Mechanistsic Studies on the Catalase Reactions: Introduction of Catalase Activity into Heme Proteins.
Mechanistsic Studies on the Catalase Reactions: Introduction of Catalase Activity into Heme Proteins.
批准号:
14209019
负责人:
WATANABE Yoshihito
金额:
$29.12万
依托单位:
依托单位国家:
日本
项目类别:
Grant-in-Aid for Scientific Research (A)
财政年份:
2002
资助国家:
日本
项目状态:
已结题
起止时间:
2002 至 2005
中文摘要
利用肌红蛋白(Mb)突变体对过氧化氢酶反应进行了详细的研究。Mb突变体的化合物I (Mb-I)是一种铁基(Fe^<IV>=O)与卟啉自由基阳离子配对,可以很容易地与接近化学计量量的间氯过苯甲酸(mCPBA)反应。在Mb-1溶液中加入H_2O_2后,Mb-1被还原回铁态,没有形成任何中间产物。这表明Mb-I能够对H_2O_2进行双电子氧化(催化反应)。用气相色谱-质谱分析H_218O_2/H_2^<16>O_2溶液中含有H64D或F43H/H64L Mb的50:50混合物中析出的O2,发现形成了18O2 (m/e=36)和16O2 (m/e= 32),但没有形成^<16>O^<18>O (m/e= 34)。这表明O2是由H_2O_2的两个电子氧化而不破坏O-O键形成的。氘同位素对Mb突变体和过氧化氢酶催化反应的影响表明,溶血性微球菌过氧化氢酶(MLC)和F43H/H64L Mb的催化反应是通过离子机制进行的,同位素效应较小,小于4.0,因为远端组氨酸残基位于合适的位置,充当离子反应的一般酸碱催化剂。相比之下,其他Mb突变体如H64X (X: A, S和D)和L29H/H64L Mb由于缺乏一般的酸碱催化剂,通过自由基机制将H_2O_2氧化,其中氢原子被Mb- i抽离,其同位素效应在10 ~ 29范围内
英文摘要
The catalase reaction has been studied in detail by using myoglobin (Mb) mutants. Compound I of Mb mutants (Mb-I), a ferryl species (Fe^<IV>=O) paired with a porphyrin radical cation, is readily prepared by the reaction with a nearly stoichiometric amount of m-chloroperbenzoic acid (mCPBA). Upon the addition of H_2O_2 to an Mb-I solution, Mb-1 is reduced back to the ferric state without forming any intermediates. This indicates that Mb-I is capable of performing two-electron oxidation of H_2O_2 (catalatic reaction). GC-MS analysis of the evolved O2 from a 50:50 mixture of H_218O_2/H_2^<16>O_2 solution containing H64D or F43H/H64L Mb showed the formation of 18O2 (m/e=36) and 16O2 (m/e = 32) but not ^<16>O^<18>O (m/e = 34). This implies that O2 is formed by two electron oxidation of H_2O_2 without breaking the O-O bond. Deuterium isotope effects on the catalatic reactions of Mb mutants and catalase suggest that the catalatic reactions of Micrococcus lysodeikticus Catalase (MLC) and F43H/H64L Mb proceed via an ionic mechanism with a small isotope effect of less than 4.0, since the distal histidine residue is located at a proper position to act as a general acid-base catalyst for the ionic reaction. In contrast, other Mb mutants such as H64X (X: A, S, and D) and L29H/H64L Mb oxidize H_2O_2 via a radical mechanism in which a hydrogen atom is abstracted by Mb-I with a large isotope effect in a range of 10 to 29, due to a lack of the general acid-base catalyst
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Watanabe, Monooxygenation of an Aromatic Ring by F43W/H64D/V681 Myoglobin Mutant and Hydrogen Peroxide.
Watanabe,F43W/H64D/V681 肌红蛋白突变体和过氧化氢对芳环的单氧合。
DOI:
--
发表时间:
2005
期刊:
J. Biol. Chem. 280
影响因子:
--
作者:
[T.D.Pfister, T.Ohki, T.Ucno, I.Hara, S.Adachi, Y.Makino, N.Ueyama, Y.Lu, Y.]
通讯作者:
Y.
