A Versatile Strategy to Main Chain Sulfur/Selenium-Functionalized Polycarbonates by Macro-Ring Closure of Diols and Subsequent Ring-Opening Polymerization.

Herein, a new class of main chain functionalized aliphatic polycarbonates with sulfur/selenium functional groups on the backbone is reported. Sulfur/selenium-containing cyclic carbonate monomers (MR ) are designed and synthesized by enzyme-catalyzed intermolecular macro-ring closure of related diols. The proposed synthetic strategy is tolerant of other functionalities such as N-substituted groups. The ring opening polymerization (ROP) of MR occurs readily as a versatile route to generate a new family of main chain sulfur/selenium substituted aliphatic polycarbonates (PR) with predictable molecular weights (MW), narrow molecular-weight distribution and controlled copolymer composition. The resultant polymers can be oxidized and/or reduced by treatment with hydrogen peroxide (H2 O2 ) or dithiothreitol (DTT), highlighting their potential for applications in the stimuli-responsive field and inflammation/cancer targeting. With these desirable results, it is revealed that this versatile technique can provide a broad-reaching method to the next generation of innovative materials, especially, well-defined biodegradable chalcogen-based main chain functional biomaterials.