Electrochemiluminescence of fluorescein in alkaline solution at a polycrystalline gold electrode

The electrochemiluminescence (ECL) behavior of fluorescein at a polycrystalline gold electrode was studied under conventional cyclic voltammetric conditions. Five ECL peaks were observed at 0.94 (ECL-1), 1.51 (ECL-2), 1.34 (ECL-3), −0.06 (ECL-4), −0.73 to −1.11 V (ECL-5, a broad weak wave) (vs. SCE), respectively, on the curve of ECL intensity versus potential. These ECL peaks were found to depend on the pH of the solution, supporting electrolyte, potential scan ranges and directions. The emitter of ECL peaks was identified as fluorescein or eosin Y produced on the electrode by analyzing the ECL spectra and fluorescence spectra. The mechanisms for ECL peaks have been proposed due to the reactions of fluorescein and the electro-oxidation product of fluorescein with various oxygen-containing species in the solution or electrogenerated at different applied potentials such as O2, O2·−, HO2−, and BrO−. Singlet molecular oxygen was generated during the reactions and transferred its energy to the ECL emitter such as fluorescein or eosin Y, emitting light.