engleski

Reductive dehalogenationof5 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 have been studied in oxygen free aqueous solutions in the presence of organic additives: formate, methanol or ethanol. For radicals production 60Co gama-radiolysis was employed and the yield of bromide was measured by means of ionchromatography. Both radical anions have reducing potential negative enough to transfer an electron to BrU. producing bromide ion and U. radical. High yields of bromide have been measured increasing proportional to the concentration of thecorresponding organic additives at a constant dose rate. This is characteristic for a chain process where regeneration of radical ionoccurs by H-atom abstraction by U. radical from formate or ethanol. Results with the neutral radicals conformed earlier proposition that the reduction reaction of a-hydroxyalkyl radicals proceeds by the proton-coupled electron transfer mechanism( Matasovic and Bonifacic, 2007. Thus, while both CH2OH and CH(CH3)OH did not react with BrU in water/alcohol solutions, addition of bicarbonate and acetate in mmoldm–3 concentrations, pH7, brought about chain debromination to occur in the case of CH(CH3)OH radicalas 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 a-hydroxy alkyl 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 U. radicals have been estimated to amount to about 85 and 1200 dm3 mol–1 s–1, respectively.

5-bromouracil ; dehalogenation ; chain reaction ; rate const ; alfa-hydroxyalkyl radicals ; PCET mechanism

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