Abstract
The growing demand for analytical methods for the detection of biological analytes has stimulated a renewed interest in electrochemical reaction sequences producing an electronically excited species prone to emit a photon upon return to the ground state, a process called electrogenerated chemiluminescence (ECL). Both known types of ECL mechanisms, the so-called annihilation and coreactant ECL, are of importance in physical chemistry, but it is the fact that many luminophore/coreactant pairs may include biological amines as coreactants that has made ECL the method of choice for bioanalytical purposes owing to its high sensitivity and immunity to noise. In this chapter we present theoretical analyses and approaches for numerical simulation of typical ECL systems of both types that help reveal limiting factors controlling the intensity of ECL emission and ways to quantitatively optimise such systems to enhance their analytical efficiency.