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Abstract
Cyclic voltammogram (CV) and simultaneous electrochemical and electron paramagnetic resonance (SEEPR) measurements have been carried out on the oxygenated carotenoids: echinenone, canthaxanthin, isozeaxanthin and rhodoxanthin in dichloromethane. The CV displays are markedly different from that of β-carotene. Comproportionation constants, deduced from EPR spin concentration measurements of electrochemically oxidized dihydroxy β-carotene and several keto carotenoids vary by four orders of magnitude. Δ H pp values deduced from the SEEPR spectra of the cation radicals are in the range 13.2 to 14.5 G and the g-factors are 2.0027 ± 0.0002. These EPR parameters are in accordance with a polyene π-cation radical structure. Theoretical CVs are calculated using DigiSim, a CV simulation program, and the proposed mechanism involves three electrode and two homogeneous reactions.
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