Two new phenolic glycosides from the aerial part of Dryopteris erythrosora
Guijae Yoo1, SeonJu Park1, Heejung Yang2, Xuan Nhiem Nguyen3, Nanyoung Kim1, Jun Hyung Park1, Seung Hyun Kim1
1 College of Pharmacy, Yonsei Institute of Pharmaceutical Science, Yonsei University, Incheon 406-840, Korea
2 Research center natural medicine research Team, Richwood Pharmaceutical company, Ltd., Seoul, 08826, Republic of Korea
3 Institute of Marine Biochemistry, Vietnam Academy of Science and Technology, 18 Hoang Quoc Viet, Caugiay, Hanoi, Vietnam
|Date of Submission||06-Jul-2016|
|Date of Acceptance||01-Sep-2016|
|Date of Web Publication||13-Nov-2017|
Seung Hyun Kim
College of Pharmacy, Yonsei University, 162-1, Songdo-dong, Yeonsu-gu, Incheon 406-840
Source of Support: None, Conflict of Interest: None
| Abstract|| |
Background: Dryopteris erythrosora (D.C. Eaton) Kuntze is a species of fern in the family of Dryopteridaceae, which is distributed throughout East Asia. The genus Dryopteris has been used as traditional medicine, especially to treat hepatitis and protect liver. However, only few studies of chemical constituents of D. erythrosora have been conducted so far. Objective: In this study, we investigated the phytochemical constituents of D. erythrosora. Materials and Methods: The 80% methanol extract of the aerial part of D. erythrosora was used for the isolation of phenolic compounds. The isolated compounds were elucidated by various spectroscopic methods including nuclear magnetic resonance and mass spectrometry. Results: The present phytochemical investigation on the aerial part of D. erythrosora led to the isolation of two new phenolic glycosides, 1 and 2, as well as nine known flavonoids including two flavones (3 and 4) and seven flavonols (5-11). Conclusion: In this study, two new phenolic glycosides together with nine known flavonoids were isolated from the aerial part of D. erythrosora. Among them, compounds 4, 8, and 11 were isolated for the first time in Dryopteridaceae family from the present investigation. These results helped us to enrich our understanding of the chemical constituents of D. erythrosora and to identify compounds 1 and 2 which could be potential chemotaxonomic markers for the species.
Abbreviations used: HPLC: High-performance liquid chromatography; Q-TOF LC/MS: Quadrupole-time-of-flight liquid chromatography/mass spectrometry; NMR: Nuclear magnetic resonance; TMS: Tetramethylsilane
Keywords: Dryopteridaceae, Dryopteris erythrosora, phenolic glycoside
|How to cite this article:|
Yoo G, Park S, Yang H, Nguyen XN, Kim N, Park JH, Kim SH. Two new phenolic glycosides from the aerial part of Dryopteris erythrosora. Phcog Mag 2017;13:673-6
|How to cite this URL:|
Yoo G, Park S, Yang H, Nguyen XN, Kim N, Park JH, Kim SH. Two new phenolic glycosides from the aerial part of Dryopteris erythrosora. Phcog Mag [serial online] 2017 [cited 2022 Jan 25];13:673-6. Available from: http://www.phcog.com/text.asp?2017/13/52/673/218118
- The genus Dryopteris has been used as traditional medicine, especially to treat hepatitis and protect liver
- Two new phenolic glycosides were isolated from D. erythrosora
- Nine known flavonoids (3-11) were isolated from D. erythrosora
- Compounds 4, 8, and 11 were isolated for the first time in Dryopteridaceae family.
| Introduction|| |
Dryopteris erythrosora (D.C. Eaton) Kuntze is a species of fern in the family of Dryopteridaceae, which is distributed throughout East Asia.Dryopteris genus is a well-known traditional medicine and extensively used to treat hepatitis and protect liver. The major identified constituents in Dryopteris genus are phenols, flavonoids, and terpenoids.,, In a previous study, the chemical constituents of 18 Dryopteris genus were investigated and compared. However, only few studies of chemical constituents of D. erythrosora have been conducted so far.
