中药中痕量手性拟除虫菊酯类农药的绿色分析体系的构建与应用

Pyrethroid pesticide is one of the most widely applied pesticide in the process of cultivation of Traditional Chinese Medicine. However, the pyrethroid residues in traditional Chinese medicines and the low sensitivity of the detection method limit the wide application of traditional Chinese medicine in the worldwide. Therefore, this project aims to take Areca-nut as the research object, and construct green analytical system for the analysis of trace amounts of chiral pyrethroid pesticides in Traditional Chinese medicine. In this research, the single drop microextraction conditions was optimized for the improvement of enrichment efficiency of pyrethroid pesticides in the Areca-nut samples. Meanwhile, the gas chromatographic conditions for the separation of pyrethroid pesticides enantiomers was investigated. Therefore, the green analytical system, which is based on ionic liquid-based single drop microextraction and chiral gas chromatography, is established for the analysis of trace amount of chiral pyrethroid residues in the traditional Chinese medicine. Based on the system, the enantioselective behavior of residual pyrethroid pesticides in the areca-nut will be carried out in order to guide the rational use of pesticides, and provide technical platform for the strict control of chiral pyrethroid residues in traditional Chinese medicine.

拟除虫菊酯类农药是中药种植过程中应用最为广泛的农药之一。中药中该类农药的残留以及其高灵敏度检测方法的落后，限制了我国的中药走向世界。本项目拟以海南省特色南药-槟榔为研究对象，尝试构建中药中痕量手性拟除虫菊酯类农药的绿色微萃取与拆分分析体系。研究中选择适宜疏水性离子液体为萃取剂，优化单滴微萃取条件，提高槟榔样品中拟除虫菊酯类农药的富集效率。同时，探讨各项气相色谱条件对拟除虫菊酯类农药对映体分离的影响，建立拟除虫菊酯类农药进行手性拆分的气相色谱分析方法，从而构建基于离子液体的单滴微萃取-气相色谱法的中药中痕量手性拟除虫菊酯类农药的绿色微萃取与拆分分析体系。基于该体系对槟榔中拟除虫菊酯类农药对映体的选择性残留行为规律进行研究，考察槟榔果实中拟除虫菊酯类农药对映体的残留量差异，以及比较对映体的降解速率等规律，从而为指导合理使用拟除虫菊酯类农药、严格控制其在中药的残留问题等提供技术平台。

拟除虫菊酯类农药是中药种植过程中应用最为广泛的农药之一。本项目构建了中药中痕量拟除虫菊酯类农药的绿色微萃取与拆分分析体系。本研究采用离子液体超声辅助分散液-液微萃取技术，结合高效液相色谱法，分析了四种中药口服液中的拟除虫菊酯类化合物；基于阴离子交换剂原位生成新型离子液体，建立了超声辅助- Fe3O4 磁性纳米粒子磁化-原位离子液体分散液液微萃取用于萃取天然椰子水中拟除虫菊酯类农药的新型样品前处理技术，简化和加快了样品前处理过程。开发QuEChERS方法，结合高效液相色谱测定中药口服液制剂中拟除虫菊酯类农药，并对提取条件进行了研究和优化。通过Chiralcel OJ色谱柱制备并收集而得的联苯菊酯手性单体。实验结果表明随着联苯菊酯手性单体1S-cis-BF和1R-cis-BF的浓度不断升高，L02细胞的存活率则随之下降；1S-cis-BF的细胞毒性大于1R-cis-BF。本项目的实施将为指导合理使用拟除虫菊酯类农药、严格控制其在中药的残留问题等提供技术支持。