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Multivalent Assembly of Flexible Polymer Chains into Supramolecular Nanofibers

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Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Am. Chem. Soc. 2020, 142, 39, 16814-16824
    Article

    Multivalent Assembly of Flexible Polymer Chains into Supramolecular Nanofibers
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    • Christopher B. Cooper
      Christopher B. Cooper
      Department of Chemical Engineering, Stanford University, Stanford, California 94305, United States
      More by Christopher B. Cooper
      Orcidhttp://orcid.org/0000-0002-4783-7778
    • Jiheong Kang
      Jiheong Kang
      Department of Chemical Engineering, Stanford University, Stanford, California 94305, United States
      More by Jiheong Kang
    • Yikai Yin
      Yikai Yin
      Department of Materials Science and Engineering, Stanford University, Stanford, California 94305, United States
      More by Yikai Yin
      Orcidhttp://orcid.org/0000-0002-6845-0329
    • Zhiao Yu
      Zhiao Yu
      Department of Chemical Engineering, Stanford University, Stanford, California 94305, United States
      More by Zhiao Yu
      Orcidhttp://orcid.org/0000-0001-8746-1640
    • Hung-Chin Wu
      Hung-Chin Wu
      Department of Chemical Engineering, Stanford University, Stanford, California 94305, United States
      More by Hung-Chin Wu
      Orcidhttp://orcid.org/0000-0001-6492-0525
    • Shayla Nikzad
      Shayla Nikzad
      Department of Chemical Engineering, Stanford University, Stanford, California 94305, United States
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      Orcidhttp://orcid.org/0000-0001-9416-4601
    • Yuto Ochiai
      Yuto Ochiai
      Department of Chemical Engineering, Stanford University, Stanford, California 94305, United States
      Department of Organic Materials Science, Yamagata University, 4-3-16 Jonan, Yonezawa, Yamagata 992-8510, Japan
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    • Hongping Yan
      Hongping Yan
      Department of Chemical Engineering, Stanford University, Stanford, California 94305, United States
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    • Wei Cai
      Wei Cai
      Department of Materials Science and Engineering, Stanford University, Stanford, California 94305, United States
      Department of Mechanical Engineering, Stanford University, Stanford, California 94305, United States
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    • Zhenan Bao*
      Zhenan Bao
      Department of Chemical Engineering, Stanford University, Stanford, California 94305, United States
      *Email: [email protected]
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      Orcidhttp://orcid.org/0000-0002-0972-1715
    Other Access OptionsSupporting Information (1)

    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2020, 142, 39, 16814–16824
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.0c07651
    Published September 9, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    Polymeric materials in nature regularly employ ordered, hierarchical structures in order to perform unique and precise functions. Importantly, these structures are often formed and stabilized by the cooperative summation of many weak interactions as opposed to the independent association of a few strong bonds. Here, we show that synthetic, flexible polymer chains with periodically placed and directional dynamic bonds collectively assemble into supramolecular nanofibers when the overall molecular weight is below the polymer’s critical entanglement molecular weight. This causes bulk films of long polymer chains to have faster dynamics than films of shorter polymer chains of identical chemical composition. The formation of nanofibers increases the bulk film modulus by over an order of magnitude and delays the onset of terminal flow by more than 100 °C, while still remaining solution processable. Systematic investigation of different polymer chain architectures and dynamic bonding moieties along with coarse-grained molecular dynamics simulations illuminate governing structure–function relationships that determine a polymer’s capacity to form supramolecular nanofibers. This report of the cooperative assembly of multivalent polymer chains into hierarchical, supramolecular structures contributes to our fundamental understanding of designing biomimetic functional materials.

    Copyright © 2020 American Chemical Society

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    Cited By

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    This article is cited by 37 publications.

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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2020, 142, 39, 16814–16824
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.0c07651
    Published September 9, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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