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Article

Maackia amurensis Rupr. et Maxim.: Supercritical CO2 Extraction and Mass Spectrometric Characterization of Chemical Constituents

by
Mayya P. Razgonova
1,2,*,
Elena I. Cherevach
2,
Lyudmila A. Tekutyeva
2,
Sergey A. Fedoreyev
2,3,
Natalia P. Mishchenko
3,
Darya V. Tarbeeva
3,
Ekaterina N. Demidova
2,
Nikita S. Kirilenko
2 and
Kirill Golokhvast
2,4,5
1
N.I. Vavilov All-Russian Institute of Plant Genetic Resources, B. Morskaya 42-44, 190000 Saint Petersburg, Russia
2
Department of Pharmacy and Pharmacology, School of Biomedicine, Far Eastern Federal University, Sukhanova 8, 690950 Vladivostok, Russia
3
G.B. Elyakov Pacific Institute of Bioorganic Chemistry, Far Eastern Branch of Russian Academy of Science, Prospect 100 let Vladivostoku 159, 690022 Vladivostok, Russia
4
Laboratory of Supercritical Fluid Research and Application in Agrobiotechnology, The National Research Tomsk State University, Lenin Str. 36, 634050 Tomsk, Russia
5
Siberian Federal Scientific Centre of Agrobiotechnology, Centralnaya, Presidium, 633501 Krasnoobsk, Russia
*
Author to whom correspondence should be addressed.
Molecules 2023, 28(5), 2026; https://doi.org/10.3390/molecules28052026
Submission received: 31 December 2022 / Revised: 19 February 2023 / Accepted: 20 February 2023 / Published: 21 February 2023
(This article belongs to the Special Issue Processing of Materials by Supercritical Fluids—Part II)
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Abstract

:
Three types of extraction were used to obtain biologically active substances from the heartwood of M. amurensis: supercritical CO2 extraction, maceration with EtOH, and maceration with MeOH. The supercritical extraction method proved to be the most effective type of extraction, giving the highest yield of biologically active substances. Several experimental conditions were investigated in the pressure range of 50–400 bar, with 2% of ethanol as co-solvent in the liquid phase at a temperature in the range of 31–70 °C. The most effective extraction conditions are: pressure of 100 bar and a temperature of 55 °C for M. amurensis heartwood. The heartwood of M. amurensis contains various polyphenolic compounds and compounds of other chemical groups with valuable biological activity. Tandem mass spectrometry (HPLC-ESI—ion trap) was applied to detect target analytes. High-accuracy mass spectrometric data were recorded on an ion trap equipped with an ESI source in the modes of negative and positive ions. The four-stage ion separation mode was implemented. Sixty-six different biologically active components have been identified in M. amurensis extracts. Twenty-two polyphenols were identified for the first time in the genus Maackia.

1. Introduction

Maackia amurensis Rupr. et Maxim. is the only representative of the Fabaceae family in the flora of the Russian Far East. Probably, this species can be considered a relic of the Tertiary flora, which survived in more severe climatic conditions than the species of the genera Cladrastis and Sophora. The distribution area of Maackia amurensis is in the Amur River basin and in the south of Primorsky Krai, Russia. The natural reserves of this plant are large and actively self-renewal [1,2,3]. A close species to maackia is M. amurensis Rupr. et Maxim. var. buergeri (Maxim.) C.K. Schneeder (Figure 1). However, its chemical composition differs sharply from that of the Far Eastern species, M. amurensis [2,3,4,5]. Until 1985, the only data on the chemical composition of Russian maackia were data on alkaloids contained in the bark and green parts of the plant. In the subsequent detailed chemical study of alcoholic extracts of heartwood, it was shown that the main components of maackia are plant polyphenols [3,4,5].
These include isoflavones: genistein, daidzein, retusin, afromosin, formononetin, orobol, tectorigenin, 3-hydroxyvestiton, pterocarpans maakiain, medicarpin [5,6,7]. The peculiarity of Maackia amurensis growing in Primorye is the high content of monomeric stilbenes resveratrol and piceatannol and isoflavonstilben maackiasin in its wood [5,6]. These polyphenols were not found in the variety Maackia amurensis (var. buergeri) growing in Japan [1].
In addition to monomeric stilbenes and isoflavones, the polar fractions of Maackia amurensis extracts contain oligomeric stilbenes maackin, scirpusin A, scirpusin B, maackin A (XVII), and stilbenolignan maackolin [8,9].
The polyphenolic complex from M. amurensis heartwood, called Maksar® preparation, is registered in the Russian Federation as a hepatoprotective medicine (P N003294/01). Maxar® increases the body’s antioxidant system activity and reduces the lipid peroxidation level. Its application in clinical practice showed that this drug is effective for treating liver fatty dystrophy. It prevents the increase in total serum lipid content and the development of hyperlipoproteinemia in experimental animals. Maxar® also possesses antithrombogenic, antiplatelet, and antitumor properties [10,11]. Recently, new research has been carried out which shows that stilbenolignan maackolin may be a good candidate as a SARS-CoV-2 Mpro inhibitor in vivo studies [12].
The use of supercritical fluids in food material applications and more broadly in the food industry began in the late 1960s and probably represents the most successful application of supercritical fluids to date. The “green technology” of supercritical CO2 extraction using high pressures is an excellent technique for obtaining natural thermolabile compounds. In addition, there are no residues of organic solvents in the products, which occurs with conventional extraction methods—conventional solvents can be toxic, for example, in the case of methanol and hexane. Easy removal of the solvent from the final product, a high selectivity, and the use of moderate temperatures in the extraction process are the main attractive factors of SFE, leading to a significant increase in research for applications in the food and pharmaceutical industries [13].
Chemical reactions that have made the greatest contribution to food technologies were enzyme-catalyzed reactions [14], hydrogenations designed to control particular trans isomers occurring in lipid mixtures [15], and hydrolysis conducted in the presence of enzymes or a medium such as subcritical water [16]. Considerable activity in producing fine particles for use in the pharmaceutical industry began in the 1990s. In the last three decades, focus on the development of technologies was displaced by the combination of SCF technologies in the food industry and the obtainment of bioactive agents from natural matrixes [17,18].
In this research, supercritical CO2 extraction, MeOH maceration, and EtOH maceration of the samples of M. amurensis were used to obtain an effective amount of biologically active substances. We used a tandem mass spectrometry to carry out a phytochemical study involving a detailed metabolomic analysis of M. amurensis. The bark of M. amurensis was collected during expedition work near Ussuri River, Primorsky Krai, Russia (N 42°36′10″ E 131°10′55″), during the period from 1 to 20 August 2022.

