扬子毛茛中的化学成分研究

扬子毛茛中的化学成分研究

潘云雪, 周长新, 张水利, 郑筱祥, 赵昱^*

1.浙江大学药学院中药与天然药物研究室, 杭州 310031;
2.浙江大学生物医学工程与仪器科学学院, 杭州 310006

收稿日期:2003-11-21 修回日期:2004-05-10 出版日期:2004-06-15 发布日期:2004-06-15
通讯作者: 赵昱*

Constituents from Ranunculus sieboldii Miq.

PAN Yun-xue, ZHOU Chang-xin, ZHANG Shui-li, ZHENG Xiao-xiang, ZHAO Yu^*

1.Department of Traditional Chinese Medicine and Natural Drug Research, College of Pharmaceutical Sciences, Zhejiang University, Hangzhou 310031, China;
2.Department of Biomedical Engineering, College of Biomedical Engineering and Instrument Sciences, Zhejiang University, Hangzhou 310006, China

Received:2003-11-21 Revised:2004-05-10 Online:2004-06-15 Published:2004-06-15
Contact: ZHAO Yu*

摘要/Abstract

摘要： 目的研究扬子毛茛的化学成分. 方法应用多种色谱方法和色谱材料进行提取、分离和纯化, 用各种现代光谱方法并结合文献对分得的化合物进行结构解析. 结果从扬子毛茛的95%乙醇提取物中分到十三个化合物, 其中五个为黄酮苷类化合物, 分别命名为芹菜素-4'-O-α-L-鼠李糖苷(1), 芹菜素-7-O-β-D-葡萄糖苷-4'-O-α-L-鼠李糖苷(2), 芹菜素-8-C-α-L-阿拉伯糖苷(3), 芹菜素-8-C-β-D-半乳糖苷(4), 小麦黄素-7-O-β-D-葡萄糖苷(5); 其余八个分别为小麦黄素(6), 木犀草素(7), 东莨菪内酯(8), 秦皮乙素(9), 滨蒿内酯(10), 阿魏酸(11), 原儿茶酸(12)和小毛茛内酯(13). 此外还对这些化合物的体外抗癌活性进行了初步的测试. 结论化合物1-12为首次从该属植物中分到, 化合物13为首次从该种植物中分到, 其中化合物1为新的天然产物, 化合物2和3首次报道了其碳谱数据.生物活性测试结果表明化合物1对BEL-7407及A549细胞的IC50值分别为43及77μg·mL^-1, 化合物8和10对KB细胞的IC50分别为78和44μg·mL^-1, 对HL-60细胞的IC50均为85μg·mL^-1.化合物7对所测试的四种肿瘤细胞株均显示一定的细胞毒活性, 其对KB, BEL-7407, A549及HL-60细胞的IC50分别为51, 55, 44和10μg·mL^-1.

关键词: 毛茛, 毛茛, 毛茛, 黄酮苷, 黄酮苷, 黄酮苷, 芹菜素-4'-O-α-L-鼠李糖苷, 芹菜素-4'-O-α-L-鼠李糖苷, 芹菜素-4'-O-α-L-鼠李糖苷, 芹菜素-8-C-α-L-阿拉伯糖苷, 芹菜素-8-C-α-L-阿拉伯糖苷, 芹菜素-8-C-α-L-阿拉伯糖苷, 芹菜素-7-O-β-D-葡萄糖苷-4'-O-α-L-鼠李糖苷, 芹菜素-7-O-β-D-葡萄糖苷-4'-O-α-L-鼠李糖苷, 芹菜素-7-O-β-D-葡萄糖苷-4'-O-α-L-鼠李糖苷, 细胞, 细胞, 细胞

Abstract: Aim To investigate the chemical composition of Ranunculus sieboldii Miq.. Methods Repeated column chromatography over silica gel, polyamide and RP-18 followed by gel filtration on sophadex LH-20 were used to isolate chemical constituents, and their structures were elucidated by extensive spoctroscopic methods (UV, IR, MS, ¹H NMR, ¹³C NMR) including 2D NMR (COSY, HMQC, HMBC, NOESY) techniques and by direct comparing spectral data with those reported in literature. Results Five flavonoid glycosides named apigenin-4'-O-α-L-rhamnopyranoside (1), apigenin-7-O-β-D-glucopyranosyl-4'-O-α-L-rhamnopyranoside (2), apigenin-8-C-α-L-arabinopyranoside (3), apigenin-8-C-β-D-ga- lactopyranoside (4), tricin-7-O-β-D-glucopyranoside (5), together with tricin (6), luteolin (7), scopoletin (8), esculetin (9), scoparone (10), ferulic acid (11), protocatechuic acid (12), and tematolide (13) were isolated from the 95% ethanolic extract of its whole plant, and their cytotoxic activities were preliminarily tested. Conclusion Compounds 1-12 were obtained from this genus and compound 13 from this species for the first time. Furthermore, compound 1 was for the first time isolated from nature while the ¹³C NMR data of compounds 2 and 3 are reported for the first time. The bioassay revealed that compound 1 was active against BEL-7407 and A549 cell lines (IC50 43, 77 μg·mL^-1), 8 and 10 showed inhibitory ac- tivities on KB cell lines (IC50 78, 44 μg·mL^-1) and HL-60 cell lines (IC50 85, 85 μg· mL^-1), while 7 exerted moderate cytotoxic activities on KB, BEL-7407, A549 and HL-60 cell lines with their IC50 being 51, 55, 44 and 10 μg·mL^-1, respecfvely.

