The Global Metabolome Profiles of Four Varieties of Lonicera caerulea, Established via Tandem Mass Spectrometry

Razgonova, Mayya P.; Navaz, Muhammad Amjad; Sabitov, Andrey S.; Zinchenko, Yulia N.; Rusakova, Elena A.; Petrusha, Elena N.; Golokhvast, Kirill S.; Tikhonova, Nadezhda G.

doi:10.3390/horticulturae9111188

Open AccessArticle

The Global Metabolome Profiles of Four Varieties of Lonicera caerulea, Established via Tandem Mass Spectrometry

by

Mayya P. Razgonova

^1,2,*

,

Muhammad Amjad Navaz

^3,4

,

Andrey S. Sabitov

¹,

Yulia N. Zinchenko

¹

,

Elena A. Rusakova

⁵,

Elena N. Petrusha

⁵,

Kirill S. Golokhvast

⁶

and

Nadezhda G. Tikhonova

¹

N.I. Vavilov All-Russian Institute of Plant Genetic Resources, B. Morskaya 42-44, 190000 Saint-Petersburg, Russia

²

Advanced Engineering School, Institute of Biotechnology, Bioengineering and Food Systems, Far Eastern Federal University, Fr. Russian, pos. Ajax, 10, 690922 Vladivostok, Russia

³

Advanced Engineering School (Agrobiotek), Tomsk State University, Lenin Ave, 36, 634050 Tomsk, Russia

⁴

Centre of Research in the Field of Materials and Technologies, Tomsk State University, Lenin Ave, 36, 634050 Tomsk, Russia

⁵

FSBSI Kamchatsky Scientific Research Institute of Agriculture, Centralnaya, 4, 684033 Sosnovka, Russia

⁶

Siberian Federal Scientific Center of Agrobiotechnology RAS, Centralnaya, 2b, Presidium, 633501 Krasnoobsk, Russia

^*

Author to whom correspondence should be addressed.

Horticulturae 2023, 9(11), 1188; https://doi.org/10.3390/horticulturae9111188

Submission received: 22 August 2023 / Revised: 4 October 2023 / Accepted: 26 October 2023 / Published: 30 October 2023

(This article belongs to the Special Issue Plant Extracts – Importance in Sustainable Horticulture)

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Abstract

:

Blue honeysuckle (Lonicera caerulea L.) bears dietary fruits that are rich in bioactive compounds. However, information on the metabolome profiles of honeysuckle varieties grown in Russia is limited. In this study, we employed tandem mass spectrometry to study the metabolome profiles of four L. caerulea varieties (Volhova, Tomichka, Goluboe vereteno, and Amfora) grown in two geographical locations in Russia, i.e., the Russian Far East and St. Petersburg. We observed that the metabolome profiles of the four varieties grown in two locations differ significantly, particularly in the polyphenol’s other compound classes. We were able to identify 122 bioactive compounds in extracts from honeysuckle berries, 75 compounds from the polyphenol group and 47 compounds from other chemical groups. Thirty chemical constituents from the polyphenol group (flavones jaceosidin, cirsiliol, sophoraisoflavone A, chrysoeriol-O-hexoside, flavonols dimethylquercetin-3-O-dehexoside, rhamnocitrin, rhamnetin II, stilbenes pinosylvin, resveratrol, dihydroresveratrol, etc.) and twenty-seven from other chemical groups were identified. The largest number of unique polyphenols is characteristic of the variety Tomichka, the selection of the regional state unitary enterprise “Bakcharskoye”, from the free pollination of L. caerulea, originating in the Primorsky Territory of Russia (L. caerulea subspecies Turczaninow). This genotype has the highest number of similar unique polyphenols, regardless of where it was grown. Blue honeysuckle genotypes originating from Primorsky Krai in Russia can be used in various breeding programs in order to improve and enrich the biochemical composition of fruits. It should also be noted that, regardless of the place of cultivation, the total amount of unique polyphenols remains quite large. Attention should be paid to the Volhova honeysuckle variety, obtained through gamma irradiation of the Pavlovskaya variety (Kamchatka ecotype). This sample is characterized by a stable composition of biologically active substances, regardless of the growing area. These data could support future research on the production of a variety of pharmaceutical products containing ultrapure extracts of L. caerulea.

Keywords:

Lonicera caerulea; metabolome profile; tandem mass spectrometry; polyphenols; blue honeysuckle

1. Introduction

Blue honeysuckle (Lonicera caerulea L.) is a young small-fruit crop belonging to the Caprifoliaceae family. The interest in L. caerulea has increased due to its early ripening and, especially in the northern regions, due to its high winter hardiness, palatability, and rich biochemical composition of berries. It is grown in China, Canada, Poland, and other European countries. In Russia, it was grown on >700 hectares (https://haskapru.com/, e.g., accessed on 1 August 2022) in 2022. A significant part of the acreage is occupied by varieties that belong to the first generation selected from wild flora, indicating a huge potential in honeysuckle breeding.

Honeysuckle berries contain a wide variety of polyphenolic compounds, including bioflavonoids, hydroxycinnamic acids, flavonols, polyphenols, anthocyanins, and compounds that are rare for berry crops such as iridoids, the high content of which has a positive effect on human health. The content of iridoids is mainly represented by derivatives of loganic acid and loganin and ranges from 78.0 to 406.4 mg/100 g depending on the genotype [1,2]. Scientific studies report the antimicrobial and anti-inflammatory activity of iridoids [3]. Fresh honeysuckle fruits are classified as dietary fruits, due to the high content of biologically active substances [4,5]. L. caerulea berries are characterized by a high content of dry matter (up to 19%) and sugars (up to 12.5%, represented by sucrose, glucose, and fructose, the content of the latter being higher than 55%). The combined action of ascorbic acid (up to 150 mg/100 g) and P-active substances (total up to 2500 mg/100 g) have a positive effect on the human body [6]. The beneficial effect of L. caerulea berries on reducing the negative effects of ultraviolet radiation and diabetes mellitus, as well as neurodegenerative diseases and atherosclerosis, has been reported [7,8]. The positive effect on human health is associated with a high content of polyphenolic compounds, primarily anthocyanins (anthocyanins, proanthocyanins, and iridoids). The content of these bioactive constituents depends on the variety and genotype [9]. The content of polyphenols is also influenced by the time of harvest, as well as solar radiation and temperature. An earlier study indicated that the geographical location can influence the accumulation of primary and secondary metabolites in the blue honeysuckle L. caerulea subsp. edulis (Turcz. ex Herder) Hultén [10]. However, such information is not available for honeysuckle varieties grown in different territories of Russia. Therefore, the determination of the composition and quantity of metabolome profiles of honeysuckle varieties from Russia will reveal a wealth of knowledge for future health-related studies and breeding strategies.

Plant metabolomic strategies are based on two analytical technologies, namely, MS and nuclear magnetic resonance (NMR). However, NMR-based approaches are inferior to MS-based approaches due to it being able to separate fewer compounds, given its relatively lower sensitivity [11]. Despite continuous progress in MS technology, the study of the plant metabolome is a major challenge in plant metabolomics research. Currently, only a few thousand metabolites (>14,000) can be measured, while in the plant kingdom, 200,000 to 1 million metabolites are expected, and its analysis is concentration dependent. However, it is difficult to predict the full extent of the complete plant metabolome, because, unlike the transcriptome and proteome, it is genome-independent [12,13]. Moreover, due to the wide dynamic range of plant metabolite concentrations and high chemical diversity, no single analytical technology can cover the entire plant metabolome, so various extraction methods and a combination of additional analytical technologies are often used for analysis.

We used tandem mass spectrometry to conduct a metabolomic study involving a detailed analysis of L. caerulea’s bioactive compounds.

2. Materials and Methods

2.1. Materials

The object of this study was the berries of the four L. caerulea varieties (Volhova, Tomichka, Goluboe vereteno, and Amfora), harvested from plantations by N.I. Vavilov All-Russian Institute of Plant Genetic Resources, Primorsky Territory (43°6′34″ N, 131°52′41″ E) and St.-Petersburg (Pushkin, 59°42′51″ N, 30°23′47″ E) (Figure 1).

The varieties of L. caerulea presented in this article were obtained from the following scientific departments: variety “Goluboe vereteno” from the M.A. Lisavenko Scientific-Research Institute of Horticulture of Siberia; variety “Tomichka” from the Regional State Unitary Enterprise “Bakcharskoye”; variety “Amfora” (also known as variety “Roxana” (Kamchatka)) from free pollination; and variety “Volhova” from the N.I. Vavilov All-Russian Institute of Plant Genetic Resources.

The berries were harvested at the end of July 2022 from two-year-old plants. All samples morphologically corresponded to the pharmacopoeial standards of the State Pharmacopoeia of the Russian Federation [14].

2.2. Chemicals and Reagents

HPLC-grade acetonitrile was purchased from Fisher Scientific (Southborough, UK), MS-grade formic acid was from Sigma-Aldrich (Steinheim, Germany). Ultrapure water was prepared from a SIEMENS ULTRA clear (SIEMENS water technologies, Günzburg, Germany), and all other chemicals were analytical grade.

2.3. Extraction

Fractional maceration technique was applied to obtain highly concentrated extracts [15]. Aqueous ethanol (80%) was selected for the extraction process due to its high efficiency in extracting polyphenol compounds and compounds of other chemical groups from plant samples. From 500 g of the berries, 50 g of berries of each variety were randomly selected for maceration. The total amount of the extractant (aqueous ethanol) was divided into 3 parts, and the plant parts were consistently infused with the first, second, and third parts. The infusion of each part of the extractant lasted seven days at room temperature. Three replicates of the extraction process were carried out on each plant sample. The extract was filtered through Whatman filter paper. The filtrates were diluted with acetonitrile to final working concentration for analysis.

