College of Chemistry and Pharmaceutical Sciences, Qingdao Agricultural University, Qingdao 266109, People's Republic of China.
Anal Chem. 2022 Mar 1;94(8):3669-3676. doi: 10.1021/acs.analchem.1c05300. Epub 2022 Feb 15.
Common homogeneous electrochemical (HEC) sensors usually suffer from the drawbacks of high background signal, low signal-to-noise ratio, and even false positive results due to the preaddition of electroactive substances. Thus, it is necessary to develop novel HEC sensors based on in situ generation of electroactive substances to overcome these shortcomings, which, however, is underexplored. In this work, two-dimensional (2D) nanozymes, i.e., cobalt-doped 2D TiC MXene nanosheets (CMNSs), with excellent peroxidase-like properties were utilized to develop HEC sensors based on the in situ generation of electroactive substances for organophosphate pesticides (OPs) detection. The 2D CMNSs were synthesized via a template-directed wet chemical approach and displayed outstanding features of hydrophilia and water dispersibility, which could catalyze the oxidation of -phenylenediamine (OPD) to generate significantly increased reduction current. Interestingly, the 2D CMNSs with peroxidase-like properties exhibited a unique response to thiol compounds and were thus employed as highly efficient catalysts to develop HEC sensors for OPs based on the hydrolysis of acetylthiocholine (ATCh) to form thiocholine catalyzed by acetylcholinesterase (AChE) and the inhibition of AChE activity by OPs. The recovery for OPs analysis of pakchoi extract solutions ranged from 97.4% to 103.3%. The as-proposed HEC sensor based on in situ generation of electroactive substances will provide a new way for the development of high-performance electrochemical sensors and demonstrate potential applicability for the determination of pesticide residues in real samples.
常见的均相电化学 (HEC) 传感器通常由于预添加电活性物质而存在背景信号高、信噪比低甚至出现假阳性结果等缺点。因此,有必要开发基于电活性物质原位生成的新型 HEC 传感器来克服这些缺点,但这方面的研究还很少。在这项工作中,我们利用具有类过氧化物酶性质的二维(2D)纳米酶,即钴掺杂二维 TiC MXene 纳米片(CMNSs),开发了基于电活性物质原位生成的用于有机磷农药(OPs)检测的 HEC 传感器。2D CMNSs 是通过模板导向的湿法化学方法合成的,具有出色的亲水性和水分散性,可催化 -苯二胺(OPD)的氧化生成明显增加的还原电流。有趣的是,具有类过氧化物酶性质的 2D CMNSs 对硫醇化合物表现出独特的响应,因此被用作高效催化剂,用于开发基于乙酰硫代胆碱(ATCh)在乙酰胆碱酯酶(AChE)作用下水解生成硫代胆碱以及 OPs 对 AChE 活性的抑制作用的 HEC 传感器来检测 OPs。对白菜提取物溶液中 OPs 的分析回收率在 97.4%至 103.3%之间。基于电活性物质原位生成的 HEC 传感器为高性能电化学传感器的发展提供了一种新方法,并展示了在实际样品中测定农药残留的潜在应用前景。