| Materials and Methods|| |
All organic solvents, such as hexane, chloroform (CHCl3), ethyl acetate (EtOAc), methanol (MeOH), and n-butanol (n-BuOH) used for extraction and column chromatography were of analytical grade and purchased from Duksan Chemical (Anseong, Korea).1H nuclear magnetic resonance (NMR) (400 MHz) and 13C NMR (100 MHz) spectra were recorded on an Agilent 400-MR NMR spectrometer (Agilent Technologies, Santa Clara, CA), and tetramethylsilane was used as an internal standard. Data processing was carried out with the MestReNova 6.0.2 program. HRESIMS spectra were obtained using an Agilent 6550 iFunnel quadrupole-time of flight (Q-TOF) liquid chromatography/mass spectrometry (LC/MS) system (Agilent Technologies, Santa Clara, CA). Preparative high-performance LC (HPLC) was carried out using an Agilent 1260 HPLC system. Column chromatography was performed on silica gel (Kieselgel 60, 70–230 mesh and 230–400 mesh, Merck, Darmstadt, Germany) and YMC RP-18 resins (Fuji Silysia Chemical, Aichi, Japan).
The whole plants of D. erythrosora were collected at Jiri Mountain, Sancheong-gun, Gyeongsangnam-do province, South Korea, in July 2013, and authenticated by Dr. Jong Hee Park, a professor emeritus of Pusan National University. A voucher specimen (YIPS-DE-141220) was deposited at the Herbarium of College of Pharmacy, Yonsei Institute of Pharmaceutical Sciences, Yonsei University, Incheon, Korea.
Extraction and isolation
The dried and powdered aerial part of D. erythrosora (270 g) was extracted with 80% MeOH four times using ultrasound for 3 days at room temperature. After removal of the solvent under reduced pressure in vacuo, the resulted MeOH extract (37.6 g, yield: 13.9%) was suspended in H2O and then partitioned successively with CH2 Cl2(3.68 g), EtOAc (13.41 g), and n-BuOH (18.6 g) fractions. The EtOAc fraction was chromatographed on a silica gel column and eluted with a gradient of CHCl3– MeOH (40:1 → 1:1, v/v) to obtain eight subfractions as follows: Fr. E1 (1.58 g), Fr. E2 (1.21 g), Fr. E3 (1.03 g), Fr. E4 (0.67 g), Fr. E5 (4.56 g), Fr. E6 (1.65 g), Fr. E7 (2.34 g), and Fr. E8 (0.42 g). The Fr. E5 fraction was chromatographed on ODS silica gel column eluted with MeOH– H2O (3:7, v/v) to yield 1 (5.1 mg), 2 (4.8 mg), and 7 (6.0 mg). The Fr. E6 fraction was chromatographed on HPLC using J'sphere ODS H-80 (250 mm × 20 mm, 4 μm, 8 nm) column eluted with 25% aqueous acetonitrile at a flow rate of 3 mL/min to yield 5 (6.4 mg) and 6 (7.5 mg). The Fr. E7 fraction was chromatographed on silica gel column eluted with CHCl3– MeOH (5:1, v/v) to yield 3 (2.3 mg) and 4 (2.8 mg). The n-BuOH fraction was chromatographed on a silica gel column and eluted with a gradient of CHCl3– MeOH (20:1 → 1:1, v/v) to obtain six subfractions as follows: Fr. B1 (1.35 g), Fr. B2 (1.54 g), Fr. B3 (2.04 g), Fr. B4 (1.87 g), Fr. B5 (5.78 g), and Fr. B6 (3.54 g). The Fr. B5 fraction was chromatographed on an silica gel column eluted with CHCl3– MeOH (5:1, v/v) to yield 8 (2.7 mg) and 9 (4.1 mg). The Fr. B6 fraction was chromatographed on HPLC using J'sphere ODS H-80 (250 mm × 20 mm, 4 μm, 8 nm) column eluted with 30% aqueous acetonitrile at a flow rate of 3 mL/min to yield 10 (3.1 mg) and 11 (2.5 mg). The isolated compounds were elucidated by ESI-Q-TOF-MS and several NMR techniques including 1D and 2D NMR spectroscopic methods and by comparison of their data with those reported previously in the related literatures.
