【作者】 王建；

【导师】 梅素容； 荆涛；

【作者基本信息】 华中科技大学 ， 公共卫生， 2013， 硕士

【摘要】 分子印迹技术（Molecular Imprinting Technique，MIT），是基于抗原/抗体的基本原理而延伸的分子识别技术。分子印迹聚合物(Molecularly Imprinted Polymers，MIPs)是在模板分子存在的情况下，运用分子印迹技术通过功能单体与交联剂的共聚反应制得，去除模板分子后，分子印迹聚合物上可形成与模板分子在空间结构上相匹配的三维孔穴，可特异性地吸附模板分子及其结构类似物，因此也被称为“人工抗体”。本文采用沉淀聚合的方法，获得了对硝基酚类污染物具有特异性识别作用的亲水性分子印迹聚合物（MIPs），并实现水体中痕量硝基酚污染物的选择性萃取及去除。主要研究内容由以下两部分组成：1.为了克服传统固相萃取所具有的缺点，本研究采用亲水性MIPs-固相微柱萃取技术对水样（东湖，长江，工业废水）中硝基酚类污染物进行萃取。固相微柱萃取技术不需要传统的萃取装置及蒸发等复杂操作流程，仅通过离心便可完成对样品的上样、淋洗和洗脱，具有操作简单、快速的优点。在最佳萃取条件下，亲水性MIPs-固相微萃取柱对硝基酚类化合物的萃取回收率达到87%-92.9%，且具有良好的净化效果。与常规的萃取吸附剂（活性炭、多壁碳纳米管、LC-C18等）相比，亲水性MIPs显示出更高的萃取效率和更好的选择性识别性能。本研究建立亲水性MIPs-固相微柱萃取结合HPLC-UV法对实际水样中硝基酚类污染物进行检测，结果显示：该方法的线性范围为2-1000ng/mL（2,4-二硝基酚，2-硝基酚）、6-1000ng/mL（4-硝基酚），相关系数（R2）大于0.998，方法检测限为0.3-0.5ng/mL,日内RSDs值为4.0%-6.7%，日间（5日）RSDs值为5.9%-8.2%。2.将亲水性MIPs作为吸附剂对地表水及工业废水中2,4-二硝基酚进行选择性去除研究。吸附动力学模型及吸附等温模型结果显示，亲水性MIPs对2,4-二硝基酚的最大吸附容量为138.9mg/g，同时，进一步研究了吸附过程中水样的流速、初始浓度、pH和腐殖酸含量对去除效果的影响。大体积上样时（上样体积高达1L），与活性炭、多壁碳纳米管、LC-C18等常规吸附柱及常规方法制备的MIPs相比，亲水性MIPs（100mg）具有最好的去除效率（92%），并可重复使用5次以上，具有较好的实际应用前景。更多还原

【Abstract】 Molecular Imprinting Technique is a kind of molecular recognition technologies thatbased on the basic principle of antigen/antibody. The molecularly imprinted polymers(MIPs) are obtained by copolymerization of functional monomer and cross-linker in thepresence of template. Then, after removal of the template, the three-dimensional sites whichare complementary to the template in shape and functionality are revealed. For the MIPscan rebind the template and its’ analogue specifically, it is also named ‘artificial antibody’.This article focused on extraction and removal of nitrophenol pollutants in water samplesby using MIPs as sorbents. In this study, hydrophilic MIPs, which had the specificrecognition for nitrophenols in water media, were prepared by precipitation polymerization.And the hydrophilic MIPs were used to selectively extract and remove nitrophenolpollutants from water samples. The main contents were described as follows:1. To overcome the disadvantages of traditional solid-phase extraction, we developed asimple and rapid spin column extraction technology packed with hydrophilic molecularlyimprinted polymers (MIPs) for extracting nitrophenol pollutants in water samples (the EastLake, the Yangtze River and wastewater). The spin column was centrifuged for sampleloading, washing and eluting, and the whole extraction procedure could be completedwithout evaporation steps and extraction equipments. Under the optimized condition, the extraction recoveries of nitrophenol pollutants on hydrophilic MIPs-packed spin columnranged from87.3%to92.9%and excellent purification effect was obtained. Compared withactivated carbon, multi-walled carbon nanotubes, LC-C18sorbents, hydrophilic MIPsexhibited highly selective recognition ability for nitrophenol pollutants and satisfactorysample extraction efficiency. Subsequently, the MIPs-packed spin column extractioncoupled with HPLC-UV method was established to detect the nitrophenol pollutants inwater samples, which was found to be linear in the range of2-1000ng/mL(2,4-dinitropehnol,2-nitropheno), and6-1000ng/mL (4-nitrophenol)， with correlationcoefficients (R2) greater than0.998. The detection limits (LODs) ranged from0.3to0.5ng/mL，and it was shown that the intra-day RSD ranged from4.0%to6.7%and theinter-day RSD ranged from5.9%to8.2%in5days.2. Novel hydrophilic molecularly imprinted polymers (MIPs) with high adsorptioncapacity were used as the sorbents to remove2,4-dinitrophenol (2,4-DNP) from surfacewater and wastewater samples. The kinetic studies, dynamic adsorption and selectivityexperiments of hydrophilic MIPs were investigated. The results indicated that themaximum adsorption capacity of2,4-DNP on hydrophilic MIPs was138.9mg/g.Furthermore, the effects of flow rate, initial concentration, pH value and humic acid on theremoval efficiency for2,4-DNP were optimized. Compared with the active carbon, carbonnanotube, C18sorbents and common MIPs, the removal efficiency of hydrophilic MIPs(100mg) was higher with all above92%even though the sampling volume was more than1L. The results of five times adsorption-desorption cycles indicated that hydrophilic MIPswere with high stability. In a word, the obtained results demonstrated that the hydrophilicMIPs could be used as the effective sorbents for2,4-DNP removal in practical application.更多还原