Takahashi Fumiki, Jin Jiye
Department of Chemistry, Faculty of Science, Shinshu University, 3-1-1 Asahi, Matsumoto, Nagano 390-8621, Japan.
Luminescence. 2008 May-Jun;23(3):121-5. doi: 10.1002/bio.1019.
In this study, electrochemiluminescence (ECL) of Ru(bpy)(3)(2+) (bpy = 2,2'-bipyridyl) using ascorbic acid (H(2)A) as co-reactant was investigated in an aqueous solution. When H(2)A was co-existent in a Ru(bpy)(3)(2+)-containing buffer solution, ECL peaks were observed at a potential corresponding to the oxidation of Ru(bpy)(3)(2+), and the intensity was proportional to H(2)A concentration at lower concentration levels. The formation of the excited state Ru(bpy)(3)(2+) was confirmed to result from the co-reaction between Ru(bpy)(3)(3+)and the intermediate of ascorbate anion radical (A(-)), which showed the maximum ECL at pH = 8.8. It is our first finding that the ECL intensity would be quenched significantly when the concentration of H(2)A was relatively higher, or upon ultrasonic irradiation. In most instances, quenching is observed with four-fold excess of H(2)A over Ru(bpy)(3)(2+). The diffusional self-quenching scheme as well as the possible reaction pathways involved in the Ru(bpy)(3)(2+)-H(2)A ECL system are discussed in this study.
在本研究中,在水溶液中研究了以抗坏血酸(H₂A)作为共反应剂时Ru(bpy)₃²⁺(bpy = 2,2'-联吡啶)的电化学发光(ECL)。当H₂A存在于含Ru(bpy)₃²⁺的缓冲溶液中时,在对应于Ru(bpy)₃²⁺氧化的电位处观察到ECL峰,并且在较低浓度水平下强度与H₂A浓度成正比。已证实激发态Ru(bpy)₃²⁺的形成是由于Ru(bpy)₃³⁺与抗坏血酸阴离子自由基(A⁻)的中间体之间的共反应,其在pH = 8.8时显示出最大ECL。这是我们首次发现当H₂A浓度相对较高或在超声照射时,ECL强度会显著猝灭。在大多数情况下,当H₂A的量超过Ru(bpy)₃²⁺四倍时会观察到猝灭。本研究讨论了Ru(bpy)₃²⁺-H₂A ECL体系中涉及的扩散自猝灭机制以及可能的反应途径。