Anodic electrochemiluminescence

Liu X, Jiang H, Lei J, Ju H (2007) Anodic electrochemiluminescence of CdTe quantum dots and its energy transfer for detection of catechol derivatives. Anal Chem 79(21) 8055-8060. doi 10.1021/ac070927i... 

Figure 5. Anodic electrochemiluminescence for MEH-FPV when final potential isEf = (a) 1.2 Vand (b) 1.30 Vvs Pt (QRE). (a) anodic (b) cathodic. Supporting electrolyte 0.1 MIFAPFe...

In this paper the electtode anodic reactions of a number of dihydropyridine (DHP) derivatives, quantum-chemical calculations of reactions between DHP cation-radicals and electrochemiluminescers anion-radicals (aromatic compounds) and DHP indirect ECL assay were investigated. The actuality of this work and its analytical value follow from the fact that objects of investigation - DHP derivatives - have pronounced importance due to its phaiTnacology properties as high effective hypertensive medical product. 

Radical 80 has been prepared as its perchlorate salt by anodic oxidation in ethyl acetate in the presence of hthium perchlorate. The reactivity toward nucleophiles of material so prepared was investigated nitrite and nitrate ions give 2-nitrodibenzo[l,4]dioxin although the mechanisms of the reactions are not clear. Pyridine gives 7V-(2-dibenzo[l,4]dioxinyl)pyridinium ion (84). Other nucleophiles acted as electron donors and largely reduced 80 back to the parent heterocycle they included amines, cyanide ion and water. In an earlier study, the reaction of 80 with water had been examined and the ultimate formation of catechol via dibenzo[l,4]dioxin-2,3-dione was inferred. The cation-radical (80) has been found to accelerate the anisylation of thianthrene cation-radical (Section lII,C,4,b) it has been found to participate in an electrochemiluminescence system with benzo-phenone involving phosphorescence of the latter in a fluid system, and it has been used in a study of relative diffusion coefficients of aromatic cations which shows that it is justified to equate voltammetric potentials for these species with formal thermodynamic redox potentials. The dibenzo[l,4]dioxin semiquinone 85 has been found to result from the alkaline autoxidation of catechol the same species may well be in-... 

Demonstration of the phenomenon employed an electrochemiluminescent reaction at the anodes and oxygen reduction at the cathodes, allowing photographic capture of signals, as shown in Fig. 6. This array design has subsequently been applied to nucleic acid detection and is discussed further in a following section of this chapter. 

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