School of Pharmacy, Hubei University of Science and Technology, Xianning 437100, China.
Hubei Key Laboratory of Radiation Chemistry and Functional Materials, Hubei University of Science and Technology, Xianning 437100, China.
Molecules. 2023 Jul 26;28(15):5649. doi: 10.3390/molecules28155649.
Constructing high-performance glucose sensors is of great significance for the prevention and diagnosis of diabetes, and the key is to develop new sensitive materials. In this paper, a series of NiCo-L MOFs (L = HBPDC: 4,4'-biphenyldicarboxylic acid; HNDC: 2,6-naphthalenedicarboxylic acid; HBDC: 1,4-benzenedicarboxylic acid) were synthesized by a room temperature stirring method. The effects of metal centers and ligands on the structure, compositions, electrochemical properties of the obtained NiCo-L MOFs were characterized, indicating the successful preparation of layered MOFs with different sizes, stacking degrees, electrochemical active areas, numbers of exposed active sites, and glucose catalytic activity. Among them, NiCo-BDC exhibits a relatively thin and homogeneous plate-like morphology, and the NiCo-BDC modified glassy carbon electrode (NiCo-BDC/GCE) has the highest electrochemical performance. Furthermore, the mechanism of the enhanced glucose oxidation signal was investigated. It was shown that glucose has a higher electron transfer capacity and a larger apparent catalytic rate constant on the NiCo-BDC/GCE surface. Therefore, tunable non-enzymatic glucose electrochemical sensing was carried out by regulating the metal centers and ligands. As a result, a high-sensitivity enzyme-free glucose sensing platform was successfully constructed based on the NiCo-BDC/GCE, which has a wide linear range of 0.5-2899.5 μM, a low detection limit of 0.29 μM (S/N = 3), and a high sensitivity of 3925.3 μA mM cm. Much more importantly, it was also successfully applied to the determination of glucose in human serum with satisfactory results, demonstrating its potential for glucose detection in real samples.
构建高性能葡萄糖传感器对于糖尿病的预防和诊断具有重要意义，关键在于开发新型敏感材料。本文采用室温搅拌法合成了一系列 NiCo-L MOFs（L=HBPDC：4,4'-联苯二甲酸；HNDC：2,6-萘二甲酸；HBDC：1,4-苯二甲酸）。研究了金属中心和配体对所得 NiCo-L MOFs 的结构、组成、电化学性能的影响，表明成功制备了具有不同尺寸、堆积度、电化学活性面积、暴露活性位数量和葡萄糖催化活性的层状 MOFs。其中，NiCo-BDC 呈现出相对较薄且均匀的片状形态，NiCo-BDC 修饰的玻碳电极（NiCo-BDC/GCE）具有最高的电化学性能。此外，还研究了增强葡萄糖氧化信号的机制。结果表明，在 NiCo-BDC/GCE 表面，葡萄糖具有更高的电子转移能力和更大的表观催化速率常数。因此，通过调节金属中心和配体，实现了可调谐的非酶葡萄糖电化学传感。由此，成功构建了基于 NiCo-BDC/GCE 的高灵敏度无酶葡萄糖传感平台，其线性范围为 0.5-2899.5 μM，检测限低至 0.29 μM（S/N=3），灵敏度高达 3925.3 μA mM cm。更重要的是，该平台还成功应用于人血清中葡萄糖的测定，结果令人满意，证明了其在实际样品中葡萄糖检测的潜力。
