Relative antioxidant efficiency of a large series of carotenoids in terms of one electron transfer reactions

The relative antioxidant efficiency, expressed as electron donating capability, of a large series of carotenoids has been studied using density functional theory. Their reactivity toward nine different radicals has been modeled as well as the electron transfer between pairs of carotenoids, one of which is present as a radical cation. The influence of the solvent polarity has also been studied. Torulene was found to be the most easily oxidized carotenoid, followed by lycopene. This higher reactivity is proposed in the present work for the first time, and the potential implications of such a finding are discussed. Since torulene has not been previously studied, compared to other carotenoids in terms of oxidation potentials, further experimental studies are Suggested in order to confirm or reject this prediction. Ionization potential seems to be a magnitude calculable at low computational cost that correctly predicts the relative ease of oxidation in a series of carotenoids. The nuclear reorganization energy associated with electron-transfer reactions has been calculated in a very simple but apparently efficient way that allows computation of free energy barriers and relative rate constants in good agreement with the experimental values. In addition, an additive correction is proposed to include the effect of increasing the size of basis sets on the energies of Car(n) -> Car(n-1)(center dot+) processes. The general agreement between different calculated magnitudes and the corresponding available experimental data supports the predictions from this work.