摘要
分子印迹聚合物通过在模板分子存在的情况下功能单体与交联剂的共聚合进行制备,将模板分子去除后,可形成与模板分子在空间结构上相匹配的的三维孔穴,因此可特异性地吸附模板分子及其结构类似物,被称为“人工抗体”。将分子印迹聚合物作为固相萃取吸附剂,可改进传统吸附剂特异性差的不足,在特异性保留目标物的同时,有效地去除干扰物,因此分子印迹-固相萃取技术成为一项简单高效的样品前处理技术。
本实验以喹诺酮类抗生素诺氟沙星作为模板分子,采用沉淀聚合法制备了分子印迹聚合物,依次优化了功能单体、交联剂等制备条件,获得了对诺氟沙星具有特异性吸附能力的分子印迹聚合物,然后对其进行了性能表征,最后将诺氟沙星分子印迹聚合物用于喹诺酮类抗生素的固相萃取研究,并优化了固相萃取条件。具体实验结果如下:
一、采用沉淀聚合法合成了一系列诺氟沙星分子印迹聚合物,通过印迹因子的比较,依次优化了致孔剂、功能单体的种类、功能单体与模板分子的比例以及交联剂的种类和用量,得到了对模板分子具有最优的特异性吸附能力的分子印迹聚合物。其制备条件是:将模板分子诺氟沙星0.32 g、功能单体MAA 4 mmol、交联剂EGDMA 10 mmol、引发剂AIBN 40 mg溶于60 mL甲醇,60℃反应24 h。在此条件下制备的分子印迹聚合物对四种喹诺酮类抗生素(诺氟沙星、环丙沙星、沙拉沙星、双氟沙星)的印迹因子分别为3.17、3.29、3.33、2.84。
二、采用一系列方法对最优分子印迹聚合物进行了性能表征:色谱评价结果表明分子印迹聚合物对模板分子及其结构类似物具有特异性吸附能力;前沿色谱实验求得分子印迹聚合物的亲和位点总数为12.08μmol/g;通过扫描电镜观察,聚合物微粒较规则;最后通过红外光谱实验证明了分子印迹聚合物与模板分子之间存在氢键作用力。
三、将最优分子印迹聚合物用于固相萃取研究,依次优化了上样、淋洗和洗脱条件,最佳的固相萃取条件为:将乙腈作为上样溶剂、3 mL乙腈/水(88/12, V/V)混合溶液进行淋洗,3 mL 5%乙酸乙腈(V/V)/水(86/14, V/V)混合溶液进行洗脱,在此条件下,以4 mL 1.25 mg/L喹诺酮类抗生素混合溶液(诺氟沙星、环丙沙星、沙拉沙星、双氟沙星)上样,回收率依次为96.92%、97.49%、56.75%、0.00%。
The molecularly imprinted polymers (MIPs) are obtained by copolymerization of functional monomer and cross-linker in the present of the template and after removal of the template the three-dimensional sites complementary to the template in shape and functionality are revealed. It can rebind the template and analogue specifically, so it is named‘artificial antibody’. Solid phase extraction (SPE) used MIPs as the sorbent can overcome the defects that the common sorbent of SPE has low specificity. It can not only retain the trace template molecule specifically but also remove the other compounds present in sample matrix. So molecularly imprinted solid phase extraction (MISPE) provides a simple and effective pre-treatment method.
In this research, MIPs were prepared by precipitation polymerization using norfloxacin, a kind of quinolone antibiotics, as the template. The conditions of polymerization, including functional monomer, cross-linnker and so on, were optimized and the MIP with the best specific adsorption capacity to norfloxacin was obtained. Then the characterization of the MIP was evaluated. At last the MIP was applied as the sorbent of SPE and the procedure of MISPE was optimized. The main contents of this research are described as follows:
1. A series of norfloxacin molecularly imprinted polymers were prepared by precipitation polymerization. The compositions of polymers, including the porogenic solvent, the functional monomer, the cross-linker, were optimized by comparison of the imprinted factor. The MIP with the best affinity to the template was abtained. The compositions of the best-performing MIP were as follows: 0.32 g norfloxacin, 4 mmol MAA, 10 mmol EGDMA and 40 mg AIBN were dissolved in 60 mL methanol and the mixture was polymerized at 60℃for 24 h. In this condition, the imprinted factors of the prepared polymer to quinolone antibiotics (norfloxacin, ciprofloxacin, sarafloxacin, difloxacin) were 3.17, 3.29, 3.33, 2.84 respectively.
2. The characterization of the best-performing polymer was examined by several different methods. The results of chromatographic evaluation indicated that the best-performing MIP can absorb the template specifically. The value of the total amount of the immobilized ligand was 12.08μmol/g by frontal chromatography. The polymer particles were regular examined by Scanning electron micrograph. At last, the hydrogen bond between MIP and the template was confirmed by infrared spectrum.
3. The best-performing molecularly imprinted polymer was applied as the sorbent of SPE and the conditions of MISPE, including loading, washing and eluting, were optimized. The optimal MISPE protocol was loading with acetonitrile, washing with 3 mL acetonitrile/water (88/12, V/V) and eluting with 3 mL 5% acetic acid solution (in acetonitrile, V/V)/water (86/14, V/V). Under this protocol, when 4 mL 1.25 mg/L quinolone antibiotics solution (in acetonitrile) were loaded onto the MISPE cartridges, the recoveries of norfloxacin, ciprofloxacin, sarafloxacin, difloxacin were 96.92%, 97.49%, 56.75%, 0.00% respectively.
引文
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