红景天化学成分研究

目的 研究景天科植物红景天Rhodiola crenulata干燥根的化学成分，考察红景天中化学成分抗缺氧损伤作用。方法 综合运用硅胶、ODS及HPLC等色谱方法进行系统的分离纯化，利用UV、IR、NMR、MS等光谱、波谱学手段对分得的化学成分进行结构鉴定。采用CCK-8法评价化合物对CoCl₂诱导PC12细胞的保护作用。结果 从红景天根70%乙醇提取物中分离并鉴定了37个化合物，包括苯丙素类19个，分别为对羟基桂皮酸（1）、咖啡酸（2）、6,7-二甲氧基香豆素（3）、2-甲氧基-4-(2-丙烯基)苯基β-D-吡喃葡萄糖苷（4）、1,2-di-O-β-D-glucopyranosyl-4-allylbenzene（5）、3,4,5-trihydroxy allylbenzene-3-O-β-D-glucopyranosyl-4-O-β-D-glucopyranoside（6）、刺五加苷B（7）、松柏苷（8）、肉桂基-O-β-D-吡喃葡萄糖苷（9）、1-feruloyloxy-2-methoxy cinnamic acid（10）、异落叶松脂素（11）、(7R,8S)-dehydrodiconiferyl alcohol 9-β-glucopyranoside（12）、(7S,8R)-脱氢双松柏醇-9''-β-D-葡萄糖苷（13）、(7R,8S)-dihydrodehydrodiconiferyl alcohol 9′-O-β-D-glucopyranoside（14）、(7R,8R)-7,8-dihydro-9′-hydroxyl-3′-methoxyl-8-hydroxymethyl-7-(4-hydroxy-3-methoxyphenyl)-1′-benzofuranpropanol 9′-O-β-D-gluco- pyranoside（15）、(7S,8R)-dihydrodehydrodiconiferyl alcohol 4-O-β-D-glucopyranoside（16）、hyuganoside IIIa（17）、3-hydroxy-1-(4-hydroxy-3-methoxyphenyl)-2-[4-(3-hydroxy-1-(E)-propenyl)-2,6-dimethoxyphenoxy]propyl-β-D-glucopyranoside（18）、金石蚕苷（19）；苯乙烷类6个，分别为酪醇（20）、苯乙醇-O-β-D-吡喃葡萄糖苷（21）、icariside D₂（22）、p-hydroxyphenethyl-O-β-D-glucopyranoside（23）、对羟基-苯乙基-6''-O-没食子酰-β-葡萄糖苷（24）、苯乙醇-β-巢菜糖苷（25）；黄酮类4个，分别为根皮素（26）、异槲皮苷（27）、山柰酚-7-O-葡萄糖苷（28）、表儿茶素-3-O-没食子酸酯（29）；其他类8个，分别为3-methyl-but-2-en-1-yl-β-D-glucopyranoside（30）、大花红天素（31）、taxilluside A（32）、trans-linalool-3,6-oxide-β-D-glucopyranoside（33）、xylogranatinin（34）、马钱苷（35）、(6Z)-4-(3-hydroxybutylidene)-3,5,5-trimethyl-2-cyclohexene-1-one-O-β-D-glucopyranoside（36）、blumenyl C-β-D-glucopyranoside（37）。在20 μmol/L时，苯丙素类、苯乙烷类及黄酮类化合物均表现出明显的的抗缺氧损伤作用。结论 化合物7、10、17～19、35为首次从景天科植物中分离得到，化合物4、6、26、28、32～34、36、37为首次从景天属植物中分离得到。体外抗缺氧损伤活性实验表明，在20μmol/L时苯乙烷类化合物20、23对CoCl₂损伤PC 12细胞保护作用最好，细胞存活率较高。

Chemical consituents of Rhodiola crenulata

Objective To study the chemical constituents of the dried roots of Rhodiola crenulata, a plant of the Crassulaceae, and to investigate the anti-hypoxic damage effects of the chemical constituents from R. crenulata. Methods The chemical components were systematically isolated and purified using silica-gel, ODS, and HPLC chromatography methods. The structures of the isolated chemical components were identified by UV, IR, NMR, and MS. The protective effect of the isolated compounds on CoCl₂ induced PC 12 cells was evaluated using the CCK-8 method. Results A total of 37 compounds were isolated and identified from the 70% ethanol extract of roots of R. crenulata, including 19 phenylpropanoids, named p-hydroxycinnamic acid (1), caffeic acid (2), 6,7-dimethoxycoumarin (3), 2-methoxy-4-(2-propenyl)phenyl β-D-glucopyranoside (4), 1,2-di-O-β-D-glucopyranosyl-4-allylbenzene (5), 3,4,5-trihydroxy allylbenzene-3-O-β-D-glucopyranosyl-4-O-β-D-glucopyranoside (6), syringin (7), abietin (8), cinnamy-O-β-D-glucopyranoside (9), 1-feruloyloxy-2-methoxy cinnamic acid (10), isolariciresinol (11), (7R,8S)-dehydrodiconiferyl alcohol 9-β-glucopyranoside (12), (7S,8R)-dehydrodiconiferyl alcohol 9''-β-D-glucoside (13), (7R,8S)-dihydro-dehydrodiconiferyl alcohol 9''-O-β-D-glucopyranoside (14), (7R,8R)-7,8-dihydro-9''-hydroxyl-3''-methoxyl-8-hydroxymethyl-7-(4-hydroxy-3-methoxyphenyl)-1''-benzofuranpropanol 9''-O-β-D-glucopyranoside (15), (7S,8R)-dihydrodehydrodiconiferyl alcohol 4-O-β-D-glucopyranosid (16), hyuganoside IIIa (17), 3-hydroxy-1-(4-hydroxy-3-methoxyphenyl)-2-[4-(3-hydroxy-1-(E)-propenyl)-2,6-dimethoxyphenoxy] propyl-β-D-glucopyranoside (18), poliumoside (19); six phenylethanes, named tyrosol (20), phenethanol-O-β-D-glucopyranoside (21), icariside D₂(22), p-hydroxyphenethyl-O-β-D-glucopyranoside (23), 4-hydroxy-phenylethyl-6''-O-galloyl-β-glucoside (24), phenethanol-β-cycloside (25); four flavonoids, named phloretin (26), isoquercetin (27), kaempferol-7-O-β-D-glucoside (28), epicatechin-3-O-gallate (29); and eight others, named 3-methyl-but-2-en-1-yl-β-D-glucopyranoside (30), crenulatin (31), taxilluside A (32), trans-linalool-3,6-oxide-β-D-glucopyranoside (33), xylogranatinin (34), loganin (35), (6Z)-4-(3-hydroxybutylidene)-3,5,5-trimethyl-2-cyclohexene-1-one-O-β-D-glucopyranoside (36), blumenyl C-β-D-glucopyranoside (37). At 20 μmol/L, phenylpropanoids, phenylethanes, and flavonoids all showed significant anti-hypoxic damage effects. Conclusion Compounds 7, 10, 17-19 and 35 were isolated from the family Sedum for the first time, and compounds 4, 6, 26, 28, 32-34, 36 and 37 were isolated from the genus Sedum for the first time. In vitro anti-hypoxia injury activity experiments showed that phenylethane compounds 20 and 23 had the best protective effect on PC 12 cells damaged by CoCl₂ at 20 μmol/L, and the cell survival rate was higher.