Electrochemiluminescence


Electrochemiluminescence or electrogenerated chemiluminescence is a kind of luminescence produced during electrochemical reactions in solutions. In electrogenerated chemiluminescence, electrochemically generated intermediates undergo a highly exergonic reaction to produce an electronically excited state that then emits light upon relaxation to a lower-level state. This wavelength of the emitted photon of light corresponds to the energy gap between these two states. ECL excitation can be caused by energetic electron transfer reactions of electrogenerated species. Such luminescence excitation is a form of chemiluminescence where one/all reactants are produced electrochemically on the electrodes.
ECL is usually observed during application of potential to electrodes of electrochemical cell that contains solution of luminescent species in aprotic organic solvent.
In organic solvents both oxidized and reduced forms of luminescent species can be produced at different electrodes simultaneously or at a single one by sweeping its potential between oxidation and reduction. The excitation energy is obtained from recombination of oxidized and reduced species.
In aqueous medium, which is mostly used for analytical applications, simultaneous oxidation and reduction of luminescent species is difficult to achieve due to electrochemical splitting of water itself so the ECL reaction with the coreactants is used. In the later case luminescent species are oxidized at the electrode together with the coreactant which gives a strong reducing agent after some chemical transformations.

Applications

ECL proved to be very useful in analytical applications as a highly sensitive and selective method. It combines analytical advantages of chemiluminescent analysis with ease of reaction control by applying electrode potential. As an analytical technique it presents outstanding advantages over other common analytical methods due to its versatility, simplified optical setup compared with photoluminescence, and good temporal and spatial control compared with chemiluminescence. Enhanced selectivity of ECL analysis is reached by variation of electrode potential thus controlling species that are oxidized/reduced at the electrode and take part in ECL reaction.
It generally uses Ruthenium complexes, especially trisruthenium chloride|2+ regenerating with TPrA in liquid phase or liquid–solid interface. It can be used as monolayer immobilized on an electrode surface or as a coreactant or more commonly as a tag and used in HPLC, Ru tagged antibody based immunoassays, Ru Tagged DNA probes for PCR etc., NADH or H2O2 generation based biosensors, oxalate and organic amine detection and many other applications and can be detected from picomolar sensitivity to dynamic range of more than six orders of magnitude. Photon detection is done with photomultiplier tubes or silicon photodiode or gold coated fiber-optic sensors. The importance of ECL techniques detection for bio-related applications has been well established. ECL is heavily used commercially for many clinical lab applications.