavage of both sugar rings on the nonreducing end was observed. In the mass spectra of steroid alkaloid glycosides linked with solatriose in the first step of fragmentation elimination of glucose ([M + H]+ − 162) or rhamnose ([M + H]+ − 146) was recorded. Due to simultaneous co-elution from LC column more than one secondary metabolite in the mass spectra were present but verification of the steroid alkaloid glycosides presence in the analyzed samples was possible. On the basis of single ion chromatograms for [M + H]+ and fragment ions unambiguous identification of compounds of interest was achieved.

5. Conclusions

Scientific studies in this work have clearly shown the presence of a large number of putative target analytes from extracts of from Siberian S. tuberosum L.: Tuleevsky, Kuznechanka, Memory of Antoshkina, Tomichka, Hybrid 15/F-2-13, Hybrid 22103-10, Hybrid 17-5/6-11, and Sinilga from the collection of Siberian Federal Scientific Centre of Agrobiotechnology of Russian Academia of Science. HPLC in combination with a BRUKER DALTONIKS ion trap was used to identify target analytes in extracts of tuber part of a potato. The results showed the presence of 87 target analytes corresponding to S. tuberosum. In addition to the reported metabolites, a number of metabolites were newly annotated in S. tuberosum. There were essential amino acid L-Tryptophan, L-glutamate, L-lysine, Nordenine; flavones Ampelopsin; Chrysoeriol, Diosmetin, Diosmin, Myricetin; flavanones Naringenin and Eriodictyol-7-O-glucoside; dihydrochalcone Phlorizin; oligomeric proanthocyanidin (Epi)afzelechin-(epi)afzelechin; Shikimic acid; Hydroxyphenyllactic acid; Fraxidin; Myristoleic acid; flavan-3-ols Epicatechin, Gallocatechin, Gibberellic acid, etc.
This study will help to further constructively navigate the introduction of new potato varieties and hybrids in order to obtain certain consumer qualities. In particular, it is now quite clear that in the breeding of new varieties of potatoes, it is necessary to focus on reducing the total proportion of steroidal alkaloids, since they worsen the quality of the product. In turn, the extended presence of compounds of the polyphenol group improves the taste and useful properties of experimental potato samples.

Author Contributions

Conceptualization, M.R. and A.Z.; methodology V.K. (Valentina Kulikova) and K.G.; validation, A.Z. and K.G.; formal analysis, L.B., T.B. and M.R.; investigation, N.P. and V.K. (Vera Khodaeva); resources, K.G.; data curation; writing—original draft preparation—M.R.; writing—review and editing M.R. and K.G.; visualization, M.R.; supervision, K.G.; project administration, K.G. All authors have read and agreed to the published version of the manuscript.

Funding

This work was supported by the Decree No. 220 by the Government of the Russian Federation (Mega-grant No. 220-2961-3099).

Institutional Review Board Statement

No applicable.

Data Availability Statement

No applicable.

Conflicts of Interest

The authors declare no conflict of interest.

