【作者】 蒋丹；

【导师】 高其品； 屠鹏飞；

【作者基本信息】 东北师范大学 ， 生物化学与分子生物学， 2006， 博士

【摘要】 木通科(Lardizabalaceae)木通属(Akebia)植物五叶木通[Akebia quinata (Thunb.)Decne.]的成熟果实是中药预知子的来源之一。其味微苦,性平,具有舒肝和胃,活血止痛,软坚散结,利小便之功效。长期以来对该属植物的研究显示,皂苷类化合物是其主要化学成分。为了更好地开发和利用我国木通属植物资源,同时为预知子的质量标准建立奠定物质基础,我们对预知子的化学成分进行了系统研究。本文利用多种色谱技术进行分离,从预知子中得到40个化合物,经过理化性质和波谱分析对其结构进行了鉴定,其中22个三萜皂苷类化合物,3个香豆素类化合物,2个环烯醚萜苷类化合物和13个其它化合物,它们分别为:3-O-α-L-吡喃阿拉伯糖常春藤皂苷(B-1);3-O-β-D-吡喃木糖-(1→2)-α-L-吡喃阿拉伯糖丝石竹皂苷(B-2);3-O-α-L-吡喃鼠李糖-(1→2)-α-L-吡喃阿拉伯糖丝石竹皂苷(B-3);3-O-α-L-吡喃鼠李糖-(1→2)-α-L-吡喃阿拉伯糖齐墩果酸(Prosapogenin, B-4);3-O-β-D-吡喃木糖-(1→2)-α-L-吡喃阿拉伯糖齐墩果酸(B-5);3-O-β-D-吡喃木糖-(1→2)-α-L-吡喃阿拉伯糖常春藤皂苷(Saponins B, B-6);3-O-α-L-吡喃鼠李糖-(1→2)-α-L-吡喃阿拉伯糖常春藤皂苷(B-7);3-O-β-D-吡喃木糖-(1→3)-α-L-吡喃鼠李糖-(1→2)-α-L -吡喃阿拉伯糖常春藤皂苷(B-8);3-O-α-L-吡喃鼠李糖-(1→2)-α-L -吡喃阿拉伯糖-28-O-β-D-吡喃葡萄糖(1→6)-β-D-吡喃葡萄糖常春藤皂苷(Dipsacoside B, B-9);3-O-β-D-吡喃葡萄糖(1→3)-α-L-吡喃鼠李糖-(1→2)-α-L-吡喃阿拉伯糖齐墩果酸(B-10);3-O-β-D-吡喃葡萄糖(1→3)-α-L-吡喃鼠李糖-(1→2)-α-L-吡喃阿拉伯糖常春藤皂苷(B-11);3-O-α-L-吡喃鼠李糖(1→2)-[β-D-吡喃葡萄糖(1→4)]-α-L-吡喃阿拉伯糖常春藤皂苷(Pulsatillasaponin D, B-12);3-α-L-吡喃鼠李糖-28-O-β-D-吡喃葡萄糖-(1→6)-β-D-吡喃葡萄糖常春藤皂苷(Saponin D, B-13);3-O-β-D-吡喃鼠李糖-(1→2)-α-L-吡喃阿拉伯糖-28-O-β-D-吡喃葡萄糖-(1→6)-β-D-吡喃葡萄糖丝石竹皂苷(B-14);3-O-β-D-吡喃木糖-(1→2)-α-L-吡喃阿拉伯糖-28-O-β-D-吡喃葡萄糖-(1→6)-β-D-吡喃葡萄糖齐墩果酸(B-15);3-O-β-D-吡喃木糖-(1→2)-α-L-吡喃阿拉伯糖-28-O-β-D-吡喃葡萄糖-(1→6)-β-D-吡喃葡萄糖常春藤皂苷(Saponin E, B-16);3-O-α-L-吡喃鼠李糖-(1→2)-α-L-吡喃阿拉伯糖-28-O-β-D-吡喃葡萄糖-(1→6)-β-D-吡喃葡萄糖齐墩果酸(B-21);3-O-α-L-吡喃鼠李糖-(1→2)-α-L-吡喃阿拉伯糖-28-O-α-L-吡喃鼠李糖-(1→4)-β-D-吡喃葡萄糖-(1→6)-β-D-吡喃葡萄糖常春藤皂苷(Kalopanaxsaponins B, B-22);3-O-β-D-吡喃葡萄糖(1→2)-α-L-吡喃阿拉伯糖-28-O-α-L-吡喃鼠李糖(1→4)-β-D-吡喃葡萄糖(1→6)-β-D-吡喃葡萄糖齐墩果酸(B-23);3-O-β-D-吡喃木糖-(1→3)-α-L-吡喃鼠李糖-(1→2)-α-L-吡喃阿拉伯糖-28-O-α-L-吡喃鼠李糖(1→4)-β-D-吡喃葡萄糖(1→6)-β-D-吡喃葡萄糖齐墩果酸(B-24);3-O-β-D-吡喃葡萄糖(1→3)-α-L-吡喃鼠李糖-(1→2)-α-L -吡喃阿拉伯糖-28-O-α-L-吡喃鼠李糖(1→4)-β-D-吡喃葡萄糖(1→6)-β-D-吡喃葡萄糖常春藤皂苷(Patrinia saponin H3, B-25);3-O-α-L-吡喃鼠李糖(1→2)-[β-D-吡喃葡萄糖更多还原

