Combining conductivity measurements and molecular weight determination by means of low-angle laser light scattering, we have found for the polyribonucleotides (polyuridylic acid (poly(U], polyadenylic acid (poly(A], polycytidylic acid (poly(C] and polyguanylic acid (poly(G] and for single-stranded DNA (ssDNA) that, on average, 8.5 counterions per single-strand break (ssb) are liberated under salt-free conditions. This relationship allows us to estimate, from conductivity measurements alone, G-values of single-strand break formation (G(ssb] for the polydeoxyribonucleotides (polydeoxyriboadenylic acid (poly(dA], polydeoxyribocytidylic acid (poly(dC], polydeoxyribothymidylic acid (poly(dT], polydeoxyribouridylic acid (poly(dU] and polydeoxyriboguanylic acid (poly(dG]. The following G(ssb) values (units of mumol J-1) have been obtained for anoxic conditions: poly(dA), 0.23; poly(dC), 0.14; poly(dT), 0.06; poly(dU), 0.046 and poly(dG), 0.009. Time-resolved conductivity measurements in pulse radiolysis enable us to measure the rate of strand break formation. The rate has been found to be similar for poly(dA) and ssDNA over a range of pH values. Poly(dC) and poly(dU) exhibit conductivity increase components with half-lives similar to those of poly(dA) and ssDNA at corresponding pH values. The implications of these results are discussed.

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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 (φ) 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 − • 4 − • 4 SO scavenging by caffeic acid, are also found to be greater than φ exptl values. These observations suggest that the thymine radicals are repaired by caffeic acid in addition to scavenging of sulphate radical anions. Keywords. Oxidation of caffeic acid; repair of thymine by caffeic acid; oxidations by sulphate radical anion.

Kinetics of oxidation of fumarate, acrylate, cinnamate, and maleate anions by hexavalent manganese has been studied in aqueous alkaline medium. The order in [oxidant] was unity while that in [substrate] was fractional. The order of reactivity of anions is fumarate -+ acrylate --f cinnamate + maleate. The reactions followed Michaelis-Menten kinetics suggesting the formation of a cyclic intermediate between Mn(V1) and the substrate followed by its disproportionation in a slow step. The equilibrium constant ( K ) for the preequilibrium step and the rate constant (k) for the slow disproportionation step have been calculated from the intercept and the slope values of the linear plot of l/kOb, versus l/[substrate]. Activation parameters are also presented and discussed. A convenient iodometric method is reported for the estimation of Mn(V1).