基于免疫反应抑制MIL-101(Fe)电催化活性的肌钙蛋白Ⅰ电化学传感器  

An Electrochemical Biosensor for Cardiac Troponin Ⅰ Based on Electrocatalytic Activity Suppression of MIL-101(Fe) by Immunoreaction

作　　者：杨海珠 褚亚茹 汪庆祥 丁彩凤[2] 高凤 YANG Hai-Zhu;CHU Ya-Ru;WANG Qing-Xiang;DING Cai-Feng;GAO Feng(Department of Chemistry and Environment Science,Fujian Provincial Key Laboratory of Modern Analytical Science and Separation Technology,Minnan Normal University,Zhangzhou 363000,China;Key Laboratory of Sensor Analysis of Tumor Marker Ministry of Education,College of Chemistry and Molecular Engineering,Qingdao University of Science and Technology,Qingdao 266042,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]青岛科技大学肿瘤标志物传感分析教育部重点实验室,青岛266042

出　　处：《分析化学》2021年第5期789-797,共9页Chinese Journal of Analytical Chemistry

基　　金：国家自然科学基金项目(Nos.21802064,21275127);福建省自然科学基金项目(Nos.2018J01435,2019J05108);青岛科技大学肿瘤标志物传感分析教育部重点实验室开放课题资助。

摘　　要：采用水热法合成了具有过氧化氢(H_(2)O_(2))模拟酶活性的金属-有机框架材料MIL-101(Fe)。将MIL-101(Fe)和心肌肌钙蛋白Ⅰ抗体(anti-cTnⅠ)依次通过共价键合法固定在氨基化石墨烯(NH 2-GR)修饰玻碳电极表面,构建了基于MIL-101(Fe)/NH 2-GR复合材料的新型cTnⅠ电化学传感界面。电化学实验结果表明,此传感界面上的anti-cTnⅠ与目标物cTnⅠ的免疫反应可显著降低MIL-101(Fe)对H_(2)O_(2)的电催化性能,从而实现对cTnⅠ的免标记传感分析。在10 fg/mL~0.1μg/mL浓度范围内,传感器催化电流差(ΔI)与cTnⅠ浓度的负对数(-lg C_(cTnⅠ))呈良好的线性关系,线性方程为ΔI(μA)=0.705×lg(C_(cTnⅠ)/(g/mL))-11.2(R=0.995),检出限为3.1 fg/mL(S/N=3)。将所构建的电化学传感器应用于人血清中cTnⅠ的检测,回收率为96.0%~103.0%。此传感器具有良好的选择性和重现性。The metal-organic framework material of MIL-101(Fe)with H_(2)O_(2)mimicking enzyme activity was synthesized by a typical hydrothermal method.MIL-101(Fe)and cardiac troponin Ⅰ antibody(anti-cTnⅠ)were then successively immobilized on the surface of glassy carbon electrode that was pre-modified with amino-modified graphene(NH 2-GR)through the covalent bonding.Thus,a novel MIL-101(Fe)/NH 2-GR-based electrochemical sensing interface for cTnⅠ was constructed.Electrochemical experiments showed that the immunoreaction between anti-cTnⅠ and target cTnⅠ on the sensing interface significantly suppressed the electrocatalytic activity of electrode-confined MIL-101(Fe)to H_(2)O_(2),realizing the label-free analysis of cTnⅠ.Under the optimal conditions,the catalytic current difference(ΔI)and the negative logarithm of the cTnⅠ concentration(-lg C_(cTnⅠ))showed a good linear relationship in the concentration range of 10 fg/mL-0.1μg/mL,and the detection limit was 3.1 fg/mL(S/N=3).The constructed sensor was applicable for detection of cTnⅠ in actual human serum samples,and the recoveries were 96.0%-103.0%.The sensor exhibited good selectivity and reproducibility.

关 键 词：MIL-101(Fe) 过氧化氢模拟酶 计时安培法 心肌肌钙蛋白Ⅰ 免疫反应 

分 类 号：TP212.2[自动化与计算机技术—检测技术与自动化装置] O657.1[自动化与计算机技术—控制科学与工程] R392[理学—分析化学]