Modulation of polymerization rate of N-carboxyanhydrides in a biphasic system

• Published in: Chinese chemical letters Vol. 35; no. 1; pp. 108872 - 331
• Main Authors: Ji, Guonan, Zheng, Xuetao, Hou, Xiangdie, Sun, Xiao, Wang, Shijie, Li, Xiaohong, Cheng, Jianjun, Song, Ziyuan
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01-01-2024; School of Engineering,Westlake University,Hangzhou 310030,China; Institute of Functional Nano & Soft Materials(FUNSOM),Jiangsu Key Laboratory for Carbon-Based Functional Materials and Devices,Soochow University,Suzhou 215123,China%School of Engineering,Westlake University,Hangzhou 310030,China%The Key Lab of Health Chemistry and Molecular Diagnosis of Suzhou,College of Chemistry,Chemical Engineering and Materials Science,Soochow University,Suzhou 215123,China%Research Center for Industries of the Future,Westlake University,Hangzhou 310030,China
• Subjects: Biphasic system; Cooperative covalent polymerization; N-carboxyanhydrides; Polymerization kinetics; Polypeptides; Cooperative covalent polymerization; Biphasic system; Polymerization kinetics; N-carboxyanhydrides; Polypeptides; N-Carboxyanhydrides
• ISSN: 1001-8417; 1878-5964
• DOI: 10.1016/j.cclet.2023.108872

The recent advances in accelerated polymerization of N-carboxyanhydrides (NCAs) offer an effective strategy to simplify the preparation of polypeptide materials. However, the fine-tuning of polymerization kinetics, which is critical to differentiate the main polymerization and the side reactions, remains largely unexplored. Herein we report the modulation of polymerization rate of NCA in a water/oil biphasic system. By altering the aqueous pH, the initial location of the initiators, and the pKa of initiating amines, we observed the change in polymerization time from several minutes to a few hours. Due to the high interfacial activity and low pKa value, controlled polymerization was observed from multi-amine initiators even if they were initially located in the aqueous phase. This work not only improves our understanding on the biphasic polymerization mechanism, but also facilitates preparation of versatile polypeptide materials.
The polymerization kinetics of N-carboxyanhydrides in a water/oil biphasic system was modulated through the tuning of aqueous pH, the initial location of initiators, and the pKa of initiating amines, which enabled the minimization of water-induced monomer degradations and facilitated the efficient preparation of branched polypeptide materials. [Display omitted]