分子印迹比率荧光探针的可控制备及对环境雌激素可视化检测性能研究

Environmental estrogens are widespread concern pollutants, which can be detected by molecularly imprinted fluorescence probe with highly selective. However, traditional molecularly imprinted fluorescence probe involved in low sensitivity resulted from the high crosslinked nature of MIPs and single response mode. In order to solve the problem, significant improvements were made based on the high affinity of molecular recognition, signal conversion and fluorescence signal amplification. With the help of boronate affinity material, target-aptamer and other high affinity materials, regular mesoporous structured (core-shell mesoporous, hollow mesoporous, janus mesoporous) MIPs were prepared by surface imprinting or solid phase imprinting to achieve efficient molecular recognition; Based on fluorescence nanoparticles, such as quantum dots, carbon dots, metal nanoclusters, several response modes based on electron transfer, internal filter effect or resonance energy transfer were designed to achieve effective signal conversion; Combined with conjugate polymer, dendritic structure and sandwich structure, the sensitive of molecularly imprinted fluorescence sensors would be improved by multiple signal amplification technology. Visualization of environmental estrogen can be achieved by ratiometic fluorescence technology. Meanwhile, the applicability of novel optical probes in real environmental sample analysis will also be explored. The successful implementation of this project is expected to achieve controllable preparation of molecularly imprinted fluorescent probe with high selectivity and high sensitivity, and supply an efficient, simple and rapid detection methodologies for trace environmental pollutants analysis.

环境雌激素是人们普遍关注的污染物，分子印迹荧光传感可高选择性检测该类物质。本项目针对该类传感灵敏度偏低的问题，从分子识别、信号转换、荧光信号放大多角度入手，探索多重信号放大在高灵敏分子印迹荧光传感构建中的作用。采用表面印迹、固相印迹等技术借助硼酸基、目标物-适配体等高亲和作用力合成有利于质量传递的规则孔结构，实现高效选择性分子识别；以量子点、碳点、贵金属纳米簇等多种荧光物质为基础，构建基于电子转移、内滤效应和共振能量转移等多种响应模式，考查荧光物质的合理引入方式，实现分子识别的有效荧光信号转化；结合共轭聚合物、树枝状、三明治等结构对荧光信号进行放大。进一步构建分子印迹比率荧光探针，探索其在实际环境样品分析中的适用性，实现环境雌激素可视化检测。该项目的实施可望实现高选择性和高灵敏度分子印迹荧光探针的可控制备，为环境化学领域痕量污染物分析提供一种高效、简单、快速的检测新技术。

分子印迹聚合物对目标检测物具有特异识别作用，基于分子印迹聚合物发展的分子印迹荧光传感，用于复杂基质中典型污染物的高灵敏、高选择性检测分析，对于构建健康生态环境、保障食品安全具有重要意义。本项目以典型有机污染物、重金属离子（如Ag+、Pb2+、Hg2+）、生物蛋白分子等为研究对象，成功构建多种分子印迹荧光传感，通过形貌控制、传感模式构建、信号放大技术等，显著提高分子印迹基化学传感的灵敏度。在ACS Sensors，Sensors and Actuators B: Chemical，ACS Applied Materials & interfaces，高分子材料科学与工程等期刊发表SCI收录期刊论文16篇。获山东省高校优秀成果奖1项，中国分析测试协会科学技术奖1项。.(1) 通过印迹后修饰、纳米颗粒信号放大构建单发射分子印迹荧光传感，通过降低 ，提高荧光信号输出值，提高检测灵敏度。.(2) 探索基于内滤效应构建比率荧光传感的可行性，将比色分析转化为高灵敏的比率荧光分析。.(3) 基于参比型分子印迹比率荧光传感构建双参比离子印迹荧光传感，实现两种离子的同时检测。进一步通过构建双通道离子印迹荧光传感，在红色和蓝色两个激发通道内实现两种离子的同时检测，进一步实现离子形态分析。. 本项目的实施丰富了印迹荧光传感构建方法，拓展了应用领域，为实现基于荧光信号输出的污染物高灵敏、高选择性、多元检测提供了科学依据。