Role of tyrosine residue in methane activation at the dicopper site of particulate methane monooxygenase: A density functional theory study

研究成果: ジャーナルへの寄稿記事

41 引用 (Scopus)

抄録

Methane hydroxylation at the dinuclear copper site of particulate methane monooxygenase (pMMO) is studied by using density functional theory calculations. The electronic, structural, and reactivity properties of a possible dinuclear copper species (μ-oxo)(μ-hydroxo)CuIICuIII are discussed with respect to the C-H bond activation of methane. We propose that the tyrosine residue in the second coordination sphere of the dicopper site donates an H atom to the μ-η22-peroxoCu IICuII species and the resultant (μ-oxo)(μ-hydroxo) CuIICuIII species can hydroxylate methane. This species for methane hydroxylation is more favorable in reactivity than the bis(μ-oxo)CuIIICuIII species. The H-atom transfer or proton-coupled electron transfer from the tyrosine residue can reasonably induce the O-O bond dissociation of the μ-η22- peroxoCuIICuII species to form the reactive (μ-oxo)(μ-hydroxo)CuIICuIII species, which is expected to be an active species for the conversion of methane to methanol at the dicopper site of pMMO. The rate-determining step for the methane hydroxylation is the C-H cleavage, which is in good agreement with experimental KIE values reported so far.

元の言語英語
ページ(範囲)7907-7917
ページ数11
ジャーナルInorganic chemistry
52
発行部数14
DOI
出版物ステータス出版済み - 7 15 2013

Fingerprint

methane monooxygenase
tyrosine
Methane
particulates
Density functional theory
Tyrosine
methane
Chemical activation
activation
density functional theory
Hydroxylation
Copper
Atoms
reactivity
copper
Methanol
Protons
atoms

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

これを引用

@article{a968f7695d744b2c8940a73a737c4f15,
title = "Role of tyrosine residue in methane activation at the dicopper site of particulate methane monooxygenase: A density functional theory study",
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 reactivity properties of a possible dinuclear copper species (μ-oxo)(μ-hydroxo)CuIICuIII are discussed with respect to the C-H bond activation of methane. We propose that the tyrosine residue in the second coordination sphere of the dicopper site donates an H atom to the μ-η2:η2-peroxoCu IICuII species and the resultant (μ-oxo)(μ-hydroxo) CuIICuIII species can hydroxylate methane. This species for methane hydroxylation is more favorable in reactivity than the bis(μ-oxo)CuIIICuIII species. The H-atom transfer or proton-coupled electron transfer from the tyrosine residue can reasonably induce the O-O bond dissociation of the μ-η2:η2- peroxoCuIICuII species to form the reactive (μ-oxo)(μ-hydroxo)CuIICuIII species, which is expected to be an active species for the conversion of methane to methanol at the dicopper site of pMMO. The rate-determining step for the methane hydroxylation is the C-H cleavage, which is in good agreement with experimental KIE values reported so far.",
author = "Yoshihito Shiota and Gergely Juh{\'a}sz and Kazunari Yoshizawa",
year = "2013",
month = "7",
day = "15",
doi = "10.1021/ic400417d",
language = "English",
volume = "52",
pages = "7907--7917",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "14",

}

TY - JOUR

T1 - Role of tyrosine residue in methane activation at the dicopper site of particulate methane monooxygenase

T2 - A density functional theory study

AU - Shiota, Yoshihito

AU - Juhász, Gergely

AU - Yoshizawa, Kazunari

PY - 2013/7/15

Y1 - 2013/7/15

N2 - Methane hydroxylation at the dinuclear copper site of particulate methane monooxygenase (pMMO) is studied by using density functional theory calculations. The electronic, structural, and reactivity properties of a possible dinuclear copper species (μ-oxo)(μ-hydroxo)CuIICuIII are discussed with respect to the C-H bond activation of methane. We propose that the tyrosine residue in the second coordination sphere of the dicopper site donates an H atom to the μ-η2:η2-peroxoCu IICuII species and the resultant (μ-oxo)(μ-hydroxo) CuIICuIII species can hydroxylate methane. This species for methane hydroxylation is more favorable in reactivity than the bis(μ-oxo)CuIIICuIII species. The H-atom transfer or proton-coupled electron transfer from the tyrosine residue can reasonably induce the O-O bond dissociation of the μ-η2:η2- peroxoCuIICuII species to form the reactive (μ-oxo)(μ-hydroxo)CuIICuIII species, which is expected to be an active species for the conversion of methane to methanol at the dicopper site of pMMO. The rate-determining step for the methane hydroxylation is the C-H cleavage, which is in good agreement with experimental KIE values reported so far.

AB - Methane hydroxylation at the dinuclear copper site of particulate methane monooxygenase (pMMO) is studied by using density functional theory calculations. The electronic, structural, and reactivity properties of a possible dinuclear copper species (μ-oxo)(μ-hydroxo)CuIICuIII are discussed with respect to the C-H bond activation of methane. We propose that the tyrosine residue in the second coordination sphere of the dicopper site donates an H atom to the μ-η2:η2-peroxoCu IICuII species and the resultant (μ-oxo)(μ-hydroxo) CuIICuIII species can hydroxylate methane. This species for methane hydroxylation is more favorable in reactivity than the bis(μ-oxo)CuIIICuIII species. The H-atom transfer or proton-coupled electron transfer from the tyrosine residue can reasonably induce the O-O bond dissociation of the μ-η2:η2- peroxoCuIICuII species to form the reactive (μ-oxo)(μ-hydroxo)CuIICuIII species, which is expected to be an active species for the conversion of methane to methanol at the dicopper site of pMMO. The rate-determining step for the methane hydroxylation is the C-H cleavage, which is in good agreement with experimental KIE values reported so far.

UR - http://www.scopus.com/inward/record.url?scp=84880320460&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84880320460&partnerID=8YFLogxK

U2 - 10.1021/ic400417d

DO - 10.1021/ic400417d

M3 - Article

C2 - 23808646

AN - SCOPUS:84880320460

VL - 52

SP - 7907

EP - 7917

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 14

ER -