Appendix A

Table A1. The target analytes isolated from the MeOH-extract of S. tuberosum L.
Table A1. The target analytes isolated from the MeOH-extract of S. tuberosum L.
NoClass of CompoundsIdentificationFormulaCalculated MassObserved Mass [M − H]Observed Mass [M + H]+MS/MS Stage 1 FragmentationMS/MS Stage 2 FragmentationReferences
POLYPHENOLS
1FlavoneApigeninC15H10O5270.2369 271243230Hedyotis diffusa [16]; Cirsium japonicum [17]; Triticum aestivum L. [18]
2FlavoneChrysoeriol [Chryseriol] C16H12O6300.2629 301269; 169241Triticum aestivum L. [18]; Rice [19]; Mentha [20]
3FlavoneDiosmetinC16H12O6300.2629 301273; 169241Cirsium japonicum [17]; Mentha [20]
4FlavoneMyricetinC15H10O8318.2351 319289; 260; 219; 173261; 191Vitis vinifera [21]; Vaccinium macrocarpon [22]; F. glaucescens [23]
5FlavoneAmpelopsinC15H12O8320.251 321304; 287; 247; 129193; 113Impatients glandulifera Royle [24]; Rhus coriaria [25]
6Flavone5,6-Dihydroxy-7,8,3’,4’-tetramethoxyflavoneC19H18O8374.3414 375345; 297; 275; 257; 245; 217315; 257; 245Mentha [20]
7FlavoneDihydroxy tetramethoxyflavanoneC19H20O8376.3573 377345; 275245G. linguiforme [23]
8FlavoneDiosmin [Diosmetin-7-O-rutinoside; Barosmin; Diosimin] C28H32O15608.5447 609591; 531531Mentha [20]; F. glaucescens [23]
9FlavonolKaempferolC15H10O6286.2363 287278; 241; 185206Potato leaves [4]; Potato [5]; Vitis vinifera [21]; Ocimum [26]
10FlavonolQuercetinC15H10O7302.2357 303275; 203; 163245; 175Potato leaves [4]; Eucalyptus [27]; Triticum [28]; Vitis vinifera [21]; Tomato [29]; Vaccinium macrocarpon [22,30]
11FlavonolHerbacetinC15H10O7302.2357 303275; 203245; 175Ocimum [26]; Rhodiola rosea [31]
12FlavonolIsorhamnetinC16H12O7316.2623 317256228; 116Vaccinium macrocarpon [22]; Eucalyptus [27]
13FlavonolQuercetin 3-O- glucosideC21H20O12464.3763 465447; 279; 136429; 279; 201Potato [5,13]; Vitis vinifera [21]; Rhus coriaria [25]; Lonicera japonica [32]; Solanaceae [33]
14FlavonolMyricetin-3-O-galactosideC21H20O13480.3757 481299; 174271Vitis vinifera [21]; Vaccinium macrocarpon [22,30]; Impatients glandulifera Royle [24]
15FlavonolKaempferol diacetyl hexosideC25H24O13532.4503 533415385; 315A. cordifolia [23]
16FlavonolQuercetin glucuronide sulfateC21H18O16S558.4230 559412; 299; 186394; 299; 186F. herrerae [23]
17FlavonolQuercetin malonyl dihexosideC30H32O20712.5631711 303; 279259; 205F. glaucescens; F. herrerae [23]
18FlavanoneNaringenin [Naringetol; Naringenine] C15H12O5272.5228 273255; 213; 161226Vitis vinifera [21]; G. linguiforme [23]; Tomato [29]
19FlavanoneEriodictyol-7-O-glucosideC21H22O11450.3928 449431; 413; 333; 267; 233; 140356; 290; 227; 150Vitis vinifera [21]; Impatients glandulifera Royle [24]
20Flavan-3-olCatechin [D-Catechol] C15H14O6290.2681 291273; 261; 243; 231; 213; 191; 175202; 157Eucalyptus [27]; Triticum [28]; Vaccinium macrocarpon [30]; Potato [34]
21Flavan-3-olEpicatechinC15H14O6290.2681 291261; 175175; 157Vitis vinifera [21]; C. edulis [23]; Eucalyptus [27]; Vaccinium macrocarpon [30]; Rubus occidentalis [35]
22Flavan-3-olGallocatechinC15H14O7306.2675 307277; 207247; 159G. linguiforme [23]; Solanaceae [33]
23Oligomeric proanthocyanidinEpiafzelechin [(epi)Afzelechin] C15H14O5274.2687 275245; 175175; 127A. cordifolia; F. glaucescens; F. herrerae [23]
24Oligomeric proanthocyanidin(Epi)Afzelechin-(epi)afzelechinC30H24O10544.5056 545535; 362; 301359; 227A. cordifolia, C. edulis [23]
25AnthocyaninPetunidinC16H13O7+317.2702 318300; 256212; 112A. cordifolia; C. edulis [23]
26DihydrochalconePhlorizin [Phloridzin; Phlorizoside] C21H24O10436.4093 437275; 329245; 176Potato [5]; Vitis vinifera [21]; A.cordifolia [23]; Eucalyptus [27]
27Hydroxycinammic acidp-Coumaric acidC9H8O3164.16 165147119Potato [5]; Tomato [29]; Vaccinium macrocarpon [30]; Rubus occidentalis [35]
28Hydroxycinnamic acidChlorogenic acid [3-O-Caffeoylquinic acid] C16H18O9354.3087353 191127; 171Potato leaves [4]; Vaccinium macrocarpon [22]; tomato [29]; Potato [5,13,14,36]
29Hydroxybenzoic acid (Phenolic acid)4-Hydroxybenzoic acid [PHBA; Benzoic acid; p-Hydroxybenzoic acid] C7H6O3138.1207 139137129Potato [5]; Vitis vinifera [21]; Triticum [28]; Vigna unguiculata [35]; Mentha [37]
30Hydroxybenzoic acid (Phenolic acid)Salvianolic acid GC18H12O7340.2837 341323; 273; 137275; 176Mentha [20]
31HydroxycoumarinFraxidinC11H10O5222.1941 208; 135189Rat plasma [38]
OTHERS
32L-alpha amino acidL-Pyroglutamic acid [Pidolic acid; 5-Oxo-L-Proline] C5H7NO3129.1140 130112 Potato leaves [4]
33Amino acidLeucine [(S)-2-Amino-Methylpentanoic acid] C6H13NO2131.1729 132129 Potato leaves [4]; Vigna unguiculata [35]
34Amino acidL-GlutamateC5H7NO4145.1134 146 Lonicera japonica [32]
35Amino acidL-LysineC6H14N2O2146.1876 147130 Lonicera japonica [32]
36Amino acidPhenylalanine [L-Phenylalanine] C9H11NO2165.1891 166120 Potato leaves [4]; G. linguiforme [23]; Vigna unguiculata [35]; Passiflora incarnata [39]
37Amino acidNordenineC10H15NO165.2322 166149; 120139; 120A. cordifolia [23]
38Cyclohexenecarboxylic acidShikimic acid [L-Schikimic acid]C7H10O5174.1513 175157; 130; 112140; 126; 112A. cordifolia [23]; Red wines [40]
39Monobasic carboxylic acidHydroxyphenyllactic acidC9H10O4182.1733 182165; 136147Mentha [37]
40Polyhydroxycarboxylic acidQuinic acidC7H12O6192.1666191 173; 129; 111 Potato leaves [4]; Potato [14]
41Tricarboxylic acidCitric acid [Anhydrous; Citrate] C6H8O7192.1235191 111; 173 Potato leaves [4]; Vigna unguiculata [35]
42Trans-cinnamic acidFerulic acidC10H10O4194.184 195193; 112 Potato [5,13]; Vaccinium macrocarpon [30]
43Essential amino acidL-Tryptophan [Tryptophan; (S)-Tryptophan] C11H12N2O2204.2252 205188146; 170Vigna unguiculata [35]; Passiflora incarnata [39]; Strawberry [41]
44Unsaturated fatty acidDodecatetraenedioic acid [2,4,8,10-Dodecateraenedioic acid] C12H14O4222.2372 223208; 163; 135190F. herrerae [23]
45Carboxylic acidMyristoleic acid [Cis-9-Tetradecanoic acid] C14H26O2226.3550 227209;138; 127F. glaucescens [23]
46Benzoic acid3,4-Diacetoxybenzoic acidC10H11O6238.1935 239222; 151123Potato leaves [4]; Triticum aestivum L. [42]
47Phenolic amineN-CaffeoylputrescineC13H18N2O3250.2936 251223; 151177Potato leaves [4]; Potato [14]
48Phenolic amineN-feruloylputrescineC14H20N2O3264.3202 265248; 177; 114177; 145Potato [14]
49Omega-3 fatty acidStearidonic acidC18H28O2276.4137 277248; 201; 132218; 189Salviae Miltiorrhizae [43]
50PhenylpropanoidTriandrin [Sachaliside] C15H20O7312.3151311 293; 201; 171265; 185Potato leaves [4]
51Unsaturated fatty acidOctadecanedioic acid [1,16-Hexadecanedicarboxylic acid] C18H34O4314.4602 315280; 199; 127135F. glaucescens [23]
52Unsaturated essential fatty acidOxo-eicosatetraenoic acidC20H30O3318.4504 319277259; 165F. potsii [23]
53 Fructose-phenylalanineC15H21NO7327.3297 328169; 291140Potato leaves [4]
54Higher-molecular-weight carboxylic acid9,10-Dihydroxy-8-oxooctadec-12-enoic acidC18H32O5328.4437327 229; 171; 127153Bituminaria [44]; Broccoli [45]; Phyllostachys nigra [46]
55OxylipinEpoxyoctadecane-dioic acidC18H32O5328.4437327 171; 201; 125153Potato leaves [4]
56Phenolic amineN-feruloyloctopamineC18H19NO5329.3472328 310295; 161; 135Potato [14]
57Oxylipin13- Trihydroxy-Octadecenoic acid [THODE] C18H34O5330.4596329 309; 229; 171; 127153Bituminaria [44]; Broccoli [45]; Phyllostachys nigra [46]
58Oxylipin9,12,13- Trihydroxy-trans-10-octadecenoic acidC18H34O5330.4596329 171; 201; 311153Potato leaves [4]
59Cyclohexenecarboxylic acid3-O-caffeoylshikimic acid [3-Csa] C16H16O8336.2934 337319; 257; 175; 112257; 175Grataegi Fructus [47]; Zostera marina [48]
60Pentacyclic diterpenoidGibberellic acidC19H22O6346.3744 347284; 154256Triticum aestivum [49]
61Higher-molecular-weight carboxylic acidPentacosenoic acidC25H48O2380.6474 381363; 263; 180275; 247; 207F. glaucescens [23]
62Steroidal alkaloidSolanidineC27H43NO397.6364 399157; 383; 327; 253142Potato [15,50]
