A series of random copolypeptides of poly（methoxy-diethylene glycol–L-glutamate）-co-poly（S-（onitrobenzyl）-L-cysteine）was synthesized by ring-open copolymerization of methoxydiethylene glycol-Lglutamate-N-carbox...A series of random copolypeptides of poly（methoxy-diethylene glycol–L-glutamate）-co-poly（S-（onitrobenzyl）-L-cysteine）was synthesized by ring-open copolymerization of methoxydiethylene glycol-Lglutamate-N-carboxyanhydride（EG2-Glu-NCA） and S-（o-nitrobenzyl）-L-cysteine-N-carboxyanhydride（NBC-NCA） in dried dimethylformamide solution, which presents quadruple thermo-photo-redox responsive self-assembly behavior and forms the related nanogel and hydrogel in water.展开更多
Polypeptides and polypeptoids were widely used as biomedical materials because of their good biocompatibility. In this work we reported a series of pH-responsive copolypeptides and polypeptide-polypeptoid block copoly...Polypeptides and polypeptoids were widely used as biomedical materials because of their good biocompatibility. In this work we reported a series of pH-responsive copolypeptides and polypeptide-polypeptoid block copolymers, i.e. random copolymers of L-glutamic acid （Glu） with L-leucine （Leu） [poly（Glu-r-Leu）s], as well as their block copolymers with polysarcosine （polySar）. Well-defined poly（Glu-r-Leu）s with predictable compositions and molecular weights were synthesized by ring opening polymerization of corresponding N-carboxyanhydride monomers. We investigated the relationship between hydrophilicity-hydrophobicity transition and copolymer composition. With increasing Leu fraction, both the pH value of cloud point and the micellar size increased. Poly（Glu-r-Leu） with 60% Leu exhibited a cloud point at the pH of 5.0 to 6.0 the same as that in endosome and lysosome. Poly（Glu-r-Leu）-b-polySars assembled in phosphate buffer and performed pH-responsive morphology change from orbicular micelles at high pH to worm-like micelles at low pH. They were potential pH-responsive carriers for drug and gene delivery to enhance cargo release in cellules.展开更多
The precise synthesis of polypeptides with varying chain topologies has attracted significant interest due to their diverse functional applications.However,conventional polymerization of environment-susceptible N-carb...The precise synthesis of polypeptides with varying chain topologies has attracted significant interest due to their diverse functional applications.However,conventional polymerization of environment-susceptible N-carboxylic anhydride monomers using primary amine initiators suffers from inevitable side reactions,which greatly compromise chain-end fidelity,thereby disabling access to polypeptides with high-order architectures.Herein,we have developed a general and robust strategy based on normal aminemechanism for the synthesis of various topological polypeptides via polymerization of moisture-insensitive and airtolerant N-phenoxycarbonyl-functionalizedα-amino acid precursors using primary amine hydrochloride as initiators.This strategy enabled the synthesis of a block,star,star-block,brush-type,and multiblock(co)polypeptides with desired sequences,predictable molecular weights,low polydispersity,and high-fidelity chain ends even under open-air conditions.Remarkably,the robustness of this approach has been exemplified by the precise synthesis of welldefined photoresponsive decablock copolypeptides,exhibiting a spontaneous morphological evolution from polymersomes to lamellae nanostructures upon light irradiation.This work provides a general and reliable tool for synthesizing polypeptides with varying topologies,shedding light on the development of synthetic polypeptide-based materials.展开更多
基金the financial support of the National Natural Science Foundation of China (No. 21474061)
文摘A series of random copolypeptides of poly（methoxy-diethylene glycol–L-glutamate）-co-poly（S-（onitrobenzyl）-L-cysteine）was synthesized by ring-open copolymerization of methoxydiethylene glycol-Lglutamate-N-carboxyanhydride（EG2-Glu-NCA） and S-（o-nitrobenzyl）-L-cysteine-N-carboxyanhydride（NBC-NCA） in dried dimethylformamide solution, which presents quadruple thermo-photo-redox responsive self-assembly behavior and forms the related nanogel and hydrogel in water.
基金financially supported by the National Natural Science Foundation of China(Nos.21174122 and 51390481)
文摘Polypeptides and polypeptoids were widely used as biomedical materials because of their good biocompatibility. In this work we reported a series of pH-responsive copolypeptides and polypeptide-polypeptoid block copolymers, i.e. random copolymers of L-glutamic acid （Glu） with L-leucine （Leu） [poly（Glu-r-Leu）s], as well as their block copolymers with polysarcosine （polySar）. Well-defined poly（Glu-r-Leu）s with predictable compositions and molecular weights were synthesized by ring opening polymerization of corresponding N-carboxyanhydride monomers. We investigated the relationship between hydrophilicity-hydrophobicity transition and copolymer composition. With increasing Leu fraction, both the pH value of cloud point and the micellar size increased. Poly（Glu-r-Leu） with 60% Leu exhibited a cloud point at the pH of 5.0 to 6.0 the same as that in endosome and lysosome. Poly（Glu-r-Leu）-b-polySars assembled in phosphate buffer and performed pH-responsive morphology change from orbicular micelles at high pH to worm-like micelles at low pH. They were potential pH-responsive carriers for drug and gene delivery to enhance cargo release in cellules.
基金The financial support from the National Key R&D Program of China(grant no.2020YFA0710700)the National Natural Science Foundation of China(NNSFC)Project(grant nos.51690150,51690154,52021002,and U19A2094)is gratefully acknowledged.
文摘The precise synthesis of polypeptides with varying chain topologies has attracted significant interest due to their diverse functional applications.However,conventional polymerization of environment-susceptible N-carboxylic anhydride monomers using primary amine initiators suffers from inevitable side reactions,which greatly compromise chain-end fidelity,thereby disabling access to polypeptides with high-order architectures.Herein,we have developed a general and robust strategy based on normal aminemechanism for the synthesis of various topological polypeptides via polymerization of moisture-insensitive and airtolerant N-phenoxycarbonyl-functionalizedα-amino acid precursors using primary amine hydrochloride as initiators.This strategy enabled the synthesis of a block,star,star-block,brush-type,and multiblock(co)polypeptides with desired sequences,predictable molecular weights,low polydispersity,and high-fidelity chain ends even under open-air conditions.Remarkably,the robustness of this approach has been exemplified by the precise synthesis of welldefined photoresponsive decablock copolypeptides,exhibiting a spontaneous morphological evolution from polymersomes to lamellae nanostructures upon light irradiation.This work provides a general and reliable tool for synthesizing polypeptides with varying topologies,shedding light on the development of synthetic polypeptide-based materials.
