文献类型：期刊文献

英文题名：Single-Center Trifunctional Organocatalyst Enables Fast and Controlled Polymerization on N-Carboxyanhydride

作者：Chen, Kang[1,2,3]; Wu, Yueming[1,2,4]; Chen, Minzhang[2,4]; Wang, Jiangzhou[2,4]; Zhou, Min[2,4]; Chen, Xin[4]; Liu, Runhui[1,2,3,4]

机构：[1] State Key Laboratory of Bioreactor Engineering, East China University of Science and Technology, Shanghai, 200237, China; [2] Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism, Frontiers Science Center for Materiobiology and Dynamic Chemistry, Engineering Research Center for Biomedical Materials, Ministry of Education, Key Laboratory of Specially Functional Polymeric Materials and Related Technology, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai, 200237, China; [3] Department of Biomaterials and Stem Cells, Suzhou Institute of Biomedical Engineering and Technology, Chinese Academy of Sciences, Suzhou, 215163, China; [4] Key Laboratory for Ultrafine Materials, Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai, 200237, China

年份：2025

卷号：11

期号：3

起止页码：382

外文期刊名：ACS Central Science

收录：EI(收录号：20244517334865)

语种：英文

外文关键词：Carboxylation - Cationic polymerization - Organocatalyst - Reaction intermediates - Reaction rates - Ring opening polymerization

摘要：Ring-opening polymerization on N-carboxyanhydrides (NCA) initiated by primary amines has been the dominantly used method to prepare polypeptides with widespread applications. However, this polymerization chemistry suffers from slow polymerization rate, limited controllability, and difficulty in preparing high molecular weight polypeptides. Herein, we develop a conjugated cationic catalyst featuring cation-dipole interaction, which remarkably enhances the reaction rate and controllability of NCA polymerization, simultaneously, to afford polypeptides in a short time with predictable molecular weights (DP = 20-500) and narrow dispersities. Experimental data and computational study altogether indicate that conjugated cationic catalysts manifest a single center with triple functions by activating C5-carbonyl on NCAs to enhance the electrophilic activity of NCA monomer, activating carbamate intermediates to accelerate decarboxylation, and moderately passivating primary amines to improve controllability. Notably, this cationic-catalyst is well recyclable while keeping excellent catalytic performance. Thus, the highly efficient cationic-catalyst strategy implies practical and promising applications, representing a new avenue of catalyst design for polymerization chemistry. ? 2024 The Authors. Published by American Chemical Society.