Electrochemiluminescence

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Electrochemiluminescence or electrogenerated chemiluminescence (ECL) 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. [1] [2] ECL excitation can be caused by energetic electron transfer (redox) reactions of electrogenerated species. Such luminescence excitation is a form of chemiluminescence where one/all reactants are produced electrochemically on the electrodes. [3]

Contents

ECL is usually observed during application of potential (several volts) to electrodes of electrochemical cell that contains solution of luminescent species (polycyclic aromatic hydrocarbons, metal complexes, quantum dots or nanoparticles [4] ) in aprotic organic solvent (ECL composition). 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 latter case luminescent species are oxidized at the electrode together with the coreactant which gives a strong reducing agent after some chemical transformations (the oxidative reduction mechanism).

Schematic representation of the "oxidative-reduction" heterogeneous ECL mechanisms for the couple Ru(bpy)3 /TPrA. The ECL generation is obtained only by TPrA oxidation and involving the homogeneous reaction of the radical cation (TPrAdeg ), as proposed by Bard. The luminophore in the excited state Ru * relaxes to the ground state and emits photon. Inset image of electrode surface during an ECL emission Heterogeneous ECL mechanism .tif
Schematic representation of the "oxidative-reduction" heterogeneous ECL mechanisms for the couple Ru(bpy)3 /TPrA. The ECL generation is obtained only by TPrA oxidation and involving the homogeneous reaction of the radical cation (TPrA° ), as proposed by Bard. The luminophore in the excited state Ru * relaxes to the ground state and emits photon. Inset image of electrode surface during an ECL emission

Applications

ECL proved to be very useful in analytical applications as a highly sensitive and selective method. [7] It combines analytical advantages of chemiluminescent analysis (absence of background optical signal) 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 (PL), and good temporal and spatial control compared with chemiluminescence (CL). 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 [8] (see electrochemical analysis).

It generally uses Ruthenium complexes, especially [Ru(bpy)3]2+ (bpy = 2,2'-bipyridine) which releases a photon at ~620 nm regenerating with TPrA (Tripropylamine) in liquid phase or liquid–solid interface. It can be used as monolayer immobilized on an electrode surface (made e.g. of nafion, or special thin films made by Langmuir–Blogett technique or self-assembly technique) 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 (PMT) or silicon photodiode or gold coated fiber-optic sensors. The importance of ECL techniques detection for bio-related applications has been well established. [9] ECL is heavily used commercially for many clinical lab applications. [10] [11] [12]

See also

Related Research Articles

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Ruthenium is a chemical element with the symbol Ru and atomic number 44. It is a rare transition metal belonging to the platinum group of the periodic table. Like the other metals of the platinum group, ruthenium is inert to most other chemicals. Russian-born scientist of Baltic-German ancestry Karl Ernst Claus discovered the element in 1844 at Kazan State University and named ruthenium in honor of Russia. Ruthenium is usually found as a minor component of platinum ores; the annual production has risen from about 19 tonnes in 2009 to some 35.5 tonnes in 2017. Most ruthenium produced is used in wear-resistant electrical contacts and thick-film resistors. A minor application for ruthenium is in platinum alloys and as a chemistry catalyst. A new application of ruthenium is as the capping layer for extreme ultraviolet photomasks. Ruthenium is generally found in ores with the other platinum group metals in the Ural Mountains and in North and South America. Small but commercially important quantities are also found in pentlandite extracted from Sudbury, Ontario, and in pyroxenite deposits in South Africa.

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