Wu Jiahui, Yang Qiaoting, Li Qian, Li Haiyin, Li Feng
College of Chemistry and Pharmaceutical Sciences, Qingdao Agricultural University, Qingdao 266109, People's Republic of China.
Anal Chem. 2021 Mar 2;93(8):4084-4091. doi: 10.1021/acs.analchem.0c05257. Epub 2021 Feb 15.
Traditional peroxidase-like nanozyme-based sensors suffer from self-decomposition and high toxicity of HO, as well as the interference of color from nanozymes themselves and testing samples. In this work, we adopt nanozymes (two-dimension (2D) MnO sheets, manganese dioxide nanosheets (MnNS)) with oxidase-like and peroxidase-like properties as advanced catalysts to develop a novel homogeneous electrochemical sensor for organophosphate pesticides (OPs) using dissolved O as a coreactant without the interference of HO and color. Owing to the large surface area and unique catalytic activity of MnNS, a large amount of tetramethylbenzidine (TMB) is catalyzed oxidation, leading to a significantly declined differential pulse voltammetry (DPV) current. Obviously, MnNS display an excellent response to thiocholine, deriving from the catalyzing hydrolysis of acetylthiocholine (ATCh) by acetylcholinesterase (AChE), which switches a homogeneous electrochemical OP detection process based on the depressing AChE activity with a limit of detection (LOD) of 0.025 ng mL. The as-proposed strategy on using nanozymes with oxidase-like and peroxidase-like properties to develop a homogeneous electrochemical sensor will provide a new pathway for improving the performance of nanozyme-based sensors, and the established MnNS-based homogeneous electrochemical sensor will find more applications for OP residue determination in food samples.
传统的基于过氧化物酶样纳米酶的传感器存在自身分解、过氧化氢毒性高以及纳米酶本身和测试样品颜色干扰等问题。在这项工作中,我们采用具有氧化酶样和过氧化物酶样性质的纳米酶(二维(2D)二氧化锰片,二氧化锰纳米片(MnNS))作为先进催化剂,以溶解氧作为共反应物,开发了一种用于有机磷农药(OPs)的新型均相电化学传感器,避免了过氧化氢和颜色的干扰。由于MnNS的大表面积和独特的催化活性,大量的四甲基联苯胺(TMB)被催化氧化,导致差分脉冲伏安法(DPV)电流显著下降。显然,MnNS对硫代胆碱表现出优异的响应,这源于乙酰胆碱酯酶(AChE)催化乙酰硫代胆碱(ATCh)水解,从而基于抑制AChE活性实现均相电化学OP检测过程,检测限(LOD)为0.025 ng/mL。所提出的利用具有氧化酶样和过氧化物酶样性质的纳米酶开发均相电化学传感器的策略将为提高基于纳米酶的传感器性能提供一条新途径,并且所建立的基于MnNS的均相电化学传感器将在食品样品中OP残留测定中得到更多应用。