Embedding Thiols into Choline Phosphate Polymer Zwitterions

The compositional scope of polymer zwitterions has grown significantly in recent years and now offers designer synthetic materials that are broadly applicable across numerous areas, including supracolloidal structures, electronic materials interfaces, and macromolecular therapeutics. Among recent developments in polymer zwitterion syntheses are those that allow insertion of reactive functionality directly into the zwitterionic moiety, yielding new monomer and polymer structures that hold potential for maximizing the impact of zwitterions on the macromolecular materials chemistry field. This manuscript describes the preparation of zwitterionic choline phosphate (CP) methacrylates containing either aromatic or aliphatic thiols embedded directly into the zwitterionic moiety. The polymerization of these functional CP methacrylates by reversible addition-fragmentation chain-transfer methodology yields polymeric zwitterionic thiols containing protected thiol functionality in the zwitterionic units. After polymerization, the protected thiols are liberated to yield thiol-rich polymer zwitterions which serve as precursors to subsequent reactions that produce polymer networks as well as polymer-protein bioconjugates. The growing library of designer polymer zwitterions is limited by available versatile/reactive functional groups. Herein, the synthesis of choline phosphate polymer zwitterions with embedded thiols integrated directly adjacent to the zwitterion moiety is reported. The resulting thiol-containing polymer zwitterions form hydrogels, stabilize oil-in-water interfaces, and create polymer-protein bioconjugates through disulfide and thiol-Michael chemistries.image