| Results And Discussion|| |
Two new phenolic glycosides (1 and 2), together with nine known compounds (3−11), were isolated from the aerial part of D. erythrosora. By comparing their spectroscopic methods with those reported in the literature, the isolated compounds were identified as apigenin-7-O-glucopyranoside and apigenin-7-O-rutinoside (3 and 4), keampferol-3-O-rhamnoside (5), kaempferol-3-O-rutinoside (6), quercetin (7), quercetin-3-O-galactoside (8), quercetin-3-O-rhamnoside (9), myricetin-3-O-rhamnoside (10), and myricetin-3-O-glucopyranoside (11) [Figure 1].
The structures of two new compounds 1 and 2 were elucidated on the basis of spectroscopic analysis [Figure 2] and comparison with literature data as described below.
Compound 1 was obtained as a pale brown amorphous powder and its molecular formula was determined as C14H20O9 by the HR-ESI-MS [M + H] + ion at m/z 333.1107 (calcd for C14H21O9, 333.1186). The 1H-NMR spectra of 1 revealed an olefinic proton at δH 6.18, a methyl at δH 2.02, and a methoxy signal at δH 3.82. The β-linkage of the glucopyranosyl moiety was deduced from the coupling constant (J = 7.2 Hz) of the anomeric proton signal at δH 4.64 [Table 1]. The 13C-NMR and DEPT spectra of 1 revealed 14 carbon signals, including five quaternary carbons (δC 110.59, 132.82, 149.63, 153.09, and 154.02), six methines (δC 71.03, 75.33, 77.84, 78.41, 100.11, and 107.24), one methylene (δC 62.25), one methyl (δC 8.81), and one methoxy (δC 61.80). Among the exhibited carbon signals,13 C chemical shifts of C-1' (δC 107.24), C-2' (δC 78.41), C-3' (δC 77.84), C-4' (δC 71.03), C-5' (δC 75.33), and C-6' (δC 62.25) suggested the presence of β-glucopyranosyl sugar moiety. The NMR data of 1 were similar to those of pseudo-aspidinol B except for the replacement of β-glucopyranosyl sugar moiety instead of a butanone. The HMBC correlations between H-1' (δH 4.64) and C-4 (δC 132.82) suggested the presence of O-β-glucopyranosyl sugar moiety at C-4. The HMBC correlations from H-OMe (δH 3.82) to C-5 (δC 153.09) suggested that the methoxy is attached at C-5. The HMBC correlations from H-7 (δH 2.02) to C-1, C-5, and C-6 (δC 154.02, 153.09, and 110.59, respectively) confirmed that methyl was located at C-6. Based on the evidence mentioned above, compound 1 was established as 1-1,3-dihydroxy-5-methoxyphenyl-4-O-β-D-glucopyranoside.
