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

Abstract

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.

Water‐Regulated Mechanisms for Degradation of Pesticides Paraoxon and Parathion by Phosphotriesterase: Insight from QM/MM and MD Simulations

“…Organophosphorus pesticides, such as paraoxon, diazinon, chlorpyrifos, fenitrothion, etc., have been proven to be harmful for the aquatic organisms and mammal animals, especially for the pregnant women and children. [1][2][3] The structures of these organophosphorus pesticides are illustrated in Scheme 1. Among them, the widely-used paraoxon (PON) and parathion (PIN) have relatively strong toxicity to the inactivation of mammalian acetylcholinesterase (AChE) by phosphorylating a serine residue in the active site of AChE.…”

“…Organophosphorus pesticides, such as paraoxon, diazinon, chlorpyrifos, fenitrothion, etc., have been proven to be harmful for the aquatic organisms and mammal animals, especially for the pregnant women and children [1–3] . The structures of these organophosphorus pesticides are illustrated in Scheme 1.…”

Recent Advances in Two-Dimensional Transition Metal Dichalcogenide Nanocomposites Biosensors for Virus Detection before and during COVID-19 Outbreak

“…These superior properties permit them on various sensing mechanisms, including optical sensation through chemiluminescence, surface plasmon resonance (SPR), and electrochemistry for a field-effect transistor (FET, voltage-current under gating control) by p-n junctions for detecting specific biomolecules and gases [54,58,59]. For instance, 2D Mn oxides-based materials exhibit a powerful catalytic property that has been employed as nanoenzymes for catalyzing the hydrolysis of biomolecules via peroxidase-like activity, thereby producing electrochemical/electrochemiluminescence signals as the detection readouts [60][61][62]. While metal oxides may play a more critical role in chemical catalysis and fuel cells, TMDs can be a significant part of sensor developments [63,64].…”

A simple and sensitive liquid chromatography–tandem mass spectrometry method for quantification of multi‐residual pesticides in blood

“…A high concentration of acetylcholine is thought to be responsible for the intense cholinergic effects that may include muscle weakness, muscle twitching, sensory and behavioral disturbances (Parkinson's, Alzheimer's) [6], motor function impairments, and respiratory depression (EPA 2013) [7]. Previous studies have reported several methods for the detection of pesticides, immunoassay [8,9], electrochemiluminescence biosensor [10,11], gas chromatography-mass spectrometry (GC-MS) [12,13], and high-performance liquid chromatography (HPLC) [14,15]. However, these methods lack behind by lengthy sample preparation, low recovery, and reproducibility, limiting their utility as diagnostic tools.…”