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21 February 2025

Supercritical Extraction and Identification of Bioactive Compounds in Dryopteris fragrans (L.) Schott

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1
N.I. Vavilov All-Russian Institute of Plant Genetic Resources, B., Saint-Petersburg 190000, Russia
2
Far Eastern Federal University, Vladivostok 690950, Russia
3
Department of Biology, North-Eastern Federal University, Yakutsk 677000, Russia
4
Advanced Engineering School «Agrobiotek», National Research Tomsk State University, Tomsk 634050, Russia
Pharmaceuticals2025, 18(3), 299;https://doi.org/10.3390/ph18030299
This article belongs to the Section Natural Products
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Abstract

Background: This is a comparative metabolomic study of the medicinal plant Dryopteris fragrans (L.) Schott from the family Dryopteridaceae Herter (or Aspidiaceae Mett. ex Frank) growing under cold pole conditions in the Oymyakon region of the Republic of Sakha (Yakutia). Methods: The aerial parts of D. fragrans were subjected to extraction using supercritical CO2 extraction and maceration methods. Several experimental conditions were investigated, including a pressure range of 50–300 bar and a temperature range of 31–60 °C. A 1% volume of ethanol was used as a co-solvent in the liquid phase of the extraction. Results: The most effective D. fragrans extraction conditions were 200 Bar pressure and a temperature of 55 °C. Tandem mass spectrometry was used to detect the target analytes. A total of 141 bioactive compounds (86 compounds from the polyphenol group and 55 compounds from other chemical groups) were tentatively identified in extracts of aerial parts of D. fragrans. Among these, thirty chemical constituents from the polyphenol group were identified for the first time. Other compound classes that were newly identified in D. fragrans include naphthoquinones (5,8-dihydroxy-6-methyl-2,3-dihydro-1,4-naphthoquinone, 1,8-dihydroxy-anthraquinone, 1,4,8-trihydroxyanthraquinone, chrysophanol, etc.), diterpenoids (tanshinone IIa, cryptotanshinone, isocryptotanshinone II, tanshinone IIb, etc.), polysaccharides, triterpenoids, and sesquiterpenes. Conclusions: These results highlight that D. fragrans is rich in bioactive compounds and put forward several newly detected compounds for further investigation.

1. Introduction

Dryopteris fragrans (L.) Schott is a perennial, grassy, low-growing fern with a short rhizome belonging to the Dryopteridaceae family (or Aspidiaceae Mett. ex Frank) (Figure 1). D. fragrans is distributed across the Far East and Eastern Siberia; outside of Siberia, it is found in Northern Europe, Northeast Asia, and North America (Figure 1) [1].
Figure 1. Dryopteris fragrans (L.) Schott. (Oymyakon Highlands; photo by Okhlopkova Zh. M.; July 2019).
In Yakutia, it is found in all floristic regions along stony larch woodlands, thickets of Siberian dwarf pines, and stone runs [2,3]. Infusions and tinctures of D. fragrans (L.) Schott were tested by Lebedev V.V. in laboratory animals and calves under production conditions. The infusion of both animals stimulated bile secretion slightly, whereas tinctures had a general anti-inflammatory effect and a pronounced vasoconstrictor effect. Up to 97.4% of calves with dyspepsia were cured via infusion and tincture of fragrant woodfern [4,5]. D. fragrans is used as a traditional medicine for the treatment of diseases such as psoriasis, rashes, dermatitis, Barbiers, and arthritis. The root of the fragrant fern is used by the local Yakut people as an anthelmintic agent, while the leaves of D. fragrans are administered to children with “fever in the abdomen” [2,4,5,6]. Previous research revealed that its major secondary metabolites, such as photoglycines, terpenes, lignans, phenolic glycosides, and essential oils, might be responsible for the pharmacological effects observed in clinical settings [7,8,9,10,11]. In traditional Yakutian medicine, a decoction or infusion of the leaves of the fragrant fern is used to treat gastric diseases, paralysis, coughs, and bone pain [4,6]. One popular name for this medicinal plant is “The herb that the wolf eats”.
Many researchers have studied the constituent compounds of D. fragrans and their potential applications.
Using spectroscopic analysis, Ito H. et al. (1997) elucidated the structure of a new sesquiterpenoid, dryofragin, isolated from D. fragrans [7]. Similarly, Kuang H. et al. (2008) isolated a new phenolic glycoside, 3,3,5-dimethyl-6-hydroxy-2-methoxy-4-O---D-glucopyranosyl-oxy-acetophenone, from the aerial parts of D. fragrans and used spectroscopic methods to identify its structure [8]. New sesquiterpene glucosides were also isolated from an aqueous extract of the aerial parts of D. fragrans, identified as 3β, 11-dihydroxy-drim-8(12)-en-11-O-β-D-glucopyranoside, 3β, 11-dihydroxy-drim-8(12)-en-3-O-β-D-glucopyranoside, and 11,14-dihydroxy-drim-8(12)-en-11-O-β-D-glucopyranoside using high-performance liquid chromatography (HPLC), high-resolution electrospray ionization mass spectrometry (HRESIMS), and 1D and 2D nuclear magnetic resonance (NMR) analysis [9].
One new coumarin, dryofracoumarin A, 8-hydroxyl-4-isopropyl-7-methyl-6-methyl-2H-benzopyran-2-one, and six known compounds, esculetin, isoscopoletin, methylphlorbutyrophenone, aspidinol, albicanol, and (E)-4-(3,4-dimethoxyphenyl)but-3-en-1-ol, were isolated from D. fragrans. The new coumarin, as well as esculetin and isoscopoletin, showed significant cytotoxic activity against two cell lines (A549 and MCF7). Scientists have suggested that these active compounds may be promising cancer treatments [10]. Similarly, one new sesquiterpene, 3-O-β-D-glucopyranosylalbicanol-11-O-β-D-glucopyranoside, and six known compounds—Dihydroconiferylalcohol, (E)-3-(4-hydroxyphenyl) acrylic acid, esculetin, and 5,7-dihydroxy-2-hydroxymethylchromone—isolated from D. fragrans showed activity against Microsporum canis and Epidermophyton floccosum [11]. Furthermore, a detailed review highlighted the phytochemical composition and biological activity of plants of the genus Dryopteris [12]. Two new phenolic glycosides—frachromone C and dryofracoulin A—and one known compound, undulatoside A, were isolated from an aqueous extract of D. fragrans collected in Wudalianchi, Heilongjiang Province, China. The structures of these compounds were elucidated using a combination of 1D and 2D NMR, HRMS, and chemical analysis [13].
The cytotoxic constituents of D. fragrans have also been reported. For example, the methanol extract of the aerial parts of D. fragrans was used to isolate dryofragone, dryofracoumarin B, and other known compounds. These compounds exhibited modest cytotoxicity toward the human HeLa cell line, with an IC50 value below 30 µM, by using the 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide assay [14]. Apart from traditional cytotoxicity studies, the use of in silico methods to understand the health beneficial activities of metabolites from this plant has also been reported. The antitumor activity of a phenolic compound isolated from D. fragrans was studied using molecular docking. Different variants of bicyclic phloroglucinol were considered in relation to A549, HepG2, and MCF-7; the ones with high binding affinity and good efficacy were selected as promising antitumor compounds [15]. Among other phenolic compounds, two new sesquiterpenoid glycosides, drioptesterpene A and drioptesterpene B, isolated from the aqueous extract of D. fragrans, exhibited anti-inflammatory activities [16]. Additionally, various modifications of the phloroglucinol compounds isolated from D. fragrans have been investigated. For example, various phloroglucinol derivatives have been synthesized with certain antiproliferative activities on cancer cell lines, as well as with the induction of apoptosis, in a concentration-dependent manner [17].
Currently, various methods are used to extract bioactive compounds from medicinal plants on a laboratory or commercial scale. A detailed review of the recent advances in the methods indicated that supercritical (SC) fluid extraction is one of the best techniques for the extraction of natural chemical constituents [18]. However, the use of such an efficient method has not been realized for D. fragrans. Most studies on Dryopteris species have reported the use of ethanol extraction [10,19,20]. Owing to its non-polar, gal-like, liquid-like properties and the ability to extract heat-sensitive compounds [18], we report its utility in D. fragrans.
As the pharmaceutical industry is increasingly focusing on the search for new health beneficial compounds from a number of medicinal plants, it is necessary to determine the phytochemical composition of D. fragrans growing in the territory of Yakutia. Here, we conducted a detailed study of the biochemical composition of the aerial part of D. fragrans collected from the Kyubeme locality of the Oymyakon district of the Republic of Sakha (Yakutia) [N 63.417262°, E 140.610894°] during the expedition work in 2019–2020 (Figure 2).
Figure 2. D. fragrans (L.) Schott specimen collection site, the area of the Kyubeme of the Oymyakon district of the Republic of Sakha (Yakutia) [blue circle in the satellite view represents the coordinates of the sampling site. N 63.417262°, E 140.610894°].

