基于烯基离子液体的磁性分子印迹固相萃取及其在芳香胺检测中的应用研究

Magnetic molecularly imprinted solid phase extraction as a sample pretreatment technique is very convenient for solid-liquid separation without preparing extraction columns. The control of the size, composition, morphology and structure of magnetic molecularly imprinted polymers are more difficult. In addition, the aim to achieve high selectivity, capacity for target molecules, and low leakage for the template molecule is another difficult point. The project systematically design and synthesis imidazole and pyridine alkenyl ionic liquids, which were used as monomers and cross-linking agents of magnetic molecularly imprinted polymers. The size, composition, morphology and structure are regulated through changing cation and anion of species for ionic liquids to prepare novel sample pretreatment technique. Under the optimization condition of separation and recognition, new method including high selective separation and recognition is coupled with chromatography instruments for the detection of aromatic amines in the environment. The factors of preparation, selective separation and recognition for these molecularly imprinted materials are extensively researched. Structure-activity relationship between structure and adsorption capacity, and molecular recognition mechanism are also systematically studied. The results of this research expounding this kind of material in complex sample pretreatment and detection application are of great significance for basic research of analytical chemistry. In order to solve the bottleneck problem, the research will provide important theoretical basis in the development of molecularly imprinted solid-phase extraction technique.

磁性分子印迹固相萃取是一种非常便于实施固-液分离且不需制备萃取小柱的样品前处理技术，调控磁性分子印迹聚合物的尺寸、组成、形貌和结构以及实现对目标分子高选择性、高容量吸附、低模板分子渗漏等目标是相关研究的难点。本项目系统设计、合成咪唑类和吡啶类烯基离子液体，其作为磁性分子印迹聚合物制备的功能单体和交联剂，探索通过调节离子液体阳离子和阴离子的种类、结构等手段来调控分子印迹聚合物材料的尺寸、组成、形貌和结构，以此构建样品前处理新技术，在最优化的分离和识别条件下，结合色谱技术，建立环境中芳香胺的高选择性分离、识别和检测新方法。深入研究影响印迹材料的制备及其选择性分离、识别因素，材料结构与吸附容量之间的构效关系以及分子识别的相关机理。通过本项目的研究，对阐明该类材料在复杂分析样品前处理与检测新技术应用的有关分析化学的科学基础问题有重要意义，为解决分子印迹固相萃取技术发展的瓶颈问题提供重要理论依据。

针对分子印迹材料存在印迹位点较少且分布不够均匀（吸附容量低）、模板分子渗漏、传质速率慢等瓶颈问题，本项目主要设计合成的烯基离子液体作为印迹功能单体和交联剂，通过调控离子液体的种类、结构等手段，实现对分子印迹聚合物的尺寸、组成、形貌和结构的可控制备；并在项目执行过程中拓展了环境分析、生化分析领域分析对象与分析方法的研究。（1）采用磁性、表面印迹技术等制备了系列分子印迹聚离子液体材料，并对环境样品中4-硝基苯胺、二苯胺等芳香胺实现了样品前处理与光/电传感一体化分离与快速检测。（2）以石墨烯、多壁碳纳米管等为载体，烯基离子液体、烯基二茂铁酸等为分子印迹功能单体，烯基离子液体等为交联剂，采用表面印迹技术制备了石墨烯/导电分子印迹复合材料、石墨烯聚离子液体分子印迹电化学传感材料、多壁碳纳米管/分子印迹聚多巴胺、香豆素荧光分子印迹聚离子液体、二氧化硅/铂纳米粒子分子印迹复合材料等，建立了对6-苄氨基嘌呤、芦丁、日落黄、4-硝基苯酚、2,4,6-三氯苯酚、5-羟基色胺等分析对象的高灵敏、高选择性检测新方法。（3）以介孔/磁性介孔材料为表面分子印迹的载体，采用半共价、伪模板印迹技术制备了系列介孔/磁性介孔表面分子印迹固相萃取材料，采用高效液相色谱法测定环境中痕量的双酚A。（4）以氧化硅/磁性氧化硅为表面分子印迹的载体，合成了两种表面蛋白分子印迹材料，并用于人体尿液中溶菌酶和牛血样品中牛血红蛋白的选择性检测与分离。（5）构建了基于离子液体的光/电传感器，用于高灵敏检测邻苯三酚、4-壬基酚、心肌肌钙蛋白I、肌红蛋白、微囊藻毒素-LR等新方法。（6）借鉴生物体系中的别构效应和基因突变，通过别构效应正调控和基因突变负调控控制靶标识别和信号分子放大组装双亲和活性，提出了一类新颖的单步电化学传感器、基于茎环爪探针的双链DNA检测方法和以循环肿瘤DNA为引发剂来调节DNA纳米线组装的新策略。