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• W1994813638 abstract "A detailed study of the radiation chemistry of the radiosensitizer Diamide (diazenedicarboxylic acid bis-dimethylamide) using 10Co irradiation, pulse radiolysis, pulse conductivity, and ESR techniques is presented. Reduction of Diamide by esq- (k = 2.8 X 101' M-1 sec-') is followed by rapid protonation of the radical anion by H+ at a diffusion-controlled rate, or by H2P04- at a rate of 7 X 107 M-1 sec-'. The protonation is confirmed by pulse conductivity experiments and supported by ESR observation of the dicarboxyhydrazyl radical. The radical anion is also formed by electron transfer from thymine-- (k = 5.0 X 109 M-1 sec-'), from PNAP-- (k = 1.6 X 10' M-1 sec-1), and from (CH,)2(OH and CO~O- (k 2.5 X 109 M-1 sec-'). The protonated radical reacts with oxygen at a rate of about 108 M-1 sec-1, but not by electron transfer. The protonated radical decays by a second-order reaction (2k = 4 X 108 M-1 sec-1) with G(-Diamide) = 3.1 in the formate system, suggesting a disproportionation reaction. 10Co irradiation of N2O saturated solutions of Diamide leads to a shift in Xmax and an increase in absorption before subsequent destruction. Optical studies using pulse radiolysis show a threefold increase in transient absorption at 400 nm between pH 6 and 9, and the relative spectra at these pH's are dissimilar, suggesting the presence of a radical with pK-% 7.5. Pulse conductivity experiments show that about 50% of the radicals are dissociated at pH 9.8. It is suggested that OH radicals react by both addition to the N=N bond and abstraction from the methyl groups at approximately equal rates and that the OH adduct dissociates with pK -- 7.5. The rate of signal formation at 400 nm is also pH dependent. A rate constant of 7 X 109 M-1 sec-' was observed at pH 2, 2.3, 2.8, 4, 4.8, 6.5, and 6.8 and a lower value is measured at higher pH. Indirect measurement of the rate of OH attack by phenylalanine competition gives a value of 4.2 X 109 M-1 sec-1 independent of pH from 4 to 8." @default.
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• W1994813638 date "1975-12-01" @default.
• W1994813638 modified "2023-10-17" @default.
• W1994813638 title "Radiation Chemical Studies of the Sensitizer Diamide" @default.
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• W1994813638 doi "https://doi.org/10.2307/3574232" @default.
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