2. Results

Supercritical CO2 Extraction from the Aerial Parts of D. fragrans Plant

The aerial parts of D. fragrans were examined via supercritical CO2 (SC-CO2) extraction under different extraction conditions. The SC pressures applied ranged from 50 to 250 bar, and the extraction temperature ranged from 31 to 70 °C. The co-solvent EtOH was used in an amount of 1% of the total solvent amount. Below is a 3D plot of the yield of bioactive substances D. fragrans under different SC extraction conditions (Figure 3).
Figure 3. A 3D graph of the yield of bioactive substances D. fragrans under different supercritical extraction conditions.
Table 1 shows the yield of bioactive substances from aerial parts of D. fragrans via CO2 extraction.
Table 1. The yield of bioactive compounds (aerial parts of D. fragrans) via CO2 extraction.
The maximum yield of bioactive substances from aerial parts of D. fragrans was observed under the following extraction conditions:
  • − Pressure of 200 bar, extraction temperature of 55 °C, extraction time of 1 h. The yield of biologically active substances was 0.0000062 kg/0.0001 kg of plant sample; the proportion of the EtOH modifier was 2%.
  • − Pressure of 250 bar, extraction temperature of 55 °C, extraction time of 1 h. The yield of biologically active substances was 0.0000059 kg/0.0001 kg of plant sample; the proportion of the EtOH modifier was 2%.

3. Discussion

3.1. Global Metabolome Profile of D. fragrans

The structural identification of each compound was performed on the basis of its mass and MS/MS fragmentation via tandem mass spectrometry. The chemical constituents were identified by comparing their retention index, mass spectra, and mass spectrometry fragmentation with a home-library database built by the Group of Biotechnology, Bioengineering and Food Systems at the Far-Eastern Federal University (FEFU) based on data from other spectroscopic techniques, such as nuclear magnetic resonance, ultraviolet spectroscopy, and mass spectrometry, as well as data from the literature that are continuously updated and revised. According to the classification developed by Schymanski et al. [18], the FEFU database belongs to the second level, which includes two components: metabolite annotation level B(i): accurate matching of FEFU database based on MS/MS secondary spectrum library; B(ii): accurate matching of the MS/MS secondary spectrum library based on computer simulation. We were able to tentatively identify 141 compounds from the extracts of the aerial parts of D. fragrans, 86 compounds from the polyphenol group, and 55 compounds from other compound classes. All tentatively identified polyphenols and other compounds, along with molecular formulae and MS/MS data for D. fragrans, are summarized in Appendix A, Table A1. The polyphenols identified in our study were categorized as flavones, flavonols, anthocyanidins, phenolic acids, lignans, coumarins, stilbenes, etc. In total, the polyphenol metabolites identified in our study belonged to 19 compound classes. The highest number of metabolites were flavones (27), followed by flavonols (16), anthocyanins (13), flavan-3-ols (3), phenolic acids (13), stilbenes (2), coumarins (6), lignans (2), etc. These numbers indicate that D. fragrans extracts are rich in flavonoids. The highest number of chemical compounds from other groups are naphthoquinones (6), diterpenoids (5), and phloroglucinol derivatives (6).
A Venn diagram showing the similarities and differences in the presence of various chemical groups in three extracts of D. fragrans (ethanol extract, methanol extract, and SC-CO2 extract) is shown in Figure 4. Twenty-six compounds were commonly identified from the three extracts of D. fragrans. These compounds belong to compound classes such as flavones, flavonols, anthocyanins, and phlorodlucinol derivatives, such as 1,3-dimethyluric acid, 8-dihydroxy-anthraquinone, albaspidin PB, flavaspidic acid BB, saroaspidin A, chlorogenic acid, chrysoeriol 6-C-glucoside, chrysoeriol 8-C-glucoside, chrysophanol, delphinidin 3-O-β-galactoside, delphinidin 3-O-hexoside, etc. The polyphenols, phlorodlucinol derivatives, naphthoquinones, and anthraquinones are major active compounds in extracts of D. fragrans. Overall, the applied methods were able to detect 107 (EtOH extract of D. fragrans), 64 (MeOH extract of D. fragrans), and 70 (CO2 extract of D. fragrans) compounds (Table 2).
Figure 4. Venn diagram showing number of common and specific compounds in D. fragrans.
Table 2. List of common and specific compounds detected in EtOH, MeOH, and CO2 extracts of the aerial parts of D. fragrans.
In addition, we used the Jaccard index to represent the similarities and differences of bioactive substances in different extracts of D. fragrans (Table 3). The Jaccard index, also known as the Jaccard similarity coefficient, is a statistic used to evaluate the similarity and diversity of sets of samples [21,22].
Table 3. Jaccard index for three extracts of D. fragrans (ethanol extract, methanol extract, and supercritical CO2 extract).
Table 3 shows that the highest degree of similarity is present between the EtOH extract and MeOH extract—0.4132.

