Enzymatic and oxidative degradation of poly(polyol sebacate).

Poly(glycerol sebacate) (PGS) and poly(xylitol sebacate) (PXS) are biodegradable elastomers with tremendous potential in soft tissue engineering. This study was aimed at exploring the enzymatic degradation mechanisms of these polyesters, using biochemical conditions similar to those occurring in vivo. To this end, PGS and PXS (crosslinked at 130 for 2 or 7 (PGS)/12 days (PXS)) were incubated in vitro under physiological conditions in tissue culture media supplemented with either a biodegrading enzyme (esterase), an oxidant species (FeSO4/H2O2 with 0.11 molar ratio of Fe(2+/)H2O2), an oxidant generating enzyme (xanthine oxidase and xanthine) or combinations of these (FeSO4/H2O2 and esterase, or (v) xanthine oxidase/xanthine and esterase), based on their independent effects on polymer degradation. Testing was performed over 35 days of continuous incubation, during which mechanical properties, mass loss, biomaterial thickness and pH value of the culture medium were determined. Degradation kinetics of both PGS and PXS samples were primarily determined by the degree of crosslink density. Esterase and FeSO4/H2O2 accelerated the degradation of both polymers, by promoting hydrolysis and free-radical degradation, although this action was not affected by the presence of xanthine oxidase and xanthine. Degradation of PGS and PXS is primarily mediated by the action of esterase, with free-radical oxidation playing a secondary role, suggesting that both could synergistically affect the biodegradability of biomaterial implants, under more complex biological conditions.