State Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmaceutical Science, Guangxi Normal University, Guilin, 541004, People's Republic of China.
Anal Bioanal Chem. 2024 Nov;416(27):6021-6031. doi: 10.1007/s00216-024-05234-8. Epub 2024 Mar 9.
The high catalytic activity of Cu-based nanozymes mainly depends on the efficient Fenton-like reaction of Cu/ HO, but Cu cannot exist stably. Trying to find a material that can stably support Cu while promoting the electron cycle of Cu/Cu still faces serious challenges. C is expected to be an ideal candidate to solve this problem due to its unique structure and rich physicochemical properties. Here, we designed and synthesized a C-doped Cu-based nanozyme (termed as C-Cu-Bpy) by loading high catalytic active site Cu onto C and coordinating with 2,2'-bipyridine (Bpy). The single crystal diffraction analysis and a series of auxiliary characterization technologies were used to demonstrate the successful preparation of C-Cu-Bpy. Significantly, the C-Cu-Bpy exhibited superior peroxidase-like activity during the catalytic oxidation of 3,3',5,5'-tetramethylbenzidine (TMB). Then, the catalytic mechanism of C-Cu-Bpy as peroxidase was elucidated in detail, mainly benefiting from the dual function of C. On the one hand, C acted as a carrier to directly support Cu, which has the ability to efficiently decompose HO to produce reactive oxygen species. The other was that C acted as an electron buffer, contributing to promoting the Cu/Cu cycle to facilitate the reaction. Furthermore, a colorimetric sensor for the quantitative analysis of bleomycin was established based on the principle of bleomycin specific inhibition of C-Cu-Bpy peroxidase-like activity, with satisfactory results in practical samples. This study provides a new strategy for the direct synthesis of Cu-based nanozymes with high catalytic performance.
基于铜的纳米酶的高催化活性主要取决于 Cu/HO 的高效类芬顿反应，但 Cu 不能稳定存在。试图寻找一种能够稳定支撑 Cu 同时促进 Cu/Cu 电子循环的材料仍然面临严峻的挑战。由于其独特的结构和丰富的物理化学性质，C 有望成为解决这一问题的理想候选材料。在这里，我们通过将高催化活性位点 Cu 负载到 C 上并与 2,2'-联吡啶（Bpy）配位，设计并合成了一种 C 掺杂的铜基纳米酶（称为 C-Cu-Bpy）。单晶衍射分析和一系列辅助表征技术用于证明 C-Cu-Bpy 的成功制备。显著地，C-Cu-Bpy 在 3,3',5,5'-四甲基联苯胺（TMB）的催化氧化过程中表现出优异的过氧化物酶样活性。然后，详细阐明了 C-Cu-Bpy 作为过氧化物酶的催化机制，主要受益于 C 的双重功能。一方面，C 作为载体直接支撑 Cu，Cu 具有高效分解 HO 产生活性氧的能力。另一方面，C 作为电子缓冲剂，有助于促进 Cu/Cu 循环，促进反应。此外，基于 bleomycin 特异性抑制 C-Cu-Bpy 过氧化物酶样活性的原理，建立了用于定量分析 bleomycin 的比色传感器，在实际样品中取得了令人满意的结果。该研究为直接合成具有高催化性能的铜基纳米酶提供了一种新策略。
