三脉马钱茎枝中酚苷类成分及其生物活性研究

Phenolic glycosides from the stems and twigs of Strychnos cathayensis and their biological activities

应用大孔树脂、硅胶、ODS、Sephadex LH-20柱色谱和半制备HPLC对三脉马钱茎枝95%乙醇提取物的正丁醇部位进行分离纯化,分离得到14个化合物,通过高分辨质谱、核磁共振波谱和文献数据分析,分别鉴定为:4-O-β-D-吡喃阿洛糖基香草酸乙酯(1)、4-O-β-D-吡喃阿洛糖基香草酸正丁酯(2)、4-O-(6′-O-丁香酰基)-β-D-吡喃阿洛糖基香草酸正丁酯(3)、4-O-(6′-O-香草酰基)-β-D-吡喃阿洛糖基香草酸正丁酯(4)、4-O-(6′-O-丁香酰基)-β-D-吡喃葡萄糖基香草酸正丁酯(5)、4-O-α-L-吡喃鼠李糖基丁香酸正丁酯(6)、3-甲氧基-4-β-D-吡喃阿洛糖氧基苯甲酸甲酯(7)、金钱松苷B (8)、丁香酸丁酯(9)、丁香酸葡萄糖苷(10)、丁香酸甲酯(11)、香草酸甲酯(12)、威灵仙苷C (13)和小木通苷A (14),其中化合物1~6为酚酸乙酯或正丁酯的人工产物。需要指出的是,化合物3和4的生源前体4-O-(6′-O-丁香酰基)-β-D-吡喃阿洛糖基香草酸和4-O-(6′-O-香草酰基)-β-D-吡喃阿洛糖基香草酸均为新化合物。化合物1~13的体外活性评价表明,在10μmol·L^(-1)的浓度下,化合物1、2和6~10均具有潜在的肝细胞保护活性,细胞存活率由扑热息痛模型组的45.4%提高到53.6%~55.5%;化合物4具有一定的抗炎作用,其一氧化氮生成抑制率为74.6%;化合物3和5具有潜在抗氧化活性,在10μmol·L^(-1)的浓度下,丙二醛生成抑制率分别为53.2%和56.1%。

Fourteen compounds were isolated from the n-butanol fraction of the 95% aqueous ethanol extract of the stems and twigs of Strychnos cathayensis by D101 macroporous resin,silica gel,ODS,Sephadex LH-20column chromatography,and semipreparative RP-HPLC.Their structures were elucidated as ethyl 4-O-β-D-allopyranosyl-vanillate(1),n-butyl 4-O-β-D-allopyranosyl-vanillate(2),n-butyl 4-O-(6′-O-syringoyl)-β-D-allopyranosylvanillate(3),n-butyl 4-O-(6′-O-vanilloyl)-β-D-allopyranosyl-vanillate(4),n-butyl 4-O-(6′-O-syringoyl)-β-D-glucopyranosyl-vanillate(5),n-butyl 4-O-α-L-rhamnopyranosyl-syringate(6),methyl 3-methoxy-4-(β-D-allopyranosyloxy) benzoate(7),pseudolaroside B(8),butyl syringate(9),glucosyringic acid(10),methyl syringate(11),methyl 4-hydroxy-3-methoxybenzoate(12),clemochinenoside C(13),and clemoarmanoside A(14),respectively,on the basis of spectroscopic data interpretation and by comparison with literature information.Compounds 1-6 are artificial products of phenolic acid esterified by ethanol or n-butanol.It is noted that the precursors(4-O-(6′-Osyringoyl)-β-D-allopyranosyl-vanillic acid and 4-O-(6′-O-vanilloyl)-β-D-allopyranosyl-vanillic acid) of compounds 3 and 4 are new compounds.The hepatoprotective,anti-inflammatory,antioxidant and cytotoxic activities of compounds 1-13 were evaluated in vitro at a concentration of 10 μmol·L^(-1).Compounds 1,2 and 6-10 exhibited potential hepatic protection effects with cell survival rates ranging from 53.6% to 55.5%(acetaminophen,45.4% at 8 mmol·L^(-1)).Compound 4 demonstrated anti-inflammatory activity with nitric oxide inhibitory rate of 74.6%.Compounds 3 and 5 showed potential antioxidant activities with malondialdehyde inhibitory rates of 53.2% and 56.1%,respectively.