Biodegradable shape-memory polymers exhibiting sharp thermal transitions and controlled drug release.

Biodegradable shape-memory polymer networks prepared by cross-linking star shape branched oligo(ε-caprolactone) (bOCL) with hexamethylene diisocyanate are introduced. The thermal and mechanical properties of these networks were investigated using differential scanning calorimetry and tensile testing, respectively, and the morphology of the phase structure was characterized by polarized optical microscopy. The shape-memory properties of the networks were quantified using thermomechanical tensile experiments and showed strain fixity rates R(f) higher than 97% and strain recovery rates R(r) as high as 100%. Of note, networks of OCL segments with a lower degree of polymerization (DP; 10) exhibited significantly improved temperature-sensitive shape recovery: 90% of the permanent shape was recovered upon heating to within a 2 °C range (37-39 °C). The networks exhibited complete shape recovery to the permanent shape within 10 s at 42 °C. Theophylline-loaded (10 and 20 wt %) shape-memory materials, prepared by cross-linking bOCL with hexamethylene diisocyanate in the presence of theophylline, are also described as a model for a controlled drug release device. The 10 wt % loaded material was sufficiently soft and flexible for complex shape transformation and also showed high R(f) (98%) and R(r) (99%). Sustained release of loaded theophylline was achieved over 1 month without initial burst-release in a phosphate buffer solution (PBS; pH 7.4) at 37 °C.