Key words: Ranunculus sieboldii Miq., Ranunculus sieboldii Miq., flavonoid glycosides, flavonoid glycosides, apigenin-4'-O-α-L-rhamnopyranoside, apigenin-4'-O-α-L-rhamnopyranoside, apigenin-8-C-α-L-arabinopyranoside, apigenin-8-C-α-L-arabinopyranoside, apigenin-7-O-β-D-glucopyranosyl-4'-O-α-L-rhamnopyranoside, apigenin-7-O-β-D-glucopyranosyl-4'-O-α-L-rhamnopyranoside, cytotoxicity, cytotoxicity

中图分类号:

R284.1

R284.2

R965

Supporting: ^*Corresponding author. Tel.: 0571-87217313; fax: 0571-87217313

潘云雪, 周长新, 张水利, 郑筱祥, 赵昱^*. 扬子毛茛中的化学成分研究[J]. .

PAN Yun-xue, ZHOU Chang-xin, ZHANG Shui-li, ZHENG Xiao-xiang, ZHAO Yu^* . Constituents from Ranunculus sieboldii Miq.[J]. .

参考文献

[1] Xie ZW. Compilation of Chinese Herb Medicine [M]. 2nd ed. Beijing: People’s Health Press, 1996, 201-202.
[2] Jean C, Dellamonica G, Besson E, et al. C-galactosylflavones from Polygonatum multiflorum [J]. Phytochemistry, 1977, 16 (2): 1999-2001.
[3] Yong J, John NS, Cecil CS. Bioactive flavonoids from endophyte-infected blue grass [J]. J Agri Food Chem, 1998, 46 (9): 3785-3788.
[4] Ma J Y, Wang ZT, Xu LS, et al. Chemical constituents of Ixens sonchifolia Hance [J]. J Chin Pharm Univ, 1998, 29 (2): 94-96.
[5] Hiroki T, Sueo H, Sansei N, et al. Coumarins from Olea africana and Olea capensis [J]. Phytochemistry, 1984, 23 (3): 699-700.
[6] Lin WH, Wang TX, Cai MS, et al. Studies on the structures of new cinnamol glucoside from the roots of Veronicastrum sibirics (L.) [J]. Acta Pharm Sin, 1995, 30 (10): 752-756.
[7] Liu WJ, Hu XB, Yang PQ. Studies on the chemical constituents of Drosera peltata Smith var. lunata collcted in Tibet [J]. West China J Pharm Sci, 1992, 7 (4): 201-202.
[8] Guo XM, Zhou ZL, Hong YF. Chemical constituents of Ranunculus ternatus Thunb [J]. Acta Pharm Sin, 1995, 30 (12): 931-934.
[9] Shen CC, Chang YS, Ho LK. Nuclear magnetic resonance studies of 5,7-dihydroxy flavonoids [J]. Phytochemistry, 1993, 34 (3): 843-845.
[10] Muhammad Z, Omar I, Pan YJ, et al. Flavonoid glycosides from Salvia moorcroftiana Wall [J]. Carbohydr Res, 2002, 337: 403-407.
[11] Markham KR, Ternai B, Stanley R, et al. ¹³C NMR studies of flavonoids-Ш [J]. Tetrohedron, 1978, 34 (9): 1389-1397.
[12] Nakagawa K, Nakajima M, Okazaki H, et al. Microbial preparation of rhamnosyl derivatives of pharmaceutical phenolic compounds [P]. J P: 02211892, 1990-08-23.
[13] NobuyasuM, Munekazu I, Toshiyuki T. Phylogenetic analysis in genus Euchresta based on secondary metabolites [J]. Biochem Syst Ecol, 1994, 22 (6): 621-629.
[14] Chopin J, Bouillant ML, Nair AG, et al. New C-glycosylflavones from Mollugo distica [J]. Phytochemistry, 1978, 17 (2): 299-300.
[15] Chopin J, Besson E, Ramachandran AG. New C-glycosylflavones from Mollugo pentaphylla [J]. Phytochemistry, 1979, 18 (12): 2059-2060.
[16] Aally MC, Scudiero DA, Monks A, et al. Feasibility of drugs screening with panels of human tumor cell lines using a microculture tetrazolium assay [J]. Cancer Res, 1988, 48 (3): 589-601.