【作者】 高霞；

【导师】 樊静；

【作者基本信息】 河南师范大学 ， 环境科学， 2014， 博士

【摘要】 离子液体由于具有极低的蒸汽压、几乎不挥发、电化学窗口宽、结构可调控等优点，近年来作为可以替代传统挥发性有机溶剂的“绿色”溶剂，应用于多个领域。然而，目前的研究发现，咪唑类离子液体的毒性与一些传统有机溶剂相当，甚至更高。由于许多离子液体在水中有一定的溶解度，它在多个领域中的广泛使用将会导致部分离子液体的流失，进而污染生态环境。但是，由于离子液体的特殊性质，给分析检测带来了一定的困难。因此，研究环境样品中微量咪唑类离子液体的分析方法对离子液体的环境监测具有重要意义。作为一种通过量身定做的方式来构建的稳定聚合物网络，分子印迹聚合物由于具有亲和性好、特异识别能力强、选择性高、抗干扰能力强、稳定性和再生性好、使用寿命长等优点，而被广泛的应用于色谱分离、固相萃取、化学传感等多个领域中。本论文采用先进的表面印迹技术，分别以氯化1-丁基-3-甲基咪唑离子液体、氯化1-乙基-3-甲基咪唑离子液体及氯化1-羟乙基-3-甲基咪唑离子液体为模板，制备了三种离子液体表面印迹聚合物。通过多种技术手段对印迹聚合物的表观形貌及化学组成进行了表征，对三种印迹聚合物的静态吸附性能、动态固相萃取性能以及在实际环境样品中的使用性能进行了系统研究。具体的内容如下：1、概述了离子液体的结构特点、毒性以及现有的分析检测方法，对分子印迹技术的研究进展进行了综述，包括分子印迹技术的分类、原理、制备方法及应用。介绍了论文的研究意义和研究内容，共引用参考文献167篇。2、设计合成了三种新型的咪唑类离子液体表面印迹聚合物。采用扫描电镜、红外光谱分析、比表面积和孔径分析等手段对聚合物的结构信息及化学组成进行表征，通过紫外光谱和核磁共振氢谱的变化研究了模板分子与功能单体之间的作用方式，以此来了解印迹聚合物对模板分子可能的识别机制。3、通过吸附等温线、吸附动力学及选择性吸附实验考察了三种表面印迹聚合物的静态吸附性能。结果显示：印迹聚合物对模板分子的吸附量远远大于非印迹聚合物对模板分子的吸附量，且吸附等温线数据可以用Langmuir模型和Langmuir-Freundlich等吸附等温模型进行拟合；三种印迹聚合物在40min内都可以达到对模板分子的吸附平衡，且吸附动力学特性可以通过假二级动力学方程进行拟合；选择性吸附研究表明，三种咪唑类离子液体表面印迹聚合物都可以从结构类似物或复杂多变的环境样品中选择性识别模板分子。4、将合成的氯化1-丁基-3-甲基咪唑离子液体表面印迹聚合物和氯化1-乙基-3-甲基咪唑离子液体表面印迹聚合物作为固相萃取剂制备成固相萃取柱。采用固相萃取技术，考察了固相萃取柱的上样体积、流速、洗脱剂的种类和用量等参数。在优化条件下，将固相萃取技术与高效液相色谱联用，对固相萃取柱的选择性分离富集性能进行评估。结果显示，由两种印迹聚合物制备的固相萃取柱均能从环境样品中选择性分离富集模板离子液体及其结构类似物，且对实际水样中相应的离子液体进行检测时，氯化1-丁基-3-甲基咪唑离子液体和氯化1-乙基-3-甲基咪唑离子液体的回收率均在90%以上，显现出很好的实用性能。5、在上述研究基础上，对论文的主要成果和结论进行了总结，对本课题和当前分子印迹技术发展中所存在的问题进行了分析，对今后分子印迹技术的发展提出了自己的见解和建议。更多还原

