基于Fe(Ⅲ)-2-氨基对苯二甲酸金属有机框架的免标记氯霉素电化学传感器的构建及应用  

Construction and Application of Fe(Ⅲ)-2-Aminoterephthalic Acid Metal-Organic Framework-based Label-free Chloramphenicol Electrochemical Sensor

作　　者：詹峰萍 吴杨仪 戴小辉 梁超 高凤 汪庆祥 ZHAN Feng-Ping;WU Yang-Yi;DAI Xiao-Hui;LIANG Chao;GAO Feng;WANG Qing-Xiang(Fujian Provincial Key Laboratory of Modern Analytical Science and Separation Technology,Department of Chemistry and Environment Science,Minnan Normal University,Zhangzhou 363000,China;Zhangzhou Products Quality Supervision Institute,Zhangzhou 363000,China)

机构地区：[1]闽南师范大学化学化工与环境学院,福建省现代分离分析科学与技术重点实验室,漳州363000 [2]漳州市产品质量检验所,漳州363000

出　　处：《分析化学》2023年第4期539-548,共10页Chinese Journal of Analytical Chemistry

基　　金：国家自然科学基金项目(No.21802064);福建省自然科学基金项目(Nos.2021J01989,2022J01899);福建省市场监督管理局科技项目(No.FJMS2020048)资助

摘　　要：快速、简便的氯霉素(CAP)传感检测技术在食品安全和环境监测等领域具有良好的应用前景。本研究以FeCl_(3)·6H_(2)O和2-氨基对苯二甲酸(2-ATPA)为原料,采用水热合成法成功制备了金属有机框架(MOF)材料NH_(2)-MIL-88(Fe),并利用2-ATPA配体上的氨基,将其共价固定在羧基化的玻碳电极表面;进一步利用磷酸基团(-PO_(4)^(3-))与铁离子(Fe(Ⅲ))之间的强配位作用,将5′-PO_(4)^(3-)修饰的CAP核酸适配体(C-Apt)直接自组装到NH_(2)-MIL-88(Fe)修饰电极表面,无需额外交联剂和预活化过程,构建了一种新型C-Apt电化学传感界面。电化学实验结果表明,基于NH_(2)-MIL-88(Fe)的类过氧化物酶活性,NH_(2)-MIL-88(Fe)修饰电极对H_(2)O_(2)/3,3′,5,5′-四甲基联苯胺(TMB)表现出明显的电催化活性;当目标物CAP被C-Apt捕获形成复合物后,在传感界面形成屏障层,抑制了NH_(2)-MIL-88(Fe)对H_(2)O_(2)/TMB体系的催化活性,从而可用于CAP的免标记电化学检测。定量分析结果表明,CAP浓度在1.0 pmol/L~0.1μmol/L范围内,传感器对H_(2)O_(2)/TMB体系的催化峰电流变化值(I_(p))与CAP浓度的负对数(-lgC)值呈良好的线性关系,检出限为330 fmol/L(S/N=3)。此传感器可用于牛奶实际样品中CAP残留的检测,为食品中CAP残留的快速、简便检测提供了一种新方法。The development of rapid and simple electrochemical sensing technology for detection of chloramphenicol(CAP)has important application prospects in food safety and environmental monitoring.Herein,NH_(2)-MIL-88(Fe)was successfully synthesized by a hydrothermal method using FeCl_(3)·6H_(2)O and 2-aminoterephthalic acid(2-ATPA)as the starting materials.Then,the NH_(2)-MIL-88(Fe)was covalently anchored on the surface of carboxylated glassy carbon electrode through the amino group on 2-ATPA.Furthermore,the 5′-PO_(4)^(3-)modified chloramphenicol aptamer(C-Apt)was self-assembled on the NH_(2)-MIL-88(Fe)surface through the coordination between-PO_(4)^(3-)and Fe3+to construct a novel label-free electrochemical biosensing interface.The immobilization of C-Apt did not need any crosslinking agent or pre-treatment.Electrochemical assays showed that the NH_(2)-MIL-88(Fe)modified electrode had strong catalytic activity for 3,3′,5,5′-tetramethylbenzidine(TMB)/H_(2)O_(2)system due to the nano enzymetic activity of NH_(2)-MIL-88(Fe);while the catalytic activity could be inhibited after forming a barrier layer that generated by the capture of CAP by C-Apt,through which the target CAP could be detected through the label-free method.The quantitative analysis results showed that the catalytic current(I_(p))for the oxidation of TMB/H_(2)O_(2)system had a good linear relationship with the negative logarithm of CAP concentration(-lgC)within the concentration range of 1.0 pmol/L-0.1μmol/L,and the detection limit was as low as 330 fmol/L(S/N=3).The biosensor could be used for detection of CAP residue in actual milk samples,which provided a new idea for the rapid detection of CAP residue in the food field.

关 键 词：NH2-MIL-88(Fe) 免标记 电化学传感器 纳米酶 氯霉素残留 

分 类 号：O657.1[理学—分析化学] TS252.7[理学—化学]