【Abstract】 The fruits of Akebia quinata (Thunb.) Decne. is one of the sources of Chinesemedicine “Yuzhizi”, which is used as an diuretic, anti-tumor, bacteriostasic agent in clinic.Previous chemical investigations revealed that the plants of the genus Akebia possessedrich saponins. In order to improve the exploiting and using of the Akebia, theinvestigations on the bioactive constituents of Akebia quinata have been carried out.Using various chromatographic methods, 40 compounds including 22 triterpenesaponins have been isolated from the fruits of Akebia quinata. On the basis of theirphysicochemical and spectroscopic evidences, their structures were elucidated as follows:3-O-α-L-arabinopyranoside hederagenin (B-1), 3-O-β-D-xylopyranosyl-(1→2)-α-L-arabinopyranosyl gypsogenin (B-2), 3-O-α -L-rhamnopyranosyl-(1 → 2)-α-L-arabinopyranosyl gypsogenin (B-3), 3-O-α -L-rhamnopyranosyl-(1 → 2)-α-L-arabinopyranosyl oleanolic acid (Prosapogenin, B-4), 3-O-β-D-xylopyranosyl-(1→2)-α-L-arabinopyranosyl oleanolic acid (B-5), 3-O-β-D-xylopyranosyl-(1→2)-α-L-arabinopyranosyl hederagenin (Saponins B, B-6), 3-O-α-L-rhamnopyranosyl-(1→2)-α-L-arabinopyranosyl hederagenin (B-7), 3-O-β -D-xylopyranosyl-(1 → 3)-α-L-rhamnopyranosyl-(1 → 2)-α -L -arabinopyranosyl hederagenin (B-8), 3-O-α-L-rhamnopyranosyl(1→2)-α-L-arabinopyranosyl-28-O-β-D-glucopyranosyl(1→6)-β-D-glucopyranoside hederagenin (Dipsacoside B, B-9), 3-O-β-D-glucopyranosyl(1→3)-α-L-rhamnopyranosyl-(1→2)-α-L-arabinopyranosyl oleanolic acid (B-10), 3-O-β-D-glucopyranosyl(1 → 3)-α -L-rhamnopyranosyl-(1 → 2)-α -L -arabinopyranosylhederagenin (B-11), 3-O-([β-D-glucopyranosyl(1→4)]-[α-L-rhamnopyranosyl-(1→2)]-α -L –arabinopyranosyl) hederagenin (Pulsatilla saponin D, B-12), 3-α -L-arabinopyranosyl-28-O-β-D-glucopyranosyl-(1→6)-β-D-glucopyranosyl hederagenin(Saponin D, B-13), 3-O-β-D-xylopyranosyl-(1→2)-α-L-arabinopyranosyl-28-O-β-D-glucopyranosyl-(1 → 6)-β -D-glucopyranosyl gypsogenin (B-14), 3-O-β -D-xylopyranosyl-(1 → 2)-α -L-arabinopyranosyl-28-O-β -D-glucopyranosyl-(1→ 6)-β-D-glucopyranosyl oleanolic acid (B-15), 3-O-β -D-xylopyranosyl -(1 → 2)-α-L-arabinopyranosyl-28-O-β -D-glucopyranosyl-(1 → 6)-β -D-glucopyranosylhederagenin (Saponin E, B-16), 3-O-α -L-rhamnopyranosyl(1 → 2)-α-L-arabinopyranosyl-28-O-β-D-glucopyranosyl(1→6)-β-D-glucopyr-anoside oleanolicacid (B-21), 3-O-α-L-rhamnopyranosyl(1→2)-α-L-arabinopyranosyl-28-O-α-L-rhamnopyranosyl-(1→4)-β-D-glucopyranosyl(1→6)-β-D-glucopyranoside