Ministry of Education Key Laboratory of Analysis and Detection for Food Safety, Fujian Provincial Key Laboratory of Analysis and Detection Technology for Food Safety, Department of Chemistry, Fuzhou University, Fuzhou 350002, China.
Talanta. 2011 Jul 15;85(1):339-44. doi: 10.1016/j.talanta.2011.03.063. Epub 2011 Apr 5.
Inhibited Ru(bpy)(3)(2+) electrochemiluminescence by inorganic oxidants is investigated. Results showed that a number of inorganic oxidants can quench the ECL of Ru(bpy)(3)(2+)/tri-n-propylamine (TPrA) system, and the logarithm of the decrease in ECL intensity (ΔI) was proportional to the logarithm of analyte concentrations. Based on which, a sensitive approach for detection of these inorganic oxidants was established, e.g. the log-log plots of ΔI versus the concentration of MnO(4)(-), Cr(2)O(7)(2-) and Fe(CN)(6)(3-) are linear in the range of 1×10(-7) to 3×10(-4)M for MnO(4)(-) and Cr(2)O(7)(2-), and 1×10(-7) to 1×10(-4)M for Fe(CN)(6)(3-), with the limit of detection (LOD) of 8.0×10(-8)M, 2×10(-8)M, and 1×10(-8)M, respectively. A series of experiments such as a comparison of the inhibitory effect of different compounds on Ru(bpy)(3)(2+)/TPrA ECL, ECL emission spectra, UV-Vis absorption spectra etc. were investigated in order to discover how these inorganic analytes quench the ECL of Ru(bpy)(3)(2+)/TPrA system. A mechanism based on consumption of TPrA intermediate (TPrA(·)) by inorganic oxidants was proposed.
研究了无机氧化剂对 Ru(bpy)(3)(2+)电化学发光的抑制作用。结果表明，许多无机氧化剂可以猝灭 Ru(bpy)(3)(2+)/三丙胺（TPrA）体系的 ECL，ECL 强度的降低（ΔI）与分析物浓度的对数成正比。基于此，建立了一种检测这些无机氧化剂的灵敏方法，例如，MnO(4)(-)、Cr(2)O(7)(2-)和 Fe(CN)(6)(3-)的ΔI 与浓度的 log-log 图在 1×10(-7)到 3×10(-4)M 范围内对于 MnO(4)(-)和 Cr(2)O(7)(2-)是线性的，对于 Fe(CN)(6)(3-)是 1×10(-7)到 1×10(-4)M，检出限（LOD）分别为 8.0×10(-8)M、2×10(-8)M 和 1×10(-8)M。为了发现这些无机分析物如何猝灭 Ru(bpy)(3)(2+)/TPrA 体系的 ECL，进行了一系列实验，例如比较不同化合物对 Ru(bpy)(3)(2+)/TPrA ECL 的抑制作用、ECL 发射光谱、UV-Vis 吸收光谱等。提出了一种基于无机氧化剂消耗 TPrA 中间体（TPrA(·)）的机制。