63SterolStigmasterol [Stigmasterin; Beta-Stigmasterol] C29H48O412.6908 413301189Hedyotis diffusa [16]; A.cordifolia; F. pottsii [23]; Salvia hypargeia [51]
64Steroidal alkaloidTomatidinolC27H43NO2413.6358 414394; 272; 204256; 204Potato [50]; Lucopersicon esculentum, Solanum nigrum [52]
65Anabolic steroidVebonolC30H44O3452.6686 453435; 336; 209336; 226Rhus coriaria [25]
66Phenolic amineN1,N8-bis(dihydrocaffeoyl) spermidineC25H35N3O6473.5619 474343228; 315Potato [14]
67Polyhydroxycarboxylic acid1-O-caffeoyl-5-O-feruloylquinic acidC26H26O12530.4774 531353; 303; 230337; 280; 143Lemon [53]; Senecio clivicolus [54]
68GlycoalkaloidUnknown glycoalkaloidC32H33NO8559.6063 560398; 183383; 253; 213; 159; 125
69Glycoalkaloidβ-chaconineC39H63NO10705.9182 706560; 493; 398; 307; 214398; 196Passiflora incarnata [39]
70GlycoalkaloidUnknown glycoalkaloidC39H63NO11721.9176 722704; 560396
71GlycoalkaloidDehydrochaconineC45H71NO14850.0435 850704; 558; 396558; 396; 272Potato [3,8]
72Glycoalkaloidα-chaconineC45H73NO14852.0594 852706; 560; 398; 253560; 398Potato [8,13,14,15]
73GlycoalkaloidSolanidadienol chacotrioseC45H71NO15866.0429 866720; 574; 412; 850574; 412Potato [8]
74GlycoalkaloidSolanidadiene solatrioseC45H71NO15866.0429 866396; 558; 704396; 325; 199; 166Potato [8]
75GlycoalkaloidSolanidenone chacotrioseC45H71NO15866.0429 866720574; 412; 254Potato [8]
76Glycoalkaloidα-solanineC45H73NO15868.9588 868398; 706; 560383; 327; 253; 157Potato [8,13,14,15]
77GlycoalkaloidLeptinine IC45H73NO15868.9588 868850; 704; 396704; 558; 396Potato [8]
78GlycoalkaloidSolanidenol chacotrioseC45H73NO15868.9588 868722; 560; 398560; 398; 326Potato [8]
79GlycoalkaloidSolanidadiene solatrioseC45H73NO15868.9588 868706; 560; 486; 398; 327560; 398; Potato [8]
80GlycoalkaloidSolanidadienol solatrioseC45H71NO16882.0423 882412; 736; 574182; 394; 341; 251Potato [8]
81GlycoalkaloidLeptinine IIC45H73NO16884.0582 884866; 704; 396396; 558; 720Potato [8]
82GlycoalkaloidSolanidenol solatrioseC45H73NO16884.0582 884866; 722; 396396; 558; 704Potato [8]
83GlycoalkaloidUnknown glycoalkaloidC45H75NO16886.0741886 850; 704704; 558
84GlycoalkaloidUnknown glycoalkaloidC45H77NO16888.0900 888870852
85GlycoalkaloidUnknown glycoalkaloidC46H75NO16898.0848897 850; 704704; 246
86GlycoalkaloidUnknown glycoalkaloidC45H76NO17903.0814902 866; 704704; 558
87GlycoalkaloidUnknown glycoalkaloidC49H79NO18970.1475969 850; 704704; 558; 492
Table A2. The presence of identified compounds in different varieties of Siberian S. tuberosum (Variety Tuleevsky—light green; variety Memory of Antoshkina—brown; variety Kuznechanka—red; variety Sinilga—violet; variety Hybrid 15/F-2-13—rose; variety Hybrid 22103-10—green; variety Hybrid 17-5/6-11—blue; variety Tomichka—light blue).
Table A2. The presence of identified compounds in different varieties of Siberian S. tuberosum (Variety Tuleevsky—light green; variety Memory of Antoshkina—brown; variety Kuznechanka—red; variety Sinilga—violet; variety Hybrid 15/F-2-13—rose; variety Hybrid 22103-10—green; variety Hybrid 17-5/6-11—blue; variety Tomichka—light blue).
NoIdentified CompoundsIdentificationFormulaCalculated MassTuleevsky Memory of Antoshkina Kuznechanka SinilgaHybrid 15/F-2-13 Hybrid 22103-10Hybrid 17-5/6-11Tomichka
Polyphenols
1FlavoneApigeninC15H10O5270.2369
2FlavoneChrysoeriolC16H12O6300.2629
3FlavoneDiosmetinC16H12O6300.2629
4FlavoneMyricetinC15H10O8318.2351
5FlavoneAmpelopsinC15H12O8320.251
6Flavone5,6-Dihydroxy-7,8,3’,4’tetramethoxyflavoneC19H18O8374.3414
7FlavoneDihydroxy tetramethoxyflavanoneC19H20O8376.3573
8FlavoneDiosminC28H32O15608.5447
9FlavonolKaempferolC15H10O6286.2363
10FlavonolQuercetinC15H10O7302.2357
11FlavonolHerbacetinC15H10O7302.2357
12FlavonolIsorhamnetinC16H12O7316.2623
13FlavonolQuercetin 3-O- glucosideC21H20O12464.3763
14FlavonolMyricetin-3-O-galactosideC21H20O13480.3757
15FlavonolKaempferol diacetyl hexosideC25H24O13532.4503
16FlavonolQuercetin glucuronide sulfateC21H18O16S558.4230
17FlavonolQuercetin malonyl dihexosideC30H32O20712.5631
18Flavan-3-olCatechinC15H14O6290.2681
19Flavan-3-olEpicatechinC15H14O6290.2681
20Flavan-3-olGallocatechinC15H14O7306.2675
21FlavanoneNaringeninC15H12O5272.5228
22FlavanoneEriodictyol-7-O-glucosideC21H22O11450.3928
23Oligomeric proanthocyanidinEpiafzelechinC15H14O5274.2687
24Oligomeric proanthocyanidinEpiafzelechin-epiafzelechinC30H24O10544.5056
25Hydroxybenzoic acid4-Hydroxybenzoic acidC7H6O3138.1207
26Hydroxycinammic acidp-Coumaric acidC9H8O3164.16
27Trans-cinnamic acidFerulic acidC10H10O4194.184
28Benzoic acid3,4-Diacetoxybenzoic acidC10H11O6238.1935
29Hydroxybenzoic acid (Phenolic acid)Salvianolic acid GC18H12O7340.2837
30Hydroxycinnamic acidChlorogenic acidC16H18O9354.3087
31AnthocyaninPetunidinC16H13O7+317.2702
32HydroxycoumarinFraxidinC11H10O5222.1941
33DihydrochalconePhlorizinC21H24O10436.4093
Others
34L-alpha amino acidL-Pyroglutamic acidC5H7NO3129.1140
35Amino acidLeucineC6H13NO2131.1729
36Amino acidL-GlutamateC5H7NO4145.1134
37Amino acidL-LysineC6H14N2O2146.1876
38Amino acidPhenylalanine [L-Phenylalanine] C9H11NO2165.1891
39Amino acidNordenineC10H15NO165.2322
40Cyclohexenecarboxylic acidSchikimic acidC7H10O5174.1513
41Monobasic carboxylic acidHydroxyphenyllactic acidC9H10O4182.1733
42Polyhydroxycarboxylic acidQuinic acidC7H12O6192.1666
43Tricarboxylic acidCitric acidC6H8O7192.1235
44Essential amino acidL-TryptophanC11H12N2O2204.2252
45Unsaturated fatty acidDodecatetraenedioic acidC12H14O4222.2372
46Carboxylic acidMyristoleic acidC14H26O2226.3550
47Phenolic amineN-CaffeoylputrescineC13H18N2O3250.2936
48Phenolic amineN-feruloylputrescineC14H20N2O3264.3202
49Omega-3 fatty acidStearidonic acidC18H28O2276.4137
50PhenylpropanoidTriandrinC15H20O7312.3151
51Unsaturated fatty acidOctadecanedioic acidC18H34O4314.4602
52Unsaturated essential fatty acidOxo-eicosatetraenoic acidC20H30O3318.4504
53 Fructose-phenylalanineC15H21NO7327.3297
54Higher-molecular-weight carboxylic acid9,10-Dihydroxy-8-oxooctadec-12-enoic acidC18H32O5328.4437
55OxylipinEpoxyoctadecane-dioic acidC18H32O5328.4437
56Phenolic amineN-feruloyloctopamineC18H19NO5329.3472
57Oxylipin13- Trihydroxy-Octadecenoic acidC18H34O5330.4596
58Oxylipin9,12,13- Trihydroxy-trans-10-octadecenoic acidC18H34O5330.4596
59Cyclohexenecarboxylic acid3-O-caffeoylshikimic acid [3-Csa] C16H16O8336.2934
60Pentacyclic diterpenoidGibberellic acidC19H22O6346.3744
61Higher-molecular-weight carboxylic acidPentacosenoic acidC25H48O2380.6474
62Steroidal alkaloidSolanidineC27H43NO397.6364
63SterolStigmasterolC29H48O412.6908
64Steroidal alkaloidTomatidinolC27H43NO2413.6358
65Anabolic steroidVebonolC30H44O3452.6686
66Phenolic amineN1,N8-bis(dihydrocaffeoyl) spermidineC25H35N3O6473.5619
67Polyhydroxycarboxylic acid1-O-caffeoyl-5-O-feruloylquinic acidC26H26O12530.4774
68Steroidal alkaloidUnknown glycoalkaloidC32H33NO8559.6063
69GlycoalkaloidBeta-chaconineC39H63NO10705.9182
70GlycoalkaloidUnknown glycoalkaloidC39H63NO11721.9176
71GlycoalkaloidDehydrochaconineC45H71NO14850.0435
72GlycoalkaloidAlpha-chaconineC45H73NO14852.0594
73GlycoalkaloidSolanidadienol chacotrioseC45H71NO15866.0429
74GlycoalkaloidSolanidadiene solatrioseC45H71NO15866.0429
75GlycoalkaloidSolanidenone chacotrioseC45H71NO15866.0429
76GlycoalkaloidAlpha-solanineC45H73NO15868.9588
77GlycoalkaloidLeptinine IC45H73NO15868.9588
78GlycoalkaloidSolanidenol chacotrioseC45H73NO15868.9588
79GlycoalkaloidSolanidadiene solatrioseC45H73NO15868.9588
80GlycoalkaloidSolanidadienol solatrioseC45H71NO16882.0423
81GlycoalkaloidLeptinine IIC45H73NO16884.0582
82GlycoalkaloidSolanidenol solatrioseC45H73NO16884.0582
83GlycoalkaloidUnknown glycoalkaloidC45H75NO16886.0741
84GlycoalkaloidUnknown glycoalkaloidC45H77NO16888.0900
85GlycoalkaloidUnknown glycoalkaloidC46H75NO16898.0848
86GlycoalkaloidUnknown glycoalkaloidC45H76NO17903.0814
87GlycoalkaloidUnknown glycoalkaloidC49H79NO18970.1475

