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通过对磷酸银加氧酶纳米酶催化活性的负反馈抑制实现对毒死蜱的比色传感。

Colorimetric sensing of chlorpyrifos through negative feedback inhibition of the catalytic activity of silver phosphate oxygenase nanozymes.

作者信息

Kushwaha Amisha, Singh Gajendar, Sharma Manu

机构信息

Central University of Gujarat Gandhinagar Gujarat-382030 India

出版信息

RSC Adv. 2020 Apr 1;10(22):13050-13065. doi: 10.1039/c9ra10719c. eCollection 2020 Mar 30.

Abstract

Intensive use of organophosphate chlorpyrifos pesticides in farming has become a serious issue due to their harmful effects on living beings. Most fruits, vegetables and soil contain chlorpyrifos, and it cannot be rinsed out completely by water washing. Therefore, a selective and sensitive detection of chlorpyrifos is significant. In the present study, the intriguing oxidase-mimicking activity of AgPO nanoparticles (NPs) is explored for the fast and selective detection of chlorpyrifos pesticides. AgPO NPs exhibit several advantages, such as great catalytic efficiency, high stability, monodispersity and reusability, over other expensive nanozymes a facile one-step sensing. The size, shape, crystal planes and diffraction patterns of the AgPO NPs were observed FESEM and HR-TEM. The surface properties and oxidation states were analyzed XPS technique. AgPO NPs possess intrinsic excellent oxidase-mimicking properties against 3,3',5,5'-tetramethylbezidyne (TMB). When chlorpyrifos and AgPO NP nanozymes come in proper orientation proximity, chlorpyrifos is oxidized. The oxidized chlorpyrifos produces sulfide ions and chlorpyrifos oxon. The produced sulfide ions in the reaction system interact with AgPO NPs and inhibit their catalytic activity by feedback inhibition. Indeed, neither any catalytic site is left to oxidize TMB nor any blue colour appears. Thus, this feedback inhibition phenomenon senses chlorpyrifos pesticides. The calculated limit of detection (LOD) for the standard chlorpyrifos is ∼9.97 ppm, and the efficacy of the AgPO NPs calculated in terms of the value was found to be 0.15 mM. A real sample analysis was carried out by the standard addition method with two soil samples collected from Pethapur and Chiloda villages.

摘要

由于有机磷毒死蜱农药对生物的有害影响,其在农业中的大量使用已成为一个严重问题。大多数水果、蔬菜和土壤中都含有毒死蜱,且无法通过水洗完全冲洗掉。因此,选择性和灵敏地检测毒死蜱具有重要意义。在本研究中,探索了AgPO纳米颗粒(NPs)有趣的类氧化酶活性,用于快速、选择性地检测毒死蜱农药。与其他昂贵的纳米酶相比,AgPO NPs具有催化效率高、稳定性好、单分散性和可重复使用性等优点,可实现简便的一步传感。通过场发射扫描电子显微镜(FESEM)和高分辨率透射电子显微镜(HR-TEM)观察了AgPO NPs的尺寸、形状、晶面和衍射图案。采用X射线光电子能谱(XPS)技术分析了其表面性质和氧化态。AgPO NPs对3,3',5,5'-四甲基联苯胺(TMB)具有内在的优异类氧化酶性质。当毒死蜱和AgPO NP纳米酶以适当的方向接近时,毒死蜱被氧化。氧化的毒死蜱产生硫离子和毒死蜱氧磷。反应体系中产生的硫离子与AgPO NPs相互作用,并通过反馈抑制作用抑制其催化活性。实际上,既没有任何催化位点可用于氧化TMB,也没有出现任何蓝色。因此,这种反馈抑制现象可检测毒死蜱农药。标准毒死蜱的计算检测限(LOD)约为9.97 ppm,以米氏常数(Km)值计算的AgPO NPs的效能为0.15 mM。采用标准加入法对从佩塔普尔村和奇洛达村采集的两个土壤样品进行了实际样品分析。

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