中药中拟除虫菊酯残留检测的石墨烯纳米传感的新方法研究

At present, the rapid determination of pyrethroids in Chinese medicines attracted more and more worldwide attention due to its difficulty and importance. So this project, taking some pyrethroids in Chinese medicines as the object of study, adopting some new graphene nano-materials which have been functionalized by physical, chemical, biological methods, is planned to develop highly sensitive and selective electrochemical sensors. In course of study, the key factors affecting electron transfer within system are located by exploring the properties of surface modification groups in molecular scale, which include its structure, size, conductivity, hydrophobicity, hydrophilicity, biocompatible, etc., as well as the interaction between surface modification groups and pyrethroids. And then, the rules and mechanism of electron transfer between graphene and pyrethroids would be obtained. In addition, to realize the rapid detection of pyrethroids, the technique rules of electrochemical sensors based on new graphene nano-materials would be futher discussed. In sum, this project may provide theoretical foundation and technical support for rapid detection of pyrethroids in Chinese medicines, and meanwhile it may have great significance in protecting human health and quality control technologies for Chinese medicines.

本项目着眼于快速检测拟除虫菊酯方法研究的热点与难点问题，以中药中拟除虫菊酯残留为研究对象，采用新型的石墨烯纳米材料，并利用物理、化学、生物等方法对其进行功能化修饰和处理，从分子尺度研究表面修饰基团的分子结构、分子大小、导电能力、亲疏水性、生物相容性、与不同拟除虫菊酯的作用方式、作用力大小等性质对电子传递的影响，找出影响体系内电子传递的关键因素，探索出石墨烯与拟除虫菊酯间的电子传递规律及机理，并探讨基于功能化石墨烯纳米材料电化学传感器在拟除虫菊酯快速检测的技术规律，发展具有高灵敏度和高选择性的电化学传感器，实现对拟除虫菊酯的快速检测。为中药中拟除虫菊酯的快速检测提供科学的理论依据与技术支撑，同时对中药质量控制安全和保护人类身体健康有着重要的意义。

本项目按照项目任务书，开展了中药中拟除虫菊酯残留检测的石墨烯纳米传感的新方法研究，同时也开展了石墨烯或其他功能纳米材料在药物分子检测中的应用研究。取得的主要研究成果包括：1. 简要评述了1996年以来检测拟除虫菊酯的电化学及生物传感器的研究进展，包括汞电极、修饰电极、分子印迹传感器、酶传感器、免疫传感器和DNA传感器等内容。2. 利用石墨烯和电活化玻碳电极构建了检测Ⅱ型拟除虫菊酯的存在的电化学传感技术方法，并应用于陈皮等中药材中拟除虫菊酯残留的检测中。3.构建了功能化石墨烯或多孔碳等其他碳基纳米材料用于传感分析，如Fe3O4微球与壳聚糖包覆石墨烯氧化物分析检测了邻苯二酚和对苯二酚，有序介孔碳(OMC)和Nafion复合修饰玻碳电极及石墨烯/十二烷基硫酸钠复合物修饰碳糊电极检测氯霉素，膨胀石墨纸电极同时检测抗坏血酸多巴胺和尿酸，一次性石墨烯修饰丝网印刷电极检测镉和铅重金属离子，电活化玻碳电极检测香兰素等药物分子。4. 还探索了金属-有机配体的MOFs材料MIL-101的电化学特性，5. 对阳极电沉积装置和光助阳极电沉积装置做了改进。总之，本项目挖掘了石墨烯或其他碳材料构建传感器应用于中药材或其他领域中药物分子或重金属离子检测的发展潜力，并探讨了传感检测机理，为后续研究打下了基础。本项目共发表论文8篇，其中SCI论文5篇，核心刊物3篇，申请专利4项，其中申请发明专利2项，已授权实用新型专利2项；参加国际会议1次和国内会议2次。