References

  1. Spooner, D.M.; Hijmans, R.J. Potato systematics and germplasm collecting, 1989–2000. Am. J. Potato Res. 2001, 78, 237–268. [Google Scholar] [CrossRef]
  2. Roessner, U.; Willmitzer, L.; Fernie, A.R. High-resolution metabolic phenotyping of genetically and environmentally diverse potato tuber systems. Identification of phenocopies. Plant Physiol. 2001, 127, 749–764. [Google Scholar] [CrossRef] [PubMed]
  3. Stobiecki, M.; Matysiak-Kata, I.; Franski, R.; Skala, J.; Szopa, J. Monitoring changes in anthocyanin and steroid alkaloid glycoside content in lines of transgenic potato plants using liquid chromatography/mass spectrometry. Phytochemistry 2003, 62, 959–969. [Google Scholar] [CrossRef] [PubMed]
  4. Rodriguez-Perez, C.; Gomez-Caravaca, A.M.; Guerra-Hernandez, E.; Cerretani, L.; Garcia-Villanova, B.; Verardo, V. Comprehensive metabolite profiling of Solanum tuberosum L. (potato) leaves T by HPLC-ESI-QTOF-MS. Molecules 2018, 112, 390–399. [Google Scholar] [CrossRef] [PubMed]
  5. Oertel, A.; Matros, A.; Hartmann, A.; Arapitsas, P.; Dehmer, K.J.; Martens, S.; Mock, H.P. Metabolite profiling of red and blue potatoes revealed cultivar and tissue specific patterns for anthocyanins and other polyphenols. Planta 2017, 246, 281–297. [Google Scholar] [CrossRef]
  6. Griffiths, D.W.; Bain, H.; Dale, M.F.B. The effect of low-temperature storage on the glycoalkaloid content of potato (Solanum tuberosum) tubers. J. Sci. Food Agric. 1997, 74, 301–307. [Google Scholar] [CrossRef]
  7. Krits, P.; Fogelman, E.; Ginzberg, I. Potato steroidal glycoalkaloid levels and the expression of key isoprenoid metabolic genes. Planta 2007, 227, 143–150. [Google Scholar] [CrossRef]
  8. Shakya, R.; Navarre, D.A. LC-MS Analysis of Solanidane Glycoalkaloid Diversity among Tubers of Four Wild Potato Species and Three Cultivars (Solanum tuberosum). J. Agric. Food Chem. 2008, 56, 6949–6958. [Google Scholar] [CrossRef]
  9. Arnqvist, L.; Dutta, P.C.; Jonsson, L.; Sitbon, F. Reduction of cholesterol and glycoalkaloid levels in transgenic potato plants by overexpression of a type 1 sterol methyltransferase cDNA. Plant Physiol. 2003, 131, 1792–1799. [Google Scholar] [CrossRef] [Green Version]
  10. Friedman, M.; McDonald, G.M. Potato glycoalkaloids: Chemistry, analysis, safety, and plant physiology. Crit. Rev. Plant Sci. 1997, 16, 55–132. [Google Scholar] [CrossRef]
  11. Pharmacopoeia of the Eurasian Economic Union. Approved by Decision of the Board of Eurasian Economic Commission No. 100. 2020. Available online: http://www.eurasiancommission.org/ru/act/texnreg/deptexreg/LSMI/Documents/Фармакoпея%20Сoюза%2011%2008.pdf (accessed on 15 July 2020).
  12. Azmir, J.; Zaidul, I.S.M.; Rahman, M.M.; Sharif, K.; Mohamed, A.; Sahena, F.; Jahurul, M.; Ghafoor, K.; Norulaini, N.; Omar, A. Techniques for extraction of bioactive compounds from plant materials: A review. J. Food Eng. 2013, 117, 426–436. [Google Scholar] [CrossRef]
  13. Deuber, H.; Guignard, C.; Hoffmann, L.; Evers, D. Polyphenol and glycoalkaloid contents in potato cultivars grown in Luxembourg. Food Chem. 2012, 135, 2814–2824. [Google Scholar]
  14. Huang, W.; Serra, O.; Dastmalchi, K.; Jin, L.; Yang, L.; Stark, R.E. Comprehensive MS and Solid-state NMR Metabolomic Profiling Reveals Molecular Variations in Native Periderms from Four Solanum tuberosum Potato Cultivars. J. Agric. Food Chem. 2017, 65, 2258–2274. [Google Scholar] [CrossRef]
  15. Hossain, M.B.; Brunton, N.P.; Rai, D.K. Effect of Drying Methods on the Steroidal Alkaloid Content of Potato Peels, Shoots and Berries. Molecules 2016, 21, 403. [Google Scholar] [CrossRef] [Green Version]
  16. Chen, X.; Zhu, P.; Liu, B.; Ge, D.; Wei, L.; Xu, Y. Simultaneous determination of fourteen compounds of Hedyotis diffusa Willd extract in rats by UHPLC–MS/MS method: Application to pharmacokinetics and tissue distribution study. J. Pharm. Biomed. Anal. 2018, 159, 490–512. [Google Scholar] [CrossRef] [PubMed]
  17. Zhang, Z.; Jia, P.; Zhang, X.; Zhang, Q.; Yang, H.; Shi, H.; Zhang, L. LC-MS/MS determination and pharmacokinetic study of seven flavonoids in rat plasma after oral administration of Cirsium japonicum DC. extract. J. Ethnopharmacol. 2014, 158, 66–75. [Google Scholar] [CrossRef] [PubMed]
  18. Wojakowska, A.; Perkowski, J.; Goral, T.; Stobiecki, M. Structural characterization of flavonoid glycosides from leaves of wheat (Triticum aestivum L.) using LC/MS/MS profiling of the target compounds. J. Mass. Spectrom. 2013, 48, 329–339. [Google Scholar] [CrossRef]
  19. Chen, W.; Gong, L.; Guo, Z.; Wang, W.; Zhang, H.; Liu, X.; Yu, S.; Xiong, L.; Luo, J. A Novel Integrated Method for Large-Scale Detection, Identification, and Quantification of Widely Targeted Metabolites: Application in the Study of Rice Metabolomics. Mol. Plant. 2013, 6, 1769–1780. [Google Scholar] [CrossRef] [Green Version]
  20. Xu, L.L.; Xu, J.J.; Zhong, K.R.; Shang, Z.P.; Wang, F.; Wang, R.F.; Liu, B. Analysis of non-volatile chemical constituents of Menthae haplocalycis herba by ultra-high performance liquid chromatography–high resolution mass spectrometry. Molecules 2017, 22, 1756. [Google Scholar] [CrossRef] [Green Version]
  21. Goufo, P.; Singh, R.K.; Cortez, I. Phytochemical A Reference List of Phenolic Compounds (Including Stilbenes) in Grapevine (Vitis vinifera L.) Roots, Woods, Canes, Stems, and Leaves. Antioxidants 2020, 9, 398. [Google Scholar] [CrossRef]
  22. Rafsanjany, N.; Senker, J.; Brandt, S.; Dobrindt, U.; Hensel, A. In Vivo Consumption of Cranberry Exerts ex Vivo Antiadhesive Activity against FimH-Dominated Uropathogenic Escherichia coli: A Combined in Vivo, ex Vivo, and in Vitro Study of an Extract from Vaccinium macrocarpon. J. Agric. Food Chem. 2015, 63, 8804–8818. [Google Scholar] [CrossRef] [PubMed]