2.4. Liquid Chromatography

The HPLC analyses were performed on a HPLC instrument of 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). The gradient elution program with two mobile phases (A, deionized water; B, acetonitrile with formic acid 0.1% (v/v)) was as follows: 0–2 min, 0% B; 2–50 min, 0–100% B; control washing 50–60 min 100% B. 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 was 0.25 mL min⁻¹. The injection volume was 10 μL. Additionally, liquid chromatography was combined with a mass spectrometric ion trap to identify compounds.

2.5. Mass Spectrometry

Mass spectrometry analysis was performed on an ion trap amaZon SL (BRUKER DALTONIKS, Bremen, Germany), equipped with an ESI source in positive and negative ion modes. 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, and collision energy: 60 eV. An ion trap was used in the scan range of m/z 100–1.700 for MS and MS/MS. The chemical constituents were characterized by their retention behavior, molecular formula, MS/MS spectral patterns, and the home-library database built by the Group of Biotechnology, Bioengineering and Food Systems at the Far-Eastern Federal University (Russia), based on data from other spectroscopic techniques, such as nuclear magnetic resonance, ultraviolet spectroscopy, and MS, as well as data from the literature that is continually updated and revised. The capture rate was one spectrum/s for MS and two spectrum/s for MS/MS. Data collection was controlled by Windows software for BRUKER DALTONIKS. All experiments were repeated three times. A four-stage ion separation mode (MS/MS mode) was implemented.

3. Results and Discussion

The HPLC conditions were optimized to obtain maximal resolution and signal within a minimal run time. Various chromatographic conditions such as the mobile phase composition, injection volume, flow rate, column temperature, and gradient program were studied and optimized for the separation of polyphenol compounds. Different mobile phase compositions (ethanol–water, ethanol-0.1% (v/v) formic acid aqueous solution, acetonitrile–water, and acetonitrile –0.1% (v/v) formic acid aqueous solution) were tested in the gradient program at a 0.25 mL/flow rate. A mobile phase composed of 0.1% (v/v) formic acid aqueous solution (A) and acetonitrile (B) at a 0.25 mL/min flow rate and 50 °C column temperature was found optimal for resolution of the maximum number of peaks in extracts of L. caerulea within 60 min.

The purpose of this study was to establish, as fully as possible, the composition of secondary metabolites in L. caerulea extracts from different geographic regions of origin and to further compare these compositions of chemical compounds both across the presented cultivars and across different geographic origins. Chemical compounds were characterized by their retention behavior, molecular formula, MS/MS spectral patterns, and the home-library database built by the Group of Biotechnology, Bioengineering and Food Systems at the Far-Eastern Federal University (Russia), which is based on data from other spectroscopic techniques, such as nuclear magnetic resonance, ultraviolet spectroscopy, and MS, as well as data from the literature and is continually updated and revised.

We were able to identify 122 chemical compounds from extracts of L. caerulea: 75 chemical compounds from the polyphenol group and 47 chemical compounds from other chemical groups. The chemical structures of some of the identified polyphenols are shown in Figure 2. All the identified polyphenols and other compounds, along with molecular formulas and MS/MS data for L. caerulea, are summarized in Table 1. Polyphenols are represented by the following chemical groups: flavones, flavonols, flavan-3-ols, flavanones, phenolic acids, anthocyanidins, lignans, and coumarins. For the first time, thirty-two compounds from the polyphenol group and twenty-seven compounds from other chemical groups were identified in berries of L. caerulea. These are flavones, such as formononetin, acacetin, rhamnocitrin, 5,7-dimethoxyluteolin, and eupatolitin-di-O-hexoside; flavonols, such as herbacetin, rhamnetin I, isorhamnetin, padmatin, myricetin-3-O-glucuronide, rhamnetin-di-O-hexoside, myricetin-O-galloyl-hexoside; flavan-3-ols (epi)-galoocatechin-3-gallate; (epi)-afzelechin derivative; flavanone hemiphloin; lignans, such as secoisolariciresinol, dimethyl-secoisolariciresinol, coumarin fraxin; etc. The chemical compounds from other chemical groups are benzofuran loliolide; aminoalkylindole 5-methoxydimethyltryptamine; sesquiterpenoid caryophyllene oxide; aporphine alkaloid anonaine; etc.

The new tentatively identified polyphenols belonged to six classes, including eleven flavones, three flavonols, two flavan-3-ols, two flavanone, seven phenolic acids and their conjugates, four stilbenes, and two coumarins (Table 1). The new tentatively identified compounds from other chemical groups belonged to 12 classes, including 1 L-alpha-amino acid, 1 cyclohexanecarboxylic acid, 3 alpha, omega dicarboxylic acid, 1 pentahydroxy hexanoic acid, 1 benzofuran, 1 sesquiterpenoid and 1 sesquiterpene lactone, 1 hydroxytetradecanoic acid, 2 omega-3 fatty acids, 1 aporphine alkaloid, 1 oxylipin, 3 iridoids, 1 sterol, and others. An approximate comparison of the chemical constituents identified in the L. caerulea varieties obtained from two different regions is shown in Appendix A, Table A1.

3.1. Flavones

3.1.1. 7-Hydroxy(iso)flavones

We identified flavone calycosin-7-O-β-D-glucoside-6″-O-malonate (compound 13 in Table 1) in extracts from the berries of L. caerulea. The CID spectrum (collision-induced spectrum), in positive ion modes, of flavone calycosin-7-O-β-D-glucoside-6″-O-malonate from the berries of L. caerulea is shown in Figure 3.

The [M+H]+ ion produced two fragment ions with m/z 287.09 and m/z 215.33 (Figure 3). The fragment ion with m/z 287.09 produced two characteristic daughter ions with m/z 273.02 and m/z 236.16. However, this flavone has already been reported from Astragali Radix [29,30]. Calycosin-7-O-β-D-glucoside-6″-O-malonate (flavonoid glycoside) is biosynthesized by the conversion of flavonoid glycoside malonate, as shown in Figure 4 [99,100,101].

3.1.2. Dihydroxyflavones

The flavones acacetin 8-C-glucoside malonylated (compound 12 in Table 1) and chrysin derivative (compound 14 in Table 1) have already been characterized as components of Mexican lupine species [31] and Embelia [32]. These flavones were tentatively identified in extracts from the berries of L. caerulea. The CID spectrum, in positive ion modes, of acacetin 8-C-glucoside malonylated from extracts from the berries of L. caerulea is shown in Figure 5.

The [M+H]⁺ ion produced three fragment ions with m/z 471.18, m/z 411.05, and m/z 315.08 (Figure 5). The fragment ion with m/z 471.18 produced two characteristic daughter ions with m/z 424.08 and m/z 281.11. The fragment ion with m/z 424.08 produced two characteristic ions with m/z 305.02 and m/z 263.46. The acacetin 8-C-glucoside has been previously reported in the extract from Mexican lupine species [31].

3.1.3. Trihydroxyflavones

The flavones apigenin (compound 1 in Table 1), trihydroxy(iso)flavone (compound 2 in Table 1), luteolin 7-O-glucoside (compound 9 in Table 1), chrysoeriol O-hexoside (compound 10 in Table 1), C-hexosyl-apigenin O-rhamnoside (compound 15 in Table 1), lonicerin (compound 16 in Table 1), luteolin 7-O-(6-O-arabinosyl-glucoside) (compound 17 in Table 1), rhamnocitrin (compound 20 in Table 1), and kaempferol 3-O-rutinoside (compound 27 in Table 1) have already been characterized as a components of Phlomis (Lamiaceae) [16], Olive oil [17], Mentha [18,41], L. henryi [19], Propolis [20], V. macrocarpon [25], L. japonica [26], T. aestivum L. [27], Ipomoea batatas [28], Astragali radix [29], Exocarpium Citri Grandis [34], Strawberry [50], R. meyeri [37], and Spondias purpurea [44]. The trihydroxyflavones were tentatively identified in extracts from the berries of L. caerulea. The CID spectrum, in positive ion modes, of Lonicerin from extracts from the berries of L. caerulea is shown in Figure 6 and Figure 7.

The [M+H]⁺ ion produced two fragment ions with m/z 449.11 and m/z 287.11 (Figure 7). The fragment ion with m/z 449.11 produced one characteristic daughter ion with m/z 287.12. The fragment ion with m/z 287.12 produced two characteristic daughter ions with m/z 287.08 and m/z 153.14. The Lonicerin was identified, using the bibliography, in extracts from L. japonica [26] and Exocarpium Citri Grandis [34].

3.1.4. Tetrahydroxyflavones

The flavonols kaempferol (compound 18 in Table 1), dihydrokaempferol (compound 19 in Table 1), rhamnetin II (compound 23 in Table 1), isorhamnetin (compound 24 in Table 1), and rutin (compound 29 in Table 1) have already been characterized as components of L. henryi [19], L. japonica [26], P. sibirica [35], Rhus coriaria [36], R. meyeri [37], Andean blueberry [38], Camellia kucha [39], Strawberry [40], Spondias purpurea [44], R. occidentalis [47], and R. magellanicum [52]. These tetrahydroxyflavones were tentatively identified in extracts from the berries of L. caerulea. The CID spectrum, in positive ion modes, of Rhamnetin II from the berries of L. caerulea is shown in Figure 8.

