Polypeptoids are widely used in biological applications owing to their diverse functions and proteolytic stability.One type of polypeptoids,poly-N-methoxyethylglycine(P-Nmeg),has been found to possess remarkable hydro...Polypeptoids are widely used in biological applications owing to their diverse functions and proteolytic stability.One type of polypeptoids,poly-N-methoxyethylglycine(P-Nmeg),has been found to possess remarkable hydrophilicity and notable properties in terms of protein,cell,and bacterial antifouling.However,the currently known synthesis methods of P-Nmeg include solid-phase synthesis,which is time-consuming and difficult to scale up,and N-substituted N-carboxyanhydride(NNCA)ring-opening polymerization,whose monomers were difficult to store.In this study,we used the chemical stable Nmeg N-phenoxycarbonyl(NPC)as the monomer,which was obtained without the use of highly toxic reactants,such as phosgene or phosphorus halide,to synthesize P-Nmeg under open-vessel conditions.By adding BnNH_(2) as an initiator at 80℃,we can obtain controllable short chain length P-Nmeg with narrow dispersity.展开更多
Anionic ring-opening polymerization(AROP)of N-sulfonyl aziridines is an important synthetic route to linear polyethyleneimine(PEI)and its derivatives.In most cases,inert atmosphere and dry solvent were needed because ...Anionic ring-opening polymerization(AROP)of N-sulfonyl aziridines is an important synthetic route to linear polyethyleneimine(PEI)and its derivatives.In most cases,inert atmosphere and dry solvent were needed because of the oxygen-and water-sensitive initiators/catalysts used.Therefore,the AROP of N-sulfonyl aziridines that can be entirely operated in air atmosphere is still a challenging task.Herein,we report a series of sulfanions,including xanthates,dithiocarbamates,dithiobenzoates,thioacetates,and thiolates,as the initiators for the AROP of N-sulfonyl aziridines.Due to their good stability,openvessel polymerization was achieved with high livingness,affording a range of well-definedα-,ω-telechelic poly(N-sulfonyl aziridine)homopolymers and block copolymers with narrow dispersities and tunable molecular weights.Theα-end group of these polyaziridines was readily converted to thiol group,which enabled further post-polymerization functionalization with benzyl acrylate and poly(ethylene glycol)via thiol-ene click chemistry.The establishment of open-vessel sulfanion-initiated AROP of N-sulfonyl aziridines thus lays a solid foundation for the bulk preparation and application of poly(N-sulfonyl aziridine)s and PEI derivatives.展开更多
基金the National Key Research and Development Program of China(No.2022YFC2303100)the National Natural Science Foundation of China(Nos.22075078,22205063)+1 种基金the Shanghai Sailing Program,China(No.22YF1410100)the Fund of the Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism(Shanghai Municipal Education Commission),China.
文摘Polypeptoids are widely used in biological applications owing to their diverse functions and proteolytic stability.One type of polypeptoids,poly-N-methoxyethylglycine(P-Nmeg),has been found to possess remarkable hydrophilicity and notable properties in terms of protein,cell,and bacterial antifouling.However,the currently known synthesis methods of P-Nmeg include solid-phase synthesis,which is time-consuming and difficult to scale up,and N-substituted N-carboxyanhydride(NNCA)ring-opening polymerization,whose monomers were difficult to store.In this study,we used the chemical stable Nmeg N-phenoxycarbonyl(NPC)as the monomer,which was obtained without the use of highly toxic reactants,such as phosgene or phosphorus halide,to synthesize P-Nmeg under open-vessel conditions.By adding BnNH_(2) as an initiator at 80℃,we can obtain controllable short chain length P-Nmeg with narrow dispersity.
基金the National Natural Science Foundation of China(21905171,21774077)Shanghai Municipal Government(18JC1410800)。
文摘Anionic ring-opening polymerization(AROP)of N-sulfonyl aziridines is an important synthetic route to linear polyethyleneimine(PEI)and its derivatives.In most cases,inert atmosphere and dry solvent were needed because of the oxygen-and water-sensitive initiators/catalysts used.Therefore,the AROP of N-sulfonyl aziridines that can be entirely operated in air atmosphere is still a challenging task.Herein,we report a series of sulfanions,including xanthates,dithiocarbamates,dithiobenzoates,thioacetates,and thiolates,as the initiators for the AROP of N-sulfonyl aziridines.Due to their good stability,openvessel polymerization was achieved with high livingness,affording a range of well-definedα-,ω-telechelic poly(N-sulfonyl aziridine)homopolymers and block copolymers with narrow dispersities and tunable molecular weights.Theα-end group of these polyaziridines was readily converted to thiol group,which enabled further post-polymerization functionalization with benzyl acrylate and poly(ethylene glycol)via thiol-ene click chemistry.The establishment of open-vessel sulfanion-initiated AROP of N-sulfonyl aziridines thus lays a solid foundation for the bulk preparation and application of poly(N-sulfonyl aziridine)s and PEI derivatives.