  23. Hamed, A.R.; El-Hawary, S.S.; Ibrahim, R.M.; Abdelmohsen, U.R.; El-Halawany, A.M. Identification of Chemopreventive Components from Halophytes Belonging to Aizoaceae and Cactaceae Through LC/MS–Bioassay Guided Approach. J. Chrom. Sci. 2021, 59, 618–626. [Google Scholar] [CrossRef]
  24. Viera, M.N.; Winterhalter, P.; Jerz, G. Flavonoids from the flowers of Impatients glandulifera Royle isolated by high performance countercurrent chromatography. Phytochem. Anal. 2016, 27, 116–125. [Google Scholar] [CrossRef] [PubMed]
  25. Abu-Reidah, I.M.; Ali-Shtayeh, M.S.; Jamous, R.M.; Arraes-Roman, D.; Segura-Carretero, A. HPLC–DAD–ESI-MS/MS screening of bioactive components from Rhus coriaria L. (Sumac) fruits. Food Chem. 2015, 166, 179–191. [Google Scholar] [CrossRef] [Green Version]
  26. Pandey, R.; Kumar, B. HPLC–QTOF–MS/MS-based rapid screening of phenolics and triterpenic acids in leaf extracts of Ocimum species and their interspecies variation. J. Liq. Chromatogr. Relat. Technol. 2016, 39, 225–238. [Google Scholar] [CrossRef]
  27. Santos, S.A.O.; Vilela, C.; Freire, C.S.R.; Neto, C.P.; Silvestre, A.J.D. Ultra-high performance liquid chromatography coupled to mass spectrometry applied to the identification of valuable phenolic compounds from Eucalyptus wood. J. Chromatogr. B 2013, 938, 65–74. [Google Scholar] [CrossRef] [PubMed]
  28. Sharma, M.; Sandhir, R.; Singh, A.; Kumar, P.; Mishra, A.; Jachak, S.; Singh, S.P.; Singh, J.; Roy, J. Comparison analysis of phenolic compound characterization and their biosynthesis genes between two diverse bread wheat (Triticum aestivum) varieties differing for chapatti (unleavened flat bread) quality. Front. Plant. Sci. 2016, 7, 1870. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  29. Vallverdu-Queralt, A.; Jauregui, O.; Medina-Remon, A.; Lamuela-Raventos, R.M. Evaluation of a Method to Characterize the Phenolic Profile of Organic and Conventional Tomatoes. Agricult. Food Chem. 2012, 60, 3373–3380. [Google Scholar] [CrossRef]
  30. Abeywickrama, G.; Debnath, S.C.; Ambigaipalan, P.; Shahidi, F. Phenolics of selected cranberry genotypes (Vaccinium macrocarpon Ait.) and their antioxidant efficacy. J. Agric. Food Chem. 2016, 64, 9342–9351. [Google Scholar] [CrossRef]
  31. Petsalo, A.; Jalonen, J.; Tolonen, A. Identification of flavonoids of Rhodiola rosea by liquid chromatography-tandem mass spectrometry. J Chromatogr. A. 2006, 1112, 224–231. [Google Scholar] [CrossRef]
  32. Cai, Z.; Wang, C.; Zou, L.; Liu, X.; Chen, J.; Tan, M.; Mei, Y.; Wei, L. Comparison of Multiple Bioactive Constituents in the Flower and the Caulis of Lonicera japonica Based on UFLC-QTRAP-MS/MS Combined with Multivariate Statistical Analysis. Molecules 2019, 24, 1936. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  33. Yasir, M.; Sultana, B.; Anwar, F. LC–ESI–MS/MS based characterization of phenolic components in fruits of two species of Solanaceae. J. Food Sci. Technol. 2018, 55, 2370–2376. [Google Scholar] [CrossRef] [PubMed]
  34. Paudel, L.; Wyzgovski, F.J.; Scheerens, J.C.; Chanon, A.M.; Reese, R.N.; Smiljanic, D.; Wesdemiotis, C.; Blakeslee, J.J.; Riedl, K.M.; Rinaldi, P.L. Nonanthocyanin Secondary Metabolites of Black Raspberry (Rubus occidentalis L.) Fruits: Identification by HPLC-DAD, NMR, HPLC-ESI-MS, and ESI-MS/MS Analyses. J. Agricult. Food. Chem. 2013, 61, 12032–12043. [Google Scholar] [CrossRef] [PubMed]
  35. Perchuk, I.; Shelenga, T.; Gurkina, M.; Miroshnichenko, E.; Burlyaeva, M. Composition of Primary and Secondary Metabolite Compounds in Seeds and Pods of Asparagus Bean (Vigna unguiculata (L.) Walp.) from China. Molecules 2020, 25, 3778. [Google Scholar] [CrossRef]
  36. De Masi, L.; Bontempo, P.; Rigano, D.; Stiuso, P.; Carafa, V.; Nebbioso, A.; Piacente, S.; Montoro, P.; Aversano, R.; D’Amelia, V.; et al. Comparative Phytochemical Characterization, Genetic Profile, and Antiproliferative Activity of Polyphenol-Rich Extracts from Pigmented Tubers of Different Solanum tuberosum Varieties. Molecules 2020, 25, 233. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  37. Cirlini, M.; Mena, P.; Tassotti, M.; Herrlinger, K.A.; Nieman, K.M.; Dall’Asta, C.; Del Rio, D. Phenolic and volatile composition of a dry spearmint (Mentha spicata L.). Molecules 2016, 21, 1007. [Google Scholar] [CrossRef] [Green Version]
  38. Yasuda, T.; Fukui, M.; Nakazawa, T.; Hoshikawa, A.; Ohsawa, K. Metabolic Fate of Fraxin Administrated Orally to Rats. J. Nat. Prod. 2006, 69, 755–757. [Google Scholar] [CrossRef]
  39. Ozarowski, M.; Piasecka, A.; Paszel-Jaworska, A.; de Chaves, D.S.A.; Romaniuk, A.; Rybczynska, M.; Gryszczynska, A.; Sawikowska, A.; Kachlicki, P.; Mikolajczak, P.L.; et al. Comparison of bioactive compounds content in leaf extracts of Passiflora incarnata, P. caerulea and P. alata and in vitro cytotoxic potential on leukemia cell lines. Braz. J. Pharmacol. 2018, 28, 179–191. [Google Scholar] [CrossRef]
  40. Ivanova-Petropulos, V.; Naceva, Z.; Sandor, V.; Makszin, L.; Deutsch-Nagy, L.; Berkics, B.; Stafilov, T.; Kilar, F. Fast determination of lactic, succinic, malic, tartaric, shikimic, and citric acids in red Vranec wines by CZE-ESI-QTOF-MS. Electrophoresis 2018, 39, 1597–1605. [Google Scholar] [CrossRef]
  41. Sun, J.; Liu, X.; Yang, T.; Slovin, J.; Chen, P. Profiling polyphenols of two diploid strawberry (Fragaria vesca) inbred lines using UHPLC-HRMSn. Food Chem. 2014, 146, 289–298. [Google Scholar] [CrossRef] [Green Version]
  42. Stallmann, J.; Schweiger, R.; Pons, C.A.A.; Muller, C. Wheat growth, applied water use efficiency and flag leaf metabolome under continuous and pulsed deficit irrigation. Sci. Rep. 2020, 10, 10112. [Google Scholar] [CrossRef] [PubMed]
  43. Yang, S.T.; Wu, X.; Rui, W.; Guo, J.; Feng, Y.F. UPLC/Q-TOF-MS analysis for identification of hydrophilic phenolics and lipophilic diterpenoids from Radix Salviae miltiorrhizae. Acta Chromatogr. 2015, 27, 711–728. [Google Scholar] [CrossRef] [Green Version]