2. Results

Three samples of wood substance of M. amurensis were subjected to supercritical CO2 extraction under different extraction conditions. The applied supercritical pressures ranged from 150 to 400 bar, and the extraction temperature ranged from 31 to 65 °C. The co-solvent EtOH was used in an amount of 2% of the total amount of solvent. A pronounced extraction extremum is shown in the 3D graph (Figure 2). The best extraction conditions for M. amurensis (heartwood) were the following: pressure of 100 bar and temperature at 55 °C. The total yield of biologically active substances under these extraction conditions was 4.3 mg per 100 mg of supercritical CO2 extract. The structural identification of each compound was carried out on the basis of their accurate mass and MS/MS fragmentation via the HPLC–ESI–ion trap–MS/MS. A total of 66 compounds were identified in extracts of M. amurensis based on their accurate MS and fragment ions by searching online databases and the references.
The research data presented in Figure 2 show the presence of a confident maximum of supercritical CO2 extraction in the pressure range of 100 to 150 bar and temperature range from 50 °C to 55 °C. In this range, the highest yield of biologically active compounds from the plant matrix of M. amurensis is observed. It should be noted that during the experiment, the extraction time was also small—1 h; therefore, what can we say about the effectiveness of the applied method of supercritical CO2-extraction?

3. Discussion

The number of constituents tentatively identified via tandem mass spectrometry was 66 chemical compounds (54 compounds from the polyphenol group and 12 compounds from other chemical groups). All the identified polyphenols and compounds from other chemical groups, their molecular formulas, and MS/MS data for M. amurense are summarized in Table A1 (Appendix A). Polyphenols are represented by the following chemical groups: flavones, flavonols, flavan-3-ols, flavanones, stilbenes, hydroxycoumarins. For the first time, 22 polyphenols were identified in M. amurense heartwood. There are polyphenols: flavones biochanin-A, 7-hydroxy-6,4′-dimethoxyisoflavone, trihydroxy methoxyflavone, cirsimaritin, dihydroxy-dimethoxy(iso)flavone, myricetin, cirsiliol, wighteone, luteone, dihydroxy tetramethoxyflavanone, hydroxy hexamethoxyflavone, odoratin-O-hexoside, 6,4′-dimethoxyisoflavone-7-O-glucoside, genistein C-glucoside malonylated, calycosin-7-O-beta-D-glucoside-6″-O-malonate, chrysoeriol 8-C-glucoside malonylated, apigenin 7-C-glucosyldideoxyhexoside, flavanones methyl-liquiritigenin, liquiritigenin dimethyl ester, padmatin, etc.
Figure 3, Figure 4, Figure 5 and Figure 6 show examples of the decoding spectra (collision-induced dissociation (CID) spectrum) of the ion chromatogram obtained using tandem mass spectrometry. The CID spectrum in negative ion modes of isoflavone 3-hydroxyvestitol from M. amurense is shown in Figure 3.
[M+H]− ion produced four fragment ions at m/z 299.13, m/z 283.13, m/z 227.24, and at m/z 177.08 (Figure 3). The fragment ion at m/z 283.06 produced three characteristic daughter ions at m/z 267.08, m/z 240.1, and m/z 150.2. The fragment ion at m/z 267.08 produced one characteristic ion at m/z 224.11. It was identified in the references in the extract from M. amurense [5,6,7]. The following is a list of polyphenols found in extracts of the wood substance of M. amurense; it should be noted separately that similar polyphenols are found in the Astragalus genus. The CID spectrum in positive ion modes of odoratin-O-hexoside from M. amurense is shown in Figure 4.
[M+H]+ ion produced five fragment ions at m/z 415.4, m/z 358.34, m/z 331.31, m/z 277.24, and at m/z 250.33 (Figure 4). The fragment ion with m/z 415.4 produced six characteristic daughter ions at m/z 331.37, m/z 303.31, m/z 261.33, m/z 206.19, m/z 176.96, and at m/z 149.18. The fragment ion at m/z 331.37 produced two characteristic daughter ions at m/z 261.99 and m/z 233.27; they were identified in extracts from Astragali Radix [19,20,21]. The CID spectrum in the positive ion mode of formononetin-7-O-glucoside-6″-O-malonate from M. amurense is shown in Figure 5.
[M–H]+ ion produced one fragment ion at m/z 269.18 (Figure 5). The fragment ion with m/z 269.18 produced four characteristic daughter ions at m/z 254.16, m/z 237.19, m/z 213.25, and at m/z 163.16. The fragment ion at m/z 254.16 formed three daughter ions with m/z 237.15, m/z 226.17, and m/z 181.24; they were identified in extracts from Astragali Radix [19,20,21]. The CID spectrum in the positive ion mode of calycosin-7-O-beta-D-glucoside-6″-O-malonate from M. amurense is shown in Figure 6.
[M+H]+ ion produced four fragment ions with m/z 285.17, m/z 387.34, m/z 354.34, and m/z 198.24 (Figure 6). The fragment ion with m/z 285.17 formed four daughter ions with m/z 167.14, m/z 257.36, m/z 229.2, and m/z 179.18; they were identified in extract from Astragali Radix [19,20,21].
It should also be noted that a detailed analysis of the presence of polyphenols and biologically active substances from other chemical groups showed the highest number of flavonoids at supercritical CO2 extraction at a pressure of 100 bar—43 compounds. Accordingly, with other types of extraction investigated in this study, such as maceration with ethanol (20 compounds), maceration with methanol (23 compounds), and supercritical CO2-extraction at a higher extraction pressure (19 compounds), the yield efficiency of biologically active substances is much lower. (Table 1).
Thus, it can be stated that as a result of the most detailed study using tandem mass spectrometry, new data on the content of biologically active substances in M. amurensis have been obtained.
M. amurensis extracts exhibited different DPPH scavenging effects compared to quercetin (Table 2). CO2 extract obtained at 100 bar possessed the most considerable activity compared to quercetin, which is mainly due to the high content of monomeric and dimeric stilbenes. EtOH extract from M. amurensis was the least active, because the main components of this extract were glycosides of isoflavones, which are rather weak antioxidants.

4. Materials and Methods

4.1. Materials

Wood substance of M. amurensis was collected during expedition work near Ussuri River, Primorsky Krai, Russia (N 42°36′10″ E 131°10′55″), during the period from 1 to 20 August 2022. All samples were morphologically authenticated according to the current standard of Russian Pharmacopeia [22].

4.2. Chemicals and Reagents

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

4.3. Fractional Maceration

The fractional maceration technique was applied to obtain highly concentrated extracts [23]. From 500 g of the wood substance, 20 g of wood were randomly selected for maceration. The total amount of the extractant (ethyl alcohol of reagent grade) was divided into 3 parts, and the parts of plant were consistently infused with the first, second, and third parts. The solid–solvent ratio was 1:20. The infusion of each part of the extractant lasted 7 days at room temperature.

4.4. Extraction

SC-CO2 extraction was performed using the SFE-500 system (Thar SCF Waters, Milford, CT, USA) supercritical pressure extraction apparatus. System options include: co-solvent pump (Thar Waters P-50 High Pressure Pump), for extracting polar samples; CO2 flow meter (Siemens, Munich, Germany), to measure the amount of CO2 being supplied to the system; and multiple extraction vessels, to extract different sample sizes or to increase the throughput of the system. The flow rate was 10–25 mL/min for liquid CO2 and 1.00 mL/min for EtOH. Extraction samples of 100 g of wood substance of M. amurensis were used. The extraction time was counted after reaching the working pressure and equilibrium flow, and it was 60–90 min for each sample.

4.5. Liquid Chromatography

HPLC was performed using 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) to perform the separation of multicomponent mixtures. 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 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.

4.6. Mass Spectrometry

MS analysis was performed on an ion trap amaZon SL (BRUKER DALTONIKS, Bremen, Germany) equipped with an ESI source in the 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; and collision energy: 60 eV. An ion trap was used in the scan range m/z 100–1.700 for MS and MS/MS. The capture rate was one spectrum/s for MS and two spectrum/s for MS/MS. Data collection was controlled using Windows software for BRUKER DALTONIKS. All experiments were repeated three times. A four-stage ion separation mode (MS/MS mode) was implemented.

