Chitosan has potential biomedical applications that may require the fi
nal products to be sterilized before use. The gamma irradiation of pur
ified and highly deacetylated chitosan fibers and films at sterilizing
doses (up to 25 kGy) caused main chain scissions. The viscosity avera
ge molecular weight of the polymer decreased with increasing irradiati
on dose, the radiation yields of scission being 1.16 in air and 1.53 i
n anoxia. Preirradiation application of a negative pressure of 100 kPa
disrupted the network structure, which may have contributed to the gr
eater radiation yield obtained by chitosan fibers in anoxia, Radiation
induced scission of the chitosan chains resulted in a lower glass tra
nsition temperature (T-g), indicative of higher segmental mobility, Th
e T-g was below ambient at an irradiation dose of 25 kGy in air. Irrad
iation in air improved the tensile strength of the chitosan him, proba
bly due to changes in chain interaction and rearrangement. Irradiation
in anoxia did not affect film properties significantly, partly becaus
e the preirradiation application of negative pressure had a negligible
effect an the structure of the chitosan film. Polymer network structu
re and the irradiation conditions are therefore important determinants
of the extent of radiation induced reactions in chitosan. (C) 1998 Jo
hn Wiley & Sons, Inc.