Abstract
Solutions containing cystamine and dithiodiglycollic acid give, upon x-irradiation, the mixed-disulfide aminoethyldithioacetic acid. Yields increase with disulfide concentration, reach G values of 100 at 50 mM disulfide concentrations in air-saturated solutions, and undoubtedly reflect the occurrence of chain reactions. Radiolytic yields in deaerated solutions are double those in aerated solutions. A plateau phenomenon is observed; at a fixed cystamine concentration, mixed disulfide yields increase with increasing dithiodiglycollate concentration up to a certain point but do not increase significantly thereafter. This behavior indicates that dithiodiglycollate is much more reactive than cystamine in the chain-propagating step. Mixtures of cystamine with methyl and ethyl disulfides behave similarly. The reactive intermediate is unlikely to be a common species such as thiyl radical produced by interaction of both hydroxyl radicals and electrons with disulfide. Rather, two distinct species such as the disu...
Published Version
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