4.7. Antiradical Activity

We determined the DPPH (2,2-diphenyl-1-picrylhydrazyl) scavenging effect of extracts from M. amurensis heartwood. The extracts were added to DPPH solution in MeOH (10−4 M) at concentrations from 1 to 85 µg/mL. We kept the reacting mixture in the dark at room temperature for 20 min. Then, we measured the absorbance at 517 nm using a Shimadzu UV-1800 spectrophotometer (Shimadzu, Canby, OR, USA). We used Equation (1) to calculate the DPPH radical-scavenging effect (%):
DPPH   scavenging   effect ,   %   = A 0 − A x A 0 × 100 ,
where A0 is the absorbance of DPPH solution without M. amurensis extracts (blank sample); Ax is the absorbance of DPPH solution in the presence of different concentrations of extracts.
Quercetin was used as a reference compound. All experiments were performed in triplicate. The half maximal inhibitory concentrations (IC50) for extracts were calculated by plotting the DPPH scavenging effect (%) against the concentrations of M. amurensis extracts. IC50 values are given as the mean ± SEM.

5. Conclusions

Three types of extraction were used to obtain biologically active substances from the wood substance of M. amurensis: supercritical CO2 extraction, maceration with EtOH, and maceration with MeOH. The supercritical extraction method proved to be the most effective type of extraction, giving the highest yield of biologically active substances. Several experimental conditions were investigated in the pressure range of 50–400 bar, with the used volume of co-solvent ethanol being 2% in the liquid phase at a temperature in the range of 31–70 °C. The most effective extraction conditions are: pressure of 100 bar and temperature at 55 °C for the wood substance of M. amurensis. The wood of M. amurensis contains various polyphenolic compounds and compounds of other chemical groups with valuable biological activity. Tandem mass spectrometry (HPLC-ESI—ion trap) was applied to detect target analytes. 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 and positive ions. The four-stage ion separation mode was implemented. Sixty-six different biologically active components have been identified in M. amurensis extracts. Twenty-two polyphenols were identified for the first time in the genus Maackia.
These data could support future research for the production of a variety of pharmaceutical products containing ultra-pure extracts of M. amurensis. The richness of various biologically active compounds, including compounds of the polyphenol group and compounds of other chemical groups (amino acids, Omega fatty acids, sterols, triterpenoids, etc.), provides great opportunities for the design of new nutritional and dietary supplements based on extracts from this Maackia genus.

Author Contributions

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

Funding

This research was carried out with financial support of the Ministry of Education and Science of the Russian Federation, agreement No. 075-15-2022-1143, 7 July 2022.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Acknowledgments

Research work according to financial support of the Ministry of Education and Science of the Russian Federation, agreement No. 075-15-2022-1143, 7 July 2022.

Conflicts of Interest

The authors declare no conflict of interest.

