光叶马鞍树化学成分的研究
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摘要
光叶马鞍树[Maackia tenuifolia(Hemsl．)Hand-Mazz]是豆科马鞍树属植物。马鞍树属(Maackia Rupr．et Maxim)植物在世界上约有10种，分布在亚洲东北部，我国有8种。其中三种植物被进行过化学成分及药理活性研究，即光叶马鞍树、朝鲜槐和岛槐，其中研究最多的是朝鲜槐，从中分出的酚性化合物大多具有生物活性。光叶马鞍树分布于我国的江苏、浙江、江西、河南、湖北等地。浙江民间用其根治疗跌打损伤、淤血肿痛及用来消炎杀菌。除了史崇生、沈建华等曾经从中分离得到14个化合物外，其他尚未见报道。这些化合物中有三个是异戊烯取代的黄酮体，异戊烯基取代的黄酮体化合物在植物界有着较广泛的分布，在结构上有着丰富的多样性而且具有较广泛的生理活性。鉴于此，为了进一步阐明光叶马鞍树民间药效的有效成分，寻找高活性的天然产物，我们对光叶马鞍树进行了较为深入的化学成分研究。我们从光叶马鞍树树根乙醇浸膏的二氯甲烷捏溶部位分离得到32个单体化合物以及4对非对映异构体，用光谱方法鉴定了它们的结构。单体化合物中，有18个为新化合物，其中N1～8，N13～16为异戊烯取代的异黄烷，N19，N22为新型骨架的双黄酮体化合物，N20属于4位芳基取代的异黄烷，4位芳基取代的异黄烷化合物，除4-5′位相连的双异黄烷化合物外，尚未见过其他报道。4对非对映异构的异黄烷化合物N9～12，它们的结构也属首次报道。简单的酚性化合物K10，K11，N18与异戊烯取代的异黄烷之间，化合物N17，N8与N19，N22之间，它们在结构上都有着密切的相关性，这表明它们在生源上可能存在着紧密联系。
我们对部分化合物进行了抗真菌、抗HIV和抗肿瘤药理活性筛选，化合物N3，N5，N6，N13，K11对三种深部感染致病真菌：白念菌(Candida albicans)、新隐球酵母(Cryptococcus neoformas)、烟曲霉(Aspergillus fumigatus)在体外显示了较好的抗真菌活性。化合物N4和N13显示了一定的抗HIV活性。在抗肿瘤活性筛选中，N22对HL-60细胞有一定的杀伤作用，N7，N19对U937有效，N22对U937有弱效。
Maackia tenuifolia (Hemsl.) Hand-Mazz distributed in Jiangsu, Zhejiang, Jiangxi, Henan and Hubai provinces of China, has been used for injuries and as fungicide in Zhejiang folk medicine. Some bioactive phenolic compounds were isolated from the plant of another species, M. amurensis, while only a few studies reported on this plant, which prompted us to investigate the chemical constituents of the title plant in order to elucidate the substance base responsible for folk medicine usage. Also, the occurrence of prenylated flavonoids in this plant enhanced our interest. Prenylated flavonoids were widely found in nature, which have a wide structure variety and extensive biological activities. Our investigation of the CHCl_2 soluble portion of ethanolic extract of the roots of the title plant afforded 18 new compounds, 14 known compounds and 4 pair of new isoflavan diastereoisomers (N9～12), their structures were determined on the basis of spectroscopic analysis and comparison with known compounds. Compounds N1～8, N13～16 are prenylated isoflavans, N19, N22 are two biflavonoids of new type skeleton. N20 is a 4-Aryl substituted isoflavan, which was not encountered in isoflavonoids except for [4-5']biisoflavans. Simple phenolic compounds K10, K11, N18 are structurally part of some prenylated isoflavans, compound N17, N8 hold part structure of N19, N22, which suggests that they should be closely relevant in biosynthesis.
Part of these compounds were subjected to antifungal, anti-HIV and antitumor tests. Compounds N3, N5, N6, N13, K11 showed promising antifungal activity in vitro against Candida albicans, Cryptococcus neoformas and Aspergillus fumigatus. N4 and N13 exhibited anti-HIV activity. In antitumor tests, N22 is effective against HL-60, N7 and N19 are effective against U937, N22 showed week activity on U937.
我们对部分化合物进行了抗真菌、抗HIV和抗肿瘤药理活性筛选，化合物N3，N5，N6，N13，K11对三种深部感染致病真菌：白念菌(Candida albicans)、新隐球酵母(Cryptococcus neoformas)、烟曲霉(Aspergillus fumigatus)在体外显示了较好的抗真菌活性。化合物N4和N13显示了一定的抗HIV活性。在抗肿瘤活性筛选中，N22对HL-60细胞有一定的杀伤作用，N7，N19对U937有效，N22对U937有弱效。
Maackia tenuifolia (Hemsl.) Hand-Mazz distributed in Jiangsu, Zhejiang, Jiangxi, Henan and Hubai provinces of China, has been used for injuries and as fungicide in Zhejiang folk medicine. Some bioactive phenolic compounds were isolated from the plant of another species, M. amurensis, while only a few studies reported on this plant, which prompted us to investigate the chemical constituents of the title plant in order to elucidate the substance base responsible for folk medicine usage. Also, the occurrence of prenylated flavonoids in this plant enhanced our interest. Prenylated flavonoids were widely found in nature, which have a wide structure variety and extensive biological activities. Our investigation of the CHCl_2 soluble portion of ethanolic extract of the roots of the title plant afforded 18 new compounds, 14 known compounds and 4 pair of new isoflavan diastereoisomers (N9～12), their structures were determined on the basis of spectroscopic analysis and comparison with known compounds. Compounds N1～8, N13～16 are prenylated isoflavans, N19, N22 are two biflavonoids of new type skeleton. N20 is a 4-Aryl substituted isoflavan, which was not encountered in isoflavonoids except for [4-5']biisoflavans. Simple phenolic compounds K10, K11, N18 are structurally part of some prenylated isoflavans, compound N17, N8 hold part structure of N19, N22, which suggests that they should be closely relevant in biosynthesis.
Part of these compounds were subjected to antifungal, anti-HIV and antitumor tests. Compounds N3, N5, N6, N13, K11 showed promising antifungal activity in vitro against Candida albicans, Cryptococcus neoformas and Aspergillus fumigatus. N4 and N13 exhibited anti-HIV activity. In antitumor tests, N22 is effective against HL-60, N7 and N19 are effective against U937, N22 showed week activity on U937.
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