文献类型：期刊文献

英文题名：Easy access to amphiphilic nitrogenous block copolymers via switchable catalysis

作者：Liang, Xue[1];Lv, Jiachen[1];Qiang, Hongru[1];Li, Jiahui[1];Wang, Wenli[1];Du, Jianzhong[2,3,4];Zhu, Yunqing[1]

机构：[1]Tongji Univ, Sch Mat Sci & Engn, Dept Polymer Mat, 4800 Caoan Rd, Shanghai 201804, Peoples R China;[2]Tongji Univ, Shanghai Peoples Hosp 4, Translat Res Inst Brain & Brain Like Intelligence, Sch Med,Clin Res Ctr Anesthesiol & Perioperat Med,, Shanghai 200434, Peoples R China;[3]Tongji Univ, Sch Mat Sci & Engn, Key Lab Adv Civil Engn Mat, Minist Educ, 4800 Caoan Rd, Shanghai 201804, Peoples R China;[4]East China Univ Sci & Technol, Sch Mat Sci & Engn, Shanghai 200237, Peoples R China

年份：2024

卷号：15

期号：44

起止页码：18650

外文期刊名：CHEMICAL SCIENCE

收录：;EI(收录号：20244317269212);WOS:【SCI-EXPANDED(收录号:WOS:001340489600001)】；

基金：This work was supported by National Natural Science Foundation of China (22175131, 22335005, and 21925505), the National Key R&D Program of China (2022YFC2402900), Innovation Program of Shanghai Municipal Education Commission (2023ZKZD28), Tongcheng Youth Research and Development Fund (CPCIF-RA-0104), and the Interdisciplinary Collaborative Research Project of Tongji University (2023-2-YB-03). J. Du is a recipient of National Science Fund for Distinguished Young Scholars.

语种：英文

外文关键词：Catalysis - Copolymerization - Monomers - Nuclear magnetic resonance - Nuclear magnetic resonance spectroscopy

摘要：A key challenge in polymer synthesis is to develop new methods that enable block copolymers to be prepared from mixed monomer feedstock. The emerging switchable polymerization catalysis can generate block copolymers with well-defined structures and tunable properties from monomer mixtures. However, constrained by the reactivity of monomers and the incompatibility of different polymerization mechanisms, this method is usually confined to oxygenated monomers. In this work, the switchable polymerization was successfully applied to nitrogenous monomers for the first time, achieving the efficient copolymerization of N-substituted N-carboxyanhydrides (NNCAs) with epoxides and cyclic anhydrides. This leads to easy access towards amphiphilic nitrogenous copolymers, such as polyester-b-polypeptoids. Density functional theory calculations demonstrated that the reaction of cyclic anhydrides with the alkoxide terminal is thermodynamically more favorable than that of NNCAs. Characterization, using nuclear magnetic resonance spectroscopy, size exclusion chromatography and in situ infrared spectroscopy, has confirmed the well-defined block structure of the obtained copolymers. This switchable polymerization strategy is applicable to a range of monomer mixtures with different oxygenated monomers and NNCAs, providing a highly efficient synthetic route towards nitrogenous block copolymers. Most importantly, the easily accessed amphiphilic polyester-b-polypeptoids demonstrated excellent anti-protein adsorption capabilities and barely any cytotoxicity, showing great potential in the field of biomedicine.