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Polymerization within a molecular-scale stereoregular template

Nature volume 429, pages 52–55 (2004)Cite this article

Abstract

Enzymes efficiently synthesize biopolymers by organizing monomer units within regularly structured molecular-scale spaces and exploiting weak non-covalent interactions, such as hydrogen bonds, to control the polymerization1 process. This ‘template’ approach is both attractive and challenging for synthetic polymer synthesis, where structurally regulated molecular-scale spaces could in principle provide solid-phase reaction sites for precision polymerization. Previously, free-radical polymerization of methyl methacrylate in solutions containing stereoregular isotactic (it) or syndiotactic (st) poly(methyl methacrylate) (PMMA) has been shown to result in template synthesis2,3 of the opposite PMMA based on stereocomplex formation4,5 with van der Waals interactions. However, using the structure of a solid to determine the stereochemical structure of a polymer has not been satisfactorily achieved6. Here we show that macromolecularly porous ultrathin films, fabricated by a single assembly step, can be used for the highly efficient stereoregular template polymerization of methacrylates through stereocomplex formation. This reaction mould accurately transfers its structural properties of stereoregularity, molecular weight and organization within the template to the new polymer.

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Figure 1: A schematic representation of template polymerization using ultrathin porous films.
Figure 2: Characterization of it-PMMAs polymerized in porous st-PMAA films for 3 h at 70 °C.
Figure 3

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Acknowledgements

We thank K. Hatada and T. Kitayama for technological support of living anionic polymerization.

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Author notes

  1. Takeshi Serizawa

    Present address: Research Center for Advanced Science and Technology, The University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo, 153-8904, Japan

  2. Mitsuru Akashi

    Present address: Department of Molecular Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamada-oka, Suita, 565-0871, Japan

Authors and Affiliations

  1. Department of Nanostructured and Advanced Materials, Graduate School of Science and Engineering, Kagoshima University, 1-21-40 Korimoto, Kagoshima, 890-0065, Japan

    Takeshi Serizawa, Ken-ichi Hamada & Mitsuru Akashi

  2. Research Center for Advanced Science and Technology, The University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo, 153-8904, Japan

    Mitsuru Akashi

  3. Department of Molecular Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamada-oka, Suita, 565-0871, Japan

    Takeshi Serizawa

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Correspondence to Mitsuru Akashi.

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Serizawa, T., Hamada, Ki. & Akashi, M. Polymerization within a molecular-scale stereoregular template. Nature 429, 52–55 (2004). https://doi.org/10.1038/nature02525

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