  44. Llorent-Martinez, E.J.; Spinola, V.; Gouveia, S.; Castilho, P.C. HPLC-ESI-MSn characterization of phenolic compounds, terpenoid saponins, and other minor compounds in Bituminaria bituminosa. Ind. Crops Prod. 2015, 69, 80–90. [Google Scholar] [CrossRef]
  45. Park, S.K.; Ha, J.S.; Kim, J.M.; Kang, J.Y.; Lee, D.S.; Guo, T.J.; Lee, U.; Kim, D.-O.; Heo, H.J. Antiamnesic Effect of Broccoli (Brassica oleracea var. italica) Leaves on Amyloid Beta (Aβ)1-42-Induced Learning and Memory Impairment. J. Agricult. Food. Chem. 2016, 64, 3353–3361. [Google Scholar] [CrossRef]
  46. Van Hoyweghen, L.; De Bosscher, K.; Haegeman, G.; Deforce, D.; Heyerick, A. In Vitro Inhibition of the Transcription Factor NF-kB and Cyclooxygenase by Bamboo Extracts. Phytother. Res. 2013, 28, 224–230. [Google Scholar] [CrossRef]
  47. Huang, Y.; Yao, P.; Leung, K.W.; Wang, H.; Kong, X.P.; Wang, L.; Dong, T.T.X.; Chen, Y.; Tsim, K.W.K. The Yin-Yang Property of Chinese Medicinal Herbs Relates to Chemical Composition but Not Anti-Oxidative Activity: An Illustration Using Spleen-Meridian Herbs. Front. Pharmacol. 2018, 9, 1304. [Google Scholar] [CrossRef] [Green Version]
  48. Razgonova, M.P.; Tekutyeva, L.A.; Podvolotskaya, A.B.; Stepochkina, V.D.; Zakharenko, A.M.; Golokhvast, K. Zostera marina L. Supercritical CO2-Extraction and Mass Spectrometric Characterization of Chemical Constituents Recovered from Seagrass. Separations 2022, 9, 182. [Google Scholar] [CrossRef]
  49. Hou, S.; Zhu, J.; Ding, M.; Lv, G. Simultaneous determination of gibberellic acid, indole-3-acetic acid and abscisic acid in wheat extracts by solid-phase extraction and liquid chromatography–electrospray tandem mass spectrometry. Talanta 2008, 76, 798–802. [Google Scholar] [CrossRef]
  50. Bianco, G.; Schmitt-Kopplin, P.; De Benedetto, G.; Kettrup, A.; Cataldi, T.R.I. Determination of glycoalkaloids and relative aglycones by nonaqueous capillary electrophoresis coupled with electrospray ionization-ion trap mass spectrometry. Electrophoresis 2002, 23, 2904–2912. [Google Scholar] [CrossRef]
  51. Bakir, D.; Akdeniz, M.; Ertas, A.; Yilmaz, M.A.; Yener, I.; Firat, M.; Kolak, U. A GC–MS method validation for quantitative investigation of some chemical markers in Salvia hypargeia Fisch. & C.A. Mey. of Turkey: Enzyme inhibitory potential of ferruginol. Food Biochem. 2020, 44, e13350. [Google Scholar] [CrossRef]
  52. Bednarz, H.; Roloff, N.; Niehaus, K. Mass Spectrometry Imaging of the Spatial and Temporal Localization of Alkaloids in Nightshades. Agric. Food Chem. 2019, 67, 13470–13477. [Google Scholar] [CrossRef] [PubMed]
  53. Spinola, V.; Pinto, J.; Castilho, P.C. Identification and quantification of phenolic compounds of selected fruits from Madeira Island by HPLC-DAD-ESI-MSn and screening for their antioxidant activity. Food Chem. 2015, 173, 14–30. [Google Scholar] [CrossRef] [PubMed]
  54. Faraone, I.; Rai, D.K.; Chiummiento, L.; Fernandez, E.; Choudhary, A.; Prinzo, F.; Milella, L. Antioxidant Activity and Phytochemical Characterization of Senecio clivicolus Wedd. Crit. Mol. 2018, 23, 2497. [Google Scholar] [CrossRef] [PubMed] [Green Version]
Figure 1. Chemical profiles of the S. tuberosum L. (variety Hybrid 15/F-2-13) sample represented total ion chromatogram from MeOH-extract.
Figure 1. Chemical profiles of the S. tuberosum L. (variety Hybrid 15/F-2-13) sample represented total ion chromatogram from MeOH-extract.
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Figure 2. Venn diagram comparing the composition of isolated bioactive components in potato samples “Tuleevsky”, “Memory of Antoshkina”, “Kuznechanka’’, “Sinilga”, “Hybrid 15/F-2-13”.
Figure 2. Venn diagram comparing the composition of isolated bioactive components in potato samples “Tuleevsky”, “Memory of Antoshkina”, “Kuznechanka’’, “Sinilga”, “Hybrid 15/F-2-13”.
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Figure 3. Venn diagram comparing the composition of isolated steroid alkaloids in potato samples “Tuleevsky”, “Memory of Antoshkina”, “Kuznechanka’’, “Sinilga”, “Hybrid 15/F-2-13”.
Figure 3. Venn diagram comparing the composition of isolated steroid alkaloids in potato samples “Tuleevsky”, “Memory of Antoshkina”, “Kuznechanka’’, “Sinilga”, “Hybrid 15/F-2-13”.
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Figure 4. CID-spectrum of α-solanine from extracts of S. tuberosum (variety Tuleevsky), m/z 868.41.
Figure 4. CID-spectrum of α-solanine from extracts of S. tuberosum (variety Tuleevsky), m/z 868.41.
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Figure 5. CID-spectrum of α-chaconine from extracts of S. tuberosum (variety Tuleevsky), m/z 852.41.
Figure 5. CID-spectrum of α-chaconine from extracts of S. tuberosum (variety Tuleevsky), m/z 852.41.
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Figure 6. CID-spectrum of Dehydrochaconine [Solanidine dehydrodimer conjugated with chacotriose] from extracts of S. tuberosum (variety Tuleevsky), m/z 850.41.
Figure 6. CID-spectrum of Dehydrochaconine [Solanidine dehydrodimer conjugated with chacotriose] from extracts of S. tuberosum (variety Tuleevsky), m/z 850.41.
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Figure 7. CID-spectrum of Leptinine II from extracts of S. tuberosum (variety Tuleevsky), m/z 884.34.
Figure 7. CID-spectrum of Leptinine II from extracts of S. tuberosum (variety Tuleevsky), m/z 884.34.
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Table 1. The description of potato varieties from Siberian Federal Scientific Centre of Agrobiotechnology.
Table 1. The description of potato varieties from Siberian Federal Scientific Centre of Agrobiotechnology.
NoVarietyVariety DescriptionPhotos of Varieties (Photos Taken by V. Kulikova, September 2021)
