【作者】 杨磊；

【导师】 吕运开；

【作者基本信息】 河北大学 ， 分析化学， 2013， 硕士

【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3.74g kg-1。更多还原

【Abstract】 A new molecularly imprinted monolithic column was successful prepared by combiningmolecular imprinting technique with the monolithic column synthesis technology for a simplepre-concentration column based on its high throughput and low backpressure. A novelmolecular imprinted organic–inorganic hybrid composite monolithic column (MIP-HCMC)was prepared in a stainless-steel chromatographic column using sol-gel technique. Themonolithic columns were used as precolumn for determination of trace antibiotics residues incomplex matrix by on-line solid-phase extraction-HPLC. This thesis consists of fourchapters and as follows:Chapter1: The dangers of antibiotics residues and its detection methods wereintroduced. The application and progress of the molecular imprinted monolithic column andsolid-phase extraction (SPE) in antibiotics residues were reviewed.Chapter2: A molecularly imprinted monolithic column (MIMC) was prepared usingenrofloxacin (ENR) as the template molecule, methylacrylic acid and2-hydroxyethylmethacrylate as functional monomer and trimethylol propane trimethylacrylate and ethyleneglycol dimethacrylate as the crosslinking monomer, toluene, dodecanol and polyethyleneglycol as porogenic solvent in traditional stainless-steel chromatographic column. Scanningelectron microscope (SEM) images and overall appearance, together with the dynamicadsorption capacity of the MIMC were employed to optimize the preparation conditions.Accordingly, the MIMC was used as on-line solid-phase extraction column for selectivelypurifying the matrix in milk.Chapter3: The tetracycline molecularly imprinted monolithic column was prepared foron-line SPE-HPLC detecting of trace TCs residue in milk. The synthesis conditions wereoptimized. The morphology and dynamic adsorption characteristic of the monolithic columnwere characterized by SEM and dynamic binding test, respectively. The on-line SPEprocedure was carefully investigated and a good clear-up and preconcentration effect wasobtained under the optimized washing condition. Chapter4: A novel molecular imprinted organic–inorganic hybrid composite monolithiccolumn (MIP-HCMC) was prepared in a stainless-steel chromatographic column for thedetermination of fluoroquinolones residues in milk by on-line solid-phase extraction couplingwith HPLC. The MIP-HCMC was prepared using enrofloxacin as the template, methacrylicacid and2-hydroxyethyl methacrylate as functional monomers, tetraethoxysilane as inorganicprecursor and methacryloxypropyltrimethoxysilane as coupling agent, toluene andpolyethylene glycol as porogenic solvent, ethylene glycol dimethacrylate as cross-linkingagent. Synthesis conditions were optimized. The chemical group, morphology, thermalstability, dynamic adsorption characteristic and swelling of the monolithic column werecharacterized by IR, SEM, TG, dynamic binding test and swelling test, respectively. Anenrichment factor (EF) of18.5along with a good sample clean-up effect was obtained underthe optimized conditions when it was applied to the milk sample analysis only aftercentrifugation. The average recoveries of four fluoroquinolones spiked milk at0.05,0.1and0.25mg kg-1were in the range of89.1-99.2%with the precision of3.55-4.32%. The limits ofdetection and quantitation of the proposed method were1.69and5.63g kg-1for ofloxacin,1.63and5.43g kg-1for lomefloxacin,3.74and12.5g kg-1for ciprofloxacin,1.37and4.56g kg-1for enrofloxacin, respectively. The proposed method was successfully applied toon-line extraction and determination of fluoroquinolones antibiotics in milk.更多还原