|Table 1: Nuclear magnetic resonance spectroscopic data for compounds 1 and 2|
Click here to view
Compound 2 was also obtained as a pale brown amorphous powder and its molecular formula was determined as C24H36O14, by the HR-ESI-MS [M + H] + ion at m/z 549.2105 (calcd for C24H37O14, 549.2137). The 1H-NMR spectra of 2 revealed an olefinic proton (δH 6.42), two methylene protons (δH 1.67 and 3.01), two methyl (δH 0.94 and 2.12), and a methoxy signal (δH 3.70). The β-linkage of the sugar moiety was deduced from the coupling constant (J = 7.7, 7.5 Hz) of the anomeric proton signal at δH 4.68 and 5.15, respectively [Table 1]. The 13C-NMR and DEPT spectra of 2 revealed 24 carbon signals, including six quaternary carbons (δC 112.02, 113.37, 161.87, 162.56, 163.37, and 207.98), eleven methines (δC 70.91, 71.21, 76.24, 77.81, 78.00, 78.10, 78.18, 82.85, 99.72, 99.82, and 105.37), four methylenes (δC 19.32, 46.19, 62.28, and 62.31), two methyls (δC9.49 and 14.32), and one methoxy (δC 62.54). The backbone of 2 was deduced from the HMBC correlations from methyl (δH 2.12) to C-4 (δC 162.56), C-5 (δC 113.37), and C-6 (δC 161.87), and from olefinic proton (δH 6.42) to C-1 (δC 112.03), C-2 (δC 163.37), C-4 (δC 162.56), and C-5 (δC 113.37). The NMR data of 2 were similar to those of methylphlorbutyrophenon except for the sugar moiety and a methoxy group. The presence of a methoxy group was confirmed by the HMBC correlation between H-OMe (δH 3.70) and C-6 (δC 161.87) suggesting that the methoxy is located at C-6. The HMBC correlations from H-7 (δH 2.12) to C-4, C-5, and C-6 (δC 162.56, 113.37, and 161.87, respectively) confirmed that methyl was located at C-5. The HMBC correlations from H-1' (δH 5.15) to C-4 (δC 162.56) and from H-1” (δH 4.68) to C-3” (δC 82.85) suggested the presence of glucopyranosyl-(1″'→3″)-glucopyranoside sugar moiety at C-4. Based on the evidence mentioned above, compound 2 was established as 4-O-β-D-glucopyranosyl-(1″'→3″)-glucopyranosyl-2-hydroxy-6-methoxy-5-methylphenyl-1-butanone.
| Conclusion|| |
The present phytochemical investigation on the aerial part of D. erythrosora led to the isolation of two new phenolic glycosides, 1and 2, as well as nine known flavonoids including two flavones (3 and 4) and seven flavonols (5-11). These results were in a good agreement with other chemical composition reports of the Dryopteris genus such as apigenin-7-O-glucoside (3) from Dryoathyrium boryanum, keampferol-3-O-rhamnoside (5) from D. crassirhizoma, kaempferol-3-O-rutinoside (6) from Dryopteris villarii, and quercetin (7) from Dracaena fragrans. Two 3-O-rhamnoside flavonols, quercetin-3-O-rhamnoside (9), and myricetin-3-O-rhamnoside (10) were previously isolated from D. erythrosora. These results led to the conclusion that apigenin-7-O-rutinoside (4), quercetin-3-O-galactoside (8), and myricetin-3-O-glucopyranoside (11) were isolated for the first time in Dryopteris genus as well as in Dryopteridaceae family from the present investigation. This phytochemical investigation helped us to enrich our understanding of the chemical constituents of D. erythrosora and to identify that compounds 1 and 2 could be potential chemotaxonomic markers for the species.
This research was supported by Basic Science Research Program through the National Research Foundation of Korea funded by the Ministry of Education, Science, and Technology (NRF-2011-0025129).
Financial support and sponsorship
Conflicts of interest
There are no conflicts of interest.
| References|| |
Zhang M, Cao J, Dai X, Chen X, Wang Q. Flavonoid contents and free radical scavenging activity of extracts from leaves, stems, rachis and roots of Dryopteris erythrosora
. Iran J Pharm Res 2012;11:991-7.
Cao J, Xia X, Chen X, Xiao J, Wang Q. Characterization of flavonoids from Dryopteris erythrosora
and evaluation of their antioxidant, anticancer and acetylcholinesterase inhibition activities. Food Chem Toxicol 2013;51:242-50.
Gao Z, Li R, Wang B, Lu Y. Progress in chemical constituents of genus Dryopteris
. China J Chin Mater Med 2003;9:50-5.