1TuleevskyMid-season, table use. Large white corolla. The tubers are elongated, the peel and flesh are yellow, the eyes are small. Resistant to the causative agent of potato cancer, moderately susceptible to late blight on tops and tubers, relatively resistant to common scab, Alternaria. The value of the variety is a high stable yield, excellent taste, resistance to viral diseases, and a long dormant period;Agriculture 13 00758 i001
2Hybrid 17-5/6-11The corolla is white. The tubers are oval, the peel and pulp are white, the eyes are small. Resistant relatively to late blight, common scab, rhizoctoniosis. Consumer qualities are high, taste is good.Agriculture 13 00758 i002
3KuznechankaVariety Kuznechanka: medium early, universal purpose. Corolla red-violet. The tubers are rounded, the skin is smooth red, the flesh is creamy, the eyes are small. The plant is multituberous. Taste and consumer qualities are good. High yield. Resistant to cancer, relatively resistant to late blight, common scab. The value of the variety is suitable for processing into crispy potatoes, high quality starch.Agriculture 13 00758 i003
4Memory of AntoshkinaVariety Memory of Antoshkina of early ripening, for table use. The corolla is white, medium in size. The tubers are oval-round, the peel is yellow mesh, the flesh is light yellow, the eyes are small. Resistant to cancer and golden potato nematode, medium resistance to late blight, relative to Alternaria, Fusarium wilt, common scab and rhizoctoniosis. The taste qualities are excellent. The value of the variety is a high early harvestAgriculture 13 00758 i004
5TomichkaVariety Tomichka of early ripening. The color of the corolla is light purple with a white tip. The tubers are round-oval, the skin is yellow, the flesh is yellow, the eyes are very small. The variety is resistant to potato cancer and golden potato nematode, relatively resistant to late blight, common scab, rhizoctoniosis, wrinkled mosaic, striped mosaic, leaf curl. Taste and consumer qualities are goodAgriculture 13 00758 i005
6Hybrid 15/F-2-13Violet corolla. The tuber is elongated-oval, the skin and flesh are purple. Susceptible to the causative agent of potato cancer and golden potato nematode, relatively resistant to viral and fungal diseases, to common scab, rhizoctoniosis and alternariosis. It is recommended for diet food, for salads both fresh and boiled.Agriculture 13 00758 i006
7SinilgaVariety Sinilga medium-early table appointment. Violet corolla. The tuber is elongated-oval, the skin and flesh are purple. Susceptible to the causative agent of potato cancer and golden potato nematode, relatively resistant to viral and fungal diseases, to common scab, rhizoctoniosis and alternariosis. It is recommended for diet food, for salads both fresh and boiled.Agriculture 13 00758 i007
Table 2. The detailed interpretation of the identified bioactive compounds in potato varieties.
Table 2. The detailed interpretation of the identified bioactive compounds in potato varieties.
ItemOcc.Present in
Alpha-chaconine;5 Tuleevsky, Memory of Atoshkina, Kuznechanka, Sinilga, Hybrid 15/F-2-13
Beta-chaconine;5 Tuleevsky, Memory of Atoshkina, Kuznechanka, Sinilga, Hybrid 15/F-2-13
Shikimic acid;5 Tuleevsky, Memory of Atoshkina, Kuznechanka, Sinilga, Hybrid 15/F-2-13
Solanidine;5 Tuleevsky, Memory of Atoshkina, Kuznechanka, Sinilga, Hybrid 15/F-2-13
Alpha-solanine;4 Tuleevsky, Kuznechanka, Sinilga, Hybrid 15/F-2-13
Epiafzelechin;4 Tuleevsky, Memory of Atoshkina, Sinilga, Hybrid 15/F-2-13
L-Tryptophan;4 Tuleevsky, Memory of Antoshkina, Kuznechanka, Sinilga
N-feruloylputrescine;4 Tuleevsky, Memory of Antoshkina, Kuznechanka, Sinilga
Solanidenol chacotriose;4 Tuleevsky, Memory of Antoshkina, Kuznechanka, Sinilga
Citric acid;3 Memory of Antoshkina, Sinilga, Hybrid 15/F-2-13
Dehydrochaconine;3 Tuleevsky, Memory of Antoshkina, Sinilga
Leptinine II;3Tuleevsky, Sinilga, Hybrid 15/F-2-13
Quercetin glucuronide sulfate;3 Tuleevsky, Memory of Antoshkina, Sinilga
5,6-Dihydroxy-7,8,3′ 4′-tetramethoxyflavone2Memory of Antoshkina, Sinilga
Catechin;2Memory of Antoshkina, Sinilga
Epoxyoctadecane-dioic acid;2Tuleevsky, Memory of Antoshkina
Ferulic acid;2Tuleevsky, Sinilga
Hydroxyphenyllactic acid;2Kuznechanka, Sinilga
Kaempferol;2Kuznechanka, Sinilga
L-Pyroglutamic acid;2Tuleevsky, Sinilga
Leptinine I;2Kuznechanka, Sinilga
Myricetin;2Tuleevsky, Kuznechanka
Myristoleic acid;2Tuleevsky, Kuznechanka
N-feruloyloctopamine;2Kuznechanka, Hybrid 15/F-2-13
Quercetin;2Tuleevsky, Kuznechanka
Solanidadiene solatriose;2Sinilga, Hybrid 15/F-2-13
Unknown glycoalkaloid 1;2Tuleevsky, Kuznechanka
Unknown glycoalkaloid 3;2Memory of Antoshkina, Kuznechanka
Unknown glycoalkaloid 6;2Memory of Antoshkina, Sinilga
Table 3. Detailed interpretation of the identified steroidal alkaloids in potato varieties.
Table 3. Detailed interpretation of the identified steroidal alkaloids in potato varieties.
ItemOcc.Present in
Alpha-chaconine;5Tuleevsky, Memory of Antoshkina, Kuznechanka, Sinilga, Hybrid-15/F-2-13
Beta-chaconine;5Tuleevsky, Memory of Antoshkina, Kuznechanka, Sinilga, Hybrid-15/F-2-13
Solanidine;5Tuleevsky, Memory of Antoshkina, Kuznechanka, Sinilga, Hybrid-15/F-2-13
Alpha-solanine;4Tuleevsky, Kuznechanka, Sinilga, Hybrid-15/F-2-13
Solanidenol chacotriose;4Tuleevsky, Memory of Antoshkina, Kuznechanka, Sinilga
Dehydrochaconine;3Tuleevsky, Memory of Antoshkina, Sinilga
Leptinine II;3Tuleevsky, Sinilga, Hybrid-15/F-2-13
Leptinine I;2Kuznechanka, Sinilga
Solanidadiene solatriose;2Sinilga, Hybrid-15/F-2-13
Unknown glycoalkaloid 1;2Tuleevsky, Kuznechanka
Unknown glycoalkaloid 3;2Memory of Antoshkina, Kuznechanka
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Razgonova, M.; Kulikova, V.; Khodaeva, V.; Bolotova, L.; Baigarashev, T.; Plotnikova, N.; Zakharenko, A.; Golokhvast, K. Simultaneous Determination of Steroidal Alkaloids and Polyphenol Group from Eight Varieties of Siberian Solanum tuberosum L. through Tandem Mass Spectrometry. Agriculture 2023, 13, 758. https://doi.org/10.3390/agriculture13040758