The [M–H]⁻ ion produced one fragment ion with m/z 300.11 (Figure 8). The fragment ion with m/z 300.11 produced three characteristic daughter ions with m/z 271.15, m/z 227.19, and m/z 151.23. The fragment ion with m/z 271.15 produced one characteristic daughter ion with m/z 227.16. The rhamnetin II was identified, using the bibliography, in extracts from P. sibirica [35], Rhus coriaria L. [36], and Spondias purpurea [44].

3.1.5. Pentahydroxyflavones

The flavonols quercetin (compound 21 in Table 1), herbacetin (compound 22 in Table 1), and pentahydroxy dimethoxyflavone (compound 7 in Table 1) have already been characterized as components of Propolis [20], G. linguiforme [22], Ocimum [23], V. macrocarpon [25,42], Rhus coriaria [36], R. meyeri [37], and Rhodiola rosea [43]. These pentahydroxyflavones were tentatively identified in extracts from the berries of L. caerulea. The CID spectrum, in positive ion modes, of the herbacetin from berries of L. caerulea is shown in Figure 9.

The [M+H]⁺ ion produced two fragment ions with m/z 203.13 and m/z 257.10 (Figure 9). The fragment ion with m/z 203.13 produced two characteristic daughter ions with m/z 157.15 and m/z 175.10. The fragment ion with m/z 175.10 produced one characteristic daughter ion with m/z 157.11. The herbacetin was identified, using the bibliography, in extracts from Ocimum [23] and Rhodiola rosea [43].

3.2. Phenolic Acids

3.2.1. Hydroxycinnamic Acids and Cinnamate Esters

The caffeic acid (compound 50 in Table 1), ferulic acid (compound 52 in Table 1), hydroxyferulic acid (compound 55 in Table 1), sinapic acid (compound 56 in Table 1), chlorogenic acid (compound 60 in Table 1), 3-O-hydroxydihydrocaffeoylquinic acid (compound 61 in Table 1), 3,4-O-dicaffeoylquinic acid (compound 64 in Table 1), 4,5-O-dicaffeoylquinic acid (compound 65 in Table 1), and dicaffeoylferuoylquinic acid (compound 67 in Table 1) have already been characterized as components of L. henryi [19], V. macrocarpon [25], L. japonica [26], R. meyeri [37], Andean blueberry [38], Strawberry [40], R. occidentalis [47], V. myrtillus [49], R. nigrum [67], and Stevia rebaudiana [72]. These acids were tentatively identified in the extracts from berries of L. caerulea. The chemical structure analysis of chlorogenic acid is shown in Figure 10.

The CID spectrum, in positive ion modes, of chlorogenic acid from the berries of L. caerulea is shown in Figure 11.

The [M+H]⁺ ion produced one fragment ion with m/z 203.13 (Figure 11). The fragment ion with m/z 163.16 produced one characteristic daughter ion with m/z 145.16. The chlorogenic acid was tentatively identified, using the bibliography, in extracts from L. henryi [19], L. japonica [26], V. macrocarpon [25,42], Andean blueberry [38], Strawberry [40], Spondias purpurea [44], cranberry [48], V. myrtillus [49], and R. magellanicum [52].

3.2.2. Hydroxybenzoic and Methylbenzoic Acids

The hydroxy methoxy dimethylbenzoic acid (compound 53 in Table 1), 2,3,4,5,6-pentahydroxybenzoic acid (compound 54 in Table 1), methylgallic acid (compound 51 in Table 1), 2,4,6-trihydroxy-3,5-dimethoxybenzoic acid (compound 57 in Table 1), ellagic acid (compound 58 in Table 1), and 6-hydroxy-3-methoxy-4-O-β-D-glucopyranoside (compound 59 in Table 1) have already been characterized as components of F. herrerae, F. glaucescens [22], Rhus coriaria [36], R. occidentalis [47], Papaya [50], Eucalyptus [66], Jatropha [68], and Actinidia [70]. These acids were tentatively identified in the extracts from berries of L. caerulea. The CID spectrum, in positive ion modes, of the methylgallic acid from berries of L. caerulea is shown in Figure 12.

The [M+H]⁺ ion produced one fragment ion with m/z 139.18 (Figure 12). The fragment ion with m/z 139.18 produced one characteristic daughter ion with m/z 111.2. The methylgallic acid was identified, using the bibliography, in extracts from Rhus coriaria [36]; Papaya [50]; and Eucalyptus [66].

A Vienna diagram showing the similarities and differences in the presence of various chemical groups in the Far Eastern L. caerulea varieties (Amfora; Tomichka; Goluboe vereteno; Volhova) is shown in Figure 13.

Table 2 below shows the distribution of the chemical groups in L. caerulea samples from the Far East presented in this study.

From Table 2, it follows that there are several compounds commonly present in the four different samples. Also, the following chemical compounds have a fairly significant repeatability in varieties from the Far East: hydroxyferulic acid; quercetin; hydroxy dodecanoic acid; rhamnocitrin; jaceosidin; pheophytin A; sebacic acid; fructose-leucine; myristoleic acid; sespendole; fraxetin; stearidonic acid; coumaroyl shiikimic acid; isorhamnetin 3-O-(6″-O-rhamnosyl-hexoside); p-coumaroyl malonyldihexose; isorhamnetin; ellagic acid; resveratrol; methylgallic acid; delphinidin 3-O-glucoside; hydroxy methoxy dimethylbenzoic acid; quinic acid; and (epi)-afzelechin derivative.

A Vienna diagram showing the similarities and differences in the presence of various chemical groups in the Saint-Petersburg L. caerulea varieties (Amfora; Tomichka; Goluboe vereteno; Volhova) is shown in Figure 14.

Table 3 below shows the distribution of the chemical groups in L. caerulea samples from the Saint-Petersburg varieties presented in the study.

From Table 3, it follows that in all four different samples, a certain number of chemical compounds is exactly repeated, and these are the following constituents: Petunidin; Sebacic acid; Apigenin; Pentahydroxy dimethoxyflavone; (Epi)-afzelechin derivative; L-Histidine; Anonaine; and Myristoleic acid.

Also, the following chemical compounds have a fairly significant repeatability in varieties from Saint-Petersburg: isorhamnetin; ellagic acid; caffeic acid isoprenyl ester; quercetin; herbacetin; (epi)-afzelechin; (epi)-catechin; 7-(β-D-glucopyranoside/galactopyranoside)-2-oxo-2H-1-benzopyran-4-acetic acid; shikimic acid; cirsiliol; methylgallic acid; hydroxy dodecanoic acid; dihydroxy-tetramethoxy(iso)flavone; p-coumaroyl monotropein hexoside; resveratrol; fructose-leucine; quinic acid; artemisinin C; 5,6,4′-trihydroxy-7,8-dimethoxyflavone; 2,3,4,5,6-pentahydroxybenzoic acid; sespendole; linolenic acid; gallocatechin; 6-trihydroxy-3,5-dimethoxybenzoic acid; 4-dihydroxy-3-methoxy-benzenepropanoic acid; 8,9,10-penthahydroxydibenzo [b d]pyran-6-one; citric acid; and hydroxy methoxydimethylbenzoic acid.

Below are Venn diagrams (Figure 15A,B, Figure 16A,B, Figure 17A,B, and Figure 18A,B showing the similarities and differences in the general complex of isolated chemical compounds from L. caerulea extracts (Amfora, Tomichka, Goluboe vereteno, and Volhova varieties) and specifically in the complex of polyphenolic compounds. Accordingly, the chemical data on secondary metabolites obtained from plantations at widely separated geographic locations are compared.

A general analysis of the degree of similarity and divergence, in particular in terms of the polyphenolic component, with a greater degree of probability, shows approximately the same percentage of occurrence of both polyphenolic compounds and compounds of other chemical classes in the same L. caerulea varieties grown at two geographical points far apart from each other. These diagrams allow us to reach a preliminary conclusion about the large geographical variability in terms of secondary metabolites of the same variety of the presented L. caerulea.

4. Conclusions

In summary, the present study described a systematic comparative screening of phenolics and other chemical groups in L. caerulea extracts using a HPLC-ESI—ion trap. A total of 122 compounds, including 75 polyphenols and 47 chemical constituents from other chemical groups were identified from L. caerulea extracts of four blue honeysuckle species. They were characterized by their retention behavior, molecular formula, MS/MS spectral patterns, and using the home-library database built by the Group of Biotechnology, Bioengineering and Food Systems at the Far-Eastern Federal University (Russia), which is based on data from other spectroscopic techniques, such as nuclear magnetic resonance, ultraviolet spectroscopy, and MS, as well as data from the literature, and is continually updated and revised. For the first time, thirty chemical constituents from the polyphenol group (flavones Jaceosidin, Cirsiliol, Sophoraisoflavone A, Chrysoeriol-O-hexoside, stilbenes Pinosylvin, Resveratrol, Dihydroresveratrol, etc.) and twenty-seven chemical constituents from other chemical groups were identified in the berries of L. caerulea.

The largest number of unique polyphenols is found in the variety Tomichka, the selection of the regional state unitary enterprise “Bakcharskoye”, obtained from the free pollination of L. caerulea and originating from the Primorsky Territory of Russia (L. caerulea subspecies Turczaninow). This genotype has the highest number of similar unique polyphenols, regardless of where it was grown. Blue honeysuckle genotypes originating from Primorsky Krai in Russia can be used in various breeding programs in order to improve and enrich the biochemical composition of fruits. It should also be noted that, regardless of the place of cultivation, the total amount of unique polyphenols remains quite significant. Attention should be paid to the Volhova honeysuckle variety, obtained through gamma irradiation of the Pavlovskaya variety (Kamchatka ecotype). This sample is characterized by a stable composition of biologically active substances, regardless of the growing area. These data could support future research on the production of a variety of pharmaceutical products containing ultrapure extracts of L. caerulea. The richness of various biologically active compounds, including compounds of the polyphenol group and compounds of other chemical groups (oxylipins, Omega- fatty acids, sterols, iridoids, etc.), provides great opportunities for the design of new nutritional and dietary supplements based on supercritical extracts from the leaves, stems, and berries of L. caerulea.

