The influence of pH on OH scavenger inhibition of damage to deoxyribose by Fenton reaction

Abstract

Hydroxyl radicals (OH.) can be formed in aqueous solution by direct reaction of hydrogen peroxide (H2O2) with ferrous salt (Fenton reaction). OH. damage to deoxyribose, measured as formation of thiobarbituric acid-reactive material, was evaluated at different pHs to study the mechanism of action of classical OH. scavengers. OH. scavenger effect on Fe2+ oxidation was also evaluated in the same experimental conditions. In the absence of OH. scavengers, OH. damage to deoxyribose is higher at acidic compared to neutral and moderately basic pH. At acidic pH deoxiribose is per se able to inhibit Fe2+ oxidation by H2O2. Most of OH. scavengers tested inhibit deoxyribose damage and Fe2+ oxidation in a similar manner: both inhibitions are most relevant at acidic pH and decrease by increasing the pH. These results are not due to OH. scavenger inhibition of Fenton reaction. The influence of pH on the parameters studied appears to be due to the competition of deoxyribose and OH. scavengers for iron. These results suggest the prominent role of iron binding in the degradation of deoxyribose and in the OH. scavenging ability of different compounds. Results obtained with triethylenetetramine, a iron chelator with a low rate constant with OH., confirm that both deoxyribose and the OH. scavengers interact with iron bringing about a site specific Fenton reaction; that the OH. formed at these sites oxidize these molecules to their radical forms which in turn reduce the Fe3+ produced by Fenton reaction. The results presented indicate that most of classical OH. scavengers exert their effect predominantly by preventing the site specific reaction between Fe2+ and H2O2 on the deoxyribose molecule.