亲水印迹共聚树脂的制备及植物中外源性生长调节剂检测新方法研究

This project focuses on the synthesis of aqueous molecular recognition materials and the improvement of selectivity in sample preparation. With hydrophilic copolymerization-molecular imprinting technique (the combination of resin preparation technique and molecular imprinting technique), a series of hydrophilic imprinted copolymerized resin microspheres which have high selectivity, large specific surface area, and controllable particle size will be synthesized by modifying hydrophilic monomers, and adding porogen and modifier. The effects of the kind and ratio of copolymerized monomers, catalyst, curing agent, porogen, and solvent on the imprinted performance, surface morphology, particle size, and mechanical strength of hydrophilic imprinted resins will be discussed to improve the molecular recognition performance and increase the adsorption capacity of materials in polar conditions. Besides, relevant theories of molecular imprinting technique will be supplemented. Biosample preparation techniques of high selectivity, and miniaturized/micro devices and methods of extraction will be developed with the synthesized hydrophilic imprinted copolymerized resin as adsorbent. Analytes in complicated samples will be separated and concentrated selectively under polar conditions because of the excellent aqueous molecular recognition performance of hydrophilic imprinted copolymerized resin, while template leakage can be avoided by mimic template and thermal treatment techniques. Several simple, rapid, and highly selective sample pretreatment methods of plants for detecting trace exogenous growth regulators will be developed.

本课题以水相分子识别材料制备和提高生物样品前处理选择性为中心，采用亲水单体共聚分子印迹技术（结合树脂制备技术和分子印迹技术），通过修饰亲水性单体、添加致孔剂和修饰剂，合成系列具有特异选择性、比表面积大、粒度可控的亲水印迹共聚树脂微球。探讨制备过程中共聚单体、催化剂、固化剂、致孔剂和反应溶剂的种类、比例等条件对亲水印迹共聚树脂的印迹性能、表面形态、微球粒径和机械强度的影响规律，提高极性条件下树脂微球的分子识别性能和吸附量，进一步完善分子印迹技术的相关理论。同时以合成的亲水印迹共聚树脂材料做吸附剂，发展高选择性生物样品前处理技术和小型化/微型化萃取装置和方法；利用亲水印迹共聚树脂的良好水相识别能力，实现极性条件下复杂样品中特定目标物质的高选择性提取和富集，通过虚拟模板技术和热处理技术解决实际样品萃取分离过程中的模板泄漏问题，建立几种植物中痕量外源性生长调节剂的简单快速高选择性的样品预处理方法。

本课题针对水相分子识别材料制备和提高生物样品前处理选择性两大热点问题，结合树脂制备技术和分子印迹技术开发了系列亲水印迹共聚树脂合成方法，通过修饰亲水性单体、添加致孔剂和修饰剂，设计合成了分子印迹脲醛树脂、分子印迹酚醛树脂、分子印迹酚脲醛树脂、分子印迹树脂-石墨烯、分子印迹树脂-介孔硅等多种具有特异选择性、比表面积大、粒度可控的亲水印迹共聚树脂材料。探讨了制备过程中共聚单体、致孔剂和溶剂等条件对亲水印迹共聚树脂形貌和性能的影响规律，明确了亲水印迹树脂材料的选择性吸附机理，进一步完善了分子印迹技术的相关理论，解决了传统分子印迹材料水相识别能力差和模板泄漏的问题。同时以合成的印迹共聚树脂材料做吸附剂，发展了微型管尖固相萃取、滤头固相萃取、一体化分散固相萃取等多种小型化/微型化萃取装置和高选择性样品前处理方法，解决了传统方法操作繁琐耗时、有机试剂消耗大、样品基质干扰严重等问题，实现了极性条件下复杂体系中目标组分的高选择性萃取和富集，通过虚拟模板技术和热处理技术解决了实际样品萃取分离过程中的模板泄漏问题，建立了多种植物中外源性植物生长调节剂（赤霉素、6-苄氨基嘌呤、对氯苯氧乙酸、噻苯隆、吲哚丁酸、α-萘乙酸、氯吡苯脲等）的简单快速高选择性的样品预处理技术和色谱检测方法，为植物体系中痕量生长调节剂的分离分析提供了理论和方法支持，具有重要科学意义。在该项目资助下课题组已于Analytical Chemistry、Journal of Agricultural and Food Chemistry、Analytica Chimica Acta、Food Chemistry、Journal of Chromatography A、Talanta等国际学术期刊发表SCI论文21篇（其中JCR一区3篇，二区18篇），申报国家发明专利6项（已授权4项），培养硕士研究生13名，超额完成任务书规定的任务要求。本项目相关研究成果获得2016年度河北省自然科学奖三等奖和2019年度河北省科技进步奖二等奖。