Accelerated polymerization of N-carboxyanhydrides catalyzed by crown ether

Yingchun Xia, Ziyuan Song, Zhengzhong Tan, Tianrui Xue, Shiqi Wei, Lingyang Zhu, Yingfeng Yang, Hailin Fu, Yunjiang Jiang, Yao Lin, Yanbing Lu, Andrew L. Ferguson, Jianjun Cheng

Research output: Contribution to journalArticlepeer-review

Abstract

The recent advances in accelerated polymerization of N-carboxyanhydrides (NCAs) enriched the toolbox to prepare well-defined polypeptide materials. Herein we report the use of crown ether (CE) to catalyze the polymerization of NCA initiated by conventional primary amine initiators in solvents with low polarity and low hydrogen-bonding ability. The cyclic structure of the CE played a crucial role in the catalysis, with 18-crown-6 enabling the fastest polymerization kinetics. The fast polymerization kinetics outpaced common side reactions, enabling the preparation of well-defined polypeptides using an α-helical macroinitiator. Experimental results as well as the simulation methods suggested that CE changed the binding geometry between NCA and propagating amino chain-end, which promoted the molecular interactions and lowered the activation energy for ring-opening reactions of NCAs. This work not only provides an efficient strategy to prepare well-defined polypeptides with functionalized C-termini, but also guides the design of catalysts for NCA polymerization.

Original languageEnglish (US)
Article number732
JournalNature communications
Volume12
Issue number1
DOIs
StatePublished - Dec 2021

ASJC Scopus subject areas

  • Chemistry(all)
  • Biochemistry, Genetics and Molecular Biology(all)
  • Physics and Astronomy(all)

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