基于介孔材料的分子印迹吸附剂制备及在动物源食品激素类药物分析中的应用

This project focuses on the preparation of new separation materials and the selectivity of the target analytes extraction from complex food samples. Based on our related work in recent years, double imprinting methodology (combination of the preparation of ordered mesoporous materials technology and molecular impriting technology) is employed to synthesize the ordered mesoporous molecular impriting polymers (MMIP), which have the characters of stable skeleton structure, large specific surface area, regular pores, high adsorption capacity and selectivity. To improve the recognition performance and adsorption capacity of the MMIP and further refine the theory of molecular imprinting technique and ordered mesoporous materials preparation technology, various factors that affect the imprinting efficiency are investigated, including imprinted template molecules, the structure-directing agent templates and functional monomers etc. And the recognition performance of the MMIP in the polar conditions is further improved by pseudo template technology and silicone surface modification technology. Selective extraction including solid phase extraction and matrix solid phase dispersive are developed using MMIP as adsorbent. The characters of high selectivity and fast adsorption made MMIP can overcome the endogenous interferences of complex sample matrices and shorten the extraction and separation time of the target analytes. Analysis of hormone in animal origin foodstuffs is one of hot topics of the current food safety. Simple, fast and high selectivity methods for extraction and detection of hormone and its metabolic products in meat and milk samples are proposed.

本课题以新型分离材料制备和提高萃取复杂食品中待测物的选择性为中心，在近几年相关工作的基础上，拟采用双模板印迹技术(有序介孔材料制备技术和分子印迹技术)合成系列具有稳定骨架结构、大比表面积、规则孔径、高吸附容量和选择性的介孔分子印迹吸附剂。探讨介孔印迹材料制备过程中印迹模板、导向剂模板、功能单体等对材料印迹性能的影响规律，以进一步提高材料的识别性能和吸附量，并进一步完善分子印迹技术和介孔材料制备技术的相关理论。同时通过虚拟模板技术和硅胶表面修饰技术等手段，进一步提高极性条件下材料的识别性能。以合成的印迹材料做吸附剂，发展高选择性的固相萃取技术和基质固相分散技术，利用介孔印迹材料的高选择快吸附特性克服样品组成复杂所造成的内源性干扰问题，缩短样品前处理时间；针对目前动物源食品安全热点问题，建立肉类、奶制品等动物源食品中激素类违禁药物残留及其代谢物的简单、快速、高选择性的分离富集方法和检测技术。

在复杂样品痕量药物残留分析中，样品前处理过程不仅耗时而且直接影响分析结果的准确度和精密度。如何从复杂样品中实现低浓度组分的有效提取和分离是目前分离科学领域的难点和热点之一。本课题以新型分离材料制备和提高复杂样品中待测物的萃取选择性为中心，分别采用溶胶-凝胶法、悬浮聚合法、沉淀聚合法等方法合成了13 种对雌二醇、三氯杀螨醇等目标物有较高特异选择性的分子印迹材料（介孔分子印迹材料、磁性分子印迹微球和离子液体-分子印迹微球材料等）。探讨了印迹材料制备过程中模板分子、功能单体、修饰试剂、反应物比例等对印迹材料性能影响的规律，并对印迹材料的形貌特征和识别机制进行了系统考察，初步得到不同结构的虚拟模板对印迹材料识别能力的影响规律。同时，采用虚拟模板技术，解决了实际样品分析中因模板泄露带来的难以准确定量问题；采用硅烷化试剂、离子液体做修饰剂或功能单体，进一步提高了极性条件下分子印迹材料的识别性能。在此基础上，以合成的分子印迹材料作选择性吸附剂/分散剂，建立了对复杂样品（牛奶、茶叶、蔬菜、尿样等）中雌二醇、己烯雌酚、三氯杀螨醇、氟喹诺酮、克伦特罗等目标物具有高选择性的分子印迹-分散固相萃取技术、分子印迹-固相萃取技术和分子印迹-微型化固相萃取技术等新型复杂样品前处理技术。这些萃取技术具有高选择、快吸附的特性，有效克服了样品组成复杂所造成的内源性干扰问题，缩短样品前处理时间，对食品、生物样品及环境样品中特定痕量组分的分离和纯化具有重要的意义，可广泛应用于食品分析、分离工程、生物工程、临床医学、环境监测等众多领域。