hederageninKalopanaxsaponins B (Kalopanaxsaponins B, B-22), 3-O-β-D-glucopyranosyl (1→2)-α-L-arabinopyranosyl-28-O-α-L-rhamnopyranosyl (1→4)-β-D-glucopyranosyl (1→6)-β-D-glucopyranoside oleanolic acid (B-23), 3-O-β -D-xylopyranosyl-(1 → 3)-α-L-rhamnopyranosyl-(1→2)-α-L– arabinopy-ranosyl-28-O-α-L-rhamnopyranosyl(1→4)-β -D-glucopyranosyl(1 → 6)-β -D-glucopyranoside oleanolic acid (B-24), 3-O-β-D-glucopyranosyl(1→3)-α-L-rhamnopyranosyl-(1→2)-α-L -arabinopyranosyl-28-O-α-L-rhamnopyranosyl(1 → 4)-β -D-glucopyranosyl (1 → 6)-β -D-glucopyranosidehederagenin(Patrinia saponin H3, B-25), 3-O-α -L-rhamnopyranosyl(1 → 2)-[ β -D-glucopyranosyl(1→4)]-α-L-arabinopyranosyl-28-O-α-L-rhamnopy-ranosyl-(1→4)-β-D-glucopyranosyl(1→6)-β-D-glucopyranoside hederagenin (Hederacholichiside F, B-26).3 coumarins: Esculetin (E-10), Hymexelsin (B-19), Scopolin (B-20);2 iridoids:geniposidic acid (B-17), 10-O-acetylgeniposidic acid (B-18);13 other compounds:15-nonacosanol (E-1), palmitic acid (E-2), stigmasterol (E-3), β -sitosterol (E-4),p-hydroxybenzoic acid (E-5), Vomifoliol (E-6), p-hydroxyphenylethyl alcohol (E-7),Oleanolic acid (E-8), (2S,3S,4S)-2-Methyl-tetrahydrofuran-3,4-diol (E-9), protocatechuicacid (E-11), caffeic acid (E-12), β -daucosterol (E-13), Stigmasterol-3-O-β-D-glucopyranoside (E-14). Among these compounds, B-2、B-3 and B-14 are newcompounds, compounds B-4、B-5、B-9、B-10、B-11、B-12、B-21、B-23、B-24、B-26 、E-1、E-2、E-5、E-6、E-7、E-9、E-10、E-11、E-12 are isolated from this genus for thefirst time.On the basis of chemical investigation, the bioactivities of the extracts and somepurified compounds have been tested. The group with high dosage of n-butanol extractsshowed significance inhibitory on Candida albicans and Cryptococcus. The group withhigh dosage of ethyl acetate extracts and 95% ethanol extracts showed significanceinhibitory on Candida albicans and Cryptococcus. The group with low dosage of totalsaponins and compound B-11 (1.25 g/kg) indicated outstanding diuretic activity. Moreover,compounds B-16 showed significance inhibitory on COX-2. All the compounds tested didnot indicate anti-tumor activities.更多还原