Structural Changes of the Trinuclear Copper Center in Bilirubin Oxidase upon Reduction

• 庄司, 光男

• 重田, 育照

• Tokiwa, Takaki

• Sladek, Vladimir

• Shibata, Naoki

• Higuchi, Yoshiki

• Kataoka, Kunishige

• Sakurai, Takeshi

• Misaizu, Fuminori

抄録

Geometric and electronic structure changes in the copper (Cu) centers in bilirubin oxidase (BOD) upon a four-electron reduction were investigated by quantum mechanics/molecular mechanics (QM/MM) calculations. For the QM region, the unrestricted density functional theory (UDFT) method was adopted for the open-shell system. We found new candidates of the native intermediate (NI, intermediate II) and the resting oxidized (RO) states, i.e., NIH+ and RO0. Elongations of the Cu-Cu atomic distances for the trinuclear Cu center (TNC) and very small structural changes around the type I Cu (T1Cu) were calculated as the results of a four-electron reduction. The QM/MM optimized structures are in good agreement with recent high-resolution X-ray structures. As the structural change in the TNC upon reduction was revealed to be the change in the size of the triangle spanned by the three Cu atoms of TNC, we introduced a new index (l) to characterize the specific structural change. Not only the wild-type, but also the M467Q, which mutates the amino acid residue coordinating T1Cu, were precisely analyzed in terms of their molecular orbital levels, and the optimized redox potential of T1Cu was theoretically reconfirmed.

収録刊行物

• Molecules

  Molecules 24 (1), 76-, 2018-12

  MDPI

キーワード

• Chemistry (miscellaneous)
• Analytical Chemistry
• Organic Chemistry
• Physical and Theoretical Chemistry
• Molecular Medicine
• Drug Discovery
• Pharmaceutical Science

詳細情報

• CRID: 1050564289152295168
• NII論文ID: 120007133588
• DOI: 10.3390/molecules24010076
• ISSN: 14203049
• HANDLE: 2241/00157299
• Web Site: https://tsukuba.repo.nii.ac.jp/records/51869
• Web Site: http://www.mdpi.com/1420-3049/24/1/76/pdf
• 本文言語コード: en
• 資料種別: journal article
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