α-Poly(_(L)-lysine)(α-PLL)is a water-soluble cationic biopolymer containing the monomeric unitα-_(L)-lysine,which not only possesses excellent intrinsic properties but also can be modified via facile reactions betw...α-Poly(_(L)-lysine)(α-PLL)is a water-soluble cationic biopolymer containing the monomeric unitα-_(L)-lysine,which not only possesses excellent intrinsic properties but also can be modified via facile reactions between the side amine groups and many other functional moieties.Ring-opening polymerization(ROP)is the most prevalently used technique for the synthesis of PL_(L)-based polypeptides,which involves initial conversion of theε-primary amine-protectedα-_(L)-lysine to the _(L)-lysine NCA monomer.However,obtaining N-carboxyanhydrides(NCAs)in high purity has been a formidable challenge for over 50 years,let alone the large-scale synthesis.Herein,we show an unprecedented scale-up synthesis of _(L)-Cbz-LysNCA monomer and its polymers,generating linearα-poly(_(L)-lysine)with molecular weight(MW)up to 13.4 kDa.This easy operated scale-up strategy will lay the foundations for the industrial preparation of _(L)-Cbz-LysNCA and its polymers,and further extend the realm of existing applications,offering a paradigm for scale-up synthesis of other polypeptides.展开更多
A series of novel bifunctional single-molecule hydrogen-bonding organocatalysts based on fluorinated tertiary alcohol were synthe-sized to mediate the metal-free polymerization of α-amino acid N-carboxyanhydride(NCA)...A series of novel bifunctional single-molecule hydrogen-bonding organocatalysts based on fluorinated tertiary alcohol were synthe-sized to mediate the metal-free polymerization of α-amino acid N-carboxyanhydride(NCA)monomer.Through the screening of catalysts,the polymerizati on catalyzed by the preferred bifun ctional fluoroalcohol catalyst proceeded in a fast and con trolled manner,af-fording high molecular weight polypeptide up to 35.2 ×10^(4) Da with relatively narrow molecular weight distribution(D<1.20).A phenomenon of self-accelerating effect of polymerization induced by a-helical structure of polypeptides was observed,and a possible polymerization pathway has been discussed.展开更多
基金supported by the National Natural Science Foundation of China(91856113 and U21A2089)the National Key Research and Development Program of China(2022YFE0130500).
文摘α-Poly(_(L)-lysine)(α-PLL)is a water-soluble cationic biopolymer containing the monomeric unitα-_(L)-lysine,which not only possesses excellent intrinsic properties but also can be modified via facile reactions between the side amine groups and many other functional moieties.Ring-opening polymerization(ROP)is the most prevalently used technique for the synthesis of PL_(L)-based polypeptides,which involves initial conversion of theε-primary amine-protectedα-_(L)-lysine to the _(L)-lysine NCA monomer.However,obtaining N-carboxyanhydrides(NCAs)in high purity has been a formidable challenge for over 50 years,let alone the large-scale synthesis.Herein,we show an unprecedented scale-up synthesis of _(L)-Cbz-LysNCA monomer and its polymers,generating linearα-poly(_(L)-lysine)with molecular weight(MW)up to 13.4 kDa.This easy operated scale-up strategy will lay the foundations for the industrial preparation of _(L)-Cbz-LysNCA and its polymers,and further extend the realm of existing applications,offering a paradigm for scale-up synthesis of other polypeptides.
基金Research reported in this publication was supported by the National Natural Science Foundation of China(Nos.91856113,51873211).
文摘A series of novel bifunctional single-molecule hydrogen-bonding organocatalysts based on fluorinated tertiary alcohol were synthe-sized to mediate the metal-free polymerization of α-amino acid N-carboxyanhydride(NCA)monomer.Through the screening of catalysts,the polymerizati on catalyzed by the preferred bifun ctional fluoroalcohol catalyst proceeded in a fast and con trolled manner,af-fording high molecular weight polypeptide up to 35.2 ×10^(4) Da with relatively narrow molecular weight distribution(D<1.20).A phenomenon of self-accelerating effect of polymerization induced by a-helical structure of polypeptides was observed,and a possible polymerization pathway has been discussed.
