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

Abstract

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 (M ) 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 M 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 (H O ) 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.

A Drug‐Free Therapeutic System for Cancer Therapy by Diselenide‐Based Polymers Themselves

“…The amphiphilic copolymers (PSeSeTMC) were synthesized by the ring opening copolymerization of diselenide‐containing macrocyclic carbonate (M SeSe ) and trimethylene carbonate (TMC) using mPEG ( M n = 2 kg mol −1 ) as the macroinitiator and lipase CA (Novozym 435: an immobilized lipase from Candida Antarctica) as the catalyst (Figure 1a) according to our previous work. [ 13 ] TMC was selected to perform copolymerization because TMC can improve polymerization capacity of M SeSe . By changing the feed ratios of TMC and M SeSe , three well‐defined copolymers (named as PSeSeTMC839, PSeSeTMC459, and PSeSeTMC280) with similar molecular weight ( M n = 10.2–11.2 kg mol −1 by 1 H NMR), yet containing different selenium contents (from 25% to 11% to 6%, measured by inductive coupled plasma emission spectrometer (ICP)) were obtained (Figures S1–S3 and Table S1 and detailed synthesis in the Supporting Information).…”

ROS‐Responsive Selenium‐Containing Carriers for Coencapsulation of Photosensitizer and Hypoxia‐Activated Prodrug and Their Cellular Behaviors

“…The structure of mPEG-b-PSe was verified by 1 H NMR spectrum and 77 Se NMR spectrum. It was observed from Figure 1B that the signal at 3.65 ppm (c) was assigned to the ethylene oxide protons (CH the MSe monomer after the ROP process, [43] suggesting that the monomer was initiated by mPEG successfully. A new peak emerged at 147 ppm (OCH 2 CH 2 Se) in the mPEG-b-PSe in Figure 1C, which was shifted from 137 ppm (OCH 2 CH 2 Se) in the MSe monomer.…”

Organoselenium chemistry-based polymer synthesis

“…Lang et al investigated the ring-opening polymerization of a selenium-containing lactone with a macroring via alcoholysis under lipase catalysis. 78,79 This synthetic methodology will expand the scope of functional polycarbonates and advance the development of selenic biomaterials in practical applications. Based on γ-butyroselenolactone and seleniumcontaining lactones with macrorings, Zhang and coworkers performed research on alternating copolymerization of γ-butyroselenolactone with epoxides.…”