College of Chemistry and Pharmaceutical Sciences, Qingdao Agricultural University, Qingdao 266109, People's Republic of China.
J Agric Food Chem. 2021 Jun 2;69(21):6087-6095. doi: 10.1021/acs.jafc.1c01006. Epub 2021 May 21.
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)]. Through electrostatic interaction, manganese dioxide nanoflakes-[Ru(bpy)] nanocomposites (MnNFs-Ru) are formed and exhibit a weak ECL signal due to the confinement of [Ru(bpy)] in MnNFs-Ru. Interestingly, MnNFs-Ru are capable of recognizing thiols due to the analyte-initiated reduction of MnNFs into Mn and release of [Ru(bpy)] 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 Mn, 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.
鉴于有机磷农药(OPs)与食品安全的相关性,开发用于 OPs 的灵敏可靠传感器非常紧迫。然而,大多数 OP 传感器是基于比色和荧光技术开发的,这些技术受到农业作物中色素和有机酸的颜色和荧光的严重干扰。在此,我们基于二氧化锰和三(2,2'-联吡啶)钌[Ru(bpy)]开发了一种基于无机识别器的均相电化学发光(ECL)传感器,用于高度灵敏和可靠地测定 OPs。通过静电相互作用,形成了二氧化锰纳米片-[Ru(bpy)]纳米复合材料(MnNFs-Ru),由于[Ru(bpy)]在 MnNFs-Ru 中的受限,其表现出较弱的 ECL 信号。有趣的是,MnNFs-Ru 能够识别硫醇,这是由于分析物引发的 MnNFs 还原为 Mn 以及 [Ru(bpy)]从 MnNFs-Ru 释放到溶液中。此外,MnNFs-Ru 用于 OPs 的均相 ECL 测定,其中乙酰胆碱酯酶(AChE)催化乙酰硫代胆碱(ATCh)水解成硫代胆碱,进而将 MnNFs-Ru 中的 MnNFs 分解为 Mn,OPs 抑制 AChE 活性。本研究将无机识别器的应用从比色法/荧光法拓宽到均相 ECL,有效地避免了颜色和荧光的干扰,为开发高性能 OP 传感器开辟了新途径,并为保证 OP 相关食品安全提供了有前途的工具。