基于限进介质-刺激响应分子印迹聚合物识别富集POPs的研究

The trace or ultra-trace concentrations of POPs found in the environment and the present method is still unable to meet the testing requirements of low concentration and complex matrix sample. In addition, the development and problem-solving of molecularly imprinted polymer (MIPs) with excellent molecular recognition performance and highly bionic intelligence, it is of significance and widely practical application for MIPs. In view of the above problems, the restricted access media – multi-stimuli responsive molecular imprinted interpenetrating polymer network system is prepared by the molecular imprinting technique incorporating with restricted access media 、interpenetrating polymer network、grafted polymer brushes、magnetic separation、controllable polymerization、photo\thermal stimuli responsive technology，respectively. Study on the polymerization conditions, structure and magnetic properties of polymers, the anti interference ability of large molecules (such as humic acid), surface hydrophilic, stimuli responsive (identification and controlled release), to investigate the mechanism of identification and synthesis. The materials are applied to the fast, sensitive identification and enrichment of PBDEs and PAHs in soil samples, water samples and tea samples in tea garden. There is provided a new way for the separation and enrichment of trace and ultra-trace organic pollutants with the high-tech means of simple, rapid, accurate, high separation selectivity, sensitivity and also provided a scientific basis for the development of theory and practice of MIPs.

环境中的POPs往往是痕量及超痕量的，目前的方法仍无法满足低浓度和复杂基质的大量环境样品分离富集的需求。此外，开发具有优异分子识别性能的高度仿生智能化的分子印迹（MIPs），并解决其中难题，对于MIPs得到广泛实用化具有重要意义。针对上述问题，项目拟将分子印迹与限进介质、互穿聚合物网络、接枝聚合物刷、可控聚合、磁性分离、光\温刺激响应等技术耦合，分别利用PBDEs及PAHs为模板，制备新型基于限进介质-多重刺激响应分子印迹互穿聚合物网络。研究聚合条件，结构与磁性表征，考察其抗腐殖酸等大分子干扰能力、表面亲水性、刺激响应性（可控识别与释放）等性能及其合成机理、识别机理探讨。应用于茶园的土壤、水及茶叶样品中PBDEs及PAHs的快速、灵敏识别富集。为高技术手段对简便、快速、准确、高选择性、高灵敏的痕量及超痕量环境有机污染物的分离富集创出新路。为MIPs理论与应用实践的发展提供科学依据。

以POPs为研究对象，项目从“磁刺激响应分子印迹”方面着手，沿着“限进”“多重磁刺激响应”“分子印迹识别技术”及“刺激响应分子印迹聚合物应用”技术路线，系统展开研究，建立了基于限进介质刺激响应新型分子印迹聚合物的制备技术和POPs的特异识别技术。. 1、开展了双功能单体、多模板的抗生素磁刺激响应新型分子印迹材料的制备、表征及作用机制研究。并应用于水、牛奶、蜂蜜等环境及食品中硝基咪唑类、四环素类及喹诺酮类抗生素的痕量多残留分析，相比于现有的方法，本方法简便易行、可批量化进行前处理，成本低，结果准确可靠。. 2、开展了基于限进介质PBDEs或PAHs温磁刺激响应新型分子印迹材料的制备、表征、识别富集性能及分离检测模式建立。合成的温控的分子印迹聚合物有着快速的识别功能，较高的选择性，并应用于茶叶、茶汤、环境水样等中痕量、超痕量的POPs残留检测。本研究建立的检测方法，减少基质干扰，可一次性完成提取、净化。. 3、开展了基于限进介质PBDEs及PAHs光温磁刺激响应新型分子印迹材料的研制对多类痕量POPs识别分析研究。制备出表面含有限进聚合物分子刷的MIP纳米颗粒。合成的光温可控的分子印迹聚合物有着快速的识别功能，较高的选择性，并且能够通过光照射温度来控制PBDEs、PAHs及类似物的释放和吸附。.为痕量及超痕量环境、食品有机污染物的分离富集创出新路。为MIPs理论与应用实践的发展提供科学依据。