Density functional study of porphyrin distortion effects on redox potential of heme

  • Yasuhiro Imada
    Research Center for State‐of‐the‐Art Functional Protein Analysis, Institute for Protein Research, Osaka University, 3‐2 Yamadaoka Suita Osaka 565‐0871 Japan
  • Haruki Nakamura
    Research Center for State‐of‐the‐Art Functional Protein Analysis, Institute for Protein Research, Osaka University, 3‐2 Yamadaoka Suita Osaka 565‐0871 Japan
  • Yu Takano
    Research Center for State‐of‐the‐Art Functional Protein Analysis, Institute for Protein Research, Osaka University, 3‐2 Yamadaoka Suita Osaka 565‐0871 Japan

書誌事項

公開日
2017-09-02
資源種別
journal article
権利情報
  • http://onlinelibrary.wiley.com/termsAndConditions#vor
DOI
  • 10.1002/jcc.25058
公開者
Wiley

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説明

<jats:p>Heme is involved in various biochemical roles in hemoproteins. In the present study, the effect of heme distortion on the redox potential was systematically investigated with density functional calculations. We focused on the ruffled and saddled distortions of heme, which correspond to the two lowest‐frequency normal modes. Our computations demonstrated that the ruffled distortion tended to reduce the redox potential of heme and that the transition of the electronic configuration occurred from (d<jats:sub>xz</jats:sub>, d<jats:sub>yz</jats:sub>)<jats:sup>3</jats:sup>(d<jats:sub>xy</jats:sub>)<jats:sup>2</jats:sup> to (d<jats:sub>xz</jats:sub>, d<jats:sub>yz</jats:sub>)<jats:sup>4</jats:sup>(d<jats:sub>xy</jats:sub>)<jats:sup>1</jats:sup>. In contrast, the saddled distortion had a tendency toward an increase in the redox potential, and no transition of the electronic configuration occurred. In experiments, these tendencies were found in the relationship between with the heme distortions and the redox potentials in cytochrome <jats:italic>c</jats:italic><jats:sub>3</jats:sub>. © 2017 Wiley Periodicals, Inc.</jats:p>

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