3.2. Flavones

The flavones dihydroxyflavone, formononetin, apigenin, trihydroxy(iso)flavone, luteolin, herbacetin, trimethoxy flavone, pentahydroxy dimethoxyflavone, vitexin, isovitexin, genistein 8-C-glucoside, etc. (compounds 1–27; Appendix A Table A1) have already been characterized as a component of Triticum aestivum [23], Dryopteris ramosa [24], Aspalathus linearis [25], Lonicera japonica [26], Passiflora incarnata [27], and Mexican lupine species [28] (Appendix A, Table A1). The CID-spectrum (collision-induced spectrum) in positive ion modes of flavone vitexin from aerial parts of D. fragrans (CO2 extract) is shown in Figure 5.
Figure 5. CID-spectrum of vitexin from aerial parts of D. fragrans, m/z 433.16. At the top is the MS scan in the range of 100–1700 m/z, and at the bottom are the fragmentation spectra (from top to bottom): MS2 of the protonated ion of vitexin (433.16 m/z, red diamond), MS3 of the fragment ion 433.16→415.14 m/z, and MS4 of the fragment ion 433.16→415.14→337.12 m/z.
The [M+H]+ ion produced a fragment ion: m/z 415.14 (Figure 5). The fragment ion with m/z 415.14 produced two characteristic daughter ions: m/z 337.12 and m/z 295.16. The m/z 337.12 daughter ion produced a characteristic m/z 309.12 ion. Detailed mass spectrometry of vitexin has been reported in studies of D. ramosa [24] and T. aestivum [23].

3.3. Flavonols

The flavonols quercetin, myricetin, kaempferol 3-O-pentoside, quercetin 3-O-pentoside, quercetin 3-D-xyloside, astragalin, hyperoside, myricitrin, rutin, etc. (compounds 28–43; Appendix A Table A1) have already been characterized as a component of Ribes meyeri [29]; Ribes magellanicum [30]; L. japonica [26]. The CID-spectrum in positive ion modes of flavonol quercetin 3-O-glucoside from aerial parts of D. fragrans (MeOH extract) is shown in Figure 6.
Figure 6. CID-spectrum of quercetin 3-O-glucoside from aerial parts of D. fragrans, m/z 465.12. At the top is the MS scan in the range of 100–1700 m/z, and at the bottom are the fragmentation spectra (from top to bottom): MS2 of the protonated ion of quercetin 3-O-glucoside (465.12 m/z, red diamond), MS3 of the fragment ion 465.12→303.08 m/z, and MS4 of the fragment ion 465.12→303.08→257.12 m/z.
The [M+H]+ ion produced one fragment ion: m/z 303.08 (Figure 6). The fragment ion with m/z 303.08 produced two characteristic daughter ions: m/z 257.12 and m/z 165.14. The daughter ion with m/z 257.12 produced two characteristic ions: m/z 229.11 and m/z 201.18. Detailed mass spectrometry of quercetin 3-O-glucoside has been reported in articles about T. aestivum [23], R. meyeri [29], Lonicera japonicum [26], Cranberry [31], Andean blueberry [32], and Citrus sinensis [33].

3.4. Anthocyanins

Cyanidin-3-O-glucoside (compound 50), cyanidin 3-O-hexoside (compound 51), cyanidin 3-O-β-galactoside (compound 52), delphinidin 3-O-glucoside (compound 53), cyanidin 3-(6”-malonylglucoside) (compound 56), etc. (compounds 49–60, Appendix A Table A1), have already been characterized as a component of Andean blueberry [32], Ribes dikuscha [34], Zostera marina [35], Medicago varia [36], T. aestivum [37], and many other plant species whose organs (mainly fruits) accumulate pigments exhibiting a range of colors. The CID-spectrum in positive ion modes of cyanidin 3-(6”-malonylglucoside) from extracts from aerial parts of D. fragrans (CO2 extract) is shown in Figure 7.
Figure 7. CID-spectrum of cyanidin 3-(6”-malonylglucoside) from aerial parts of D. fragrans, m/z 535.12. At the top is the MS scan in the range of 100−1700 m/z; at the bottom are the fragmentation spectra (from top to bottom): MS2 of the protonated ion of cyanidin 3-(6”-malonylglucoside) (535.13 m/z, red diamond), MS3 of the fragment ion 535.13→287.11 m/z, and MS4 of the fragment ion 535.13→287.11→241.13 m/z.
The [M+H]+ ion produced one fragment ion: m/z 287.11. (Figure 7). The fragment ion with m/z 287.11 produced two characteristic daughter ions: m/z 241.13, and m/z 165.12. The anthocyanin cyanidin 3-(6”-malonylglucoside) glucoside has been tentatively identified in the extracts from several plant species, some of which are mentioned at the beginning of this paragraph along with others, such as Z. marina [35], M. varia [36], and T. aestivum [37].

3.5. Diterpenoids

Tanshinone IIA (compound 109), cryptotanshinone (compound 110), isocryptotanshinone II (compound 111), tanshinone IIB (compound 112), and 7-dehydroabietic acid (compound 113) (Appendix A Table A1) have already been characterized as a component of Huolisu Oral Liquid [38], Chinese herbal formula Jian-Pi-Yi-Shen pill [39], Radix Salviae [40]. The CID-spectrum in positive ion modes of tanshinone IIB from extracts from aerial parts of D. fragrans (CO2 extract) is shown in Figure 8.
Figure 8. CID-spectrum of tanshinone IIB from aerial parts of D. fragrans, m/z 311.17. At the top is the MS scan in the range of 100−1700 m/z; at the bottom are the fragmentation spectra (from top to bottom): MS2 of the protonated ion of tanshinone IIB (311.17 m/z, red diamond), MS3 of the fragment ion 311.17→267.08 m/z, and MS4 of the fragment ion 311.17→267.08→219.01 m/z.
The [M+H]+ ion produced three fragment ions: m/z 267.08, m/z 237.21, and m/z 163.15. (Figure 8). The fragment ion with m/z 267.08 produced two characteristic daughter ions: m/z 219.01 and m/z 189.26. Detailed mass spectrometry of tanshinone IIB has been reported in Salviae Miltiorrhizae [41] and Huolisu Oral Liquid [38].

