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CeO@NC 纳米酶具有强大的去膦能力:一种用于快速和选择性检测对氧磷的简单比色法测定。

CeO@NC nanozyme with robust dephosphorylation ability of phosphotriester: A simple colorimetric assay for rapid and selective detection of paraoxon.

机构信息

College of Chemistry and Pharmaceutical Sciences, Qingdao Agricultural University, Qingdao, 266109, PR China.

College of Chemistry and Pharmaceutical Sciences, Qingdao Agricultural University, Qingdao, 266109, PR China.

出版信息

Biosens Bioelectron. 2023 Jan 15;220:114841. doi: 10.1016/j.bios.2022.114841. Epub 2022 Oct 26.

DOI:10.1016/j.bios.2022.114841
PMID:36323162
Abstract

Enzyme-mediated dephosphorylation reaction is the important approach to realize the inactivation and detection of hazardous phosphate chemicals. To date, many phosphatases-like nanozymes (e.g., CeO) have demonstrated the catalytic hydrolysis ability of the phosphomonoesters, rather than phosphotriester, and the CeO nanozyme only work under relatively harsh conditions of high temperature, and large dosage. Thus, exploration of efficient nanozymes for the rapid dephosphorylation of phosphotriester under mild conditions remains a challenge. Here, a novel CeO@NC nanozyme is developed with excellent phosphatases-like activity based on substrate synergistic effect, in which, CeO nanoparticles embedded in N-doped carbon (NC) material. Taking paraoxon as the model substrate, such CeO@NC nanozyme can drive rapid dephosphorylation of phosphotriester over a broad temperature range, which not only significantly outperforms natural phosphatases and neat CeO, but also can preserve >80% of the optimal activity after exposure of harsh conditions, such as strong acidic/basic medium, high temperature of up to 80 °C. The excellent catalytic performance could be due to that Ce(IV)/Ce(III) species act as the active sites to realize the polarization and hydrolysis of P-O bond while NC template works as the synergistic group to adsorb the substrate. Furthermore, a simple colorimetric assay is developed for the rapid and selective detection of paraoxon. Overall, this work not only develops a highly efficient phosphatases-like nanozyme via substrate synergetic strategy, but also opens an interesting avenue for the rapid detection of organophosphorus pesticides.

摘要

酶介导的去磷酸化反应是实现危险磷酸盐化学物质失活和检测的重要方法。迄今为止,许多类磷酸酶纳米酶(例如 CeO)已经表现出对磷酸单酯的催化水解能力,而不是对磷酸三酯的催化水解能力,并且 CeO 纳米酶仅在高温和大剂量等相对苛刻的条件下才起作用。因此,探索在温和条件下快速去磷酸化磷酸三酯的高效纳米酶仍然是一个挑战。在这里,基于底物协同效应,开发了一种新型的具有优异类磷酸酶活性的 CeO@NC 纳米酶,其中 CeO 纳米颗粒嵌入在 N 掺杂的碳(NC)材料中。以对氧磷作为模型底物,这种 CeO@NC 纳米酶可以在很宽的温度范围内驱动磷酸三酯的快速去磷酸化,其不仅明显优于天然磷酸酶和纯 CeO,而且在暴露于苛刻条件(如强酸/碱性介质、高达 80°C 的高温)后,仍能保持超过 80%的最佳活性。优异的催化性能可能归因于 Ce(IV)/Ce(III)物种作为活性位点,实现了 P-O 键的极化和水解,而 NC 模板则作为协同基团吸附底物。此外,还开发了一种简单的比色测定法,用于快速和选择性检测对氧磷。总体而言,这项工作不仅通过底物协同策略开发了一种高效的类磷酸酶纳米酶,而且为有机磷农药的快速检测开辟了一条有趣的途径。

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