Shape Memory Behavior of Biocompatible Polyurethane Stereoelastomers Synthesized via Thiol-Yne Michael Addition

Biodegradable shape memory elastomers have the potential for use in soft tissue engineering, drug delivery, and device fabrication applications. Unfortunately, few materials are able to meet the targeted degradation and mechanical properties needed for long-term implantable devices. In order to overcome these limitations, we have designed and synthesized a series of unsaturated polyurethanes that are elastic, degradable, and nontoxic to cells in vitro. The polymerization included a nucleophilic thiol-yne Michael addition between a urethane-based dipropiolate and a dithiol to yield an alpha,beta-unsaturated carbonyl moiety along the polymer backbone. The alkene stereochemistry of the materials was tuned between 32 and 82% cis content using a combination of an organic base and solvent polarity, which collectively direct the nucleophilic addition. The bulk properties such as tensile strength, modulus, and glass transition temperature can also be tuned broadly, and the hydrogen bonding imparted by the urethane moiety allows for these materials to elicit cyclic shape memory behavior. We also demonstrated that the in vitro degradation properties are highly dependent on the alkene stereochemistry.

Automated summary

Biodegradable shape memory elastomers show great potential for various applications such as soft tissue engineering, drug delivery, and device fabrication. In this study, a series of unsaturated polyurethanes were designed and synthesized to meet the requirements of long-term implantable devices in terms of degradation and mechanical properties. The alkene stereochemistry of the materials could be tuned, and the materials showed cyclic shape memory behavior. The in vitro degradation properties were found to be highly dependent on the alkene stereochemistry.