3.6. Phlorodlucinol Derivatives

Disflavaspidic acid PB (compound 122), aspidin AB (compound 123), and albaspidin PP (compound 124) (Appendix A Table A1) have already been characterized as a component of D. fragrans [20]. The CID-spectrum in positive ion modes of aspidin AB from extracts from aerial parts of D. fragrans (CO2 extract) is shown in Figure 9.
Figure 9. CID-spectrum of aspidin AB from aerial parts of D. fragrans, m/z 311.17. At the top is the MS scan in the range of 100−1700 m/z; at the bottom are the fragmentation spectra (from top to bottom): MS2 of the protonated ion of aspidin AB (311.17 m/z, red diamond), MS3 of the fragment ion 311.17→267.08 m/z, and MS4 of the fragment ion 311.17→267.08→219.01 m/z.
The [M+H]+ ion produced three fragment ions: m/z 267.08, m/z 237.21, and m/z 163.15. (Figure 9). The fragment ion with m/z 267.08 produced two characteristic daughter ions: m/z 219.01 and m/z 189.26. The detailed mass spectrometry of aspidin AB has been reported in an article about D. fragrans [20].

3.7. Newly Identified Chemical Compounds in D. Fragrans

Among the identified metabolites in the three D. fragrans extracts (EtOH extract, MeOH extract, and SC-CO2 extract), thirty compounds from the polyphenol group and 21 compounds from other chemical groups were identified for the first time. The newly identified polyphenols include flavones (dihydroxyflavone, formononetin, luteolin, herbacetin, genistein 8-C-glucoside, genistein 6-C-glucoside, acacetin 8-C-glucoside, luteolin C-hexoside, and eriodictyol 7-O-glucuronide), flavonols (astragalin, quercitrin, and myricitrin), anthocyanins (cyanidin 3-(6″-malonylglucoside, delphinidin-3-O-(6″-O-malonul)-β-D-glucoside, and delphinidin-3-O-(6-O-p-coumaroyl) glucoside), stilbenes pinosylvin and resveratrol, coumarins umbelliferone, fraxetin, 4/6,8-Dihydro-5,7-dihydroxy-2-oxo-2H-1-benzopyran-3-acetic acid, umbelliferone hexoside, tomenin, etc. Interestingly, the other compound classes that we also tentatively identified in D. fragrans are naphthoquinones (5,8-Dihydroxy-6-methyl-2,3-dihydro-1,4-naphthalenedione, 1,8-Dihydroxy-anthraquinone, 1,4,8-Trihydroxyanthraquinone, chrysophanol, etc.), diterpenoids (tanshinone IIA, cryptotanshinone, isocryptotanshinone II, tanshinone IIB, etc.), polysaccharides, triterpenoids, sesquiterpenes, etc. (Appendix A Table A1).
Biologically active compounds from the aerial parts and underground parts of plants are efficiently extracted using organic solvents, but the resulting extracts at the final stage require additional purification from traces of the solvents used. Supercritical CO2 extraction is declared as “green extraction” and is effectively used in various food processing processes as an alternative to traditional extraction methods [42,43]. With SC extraction, the resulting products do not contain residues of organic solvents, which are present in conventional extraction methods where solvents are often toxic or can be toxic. A low extraction temperature, easy removal of solvent from the final product, and high selectivity are the main attractive features of SC technology, leading to a significant increase in research opportunities for application in the food and pharmaceutical industries. Our research group has successfully applied the SC extraction method to extract bioactive components from Z. marina [35]. We also investigated the effects of SC-CO2 extraction parameters and the quality of Panax ginseng raw material on the yield of ginsenosides in the extraction of ginseng root [44]. Supercritical extraction has been successfully applied in the extraction of East Sikhotinsky rhododendron (Rhododendron sichotense) and East Siberian rhododendron (Rhododendron adamsii), which also showed that the SC-CO2 extraction is an effective method and provides additional opportunities for research [45]. Thus, the use of SC-CO2 extraction is an effective approach for the extraction of bioactive compounds. The results obtained in the extraction of D. fragrans are consistent with these reports that SC-CO2 is a useful approach for the extraction and study of bioactive compounds.

4. Materials and Methods

4.1. Materials

The aerial parts of D. fragrans plant were collected in the area of the Kyubeme, Oymyakon district, Republic of Sakha (Yakutia) [N 63.417262°, E 140.610894°] during the expedition work in 2019–2020. The plant material was dried on a horizontal surface in a ventilated room with periodic mixing. Before extraction, the dried material (the aerial parts) of D. fragrans was stored in a refrigerator at 4−6 °C. All samples complied with the morphological standards of the Pharmacopoeia of the Eurasian Economic Union [46].

4.2. Chemicals and Reagents

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

4.3. Extraction

Supercritical CO2 extraction was performed using the SFE-500 SC pressure extraction system (Thar SCF Waters Corporation, Milford, MA, USA). System options include co-solvent pump (Thar Waters P-50 High Pressure Pump, Waters Corporation, Milford, MA, USA) for extraction of polar samples, CO2 flow meter (Siemens AG, Günzburg, Germany) to measure the amount of CO2 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 200 g aerial parts of D. fragrans were used. Extraction time was counted after reaching working pressure and equilibrium flow and was 60−90 min for each sample. This method of SC extraction of plant matrices was previously tested by our team on aerial and/or underground parts of different plant species [35,42,43].

4.4. Liquid Chromatography

We used high-performance liquid chromatography as well as mass spectrometry for the detection and identification of compounds in the extracts of D. fragrans, as reported in our earlier work [33,34].
High-performance liquid chromatography 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). The mobile phase eluent A was deionized water containing 0.1% formic acid, and eluent B was acetonitrile containing 0.1% formic acid. Gradient elution was started at 0–2 min; 0% eluent B at 2−50 min, 0−100% B; and control washing at 50–60 min, 100% B. The mobile phase flow rate and column temperature were maintained at 0.3 mL/min and 30 ℃, respectively. The entire HPLC analysis was performed with an electrospray ionization (ESI) detector at a wavelength of 230 nm for identification compounds; the temperature was 18 °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 for compound identification.

