Reducing radicals, radiolytic production

Even more important are reactions of radiolytic products with the precursors of these excited states. Results from recent experiments in which the solute luminescence and magnetic field effect were compared for radiolysis of cyclohexane or isooctane with 0.5-2.2 MeV electrons, 1-5 MeV protons, and 2-20 MeV a-particles suggested that the decrease in the solute luminescence and the magnetic field effect was due to both the increasing importance of crossrecombination and the "intervention of radicals or other transient species with the precursors" with the fluorescent states [63]. The effects of spin relaxation and ion-radical reactions in dense spurs were identified as likely causes for reduced magnetic field effects, fluorescence yields, and probabilities 0 in spurs from 17-40 keV x-rays as compared to the spurs from fast electrons [80]. 

SCHEME 4.1 Schematics of radiolysis and reducing species. As a result of ionization of the water molecule, hydroxyl radicals and hydrated electrons are formed. The final radiolytic yield depends on the secondary reactions in spurs and on the presence of other compounds. See Refs 25,26,190, and 191 for the detailed discussion and references. Solvated electrons are mobile enough to escape spurs and to react with the heme protein complexes even at 77K. All other reactive products of radiolysis are immobilized in the solid solvent matrix, or trapped by radical quenchers. 

In the electrochemical reduction of 5-bromo-l-methyl-4-nitroimidazole some cleavage of the C—Br bond is evident giving rise to the debrominated product (79JGU1877). Imidazole itself is not reducible cathodically in aqueous media, but electrons have been attached to imidazole and histidine in aqueous solution the rate of oxidation depends on pH. Protonated or quaternized imidazoles form the neutral conjugate acids of the true anion radical, and a number of anion radicals have been made from nitroimidazoles under various radiolytic conditions (79AHC(25)205). The electrochemical reduction of 2-cyanobenzimidazole 3-oxide gives sequentially 2-cyanobenzimidazole and 2-aminomethylbenzimidazole (80ZC263). 

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