Novel Ru(bpy)₂(cpaphen)²⁺/TPrA/TiO₂ Ternary ECL System: An Efficient Platform for the Detection of Glutathione with Mn²⁺ as Substitute Target

Abstract

A sensitive electrochemiluminescence (ECL) biosensor was developed for glutathione (GSH) detection based on a novel Ru(bpy)₂(cpaphen)²⁺/TPrA/TiO₂ ternary ECL system with Mn²⁺ as substitute target for signal amplification. Specifically, the TiO₂ nanoneedles (TiO₂ 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)₂(cpaphen)²⁺ for an amplified initial signal. Meanwhile, a novel target conversion strategy for GSH was developed by reducing MnO₂ nanosheets to Mn²⁺ as a substitute target, which played the role of a coenzyme factor for cleaving DNA double strands intercalated with Ru(bpy)₂(cpaphen)²⁺ 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.