Synthetic Polypeptide–Polyester PolyHIPEs Prepared by Thiol–Ene Photopolymerization

Abstract

Synthetic polypeptides and aliphatic polyesters represent promising materials in biomedical applications due to their degradability and biocompatibility. In this work, we investigated the preparation and properties of porous synthetic polypeptide–polyester materials prepared by thiol–ene photopolymerization of allyl-functionalized star macromonomers based on poly(γ-benzyl-l-glutamate) (PBLG) and poly(ε-caprolactone) (PCL). We copolymerized the macromonomers in the continuous phase of high internal phase emulsions (HIPEs) to obtain highly porous polyHIPEs. We demonstrated that the PBLG polyHIPE is a stiffer material compared to the softer PCL polyHIPE, while the copolyHIPEs composed of both components have a combination of thermomechanical properties that can be tuned by varying the chemical composition. Moreover, using a thiol–ene HIPE-templating approach, we were able to prepare a bilayered PBLG–PCL polyHIPE consisting of two chemically and mechanically distinct layers covalently bonded with a thin and robust interface while maintaining the typical polyHIPE morphology throughout the material.