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Controlling the Hydration Structure with a Small Amount of Fluorine To Produce Blood Compatible Fluorinated Poly(2-methoxyethyl acrylate)
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    Controlling the Hydration Structure with a Small Amount of Fluorine To Produce Blood Compatible Fluorinated Poly(2-methoxyethyl acrylate)
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    • Ryohei Koguchi
      Ryohei Koguchi
      Soft Materials Chemistry, Institute for Materials Chemistry and Engineering, Kyushu University, Build. CE41, 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan
      AGC Incorporation New Product R&D Center, 1150 Hazawa-cho, Kanagawa-ku, Yokohama, Kanagawa 221-8755, Japan
    • Katja Jankova
      Katja Jankova
      Soft Materials Chemistry, Institute for Materials Chemistry and Engineering, Kyushu University, Build. CE41, 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan
      Department of Energy Conversion and Storage, Technical University of Denmark, Elektrovej, Build. 375, 2800 Kongens Lyngby, Denmark
    • Noriko Tanabe
      Noriko Tanabe
      AGC Incorporation Innovative Technology Research Center, 1150 Hazawa-cho, Kanagawa-ku, Yokohama, Kanagawa 221-8755, Japan
    • Yosuke Amino
      Yosuke Amino
      AGC Incorporation Innovative Technology Research Center, 1150 Hazawa-cho, Kanagawa-ku, Yokohama, Kanagawa 221-8755, Japan
      More by Yosuke Amino
    • Yuki Hayasaka
      Yuki Hayasaka
      AGC Incorporation Innovative Technology Research Center, 1150 Hazawa-cho, Kanagawa-ku, Yokohama, Kanagawa 221-8755, Japan
    • Daisuke Kobayashi
      Daisuke Kobayashi
      AGC Incorporation Innovative Technology Research Center, 1150 Hazawa-cho, Kanagawa-ku, Yokohama, Kanagawa 221-8755, Japan
    • Tatsuya Miyajima
      Tatsuya Miyajima
      AGC Incorporation Innovative Technology Research Center, 1150 Hazawa-cho, Kanagawa-ku, Yokohama, Kanagawa 221-8755, Japan
    • Kyoko Yamamoto
      Kyoko Yamamoto
      AGC Incorporation New Product R&D Center, 1150 Hazawa-cho, Kanagawa-ku, Yokohama, Kanagawa 221-8755, Japan
    • Masaru Tanaka*
      Masaru Tanaka
      Soft Materials Chemistry, Institute for Materials Chemistry and Engineering, Kyushu University, Build. CE41, 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan
      *E-mail: [email protected]
    Other Access OptionsSupporting Information (1)

    Biomacromolecules

    Cite this: Biomacromolecules 2019, 20, 6, 2265–2275
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    https://doi.org/10.1021/acs.biomac.9b00201
    Published May 1, 2019
    Copyright © 2019 American Chemical Society

    Abstract

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    Poly(2-methoxyethyl acrylate) (PMEA) shows excellent blood compatibility because of the existence of intermediate water. Various modifications of PMEA by changing its main or side chain’s chemical structure allowed tuning of the water content and the blood compatibility of numerous novel polymers. Here, we exploit a possibility of manipulating the surface hydration structure of PMEA by incorporation of small amounts of hydrophobic fluorine groups in MEA polymers using atom-transfer radical polymerization and the (macro) initiator concept. Two kinds of fluorinated MEA polymers with similar molecular weights and the same 5.5 mol % of fluorine content were synthesized using the bromoester of 2,2,3,3,4,4,5,5,6,6,7,7,8,8-pentadecafluoro-1-octanol (F15) and poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) as (macro) initiators, appearing liquid and solid at room temperature, respectively. The fibrinogen adsorption of the two varieties of fluorinated MEA polymers was different, which could not be explained only by the bulk hydration structure. Both polymers show a nanostructured morphology in the hydrated state with different sizes of the features. The measured elastic modulus of the domains appearing in atomic force microscopy and the intermediate water content shed light on the distinct mechanism of blood compatibility. Contact angle measurements reveal the surface hydration dynamics—while in the hydrated state, F15-b-PMEA reorients easily to the surface exposing its PMEA part to the water, the small solid PTFEMA block with high glass-transition temperature suppresses the movement of PTFEMA-b-PMEA and its reconstruction on the surface. These findings illustrate that in order to make a better blood compatible polymer, the chains containing sufficient intermediate water need to be mobile and efficiently oriented to the water surface.

    Copyright © 2019 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.biomac.9b00201.

    • Experimental details, detailed characterization data, DSC profiles, SEM and additional AFM images, and XPS and NMR spectra for the discussed polymers (PDF)

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    This article is cited by 20 publications.

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    Biomacromolecules

    Cite this: Biomacromolecules 2019, 20, 6, 2265–2275
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.biomac.9b00201
    Published May 1, 2019
    Copyright © 2019 American Chemical Society

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