Temperature-Directed Assembly of Crystalline Cellulose Oligomers into Kinetically Trapped Structures during Biocatalytic Synthesis

  • Yuuki Hata
    Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8550, Japan
  • Toshiki Sawada
    Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8550, Japan
  • Hironori Marubayashi
    Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8550, Japan
  • Shuichi Nojima
    Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8550, Japan
  • Takeshi Serizawa
    Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8550, Japan

書誌事項

公開日
2019-05-02
資源種別
journal article
権利情報
  • https://doi.org/10.15223/policy-029
  • https://doi.org/10.15223/policy-037
  • https://doi.org/10.15223/policy-045
DOI
  • 10.1021/acs.langmuir.9b00850
公開者
American Chemical Society (ACS)

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説明

Crystalline polysaccharides, such as cellulose and chitin, can form superior assemblies in terms of physicochemical stability and mechanical properties. However, their use as molecular building blocks for self-assembled materials is rare, possibly because each crystalline polysaccharide has its own unique monomer unit, preventing molecular design for controlling the self-assembly. Herein, we demonstrate the temperature-directed assembly of crystalline cellulose oligomers into kinetically trapped structures, namely, precipitated nanosheets, nanoribbon network hydrogels, and dispersed nanosheets (in descending order of temperature). It was found that enzymatically synthesized cellulose oligomers self-assembled in situ into those structures depending on the synthetic temperatures. Mechanistic studies suggested that the formation of the nanoribbon networks and the dispersed nanosheets at lower temperatures were driven by synergy between the decreased hydrophobic effect and the simultaneously induced self-crowding effect. Furthermore, nanoribbon network formation was exploited for the construction of cellulose oligomer-based hybrid gels with colloidal particles. Our findings promote the development of robust self-assembled materials composed of crystalline polysaccharides with highly ordered nano-to-macroscale structures.

収録刊行物

  • Langmuir

    Langmuir 35 (21), 7026-7034, 2019-05-02

    American Chemical Society (ACS)

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