卡马西平印迹吸附剂的分子模拟与吸附机理  

Molecular Simulation and Adsorption Mechanism of Carbamazepine Imprinted Adsorbent

作　　者：梁建军[1] 何芹 郑怀礼[1] 向冰彦 LIANG Jian-Jun;HE Qin;ZHENG Huai-Li;XIANG Bing-Yan(Key Laboratory of the Three Gorges Reservoir Region's Eco-Environment (Ministry of Education,Chongqing University, Chongqing 400045, China)

机构地区：[1]重庆大学三峡库区生态环境教育部重点实验室,重庆400045

出　　处：《分析化学》2019年第6期846-854,I0004-I0005,共10页Chinese Journal of Analytical Chemistry

基　　金：国家自然科学基金项目(No.21477010)资助~~

摘　　要：分子模拟可为优选印迹吸附剂的功能单体提供理论指导。本研究构建了目标污染物卡马西平(模板分子)与14种功能单体的印迹识别体系,采用模拟淬火算法搜寻模板-单体相互作用的低能稳定构象,改善了现有研究在搜寻构象时易陷入局部势能阱的不足。分子模拟发现,功能单体衣康酸对卡马西平的结合能力最强;吸附实验结果表明,以其为单体制备的吸附剂在水溶液中的吸附量可达9.28 mg/g,在实际水样中也表现出较高的选择性,重复使用10次后,吸附量仅下降1.3%,吸附性能优于以传统单体甲基丙烯酸制备的吸附剂。模拟并测量了印迹体系的紫外光谱,结果表明,衣康酸和卡马西平之间形成了新的作用体系,分子模拟能够很好地预测二者在水溶液中的紫外光谱,但由于实际发生吸附时二者间会形成多种结合构象,分子模拟对相互作用体系的紫外光谱预测不够理想。能量计算和氢键分析表明,范德华力和静电作用在识别过程中起主要作用,红外分析印证了体系中存在氢键,识别位点位于衣康酸羧基和卡马西平酰胺之间,与分子模拟结果一致。Molecular simulation can provide valuable theoretical guidance for rapid selection of functional monomers in imprinted adsorbents. The recognition systems were constructed, which consisted of targeted pollutant carbamazepine(CBZ) as template molecule and 14 functional monomers respectively. The low-energy conformations of template-monomer interaction system were searched by simulated quenching method. This method overcame the shortcoming of the existing searching method by which the conformations were prone to fall into local potential wells. Molecular simulation indicated that the binding capacity of itaconic acid(IA) as monomer to CBZ was the strongest. Adsorption experiments showed that IA-prepared imprinted adsorbent(IA-MIP) performed better than the adsorbent prepared by traditional monomer methylacrylic acid. The adsorption capacity of IA-MIP could reach 9.28 mg/g in aqueous solution. IA-MIP also showed high selectivity to carbamazepine in filtration effluent. After 10 reuses, the adsorption capacity decreased by only 1.3%. The ultraviolet spectra of the imprinted system were calculated theoretically and measured. The experimental results confirmed that a new interaction system was formed between IA and CBZ. Molecular simulation could predict the ultraviolet spectra of IA and CBZ in aqueous solution very well. However, the prediction of the ultraviolet spectra of the interaction system was not ideal, which suggested that there existed a variety of interaction conformations during the specific adsorption process. Energy calculation and hydrogen bond analysis demonstrated that van der Waals and electrostatic force played a major role in the recognition process. Infrared analysis confirmed the existence of hydrogen bond in the system, and the recognition site was located between the carboxylic group of IA and carbamazepine amide, which was consistent with the results of molecular simulation.

关 键 词：分子印迹 分子模拟 吸附机理 水污染控制 卡马西平 

分 类 号：TQ424[化学工程]