In this paper the relationship between the ascorbate anion (AH-) and its oxidation products, ascorbyl radical anion (A·-) and dehydroascorbic acid (DHA), are studied by means of theoretical calculations. Additional calculations are performed on α-hydroxytetronate, a model compound of ascorbate lacking the side chain. The method uses density functional theory with the B3LYP functional and a polarizable conductor dielectric model to compute solvation effects. Our results indicate that the model compound reacts with the α-tocopheroxyl radical to regenerate vitamin E with a free energy change of reaction (in water) of -7.4 kcal/mol. This reaction is 2.9 kcal/mol more exergonic than the corresponding reaction involving ascorbate, suggesting that the model compound may make a more effective antioxidant than ascorbate. However, the disproportionation of the ascorbyl radical anion, a reaction that regenerates AH-, is found to be exergonic while the similar reaction involving the model compound is slightly endergonic. The reason for the difference is that the disproportionation of A·- is found to be driven by the formation of the hemiketal structure of dehydroascorbic acid (DHA). (C) 2000 Elsevier Science Inc.

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Keywords Ascorbyl free radical, Dehydroascorbic acid, Density functional theory, Disproportionation, Free radicals, Solvent effects
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Journal Free Radical Biology and Medicine
DiLabio, G.A. (Gino A.), & Wright, J.S. (2000). Hemiketal formation of dehydroascorbic acid drives ascorbyl radical anion disproportionation. Free Radical Biology and Medicine, 29(5), 480–485. doi:10.1016/S0891-5849(00)00357-9