Antioxidant and Prooxidant Actions of Ascorbate

Chemically, ascorbate is a potent reducing agent, both reducing hydrogen peroxide and also acting as a radical trapping antioxidant, reacting with superoxide and a proton to yield hydrogen peroxide or with the hydroxy radical to yield water. In each case the product is monodehydroascorbate, which, as shown in Figure 1, undergoes dismutation to ascorbate and dehydroascorbate. In studies of ascor-bate depletion in men there is a significant increase in abnormalities of sperm DNA, suggesting that vitamin C may have a general, nonspecific radical-trapping antioxidant function.

Ascorbate also acts to reduce the tocopheroxyl radical formed by oxidation of vitamin E in cell membranes and plasma lipoproteins. It thus has a vitamin E sparing antioxidant action, coupling lipo-philic and hydrophilic antioxidant reactions.

The antioxidant efficiency of ascorbate is variable. From the chemistry involved, it would be expected that overall 2 mol of tocopheroxyl radical would be reduced per mole of ascorbate because of the reaction of 2 mol of monodehydroascorbate to yield ascorbate and dehydroascorbate. However, as the concentration of ascorbate increases, so the molar ratio decreases, and it is only at very low concentrations of ascorbate that it tends toward the theoretical ratio. This is because, as well as its antioxidant role, ascorbate can be a source of hydroxyl and superoxide radicals.

At high concentrations, ascorbate can reduce molecular oxygen to superoxide, being oxidized to monodehydroascorbate. Both Fe3+ and Cu2+ ions are reduced by ascorbate, again yielding monodehy-droascorbate; the resultant Fe2+ and Cu+ are reox-idized by reaction with hydrogen peroxide to yield hydroxide ions and hydroxyl radicals. Thus, as well as its antioxidant role, ascorbate has prooxidant action; the net result will depend on the relative rates of formation of superoxide and hydroxyl radicals by autooxidation and metal-catalyzed reactions of ascorbate, and the trapping of these radicals by ascorbate.

It seems likely that the prooxidant actions of ascor-bate are of relatively little importance in vivo. Except in cases of iron overload there are almost no transition metal ions in free solution, they are all bound to proteins, and because the renal transport system is readily saturated, plasma and tissue concentrations of ascorbate are unlikely to rise to a sufficient extent to lead to significant radical formation.

Breaking Bulimia

Breaking Bulimia

We have all been there: turning to the refrigerator if feeling lonely or bored or indulging in seconds or thirds if strained. But if you suffer from bulimia, the from time to time urge to overeat is more like an obsession.

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