Towards Determining Kinetics of Annihilation Electrogenerated Chemiluminescence by Concentration-Dependent Luminescent Intensity

作     者：Klaus Mathwig Neso Sojic 

作者机构：Groningen Research Institute of PharmacyPharmaceutical AnalysisUniversity of GroningenP.O.Box 1969700 AG GroningenThe Netherlands Bordeaux INPUniv.BordeauxCNRSUMR 5255Site ENSCBP33607 PessacFrance Department of ChemistrySouth Ural State UniversityChelyabinsk 454080Russian Federation 

出 版 物：《Journal of Analysis and Testing》 (分析检测（英文）)

年 卷 期：2019年第3卷第2期

页      面：160-165页

核心收录：

学科分类：0830[工学-环境科学与工程（可授工学、理学、农学学位）] 07[理学] 0817[工学-化学工程与技术] 0804[工学-仪器科学与技术] 0805[工学-材料科学与工程（可授工学、理学学位）] 0703[理学-化学] 070202[理学-粒子物理与原子核物理] 0702[理学-物理学] 

主　　题：Electrogenerated chemiluminescence Annihilation Mechanisms Ion-annihilation kinetics Redox cycling Nanogap transducer 

摘      要：In ion-annihilation electrochemiluminescence(ECL),luminophore ions are generated by oxidation as well as reduction at electrodes surfaces,and subsequently recombine into an electronically excited state,which emits light.The intensity of the emitted light is often limited by the kinetic rate of recombination of the luminophore ion species.Recombination or annihilation rates are high ranging up to approximately 10^(10) M^(−1) s^(−1) and can be difficult to determine using scanning electrochemical microscopy or high-frequency oscillations of an electrode potential.Here,we propose determining annihilation kinetics by measuring the relative change of the emitted light intensity as a function of luminophore concentration.Using finite element simulations of annihilation ECL in a geometry of two closely spaced electrodes biased at constant potentials,we show that,with increasing concentrations,luminescence intensity crosses over from a quadratic dependence on concentration to a linear regime-depending on the rate of annihilation.Our numerical results are applicable to scanning electrochemical microscopy as well as nanofluidic electrochemical devices to determine fast ion-annihilation kinetics.