溶胶凝胶法制备双酚A分子印迹纳米硅胶搅拌棒及其应用

发布时间：2018-12-14 02:46

【摘要】：双酚A (Bisphenol A, BPA)是一种常见的环境雌激素，在痕量浓度就可以干扰人体的内分泌系统并引发多种毒性作用；而且BPA在日常生活及工业生产中的用途非常广泛，所以简便、灵敏地监测BPA非常重要。在本研究中，我们采用溶胶凝胶法制备了以BPA伪模板分子印迹聚合物(Dummy molecularlyimprinted polymers, DMIPs)为涂层材料的搅拌棒，并应用其吸附萃取自来水中痕量的BPA。搅拌棒吸附萃取技术(Stir bar sorptive extraction, SBSE)是将对待测物具有吸附作用的萃取材料涂附在搅拌棒表面，使搅拌棒在自身搅拌的同时完成对待测物的富集，具有灵敏度高、溶剂耗费少、操作简便等优点。但是现有的市售搅拌棒只有非极性涂层材料，对极性物质吸附能力非常差，而且缺乏特异选择性。为了克服这一缺陷，我们利用分子印迹聚合物吸附的特异性，采用溶胶凝胶法制备了对BPA有良好特异吸附作用的BPA伪模板分子印迹搅拌棒(DMIPs搅拌棒)。扫描电镜图显示，BPA伪模板分子印迹涂层具有粗糙、均匀的表面结构，涂层厚度约57μm。DMIPs、聚二甲基硅氧烷涂层和BPA伪模板分子印迹涂层的红外图谱表明DMIPs被成功嵌入到凝胶结构中。选择性吸附实验数据显示：在对含有BPA和BPA结构类似物的混合水溶液进行吸附萃取时，DMIPs搅拌棒对BPA的回收率分别是联苯二酚的3~4倍，是4-叔丁基酚的3~7倍，是四溴双酚A的61~103倍。这充分表明DMIPs搅拌棒对BPA具有良好的选择性吸附能力。此外，DMIPs搅拌棒对BPA的萃取能力并不随着混合溶液中BPA结构类似物浓度的增加而下降，而是保持相对稳定(回收率在88~98%之间)，这显示DMIPs搅拌棒具有较强的抗干扰能力。同时，我们比较了DMIPs搅拌棒、以空白印迹聚合物(Non-imprintedpolymers, NIPs)为涂层的搅拌棒(NIPs搅拌棒)和以聚二甲基硅氧烷(Polydimethylsiloxane, PDMS)为涂层的搅拌棒(PDMS搅拌棒)对BPA的吸附能力。数据显示，DMIPs搅拌棒对BPA的回收率分别是NIPs搅拌棒的7倍，是PDMS搅拌棒的24倍。显然，DMIPs搅拌棒对BPA的吸附能力远远优于其它两种搅拌棒。最后，我们优化了应用DMIPs搅拌棒进行吸附萃取的实验条件，并成功地将DMIPs-SBSE与高效液相荧光检测法联合，，测定了自来水中的BPA。该分析方法的标准曲线在BPA浓度0.0228-0.456 ng mL-1范围内线性良好，相关系数为0.9994。BPA的检测限为5.70 pg mL-1 (S/N=3)。我们应用该方法测定了自来水中痕量的BPA，得到了满意的结果。BPA加标回收率在81.7?98.2%范围内，相对标准偏差为10.2%。
[Abstract]:Bisphenol A (Bisphenol A, BPA) (BPA) is a common environmental estrogen, which can disturb the endocrine system of human body at trace concentration and induce many toxic effects. BPA is widely used in daily life and industrial production, so it is very important to monitor BPA easily and sensitively. In this study, we prepared the agitator rod using BPA pseudo-template molecularly imprinted polymer (Dummy molecularlyimprinted polymers, DMIPs) as coating material by sol-gel method, and used it to adsorb and extract trace BPA. from tap water. Agitator rod adsorption extraction technology (Stir bar sorptive extraction, SBSE) is a kind of extraction material which can be adsorbed on the surface of agitator rod. The agitator rod has high sensitivity and high sensitivity, which makes the agitator complete the enrichment of the test material while stirring itself at the same time. The solvent consumption is less, the operation is simple and so on. However, the non-polar coating materials are the only available agitator rods, and the adsorption ability of polar materials is very poor, and there is no specific selectivity. In order to overcome this defect, BPA pseudo-template molecular imprinted agitator (DMIPs) was prepared by sol-gel method by using molecular imprinted polymer adsorption specificity. Scanning electron microscopy showed that the BPA pseudo-template molecular imprinted coating had a rough and uniform surface structure, and the coating thickness was about 57 渭 m.DMIPs. The IR spectra of polydimethylsiloxane coating and BPA pseudo-template molecular imprinted coating show that DMIPs is successfully embedded into the gel structure. The experimental data of selective adsorption showed that the recovery of BPA by DMIPs agitator was 3 4 times of that of dihydroxybenzene and 37 times of that of 4 tert-Ding Ji phenol when the mixed aqueous solution containing BPA and BPA analogues was adsorbed and extracted. It is 103 times higher than tetrabromobisphenol A (BPA). This fully indicates that DMIPs agitator has a good selective adsorption capacity for BPA. In addition, the extraction ability of DMIPs agitator for BPA does not decrease with the increase of BPA structure analogue concentration in mixed solution, but remains relatively stable (recovery rate is between 88% and 98%), which indicates that DMIPs stirring rod has strong anti-interference ability. At the same time, we compared the adsorption ability of DMIPs agitator rod, NIPs agitator rod coated with blank imprinted polymer (Non-imprintedpolymers, NIPs) and PDMS agitator rod coated with polydimethylsiloxane (Polydimethylsiloxane, PDMS). The results showed that the recovery of BPA by DMIPs was 7 times of that of NIPs and 24 times of that of PDMS. Obviously, the adsorption ability of DMIPs agitator to BPA is much better than that of other two agitators. Finally, we optimized the experimental conditions of adsorption and extraction with DMIPs agitator, and successfully combined DMIPs-SBSE with high performance liquid phase fluorescence detection method to determine BPA. in tap water. The standard curve was linear in the range of 0.0228-0.456 ng mL-1 for BPA, and the detection limit of 0.9994.BPA was 5.70 pg mL-1 (S/N=3). The method has been applied to the determination of trace BPA, in tap water with satisfactory results. The recoveries of BPA are within the range of 81.7% and 98.2%, and the relative standard deviation is 10.2%.
【学位授予单位】：南京医科大学
【学位级别】：硕士
【学位授予年份】：2011
【分类号】：TB383.1

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