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]East China Univ Sci & Technol, State Key Lab Bioreactor Engn, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Key Lab Specially Funct Polymer Mat & Related Tech, Sch Mat Sci & Engn, Shanghai Frontiers Sci Ctr Optogenet Tech Cell Met, Shanghai 200237, Peoples R China;[3]Chinese Acad Sci, Suzhou Inst Biomed Engn & Technol, Dept Biomat & Stem Cells, Suzhou 215163, Peoples R China;[4]East China Univ Sci & Technol, Sch Mat Sci & Engn, Key Lab Ultrafine Mat, Minist Educ, Shanghai 200237, Peoples R China

年份：2024

卷号：11

期号：3

起止页码：382

外文期刊名：ACS CENTRAL SCIENCE

收录：;WOS:【SCI-EXPANDED(收录号:WOS:001344916300001)】；

基金：This research was supported by the National Natural Science Foundation of China (Nos. T2325010, 22075078, 52203162, 52361165622), the National Key Research and Development Program of China (2022YFC2303100), the Fundamental Research Funds for the Central Universities (Nos. JKVD1241029, JKD01241701), Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism (Shanghai Municipal Education Commission). The authors thank the Research Center of Analysis and Test of East China University of Science and Technology for help with the characterization for studies reviewed in this manuscript. The authors thank the Research Center of Analysis and Test of Shanghai University of Science and Technology for the low-temperature NMR tests. The authors thank Qingyu Fu and Professor Yijun Zheng from Shanghai University of Science and Technology for their help in low-temperature NMR tests. The authors also thank the staff members of the Mass Spectrometry System at the National Facility for Protein Science in Shanghai (NFPS), Zhangjiang Lab, China, for providing technical support and assistance in data collection and analysis.

语种：英文

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.