Although the clinical use of immunoassays based on the oxidative-reduction electrochemiluminescence (ECL) of tris(2,2'-bipyridine)ruthenium (II)/tri-n-propylamine has been a great success, elucidation of the ECL generation mechanism still remains unsatisfactory. We report here our experimental observations of long-lived luminescence that remains detectable for several seconds after termination of electrochemical heterogeneous oxidation. Long-lived luminescence was observed in both a surfactant-free buffer and a surfactant-containing broadly used commercial buffer under different conditions. The slow decay of emission seems to have been unnoticed in previous ECL mechanistic studies. Within the frame of the reaction schemes so far proposed, its origin is inconclusively ascribed to the reductive-oxidation process of ruthenium (II) complex, that is Ru(bpy)3 2+ → Ru(bpy)3 1+ → Ru(bpy)3 2+ * → Ru(bpy)3 2+ with the involvement of the tri-n-propylamine-derived radical cation. It is anticipated that long-lived ECL will suggest a research approach to separate some homogeneous reactions from the complicated reaction system and therefore help to resolve the mechanistic mystery.

中文翻译：

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钌（II）配合物/三正丙胺在水溶液中的长寿命电化学发光。

尽管基于三（2,2'-联吡啶）钌（II）/三正丙胺的氧化还原电化学发光（ECL）的免疫测定的临床应用取得了巨大的成功，但仍需要阐明ECL的产生机理不满意。我们在这里报告了长寿命发光的实验观察结果，该现象在电化学异质氧化终止后几秒钟内仍可检测到。在无表面活性剂的缓冲液和广泛使用的含表面活性剂的市售缓冲液中，在不同条件下均观察到长寿命的发光。在以前的ECL机理研究中似乎没有注意到排放的缓慢衰减。在到目前为止提出的反应方案的框架内，其起源并不确定地归因于钌（II）络合物的还原-氧化过程，就是Ru（bpy）3 2+→Ru（bpy）3 1+→Ru（bpy）3 2+ *→Ru（bpy）3 2+，其中三正丙胺衍生的自由基阳离子参与其中。预期寿命长的ECL将提出一种研究方法，以从复杂的反应系统中分离出一些均相反应，从而有助于解决机理上的奥秘。