分子印迹整体柱制备及在线固相萃取-液相色谱测定食品中兽药残留-preparation of molecularly imprinted monolithic column and determination of veterinary drug residues in food by on-line solid phase extraction and liquid chromatography.docxVIP

摘要摘要将分子印迹技术，结合整体柱高通量、低柱压且简单实用的特点，合成了一种作为 预富集柱使用的分子印迹有机整体柱，并在此基础上，结合溶胶-凝胶技术，引入无机 组份杂化复合，改进了分子印迹有机整体柱易溶胀、使用寿命短等缺陷。将分子印迹整 体柱作为预富集柱与高效液相色谱联用，从而发展了一种在线固相萃取-液相色谱测定 复杂基质中痕量药物残留的简单高效新方法。全文共分四个部分，主要工作如下：第一章：评述兽药残留的危害及其检测方法，分子印迹固相萃取及在线固相萃取兽 药残留检测的应用，整体柱及杂化整体柱的研究进展。第二章：以恩诺沙星为模板，甲基丙烯酸和甲基丙烯酸羟乙酯为功能单体，乙二醇 二甲基丙烯酸酯和三羟甲基丙烷三甲基丙烯酸酯为交联剂，甲苯、十二醇为溶剂，聚乙 二醇为分散剂，在不锈钢色谱柱中合成了恩诺沙星印迹整体柱，优化合成条件，并通过 整体材料外观，扫描电镜图及动态穿透实验对其性能进行了表征，作为预柱应用于在线 固相萃取过程，对牛奶样品中的基质净化效果很好。第三章：制备四环素印迹有机整体柱，并应用于在线固相萃取-液相色谱法测定奶 粉中四环素类残留，优化了合成条件，通过扫描电镜图和动态穿透实验对其特异性和选 择性进行了表征，并系统研究了在线固相萃取步骤，优化了淋洗溶剂的选择和用量，得 到了很好的净化和富集效果。第四章：以恩诺沙星为模板分子，甲基丙烯酸和甲基丙烯酸羟乙酯为功能单体，四 乙氧基硅烷和甲基丙烯酰氧丙基三甲氧基硅烷为无机前驱体，甲苯和聚乙二醇-200 为致 孔剂，乙二醇二甲基丙烯酸酯为交联剂，在不锈钢色谱柱中，制备了一种新的分子印迹 有机-无机杂化复合整体柱。采用红外、扫描电镜、热重分析、动态吸附实验和溶胀实 验分别表征了整体柱的化学基团变化、形貌、热稳定性、动态吸附特征和溶胀性。将制 备的整体柱用作预富集柱，实现了样品离心后直接进样的在线固相萃取-高效液相色谱 法分离和测定牛奶中痕量氟喹诺酮类药物残留，获得了较好的净化和富集效果（18.5）， 平均回收率为 89.1-99.2%，精密度为 3.55-4.32%，方法检出限小于 3.74 ?g kg-1。关键词分子印迹整体柱杂化复合材料在线固相萃取兽药残留奶制品IAbstractAbstractA new molecularly imprinted monolithic column was successful prepared by combining molecular imprinting technique with the monolithic column synthesis technology for a simple pre-concentration column based on its high throughput and low backpressure. A novel molecular imprinted organic–inorganic hybrid composite monolithic column (MIP-HCMC) was prepared in a stainless-steel chromatographic column using sol-gel technique. The monolithic columns were used as precolumn for determination of trace antibiotics residues in complex matrix by on-line solid-phase extraction - HPLC. This thesis consists of four chapters and as follows:Chapter 1: The dangers of antibiotics residues and its detection methods were introduced. The application and progress of the molecular imprinted monolithic column and solid-phase extraction (SPE) in antibiotics residues were reviewed.Chapter 2: A molecularly imprinted monolithic column (MIMC) was prepared using enrofloxacin (ENR) as the template molecule, methylacrylic acid and 2-hydroxyethyl methacrylate as functional mono