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Antioxidants are compounds that prevent or delay the oxidation process, acting at a much smaller concentration, in comparison to that of the preserved substrate. Primary antioxidants act as scavenging or chain breaking antioxidants, delaying initiation or interrupting propagation step. Secondary antioxidants quench singlet oxygen, decompose peroxides in non-radical species, chelate prooxidative metal ions, inhibit oxidative enzymes. Based on antioxidants’ reactivity, four lines of defense have been described: Preventative antioxidants, radical scavengers, repair antioxidants, and antioxidants relying on adaptation mechanisms. Carbon-based electrodes are largely employed in electroanalysis given their special features, that encompass large surface area, high electroconductivity, chemical stability, nanostructuring possibilities, facility of manufacturing at low cost, and easiness of surface modification. Largely employed methods encompass voltammetry, amperometry, biamperometry and potentiometry. Determination of key endogenous and exogenous individual antioxidants, as well as of antioxidant activity and its main contributors relied on unmodified or modified carbon electrodes, whose analytical parameters are detailed. Recent advances based on modifications with carbon-nanotubes or the use of hybrid nanocomposite materials are described. Large effective surface area, increased mass transport, electrocatalytical effects, improved sensitivity, and low detection limits in the nanomolar range were reported, with applications validated in complex media such as foodstuffs and biological samples.

Antioxidant Determination with the Use of Carbon-Based Electrodes