高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (1): 78-86.doi: 10.7503/cjcu20190485

• 分析化学 • 上一篇    下一篇

基于多壁碳纳米管增敏材料的辣根过氧化物酶分子印迹电化学传感器的制备及对H2O2的检测

滕渝,杨绍明(),柏朝朋,张剑   

  1. 华东交通大学材料科学与工程学院, 南昌 330013
  • 收稿日期:2019-09-10 出版日期:2019-12-21 发布日期:2019-10-29
  • 通讯作者: 杨绍明 E-mail:yangsm79@163.com
  • 基金资助:
    国家自然科学基金资助批准号:(21465012)

Preparation of HRP Molecularly Imprinted Electrochemical Sensor with Multi-walled Carbon Nanotubes as Sensitizing Materials and the Detection of H2O2

TENG Yu,YANG Shaoming(),BAI Chaopeng,ZHANG Jian   

  1. School of Material Science and Engineering, East China Jiaotong University, Nanchang 330013, China
  • Received:2019-09-10 Online:2019-12-21 Published:2019-10-29
  • Contact: Shaoming YANG E-mail:yangsm79@163.com
  • Supported by:
    ? Supported by the National Natural Science Foundation of China(21465012)

摘要:

以辣根过氧化物酶(HRP)为蛋白质模板分子, 邻苯二胺(o-PD)为聚合单体, 首先将预先羧基化的多壁碳纳米管(MWCNTs)通过阶跃电位法电沉积在玻碳电极上作为增敏材料, 然后在该电极上电聚合含HRP的邻苯二胺电沉积液形成一层聚合膜, 去除模板化合物后, 制得对HRP具有特异性识别能力的分子印迹聚合物(MIPs)膜; 利用聚邻苯二胺(POPD)的自探针效应构建了分子印迹电化学传感器. 该传感器的响应电流与HRP浓度在1.0×10 -10~1.0×10 -5 mg/mL范围内有良好的线性关系, 相关系数为0.991, 检出限为1.5×10 -11 mg/mL(S/N=3); 该传感器的响应电流与H2O2浓度在4.0×10 -7~1.4×10 -5 mol/L范围内有良好的线性响应, 相关系数为0.992, 检出限为2.6×10 -7 mol/L(S/N=3), 将该传感器用于实际样品H2O2的检测, 回收率在91.2%~97.1%之间. 建立了基于MIPs膜的HRP和H2O2双分析物传感器的制备方法, 该方法可应用于酶及其酶促底物双分析物传感器.

关键词: 分子印迹聚合物, 自探针, 分子印迹电化学酶传感器, 辣根过氧化物酶, 过氧化氢

Abstract:

Firstly, the pre-carboxylated multi-walled carbon nanotubes(MWCNTs) were electrodeposited on the surface of the glassy carbon electrode as sensitivity-enhanced materials. Then, a layer of polymeric film was formed on the modified electrode through the electropolymerization in the o-phenylenediamine(o-PD) monomer solution containing horseradish peroxidase template molecule. After removing the templates, the molecularly imprinted polymer membrane with specific recognition ability towards horseradish peroxidase was formed. The prepared molecularly imprinted electrochemical sensor had a good linear relationship with horseradish peroxidase(HRP) in the concentration range of 1.0×10 -10—1.0×10 -5 mg/mL, the correlation coefficient was 0.991, and the detection limit was 1.5×10 -11 mg/mL(S/N=3); and also exhibited a good linear response for H2O2 in the concentration range of 4.0×10 -7—1.4×10 -5 mol/L, with a correlation coefficient of 0.992 and a detection limit of 2.6×10 -7 mol/L(S/N=3). And this molecularly imprinted sensor was used for the detection of the actual sample, the recovery rate is between 91.2% and 97.1%. HRP and H2O2 bi-analyte sensor based on MIP film was successfully developed in this work. The developed method can also be applicable for enzyme and its enzymatic substrate bi-analyte sensor.

Key words: Molecularly imprinted polymer, Self-probe, Molecularly imprinted electrochemical enzyme sensor, Horseradish peroxidase, Hydrogen peroxide