新型分子印迹材料的制备及其应用

发布时间：2018-08-07 17:56

【摘要】：分子印迹是产生能够记忆模板分子形状、大小和功能基团的特异性识别位点的新技术,具有预定性、识别性和实用性的特点。近年来,分子印迹技术已经成为研究热点,在复杂生物、食品和环境样品前处理,色谱分离和化学传感器等领域的应用更是引起了研究人员的极大兴趣。本文针对新型环境污染物二苯甲酮类和双酚类的检测,制备了具有高选择性的分子印迹聚合物。首先制备了分子印迹聚合物并对水体中的四种二苯甲酮类化合物进行了选择性的萃取和检测。在合成过程中,我们用4-乙烯基吡啶作为功能单体,二甲基丙烯酸乙二醇酯作为交联剂,乙腈作为致孔剂,2,2',4,4'-四羟基二苯甲酮(BP-2)作为模板合成了这种分子印迹聚合物。在吸附实验中,材料显示出了对BP-2良好的吸附能力；而在色谱评价实验中,材料显示出了对四种二苯甲酮的类选择性。同时,影响分子印迹-固相萃取过程的因素也被系统地探究。一种分子印迹-固相萃取结合高效液相色谱-紫外检测的准确又灵敏的方法被成功地建立起来,并用来检测河水和自来水中的四种二苯甲酮的含量,方法的检出限为0.25-0.72 ng mL-1。水样品中四种二苯甲酮在两种量级(500和5000 ng mL-1)下的回收率在86.9-103.3%范围内,相对标准偏差小于9.2%(n=3)。其次,通过皮克林乳液聚合的方式合成了分子印迹聚合物。BPAP,一种名为4,4'-(1-苯乙基)双酚的化合物,被选为替代模板用来阻止目标化合物泄露的问题。微球粒子通过扫描电镜和氮气吸附-解附平衡来表征,从中可以发现实验中合成了形状规则和粒径大小中等的粒子,它们的比表面积是355.759 m2g-1,孔体积是0.561 cm3 g-1。微粒的性质通过静态吸附和固相萃取实验来评价。材料对BPA的亲和常数和最大吸附量通过斯卡查得分析分别计算为0.115 mmolL-1和3.327μmol g-1。材料对七种双酚良好的类选择性在色谱评价中得到。微球粒子作为固相萃取的填料来装载固相萃取柱,分子印迹-固相萃取结合高效液相色谱-紫外检测被成功地建立起来,并用来对环境底泥样品中的七种双酚进行选择性萃取和检测,方法的检出限为0.6-1.1 ng g-1。七种双酚在两个量级下的回收率(500和250 ng g-1)在75.5-105.2%范围内,相对标准偏差小于7.7%(n=3)。
[Abstract]:Molecular imprinting is a new technology that produces specific identification sites that can memorize the shape, size and functional group of template molecules. It has the characteristics of predetermined, identifiability and practicability. In recent years, molecular imprinting technology has become a hot topic in the fields of complex biology, food and environmental sample pretreatment, chromatographic separation and chemical sensors. In this paper, a highly selective molecularly imprinted polymer was prepared for the detection of two benzophenones and bisphenols of the new environmental pollutants. First, molecularly imprinted polymers were prepared and selective extraction and detection of four kinds of two benzophenone compounds in water were carried out. In the process, we use 4- vinyl pyridine as a functional monomer, two ethylene glycol methacrylate as a crosslinker, acetonitrile as a pore agent, 2,2', 4,4'- four hydroxyl two benzophenone (BP-2) as a template for the synthesis of this molecularly imprinted polymer. In the adsorption experiment, the material showed a good adsorption capacity to BP-2; and in chromatographic evaluation In the experiment, the material showed the class selectivity for four kinds of two benzophenone. At the same time, the factors affecting the molecular imprinting solid phase extraction process were systematically explored. An accurate and sensitive method of molecularly imprinted solid phase extraction combined with high performance liquid chromatography UV detection was successfully built and used to detect the water and water in water. The detection limit of the four kinds of two benzophenone is that the recovery rate of four kinds of two benzophenone in 0.25-0.72 ng mL-1. water samples at two orders of magnitude (500 and 5000 ng mL-1) is within the range of 86.9-103.3%, and the relative standard deviation is less than 9.2% (n=3). Secondly, the molecularly imprinted polymer.BPAP is synthesized by Pickering emulsion polymerization, one is called 4,4. "- (1- phenyl ethyl) bisphenol compound is selected as a substitute for templates to prevent the leakage of target compounds. Microspheres are characterized by scanning electron microscopy and nitrogen adsorption desorption equilibrium. In the experiment, the shape rules and size of particles of medium size can be found in the experiment. Their specific surface area is 355.759 m2g-1 and the pore volume is 0.56. The properties of 1 cm3 g-1. particles are evaluated by static adsorption and solid phase extraction. The affinity constants and maximum adsorbability of the materials to BPA are calculated to 0.115 mmolL-1 and 3.327 Mu mol g-1. for good selectivity in the chromatographic evaluation. Microsphere particles are used as solid phase extraction fillers. Solid phase extraction column, molecularly imprinted solid phase extraction combined with high performance liquid chromatography UV detection were successfully established and used for selective extraction and detection of seven kinds of bisphenol in environmental sediment samples. The detection limit of the method was 0.6-1.1 ng g-1. and seven kinds of bisphenol at two magnitude levels (500 and 250 ng g-1) in 75.5-105.2% Within the range, the relative standard deviation is less than 7.7% (n=3).
【学位授予单位】：辽宁大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O631.3

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