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基于还原 CoO 纳米复合材料的氧空位增强过氧化物酶样活性用于 HO 和葡萄糖的比色检测。

Oxygen-Vacancy-Enhanced Peroxidase-like Activity of Reduced CoO Nanocomposites for the Colorimetric Detection of HO and Glucose.

机构信息

College of Chemical Engineering and Environmental Chemistry, Weifang University, Weifang 261061, China.

Weifang Traditional Chinese Hospital, Weifang 261061, China.

出版信息

Inorg Chem. 2020 Mar 2;59(5):3152-3159. doi: 10.1021/acs.inorgchem.9b03512. Epub 2020 Feb 11.

DOI:10.1021/acs.inorgchem.9b03512
PMID:32045227
Abstract

Colorimetric assays have drawn increasing research interest with respect to the quantitative detection of hydrogen peroxide (HO) based on artificial enzymes because of their advantages with respect to natural enzymes, including design flexibility, low cost, and high stability. Regardless, the majority of the artificial enzymes exhibit low affinity to HO with large Michaelis-Menten constants (). This indicates that the catalytic oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) to blue-colored oxTMB requires a high HO concentration, hindering the sensitivity of the colorimetric assay. To address this problem, novel reduced CoO nanoparticles (R-CoO) have been synthesized in this study via a step-by-step procedure using ZIF-67 as the precursor. R-CoO exhibits a considerably enhanced peroxidase-like activity when compared with that exhibited by pristine CoO (P-CoO). The catalytic process in the case of R-CoO occurs in accordance with the typical Michaelis-Menten equation, and the affinity of R-CoO to HO is apparently higher than that of P-CoO. Furthermore, the density functional theory calculations revealed that the introduction of oxygen vacancies to R-CoO enhances its HO adsorption ability and facilitates the decomposition of HO to produce ·OH radicals, resulting in improved peroxidase-like activity. A simple and convenient colorimetric assay has been established based on the excellent peroxidase-like activity of R-CoO for detecting HO in concentrations of 1-30 μM with a detection limit of 4.3 × 10 mol/L (S/N = 3). Furthermore, the R-CoO-based colorimetric method was successfully applied to glucose detection in human serum samples, demonstrating its potential for application in complex biological systems.

摘要

比色法由于其相对于天然酶的优势,包括设计灵活性、低成本和高稳定性,在基于人工酶的定量检测过氧化氢(HO)方面引起了越来越多的研究兴趣。尽管如此,大多数人工酶对 HO 的亲和力较低,米氏常数()较大。这表明 3,3',5,5'-四甲基联苯胺(TMB)的催化氧化为蓝色氧化 TMB 需要高 HO 浓度,这阻碍了比色法的灵敏度。为了解决这个问题,本研究通过使用 ZIF-67 作为前体制备,通过逐步程序合成了新型还原 CoO 纳米粒子(R-CoO)。与原始 CoO(P-CoO)相比,R-CoO 表现出相当增强的过氧化物酶样活性。在 R-CoO 的情况下,催化过程符合典型的米氏方程,并且 R-CoO 对 HO 的亲和力显然高于 P-CoO。此外,密度泛函理论计算表明,向 R-CoO 中引入氧空位增强了其 HO 吸附能力,并促进了 HO 的分解以产生·OH 自由基,从而提高了过氧化物酶样活性。基于 R-CoO 优异的过氧化物酶样活性,建立了一种简单方便的比色法来检测 1-30 μM 浓度范围内的 HO,检测限为 4.3×10-6 mol/L(S/N = 3)。此外,基于 R-CoO 的比色法成功应用于人血清样品中的葡萄糖检测,证明了其在复杂生物体系中应用的潜力。

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