Author Contributions

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

Funding

This study was carried out at the N.I. Vavilov All-Russian Institute of Plant Genetic Resources at the expense of the Russian Science Foundation Grant No. 23-74-00044, https://rscf.ru/en/project/23-74-00044/.

Data Availability Statement

Not applicable.

Acknowledgments

The work was supported financially by the Russian Ministry of Education and Science (Agreement No. 23-74-00044 dated 13 April 2023).

Conflicts of Interest

The authors declare no conflict of interest.

Appendix A

Table A1. Approximate comparison of chemical constituents identified in L. caerulea varieties obtained from two different regions.

Class of Compounds	Identification	Amfora Far East	Amfora SPb	Tomichka Far East	Tomichka SPb	Goluboe Far East	Goluboe SPb	Volhova Far East	Volnova SPb
Flavone	Apigenin
Flavone	Trihydroxy(iso)flavone
Flavone	5,6,4′-Trihydroxy-7,8-dimethoxyflavone
Flavone	Jaceosidin
Flavone	Cirsiliol
Flavone	Sophoraisoflavone A
Flavone	Pentahydroxy dimethoxyflavone
Flavone	Dihydroxy-tetramethoxy(iso)flavone
Flavone	Luteolin 7-O-glucoside
Flavone	Chrysoeriol O-hexoside
Flavone	Formononetin-7-O-glucoside-6″-O-malonate
Flavone	Acacetin 8-C-glucoside malonylated
Flavone	Calycosin-7-O-beta-D-glucoside-6″-O-malonate
Flavone	Chrysin derivative
Flavone	C-hexosyl-apigenin O-rhamnoside
Flavone	Lonicerin
Flavone	Luteolin 7-O-(6-O-arabinosyl-glucoside)
Flavonol	Kaempferol
Flavonol	Dihydrokaempferol
Flavone	Rhamnocitrin
Flavonol	Quercetin
Flavone	Herbacetin
Flavonol	Rhamnetin II
Flavonol	Isorhamnetin
Flavonol	Kaempferol-3-O-α-L-rhamnoside
Flavonol	Quercetin 3-O-glucoside
Flavonol	Kaempferol 3-O-rutinoside
Flavonol	Quercetin 3-O-pentosyl hexoside
Flavonol	Rutin
Flavonol	Isorhamnetin 3-O-(6″-O-rhamnosyl-hexoside)
Flavonol	Dimethylquercetin-3-O-dehexoside
Flavonol	Derivative of Quercetin rhamnosyl hexoside
Flavan-3-ol	Epiafzelechin
Flavan-3-ol	(Epi)-catechin
Flavan-3-ol	Gallocatechin
Flavan-3-ol	(Epi)-afzelechin derivative
Flavan-3-ol	(Epi)-catechin derivative
Flavan-3-ol	(−)-Epicatechin Gallate
Flavanone	Naringenin
Flavanone	Butin
Anthocyanin	Anthocyanidin
Anthocyanin	Petunidin
Anthocyanin	Pelargonidin-3-O-glucoside
Anthocyanin	Delphinidin 3-O-glucoside
Anthocyanin	Pelargonidin 3-O-(6-O-malonyl-β-D-glucoside)
Anthocyanin	Delphinidin 3-O-β-D-sambubioside
Anthocyanin	Delphinidin 3-O-rutinoside
Anthocyanin	Petunidin-3-rutinoside
Hydroxybenzoic acid (Phenolic acid)	Protocatechuic acid
Hydroxycinnamic acid	Caffeic acid
Methylbenzoic acid	Methylgallic acid
Trans-cinnamic acid	Ferulic acid
Phenolic acid	Hydroxy methoxy dimethylbenzoic acid
Phenolic acid	2,3,4,5,6-pentahydroxybenzoic acid
Hydroxycinnamic acid	Hydroxyferulic acid
Hydroxycinnamic acid	Sinapic acid
Phenolic acid	2,4,6-Trihydroxy-3,5-dimethoxybenzoic acid
Hydroxybenzoic acid (Phenolic acid)	Ellagic acid
Phenolic acid	6-Hydroxy-3-methoxy-4-O-β-D-glucopyranoside
Hydroxycinnamic acid	Chlorogenic acid
Hydroxycinnamic acid	3-O-Hydroxydihydrocaffeoylquinic acid
Phenolic acid	Caffeoylquinic acid derivative
Flavonoid	p-Coumaroylhexose-4-O-hexoside
Phenolic acid	3,4-O-dicaffeoylquinic acid
Phenolic acid	4,5-O-dicaffeoylquinic acid
Phenolic acid	p-Coumaroyl malonyldihexose
Phenolic acid	Dicaffeoylferuoylquinic acid
Stilbene	Pinosylvin
Stilbene	Resveratrol
Stilbene	Dihydroresveratrol
Hydroxycoumarin	Umbelliferone
Coumarin	Fraxetin
Coumarin	3,4/6,8-Dihydro-5,7-dihydroxy-2-oxo-2H-1-benzopyran-3-acetic acid
Coumarin	Umbelliferone hexoside
Coumarin	7-(β-D-Glucopyranoside/galactopyranoside)-2-oxo-2H-1-benzopyran-4-acetic acid
OTHERS
Amino acid	L-Proline
Non-proteinogenic L-alpha-amino acid	L-Pyroglutamic acid
Amino acid	L-Histidine
Amino acid	L-threanine
Amino acid	L-Arginine
Cyclohexenecarboxylic acid	Shikimic acid
Tricarboxylic acid	Citric acid
Polyhydroxycarboxylic acid	Quinic acid
Pentahydroxyhexanoic acid	Gluconic acid
Benzofuran	Loliolide
Alpha, omega dicarboxylic acid	Sebacic acid
	4-Dihydroxy-3-methoxy-benzenepropanoic acid
Sesquiterpenoid	Caryophyllene oxide
Carboxylic acid	Myristoleic acid
Pyrimidine nucleoside	Cytidine
Glycosylated pyrimidine analog	Uridine
Hydroxytetradecanoic acid	Hydroxy myristic acid
Medium-chain fatty acid	Hydroxy dodecanoic acid
	Caffeic acid isoprenyl ester
Sesquiterpene lactone	Artemisinin C
Aporphine alkaloid	Anonaine
Ribonucleoside composite of adenine (purine)	Adenosine
	3,4,8,9,10-Penthahydroxydibenzo [b,d]pyran-6-one
Omega-3-fatty acid	Stearidonic acid
Omega-3-fatty acid	Linolenic acid
Mixture of diastereomers	Fructose-leucine
Cyclohexenecarboxylic acid	Coumaroyl shiikimic acid
Oxylipin	13-Trihydroxy-Octadecenoic acid
Alpha, omega-dicarboxylic acid	Eicosatetraenedioic acid
Cyclohexenecarboxylic acid	Caffeoyl shikimic acid
Alpha, omega-dicarboxylic acid	Trihydroxy eicosatetraenoic acid
Dicarboxylic acid sugar	Caffeoyl gluconic acid
Iridoid glucoside	Sweroside
Cyclopentapyran	Loganin acid
	7-(β-D-Galactopyranosyloxy)-6,8-dimethoxy-2H-1-benzopyran-2-one
Iridoid	Monotropein
Sterol	Beta-Sitostenone
Anabolic steroid	Vebonol
Phenylpropanoid glucoside	Grayanoside A
Thromboxane receptor antagonist	Vapiprost
Indole sesquiterpene alkaloid	Sespendole
Iridoid glucoside	p-Coumaroyl monotropein
Iridoid glucoside	p-coumaroyl-6,7-dihydromonotropein
Carotenoid	Zeaxanthin
Carotenoid	(all-E)-lutein 3-O-C(4:0)
Iridoid	p-Coumaroyl monotropein hexoside
Product of chlorophyll degradation	Pheophytin A

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Figure 1. (A) Berries of L. caerulea. A. Variety “Atlant”; (B) Variety “Vilyuyka” (Photo by E. Rusakova).

Figure 2. Chemical structure of some identified polyphenols in extracts of L. caerulea.

Figure 3. CID spectrum of calycosin-7-O-β-D-glucoside-6″-O-malonate from L. caerulea (variety Goluboe vereteno from Saint-Petersburg), m/z 533.80.

Figure 4. Chemical structure analysis of conversion of flavonoid glycoside malonate to their related flavonoid glycoside (1. calycosin-7-O-β-D-glucoside-6″-O-malonate; 2. calycosin-7-O-β-D-glucoside; 3. ononin).

Figure 5. CID spectrum of acacetin 8-C-glucoside from L. caerulea (variety Goluboe vereteno from Saint-Petersburg), m/z 533.63.

Figure 6. CID spectrum of lonicerin from L. caerulea (variety Tomichka from Far East), m/z 594.56.

Figure 7. CID spectrum of lonicerin from L. caerulea (variety Amfora from Saint-Petersburg), m/z 595.22.

Figure 8. CID spectrum of rhamnetin II from berries of L. caerulea (variety Amfora from Saint-Petersburg), m/z 315.23.

Figure 9. CID spectrum of herbacetin from berries of L. caerulea (variety Amfora from Saint-Petersburg), m/z 303.11.

Figure 10. The chemical structure analysis of chlorogenic acid.

