Adamson Natasha S, Blom Steven J, Doeven Egan H, Connell Timothy U, Hadden Callum, Knežević Sara, Sojic Neso, Fracassa Alessandro, Valenti Giovanni, Paolucci Francesco, Ding Jialian, Wang Yafeng, Su Bin, Hua Carol, Francis Paul S
Centre for Sustainable Bioproducts, Faculty of Science, Engineering and Built Environment, Deakin University, Geelong, Victoria, 3220, Australia.
UMR 5255, CNRS, Bordeaux INP, Institut des Sciences Moléculaires, University of Bordeaux, 33607, Pessac, France.
Angew Chem Int Ed Engl. 2024 Dec 9;63(50):e202412097. doi: 10.1002/anie.202412097. Epub 2024 Oct 29.
A sulfonated tris(1-phenylpyrazolato)iridium(III) complex ([Ir(sppz)]) serves as a proof-of-concept non-emissive enhancer of the widely used ECL detection system of tris(2,2'-bipyridine)ruthenium(II) ([Ru(bpy)]) with tri-n-propylamine (TPrA) co-reactant, acting through electrocatalysis of TPrA oxidation and efficient chemi-excitation of the luminophore. Using self-interference ECL spectroscopy, we show that the enhancer extends diffusion of the required electrogenerated precursors from the electrode surface. Previously reported enhancement through these pathways has been confounded by the inherent ECL of the enhancer, but the increase in [Ru(bpy)] ECL intensity using [Ir(sppz)] was obtained without its concomitant emission. The most prominent enhancement (11-fold) occurred at low potentials associated with the 'indirect' co-reactant ECL pathway, which translated to between 2- and 6-fold enhancement when the luminophore was immobilised on microbeads as a general model for enhanced ECL assays.
一种磺化三（1-苯基吡唑）铱（III）配合物（[Ir(sppz)]）作为概念验证的非发光增强剂，用于广泛使用的三联吡啶钌（II）（[Ru(bpy)]）与三正丙胺（TPrA）共反应物的电化学发光（ECL）检测系统，其作用方式是通过TPrA氧化的电催化和发光体的高效化学激发。使用自干扰ECL光谱，我们表明该增强剂扩展了所需电生前驱体从电极表面的扩散。以前通过这些途径报道的增强作用因增强剂固有的ECL而混淆，但使用[Ir(sppz)]时[Ru(bpy)]的ECL强度增加是在其不伴随发射的情况下获得的。最显著的增强（11倍）发生在与“间接”共反应物ECL途径相关的低电位下，当发光体固定在微珠上作为增强ECL分析的通用模型时，这转化为2至6倍的增强。
