Abstract

Cross-linking predominates over chain scission during the irradiation of concentrated aqueous dextran solutions by cobalt-60 gamma rays in the absence of oxygen. An extensive and long-lived postirradiative viscosity decay, which has not been previously reported, is attributed to the agency of hydrogen peroxide formed during the radiolysis of water. Solid dextran primarily degrades upon γ-irradiation while dextran triacetate is borderline between dominant scission and cross-linking. Both exhibit a postirradiative viscosity decrease when irradiated in the presence of water vapor. Electron spin resonance spectra of dextran in the solid state and in aqueous solution are presented and compared. Spin resonance spectral and chemical evidence concerning the mechanism of cross-linking and postirradiative decay reactions is presented. There is conflicting evidence for the presence of oxyradicals. Speculations are made concerning possible mechanisms of oxyradical formation and their role in the production of ether and peroxy linkages.

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