Biodegradable Zwitterionic Polymer Coatings for Magnesium Alloy Stents

Degradable metallic stents, most commonly composed of Mg-based alloys, are of interest as an alternative to traditional metallic stents for application in cardiac and peripheral vasculature. Two major design challenges with such stents are control of the corrosion rate and acute presentation of a nonthrombogenic surface to passing blood. In this study, several types of sulfobetaine (SB)-bearing biodegradable polyurethanes were developed and assessed as physical, chemical, and combination-type coatings for a model degradable Mg alloy, AZ31. For physical coatings, poly(ester sulfobetaine)urethane ureas, PESBUUs were synthesized using variable monomers that allowed the incorporation of a varying extent of carboxyl groups. Introduction of the carboxyl groups was associated with faster polymer degradation time. Simple physical coating of PESBUUs reduced macro- and microscopic thrombogenic deposition together with good stability of the coating attachment compared to a control coating of polylactic-co-glycolic acid. For PESBUUs incorporating carboxyl groups (PESBUUs-COOH), these groups could be converted to siloxane groups (PESBUUs-Si), thus creating polymers that could be surface reacted with the oxidized or phytic acid treated AZ31 surface. Chemical (silanization) attachment of these polymers reduced underlying alloy corrosion rates, but following the salination reaction with physical coating most reduced corrosion rates and protected the surface better from the consequences of oxidation occurring under the coating, such as blistering. The application of a multilayered coating approach using a sulfobetaine-based biodegradable elastomer thus offers options for degradable metallic stent design where thromboresistance is desired in combination with a means to control both polymeric coating degradation rates and underlying alloy corrosion rates.