Chang X, Li W, Koike K, Wu L, Nikaido T. Phenolic constituents from the rhizomes of Dryopteris crassirhizoma
. Chem Pharm Bull (Tokyo) 2006;54:748-50.
Zhao DD, Zhao QS, Liu L, Chen ZQ, Zeng WM, Lei H, et al.
Compounds from Dryopteris fragrans
(L.) Schott with cytotoxic activity. Molecules 2014;19:3345-55.
Hiraoka A. Flavonoid patterns in Athyriaceae and Dryopteridaceae
. Biochem Syst Ecol 1978;6:171-5.
Chang Y, Hu J, Jiang S, Qiang S. Study on the distribution and the total flavonoids content of medical pteridophytes in Nanjing Zijin Mountain. J Northeast Agric Univ 2005;36:320-3.
Baris O, Karadayi M, Yanmis D, Guvenalp Z, Bal T, Gulluce M. Isolation of 3 flavonoids from Mentha longifolia
(L.) Hudson subsp. longifolia and determination of their genotoxic potentials by using the E. coli
WP2 test system. J Food Sci 2011;76:T212-7.
Kim SK, Kim HJ, Choi SE, Park KH, Choi HK, Lee MW. Anti-oxidative and inhibitory activities on nitric oxide (NO) and prostaglandin E2 (COX-2) production of flavonoids from seeds of Prunus tomentosa
Thunberg. Arch Pharm Res 2008;31:424-8.
Song N, Xu W, Guan H, Liu X, Wang Y, Nie X. Several flavonoids from Capsella bursa-pastoris
(L.) Medic. Asian J Tradit Med 2007;2:218-22.
Dhasan PB, Jegadeesan M, Kavimani S. Cucurbitacins isolated from the fruits of Momordica cymbalaria
Hook f. Pharmacogn Mag 2008;4:96.
Wei Y, Ito Y. Isolation of hyperoside and luteolin-glucoside from Agrimonia pilosa
ledeb using stepwise elution by high-speed countercurrent chromatography. J Liq Chromatogr Relat Technol 2007;30:1465-73.
Hema K, Sukumar D. Isolation and phytochemical studies of quercetin and quercetin 3-O-rhamnoside. Int J Pharm Bio Sci 2013;4:519-24.
Gedara SR, Galala AA. New cytotoxic spirostane saponin and biflavonoid glycoside from the leaves of Acacia saligna
(Labill.) H.L. Wendl. Nat Prod Res 2014;28:324-9.
Manguro LOA, Ugi I, Lemen P. Further flavonol glycosides of Embelia schimperi leaves. B CHEM SOC ETHIOPIA. 2004;18:51-7.
Zuo L, Wang HQ, Chen RY. Chemical constituents in roots of Dryopteris championii.
Zhong Cao Yao 2005;2:177-9.
Cao J, Xia X, Dai X, Xiao J, Wang Q, Andrae-Marobela K, et al.
Flavonoids profiles, antioxidant, acetylcholinesterase inhibition activities of extract from Dryoathyrium boryanum
(Willd.) Ching. Food Chem Toxicol 2013;55:121-8.
Min BS, Tomiyama M, Ma CM, Nakamura N, Hattori M. Kaempferol acetylrhamnosides from the rhizome of Dryopteris crassirhizoma
and their inhibitory effects on three different activities of human immunodeficiency virus-1 reverse transcriptase. Chem Pharm Bull (Tokyo) 2001;49:546-50.
Imperato F. Kaempferol 3-O-(acetylrutinoside), a new flavonoid and two new fern constituents, quercetin 3-O-(acetylglucoside) and 3-O-(acetylrutinoside) from Dryopteris villarii
. Am Fern J 2006;96:93-6.
Li B, Zhu JF, Zou ZJ, Yin YQ, Shen ZB. Studies on the chemical constituents of Dryopteris fragrans
. Zhong Yao Cai 2009;32:1232-3.
[Figure 1], [Figure 2]