Key Laboratory of Functional Small Organic Molecule, Ministry of Education, College of Chemistry and Chemical Engineering, Jiangxi Normal University, 99 Ziyang Road, Nanchang 330022, People's Republic of China.
Sci Rep. 2016 Nov 4;6:36637. doi: 10.1038/srep36637.
Herein, a smart porous material, Cu-hemin metal-organic-frameworks (Cu-hemin MOFs), was synthesized via assembling of Cu with hemin to load glucose oxidase (GOD) for electrochemical glucose biosensing for the first time. The formation of the Cu-hemin MOFs was verified by scanning electron microscopy, X-ray powder diffraction, Fourier transform infrared spectroscopy, N adsorption/desorption isotherms, UV-vis absorption spectroscopy, fluorescence spectroscopy, thermal analysis and electrochemical techniques. The results indicated that the Cu-hemin MOFs showed a ball-flower-like hollow cage structure with a large specific surface area and a large number of mesopores. A large number of GOD molecules could be successfully loaded in the pores of Cu-hemin MOFs to keep their bioactivity just like in a solution. The GOD/Cu-hemin MOFs exhibited both good performance toward oxygen reduction reaction via Cu-hemin MOFs and catalytic oxidation of glucose via GOD, superior to other GOD/MOFs and GOD/nanomaterials. Accordingly, the performance of GOD/Cu-hemin MOFs-based electrochemical glucose sensor was enhanced greatly, showing a wide linear range from 9.10 μM to 36.0 mM and a low detection limit of 2.73 μM. Moreover, the sensor showed satisfactory results in detection of glucose in human serum. This work provides a practical design of new electrochemical sensing platform based on MOFs and biomolecules.
本文首次通过将铜与血红素组装，合成了一种智能多孔材料——Cu-血红素金属有机骨架（Cu-hemin MOFs），用于负载葡萄糖氧化酶（GOD）进行电化学葡萄糖生物传感。通过扫描电子显微镜、X 射线粉末衍射、傅里叶变换红外光谱、N 吸附/解吸等温线、紫外-可见吸收光谱、荧光光谱、热分析和电化学技术验证了 Cu-hemin MOFs 的形成。结果表明，Cu-hemin MOFs 呈现出具有大比表面积和大量中孔的球花状空心笼结构。大量的 GOD 分子可以成功地负载在 Cu-hemin MOFs 的孔中，以保持其生物活性，就像在溶液中一样。GOD/Cu-hemin MOFs 对 Cu-hemin MOFs 中的氧还原反应和 GOD 催化氧化葡萄糖均表现出良好的性能，优于其他 GOD/MOFs 和 GOD/纳米材料。因此，基于 GOD/Cu-hemin MOFs 的电化学葡萄糖传感器的性能得到了极大的提高，显示出从 9.10 μM 到 36.0 mM 的宽线性范围和 2.73 μM 的低检测限。此外，该传感器在人血清中葡萄糖的检测中表现出令人满意的结果。这项工作为基于 MOFs 和生物分子的新型电化学传感平台提供了实用的设计。