Appendix A

Table
Table A1. Compounds identified from the CO2 extracts of M. amurensis in positive and negative ionization modes using HPLC–ion trap–MS/MS.
Table A1. Compounds identified from the CO2 extracts of M. amurensis in positive and negative ionization modes using HPLC–ion trap–MS/MS.
№Class of CompoundsIdentified CompoundsFormulaMassMolecular Ion [M-H]-Molecular Ion [M+H]+2 Fragmentation MS/MS 3 Fragmentation MS/MS 4 Fragmentation MS/MS References
POLYPHENOLS
1Flavone2′-Hydroxyformononetin [Xenognosin B]C16H12O5 284.2635283 270; 255; 185; 151255; 150169Maackia amurense [5,6,7,8]
2FlavoneDaidzein [4′,7-Dihydroxyisoflavone; Daidzeol]C15H10O4 254.2375 255227; 211; 199; 163; 145 Maackia amurense [5,6,7,8]; Hedyotis diffusa [24]; Isoflavones [25]
3FlavoneFormononetin [Biochanin B; Formononetol]C16H12O4 268.2641 269253236; 153209; 181Astragali Radix [21,22,23]; Isoflavones [25]; Huolisu Oral Liquid [26]
4FlavoneApigenin [5,7-Dixydroxy-2-(40Hydroxyphenyl)-4H-Chromen-4-One]C15H10O5 270.2369269 225181181; 155Dracocephalum palmatum [27]; Lonicera japonica [28]; Andean blueberry [29]; Mexican lupine species [30]; Dracocephalum [31]
5FlavoneGenistein [Pruneton; 4′,5,5-Trihydroxyisoflavone; Sophoricol]C15H10O5 270.2369 271253; 225; 215; 201; 179; 153151 Maackia amurense [5,6,7,8]; Mexican lupine species [30]; Isoflavones [25]
6FlavoneCalycosin [3′-Hydroxyformononetin]C16H12O5 284.2635283 268; 254; 224; 187224; 195; 175224 Maackia amurense [5,6,7,8]; Astragali radix [21,22,23]; Huolisu Oral Liquid [26]
7Flavone5-MethoxydaidzeinC16H12O5 284.2635 285229; 211; 177; 163211; 197; 183; 153153Maackia amurense [1,2,5,6]
8FlavoneBiochanin-A [4′-Methylgenistein; 5,7-Dihydroxy-4′-Methoxyisoflavone] *C16H12O5 284.2635 285270; 229; 152242; 152213; 158Astragali radix [21,22,23]
9FlavoneOrobol [Isoluteolin; 5,7,3′,4′ -Tetrahydroxyisoflavone]C15H10O6286.2363285 283; 173268; 224224Maackia amurense [1,2,5,6]
10Flavone7-Hydroxy-6,4′-dimethoxyisoflavone *C17H14O5 298.2901 299286; 269; 245; 223; 167152 Astragali radix [21,22,23]
11FlavoneAfromosin [Castanin]C17H14O5 298.2901 299284; 239253; 213; 178; 152225; 167Maackia amurense [1,2,5,6]
12FlavoneTectorigeninC16H12O6300.2629 301286; 269; 245; 226; 175; 153258; 240; 212; 187; 168; 153229; 212; 184; 156Maackia amurense [1,2,5,6]
13FlavoneTrihydroxy methoxyflavone *C16H12O6300.2629299 284; 240; 177240; 211; 176; 150213; 196; 156A. cordifolia [32]; Rosmarinus officinalis [33]
14Flavone3-HydroxyvestitonC16H14O6 302.2788301 283; 299; 227; 177267; 240; 150224Maackia amurense [1,2,5,6]
15FlavoneOdoratinC17H14O6 314.2895 315300; 287; 255; 193; 167148 Astragali radix [21,22,23]
16FlavoneCirsimaritin [Scrophulein; 4′,5-Dihydroxy-6,7-Dimethoxyflavone; 7-Methylcapillarisin] *C17H14O6 314.2895313 298; 269283; 255; 239; 195255; 211Rosmarinus officinalis [33]; Artemisia annua [34]; Ocimum [35]
17FlavoneDihydroxy-dimethoxy(iso)flavone * C17H14O6 314.2895 315313; 298; 269; 189269; 167237; 213; 154Astragali radix [21; 22; 23]; Rosmarinus officinalis [33]; Propolis [36]
18FlavoneMyricetin * C15H10O8 318.2351 319291; 219; 143191; 143173Andean blueberry [29]; F. glaucescens [32]; Propolis [36]; Solanaceae [37]
19FlavoneCirsiliol *C17H14O7 330.2889329 311; 249; 229; 171153 Ocimum [35]
20FlavoneWighteone [Erythrinin B] *C20H18O5338.3539 339283255; 237; 183; 165183Mexican lupine species [30]