Figure 11. CID spectrum of chlorogenic acid from berries of L. caerulea (variety Tomichka from Far East), m/z 355.16.

Figure 12. CID spectrum of methylgallic acid from berries of L. caerulea (variety Volhova from Far East), m/z 185.17.

Figure 13. Vienna diagram showing similarities and differences in the presence of various chemical groups in Far Eastern L. caerulea varieties.

Figure 14. Vienna diagram showing similarities and differences in the presence of various polyphenolic groups in Saint-Petersburg L. caerulea varieties.

Figure 15. (A) The similarities and differences in the overall complex of isolated chemical constituents from extracts of L. caerulea (variety Amfora); (B) The similarities in the complex of polyphenolic compounds of L. caerulea (variety Amfora).

Figure 16. (A) The similarities and differences in the overall complex of isolated chemical constituents from extracts of L. caerulea (variety Tomichka); (B) The similarities in the complex of polyphenolic compounds of L. caerulea (variety Tomichka).

Figure 17. (A) The similarities and differences in the overall complex of isolated chemical constituents from extracts of L. caerulea (variety Goluboe vereteno); (B) The similarities in the complex of polyphenolic compounds of L. caerulea (variety Goluboe vereteno).

Figure 18. (A) The similarities and differences in the overall complex of isolated chemical constituents from extracts of L. caerulea (variety Volhova); (B) The similarities in the complex of polyphenolic compounds of L. caerulea (variety Volhova).

Table 1. Characterization of the constituents of the extracts of L. caerulea in positive and negative ionization modes via HPLC-ion trap-MS/MS.