AMA Style

Razgonova M, Kulikova V, Khodaeva V, Bolotova L, Baigarashev T, Plotnikova N, Zakharenko A, Golokhvast K. Simultaneous Determination of Steroidal Alkaloids and Polyphenol Group from Eight Varieties of Siberian Solanum tuberosum L. through Tandem Mass Spectrometry. Agriculture. 2023; 13(4):758. https://doi.org/10.3390/agriculture13040758

Chicago/Turabian Style

Razgonova, Mayya, Valentina Kulikova, Vera Khodaeva, Lyudmila Bolotova, Timur Baigarashev, Nina Plotnikova, Alexander Zakharenko, and Kirill Golokhvast. 2023. "Simultaneous Determination of Steroidal Alkaloids and Polyphenol Group from Eight Varieties of Siberian Solanum tuberosum L. through Tandem Mass Spectrometry" Agriculture 13, no. 4: 758. https://doi.org/10.3390/agriculture13040758

APA Style

Razgonova, M., Kulikova, V., Khodaeva, V., Bolotova, L., Baigarashev, T., Plotnikova, N., Zakharenko, A., & Golokhvast, K. (2023). Simultaneous Determination of Steroidal Alkaloids and Polyphenol Group from Eight Varieties of Siberian Solanum tuberosum L. through Tandem Mass Spectrometry. Agriculture, 13(4), 758. https://doi.org/10.3390/agriculture13040758

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