功能化微孔有机聚合物介质的研制及在痕量组分富集中的应用

Microporous organic polymers (MOPs) is a kind of new microporous materials composed of pure organic molecules and connected with covalent bonds. This study covers the latest research of material science frontiers. Therefore, MOPs based on the organic molecule block are prepared and investigated. The high specific surface area, the controllable network structure and the high stability of the covalent bonds for connection of MOPs make them good candidates as highly efficient enrichment material. Firstly, based on kinds of synthetic strategy, a series of MOPs with novel structure, high specific surface area and high stability are prepared and screened. Then the as-synthesized MOPs were immobilized, such as packing into the adsorption/desorption tube, coating on solid-phase microextraction fiber and preparing the magnetic hybrid material. The MOPs can be connected with the substrate and the magnetic nanoparticles through covalent bonds, making the resultant enrichment media highly stable. Finally the novel enrichment media are coupled with chromatography and mass spectroscopy to develop the analytical method for analysis of trace components in complicated samples, such as volatile organic components, biological metabolites and disease marker in food and biological samples. The investigation provides new idea for the design and synthesis of novel enrichment media to improve the sensitivity, speed and accuracy of trace components in complicated samples.

微孔有机聚合物（MOPs）是一种由纯粹有机分子组成并相互以共价键连接的新型微孔材料，本项目拟结合材料科学的最新研究前沿，研制基于有机分子砌块的微孔有机聚合物分离富集介质，利用其超高比表面积、结构功能的分子水平可调控性、共价键结构的高稳定性等优势，高效富集痕量组分。首先，运用各种MOPs合成策略，合成并筛选一系列结构新颖、比表面积大、稳定性高的MOPs。在此基础上发展多种MOPs固载策略，通过填装热脱附管、层层共价键组装法制备固相微萃取涂层和研制磁性功能化复合材料，MOPs涂层与底材或磁性粒子间以化学键连接，获得稳定、牢固的分离富集介质。利用制备的新型介质结合色谱、质谱分离分析技术，发展复杂体系中痕量组分分离与富集的新方法，并用于食品、生物样品中挥发性小分子、生物代谢物、疾病标记物等分析。期望为设计和合成新型样品前处理介质，开展复杂体系痕量组分的高灵敏、快速、准确分析提供新思路。

本项目开展了微孔有机聚合物介质的研制及其在痕量组分分离富集中的应用研究。（1）设计和研制了一系列基于有机分子砌块的微孔有机聚合物分离富集介质，包括具有席夫碱网络结构和卟啉骨架的共轭微孔有机聚合物固相微萃取涂层、嵌入型和核-壳型磁性共轭微孔聚合物微球、贵金属和碳纳米管掺杂共价有机骨架复合材料、微孔有机聚合物膜以及大环分子多孔聚合物微球等。介质具有结构可控，比表面积大，稳定性高，吸附性能优异等特点。（2）利用制备的新型介质结合色谱/质谱分离分析技术和光谱技术，发展了复杂体系中痕量组分分离与富集的样品前处理新方法，可实现快速、高效富集，提高了分析方法的灵敏度。（3）建立的分析方法用于食品中挥发性风味成分、农药残留、生物代谢物、疾病标记物等实际复杂体系的分离分析，如烟叶中挥发性有机酸、蔬果中杀菌剂、生长剂农药残留、血清中胰岛素、尿液中羟基多环芳烃等，为复杂体系痕量组分的高灵敏、快速、准确分析提供了新的策略。以上研究工作分别在Analytical Chemistry、 Journal of Chromatography A, Nanoscale等刊物发表，标注基金资助的论文共21篇，其中SCI收录期刊发表论文12篇，申请发明专利6件，其中授权发明专利2件， 研究成果“复杂样品高效前处理新方法研究”获教育部高校科研优秀成果奖自然科学二等奖。