Effect of oxygen on the radiolysis of tyrosine in aqueous solutions

The effect of oxygen on the radiolysis of tyrosine in aqueous solutions was investigated by using gamma and pulsed electron irradiation. Steady-state radiolysis was reexamined and extended to include the effect of pH and determination of hydrogen peroxide. The loss of tyrosine, G(-Tyr), during irradiation and yields of 3,4-dihydroxyphenylalanine, G(DOPA), and hydrogen peroxide, G(H2O2), are determined in the pH range from 1 to 9. In the whole pH range used G(-Tyr) equals G(DOPA), and a higher G(H2O2) than expected was observed. In slightly acid and neutral media, both G(-Tyr) and G(DOPA) equal the yield of hydroxyl radicals, GOH, formed in the radiolysis of water, while the excess of hydrogen peroxide equals 1/2 GOH. Hence it was concluded that all tyrosine OH-adducts react with oxygen yielding peroxy radicals. In acid and alkaline media all measured yields decrease. This is caused by formation of tyrosine phenoxyl radicals (TyrO), which react with superoxide anion (O2-) and hydroperoxy (HO2) radicals regenerating tyrosine. By using pulse radiolysis K(TyrO + O2) less than or equal to 2 X 10(5) mol-1 dm3 s-1 and k(TyrO + O2-) = (1.7 +/- 0.2) X 10(9) mol-1 dm3 s-1 were determined. On the basis of the results, a reaction mechanism is proposed