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新型 Ru(bpy)(cpaphen)/TPrA/TiO 三元 ECL 体系:以 Mn 替代目标物的高效谷胱甘肽检测平台。

Novel Ru(bpy)(cpaphen)/TPrA/TiO Ternary ECL System: An Efficient Platform for the Detection of Glutathione with Mn as Substitute Target.

机构信息

Key Laboratory of Luminescent and Real-Time Analytical Chemistry (Southwest University), Ministry of Education, College of Chemistry and Chemical Engineering , Southwest University , Chongqing 400715 , P. R. China.

出版信息

Anal Chem. 2019 Mar 5;91(5):3681-3686. doi: 10.1021/acs.analchem.8b05795. Epub 2019 Feb 11.

Abstract

A sensitive electrochemiluminescence (ECL) biosensor was developed for glutathione (GSH) detection based on a novel Ru(bpy)(cpaphen)/TPrA/TiO ternary ECL system with Mn as substitute target for signal amplification. Specifically, the TiO nanoneedles (TiO NNs) were used as the coreaction accelerator for the first time to promote the oxidation process of coreactant tripropylamine (TPrA) in the anode and significantly increase the ECL signal of Ru(bpy)(cpaphen) for an amplified initial signal. Meanwhile, a novel target conversion strategy for GSH was developed by reducing MnO nanosheets to Mn as a substitute target, which played the role of a coenzyme factor for cleaving DNA double strands intercalated with Ru(bpy)(cpaphen) to markedly weaken initial signal. As a result, the novel "on-off" biosensor achieved a sensitive detection of GSH range from 5 μM to 215 μM with a detection limit of 0.33 μM. Importantly, the proposed strategy enriched the application of Ru complex and TPrA ECL system in bioanalytical applications, and provided a new signal amplification strategy for bioactive small molecules.

摘要

基于新型 Ru(bpy)(cpaphen)/TPrA/TiO 三元 ECL 体系,我们开发了一种用于谷胱甘肽(GSH)检测的灵敏电化学发光(ECL)生物传感器。该体系以 Mn 替代目标物进行信号放大。具体来说,首次将 TiO 纳米针(TiO NNs)用作共反应加速剂,以促进阳极中共反应物三丙胺(TPrA)的氧化过程,从而显著提高 Ru(bpy)(cpaphen)的 ECL 信号,实现初始信号的放大。同时,我们开发了一种新颖的 GSH 目标物转换策略,通过将 MnO 纳米片还原为 Mn 替代目标物,充当与 Ru(bpy)(cpaphen)插入的 DNA 双链相互作用的酶因子,从而显著削弱初始信号。因此,新型“开-关”生物传感器实现了对 5 μM 至 215 μM 的 GSH 的灵敏检测,检测限低至 0.33 μM。重要的是,该策略丰富了 Ru 配合物和 TPrA ECL 体系在生物分析中的应用,并为生物活性小分子提供了新的信号放大策略。

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