针对环境水中极性有机污染物富集分离的金属有机框架材料的靶向设计及微固相萃取体系的构建

This project is proposed based on the present situation which lacks of efficient separation enrichment technology for novel polar pollutants. Non-steroidal anti-inflammatory drugs (NSAIDs), a significant source for new and emerging PPCPs contaminants, are chosen as the research object. Since such pollutants are polar, low content in the samples and so difficult to separate and enrich, targeted novel porous metal organic frameworks (MOFs) materials are designed and synthesized. Simultaneously, micro solid phase extraction technique using novel MOFs material, basing on multiple effects of electrostatic interaction, hydrogen bonding and porous adsorption, is constructed. Molecular simulation is used to discover the relationship between the structure and performance of MOFs materials preliminarily. And the mechanism of extraction and enrichment is studied. These studies would provide technical supports for further application of MOFs materials in the field of enrichment and separation. The configuration of MOFs is screened and designed for the target polar pollutant using molecular simulation technique in MIL and ZIFs series MOFs. And its enrichment and separation selectivity is improved through regulation of the properties of function group by introduction of an ion exchange function to organic ligands using post-synthetic modification (PSM) technique. This project would provide sensitive and accurate technical support and theoretical basis for study of the concentration levels、distribution and fate of the new polar organic pollutants in water.

本申请拟针对目前极性新型污染物缺少高效分离富集技术的现状，以芳酸类非甾体抗炎剂（NSAIDs）作为研究对象，根据其在环境水样中含量低、极性大、难以富集等特点，靶向设计及合成新型多孔金属有机框架（MOFs）材料，构建基于静电作用、氢键作用和多孔吸附等多重作用的MOFs微固相萃取体系；并利用分子模拟初步探讨MOFs材料“结构-性能”关系，研究其萃取富集机理，为进一步拓展MOFs材料在富集分离领域的应用提供技术支持。本课题拟选择MIL和ZIFs系列MOFs，通过分子模拟技术筛选及靶向设计对极性目标有机物有选择性富集作用的MOFs构型，并通过后修饰（PSM）在有机配体上引入具有离子交换功能的基团，进一步调节功能基团属性并提高其富集分离选择性，从而实现极性NSAIDs的高效富集与分离相结合的快速分离检测技术，为研究水体中新型极性有机污染物的浓度水平，保障水质安全提供快速、灵敏的技术支持和理论依据。

PPCPs类药物通过循环系统进入水环境后，存在内分泌干扰效应、产生抗菌性、破坏自然生态系统等潜在危害。其中一些极性新型污染物如抗生素、非甾体抗炎剂（NSAIDs）具有一定的极性和水溶性，在环境中多数以微量或痕量状态存在，从水体中高效地富积和分离这类极性有机污染物仍然成为一个非常大的挑战。根据其在环境水样中含量低、极性大、难以富集等特点，项目设计并合成新型有核-壳结构的磁性多孔金属有机骨架（MOFs）材料Fe3O4@[Cu3(btc)2]、Fe3O4@ZIF 和Fe3O4@G材料，通过在MOFs材料表面修饰了具有高顺磁性的Fe3O4微球，实现了外加磁场作用下的简单快速的富集分离；初步探讨MOFs材料“结构-性能”关系，建立了表面形态、磁性、化学吸附等多种评价体系，研究不同环境因素作用下的萃取富集机理。构建了基于静电作用、氢键作用和多孔吸附等多重作用的MOFs微固相萃取体系，实现了水体中极性TCs药物和NSAIDs药物高效富集与分离相结合的快速分离检测技术，为进一步拓展MOFs材料在富集分离领域的应用提供技术支持。