4.5. Mass Spectrometry

MS analysis was performed on an ion trap amaZon SL (Bruker Daltoniks, Bremen, Germany) equipped with an ESI source in negative ion mode. MS analysis was carried out in ESI mode using negative and positive polarity for all samples with data-independent MSE acquisition. The optimized parameters were obtained as follows: ionization source temperature: 70 °C, gas flow: 4 L/min, nebulizer gas (atomizer): 7.3 psi, capillary voltage: 4500 V, end plate bend voltage: 1500 V, fragmentary: 280 V, collision energy: 60 eV. An ion trap was used in the scan range m/z 100−1.700 for MS and MS/MS. The chemical constituents were identified by comparing their retention index, mass spectra, and mass spectrometric fragmentation with a home-library database built by the Group of Biotechnology, Bioengineering and Food Systems at the Far Eastern Federal University (Russia). 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 replicated in triplicate. A four-stage ion separation mode (MS/MS mode) was implemented.

5. Conclusions

The aerial parts of the D. fragrans plant contain many polyphenolic constituents and constituents of other chemical groups with valuable bioactivity. Tandem mass spectrometry was applied to detect target analytes. Supercritical CO2 extraction of D. fragrans was successfully carried out by a team of authors; certain extraction conditions were selected. The extracts obtained showed both a high content of polyphenolic compounds and a high content of the naphthoquinones, diterpenes polysaccharides, triterpenoids, sesquiterpenes, etc. One hundred and forty-one different bioactive compounds were tentatively identified in D. fragrans extracts. For the first time, 51 chemical constituents from extracts of aerial parts of D. fragrans were tentatively identified. These include flavones, flavonols, anthocyanins, stilbenes pinosylvin and resveratrol, coumarins umbelliferone, fraxetin, 4/6,8-Dihydro-5,7-dihydroxy-2-oxo-2H-1-benzopyran-3-acetic acid, umbelliferone hexoside, tomenin, etc. The other newly identified compounds of D. fragrans belonged to classes such as naphthoquinones, diterpenoids, polysaccharides, triterpenoids, sesquiterpenes, etc.
The newly obtained mass spectrometric data on the composition of bioactive substances of both polyphenolic and other chemical groups in the aerial parts of D. fragrans can be widely used in further research both in the pharmaceutical industry in the development of new medicinal substances and in the cosmetology industry in the development of a wide range of various drugs.

Author Contributions

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

Funding

This work was carried out with the financial support of the Russian Science Foundation Grant No. 22-14-20031, https://rscf.ru/en/project/22-14-20031/.

Data Availability Statement

Data is contained within the article.

Acknowledgments

This study was carried out at the North-Eastern Federal University at the expense of the Russian Science Foundation Grant No. 22-14-20031, https://rscf.ru/en/project/22-14-20031/.

Conflicts of Interest

The authors declare no conflicts of interest.

