组合分子印迹技术用于海岸带水体磺胺类抗生素的识别和检测

Antibiotics-caused environmental pollution issue is increasingly serious owing to their mass production and abuse. How to selectively recognize and determine the low level multisource antibiotics in complicated waters especially seawater matrices? It has become a research hotspot in recent years. Molecularly imprinted polymers (MIPs) with high selectivity have become efficient recognition materials for seawwater sample preparation. In this project, we purpose to choose sulfonamides (SAs) antibiotics as model targeted-analytes and to prepare new SAs-MIPs materials with excellent (magnetic/temperature responsive) imprinting performances for solid-phase extraction (SPE) of SAs by virtue of the rationally combined molecular imprinting technology. Herein, we plan to devise optimal core-shell structure for SAs-MIPs by utilizing ingenious surface imprinting and nanoimprinting technologies, coupled with the smart use of the special imprinting strategies of dummy template, multi-template, multi-functional monomer, and magnetic/temperature responsive imprinting strategies. The reasonable, effective and synergic combination modes of the special imprinting strategies will be deeply explored and related mechanisms in the selective recognition and adsorption of SAs by the MIPs materials will also be discussed in depth. The as-prepared SAs-MIPs will be applied as dispersive or magnetic SPE (DSPE/MSPE) adsorbents for sample pretreatment, coupled with instrumental analytical technologies such as liquid chromatography-mass spectrometry hyphenated technologies, and thereby will facilitate to realize rapid, simultaneous and selective enrichment and sensitive determination of low levels (e.g. ng/L) but multiple kinds of SAs in complicated coastal zone waters. The smooth implementation of the project will not only promote the development of combined molecular imprinting technology, but also provide a general analytical detection strategy for related studies on antibiotics pollution in coastal zone waters and boost the sustainable development of coastal zone ecological environment.

抗生素的大量生产及滥用引起的环境污染问题日趋严重，如何选择性识别和检测复杂水体尤其是海水基质中低含量、多源抗生素污染成为近年研究热点。具有选择性的分子印迹聚合物(MIPs)，已成为海水样品制备中的有效识别材料。本项目拟选取典型磺胺类(SAs)抗生素为研究对象，借助分子印迹的表面印迹、纳米印迹技术设计优化核壳结构，探索虚拟模板、多模板、多功能单体、磁/温度响应等印迹策略的合理有效、协同组合方式，制备具有良好(磁/温响应)印迹性能的SAs-MIPs材料，并深入探讨材料对SAs的选择性识别和吸附机理。发展基于SAs-MIPs的分散或磁固相萃取前处理方法，结合液相色谱-质谱联用等技术，实现海岸带水体中多种类、低含量(如ng/L)SAs的快速同时、选择性富集和灵敏检测。该项目的实施，能够推动组合分子印迹技术发展，为海岸带水体抗生素污染研究提供普适性的分析检测思路，助力可持续发展的海岸带生态环境建设。

选择性识别和高灵敏检测复杂基质尤其是海岸带水体中低含量、多种类抗生素污染成为研究热点，其中，基于分子印迹聚合物（MIPs）的固相萃取（SPE）已广泛用于抗生素残留测定的样品前处理中，而组合分子印迹技术在MIPs制备中具有明显优势。本项目以典型磺胺类（SAs）抗生素等为研究对象，借助分子印迹技术的表面印迹、纳米印迹技术设计优化核壳结构，探索了虚拟模板、多模板、多功能单体、磁/温度响应等印迹策略的合理有效、协同组合，制备了多种具有良好（磁/温响应）印迹性能的MIPs材料，并深入探讨了材料对SAs等的选择性识别和吸附机理。发展了基于MIPs材料的分散SPE（DSPE）、磁SPE（MSPE）等前处理方法，结合高效液相色谱（HPLC）、毛细管电泳（CE）等，实现了对海岸带水体（海水、河水、湖水、废水等）等复杂基质中痕量SAs等的快速、同时、选择性富集和灵敏检测。也发展了分散液液微萃取（DLLME）前处理技术，结合HPLC，测定了海岸带样品中7种SAs；利用CE压力辅助电动进样，富集了6种SAs；DLLME组合CE的场放大进样，两步高效富集了4种SAs。相关研究结果，在Advanced Materials、Analyst、Analytical Chemistry、Journal of Hazardous Materials、Talanta、化学试剂、色谱等期刊发表论文40余篇（含SCI论文30余篇），授权发明专利8项。培养毕业于中国科学院大学的硕士研究生1人，获国家奖学金；新增国家自然科学基金等项目3项。通过该项目相关研究，发展了SAs-MIPs制备等的相关技术，体现了多种技术和策略进行组合协同的优势，发展了高效的样品前处理方法。不仅有望推动组合分子印迹技术、组合富集技术的发展，丰富环境分析化学的研究内涵，具有重要科学意义；而且有望为海岸带水体抗生素污染研究提供普适性的分析检测思路，助力可持续发展的海岸带生态环境建设，应用前景广阔。