狭叶金粟兰中抑制斜纹夜蛾生殖力倍半萜内酯二聚体成分的发现及其构效关系

Lindenane-type disesquiterpenoids, mainly isolated from chloranthaceae, are a kind of star natural products, which known as novel framework, impressing bioactivities and rich content in chloranthacea. Previous studies on the extract of C. angustifolius, an endemic flora of China, indicated remarkable antifeeding activities to Spodoptera litura Fabricius. We are wondering if the lindenane-type disesquiterpenoids in the plant are responsible for the activities. In our research, the Shizukaol B and Shizukaol F showed significant effects on fecundity and ovary development of S. litura Fabricius. Based on the work above, this project intends to construct a lindenane-type disesquiterpenoids library based upon systematic separation from C. angustifolius and chemical modification. Then screen their inhibitory activities against the fecundity of S. litura Fabricius, and analysis their structure-activity relationship. Finally, studying on the relationship and inhibitory mechanisms between the activity compounds and ovary development of S. litura Fabricius. This study is expected to obtain lead compounds from these lindenane-type disesquiterpenoids as botanical insecticides to be used in controlling of S. litura Fabricius.

金粟兰科特征性成分乌药烷型（lindenrane）倍半萜内酯聚合物以其结构新颖、活性独特多样及在金粟兰科植物中含量丰富分布广泛，成为近年来研究的热点分子。我国特有植物狭叶金粟兰（Chloranthus angustifolius）提取物对家蝇成虫、卷库蚊4龄幼虫具有毒杀活性，对斜纹夜蛾具有拒食活性，启发我们对该类型成分的杀虫活性进行探索。前期研究首次发现该类型结构的二聚体Shizukaol B 和Shizukaol F 具有显著的斜纹夜蛾生殖力抑制活性，导致试虫卵巢萎缩现象。本项目在此基础上，拟针对狭叶金粟兰中乌药烷型倍半萜内酯聚合物进行全面系统地分离富集并结合化学结构修饰，从而构建该类型成分的化合物库；对所得成分进行斜纹夜蛾生殖力抑制活性评价，并对活性成分与卵巢萎缩的响应机制及其构效关系进行初步研究。为开发乌药烷型倍半萜内酯聚合物作为害虫化学不育剂提供理论基础。

项目主要针对我国特有植物狭叶金粟兰（Chloranthus angustifolius）中所含特征性成分乌药烷型倍半萜内酯类化合物，特别是其二聚体类型化合物，开展分离富集、结构修饰，及其对斜纹夜蛾生殖力抑制活性与机理的研究。最终从植物材料中分离鉴定乌药烷型倍半萜内酯合物17个，并完成它们的HPLC分析检测条件优化，阐明其结构类型及含量关系。通过结构修饰获得衍生物15个，构建总共32个化合物用于活性筛选；构效关系结果表明乌药烷型倍半萜二聚体结构中的游离羟基数与斜纹夜蛾生殖力抑制活性相关，菊酯化基团引入不能达到增效。化合物作用机制初步结论： Shizukaol B被斜纹夜蛾取食后，该化合物能到达试虫卵巢组织，并对卵巢细胞( PL细胞)的增殖表现出抑制活性，是其可能的作用机制；Shizukaol F主要表现为对试虫的拒食及消化相关酶抑制活性，营养恶化影响试虫生殖。本研究已发表论文3篇，获国家发明专利1项。