Appendix A

Table A1. Chemical compounds identified from the extracts of aerial parts of D. fragrans (EtOH extract, MeOH extract, and supercritical CO2 extract) in positive and negative ionization modes via ion trap-MS/MS.
Table A1. Chemical compounds identified from the extracts of aerial parts of D. fragrans (EtOH extract, MeOH extract, and supercritical CO2 extract) in positive and negative ionization modes via ion trap-MS/MS.
Class of CompoundsIdentificationFormulaCalculated MassObserved Mass [M−H]−Observed Mass [M+H]+MS/MS Stage 1 FragmentationMS/MS Stage 2 FragmentationMS/MS Stage 3 FragmentationReferences
POLYPHENOLS
1Flavone Dihydroxyflavone *C15H10O4 254.237 255237; 185; 113167125Chinese herbal formula Jian-Pi-Yi-Shen pill [39]; Ribes pauciflorum [34]
2FlavoneFormononetin [Biochanin B; Formononetol] *C16H12O4 268.264 269241; 223223 D. jacutense [47]; M. varia [36]; M. amurensis [43], R. fragrans [42]; Chinese herbal formula Jian-Pi-Yi-Shen pill [39]
3FlavoneApigenin [5,7-Dixydroxy-2-(4-Hydroxyphenyl)-4H-Chromen-4-One]C15H10O5 270.236 271225179 R. meyeri [29]; L. japonica [26]; Andean blueberry [32]
4FlavoneTrihydroxy(iso)flavoneC15H10O5 270.236 271196168113Propolis [48]
5FlavoneLuteolin * C15H10O6286.236 287187; 277 Inula gaveolens [49]; A. absinthium [50]
6FlavoneHerbacetin [3,5,7,8-Tetrahydroxy-2-(4-hydro-xyphenyl)-4H-chromen-4-one] *C15H10O7 302.235 303275; 203245; 175233; 175L. caerulea [51]
7FlavoneTrimethoxy flavoneC18H16O5312.316 313267239197; 113A. cordifolia [52]
8FlavonePentahydroxy dimethoxyflavoneC17H14O9362.287 363344; 300; 256238; 146 G. linguiforme [52]
9FlavoneVitexin [Apigenin 8-C-Glucoside]C21H20O10 432.377 433415; 367; 313337; 283309T. aestivum [23]; D. ramosa [24]
10FlavoneIsovitexin [Saponaretin; Homovitexin]C21H20O10 432.377 433415; 367; 313337; 283309Passiflora incarnata [27]; Chilean currants [30]
11FlavoneGenistein 8-C-glucoside *C21H20O10 432.377 433415337309Mexican lupine species [28]
12FlavoneGenistein 6-C-glucoside *C21H20O10 432.377 433415337309Mexican lupine species [28]
13FlavoneAcacetin 8-C-glucoside *C22H22O10446.404 447429; 377410; 358; 301; 251377; 340; 251Mexican lupine species [28]
14FlavoneLuteolin 7-O-glucoside [Cynaroside; Luteoloside]C21H20O11 448.376 449431; 287213 T. aestivum [23]; L. japonicum [26]; Passiflora incarnata [27]; Mexican lupine species [28]
15FlavoneLuteolin 8-C-Glucoside [Orientin; Lutexin]C21H20O11 448.376 449431353; 299325T. aestivum [23]; Aspalathus linearis [25]
16FlavoneLuteolin 6-C-glucoside [Isoorientin; Homoorientin]C21H20O11 448.376 449431353; 299325T. aestivum [23]; D. ramosa [24]; Aspalathus linearis [25]
17FlavoneLuteolin C-hexoside *C21H20O11 448.376 449431353; 299325T. aestivum [23]
18FlavoneEriodictyol-O-hexoside C21H22O11 450.392449 287151 Andean blueberry [32]; F. glaucescens; F. pottsii [52]
19Flavone(S)-eriodictyol-6-C-β-D-glucopyranosideC21H22O11 450.392 451433414; 363; 299; 233344; 258; 213Aspalathus linearis [25]
20Flavone(R)-eriodictyol-6-C-β-D-glucopyranosideC21H22O11 450.392 451433414; 363; 299; 233344; 258; 213Aspalathus linearis [25]
21Flavone6,4′-Dimethoxyisoflavone-7-O-glucoside *C23H24O10 460.430 461443; 419; 306425; 373; 186407; 257Astragali radix [53]
22FlavoneChrysoeriol 6-C-glucoside C22H22O11 462.403 463445; 403; 375; 329; 237426; 401; 347385; 357; 269T. aestivum [54]
23FlavoneChrysoeriol 8-C-glucoside [Scoparin]C22H22O11 462.403 463445; 403; 375; 329; 237426; 401; 347385; 357; 269Mexican lupine species [28]; Citrus sinensis [33]
24FlavoneChrysoeriol C-hexosideC22H22O11 462.403 463445; 403; 375; 329; 237426; 401; 347385; 357; 269T. aestivum [54]
25FlavoneEriodictyol-7-O-glucuronide *C21H20O12464.376 465289271; 163145Mentha [55]
26FlavoneLuteolin 8-C-pentoside-6-C-hexosideC26H28O15 580.491 581563; 397; 325251223T. aestivum [56]
27FlavoneLuteolin 8-C-hexoside-6-C-pentosideC26H28O15 580.491 581563; 397; 325251223T. aestivum [56]
28FlavonolKaempferol C15H10O6286.236 287269; 149239; 181 L. japonica [26]; R. meyeri [29]; Andean blueberry [32]
29FlavonolQuercetin C15H10O7 302.235 303284240 R. meyeri [29]; Propolis [48]
30FlavonolMyricetin C15H10O8 318.235 319273; 219191209Andean blueberry [32]
31FlavonolKaempferol 3-O-pentosideC20H18O10418.350417 195151136Andean blueberry [32]; R. dikuscha [34]
32FlavonolQuercetin 3-O-pentoside C20H18O11 434.350433 387301; 231283R. meyeri [29]
33FlavonolQuercetin 3-D-xyloside [Reynoutrin]C20H18O11 434.350433 387301284Cranberry [31]
34Flavonol Quercetin-3-O-arabinoside C20H18O11 434.350433 387301; 233285Cranberry [31]
35FlavonolAstragalin [Kaempferol 3-O-glucoside] *C21H20O11448.376447 429; 225183181L. japonica [26]; R. meyeri [29]
36FlavonolKaempferol-3-O-hexoside C21H20O11448.376447 327; 285; 151255 Andean blueberry [32]
37FlavonolQuercitrin [Quercetin 3-O-rhamnoside] *C21H20O11448.376447 327299 Cranberry [31]
38FlavonolQuercetin-3-O-hexoside C21H20O12464.376463 301271; 179151A. absinthium [50]
39FlavonolHyperoside [Quercetin 3-O-galactoside; Hyperin]C21H20O12464.376463 301271; 179151T. aestivum [23]; L. japonica [26]; Cranberry [31]; Andean blueberry [32]
40FlavonolQuercetin 3-O-glucoside [Isoquercitrin; Hirsutrin]C21H20O12464.376 465303229; 165201; 161T. aestivum [23]; R. meyeri [29]; L. japonica [26]; Cranberry [31]
41FlavonolMyricitrin *C21H20O12464.376 465447428; 235383Chilean currants [30]
42FlavonolRutin [Quercetin 3-O-rutinoside]C27H30O16610.517 611303257; 165229R. meyeri [29]; R. magellanicum [30]; L. japonica [26]
