双酚A磁性分子印迹聚合物纳米球的合成及分离分析性能研究

发布时间：2018-05-13 14:37

本文选题：磁性分子印迹聚合物 + 虚拟模板　；参考：《中国科学技术大学》2017年硕士论文

【摘要】：本文对环境样品中痕量双酚A(BPA)的分离富集技术、磁性分子印迹技术、磁性表面分子印迹固相萃取技术、BPA分子印迹聚合物的制备技术的研究进展和发展趋势进行了综述;研究了 BPA的磁性表面分子印迹聚合物的合成方法和对环境水样品中BPA的分离富集性能;合成了 BPA的磁性虚拟模板分子印迹聚合物,并将其作为磁性固相萃取的新型材料,应用于塑料瓶装饮品中痕量BPA的分离富集,建立了磁性虚拟模板分子印迹-固相萃取-高效液相色谱测定塑料瓶装饮品中痕量BPA的新方法。将表面分子印迹技术与溶胶-凝胶方法相结合,在磁性核表面直接一步合成了均一、单分散、超顺磁的双酚A磁性分子印迹聚合物(MMIP),并通过磁性分析、傅里叶红外光谱、X射线衍射分析、扫描电镜、透射电镜等方法对聚合物材料的形貌、结构以及稳定性进行表征和分析,探究了 NH3·H2O的用量、溶剂组成、以及功能单体与交联剂的比例对聚合物形貌的影响。在最佳条件下,对Fe3O4@MIP与Fe3O4@NIP在水溶液中的吸附性能进行了研究。结果表明,此方法不仅简单高效,避免了传统过程中繁琐的磁性核表面修饰过程,为聚合物材料的批量生产提供了一种新的方法,且合成的材料具有高吸附量(402.3μmolg-1)、快速的吸附速度(30 min)、良好的选择性以及较高的循环适用性等优点。以BPA的结构类似物4,4'-二羟基联苯(DDBP)作为虚拟模板分子,采用溶胶-凝胶法,在四氧化三铁表面直接一步合成了 BPA的磁性虚拟模板分子印迹聚合物(BPA-DMMIP),对BPA-DMMIP进行了红外光谱、透射电镜、扫描电镜的表征,评价了虚拟模板表面印迹聚合物的吸附性能。结果表明:该虚拟模板聚合物对BPA有较大的吸附容量(444.6 μmol g-1),对BPA的吸附在30 min即可达到平衡,并显示了对BPA的高选择性和特别的亲和力。此外,DMMIP避免了模板分子BPA的泄露,也极大简化了固相萃取过程,为建立环境样品中痕量BPA的分析测定方法奠定了基础。基于磁性分子印迹固相萃取的方法,将磁性虚拟模板分子印迹聚合物(DMMIP)材料应用于塑料瓶装饮品中BPA的分离富集。探究了吸附剂用量、溶液pH、洗脱液组成以及洗脱时间等因素对固相萃取回收率的影响,建立了DMMIP-SPE-HPLC测定痕量BPA的新方法。结果表明,在最佳条件下,BPA在30 s即可从DMMIP材料上洗脱下来,方法的富集倍数达400倍时回收率仍然大于899%,且对磁性固相萃取的吸附-洗脱过程重复6次后仍具有较好的回收率。此外,通过加标回收法测定了塑料瓶装饮品中的BPA,方法的回收率为88.6-99.5%,最低检测限(LOD)为0.083 ngmL-1,相对标准偏差均低于9.5%。
[Abstract]:In this paper, the separation and enrichment of BPA in environmental samples, magnetic molecular imprinting, and molecular imprinted solid phase extraction (SPE) of magnetic surface are reviewed in this paper, and the research progress and development trend of BPA molecularly imprinted polymers are reviewed. The synthesis and separation and enrichment of BPA from environmental water samples of BPA were studied, and the magnetic virtual template molecularly imprinted polymer of BPA was synthesized and used as a new material for magnetic solid phase extraction (SPE). A new method for the determination of trace BPA in plastic bottled drinks by high performance liquid chromatography (HPLC) and imprinting of magnetic virtual template molecular imprinting solid phase extraction (SPE) has been developed for the separation and enrichment of trace BPA in plastic bottled drinks. A homogeneous, monodisperse, super-paramagnetic bisphenol A magnetic molecularly imprinted polymer was synthesized by combining the surface molecular imprinting technique with the sol-gel method. The morphology, structure and stability of the polymer were characterized and analyzed by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The amount of NH3 H2O and the composition of the solvent were investigated. And the influence of the ratio of functional monomer to crosslinking agent on the morphology of polymer. The adsorption properties of Fe3O4@MIP and Fe3O4@NIP in aqueous solution were studied under the optimum conditions. The results show that this method is not only simple and efficient, but also avoids the complicated surface modification process of magnetic nuclei in the traditional process, and provides a new method for batch production of polymer materials. The synthesized material has the advantages of high adsorption capacity of 402.3 渭 mol g-1g ~ (-1), fast adsorption rate of 30 min, good selectivity and high cycle applicability. The magnetic virtual template molecular imprinted polymer (BPA-DMMIP) of BPA was synthesized by sol-gel method using the structural analogue of BPA, 4H4 (4-dihydroxybiphenyl) DDBP, as a virtual template molecule. The imprinted polymer BPA-DMMIPe of BPA was synthesized directly on the surface of Fe _ 2O _ 4 by sol-gel method. The IR spectra of the imprinted polymer (BPA-DMMIP-) of BPA were studied. The adsorption properties of imprinted polymers on the surface of virtual templates were evaluated by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The results show that the virtual template polymer has a large adsorption capacity of 444.6 渭 mol g-1g ~ (-1) on BPA, and the adsorption of BPA can reach equilibrium at 30 min. It also shows high selectivity and special affinity to BPA. In addition, DMMIP avoids the leakage of template molecule BPA and greatly simplifies the solid-phase extraction process, which lays a foundation for the determination of trace BPA in environmental samples. Based on the method of magnetic molecularly imprinted solid phase extraction, the magnetic virtual template molecularly imprinted polymer (DMMIP) was applied to the separation and enrichment of BPA in plastic bottles. The effects of the amount of adsorbent, pH of solution, composition of eluent and elution time on the recovery rate of solid phase extraction (SPE) were investigated. A new method for the determination of trace BPA by DMMIP-SPE-HPLC was established. The results showed that under the optimum conditions, DMMIP could be eluted from the DMMIP material at 30 s. The recovery rate was still greater than 899 when the enrichment ratio of the method was 400 times, and the adsorption-elution process of magnetic solid phase extraction was repeated for 6 times and still had a good recovery. In addition, the recovery rate of BPA in plastic bottled drinks was 88.6-99.5, the lowest detection limit was 0.083 ngmL-1, and the relative standard deviation was lower than 9.5%.
【学位授予单位】：中国科学技术大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O631.3

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