Ding Jialian, Su Bin
Institute of Analytical Chemistry, Department of Chemistry, Zhejiang University, Hangzhou, 310058, China.
Chemistry. 2025 Feb 3;31(7):e202403804. doi: 10.1002/chem.202403804. Epub 2024 Nov 27.
The electrochemiluminescence (ECL) of ruthenium(II) tris(2,2'-bipyridyl) (Ru(bpy) ) with tri-n-propylamine (TPrA) as the good coreactant can be unexpectedly enhanced by a weak coreactant, such as triethanolamine (TEOA). First, the intensity of ECL emitted by Ru(bpy) /TPrA can be remarkably amplified by 10.8-fold after adding some amount of TEOA. Moreover, the ECL layer thickness, measured by self-interference spectroscopy, is also doubled. The enhancement far exceeding the superposition of respective contribution of TPrA and TEOA was elucidated by a "chemical oxidation mechanism", in which TEOA⋅ acts as a chemical enhancer to oxidize TPrA in solution and to accelerate significantly the ECL reaction kinetics. This mechanism was proved by single-photon counting experiment and finite element simulations. In addition, the dual-coreactants strategy works well not only in solution with freely diffusive Ru(bpy) , but also on Ru(bpy) -functionalized microbeads, suggesting that ethanolamines could act as cheap, easily available and low-background enhancers for ECL-based bioanalysis and microscopy.
以三正丙胺(TPrA)作为良好共反应剂时,三联吡啶钌(II)(Ru(bpy) )的电化学发光(ECL)可被一种较弱的共反应剂,如三乙醇胺(TEOA)意外增强。首先,加入一定量的TEOA后,Ru(bpy) /TPrA发出的ECL强度可显著放大10.8倍。此外,通过自干涉光谱法测量的ECL层厚度也增加了一倍。通过“化学氧化机制”阐明了这种增强效果远远超过TPrA和TEOA各自贡献的叠加,其中TEOA⋅作为化学增强剂在溶液中氧化TPrA并显著加速ECL反应动力学。该机制通过单光子计数实验和有限元模拟得到证实。此外,双共反应剂策略不仅在Ru(bpy) 自由扩散的溶液中有效,在Ru(bpy) 功能化微珠上也表现良好,这表明乙醇胺可作为基于ECL的生物分析和显微镜检测中廉价、易于获得且背景低的增强剂。