a b s t r a c tThe electrochemical behaviour of phenol, catechol, hydroquinone, resorcinol, dopamine, and para-substituted phenolic compounds, 4-ethylphenol, tyrosine, and tyramine, was studied over a wide pH range using a glassy carbon electrode. The oxidation of phenol is pH dependent and irreversible, occurring in one step, and followed by hydrolyse in ortho-and para-positions, leading to two oxidation products, catechol and hydroquinone. The oxidation of phenol oxidation products, ortho-phenol and para-phenol, is reversible and pH dependent. The oxidation potential of para-substituted phenols varies slightly due to their substituent group in position C4, and occurs in one oxidation step corresponding to the oxidation of phenol. The oxidation products of this group of para-substituted phenols are reversibly oxidised and adsorb on the electrode surface.
The oxidation of flavonoids is of great interest because of their action as antioxidants with the ability to scavenge radicals by electron transfer processes. The electrochemical oxidation of the flavonoid (+)-catechin, was investigated, over a wide range of conditions, using cyclic, differential and square wave voltammetry. The oxidation mechanism proceeds in sequential steps, related with the catechol and resorcinol groups and the oxidation is pH dependent. The oxidation of the catechol 3 ,4 -dihydroxyl electron-donating groups occurs first, at very low positive potentials, and is a reversible reaction. The hydroxyl groups of the resorcinol moiety oxidised afterwards were shown to undergo an irreversible oxidation reaction. (+)-Catechin also adsorbs strongly on the electrode surface and the final oxidation product is not electroactive and blocks the electrode surface.
The voltammetric oxidation of all deoxyribonucleic acid (DNA) monophosphate nucleotides is investigated for the first time over a wide pH range by differential pulse voltammetry with a glassy carbon electrode. Experimental conditions such as the electrode size, supporting electrolyte composition, and pH were optimized to obtain the best peak potential separation and higher currents. This enabled the simultaneous voltammetric determination of all four DNA bases in equimolar mixtures and detection limits in the nanomolar range at physiological pH. It was also possible to detect for the first time the oxidation of each of the purine and pyrimidine nucleotides free in solution or as monomers in single-stranded DNA.
The mechanism of electrochemical oxidation of quercetin on a glassy carbon electrode has been studied using cyclic, differential pulse and square-wave voltammetry at different pH. It proceeds in a cascade mechanism, related with the two catechol hydroxyl groups and the other three hydroxyl groups which all present electroactivity, and the oxidation is pH dependent. Quercetin also adsorbs strongly on the electrode surface; and the final oxidation product is not electroactive and blocks the electrode surface. The oxidation of the catechol 3',4'-dihydroxyl electron-donating groups, occurs first, at very low positive potentials, and is a two electron two proton reversible reaction. The hydroxyl group oxidized next was shown to undergo an irreversible oxidation reaction, and this hydroxyl group can form a intermolecular hydrogen bond with the neighboring oxygen. The other two hydroxyl groups also have an electron donating effect and their oxidation is reversible.
An electrochemical nucleic acid (NA)-based biosensor is a biosensor that integrates a nucleic acid as the biological recognition element and an electrode as the electrochemical signal transducer. The present report provides concepts, terms, and methodology related to biorecognition elements, detection principles, type of interactions to be addressed, and construction and performance of electrochemical NA biosensors, including their critical evaluation, which should be valuable for a wide audience, from academic, biomedical, environmental, and food-testing, drug-developing, etc. laboratories to sensor producers.
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