	Class of Compounds	Identification	Formula	Retention Time	Observed Mass [M-H]-	Observed Mass [M+H]+	MS/MS Stage 1 Fragmentation	MS/MS Stage 2 Fragmentation	MS/MS Stage 3 Fragmentation	References
1	Flavone	Apigenin	C₁₅H₁₀O₅	20.2		271	225	179		Phlomis (Lamiaceae) [16]; Olive oil [17]; Mentha [18]; L. henryl [19]
2	Flavone	Trihydroxy(iso)flavone	C₁₅H₁₀O₅	25.6		271	197	129		Propolis [20]
3	Flavone	5,6,4′-Trihydroxy-7,8-dimethoxyflavone	C₁₇H₁₄O₇	24.4		331	303; 185	203	157	Mentha [21]; F. glaucescens; F. herrerae [22]
4	Flavone	Jaceosidin [5,7,4′-trihydroxy-6′,5′-dimetoxyflavone] *	C₁₇H₁₄O₇	33.2		331	303; 203	203; 157	175	Mentha [18,21]
5	Flavone	Cirsiliol *	C₁₇H₁₄O₇	34.0	329		229; 311	211	211	Ocimum [23]
6	Flavone	Sophoraisoflavone A *	C₂₀H₁₆O₆	33.7		353	335; 294; 235; 195	317; 277; 229		Chinese herbal formula Jian-Pi-Yi-Shen pill [24]
7	Flavone	Pentahydroxy dimethoxyflavone *	C₁₇H₁₄O₉	35.6		363	344; 300; 256	238; 146		G. linguiforme [22]
8	Flavone	Dihydroxy-tetramethoxy(iso)flavone *	C₁₉H₁₈O₈	27.5		375	345	245	175; 227	Propolis [20]
9	Flavone	Luteolin 7-O-glucoside [Cynaroside]	C₂₁H₂₀O₁₁	27.1		449	297	269	241	L. henryi [19]; V. macrocarpon [25]; L. japonica [26]
10	Flavone	Chrysoeriol O-hexoside *	C₂₂H₂₂O₁₁	7.3		463	445; 243			T. aestivum L. [27]; Ipomoea batatas [28]
11	Flavone	Formononetin-7-O-glucoside-6″-O-malonate *	C₂₅H₂₄O₁₂	18.7		517	271	243		Astragali radix [29,30]
12	Flavone	Acacetin 8-C-glucoside malonylated *	C₂₅H₂₄O₁₃	44.6		533	471; 411; 315	424; 281	305; 263	Mexican lupine species [31]
13	Flavone	Calycosin-7-O-β-D-glucoside-6″-O-malonate *	C₂₅H₂₄O₁₃	7.5		533	287	273; 236		Radix astragali [29,30]
14	Flavone	Chrysin derivative	C₂₆H₂₄O₁₄	44.8	559		277	233; 177		Embelia [32]
15	Flavone	C-hexosyl-apigenin O-rhamnoside *	C₂₇H₃₀O₁₄	36.2		579	561; 337; 317	319; 262	161	T. aestivum [33]
16	Flavone	Lonicerin [Luteolin-7-O-Rhamnoside; Veronicastroside; Scolymoside; Luteolin-7-Rhamnoglucoside]	C₂₇H₃₀O₁₅	22.8		595	449; 287	287	287; 153	L. japonica [26]; Exocarpium Citri Grandis [34]
17	Flavone	Luteolin 7-O-(6-O-arabinosyl-glucoside)	C₂₆H₂₈O₁₅	22.9		581	287	153; 241; 287		L. henryi [19]
18	Flavonol	Kaempferol	C₁₅H₁₀O₆	23.0		287	269; 149	239; 181		L. japonica [26]; P. sibirica [35]; Rhus coriaria [36]; R. meyeri [37]; Andean blueberry [38]
19	Flavonol	Dihydrokaempferol	C₁₅H₁₂O₆	25.4	287		259	215	173	Andean blueberry [38]; Camellia kucha [39]; Strawberry [40]
20	Flavonol	Rhamnocitrin *	C₁₆H₁₂O₆	27.5		301	273	245	217; 177; 131	Astragali radix [29]; Mentha [41]
21	Flavonol	Quercetin	C₁₅H₁₀O₇	31.3		303	257; 146	229	201; 145	Propolis [20]; Ocimum [23]; V. macrocarpon [25,42]; Rhus coriaria [36]; R. meyeri [37]
22	Flavonol	Herbacetin [3,5,7,8-Tetrahydroxy-2-(4-hydro- xyphenyl)-4H-chromen-4-one] *	C₁₅H₁₀O₇	26.6		303	203	175		Rhodiola rosea [43]
23	Flavonol	Rhamnetin II *	C₁₆H₁₂O₇	32.9		317	302	274; 153; 121	229; 153; 121	P. sibirica [35]; Rhus coriaria L. (Sumac) [36]; Spondias purpurea [44]
24	Flavonol	Isorhamnetin [Isorhamnetol; Quercetin 3′-Methyl ether; 3-Methylquercetin]	C₁₆H₁₂O₇	24.4	315		283	255; 211	227	Andean blueberry [38]; V. macrocarpon [42]; Spondias purpurea [44]
25	Flavonol	Kaempferol-3-O-α-L-rhamnoside *	C₂₁H₂₀O₁₀	22.9		433	287	187		C.edulis; F. glaucescens [22]; Rhus coriaria [36]; P. aculeata [45]; Cassia abbreviata [46]
26	Flavonol	Quercetin 3-O- glucoside [Isoquercitrin; Hirsutrin; Quercetin-3-O-Glucopyranoside; 3-Glucosylquercetin]	C₂₁H₂₀O₁₂	23.4		465	303	229; 165	201; 161	L. henryi [19]; L. japonica [26]; Ribes meyeri [37]; Andean blueberry [38]; Spondias purpurea [44]; R. occidentalis [47]; Cranberry [48]; V. myrtillus [49]
27	Flavonol	Kaempferol 3-O-rutinoside	C₂₇H₃₀O₁₅	22.6		595	449; 287	287	287	L. japonica [26]; R. meyeri [37]; Spondias purpurea [44]; Strawberry [50]
28	Flavonol	Quercetin 3-O-pentosyl hexoside	C₂₆H₂₈O₁₆	21.9		597	303; 257; 211	257; 195; 165	229	F. pottsii [22]; Spondias purpurea [44]; V. myrtillus [51]
29	Flavonol	Rutin (Quercetin 3-O-rutinoside)	C₂₇H₃₀O₁₆	22.1		611	303	257; 165	229	L. henryi [19]; L. japonica [26]; Ribes meyeri [37]; Spondias purpurea [44]; R. occidentalis [47]; R. magellanicum [52]
30	Flavonol	Isorhamnetin 3-O-(6″-O-rhamnosyl-hexoside)	C₂₈H₃₂O₁₆	24.3		625	317	302		L. henryi [19]; Bee-pollen [53]
31	Flavonol	Dimethylquercetin-3-O-dehexoside *	C₂₉H₃₄O₁₇	38.4	653		507; 353; 311	329	287; 190	Capsicum annuum [54]
32	Flavonol	Derivative of Quercetin rhamnosyl hexoside	C₃₆H₄₆O₂₂	8.5	829		609	301	300	Pubchem
33	Flavan-3-ol	Epiafzelechin [(epi)Afzelechin] *	C₁₅H₁₄O₅	19.4		275	245; 219; 175	215; 193; 175; 157; 127	175; 157; 145	A. cordifolia; F. glaucescens; F. herrerae [22]; Cassia abbreviata [46]
34	Flavan-3-ol	(Epi)-catechin	C₁₅H₁₄O₆	22.6		291	273; 137			V. macrocarpon [25]; Andean blueberry [38]; Rubus occidentalis [47]; Cranberry [48]; V. myrtillus [49,51]
35	Flavan-3-ol	Gallocatechin [+(−)Gallocatechin]	C₁₅H₁₄O₇	55.3		307	261; 243; 163; 137	187; 159	131	G. linguiforme [22]; Embelia [32]; R. meyeri [37]; V. myrtillus [51]
36	Flavan-3-ol	(Epi)-afzelechin derivative	C₁₈H₁₆O₁₀	19.1		393	275; 245; 215	245; 175	175; 127	Zostera marina [55]
37	Flavan-3-ol	(Epi)-catechin derivative	C₁₈H₁₆O₁₁	19.4		409	291; 275	261; 242; 208; 173	244; 214; 191; 173; 160; 124	Pubchem
38	Flavan-3-ol	(−)-Epicatechin Gallate [(−)-Epicatechin-3-O-Gallate; L-Epicatechin Gallate] *	C₂₂H₁₈O₁₀	23.3	441		330; 139	150		Chinese herbal formula Jian-Pi-Yi-Shen pill [24]; R. meyeri [37]; Camellia kucha [39]; Cassia abbreviates [46]; Terminalia arjuna [56]
39	Flavanone	Naringenin [Naringetol; Naringenine] *	C₁₅H₁₂O₅	31.3		273	153; 189	111		G. linguiforme [22]; Mexican lupine species [31]; Exocarpium Citri Grandis [33]; Andean blueberry [38]; Rapeseed petals [57]
40	Flavanone	Butin [7,3′,4′-Trihydroxyflavanone] *	C₁₅H₁₂O₅	31.7		273	153	171	153	Ribes meyeri [38]
41	Anthocyanin	Anthocyanidin [cyanidin chloride; Cyanidin]	C₁₅H₁₁O₆₊	7.9		287	286; 270; 247; 205	221		F. herrerae [22]; Andean blueberry [38]; Phoenix dactylifera [58]
42	Anthocyanin	Petunidin	C₁₆H₁₃O₇₊	35.6		318	256	238; 113	238	A. cordifolia; C. edulis [22]
43	Anthocyanin	Pelargonidin-3-O-glucoside (callistephin)	C₂₁H₂₁O₁₀	25.9		431	257; 331	227	215	R. ulmifolius [59]; Black currant, Elderberry [60]
44	Anthocyanin	Delphinidin 3-O-glucoside	C₂₁H₂₁O₁₂₊	23.3		465	303	257; 165	229; 201	R. magellanicum [52]; Black currant [60]; B. lycium [61]; B. ilicifolia; B.s empetrifolia; R. maellanicum; R. cucullatum; M. nummalaria [62]; B. microphylla [63]
45	Anthocyanin	Pelargonidin 3-O-(6-O-malonyl-β-D-glucoside)	C₂₄H₂₃O₁₃	11.8		519	271	243	197	Gentiana lutea [64]; T. aestivum [65]
46	Anthocyanin	Delphinidin 3-O-β-D-sambubioside	C₂₆H₂₉O₁₆	21.6		597	303; 465; 229	229; 165	201; 172	Red currant [60]; B. microphylla [63]; T. aestivum [65]
47	Anthocyanin	Delphinidin 3-O-rutinoside [Tulipanin; Delphinidin 3-Rhamnosyl-Glucoside]	C₂₇H₃₁O₁₆	22.4		611	303	257; 165	229	Black currant [60]; B. ilicifolia; B. empetrifolia; R. maellanicum; R. cucullatum [62]; B. microphylla [63]
48	Anthocyanin	Petunidin-3-rutinoside	C₂₈H₃₃O₁₆	24.2		625	317; 479	302; 139	274; 229; 153	Black currant [60]; B. ilicifolia; B. empetrifolia [62]; B. microphylla [63]
49	Hydroxybenzoic acid (Phenolic acid)	Protocatechuic acid	C₇H₆O₄	29.8		155	127			V. macrocarpon [25]; L. japonica [26]; R. meyeri [37]
50	Hydroxycinnamic acid	Caffeic acid [(2E)-3-(3,4-Dihydroxyphenyl)acrylic acid]	C₉H₈O₄	13.3		181	135	119		V. macrocarpon [25]; L. japonica [26]; R. meyeri [37]; Strawberry [40]; R. occidentalis [47]; V. myrtillus [49]
51	Methylbenzoic acid	Methylgallic acid [Methyl gallate] *	C₈H₈O₅	15.3		185	139	111		Rhus coriaria [36]; Papaya [50]; Eucalyptus [66]
52	Trans-cinnamic acid	Ferulic acid	C₁₀H₁₀O₄	7.3	193		176	132		V. macrocarpon [25]; L. japonica [26]; Andean blueberry [38]; R. nigrum [67];
53	Phenolic acid	Hydroxy methoxy dimethylbenzoic acid *	C₁₀H₁₂O₄	20.4		197	188	179		F. herrerae; F. glaucescens [22]
54	Phenolic acid	2,3,4,5,6-pentahydroxybenzoic acid *	C₇H₆O₇	8.6		203	156	129		Jatropha [68]
55	Hydroxycinnamic acid	Hydroxyferulic acid *	C₁₀H₁₀O₅	8.1		211	193	75; 147	157; 129	Andean blueberry [38]; Strawberry [40]; Rosa davurica [69]
56	Hydroxycinnamic acid	Sinapic acid [trans-Sinapic acid]	C₁₁H₁₂O₅	29.2		225	207; 179	151; 123	123	V. macrocarpon [25]; Cranberry [48]; Andean blueberry [38]
57	Phenolic acid	2,4,6-Trihydroxy-3,5-dimethoxybenzoic acid *	C₉H₁₀O₇	35.6		230	212	195		Actinidia [70]