21IsoflavoneLuteone *C20H18O6 354.3533 355299281; 229; 165183Mexican lupine species [30]
22FlavoneDihydroxy tetramethoxyflavanone *C19H20O8376.3573 377359; 341; 231; 189341; 313; 239; 173323; 295; 229; 179G. linguiforme [32]
23FlavoneHydroxy hexamethoxyflavone *C21H24O9 420.4099419 404; 389; 373; 329373; 359; 202358; 328F. pottsii [32]
24FlavoneFormononetin (Glycosylated and methylated)C23H24O9 444.4313 445293; 267; 235; 217; 179183 Triticum aestivum L. [38,39]
25FlavoneOdoratin-O-hexoside *C23H24O11476.4301 477415; 358; 331; 277331; 303; 261; 206261; 233Astragali radix [21,22,23]
26Flavone6,4′-Dimethoxyisoflavone-7-O-glucoside *C23H24O10 460.4307 461283; 257; 215; 179265; 237; 221; 197; 175247; 219; 191; 181Astragali radix [21,22,23]
27FlavoneFormononetin-7-O-glucoside-6″-O-malonate *C25H24O12516.4509 517269254; 237; 213; 163253; 237; 226; 181Astragali radix [21,22,23]
28FlavoneGenistein C-glucoside malonylated *C24H22O13518.4237 519415; 369; 331331; 261; 206 Mexican lupine species [30]
29FlavoneMaackiasinC30H22O9526.4903 527283; 255; 212; 171255; 229; 152240; 212; 184; 171Maackia amurense [1,2,5,6]
30FlavoneCalycosin-7-O-beta-D-glucoside-6″-O-malonate *C25H24O13532.4503 533285; 198257; 229; 179; 167 Astragali radix [21,22,23]
31FlavoneChrysoeriol 8-C-glucoside malonylated *C25H24O14548.4497 549487; 459; 365; 333; 245245; 219; 167 Mexican lupine species [30]
32FlavoneApigenin 7-C-glucosyldideoxyhexoside *C27H30O13562.5193 563431; 269254; 237; 213; 199; 163253; 237; 225; 181Passiflora incarnata [40]
33IsoflavoneOnonin derivativeC27H28O15592.5022 593269254; 237; 213237; 226; 200Isoflavones [25]
34FlavoneApigenin 6-C-[6″-acetyl-2”-O-deoxyhexoside]-glucoside * C29H32O15620.5554 621561533; 461433Passiflora incarnata [40]
35FlavonolKaempferol [3,5,7-Trihydroxy-2-(4-hydro-xyphenyl)-4H-chromen-4-one] C15H10O6286.2363 287269; 259; 229; 213; 177; 163; 153213; 171; 152198; 181; 153Lonicera japonica [28]; Andean blueberry [29]; Dracocephalum [31]; Rhus coriaria (Sumac) [41]
36FlavonolQuercetinC15H10O7 302.2357 303285; 228; 165229; 165141Astragali radix [21,22,23]; Propolis [36]; Rhus coriaria [41]
37FlavonoidDi-O-galloyl-glucoside *C20H20O14484.3644 485331; 267; 225; 169225; 199; 163215; 197Rosa rugosa [42]; Rosa canina [43]; Euphorbia hirta [44]
38IsoflavanVestitolC16H16O4272.2958 273255; 227; 179227; 197209Maackia amurense [1,2,5,6]
39Prenyl flavonoidPrenyl naringenin [8-Prenylnaringenin; Flavaprenyl] *C20H20O5340.3698 341285; 221; 179; 153267; 221; 179249; 171A. cordifolia [32]; Beer [45]; Hop Prenylflavonoids [46]
40Flavan-3-ol(epi)Catechin-5-O-D-glycopyranoside * C21H24O11452.4087 453343; 315; 281; 269; 227161; 151143Actinidia [47]
41FlavanoneLiquiritigenin [4′,7-Dihydroxyflavanone; 5-Deoxyflavanone]C15H12O4 256.2534255 237; 213; 187; 151185; 169; 145 Bauninia championii [48]; Maackia amurense [1,2,5,6]
42FlavanoneMethyl-liquiritigenin [7-O-Methyl-liquiritigenin] *C16H14O4 270.2800 271243; 221; 183; 161183; 173; 155155PubChem
43FlavanoneLiquiritigenin dimethyl ester [4′,7-Dimethoxyflavanone] *C17H16O4 284.3065 285257; 227225; 197; 173 PubChem
44FlavanonePadmatin [7-Methoxy-3,3′,4′,5-tetrahydroxyflavanone] *C16H14O7 318.2782317 299; 287; 270; 193284; 256; 240283; 256; 240; 228Propolis [36]
45FlavanoneMaackiaflavanone BC30H34O5474.5880 475457; 413; 389; 349; 301; 255; 173173; 145 PubChem
