物理化学学报 >> 2011, Vol. 27 >> Issue (01): 233-240.doi: 10.3866/PKU.WHXB20110125

材料物理化学 上一篇    下一篇

氨基吡啶修饰碳纳米管的制备及其与辣根过氧化酶的相互作用

郝平1, 高云燕1, 欧植泽1, 李嫕2, 王中丽1, 王雪松2   

  1. 1. 西北工业大学理学院应用化学系, 西安710072;
    2. 中国科学院理化技术研究所,光化学转换与功能材料重点实验室, 北京 100190
  • 收稿日期:2010-08-17 修回日期:2010-11-23 发布日期:2010-12-31
  • 通讯作者: 高云燕,欧植泽 E-mail:gaoyunyan@nwpu.edu.cn, ouzhize@nwpu.edu.cn
  • 基金资助:

    教育部留学回国人员科研启动基金(N9YK0003, N9YK0005), 西北工业大学基础研究基金(NPU-FFR-JC200822)及西北工业大学翱翔之星项目(07XE0152)资助

Preparation of Aminopyridine Grafted Carbon Nanotube and Its Interaction with Horseradish Peroxidase

HAO Ping1, GAO Yun-Yan1, OU Zhi-Ze1, LI Yi2, WANG Zhong-Li1, WANG Xue-Song2   

  1. 1. Department of Applied Chemistry, School of Science, Northwestern Polytechnical University, Xi′an 710072, P. R. China;
    2. Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry,Chinese Academy of Sciences, Beijing 100190, P. R. China
  • Received:2010-08-17 Revised:2010-11-23 Published:2010-12-31
  • Contact: GAO Yun-Yan, OU Zhi-Ze E-mail:gaoyunyan@nwpu.edu.cn, ouzhize@nwpu.edu.cn
  • Supported by:

    The project was supported by the Scientific Research Foundation for the Returned Overseas Chinese Scholars, Ministry of Education, China (N9YK0003, N9YK0005), Northwestern Polytechnical University (NPU) Foundation for Fundamental Research, China (NPU-FFR-JC200822), and Ao Xiang Foundation for Youth NPU Teachers, China (07XE0152).

摘要:

用重铬酸钾氧化法获得了表面羧基化的碳纳米管(MWCNT-COOH), 进一步通过酰胺化反应合成了2-氨基吡啶修饰的碳纳米管(MWCNT-AP). 利用傅里叶变换红外(FT-IR)光谱、核磁共振氢谱(1H NMR)、X射线光电子能谱(XPS)等对合成的碳纳米管进行了表征. 透射电镜(TEM)结果表明MWCNT-COOH在乙醇等极性溶剂中易于簇集, 而MWCNT-AP 溶液具有良好的分散性和稳定性. 辣根过氧化酶(HRP)可通过物理作用吸附于MWCNT-AP 和MWCNT-COOH表面, 负载量分别为187.5 和153.0 μg·mg-1. HRP被吸附后, 其Soret 带明显红移, 说明HRP 与MWCNT-AP 或MWCNT-COOH 的结合位点位于血红素辅基的附近. 圆二色谱结果表明MWCNT-AP 对HRP的二级结构也有一定影响. 酶动力学实验结果表明MWCNT-AP 能有效地吸附HRP及其底物3,3',5,5'-四甲基联苯胺(TMB), 并使HRP的酶催化反应最大速率(Vmax)显著提高.

关键词: 碳纳米管, 表面修饰, 辣根过氧化酶, 酶催化活性, 氢键作用

Abstract:

Carboxylic-functionalized multiwalled carbon nanotube (MWCNT-COOH) is obtained by oxidation with potassium bichromate and further modification by amide condensation afforded aminopyridine-grafted MWCNT (MWCNT-AP). The MWCNT-AP was characterized by Fourier transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance spectroscopy (1H-NMR) and X-ray photoelectron spectroscopy (XPS). Transmission electron microscopy (TEM) results suggest that MWCNTCOOH aggregates in ethanol and that MWCNT-AP is stable and well dispersed in solution. Horseradish peroxidase (HRP) physically adsorbed onto the surfaces of MWCNT-AP and MWCNT-COOH and the adsorption amounts were 187.5 and 153.0 μg·mg-1, respectively. UV-Vis spectra showed that the Soret band of HRP red-shifted markedly after adsorption onto MWCNT-AP or MWCNT-COOH indicating that the binding site of MWCNT-AP or MWCNT-COOH is near the heme pocket of HRP. Circular dichroism spectral results demonstrate that the secondary structure of HRP is influenced by MWCNT-AP. Enzyme-kinetic studies show that MWCNT-AP may adsorb HRP and its substrate 3,3',5,5'-tetramethylbenzidine (TMB) effectively, and the maximum reaction rate (Vmax) of HRP increases significantly after interaction with MWCNT-AP.

Key words: Carbon nanotube, Surface functionalization, Horseradish peroxidase, Catalytic activity of enzyme, Hydrogen bonding

MSC2000: 

  • O647