58	Hydroxybenzoic acid (Phenolic acid)	Ellagic acid [Benzoaric acid; Elagostasine; Lagistase; Eleagic acid]	C₁₄H₆O₈	21.7	301		257	229	201	Rubus occidentalis [47]; Eucalyptus [66]
59	Phenolic acid	6-Hydroxy-3-methoxy-4-O-β-D-glucopyranoside *	C₁₄H₂₀O₁₀	8.4	347		301; 165	165; 137		Actinidia [70]
60	Phenylpropanoid (cinnamic acid derivative glycoside); Hydroxycinnamic acid;	Chlorogenic acid [3-O-Caffeoylquinic acid]	C₁₆H₁₈O₉	18.5	353		191	127		L. henryi [19]; L. japonica [26]; V. macrocarpon [25,42]; Andean blueberry [38]; Strawberry [40]; Spondias purpurea [44]; Cranberry [48]; V. myrtillus [49]; R. magellanicum [52]
61	Hydroxycinnamic acid;	3-O-Hydroxydihydrocaffeoylquinic acid	C₁₆H₂₀O₁₀	6.7	6.7		191	173; 127		L. henryi [19]
62	Phenolic acid	Caffeoylquinic acid derivative		25.5	381		179; 135	135		V. myrtillus [51]
63	Flavonoid	p-Coumaroylhexose-4-O-hexoside *	C₂₅H₂₈O₁₀	23.3		489	327	299; 253	253; 225	Strawberry [40]; Gmelina arborea [71]
64	Phenolic acid	3,4-O-dicaffeoylquinic acid [Isochlorogenic acid B]	C₂₅H₂₄O₁₂	23.7	515		353	191	173	L. henryi [19]; L. japonica [26]; Stevia rebaudiana [72]
65	Phenolic acid	4,5-O-dicaffeoylquinic acid [Isochlorogenic acid C]	C₂₅H₂₄O₁₂	24.7	515		353	191	171	L. henryi [19]; L. japonica [26]; Lemon [50]
66	Phenolic acid	p-Coumaroyl malonyldihexose		23.8		575	413; 335; 188	395; 340; 226; 188	346; 290; 211	V. myrtillus [51]
67	Phenolic acid	Dicaffeoylferuoylquinic acid *		42.5		693	353; 261	335; 261; 135	243; 149	Artemisia annua [73]
68	Stilbene	Pinosylvin [3,5-Stilbenediol; Trans-3,5-Dihydroxystilbene] *	C₁₄H₁₂O₂	32.7		213	167; 139	139		P. resinosa [74]; P. sylvestris [75]
69	Stilbene	Resveratrol [trans-Resveratrol; 3,4′,5-Trihydroxystilbene; Stilbentriol] *	C₁₄H₁₂O₃	20.3		229	211	183; 127	138	A. cordifolia; F. glaucescens; F. herrerae [22]; Embelia [32]; Radix polygoni multiflori [76]
70	Stilbene	Dihydroresveratrol [Alpha, Beta-Dihydroresveratrol] *	C₁₄H₁₄O₃	19.4		231	214; 158	196; 168		Maackia amurense [77]
71	Hydroxycoumarin	Umbelliferone [Skimmetin; Hydragin] *	C₉H₆O₃	16.5		163	145	117		F. glaucescens [22]; Actinidia [70]; Zostera marina [55]; S. officinalis [78]
72	Coumarin	Fraxetin *	C₁₀H₈O₅	23.7		209	191	117		Embelia [32]; Actinidia [70]; Jatropha [68]
73	Coumarin	3,4/6,8-Dihydro-5,7-dihydroxy-2-oxo-2H-1-benzopyran-3-acetic acid	C₁₁H₁₀O₆	7.3		239	221	203	185	Actinidia [70]
74	Coumarin	Umbelliferone hexoside *	C₁₅H₁₆O₈	52.8		325	289; 127	271; 127	253; 146	G. linguiforme [22]
75	Coumarin	7-(β-D-Glucopyranoside/galactopyranoside)-2-oxo-2H-1-benzopyran-4-acetic acid	C₁₇H₁₈O₁₀	6.7		383	163; 365	145		Actinidia [70]
	OTHERS
76	Amino acid	L-Proline [(2-Pyrrolidinecarboxylic acid]	C₅H₉NO₂	16.3		116	70			L. japonica [26]; V. unguiculata [79]
77	Non-proteinogenic L-alpha-amino acid	L-Pyroglutamic acid [Pidolic acid; 5-Oxo-L-Proline] *	C₅H₇NO₃	7.8		130	111			Potato leaves [80]
78	Amino acid	L-Histidine	C₆H₉N₃O₂	26.2		156	129	110		L. japonica [26]; Camellia kucha [39]; Actinidia deliciosa [81]
79	Amino acid	L-threanine	C₇H₁₄N₂O₃	7.6		175	157; 129	129; 115		Camellia kucha [39]
80	Amino acid	L-Arginine	C₆H₁₄N₄O₂	9.9		175	130	111		L. japonica [26]; Hylocereus polyrhizus [82]
81	Cyclohexenecarboxylic acid	Shikimic acid [L-Schikimic acid] *	C₇H₁₀O₅	8.1		175	157	129	111	A. cordifolia [22]; R. meyeri [37]; Camellia kucha [39]
82	Tricarboxylic acid	Citric acid [Anhydrous; Citrate]	C₆H₈O₇	6.7	191		111; 173			Mentha [18]; Strawberry, Lemon, Cherimoya, Papaya, Passion fruit [50]; V. unguiculata [79]; Potato leaves [80]
83	Polyhydroxycarboxylic acid	Quinic acid	C₇H₁₂O₆	7.9	191		111; 173	111		L. japonica [26]; R. meyeri [37]; Andean blueberry [38]; Potato leaves [80]
84	Pentahydroxy hexanoic acid	Gluconic acid [Dextronic acid; Maltonic acid; Glycogenic acid; Pentahydroxy hexanoic acid] *	C₆H₁₂O₇	19.1		197	188; 179; 156; 119	156; 148		R. meyeri [37]; Colchicum micranthum [83]
85	Benzofuran	Loliolide *	C₁₁H₁₆O₃	20.7		197	179; 127	111		Jatropha [68]
86	Alpha, omega dicarboxylic acid	Sebacic acid [Decanedioic acid] *	C₁₀H₁₈O₄	17.6		203	185	139	111; 157	Jatropha [68]
87		4-Dihydroxy-3-methoxy-benzenepropanoic acid *	C₁₀H₁₂O₅	25.7		213	193; 167; 139; 119			Actinidia [70]
88	Sesquiterpenoid	Caryophyllene oxide [Caryophyllene-alpha-oxide] *	C₁₅H₂₄O	16.4	219		173; 111	111		R. davurica [69]; Olive leaves [84]
89	Carboxylic acid	Myristoleic acid [Cis-9-Tetradecanoic acid] *	C₁₄H₂₆O₂	20.2		227	209; 165	121		F. glaucescens [22]; Maackia amurensis [85]
90	Pyrimidine nucleoside	Cytidine	C₉H₁₃N₃O₅	29.2		244	225; 179	179	151	L. japonica [26]
91	Glycosylated pyrimidine analog	Uridine	C₉H₁₂N₂O₆	28.3		245	145	117		L. japonica [26]; Potato leaves [80]
92	Hydroxy tetradecanoic acid	Hydroxy myristic acid [2S-Hydroxytetradecanoic acid; Alpha-Hydroxy Myristic acid] *	C₁₄H₂₈O₃	30.8		245	228	183		F. pottsii [22]
93	Medium-chain fatty acid	Hydroxy dodecanoic acid *	C₁₂H₂₂O₅	27.5		247	229; 201	187	159; 145	F. glaucescens [22]
94		Caffeic acid isoprenyl ester	C₁₄H₁₆O₄	25.4		249	203	157	129	Eucalyptus [66]; Brazilian propolis [86]
95	Sesquiterpene lactone	Artemisinin C *	C₁₅H₂₀O₃	25.7		249	202; 157; 125	157; 185	129	Artemisia annua [87]
96	Aporphine alkaloid	Anonaine *	C₁₇H₁₅NO₂	25.8		266	249	203	157	R. rugosa [69]; Magnolia [88]
97	Ribonucleoside composite of adenine (purine)	Adenosine	C₁₀H₁₃N₅O₄	20.2		268	250	204; 158	157	L. japonica [26]; R. acicularis [69]; Huolisu Oral Liquid [89]
98		3,4,8,9,10-Penthahydroxydibenzo [b,d]pyran-6-one *	C₁₃H₈O₇	33.3		277	203	157	129	Terminalia arjuna [56]
99	Omega-3-fatty acid	Stearidonic acid [6,9,12,15-Octadecatetraenoic acid; Moroctic acid] *	C₁₈H₂₈O₂	40.0		277	261	215; 115	129	G. linguiforme [22]; Rhus coriaria [36]; Jatropha [68]; Salviae Miltiorrhizae [90]
100	Omega-3-fatty acid	Linolenic acid (Alpha-Linolenic acid; Linolenate) *	C₁₈H₃₀O₂	42.2		279	261	219	163	Jatropha [68]; P. sylvestris [75]; Maackia amurensis [85]; Salviae Miltiorrhizae [90]
101	Mixture of diastereomers	Fructose-leucine	C₁₂H₂₃NO₇	7.8		294	276	258	210	Potato leaves [80]
102	Cyclohexenecarboxylic acid	Coumaroyl shiikimic acid	C₁₆H₁₆O₇	19.4		321	219; 173	201; 173	155	Andean blueberry [38]
103	Oxylipin	13- Trihydroxy-Octadecenoic acid [THODE] *	C₁₈H₃₄O₅	32.6	329		229; 171	210	209; 183	Phoenix dactylifera [58]; Jatropha [68]; Broccoli [91]
104	Alpha, omega-dicarboxylic acid	Eicosatetraenedioic acid *	C₂₀H₃₀O₄	32.1	333		287; 197; 151	151		G. linguiforme [22]
105	Cyclohexenecarboxylic acid	Caffeoyl shikimic acid	C₁₆H₁₆O₈	38.0		337	273; 173	128		R. meyeri [37]
106	Alpha, omega-dicarboxylic acid	Trihydroxy eicosatetraenoic acid *	C₂₀H₃₂O₅	45.6		353	261	243	159	F. glaucescens [22]
107	Dicarboxylic acid sugar	Caffeoyl gluconic acid	C₁₅H₁₈O₁₀	21.6		359	340; 312; 284; 228; 196			R. meyeri [37]
108	Iridoid glucoside	Sweroside	C₁₆H₂₂O₉	21.6		359	197; 127	179	111	L. japonica [26]
109	Cyclopentapyran	Loganin acid	C₁₆H₂₄O₁₀	18.9		377	158; 359	130		L. japonica [26]
110		7-(β-D-Galactopyranosyloxy)-6,8-dimethoxy-2H-1-benzopyran-2-one	C₁₇H₂₀O₁₀	6.7	383		191	172; 127	171	Actinidia [70]
111	Iridoid	Monotropein *	C₁₆H₂₂O₁₁	31.2		391	373; 329; 251; 187	311; 202	203	V. myrtillus [51,92]
112	Sterol	Beta-Sitostenone [Stigmast-4-En-3-One; Sitostenone] *	C₂₉H₄₈O	2.1		413	301; 171	189		F. herrerae [22]; Terminalia laxiflora [93]
113	Anabolic steroid	Vebonol *	C₃₀H₄₄O₃	24.9		453	435; 210	226; 336	210	Rhus coriaria [36]; Hylosereus polyrhizus [82]
114	Phenylpropanoid glucoside	Grayanoside A [Hydroxyphenylethyl feruloyl glucopyranoside] *	C₂₄H₂₈O₁₀	23.4	475		375; 275	347; 275; 175	247; 175	Strawberry [40]
115	Thromboxane receptor antagonist	Vapiprost *	C₃₀H₃₉NO₄	44.7		478	337	263; 121	119	Rhus coriaria [36]; Hylosereus polyrhizus [82]
116	Indole sesquiterpene alkaloid	Sespendole *	C₃₃H₄₅NO₄	45.7		520	184	125		Rhus coriaria [36]
117	Iridoid glucoside	p-Coumaroyl monotropein *	C₂₅H₂₈O₁₃	44.6		537	375; 256; 185			Cranberry [52]; V. myrtillus [49,51]
118	Iridoid glucoside	p-Coumaroyl-6,7-dihydromonotropein *	C₂₅H₃₀O₁₃	20.2		540	373; 229; 179	179		Cranberry [48]; V. myrtillus [51]
119	Carotenoid	Zeaxanthin [All-Trans-Zeaxanthin; Anchovyxanthin]	C₄₀H₅₆O₂	28.4		570	552; 412; 184	534; 317; 184	487; 404; 321; 149	Sarsaparilla [94]; Carotenoids [95]
120	Carotenoid	(all-E)-lutein 3-O-C(4:0)		41.8		638	620; 554	536; 335; 220	414; 276; 241	Carotenoids [96]
121	Iridoid	p-Coumaroyl monotropein hexoside *		42.5		699	537; 347; 259	375; 259; 185		V. myrtillus [51]
122	Product of chlorophyll degradation	Pheophytin A	C₅₅H₇₄N₄O₅	0.6		872	593	533	461	Physalis peruviana [97]; Capsicum [98]

