基于NNTA可控聚合的环形聚类肽合成与表征.docx

基于NNTA可控聚合的环形聚类肽合成与表征华东理工大学胡祖佳，颜舒婷，戚家乐，陶鑫峰*,林绍梁*(华东理工大学材料科学与工程学院，上海市200237)陶鑫峰特聘副研究员中文摘要：研究了 1,8-二氮杂二环十一碳-7-烯(DBU)引发的N-取代甘氨酸-N-硫代较酸酎(NNTA) 开环聚合。聚合通过两性离子开环聚合机理进行，表现出良好的可控性，聚合产率高(>86%),分子量可 控(900-7500gmol),分子量分布较窄(1.131.25)。通过 IH-NMR 谱图、"C-NMR 谱图、MALDI-ToF 质谱和红外光谱等表征手段，证明所得聚合产物具有环形结构，且聚合物链上带有DBU残基和硫代氨基甲 酸酯基团。与茉胺引发所得的线形聚类肽相比，DBU引发所得的聚类肽具有更小的流体力学体积，进一步 证明了其环形结构。扩链反应表明，加入新单体后聚合反应仍可以继续进行，产物分子量显著增加，表明 了 DBU引发的NNTA聚合具有活性特征。DBU引发的NNTA两性离子开环聚合是一种简便、高效的环 形聚类肽合成方法。英文摘要：The ring-opening polymerizations of -substituted glycine -thiocarboxyanhydrides (NNTAs) initiated by l,8-diazabicycloundec-7-ene (DBU) were carried out in a well-controlled way through zwitterionic ring-opening polymerization mechanism, which produced polypeptoids with high yield (> 86%), controllable molecular weights (900 7500 gmol), and narrow dispersities (1.13 1.25). According to NMR and MALDI-ToF mass analyses, cyclic polypeptoids containing DBU moiety and thiocarbamate group were prepared. The chain extension reaction revealed that the polymer was able to continue propagating after the addition of another batch of monomers, and the molecular weight of the product increased significantly. The result indicates that DBU-initiated NNTA polymerizations have living characteristics. Therefore, DBU-initiated NNTA zwitterionic ring-opening polymerization is a simple and easy method for the synthesis of cyclic polypeptoids.（高分子学报发表时间2021年5月18日）