Inorganic Recognizer-Assisted Homogeneous Electrochemiluminescence Determination of Organophosphorus Pesticides via Target-Controlled Emitter Release

摘要

Given the relevance of organophosphorus pesticides (OPs) with food safety, it is highly urgent to develop sensitive and reliable sensors for OPs. However, most of the OP sensors are developed based on colorimetric and fluorescent techniques, which are limited to severe interference of color and fluorescence from pigments and organic acids in agricultural crops. Herein, we develop an inorganic recognizer-based homogeneous electrochemiluminescence (ECL) sensor for the highly sensitive and credible determination of OPs based on manganese dioxide and tris(2,2'-bipyridine)ruthenium [Ru(bpy)(3)](2+). Through electrostatic interaction, manganese dioxide nanoflakes-[Ru(bpy)(3)](2+) nanocomposites (MnNFs-Ru) are formed and exhibit a weak ECL signal due to the confinement of [Ru(bpy)(3)](2+) in MnNFs-Ru. Interestingly, MnNFs-Ru are capable of recognizing thiols due to the analyte-initiated reduction of MnNFs into Mn2+ and release of [Ru(bpy)(3)](2+) from MnNFs-Ru into solution. Further, MnNFs-Ru are employed for the homogeneous ECL determination of OPs, where acetylcholinesterase (AChE) catalyzes the hydrolysis of acetylthiocholine (ATCh) into thiocholine, which in turn decomposes MnNFs of MnNFs-Ru into Mn2+, and OPs inhibit AChE activity. This study widens the application of inorganic recognizers from colorimetry/fluorescence to homogeneous ECL and effectively avoids the interference of color and fluorescence, opening up a new path to the development of high-performance OP sensors and supplying a promising tool for guaranteed OP-related food safety.