Combined Spectroelectrochemical and Simulated Insights into the Electrogenerated Chemiluminescence Coreactant Mechanism.

Electrogenerated chemiluminescence (ECL) based sensors have the intrinsic advantage of having zero theoretical background signal, derived from the electrochemical initiation of the luminescence process. Since the limit of detection (LOD) for sensors is defined as three times the noise of the background over the sensitivity of the system, further improvement to an ECL based detection limit is tied to improving sensitivity. Enhancing ECL sensitivity can be achieved through optimizing the mechanistic or kinetic performance of the reagents. While the mechanism for many luminophore-coreactant pairs have been established, the kinetics for the competing homogeneous reactions responsible for photon emission have not been directly resolved. This is due to the difficulty in experimentally probing and isolating a single homogeneous reaction while multiple simultaneous heterogeneous and homogeneous reactions are occurring. Combining the techniques of spectroelectrochemistry and finite element modeling, we monitor the homogeneous reactions for the coreactant pair, tris(2,2'-bipyridine)ruthenium(II) (Ru(BPY)32+) and tripropylamine (TPA). Corresponding trends found in the experimental absorbance and theoretical concentration profiles demonstrated that the reaction between Ru(BPY)33+ and TPA• intermediates proceeds significantly faster than the other available pathways. The identification of the oxidized intermediates as the dominant electron transfer pathway implies that the screening of luminophore and coreactant pairs that increase the stability of these kinetically labile intermediates would increase ECL sensitivity and ultimately performance.