Post-Crystal Engineering of Zinc-Substituted Myoglobin to Construct a Long-Lived Photoinduced Charge-Separation System

Authors

  • Dr. Tomomi Koshiyama,

    1. Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University iCeMS Lab Funai Center, Kyoto University Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan), Fax: (+81) 75-383-2812
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  • Dr. Masanobu Shirai,

    1. Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University iCeMS Lab Funai Center, Kyoto University Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan), Fax: (+81) 75-383-2812
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  • Tatsuo Hikage,

    1. High Intensity X-ray Diffraction Laboratory, Nagoya University (Japan)
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  • Hiroyasu Tabe,

    1. Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan)
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  • Prof. Dr. Koichiro Tanaka,

    1. Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University iCeMS Lab Funai Center, Kyoto University Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan), Fax: (+81) 75-383-2812
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  • Prof. Dr. Susumu Kitagawa,

    Corresponding author
    1. Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University iCeMS Lab Funai Center, Kyoto University Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan), Fax: (+81) 75-383-2812
    2. Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan)
    • Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University iCeMS Lab Funai Center, Kyoto University Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan), Fax: (+81) 75-383-2812
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  • Prof. Dr. Takafumi Ueno

    Corresponding author
    1. Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University iCeMS Lab Funai Center, Kyoto University Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan), Fax: (+81) 75-383-2812
    2. PRESTO (Japan) Science and Technology Agency (JST), Honcho Kawaguchi, Saitama 332-0012 (Japan)
    • Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University iCeMS Lab Funai Center, Kyoto University Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan), Fax: (+81) 75-383-2812
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  • We thank Dr. Y. Tokita (Sony Corporation) for suggestions, and the members of BL38B1 of SPring-8 for assistance during the diffraction data collection. A Grant-in-Aid for Scientific Research (Grant No. 18655054 for T.U.) was awarded from the Ministry of Education, Culture, Sports, Science and Technology (Japan), and PRESTO, JST. Synchrotron radiation experiments were conducted under the approval of 2008A1124 and 2009B1065 at SPring-8.

Abstract

original image

An artificial photoinduced electron-transfer system has been constructed by accumulating redox cofactors in a myoglobin crystal. The crystal space allowed the construction of a site-specific dense array, and the different redox cofactors had low reorganization energies, as observed in native photosynthesis. A charge-separated state with a half-life 2800 times longer than that of one previously reported in organic solution was achieved.

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