43FlavonolQuercetin-O-rhamnosyl-hexosideC27H30O16610.517 611303; 465257; 165229; 201Papaya [57]
44Flavan-3-ol(Epi)-catechin derivative 379 379261233151PubChem
45Flavan-3-ol(Epi)-afzelechin derivativeC18H16O10 392.313 393275; 245; 215245; 175175; 127Z. marina [35]
46Flavan-3-ol(Epi)-catechin derivative 424 425291261; 191191PubChem
47GallotanninStrictinin [galloyl-HHDP-hexose]C27H22O18634.453 635561; 461433 Juglans regia [58]
48AnthocyaninApigenidin C15H11O4 255.245 256182154113T. aestivum [59]
49AnthocyaninDelphinidinC15H11O7 303.243 303257; 165229 A. cordifolia [52]
50AnthocyaninCyanidin-3-O-glucoside C21H21O11+449.384 449287213185R. magellanicum [30]
51AnthocyaninCyanidin-3-O-hexosideC21H21O11+449.384 449287213; 165 Andean blueberry [32]
52AnthocyaninCyanidin-3-O-β-galactosideC21H21O11449.384 449287287; 213185T. aestivum [23,59]
53AnthocyaninDelphinidin 3-O-glucosideC21H21O12+ 465.390 465303257; 165229; 201R. magellanicum [30]
54AnthocyaninDelphinidin 3-O-hexosideC21H21O12+ 465.390 465303257; 165229; 173Andean blueberry [32]; R. dikuscha [34]
55AnthocyaninDelphinidin 3-O-β-galactosideC21H21O12+ 465.390 465303257; 165229; 173R. dikuscha [34]
56AnthocyaninCyanidin 3-(6”-malonylglucoside) *C24H23O14535.431 535287241; 165213Medicago varia [36]; T. aestivum [37]
57AnthocyaninCyanidin malonyl hexoside *C24H23O14535.431 535287241; 165213T. aestivum [23]; R. magellanicum [30]
58AnthocyaninDelphinidin-3-O-(6”-O-malonyl)-β-D-glucoside *C24H23O15551.430 551303257; 165229T. aestivum [37]
59AnthocyaninDelphinidin 3-O-rutinoside [Tulipanin]C27H31O16611.525 611303; 465257; 165 L. caerulea [51]; R. aureum [34]
60AnthocyaninDelphinidin 3-O-(6-O-p-coumaroyl) glucoside *C30H27O14611.527 611303; 465257; 165 R. pauciflorum [34]
61Hydroxycinnamic acidCaffeic acid [(2E)-3-(3,4-Dihydroxyphenyl)acrylic acid] C9H8O4 180.157 181135119 R. meyeri [29]; L. japonica [26]
62Hydroxycinnamic acid3,4-Dihydroxyhydrocinnamic acid [Dihydrocaffeic acid]C9H10O4 182.173 183155127145Chilean currants [30]
63 Ethyl protocatechuate [3,4-Dihydroxybenzoic Acid Ethyl Ester]C9H10O4 182.173 183155126 Medicago varia [36]
64Trans-cinnamic acidFerulic acidC10H10O4194.184193 176132 L. japonica [26]; Andean blueberry [32]
65Hydroxycinnamic acidHydroxyferulic acidC10H10O5210.183 211183; 113165; 113 Andean blueberry [32]; R. davurica [60]
66Hydroxycinnamic acidSinapic acid [trans-Sinapic acid] *C11H12O5 224.21 225197152151Andean blueberry [32]
67Hydroxybenzoic acid Ellagic acid [Benzoaric acid; Elagostasine]C14H6O8302.192301 257; 165229201; 173R. meyeri [29]
68Hydroxycinnamic acid; Chlorogenic acid [3-O-Caffeoylquinic acid]C16H18O9 354.308353 163145117Artemisia annua [50]; R. magellanicum [30]
69Hydroxycinnamic acidCryptochlorogenic acid [4-O-Caffeoylquinic acid; Quinic acid 4-O-Caffeate]C16H18O9 354.308353 163145117Juglans regia [58]; Artemisia annua [50]; R. magellanicum [30];
70 Neochlorogenic acid [5-O-Caffeoylquinic acid]C16H18O9 354.308 355163145117Artemisia annua [50]; R. magellanicum [30]; L. japonica [26]
71 Caffeic acid derivativeC16H18O9Na377.298377 341179 Embelia [61]
72Phenolic acidEllagic acid pentoside [Ellagic acid 4-O-xylopyranoside]C19H14O12 434.307433 387301; 271283; 257; 231R. pauciflorum; R. aureum [34]
73Phenolic acidDicaffeoylferuoylquinic acid * 692.345 693352; 261261; 123149PubChem
74Phenylpropanoid1-O-Caffeoylquininc acid methyl etherC17H20O9368.335 369207192153Pear [62]
75DihydrochalconePhloretin [Dihydronaringenin; Phloretol] *C15H14O5274.268 275257230229G. linguiforme [51,52]
76StilbenePinosylvin [ 3,5-Stilbenediol] *C14H12O2212.243 213167; 139139 L. caerulea [51]; R. triste [34]
77StilbeneResveratrol [trans-Resveratrol; 3,4′,5-Trihydroxystilbene] *C14H12O3228.243 229211183; 127138A. cordifolia; F. glaucescens; F. herrerae [52]; R. pauciflorum [34]
78HydroxycoumarinUmbelliferone [Skimmetin; Hydragin] *C9H6O3162.142 163145117 Z. marina [35]; L. caerulea [51]
79CoumarinFraxetin *C10H8O5 208.167 209191117 Embelia [61]
80Coumarin3,4/6,8-Dihydro-5,7-dihydroxy-2-oxo-2H-1-benzopyran-3-acetic acid *C11H10O6238.193 239221203185PubChem
81CoumarinUmbelliferone hexoside *C15H16O8 324.282 325289; 127271; 127253; 146F. glaucescens [52]; R. triste [34]
82Coumarin glucosideTomenin *C17H20O10384.334 385223177149Pubchem
83CoumarinFraxin (Fraxetin-8-O-glucoside) *C16H18O10 370.308 371209163; 111119R. rugosa [60]
85LignanDimethyl-secoisolariciresinol *C22H30O6390.470 391373; 211345; 239299; 247Lignans [63]
86LignanPodophyllotoxin [Podofilox; Condylox; Condyline] *C22H22O8 414.405 415396; 344; 284; 209378; 326350Lignans [63]
OTHERS
87 2,3-Dihydro-3,5-dihydroxy-6-methyl-4(H)-pyran-4-one [DDMP]C6H8O4144.125 145127 Radix polygoni multiflori [64]
88 MethoxyeugenolC11H14O3194.227 195163145117Ocimum [65]
89 1,3-Dimethyluric acid [Oxytheophylline; 1,3-Dimethylurate]C7H8N4O3196.163 197169113; 151 Coffee [66]
90BenzofuranLoliolideC11H16O3 196.242 197179161133D. ramosa [24]; Jatropha [67]; A. martjanovii [68]
91Naphthoquinone5,8-Dihydroxy-6-methyl-2,3-dihydro-1,4-naphthalenedione/8-Hydroxy-2-methoxy-2,3-dihydro-1,4-naphthalenedione *C11H10O4 206.194 207189161133J. mandshurica [69]
92 Galactaric acid [Mucic acid;] *C6H10O8210.138 211193; 165165 Soybean [70]; Stevia rebaudiana [71]
93PolysaccharidesGlucaric acid [D-Glucaric acid; Saccharic acid; D-Glutarate] *C6H10O8210.138 211193165147Soybean [70]; Cherimoya, Papaya [57]
94Aminoalkylindole5-Methoxydimethyltryptamine *C13H18N2O218.294 219201; 161159 Camellia kucha [72]