【Abstract】 Because of their attractive properties such as negligible vapor pressure, non-volatility, wideelectrochemical window and regulatable structure and so on, ionic liquids (ILs) have been extensivelyapplied to many areas as “green” substitutes for conventionally volatile organic solvents. However, somestudies suggested that toxicity of alkyl-imidazolium ILs is similar to some conventionally used organicsolvents, or even higher. Wide application would inevitably result in the loss of them, and resulting inpollutions of eco-environment. While the special properties of ILs made them difficult to be analyzed anddetected. Therefore, it is important to determine trace alkyl-imidazolium ILs in environmental samples.Molecular imprinting has become the topic research of many researchers for the construction of stablepolymeric networks in tailor-made fashion in recent years. Due to its outstanding advantages of goodaffinity, strong specific recognition ability, high selectivity, powerful anti-interference ability, betterstability and reusability, long life and among others, molecular imprinting technology has been wildly usedin many fields such as chromate-graphic separation, solid phase extraction, and chemical sensors and soon.In this paper, three novel surface molecular imprinted polymers(MIP) were prepared by using1-butyl-3-methylimidazolium chloride ILs (C4mimCl),1-ethyl-3-methylimidazolium chloride ILs(C2mimCl) and1-ethyl hydroxyl-3-methylimidazolium chloride ILs (C2OHmimCl) as the template,respectively. The as-prepared imprinting polymers were characterized by various techniques, its staticadsorption properties such as adsorption isotherm, adsorption kinetics and absorption selectivity, dynamicadsorption properties and adsorption properties in environmental water samples were studied in detail. Themain research results are listed as follows:1, The structural properties, toxicity and the present analytical methods were first discussed, then thestudies on the molecular imprinting technique, including the classification, preparation principle, methods,application in solid phase extract, were reviewed. Finally, the target, content and novelty stament have beenintroduced briefly. Here167references were cited.2, Three novel alkyl-imidazolium ILs surface molecular imprinted polymers were prepared. SEM micrographs, BET surface area analysis and (FT-Ir) spectra were selected to characterize the structuralinformation and chemical composition. Interaction between the template molecule and functional monomerwas studied through the changes of UV spectroscopy and1HNMR titration. Accordingly, the possiblemolecular recognition mechanism was also investigated3, The static adsorption performance of the three surface molecularly imprinted polymers was testedby the adsorption isotherms, kinetic curve and selective adsorption experiments. And the results suggestedthat the molecularly imprinted polymer had a significantly higher adsorption capacity for the templatecompared with the corresponding non-imprinted polymer. The experimental data of adsorption isothermfitted to the Langmuir and the Langmuir-Freundlich model very well, and the maximum adsorptioncapacity, the total number of binding sites and the mean association constant were calculated accordingly.The adsorption kinetic experiments suggested that three imprinted polymers achieved the adsorptionequilibrium within40min, and the adsorption process could be described by pseudo-second order kinetics.Results from the adsorption selectivity experiments showed that this three surface molecularly imprintedpolymers can separate and extract the template selectively from the complex matrixes and structuralanalogs.4, The solid phase extraction columns were prepared by using C4mimClMIP and C2mimClMIP as thesolid phase sorbents. Various parameters were optimized for the solid phase extraction columns, such asloading volumn, flow rate, eluent solvent and so on. Under the optimized column parameters, solid phaseextraction column coupled with HPLC was used for the evaluation of the separation and extractionproperties for alkyl-imidazolium ionic liquids. The results showed that the two solid phase extractioncolumns can separate and extract the template IL and its structural analogs from complex matrix, and whenthey were applied to the determination of the IL in environmental water samples, the recoveries was i over90%for the two ILs, and exhibited excellent practical properties.5, Summarized the main research results and conclusions of this thesis; point out the problems need tobe resolved in this topic and present molecular imprinted technique; and put forward my views andsuggestions for the future work of the this technique.更多还原