磁光热多重刺激响应分子印迹聚合物对水体酚类雌激素的识别研究

Phenolic environmental estrogens were widespread concern water pollutants. Molecularly imprinted polymers (MIPs) can be used as extracting material to selective enrich, separate of such substances. However, traditional MIPs involved in low binding capacity, incompatibility with aqueous media, and template molecules eluting difficulties, et al. problems. In order to solve those problems, magnetic, photo and thermo multi stimuli responsive MIPs were prepared by combining living polymerization techniques, click chemistry,stimuli-responsive polymer preparation technology and molecular imprinting technique.In order to achieve this goal, multi structures, such as core-shell structure, interpenetrating polymer network structure, grafted network structure were designed to explore the reasonable method to combine multiple stimulation into one system. The detection method based on magnetic, photo and thermo multi stimuli responsive MIPs extraction-capillary electrophoresis detection enjoy some advantages, such as higher sensitivety resulted from MIPs and CE dual signal amplification, higher binding capacity resulted from surface imprinting, simple and rapid separation resulted from magnetic separation, environment friendly resulted from photo controlled template release, and water compatibility resulted from the hydrophilic thermo responsive polymer brush.Nanomolar level of PEEs in aqueous media were expected to be detected using the method proposed in this work.

酚类雌激素(PEEs)是人们普遍关注的水体污染物，以分子印迹聚合物（MIPs）为萃取材料可高选择性分离、富集该类物质。本项目针对传统MIPs水体相容性差、结合容量低、模板分子洗脱困难等问题，将活性聚合、点击化学、刺激响应聚合物制备技术与分子印迹技术有机结合，探索磁、光、热多重刺激响应的合理结合方式，设计核壳结构、互穿聚合物网络、接枝网络等多种结构，制备磁、光、热多重响应MIPs，发展基于多重响应MIPs的样品前处理方法，结合毛细管电泳（CE）检测技术，实现水体中PEEs的分离和检测。与传统分析方法相比，本项目中所发展的基于磁、光、热三重响应MIPs萃取－CE检测方法具有灵敏度高（MIPs离线富集和CE在线富集双重信号放大）,水体识别能力强（引入温敏性亲水聚合物），分离简单快速（磁分离手段），环境友好（光控释手段，目标分子洗脱简单可控）等优势，有望实现水体环境中纳摩尔级PEEs的分离检测。

本项目主要针对目前分子印迹技术检测环境雌激素污染物存在的水体相容性差，模板分子洗脱困难和结合容量偏低的问题，提出通过提高分子印迹聚合物基体的传质效率增加结合容量；通过印迹聚合物表面的亲水性接枝改性，提高其在水体环境中的应用适应性，最终实现水体环境中典型环境污染物的分离、富集和检测。针对环境中三嗪类除草剂、雌酮类雌激素等检测目标物，设计合成了三种新型固相萃取填料：内部为亲水性单体聚合制备外部用亲水性聚合物刷接枝的双亲水性印迹聚合物，可增加与水体环境的相容性，适用于水体环境中三嗪类除草剂的浓缩富集；内部为磁性微球外部为介孔结构印迹层的磁性印迹颗粒，可实现对雌酮类的高效富集；内部为中空印迹聚合物层，表面为原位生长的纳米磁性颗粒，实现对三嗪类除草剂的高结合容量、高效分离富集和检测。.针对目前分子印迹荧光传感构建过程中出现的灵敏度偏低的问题，提出通过提高质量传递效率和增加目标物与荧光纳米颗粒之间的作用效率，提高分子印迹荧光传感的检测灵敏度。具体研究内容为针对环境中TNT等环境爆炸物，设计三种高灵敏分子印迹荧光传感：基于TNT对半导体量子点的猝灭作用，构建核壳结构比率荧光探针，提高分子印迹荧光传感的灵敏度，实现TNT 的可视化检测；基于TNT对氨基化荧光碳点的猝灭作用，以氨基化荧光碳点为功能单体制备介孔结构荧光探针，通过增加目标分子TNT与碳点的作用几率，提高检测灵敏度；基于三聚氰胺对半导体量子点的荧光猝灭作用，通过一步合成法制备介孔结构比率荧光探针，实现对奶粉等样品中三聚氰胺的可视化检测。这些方法的提出将对提高分子印迹荧光传感灵敏度，开拓其应用领域具有重要的意义。