95SesquiterpenoidCaryophyllene oxide [Caryophyllene-alpha-oxide] *C15H24O220.350 221203; 163135 R. davurica [60]
96Naphthoquinone1,8-Dihydroxy-anthraquinone [Chrysazin] *C14H8O4 240.210 241213195 J. mandshurica [69]
97Peptide5-oxo-L-propyl-L-isoleucineC11H18N2O4242.271 243197169113Solanum tuberosum [73]
98Propionic acidKetoprofen [Orudis; 2-(3-Benzoylphenyl) propionic acid; Profenid] *C16H14O3254.280253 209; 191; 165; 141194; 167; 124165; 125Ginkgo biloba [74]
99NaphthoquinoneChrysophanol [Chrysophanolic acid] *C15H10O4 254.237 255237; 112112 Chinese herbal formula Jian-Pi-Yi-Shen pill [39]
100Naphthoquinone1,4,8-Trihydroxyanthraquinone *C14H8O5 256.210 257183; 113155113J. mandshurica [69]
101Naphthoquinone1,2,5-Trihydroxyanthraquinone * C14H8O5 256.210 257183; 113155113J. sigillata [75]
102Omega-3-fatty acidStearidonic acid [6,9,12,15-Octadecatetraenoic acid]C18H28O2276.413 277257229187G. linguiforme [52]; R. triste [34]
103 Dihydrotanshinone I *C18H20O3278.302 279261; 123177135Salviae Miltiorrhizae [40]
104Omega-3-fatty acidLinolenic acid (Alpha-Linolenic acid; Linolenate)C18H30O2 278.429 279261; 219; 177177; 219135Salviae Miltiorrhizae [41]; M. amurensis [43]
105SesquiterpenoidArtemisinin [Arteannuin; Artemisinine] *C15H22O5282.332281 237235191A. absinthium [50]; A. martjanovii [68]
106Omega-9 unsaturated fatty acidOleic acid (Cis-9-Octadecenoic acid; Cis-Oleic acid)C18H34O2 282.461281 237235191Huolisu Oral Liquid [38]
107Dihydroxy anthraquinone6-methyl-aloe-emodinC16H12O5 284.263 285211; 141183; 113165Chinese herbal formula Jian-Pi-Yi-Shen pill [39]
108IsocoumarinBrevifolincarboxylic acid *C13H8O8292.197291 248205204; 146P. granatum [76]; Carpinus betulus [77]
109 1-(3,4-Dihydroxyphenyl)-3-(2,4,6-trihydroxyphenyl)-2-propanolC15H16O6292.283291 248205; 178148Ribes magellanicum [30]
110DiterpenoidTanshinone IIA * [Tanshinone II; Tanshinone B]C19H18O3 294.344 295277259; 175199Huolisu Oral Liquid [38]; Radix Salviae [40]
111DiterpenoidCryptotanshinone * C19H20O3296.360 297279261; 177177Huolisu Oral Liquid [38]; Radix Salviae [40]
112DiterpenoidIsocryptotanshinone II *C19H20O3296.360 297279261; 177177Salviae Miltiorrhizae [41]
113DiterpenoidTanshinone IIB [(S)-6-(Hydroxymethyl)-1,6-Dimethyl-6,7,8,9-Tetrahydrophenanthro[1,2-B]Furan-10,11-Dione] *C19H18O4310.343309 237222180Salviae Miltiorrhizae [41]; Huolisu Oral Liquid [38]
114Diterpenoid7-Dehydroabietic acidC20H26O3314.418 315287187; 259 D. ramosa [24]
115Long-Chain Polyunsaturated Fatty AcidDocosahexaenoic acid [Doconexent; Cervonic acid]C22H32O2 328.488 329311; 283; 255283 PubChem
116Cyclohexenecarboxylic acidCaffeoyl shikimic acidC16H16O8336.293 337301; 193255; 227; 173199; 170R. aureum, R. pauciflorum [34]; Carpinus betulus [77]
117Cyclohexenecarboxylic acid4-O-caffeoyl shikimic acidC16H16O8336.293335 317273; 205189; 121Inula viscosa [77,78]
118Naphthoquinone4,8-Dihydroxy-1-naphthyl-beta-D-glucopyranosideC16H18O8338.309 339147119 J. mandshurica [68,69]
119DisaccharideTrehalose C13H24O13 388.321387 341178 Pubchem
120SterolFucosterol [Fucostein; Trans-24-Ethylidenecholesterol]C29H48O 412.690 413395; 268; 209378; 254350; 208F. pottsii [52]; L. caerulea [51]
121SterolBeta-Sitostenone C29H48O 412.690 413209; 149191; 149149F. herrerae [52];
122Steroidal alkaloidSolasodine C27H43NO2 413.635 414396; 209378; 326350Jatropha [67]
123Phlorodlucinol derivativeDisflavaspidic acid PBC23H28O8432.463 433415337309D. fragrans [20]
124Phlorodlucinol derivativeAspidin ABC23H28O8432.463 433415337309D. fragrans [20]
125Phlorodlucinol derivativeAlbaspidin PPC23H28O8432.463 433415337309D. fragrans [20]
126AmorphygeninDalbinol [12A-Hydroxyamorphygenin]C23H22O8426.416 427409; 291; 233339241; 173D. ramosa [24]
127Pentacyclic triterpeneLupeol [Fagarasterol; Clerodol; Lupenol] *C30H50O 426.717 427409; 291; 233339241; 173J. mandshurica [69]
128TriterpenoidUvaolC30H50O2 442.716 443425; 219206; 151 F. herrerae [52]
129Phlorodlucinol derivativeAlbaspidin PBC24H30O8446.490445 427; 401; 347; 247385; 341; 297; 247368; 343; 398; 283D. fragrans [20]
130Phlorodlucinol derivativeFlavaspidic acid BBC24H30O8446.490445 401; 223179; 153150D. fragrans [20]
131Phlorodlucinol dimerSaroaspidin AC24H30O8446.490445 427; 401; 347; 247385; 341; 297; 247368; 343; 398; 283D. fragrans [20]
132Anabolic steroidVebonol *C30H44O3452.668 453435; 210226; 336210H. polyrhizus [79]
133TriterpenoidBetulonic acid *C30H46O3 454.684 455438; 237420; 321; 248; 159375R. rugosa [60]
134Triterpenic acidUrsolic acid *C30H48O3 456.700 457439; 223421; 209379; 268J. mandshurica [69]; Ocimum [65]; Pear [62]
135Triterpenoid1-Hydroxy-3-oxours-12-en-28-oic acidC30H46O4470.683 471453; 237435; 383417; 365Pear [62]
136Cyclohexenecarboxylic acidCaffeoylquinate shikimate derivative 510.618 511493; 317475; 282457; 405Phoenix dactylifera [80]
137Indole sesquiterpene alkaloidSespendole *C33H45NO4519.714 520184125 H. polyrhizus [79]
138 Eucaglobulin B *C25H34O12526.530 527509; 351; 182464; 291418; 139Eucalyptus genus [81]
139CarotenoidAntheraxanthin [All-Trans-Antheraxanthin]C40H56O3584.870 585566; 377; 237548; 475; 381485; 389; 259Carotenoids [82]
140 (all-E)-violaxanthin butyrate 670.123 671653; 431575; 353353Carotenoids [82]
141Steroidal alkaloidAlpha-solanineC45H73NO15868.958 868706; 560; 398327; 157 S. tuberosum [83]
* Chemical compounds identified for the first time in D. fragrans.

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