Kinetics and mechanism of protection of thymine from sulphate radical anion under anoxic conditions

The rates of photooxidation of thymine in presence of peroxydisulphate (PDS) have been determined by measuring the absorbance of thymine at 264 nm spectrophotometrically. The rates and the quantum yields (phi) of oxidation of thymine by sulphate radical anion have been determined in the presence of different concentrations of caffeic acid. Increase in [caffeic acid] is found to decrease the rate of oxidation of thymine suggesting that caffeic acid acts as an efficient scavenger of •- SO4 and protects thymine from it. Sulphate radical anion competes for thymine as well as for caffeic acid. The rate constant of sulphate radical anion with caffeic acid has been calculated to be 1,24cross 10^10 dm3 mol^–1 s^–1. The quantum yields of photooxidation of thymine have been calculated from the rates of oxidation of thymine and the light intensity absorbed by PDS at 254 nm, the wavelength at which PDS is activated to sulphate radical anion. From the results of experimentally determined quantum yields (phiexptl) and the quantum yields calculated (phicl) assuming caffeic acid acting only as a scavenger of •- SO4 radicals show that phiexptl values are lower than phicl values. The f ¢ values, which are experimentally found quantum yield values at each caffeic acid concentration and corrected for •- SO4 scavenging by caffeic acid, are also found to be greater than phiexptl values. These observations suggest that the thymine radicals are repaired by caffeic acid in addition to scavenging of sulphate radical anions.