替代模板分子印迹技术及其在水相样品前处理中的应用研究

Molecularly imprinted sample pretreatment techniques have the advantage of high selectivity. It can also eliminate the interferences of complicated matrix. But the template molecule is hard to elute completely and it may be leaked in the analysis. The leaking problem may be solved by using a dummy template to replace the template molecule. This research would employ the dummy template technique to prepare water-compatible molecularly imprinted polymer coatings for stir bar and monolithic bar sorptive extraction. The dummy template molecularly imprinted polymer coatings would be applied for selective extraction and sensitive analysis of environmental estrogens in complicated samples. Molecularly imprinted stir bar sorptive extraction has the advantage of large solid phase volume. It can also enrich analytes during the self-stirring without competitive adsorption by an additional stirrer. Molecularly imprinted monolithic bar has the advantages of easy to prepare, size-controlled and high extraction capacity. Bisphenol B, bisphenol F, 4-tert-butyl phenol and isotope labeled bisphenol A (BPA-d16) would be selected as dummy templates, respectively. Acrylamide and ethyl glycol dimethacrylate were selected as functional monomer and cross linker, respectively. The dummy template molecularly imprinted polymers were synthesized for stir bar and monolithic bar. The dummy template molecularly imprinted polymer coatings would be also applied for efficient analysis of bisphenol A and other environmental estrogens in environmental water samples, food packing materials and biological samples.

分子印迹样品前处理技术具有选择性高、能抵抗复杂环境干扰等优点，但存在模板分子难以彻底洗脱和泄露问题，而采用替代模板分子印迹技术，可避免模板分子的泄露问题。将替代模板技术应用于分子印迹聚合物涂层的制备，分别研制出适于水相萃取的替代模板分子印迹吸附萃取搅拌棒和替代模板分子印迹吸附萃取整体棒，应用于复杂样品中酚类环境雌激素的高选择性萃取和高灵敏分析。分子印迹吸附萃取搅拌棒具有固定相体积大、能在搅拌的同时完成萃取、避免外加搅拌子的竞争性吸附等优点；分子印迹整体棒具有制备简单、尺寸可控、萃取容量高等优势。分别以双酚B、双酚F、对特丁基苯酚、同位素标记双酚A（BPA-d16）为替代模板，以水溶性丙烯酰胺为功能单体、乙二醇二甲基丙烯酸酯为交联剂，制备适于水相萃取的分子印迹聚合物，并结合吸附萃取搅拌棒、整体棒萃取形式，应用于环境水样、食品包装材料和生物样品中痕量双酚A及其它环境雌激素的高效分离分析。

常用的分子印迹样品前处理方法在痕量分析中存在模板残留和泄露的风险，采用替代模板分子印迹技术可有效的避免这一问题，从而提高分析结果的准确性。本项目分别采用双酚B（BPB）、双酚F（BPF）、对特丁基苯酚（PTBP）、四溴双酚A（BPA-Br4）为替代模板分子，通过原位聚合法一次制备得到长度和厚度可控的分子印迹吸附萃取搅拌棒涂层和分子印迹吸附萃取整体棒，研究替代模板分子印迹聚合物的结构性能和萃取性能，并应用于复杂实际样品中痕量雌激素的高效分离富集，建立了替代模板分子印迹聚合物微萃取联用高效液相色谱测定环境水样和塑料样品中痕量的BPA及结构类似的环境雌激素的快速和灵敏检测分析方法。制备的替代模板分子印迹吸附萃取搅拌棒和替代模板分子印迹整体棒，具有良好的耐溶剂性能和化学稳定性，使用寿命在100次以上。替代模板分子印迹微萃取技术可有效避免模板泄露，还能直接用于水相样品的前处理。课题研究成果对于丰富分子印迹样品前处理方法与技术具有重要的意义，对进一步探索水相样品中的分子印迹技术也具有重要的启示作用。