Gamma radiation of poly (lactide-co-glycolide) raw polymers and processed microspheres under vacuum and at 77 K results in the formation of a series of free radicals. The resulting powder electron paramagnetic resonance (EPR) spectrum contains a distribution of several different radicals, depending on the annealing temperature, and is therefore difficult to interpret. By utilising the selectivity of the electron nuclear DOuble resonance (ENDOR) and associated ENDOR induced EPR (EIE) techniques, a more direct approach for the deconvolution of the EPR spectrum can be achieved. Using this approach, the radiolytically induced CH3 *CHC(O)R- chain scission radical was identified at 120 K by simulation of the EIE spectrum. At elevated temperatures (250 K), this radical decays considerably and the more stable radicals -O*CHC(O)-, CH3 *C(OR)C(O)- and CH3 *C(OH)C(O)- predominate. This work demonstrates the utility of the EIE approach to supplement and aid the interpretation of powder EPR spectra of radicals in a polymer matrix.

EPR/ENDOR spectroscopy was used to characterise the free radicals generated in a series of PLGA raw polymers and microspheres (with lactide:glycolide compositions of (75:25), (65:35) and (50:50)) after exposure to gamma (gamma-) and electron beam (beta-) irradiation at room temperature. Both sets of irradiated samples produced analogous EPR spectra, indicating that the type and distribution of free radicals generated by gamma-irradiation are similar to those generated by beta-irradiation. The radicals were identified by EPR simulations as the chain scission species -(CHO-(approximately 27% abundance),-C(CH(3))O- ( approximately 23% abundance) and the terminal-C(CH(3))-OR fragment (approximately 50% abundance), and these assignments were supported by the ENDOR analysis. The latter two radical species were demonstrated to originate from the lactide component of the PLGA polymer. Overall systematically higher radical concentrations were found as the lactide content of the PLGA raw polymer and microspheres increases (ie., 75:25 > 65:35 > 50:50) for both gamma- and beta-irradiation. However, while the relative concentrations of free radicals was similar in the raw polymer samples after exposure to gamma- or beta-irradiation, a substantial difference was found for the microsphere samples; an approximate doubling of the radical content was found in the gamma-irradiated PLGA microspheres compared to the identical beta-irradiated microspheres.