Activity of copper enzymes and new development of quantum calculation
Project/Area Number |
21750063
|
Research Category |
Grant-in-Aid for Young Scientists (B)
|
Allocation Type | Single-year Grants |
Research Field |
Inorganic chemistry
|
Research Institution | Kyushu University |
Principal Investigator |
|
Project Period (FY) |
2009 – 2012
|
Project Status |
Completed (Fiscal Year 2012)
|
Budget Amount *help |
¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2012: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000)
Fiscal Year 2011: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2010: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2009: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
|
Keywords | 基礎化学 / 無機化学 / 理論化学 / 遷移状態 / メタン活性化 / 金属錯体 / 理論計算 / 密度汎関数法 / スピンクロスオーバー / 原子価互変異性 / 密度汎関数理論 / 鉄錯体 / コバルト錯体 / ミニマムクロッシングポイント / 量子化学 / 遷移金属錯体 / 金属酵素 / 電子状態 / 酸素活性化 |
Research Abstract |
Methane hydroxylation at the dinuclear copper site of particulate methane monooxygenase (pMMO) is studied by using density functional theory calculations. The electronic, structural, and reactive properties of a possible dinuclear copper species (n-oxo)(n-hydroxo)CuIICuIIIare discussed with respect to the C-H bond activation of methane.We propose that the Tyr374 residue in the second coordination sphere of the dicopper site donates an H atom to the n-n2:n2-peroxoCuIICuIIspecies and the resultant (n-oxo)(n-hydroxo)CuIICuIIIspecies is able to hydroxylate methane. This species for methane hydroxylation is more favorable in reactivity than the bis(n-oxo)CuIIICuIIIspecies. The H-atom transfer or proton-coupled electron transfer from the tyrosine residue can reasonably induce the O-O bond dissociation of the n-n2:n2-peroxoCuIICuIIspecies to form the reactive (n-oxo)(n-hydroxo)CuIICuIIIspecies, which is expected to be an active species for the conversion of methane to methanol at the dicopper site of pMMO
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Report
(5 results)
Research Products
(48 results)
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[Journal Article] Reversible Electron Transfer in a Linear {Fe2Co} Trinuclear Complex Induced by Thermal Treatment and Photoirraditaion2012
Author(s)
T. Liu, D.-P. Dong, S. Kanegawa, S. Kang, O. Sato, Y. Shiota, K. Yoshizawa, S. Hayami, S. Wu, C. He, C.-Y. Duan
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Journal Title
Angewandte Chemie International Edition
Volume: 51
Issue: 18
Pages: 4367-4370
DOI
Related Report
Peer Reviewed
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[Journal Article] Theoretical study on the formation of silacyclopropene from acylsilane and acetylene via silene-to-silylene rearrangement2011
Author(s)
Tanaka, H, Kondo, Y, Shiota, Y Naka, A, Ishikawa, M, Yoshizawa, K
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Journal Title
Organometallics
Volume: 30
Issue: 11
Pages: 3160-3167
DOI
Related Report
Peer Reviewed
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