46Phenolic acidFerulic acidC10H10O4194.184 195 Astragali radix [21,22,23]; Actinidia [47]; Codonopsis Radix [49]
47StilbeneResveratrol [trans-Resveratrol; 3,4′,5-Trihydroxystilbene; Stilbentriol]C14H12O3228.2433 229211; 183183; 171; 155 Maackia amurense [1,2,5,6]; Radix polygoni multiflori [50]; Embelia [51]
48Stilbene3-Hydroxyresveratrol [Piceatannol]C14H12O4244.2427243 225; 201225; 157; 197 Maackia amurense [1,2,5,6]; G. linguiforme [32]; Vine stilbenoids [52]
49StilbenePiacetannol-3-O-glucoside [Quzhaqigan] *C20H22O9406.3833 407351; 333; 295; 229333; 295; 217; 179319; 265; 235; 200PubChem
50StilbenolignanMaackolinC25H24O8452.4533 453343; 281; 161315; 283; 222; 161283; 251; 205; 161Maackia amurense [1,2,5,6]
51Dimeric stilbeneResveratrol-piceatannol *C28H22O7470.4701 471377; 365; 343; 307; 267; 215267; 249; 221249; 221; 199Vine stilbenoids [52]; vinery products [53]
52Dimeric stilbeneScirpusin AC28H22O7470.4701469 345; 304; 241317; 299; 275; 251; 223315; 288; 258Maackia amurense [1,2,5,6]
53Dimeric stilbeneScirpusin BC28H22O8486.4695 487377; 255; 231; 157267; 249249Maackia amurense [1,2,5,6]
54HydroxycoumarinEsculin [Aesculin; Esculoside; Polichrome; Esculetin-6-O-glucoside] *C15H16O9340.2821 341179; 165151 Artemisia annua [34]; A. cordifolia [32]; Actinidia [47]; Stevia rebaudiana [54]
OTHERS
55Omega-5 fatty acidMyristoleic acid [Cis-9-Tetradecanoic acid] *C14H26O2226.3550 227209139 F. glaucescens [32]; Dracocephalum [31]
56PterocarpanMedicarpin [(+)-Medicarpin; Demethylhomopterocarpin; 3-Hydroxy-9-Methoxypterocarpan]C16H14O4 270.2800 271215; 181; 161197; 187; 169; 159169Maackia amurense [1,2,5,6]; Astragali radix [21,22,23]
57Omega-3 fatty acidStearidonic acid [6,9,12,15-Octadecatetraenoic acid; Moroctic acid] *C18H28O2276.4137 277177; 276; 259; 241; 219; 195; 149161 G. linguiforme [32]; Rhus coriaria [41]; Salviae Miltiorrhizae [55]; Jatropha [56]
58Omega 3-fatty acidLinolenic acid (Alpha-Linolenic acid; Linolenate) *C18H30O2 278.4296 279219; 259159 Salviae Miltiorrhizae [55]; Jatropha [56]; Pinus sylvestris [57]
59PterocarpanMaakiain [Inermin]C16H12O5 284.2635 285283; 269; 252; 228; 200; 169254; 238; 210 Maackia amurense [1,2,5,6]
60 Omega 3-fatty acidHydroxy linolenic acid *C18H30O3294.4290 295276; 248; 171231; 221; 159 A. cordifolia [32]
61Higher-molecular-weight carboxylic acidOxo-nonadecanoic acid *C19H36O3312.4873 313298; 269269; 252; 213; 165269; 213; 181G. linguiforme; F. pottsii; A. cordifolia [32]
62Oxylipins13-Trihydroxy-Octadecenoic acid [THODE] *C18H34O5330.4596329 171; 311; 275; 229; 211; 201311; 201; 171183; 211Dracocephalum [31]; Bituminaria [58]; Brassica oleracea [59]
63Unsaturated fatty acidPentacosenoic acid *C25H48O2380.6474379 361; 337; 319; 295; 255343; 333; 302; 273; 250343; 315; 301F. glaucescens [32]
64Anabolic steroidVebonol *C30H44O3452.6686 453435; 417; 336; 302; 245336; 309; 281; 243; 226; 209209; 192; 147Rhus coriaria [41]; Rosa rugosa [60]; Zostera marina [61]
65Triterpenic acidUrsolic acid *C30H48O3 456.7003 457411; 367; 323; 236; 189393; 263; 163348Hedyotis diffusa [24]; Ocimum [35]
66Product of chlorophylle degradationPheophytin A *C55H74N4O5871.1999 593; 533533; 461461; 433Physalis peruviana [62]; Capsicum [63]
* Chemical compounds identified for the first time in M. amurensis.

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Molecules 28 02026 g001 550
Figure 1. (A) Maackia amurensis L.; (B) fruits of Maackia amurensis species. Photo taken by N.P. Mishchenko (August 2020).
Figure 1. (A) Maackia amurensis L.; (B) fruits of Maackia amurensis species. Photo taken by N.P. Mishchenko (August 2020).
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Molecules 28 02026 g002 550
Figure 2. 3D graph data of supercritical CO2 extraction. Complex yield of biologically active substances from CO2 extracts of wood substance of M. amurensis.
Figure 2. 3D graph data of supercritical CO2 extraction. Complex yield of biologically active substances from CO2 extracts of wood substance of M. amurensis.
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Molecules 28 02026 g003 550
Figure 3. CID spectrum of 3-Hydroxyrvestitol from M. amurense, at m/z 275.01.
Figure 3. CID spectrum of 3-Hydroxyrvestitol from M. amurense, at m/z 275.01.
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Molecules 28 02026 g004 550
Figure 4. CID spectrum of odoratin-O-hexoside from M. amurense, at m/z 477.45.
Figure 4. CID spectrum of odoratin-O-hexoside from M. amurense, at m/z 477.45.
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Molecules 28 02026 g005 550
Figure 5. CID spectrum of formononetin-7-O-glucoside-6″-O-malonate from M. amurense, at m/z 517.19.
Figure 5. CID spectrum of formononetin-7-O-glucoside-6″-O-malonate from M. amurense, at m/z 517.19.
Molecules 28 02026 g005
Molecules 28 02026 g006 550
Figure 6. CID spectrum of calycosin-7-O-beta-D-glucoside-6″-O-malonate acid from M. amurense, at m/z 533.22.
Figure 6. CID spectrum of calycosin-7-O-beta-D-glucoside-6″-O-malonate acid from M. amurense, at m/z 533.22.
Molecules 28 02026 g006
Table
Table 1. Identified chemical constituents by tandem mass spectrometry in three types of extraction: supercritical CO2 extraction, maceration with EtOH, maceration with MeOH.
Table 1. Identified chemical constituents by tandem mass spectrometry in three types of extraction: supercritical CO2 extraction, maceration with EtOH, maceration with MeOH.
№Class of CompoundsIdentified CompoundsMeOH ExtractionEtOH ExtractionStatic CO2 ExtractionCO2 Extraction 100 BarCO2 Extraction 300 Bar
POLYPHENOLS
1Flavone2′-Hydroxyformononetin [Xenognosin B]+
2FlavoneDaidzein [4′,7-Dihydroxyisoflavone; Daidzeol]+ ++
3FlavoneFormononetin [Biochanin B; Formononetol]+++
4FlavoneApigenin ++ ++
5FlavoneGenistein+ +
6FlavoneCalycosin [3′-Hydroxyformononetin] + +
7Flavone5-Methoxydaidzein+++++
8FlavoneBiochanin-A * + +
9FlavoneOrobol + +++
10Flavone7-Hydroxy-6,4′-dimethoxyisoflavone* +
11FlavoneAfromosin [Castanin] +++
12FlavoneTectorigenin+++++
13FlavoneTrihydroxy methoxyflavone * ++
14Flavone3-Hydroxyvestiton ++
15FlavoneOdoratin+++++
16FlavoneCirsimaritin * +
17FlavoneDihydroxy-dimethoxy(iso)flavone * +
18FlavoneMyricetin * +
19FlavoneCirsiliol * +
20FlavoneWighteone [Erythrinin B] *++ ++
21IsoflavoneLuteone * +
22FlavoneDihydroxy tetramethoxyflavanone *+
23FlavoneHydroxy hexamethoxyflavone * +
24FlavoneFormononetin (Glycosylated and methylated) +
25FlavoneOdoratin-O-hexoside *+ +
26Flavone6,4′-Dimethoxyisoflavone-7-O-glucoside * +
27FlavoneFormononetin-7-O-glucoside-6″-O-malonate +
