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

doi:10.1038/s41467-020-20724-w

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 journal › Article › peer-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 language	English (US)
Article number	732
Journal	Nature communications
Volume	12
Issue number	1
DOIs	https://doi.org/10.1038/s41467-020-20724-w
State	Published - Dec 2021
Externally published	Yes

ASJC Scopus subject areas

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

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10.1038/s41467-020-20724-w

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title = "Accelerated polymerization of N-carboxyanhydrides catalyzed by crown ether",

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.",

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

note = "Funding Information: This material is based upon work supported by National Science Foundation under Grant Nos. CHE-1709820, CHE-1905097, and DMS-1841810. We thank R. Wang and K. Cai for helpful discussions. Y. X., a visiting student from Hunan University, China, acknowledges the support from China Scholarship Council for her studies in Professor Jianjun Cheng{\textquoteright}s laboratory at UIUC. Publisher Copyright: {\textcopyright} 2021, The Author(s).",

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doi = "10.1038/s41467-020-20724-w",

language = "English (US)",

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AU - Xia, Yingchun

AU - Song, Ziyuan

AU - Tan, Zhengzhong

AU - Xue, Tianrui

AU - Wei, Shiqi

AU - Zhu, Lingyang

AU - Yang, Yingfeng

AU - Fu, Hailin

AU - Jiang, Yunjiang

AU - Lin, Yao

AU - Lu, Yanbing

AU - Ferguson, Andrew L.

AU - Cheng, Jianjun

N1 - Funding Information: This material is based upon work supported by National Science Foundation under Grant Nos. CHE-1709820, CHE-1905097, and DMS-1841810. We thank R. Wang and K. Cai for helpful discussions. Y. X., a visiting student from Hunan University, China, acknowledges the support from China Scholarship Council for her studies in Professor Jianjun Cheng’s laboratory at UIUC. Publisher Copyright: © 2021, The Author(s).

PY - 2021/12

Y1 - 2021/12

N2 - 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.

AB - 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.

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Accelerated polymerization of N-carboxyanhydrides catalyzed by crown ether

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