Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals in aqueous solutions; electron transfer and proton-coupled electron transfer mechanisms

Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals center dot CO2-, center dot CH2OH, center dot CH(CH3)OH, and (CH)-C-center dot(CH3)O- have been studied in oxygen free aqueous solutions in the presence of organic additives: formate, methanol or ethanol. For radicals production Co-60 gamma-radiolysis was employed and the yield of bromide was measured by means of ion chromatography. Both radical anions have reducing potential negative enough to transfer an electron to BrU producing bromide ion and U center dot radical. High yields of bromide have been measured increasing proportional to the concentration of the corresponding organic additives at a constant dose rate. This is characteristic for a chain process where regeneration of radical ions occurs by H-atom abstraction by U center dot radical from formate or ethanol. Results with the neutral radicals conformed earlier proposition that the reduction reaction of alpha-hydroxyalkyl radicals proceeds by the proton-coupled electron transfer mechanism (Matasovk and Bonifacic, 2007). Thus, while both center dot CH2OH and center dot CH(CH3)OH did not react with BrU in water/alcohol solutions, addition of bicarbonate and acetate in mmol dm(-3) concentrations, pH 7, brought about chain debromination to occur in the case of (CH)-C-center dot(CH3)OH radical as reactant. Under the same conditions phosphate buffer, a base with higher bulk proton affinity, failed to have any influence. The results are taken as additional proofs for the specific complex formation of alpha-hydroxyalkyl radicals with suitable bases which enhances radicals' reduction potential in comparison with only water molecules as proton acceptors. Rate constants for the H-atom abstraction from ethanol and formate by radicals have been estimated to amount to about >= 85 and 1200 dm(3) mol(-1) s(-1), respectively. (C) 2011 Elsevier Ltd. All rights reserved.