* Chemical constituents identified for the first time in L. caerulea.

Table 2. The distribution of the constituents in extracts of L. caerulea samples from the Far East.

Names	Total	Elements
Amfora; Goluboe vereteno; Tomichka; Volhova	7	kaempferol; herbacetin; 2,3,4,5,6-pentahydroxybenzoic acid; caffeic acid isoprenyl ester; L-histidine; anonaine; 8,9,10-penthahydroxydibenzo [bd]pyran-6-one
Amfora; Goluboe vereteno; Tomichka	1	hydroxyferulic acid
Amfora; Tomichka; Volhova	3	quercetin; hydroxy dodecanoic acid; rhamnocitrin
Amfora; Goluboe vereteno; Volhova	1	jaceosidin
Goluboe vereteno; Tomichka; Volhova	4	pheophytin A; sebacic acid; fructose-leucine; myristoleic acid
Amfora; Tomichka	2	sespendole; fraxetin
Amfora; Volhova	1	stearidonic acid
Tomichka; Volhova	10	p-coumaroyl shiikimic acid; isorhamnetin 3-O-(6″-O-rhamnosyl-hexoside); p-coumaroyl malonyldihexose; isorhamnetin; ellagic acid; resveratrol; methylgallic acid; delphinidin 3-O-glucoside; hydroxy methoxy dimethylbenzoic acid; quinic acid
Goluboe vereteno; Volhova	1	(epi)-afzelechin derivative
Amfora	19	4/6,8-dihydro-5,7-dihydroxy-2-oxo-2H-1-benzopyran-3-acetic acid; trihydroxyisoflavone; dimethylquercetin-3-O-dehexoside; chrysoeriol O-hexoside; 6-hydroxy-3-methoxy-4-O-β-D-glucopyranoside; formononetin-7-O-glucoside-6″-O-malonate; 13- trihydroxy-Octadecenoic acid; linolenic acid; cirsiliol; adenosine; pelargonidin-3-O-glucoside; citric acid; apigenin; gallocatechin; grayanoside A; pelargonidin 3-O-(6-O-malonyl-β-D-glucoside); C-hexosyl-apigenin O-rhamnoside; artemisinin C; vapiprost
Tomichka	30	rutin; 7-(β-D-glucopyranoside/galactopyranoside)-2-oxo-2H-1-benzopyran-4-acetic acid; umbelliferone; sinapic acid; vebonol; umbelliferone hexoside; lonicerin; (−)-epicatechin gallate; caffeic acid; L-arginine; quercetin 3-O-glucoside; ferulic acid; L-threanine; quercetin 3-O-pentosyl hexoside; p-coumaroyl-6,7-dihydromonotropein; p-coumaroylhexose-4-O-hexoside; 5-O-dicaffeoylquinic acid; eicosatetraenedioic acid; uridine; delphinidin 3-O-β-D-sambubioside; chlorogenic acid; delphinidin 3-O-rutinoside; caffeoyl gluconic acid; caffeoylquinic acid derivative; cytidine; naringenin; petunidin-3-rutinoside; dicaffeoylferuoylquinic acid; kaempferol 3-O-rutinoside; zeaxanthin; pentahydroxy dimethoxyflavone
Goluboe vereteno	4	caffeoyl shikimic acid; calycosin-7-O-β-D-glucoside-6″-O-malonate; pinosylvin; dihydroxy-tetramethoxy(iso)flavone
Volhova	5	trihydroxy eicosatetraenoic acid; 4-O-dicaffeoylquinic acid; derivative of quercetin rhamnosyl hexoside; monotropein; butin

Table 3. Distribution of chemicals in extracts of L. caerulea cultivars from Saint-Petersburg, shown in detail by variety of sample.

Names	Total	Elements
Amfora SPb Goluboe vereteno SPb Tomichka SPb Volhova SPb	4	(epi)-afzelechin derivative; L-histidine; anonaine; myristoleic acid
Amfora SPb Goluboe vereteno SPb Tomichka SPb	4	petunidin; sebacic acid; apigenin; pentahydroxy dimethoxyflavone
Amfora SPb Tomichka SPb Volhova SPb	2	isorhamnetin; ellagic acid
Amfora SPb Goluboe vereteno SPb Volhova SPb	2	caffeic acid isoprenyl ester; quercetin
Goluboe vereteno SPb Tomichka SPb Volhova SPb	3	herbacetin; (epi)-afzelechin; (epi)-catechin
Amfora SPb Tomichka SPb	6	7-(β-D-glucopyranoside/galactopyranoside)-2-oxo-2H-1-benzopyran-4-acetic acid; shikimic acid; cirsiliol; methylgallic acid; hydroxy dodecanoic acid; dihydroxy-tetramethoxy(iso)flavone
Amfora SPb Goluboe vereteno SPb	5	p-coumaroyl monotropein hexoside; resveratrol; fructose-leucine; quinic acid; artemisinin C
Amfora SPb Volhova SPb	1	5,6,4′-trihydroxy-7,8-dimethoxyflavone
Goluboe vereteno SPb Tomichka SPb	6	2,3,4,5,6-pentahydroxybenzoic acid; sespendole; linolenic acid; gallocatechin; 6-trihydroxy-3,5-dimethoxybenzoic acid; 4-dihydroxy-3-methoxy-benzenepropanoic acid
Tomichka SPb Volhova SPb	1	8,9,10-penthahydroxydibenzo [b d]pyran-6-one
Goluboe vereteno SPb Volhova SPb	2	citric acid; hydroxy methoxy dimethylbenzoic acid
Amfora SPb	31	coumaroyl shiikimic acid; loganin acid; isorhamnetin 3-O-(6″-O-rhamnosyl-hexoside); 2,4,6-trihydroxy-3,5-dimethoxybenzoic acid; lonicerin; p-coumaroyl malonyldihexose; caryophyllene oxide; L-pyroglutamic acid; 3,8,9,10-penthahydroxydibenzo [bd]pyran-6-one; hydroxyferulic acid; caffeic acid; L-arginine; 3-O-hydroxydihydrocaffeoylquinic acid; quercetin 3-O-glucoside; pheophytin A; L-proline; eicosatetraenedioic acid; rhamnetin II; rhamnocitrin; loliolide; 7-(β-D-galactopyranosyloxy)-6,8-dimethoxy-2H-1-benzopyran-2-one; p-coumaroyl-6,7-dihydromonotropein; delphinidin 3-O-β-D-sambubioside; chlorogenic acid; delphinidin 3-O-rutinoside; kaempferol-3-O-α-L-rhamnoside; caffeoyl gluconic acid; pinosylvin; caffeoylquinic acid derivative; dihydroresveratrol; sweroside; luteolin 7-O-(6-O-arabinosyl-glucoside)
Tomichka SPb	9	trihydroxy eicosatetraenoic acid; dimethylquercetin-3-O-dehexoside; sophoraisoflavone A; (all-E)-lutein 3-O-C(4:0); dihydrokaempferol; hydroxy myristic acid; jaceosidin; luteolin 7-O-glucoside; naringenin
Goluboe vereteno SPb	12	acacetin 8-C-glucoside malonylated; gluconic acid; kaempferol; stearidonic acid; β-Sitostenone; p-coumaroyl monotropein; anthocyanidin; adenosine; (epi)-catechin derivative; protocatechuic acid; calycosin-7-O-β-D-glucoside-6″-O-malonate; chrysin derivative
Volhova SPb	1	2,3,4,6-pentahydroxybenzoic acid

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Razgonova, M.P.; Navaz, M.A.; Sabitov, A.S.; Zinchenko, Y.N.; Rusakova, E.A.; Petrusha, E.N.; Golokhvast, K.S.; Tikhonova, N.G. The Global Metabolome Profiles of Four Varieties of Lonicera caerulea, Established via Tandem Mass Spectrometry. Horticulturae 2023, 9, 1188. https://doi.org/10.3390/horticulturae9111188

AMA Style

Razgonova MP, Navaz MA, Sabitov AS, Zinchenko YN, Rusakova EA, Petrusha EN, Golokhvast KS, Tikhonova NG. The Global Metabolome Profiles of Four Varieties of Lonicera caerulea, Established via Tandem Mass Spectrometry. Horticulturae. 2023; 9(11):1188. https://doi.org/10.3390/horticulturae9111188

Chicago/Turabian Style

Razgonova, Mayya P., Muhammad Amjad Navaz, Andrey S. Sabitov, Yulia N. Zinchenko, Elena A. Rusakova, Elena N. Petrusha, Kirill S. Golokhvast, and Nadezhda G. Tikhonova. 2023. "The Global Metabolome Profiles of Four Varieties of Lonicera caerulea, Established via Tandem Mass Spectrometry" Horticulturae 9, no. 11: 1188. https://doi.org/10.3390/horticulturae9111188

APA Style

Razgonova, M. P., Navaz, M. A., Sabitov, A. S., Zinchenko, Y. N., Rusakova, E. A., Petrusha, E. N., Golokhvast, K. S., & Tikhonova, N. G. (2023). The Global Metabolome Profiles of Four Varieties of Lonicera caerulea, Established via Tandem Mass Spectrometry. Horticulturae, 9(11), 1188. https://doi.org/10.3390/horticulturae9111188

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The Global Metabolome Profiles of Four Varieties of Lonicera caerulea, Established via Tandem Mass Spectrometry

Abstract

1. Introduction

2. Materials and Methods

2.1. Materials

2.2. Chemicals and Reagents

2.3. Extraction

2.4. Liquid Chromatography

2.5. Mass Spectrometry

3. Results and Discussion

3.1. Flavones

3.1.1. 7-Hydroxy(iso)flavones

3.1.2. Dihydroxyflavones

3.1.3. Trihydroxyflavones

3.1.4. Tetrahydroxyflavones

3.1.5. Pentahydroxyflavones

3.2. Phenolic Acids

3.2.1. Hydroxycinnamic Acids and Cinnamate Esters

3.2.2. Hydroxybenzoic and Methylbenzoic Acids

4. Conclusions

Author Contributions

Funding

Data Availability Statement

Acknowledgments

Conflicts of Interest

Appendix A

References

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