Harnessing biopolyesters in the design of functional materials for biomedical applications

The present contribution illustrates the versatility of poly(3-hydroxyalkanoate)s (PHAs) in the design of a wide variety of biodegradable and/or biocompatible macromolecular architectures with controlled degradability. Firstly, functionalized PHAs were prepared from unsaturated PHAs. Pendant double bonds have been turned into carboxyl, hydroxyl, alkyne or epoxy groups. These reactive functions were used for further grafting hydrolyzable polylactide (PLA) or poly(ε-caprolactone) (PCL) as well as hydrophilic poly(ethylene glycol) (PEG). Additionally, block copolymers with a PLA, PCL or PEG segment have been prepared by ring-opening polymerization or "click" chemistry from a PHA oligomeric macroinitiator. Functional PHAs represent biodegradable aliphatic polyesters with many possibilities to tune physico-chemical characteristics, such as hydrophilicity and degradation rate, thus making the resulting materials suitable as devices for drug delivery or as scaffolds for tissue engineering. Herein, we address the recent trends in the synthesis of these polymeric materials and their applications in controlled drug delivery and tissue engineering.