Molecular Engineering of Cytochrome P450 and Myoglobin for Selective Oxygenations
用于选择性氧化的细胞色素 P450 和肌红蛋白的分子工程
DOI:
--
发表时间:
2004
期刊:
J.Por.Phthal. 8
影响因子:
--
作者:
[T.Ueno, T.Ohki, Y.Watanabe]
通讯作者:
Y.Watanabe
T.Abura, S.Ogo, Y.Watanabe, S.Fukuzumi: "Isolation and Crystal Structure of Water-Soluble Iridium Hydride. Robust and Highly Active Catalyst for Acid-Catalyzed Transfer Hydrogenations of Carbonyl Compounds in Acidic Media"J.Am.Chem.Soc. 125. 4149-4154 (20
T.Abura、S.Ogo、Y.Watanabe、S.Fukuzumi:“水溶性氢化铱的分离和晶体结构。酸性介质中羰基化合物酸催化转移氢化的稳健且高活性的催化剂”J.Am.
DOI:
--
发表时间:
期刊:
影响因子:
--
作者:
[]
通讯作者:
Reversible and regioselective Reaction of La@C62 with Cyclepentadiene
La@C62 与环戊二烯的可逆区域选择性反应
DOI:
--
发表时间:
2005
期刊:
J. Am. Chem. Soc. 127
影响因子:
--
作者:
[Y.Maed, J.Miyashita, T.Hasegawa, T.Wakahara, T.Tsuchiya, T.Nakahodo, T.Akasaka, N.Mizorogi, K.Kobayashi, S.Nagase, T.Kato, N.Ban, H.Nakajima, Y.Watanabe]
通讯作者:
Y.Watanabe
Structural and Spectroscopic Characterization of (μ-Hydroxo or μ-Oxo)(μ-Peroxo)diiron(111) Complexes : Models for Peroxo Intermediates of Non-Heme Diiron Proteins.
(μ-Hydroxo 或 μ-Oxo)(μ-Peroxo)diron(111) 复合物的结构和光谱表征:非血红素 Diiron 蛋白的 Peroxo 中间体模型。
DOI:
--
发表时间:
2005
期刊:
J. Am. Chem. Soc. 127
影响因子:
--
作者:
[X.Zhang, H.Furutachi, S.Fujinami, S.Nagatomo, Y.Maeda, Y.Watanabe, T.Kitagawa, M.Suzuki]
通讯作者:
M.Suzuki
共 37 条
Molecular Design of Oxygenases Applicable to Synthetic Chemistry
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批准号:19105004
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项目类别:Grant-in-Aid for Scientific Research (S)
-
资助金额:$71.14万
-
财政年份:2007
-
负责人:WATANABE Yoshihito
-
依托单位:
Structures and functions of reaction spaces constructed using metalloprotiens
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批准号:16074208
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项目类别:Grant-in-Aid for Scientific Research on Priority Areas
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资助金额:$37.76万
-
财政年份:2004
-
负责人:WATANABE Yoshihito
-
依托单位:
Molecular Design of Metalloproteins
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批准号:11228208
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项目类别:Grant-in-Aid for Scientific Research on Priority Areas
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资助金额:$39.42万
-
财政年份:1999
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负责人:WATANABE Yoshihito
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依托单位:
CHARACTERIZATION OF UNSTABLE INTERMEDIATES OF HEME ENZYMES BY UTILIZING ENZYMES AND THEIR HYBRIDES
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批准号:07458147
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项目类别:Grant-in-Aid for Scientific Research (B)
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资助金额:$3.71万
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财政年份:1995
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负责人:WATANABE Yoshihito
-
依托单位:
MECHANISM OF OXYGEN ACTIVATION BY IRON-CHLORIN COMPLEXES AND THEIR REACTIVITIES.
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批准号:05453043
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项目类别:Grant-in-Aid for General Scientific Research (B)
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资助金额:$3.9万
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财政年份:1993
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负责人:WATANABE Yoshihito
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依托单位:
国内基金
海外基金
myoglobin基因在前庭毛细胞发育和功能中的作用及其分子机制研究
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批准号:82301317
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项目类别:青年科学基金项目
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资助金额:30万元
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批准年份:2023
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负责人:钱付平
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依托单位: