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Article

Rapid Mass Spectrometric Study of a Supercritical CO2-extract from Woody Liana Schisandra chinensis by HPLC-SPD-ESI-MS/MS

by
Mayya Razgonova
1,2,*,
Alexander Zakharenko
1,2,
Konstantin Pikula
1,2,
Ekaterina Kim
1,
Valery Chernyshev
1,2,
Sezai Ercisli
3,
Giancarlo Cravotto
4 and
Kirill Golokhvast
1,2,5
1
REC Nanotechnology, School of Engineering, Far Eastern Federal University, Sukhanova 8, 690950 Vladivostok, Russia
2
N.I. Vavilov All-Russian Institute of Plant Genetic Resources, B. Morskaya 42-44, 190000 Saint-Petersburg, Russia
3
Agricultural Faculty, Department of Horticulture, Ataturk University, Erzurum 25240, Turkey
4
Dipartimento di Scienza e Technologia del Farmaco, University of Turin, Via P. Giuria 9, 10125 Turin, Italy
5
Pacific Geographical Institute, Far Eastern Branch of the Russian Academy of Sciences, Radio 7, 690041 Vladivostok, Russia
*
Author to whom correspondence should be addressed.
Molecules 2020, 25(11), 2689; https://doi.org/10.3390/molecules25112689
Submission received: 20 April 2020 / Revised: 5 June 2020 / Accepted: 8 June 2020 / Published: 10 June 2020
(This article belongs to the Special Issue New Biologically Active Substances from Plants and Animals of the Pacific Region)
Browse Figures
Versions Notes

Abstract

:
Woody liana Schisandra chinensis contains valuable lignans, which are phenylpropanoids with valuable biological activity. Among green and selective extraction methods, supercritical carbon dioxide (SC-CO2) was shown to be the method of choice for the recovery of these naturally occurring compounds. Carbon dioxide (CO2) was the solvent with the flow rate (10−25 g/min) with 2% ethanol as co-solvent. In this piece of work operative parameters and working conditions were optimized by experimenting with different pressures (200–400 bars) and temperatures (40–60 °C). The extraction time varied from 60 to 120 min. HPLC-SPD-ESI -MS/MS techniques were applied to detect target analytes. Twenty-six different lignans were identified in the S. chinensis SC-CO2 extracts.

1. Introduction

Schisandra chinensis (Turczaninowia) Baillon, is a medicinal plant (of the Schisandraceae family), known for its ethnomedicinal applications [1]. Its use in Chinese medicine dates back about 15 centuries, second only to ginseng. S. chinensis is included in the traditional Chinese medicine formula Sheng-Mai San, which has been used in the treatment of cardiovascular diseases [2]. Schisandra-based drugs, with the common names Shengmai-injection, Shengi Wuweizi-Pan and Shengmai-Yin are also included in the Chinese Pharmacopoeia [3].
The genus Schisandra (Schisandraceae family) consists of 25 species, two of which, namely Schisandra chinensis and Schisandra repanda (Maximowiczia nigra (Maxim.) Nakai), have a history of medicinal use [4]. Schisandra chinensis (synonyms: Kadsura chinensis, Maximoviczia amurensis, Maximoviczia chinensis, Maximoviczia japonica, Sphaerostemma japonicum, Wu wei zi) is endemic in northwest China (Heilongjiang Province), Korea, Russia (Primorye and Amur regions as well as Khabarovsk territory), Shikotan, Kunashir, Iturup, and on the island of Sakhalin.
Russian academician Komarov V.L. made a botanical description of S. chinensis (Turcz.) Baill. for the first time in 1901 and gave the first information about its healing effect, having brought it from expeditions to the Far East [5,6]. This is a deciduous liana, climbing up neighboring trees, up to 10−15 m long. The stem is covered with wrinkled, flaky dark brown bark. The leaves are elliptical 5−10 cm long, 3−5 cm wide, dicotyledonous flowers, up to 1.5 cm in diameter, with a distinct lemon aroma, multi-berry fruits, up to 10 cm long, juicy red seeds with a smooth shiny surface, yellowish-brown. Plant grinding develops an intense characteristic smell while the taste is spicy and bitter-burning. The whole plant has a specific lemon smell. The modern use of S. chinensis started with a large number of pharmacological and clinical studies conducted in the former USSR in the period 1940−1960 [7,8].
Various descriptions of the specific properties of S. chinensis are available in English in reviews of Far Eastern medicinal plants. [9]. However, a large amount of information that was reported in Russian journals [4,10,11,12,13,14] is practically not accessible to foreign scientists [15].
More than 40 individual lignans have been reported in the literature, 11 of them, namely schisandrin, gomisin J, gomisin A, gomisin G, angeloygomisin H, angeloygomisin O, schisantherin A, schisantherin B, γ-schisandrin (schisandrin B) and schisandrin C, characterize the S. chinensis (Turcz.) Baill. present in several pharmacopeias. It has a chemical composition that differs from the non-pharmacopeia species Schizandra sphenanthera Rehd. et Wils [16,17].
Lignans are phenylpropane dimers consisting of two propane residues C6–C3. Lignans are found in various parts of the plant, especially in the seeds, the underground parts, the wood and woody stems. They may be present in plants in free form and in the form of glycosides [18]. Schizandra lignans are called schisandrins. The chemical skeleton of S. chinensis lignans is depicted in Figure 1 and all the substituents are presented in Table 1.
The lignans of S. chinensis have been typically extracted with ethanol or hazardous potentially toxic organic solvents such as methanol, chloroform and n-hexane. A valid green alternative, in which there is no need to work with a large number of organic solvents and the production does not need explosion-proof rooms, is represented by supercritical fluid extraction (SFE) with many advantages compared to common extraction methods (maceration, percolation Soxhlet extraction) [19,20].
SFE is a green, mild and selective extraction process, one of the best processes to get rid of residual solvent in the extract. Among the supercritical solvents, carbon dioxide is the most common, offering several advantages, because it is non-toxic, non-flammable, cost-effective, environmentally friendly and renewable [25,26,27]. The SFE method is actively studied and applied in the processing of plant materials [28,29].
The lignans of S. chinensis were extracted by supercritical CO2 (SC-CO2) using ethanol as co-solvent [30,31,32]. Different parts of the plant were extracted by SFE, isolating 36 compounds from the leaves, 43 compounds from lignified stems and 36 compounds from rhizomes and roots. S. chinensis extracts contain a volatile fraction rich in essential oils (terpenes: monoterpenes, sesquiterpenes; terpenoids: alcohols, esters, ketones) and a non-volatile part (carboxylic acids and lignans).

2. Results and Discussion

Aiming to optimize the extraction of target analytes from the S. chinensis woody liana, several experimental conditions were investigated. Carbon dioxide (CO2) was the solvent with the flow rate (10−25 g/min) and 2% ethanol as co-solvent in the liquid phase. Extraction was performed in the pressure range of 200–400 bar and the temperature range of 40–60 °C. The best results were obtained at 350 bar and 60 °C. Increasing the pressure from 350 to 400 bar practically gave no increase in yields. The temperature of 60 °C was chosen as the maximum allowable to avoid the decomposition of target analytes. In this work HPLC-SPD-ESI-MS/MS techniques were used with additional ionization and analysis of fragmented ions. 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 ions. The three-stage ion separation mode was implemented. Under these conditions a total of 800 peaks were detected in the ion chromatogram (Figure 2).
Although this approach is not quantitative for evaluating each analyte, it is semiquantitative when comparing a series of extractions and allows better comparison of the yield without loss of individual analytes during fractionation and sample preparation. Only the total extraction yields were completely quantified.
Table 2 summarizes all the molecular masses of the target analytes isolated from SC-CO2 of S. chinensis. Among them, 26 biologically active substances were authenticated as lignans (m/z values and fragment ions) by comparison with literature data [2,22,23,33,34,35,36].
Figure 3 shows examples of the decoding spectra (collision-induced dissociation (CID) spectrum) of the ion chromatogram obtained using tandem mass spectrometry. The CID spectrum in positive ion modes of schisandrin B (gomisin N, isokadsuranin) from Russian S. chinensis.
The [M + H]+ ion produced one fragment with m/z 369.04 (Figure 3). The fragment ion with m/z 369.04 further formed two daughter ions with m/z 354.04 and m/z 338.00. The fragment ion with m/z 354.04 produced three daughter ions with m/z 322.97, m/z 295.03, and m/z 264.03.
The CID spectrum in positive ion modes of schisantherin A (gomisin C) from S. chinensis is shown in Figure 4.
The [M + H]+ ion produced three fragments with m/z 414.99, m/z 371.05 and m/z 340.98 (Figure 4). The fragment ion with m/z 414.99 produced two characteristic daughter ions with m/z 370.99 and m/z 341.02. The fragment ion with m/z 370.99 formed three daughter ions with m/z 341.01, m/z 310.01, and m/z 282.06.
The CID spectrum in positive ion modes of benzoylgomisin Q is shown in Figure 5.
The [M + H]+ ion produced three fragments with m/z 415.05, m/z 436.98 and m/z 384.03 (Figure 5). The fragment ion with m/z 415.05 produced three daughter ions with m/z 400.0, m/z 384.03 and m/z 359.00. The fragment ion with m/z 384.03 yielded three daughter ions with m/z 369.02, m/z 352.99, and m/z 338.00.

3. Materials and Methods

3.1. Materials

As the objects of the study, samples of S. chinensis (woody liana) were purchased from the area of the Peschanka river near Lazovsky district (Sikhote Alin), Primorsky Krai, located at 43°32′ N and 134°33′ E, Russia. All samples were morphologically authenticated according to the current standard of Russian Pharmacopeia [37].

3.2. 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, Germany), and all the other chemicals were analytical grade.

3.3. SC-CO2 Extraction

SC-CO2 extraction was performed using the SFE-500 system (Thar SCF Waters, Milford, USA) supercritical pressure extraction apparatus. System options included co-solvent pump (Thar Waters P-50 High Pressure Pump), for extracting polar samples. CO2 flow meter (Siemens, Germany), to measure the amount of CO2 being supplied to the system, multiple extraction vessels, to extract different sample sizes or to increase the throughput of the system. Flow rate was 50 mL/min for liquid CO2 and 1.76 mL/min for EtOH. Extraction samples of 10 g Schisandra chinensis wood were used. The extraction time was counted after reaching the working pressure and equilibrium flow, and it was 6 h for each sample.

3.4. Liquid Chromatography

HPLC was performed using Shimadzu LC-20 Prominence HPLC (Shimadzu, Japan), equipped with an UV−VIS detector. The analytical reverse phase column used was a Shodex ODP-40 4E C18 (4.6 × 250 mm, particle size: 4 μm) to perform the separation of multicomponent mixtures. The gradient elution program was as follows: 0.01−4 min, 100% A; 4−60 min, 100−25% A; 60−75 min, 25−0% A; control washing 75−120 min 0% A. The entire HPLC analysis was performed using a UV−VIS detector SPD-20A (Shimadzu, Japan) at wavelengths of 230 and 330 nm, at 17 °C provided with column oven CTO-20A (Shimadzu, Japan) with an injection volume of 20 μL.

3.5. Mass Spectrometry

MS analysis was performed on an ion trap amaZon SL (BRUKER DALTONIKS, Germany) equipped with an ESI source in negative ion mode. The optimized parameters were obtained as follows: ionization source temperature: 70 °C, gas flow: 4 L/min, nebulizer gas (atomizer): 7.3 psi, capillary voltage: 4500 V, end plate bend voltage: 1500V, fragmentary: 280 V, 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 for MS and two spectra for MS/MS. Data collection was controlled by Windows software for BRUKER DALTONIKS. All experiments were repeated three times. A two-stage ion separation mode (MS/MS mode) was implemented.

4. Conclusions

An optimized extraction process with SC-CO2 (and co-solvent 2% ethanol) of woody liana S. chinensis provided the samples for an accurate analytical study by HPLC-SPD-MS/MS techniques. Twenty-six different lignans typical of S. chinensis species were identified. This method allows one to get all the studied ligands in a single extract without using a series of approaches and solvents, different in polarity, which not only reduces the environmental pressure, but also simplifies the production process. These data could support future investigations on the quality of pharmaceutical preparations containing these S. chinensis extracts. This is because the biological activity is related to the presence of the identified lignans. Their excellent transcutaneous penetration may offer new therapeutic approaches with transdermal preparations based on SC-CO2 extracts of S. chinensis.

Author Contributions

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

Funding

This research was funded by Council on Grants of the President of the Russian Federation (CП-3156.2019.4).

Conflicts of Interest

The authors declare no conflict of interest.

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Sample Availability: Samples fractions are available from the authors.
Molecules 25 02689 g001 550
Figure 1. Structure of S. chinensis lignans.
Figure 1. Structure of S. chinensis lignans.
Molecules 25 02689 g001
Molecules 25 02689 g002 550
Figure 2. Chemical profiles of S. chinensis (Russia), ion chromatogram from SC-CO2 extract.
Figure 2. Chemical profiles of S. chinensis (Russia), ion chromatogram from SC-CO2 extract.
Molecules 25 02689 g002
Molecules 25 02689 g003 550
Figure 3. Collision-induced dissociation (CID) spectrum of the schisandrin B (gomisin N, isokadsuranin) from S. chinensis, m/z 401.07.
Figure 3. Collision-induced dissociation (CID) spectrum of the schisandrin B (gomisin N, isokadsuranin) from S. chinensis, m/z 401.07.
Molecules 25 02689 g003
Molecules 25 02689 g004 550
Figure 4. CID spectrum of the schisantherin A (gomisin C) from S. chinensis, m/z 537.95.
Figure 4. CID spectrum of the schisantherin A (gomisin C) from S. chinensis, m/z 537.95.
Molecules 25 02689 g004
Molecules 25 02689 g005 550
Figure 5. CID spectrum of the benzoylgomisin Q from S. chinensis, m/z 522.99.
Figure 5. CID spectrum of the benzoylgomisin Q from S. chinensis, m/z 522.99.
Molecules 25 02689 g005
Table
Table 1. Chemical structures of S. chinensis lignans, according to the authors [18,21,22,23,24].
Table 1. Chemical structures of S. chinensis lignans, according to the authors [18,21,22,23,24].
№Compound FormulaR1R2R3R4R5R6R7R8R9R10R11
1Schisandrin A (Deoxyschisandrin) C24H32O6CH3CH3CH3CH3CH3CH3CH3HCH3CH3H
2Schisandrol A (Schisandrin) C24H32O7CH3CH3CH3CH3CH3CH3CH3HCH3OHH
3Schisandrin B (Gomisin N, Isokadsuranin) C23H28O6 CH3CH3CH3CH3CH2 HCH3HCH3H
4Schisandrol B (Gomisin A) C23H28O7 CH2 CH3CH3CH3CH3CH3HCH3OHH
5Schisandrin C C22H24O6 CH2 CH3CH3CH3CH3HCH3HCH3H
6Isoschisandrin C24H32O7CH3CH3CH3CH3CH3CH3CH3OHCH3HH
7Gomisin K1C23H30O6 HCH3CH3CH3CH3CH3HCH3HCH3H
8Gomisin K2C23H30O6 HCH3CH3CH3CH3CH3CH3HCH3HH
9Schisanhenol (Gomisin K3) C23H30O6 CH3CH3HCH3CH3CH3CH3HCH3HH
10Gomisin H C23H30O7CH3CH3HCH3CH3CH3CH3HCH3OHH
11Tigloylgomisin H C28H36O8CH3CH3TigloylCH3CH3CH3CH3HCH3OHH
12Angeloygomisin HC28H36O8CH3CH3AngeloylCH3CH3CH3CH3HCH3OHH
13Benzoylgomisin HC30H34O8CH3CH3BenzoylCH3CH3CH3CH3HCH3OHH
4Gomisin JC22H28O6 HCH3CH3CH3CH3HHCH3HCH3H
15Schisanhenol BC22H26O6 CH3CH3HCH3CH2 HCH3HCH3H
16Gomisin NC23H28O6 CH3CH3CH3CH3CH2 CH3HCH3HH
17Gomisin L1C22H26O6 CH3CH3HCH3CH2 HCH3HCH3H
18Gomisin L2C22H26O6 HCH3CH3CH3CH2 HCH3HCH3H
19Gomisin M1C22H26O6 CH3CH3HCH3CH2 CH3HCH3HH
20Gomisin M2C22H26O6 CH3CH3CH3HCH2 CH3HCH3HH
21Gomisin OC23H28O7 CH2 CH3CH3CH3CH3CH3CH3HHOH
22Isogomisin OC23H28O7 CH3CH3CH3CH3CH2 HCH3HCH3OH
23Angeloylsogomisin O C28H34O8CH2 CH3CH3CH3CH3CH3CH3HHO-angeloyl
24Gomisin PC23H28O8 CH2 CH3CH3CH3CH3HCH3OHCH3OH
25Tigloylgomisin P C28H34O9CH2 CH3CH3CH3CH3HCH3OHCH3O-tigloyl
26Angeloylgomisin P (Schisantherin C)C28H34O9CH2 CH3CH3CH3CH3HCH3OHCH3O-angeloyl
27Schisantherin A (Gomisin C)C30H32O9CH2 CH3CH3CH3CH3CH3CH3OHHO-bensoyl
28Schisantherin B (Gomisin B, Schisandrer B)C28H34O9CH2 CH3CH3CH3CH3CH3CH3OHHO-angeloyl
29Gomisin SC23H30O7 CH3CH3CH3CH3CH3CH3HCH3HCH3OH
30Gomisin R (6-Epi-gomisin)C22H24O7 CH2 CH3CH3CH2 CH3HCH3HH
31Deangeloylgomisin BC23H28O8 CH2 CH3CH3CH3CH3CH3CH3OHHOH
32Gomisin FC28H34O9CH3CH3CH3CH3CH2 CH3CH3OHHO-angeloyl
33Gomisin GC30H32O9CH3CH3CH3CH3CH2 CH3CH3OHHO-bensoyl
34Epigomisin OC23H28O7 CH2 CH3CH3CH3CH3CH3CH3CH3HH
35Angeloylgomisin QC29H38O9CH3CH3CH3CH3CH3CH3HCH3CH3OHO-angeloyl
Table
Table 2. Lignans from S. chinensis SC-CO2 extract.
Table 2. Lignans from S. chinensis SC-CO2 extract.
№IdentificationFormulaCalcula-ted MassObserved Mass [M + H]+Observed Mass [M + Na]+MS/MS Stage 1 FragmentationMS/MS Stage 2 Fragmentati-onMS/MS Stage 3 Fragmentation
1Schisandrin C [(12S,13R)-3,22-dimethoxy-12,13-dimethyl-5,7,18,20-tetraoxapentacyclo [13.7.0.02,10.04,8.017,21]docosa-1(22),2,4(8),9,15,17(21)-hexaene]C22H24O6 384.4224385.02 355.01; 323.02323.01; 299.02; 269.03; 234.98307.98; 235.05
2Gomisin M1 (Gomisin L1) [(9S,10R)-4,5,19-trimethoxy-9,10-dimethyl-15,17-dioxatetracyclo [10.7.0.02,7.014,18]nonadeca-1(19),2,4,6,12,14(18)-hexaen-3-ol]C22H26O6 386.4382 408.95290.99; 394.03; 326.08; 274.96260.97; 242.89; 172.97
3Gomisin L2 [(9S,10R)-3,4,19-trimethoxy-9,10-dimethyl-15,17-dioxatetracyclo[10.7.0.02,7.014,18]nonadeca-1(19),2,4,6,12,14(18)-hexaen-5-ol]C22H26O6 386.4382386.98 356.98; 325.00; 284.93; 259.03; 226.99; 167.02; 137.17297.04; 226.98; 182.97
4Gomisin M2 [(9S,10R)-3,4,5-trimethoxy-9,10-dimethyl-15,17-dioxatetracyclo[10.7.0.02,7.014,18]nonadeca-1(19),2,4,6,12,14(18)-hexaen-19-ol]C22H26O6 386.4382387.01 355.01; 324.01; 284.97339.98; 324.02; 284.97; 226.96324.94; 296.90
5Gomisin J [(9S,10R)-3,4,15,16-tetramethoxy-9,10-dimethyltricyclo[10.4.0.02,7]hexadeca-1(16),2,4,6,12,14-hexaene-5,14-diol] C22H28O6 388.4541389.04 325.03; 357.01; 226.96; 286.97227.01; 241.00; 269.03; 297.01226.98; 198.98
6Pregomisin [5-[(2S,3R)-4-(3-hydroxy-4,5-dimethoxyphenyl)-2,3-dimethylbutyl]-2,3-dimethoxyphenol]C22H30O6 390.47391.00 237.07; 205.03; 288.91; 326.96; 359.00205.00; 173.00
7Schisandrin B (Gomisin N, Isokadsuranin) [3,4,5,19-tetramethoxy-9,10-dimethyl-15,17-dioxatetracyclo[10.7.0.02,7.014,18]nonadeca-1(19),2,4,6,12,14(18)-hexaene]C23H28O6 400.3648401.07 369.04354.04; 338.00322.97; 295.03; 264.03
8Schisanhenol (Gomisin K3) [(9S,10R)-4,5,14,15,16-pentamethoxy-9,10-dimethyltricyclo[10.4.0.02,7]hexadeca-1(16),2,4,6,12,14-hexaen-3-ol]C23H30O6 402.4807403.05 371.01; 340.03; 301.01; 259.00340.03; 315.01; 300.98; 286.01; 233.07324.99; 270.99; 227.02
9Gomisin O [(8R,9S,10S)-3,4,5,19-tetramethoxy-9,10-dimethyl-15,17-dioxatetracyclo[10.7.0.02,7.014,18]nonadeca-1(19),2,4,6,12,14(18)-hexaen-8-ol]C23H28O7416.3642417.01 356.97; 373.01329.00313.97; 270.00
10Erigomisin O [(8S,9S,10S)-3,4,5,19-tetramethoxy-9,10-dimethyl-15,17-dioxatetracyclo[10.7.0.02,7.014,18]nonadeca-1(19),2,4,6,12,14(18)-hexaen-8-ol]C23H28O7416.3642416.96 356.98; 340.98; 308.97328.95; 313.98
11Schisandrin A (Deoxyschisandrin) [(9R,10S)-3,4,5,14,15,16-hexamethoxy-9,10-dimethyltricyclo[10.4.0.02,7]hexadeca-1(16),2,4,6,12,14-hexaene]C24H32O6416.5073417.01 316.00; 346.99; 402.01300.96; 284.95; 242.02
12Demethylated metabolites of Schisandrol A 440.95279.00; 322.89; 306.86; 258.89; 202.99259.94;220.86; 137.02
13Schisandrol A (Schisandrin) [(9R,10S)-3,4,5,14,15,16-hexamethoxy-9,10-dimethyltricyclo[10.4.0.02,7]hexadeca-1(16),2,4,6,12,14-hexaen-9-ol]C24H32O7432.5067433.50 415.03384.04; 359.03368.99; 353.05
147, 8-Dihydroxy-schisandrinC24H32O8448.5061 470.95332.90; 348.90; 200.84; 230.30; 274.74332.89; 274.94; 244.93; 202.98; 155.17
15Tigloylgomisin O [[(8R,9S,10S)-3,4,5,19-tetramethoxy-9,10-dimethyl-15,17-dioxatetracyclo[10.7.0.02,7.014,18]nonadeca-1(19),2,4,6,12,14(18)-hexaen-8-yl] (E)-2-methylbut-2-enoate]C28H34O8498.5648 521.92208.01; 250.08; 304.99; 359.99; 402.85; 436.83191.00; 375.89
16Angeloylsogomisin O [[(9S,10S,11R)-3,4,5,19-tetramethoxy-9,10-dimethyl-15,17-dioxatetracyclo[10.7.0.02,7.014,18]nonadeca-1(19),2,4,6,12,14(18)-hexaen-11-yl] (Z)-2-methylbut-2-enoate]C28H34O8498.5648387.16 355.12323.00; 341.00; 295.02; 262.94; 210.100308.98; 262.97; 220.24
17Angeloygomisin H [[(9S,10S)-10-hydroxy-4,5,14,15,16-pentamethoxy-9,10-dimethyl-3-tricyclo[10.4.0.02,7]hexadeca-1(16),2,4,6,12,14-hexaenyl] (Z)-2-methylbut-2-enoate]C28H36O8500.3806500.95 368.93; 433.87; 472.83; 334.94; 288.84; 244.92; 207.21; 169.02368.92; 352.97; 299.90; 244.80; 208.95; 156.99; 125.89
18Micrantherin AC28H36O8500.5806522.93 422.91; 328.94; 386.00; 476.94407.87; 392.92; 364.93; 350.88; 320.91; 295.02
19Gomisin E [(11R,12R,15R,24S,25S)-12-hydroxy-18,19,20-trimethoxy-11,12,24,25-tetramethyl-4,6,9,14-tetraoxapentacyclo[13.7.3.03,7.08,22.016,21]pentacosa-1,3(7),8(22),16,18,20-hexaen-13-one]C28H34O9514.3642514.99 384.98; 355.03; 322.99354.99; 322.97
20Schisantherin D [[(11S,12S,13S)-12-hydroxy-3,22-dimethoxy-12,13-dimethyl-5,7,18,20-tetraoxapentacyclo[13.7.0.02,10.04,8.017,21]docosa-1(22),2,4(8),9,15,17(21)-hexaen-11-yl] C29H28O9520.5272 542.89380.89; 408.36; 451.55; 334.99; 200.93
21Benzoylgomisin O [[(8R,9S,10S)-3,4,5,19-tetramethoxy-9,10-dimethyl-15,17-dioxatetracyclo[10.7.0.02,7.014,18]nonadeca-1(19),2,4,6,12,14(18)-hexaen-8-yl] benzoate] C30H32O9520.5703 542.91380.89364.66; 308.93; 193.02
22Benzoylgomisin H [[(9S,10S)-10-hydroxy-4,5,14,15,16-pentamethoxy-9,10-dimethyl-3-tricyclo[10.4.0.02,7]hexadeca-1(16),2,4,6,12,14-hexaenyl] benzoate]C30H34O8522.5862522.99 491.30; 448.09; 421.07; 399.03; 377.05; 335.11; 302.95; 269.78271.39; 213.02
23Gomisin D [12,25-dihydroxy-18,19,20-trimethoxy-11,12,24,25-tetramethyl-4,6,9,14-tetraoxapentacyclo[13.7.3.03,7.08,22.016,21]pentacosa-1,3(7),8(22),16,18,20-hexaen-13-one]C28H34O10530.5636 553.97510.97; 478.98; 400.97; 372.91; 334.94; 248.99; 202.87382.92; 354.95; 339.03; 312.11; 277.00; 248.99; 189.03
24Gomisin G [[(9S,10S,11S)-10-hydroxy-3,4,5,19-tetramethoxy-9,10-dimethyl-15,17-dioxatetracyclo[10.7.0.02,7.014,18]nonadeca-1(19),2,4,6,12,14(18)-hexaen-11-yl] benzoate]C30H32O9536.3697536.93 436.92; 414.99; 371.03; 341.04422.80; 390.84; 360.99
25Schisantherin A (Gomisin C) [[(8S,9S,10S)-9-hydroxy-3,4,5,19-tetramethoxy-9,10-dimethyl-15,17-dioxatetracyclo[10.7.0.02,7.014,18]nonadeca-1(19),2,4,6,12,14(18)-hexaen-8-yl] benzoate] C30H32O9536.5697537.95 414.99; 371.05; 340.98370.99; 341.02341.01; 310.01; 282.06
26Benzoylgomisin Q [[(8S,9S,10S)-9-hydroxy-3,4,5,14,15,16-hexamethoxy-9,10-dimethyl-8-tricyclo[10.4.0.02,7]hexadeca-1(16),2,4,6,12,14-hexaenyl] benzoate] C31H36O9552.3121552.99 415.05; 436.98; 384.03384.03; 400.01; 359.00369.02; 352.99; 338.00

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MDPI and ACS Style

Razgonova, M.; Zakharenko, A.; Pikula, K.; Kim, E.; Chernyshev, V.; Ercisli, S.; Cravotto, G.; Golokhvast, K. Rapid Mass Spectrometric Study of a Supercritical CO2-extract from Woody Liana Schisandra chinensis by HPLC-SPD-ESI-MS/MS. Molecules 2020, 25, 2689. https://doi.org/10.3390/molecules25112689

AMA Style

Razgonova M, Zakharenko A, Pikula K, Kim E, Chernyshev V, Ercisli S, Cravotto G, Golokhvast K. Rapid Mass Spectrometric Study of a Supercritical CO2-extract from Woody Liana Schisandra chinensis by HPLC-SPD-ESI-MS/MS. Molecules. 2020; 25(11):2689. https://doi.org/10.3390/molecules25112689

Chicago/Turabian Style

Razgonova, Mayya, Alexander Zakharenko, Konstantin Pikula, Ekaterina Kim, Valery Chernyshev, Sezai Ercisli, Giancarlo Cravotto, and Kirill Golokhvast. 2020. "Rapid Mass Spectrometric Study of a Supercritical CO2-extract from Woody Liana Schisandra chinensis by HPLC-SPD-ESI-MS/MS" Molecules 25, no. 11: 2689. https://doi.org/10.3390/molecules25112689

APA Style

Razgonova, M., Zakharenko, A., Pikula, K., Kim, E., Chernyshev, V., Ercisli, S., Cravotto, G., & Golokhvast, K. (2020). Rapid Mass Spectrometric Study of a Supercritical CO2-extract from Woody Liana Schisandra chinensis by HPLC-SPD-ESI-MS/MS. Molecules, 25(11), 2689. https://doi.org/10.3390/molecules25112689

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