State Key Laboratory of Green Pesticide, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, Wuhan 430079, P. R. China.
Institute of Nano-Science and Technology, College of Physical Science and Technology, Central China Normal University, Wuhan 430079, P. R. China.
Nano Lett. 2024 Aug 14;24(32):9974-9982. doi: 10.1021/acs.nanolett.4c02594. Epub 2024 Jul 31.
Various applications related to glucose catalysis have led to the development of functional nanozymes with glucose oxidase (GOX)-like activity. However, the unsatisfactory catalytic activity of nanozymes is a major challenge for their practical applications due to their inefficient hydrogen and electron transfer. Herein, we present the synthesis of AuFe/polydopamine (PDA) superparticles that exhibit photothermal-enhanced GOX-like activity. Experimental investigations and theoretical calculations reveal that the glucose oxidation process catalyzed by AuFe/PDA follows an artificial-cofactor-mediated hydrogen atom transfer mechanism, which facilitates the generation of carbon-centered radical intermediates. Rather than depending on charged Au surfaces for thermodynamically unstable hydride transfer, Fe(III)-coordinated PDA with abundant amino and phenolic hydroxyl groups serves as cofactor mimics, facilitating both hydrogen atom and electron transfer in the catalytic process. Finally, leveraging the photothermal-enhanced GOX-like and catalase-like activities of AuFe/PDA, we establish a highly sensitive and accurate point-of-care testing blood glucose determination with exceptional anti-jamming capabilities.
各种与葡萄糖催化相关的应用促使具有葡萄糖氧化酶（GOX）样活性的功能纳米酶得到发展。然而，由于其氢和电子转移效率低下，纳米酶的催化活性不理想，这是其实际应用的主要挑战。在此，我们提出了合成具有光热增强 GOX 样活性的 AuFe/聚多巴胺（PDA）超粒子的方法。实验研究和理论计算表明，AuFe/PDA 催化的葡萄糖氧化过程遵循人工辅因子介导的氢原子转移机制，有利于生成碳中心自由基中间体。该过程不是依赖带电荷的 Au 表面进行热力学不稳定的氢化物转移，而是利用富含氨基和酚羟基的 Fe(III)配位的 PDA 作为辅因子模拟物，促进催化过程中的氢原子和电子转移。最后，利用 AuFe/PDA 的光热增强 GOX 样和过氧化物酶样活性，我们建立了一种具有高度灵敏性和准确性的即时检测血糖仪，具有出色的抗干扰能力。