28FlavoneGenistein C-glucoside malonylated *+
29FlavoneMaackiasin +
30FlavoneCalycosin-7-O-beta-D-glucoside-6″-O-malonate * +
31FlavoneChrysoeriol 8-C-glucoside malonylated * +
32FlavoneApigenin 7-C-glucosyldideoxyhexoside * +
33IsoflavoneOnonin derivative +
34FlavoneApigenin 6-C-[6″-acetyl-2″-O-deoxyhexoside]-glucoside +
35FlavonolKaempferol+ +
36FlavonolQuercetin +
37FlavonoidDi-O-galloyl-glucoside * +
38IsoflavanVestitol +
39Prenyl flavonoidPrenyl naringenin *+ +
40Flavan-3-ol(epi)Catechin-5-O-D-glycopyranoside * +
41FlavanoneLiquiritigenin ++ +
42FlavanoneMethyl-Liquiritigenin * + +
43FlavanoneLiquiritigenin dimethyl ester * ++
44FlavanonePadmatin * +
45FlavanoneMaackiaflavanone B +
46Phenolic acidFerulic acid +
47StilbeneResveratrol +
48Stilbene3-Hydroxyresveratrol [Piceatannol] + ++
49StilbenePiacetannol-3-O-glucoside [Quzhaqigan] +
50StilbenolignanMaackolin +
51Dimeric stilbeneResveratrol-piceatannol * +
52Dimeric stilbeneScirpusin A +
53Dimeric stilbeneScirpusin B +
54HydroxycoumarinEsculin * +
OTHERS
55Omega-5 fatty acidMyristoleic acid [Cis-9-Tetradecanoic acid] *++ +
56PterocarpanMedicarpin +
57Omega-3 fatty acidStearidonic acid * +
58Omega 3-fatty acidLinolenic acid * +
59PterocarpanMaakiain [Inermin]++
60Omega 3-fatty acidHydroxy linolenic acid * +
61Higher-molecular-weight carboxylic acidOxo-nonadecanoic acid +
62Oxylipins13-Trihydroxy-Octadecenoic acid * +
63Unsaturated fatty acidPentacosenoic acid * +
64Anabolic steroidVebonol * +
65Triterpenic acidUrsolic acid * +
66Product of chlorophyll degradationPheophytin A *++ ++
* Chemical compounds identified for the first time in M. amurensis.
Table
Table 2. DPPH scavenging activity of M. amurensis extracts.
Table 2. DPPH scavenging activity of M. amurensis extracts.
CompoundDPPH Scavenging Effect
IC50 µg, 20 min
Quercetin3.05 ± 0.12
MeOH extraction22.26 ± 1.95
EtOH extraction38.35 ± 4.09
Static CO2 extraction30.11 ± 3.10
CO2 extraction 100 Bar5.13 ± 0.42
CO2 extraction 300 Bar15.32 ± 2.02
Data are presented as the mean values ± SEM, n = 3.
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Razgonova, M.P.; Cherevach, E.I.; Tekutyeva, L.A.; Fedoreyev, S.A.; Mishchenko, N.P.; Tarbeeva, D.V.; Demidova, E.N.; Kirilenko, N.S.; Golokhvast, K. Maackia amurensis Rupr. et Maxim.: Supercritical CO2 Extraction and Mass Spectrometric Characterization of Chemical Constituents. Molecules 2023, 28, 2026. https://doi.org/10.3390/molecules28052026

AMA Style

Razgonova MP, Cherevach EI, Tekutyeva LA, Fedoreyev SA, Mishchenko NP, Tarbeeva DV, Demidova EN, Kirilenko NS, Golokhvast K. Maackia amurensis Rupr. et Maxim.: Supercritical CO2 Extraction and Mass Spectrometric Characterization of Chemical Constituents. Molecules. 2023; 28(5):2026. https://doi.org/10.3390/molecules28052026

Chicago/Turabian Style

Razgonova, Mayya P., Elena I. Cherevach, Lyudmila A. Tekutyeva, Sergey A. Fedoreyev, Natalia P. Mishchenko, Darya V. Tarbeeva, Ekaterina N. Demidova, Nikita S. Kirilenko, and Kirill Golokhvast. 2023. "Maackia amurensis Rupr. et Maxim.: Supercritical CO2 Extraction and Mass Spectrometric Characterization of Chemical Constituents" Molecules 28, no. 5: 2026. https://doi.org/10.3390/molecules28052026

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