One-Step Synthesis of One-Dimensional Supramolecular Assemblies Composed of Helical Macromolecular Building Blocks

Living systems achieve sophisticated functions using supramolecular protein assemblies, in which the protein building blocks possess a specific secondary structure and are noncovalently arranged in a preprogrammed manner. Herein, we demonstrate the one-step synthesis of one-dimensional macromolecula...

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Veröffentlicht in:Journal of the American Chemical Society 2019-09, Vol.141 (35), p.13995-14002
Hauptverfasser: Wada, Yuya, Shinohara, Ken-ichi, Asakawa, Hitoshi, Matsui, Sayaka, Taima, Tetsuya, Ikai, Tomoyuki
Format: Artikel
Sprache:eng
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Zusammenfassung:Living systems achieve sophisticated functions using supramolecular protein assemblies, in which the protein building blocks possess a specific secondary structure and are noncovalently arranged in a preprogrammed manner. Herein, we demonstrate the one-step synthesis of one-dimensional macromolecular assemblies by simply mixing a glycine-based isocyanide with a nickel catalyst, in which helical constituent polymers are linked end-to-end through multiple hydrogen bonds. The applicable scope of this approach is not confined to a particular monomer bearing a specially designed pendant, but covers a wide range of glycine-based isocyanides with or without aromatic and other functional groups. Surprisingly, copolymerization with an analogous chiral isocyanide (1 mol %) afforded an almost perfect one-handed helical supramolecular fiber owing to intramolecular/intermolecular dual chiral amplifications. The simplicity and broad applicability of this approach, which can also afford exquisite chiral amplification, enable the creation of a wide variety of functional supramolecular assemblies and provide access to new supramolecular materials.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.9b07417