Mechanistic analysis of metal-oxygen active species and their synthetic application to new catalytic oxidation

金属氧活性物质的机理分析及其在新型催化氧化中的合成应用

基本信息

  • 批准号:
    17350029
  • 负责人:
  • 金额:
    $ 9.66万
  • 依托单位:
  • 依托单位国家:
    日本
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
  • 财政年份:
    2005
  • 资助国家:
    日本
  • 起止时间:
    2005 至 2006
  • 项目状态:
    已结题

项目摘要

This study is intended to clarify the dioxygen activation process by artificial model complexes for heme enzymes through the spectroscopic characterization of the reactive intermediates such as peroxo-and hydroperoxo heme species, which are generated by the cryoradiolysis with γ-ray (one-electron reduction) of the corresponding dioxygen adducts. The employed complexes have the mimics of the essential functional groups, a) axial ligand, b) hydrogen bondings toward dioxygen, found in the active sites of heme enzymes. The resulting species from the 2K-cryoradiolysis of oxy-complex was assignable to a low-spin six-coordinated peroxoferric heme. After annealing at 133K, a hydroperoxo species was formed. These results confirm that the present complex can reproduce the first important part of the dioxygen activation process composed of the reduction of the coordinated dioxygen and the protonation of the resulting peroxo group.Iron porphyrin complexes, which bear four or two naphtholic hydroxyl groups in the vicinity of the metal center, were synthesized as models of prostaglandin H synthase. In the catalytic cycle of this enzyme, the tyrosyl residue is oxidized to the phenoxyl radical, which abstracts the specific hydrogen atom of the polyolefinic substrate. The present model complexes were oxidized with peroxy acid to give the active species composed of naphthoxyl radical and ferryl ion, as observed in the enzyme. The active species can oxidize non-conjugated diene substrate to the corresponding hydroperoxide with the recovery of the starting naphthol-appended ferric complex. The structure of one of the model complexes was determined by X-ray crystallography.
本研究旨在通过对过氧化血红素和氢过氧化血红素等反应中间体的光谱表征,阐明血红素酶的人工模型配合物的双氧活化过程,这些反应中间体是由相应的双氧加合物用γ射线(单电子还原)冷裂解产生的。所采用的配合物具有在血红素酶活性位点发现的基本官能团的模拟物,a)轴向配体,b)向二氧氢键。由氧配合物的2k -低温分解得到的产物可分配给低自旋六配位过氧铁血红素。在133K退火后,形成氢过氧化物。这些结果证实,该配合物可以重现双氧原子活化过程的第一个重要部分,即配位双氧原子的还原和生成的过氧基团的质子化。铁卟啉配合物在金属中心附近具有四个或两个萘酚羟基,被合成为前列腺素H合酶的模型。在该酶的催化循环中,酪氨酸残基被氧化为苯氧基自由基,苯氧基自由基抽象出聚烯烃底物的特定氢原子。模型配合物经过氧酸氧化后,得到由萘氧基自由基和铁离子组成的活性物质,如酶中所见。活性物质可以将非共轭二烯底物氧化为相应的氢过氧化物,同时回收起始萘酚附加的铁配合物。用x射线晶体学测定了其中一个模型配合物的结构。

项目成果

期刊论文数量(0)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
A functional model of the cytochrome c oxidase active site; Unique conversion of a heme-μ-peroxo Cu^<II> intermediate into heme-superoxo/Cu^<II>
细胞色素 c 氧化酶活性位点的功能模型;血红素-μ-过氧 Cu^<II> 中间体独特转化为血红素-superoxo/Cu^<II>
  • DOI:
  • 发表时间:
    2005
  • 期刊:
  • 影响因子:
    0
  • 作者:
    M.Yamada;E.Fukumoto;M.Ooidemizu;N.Brefuel;N.Matsumoto;S.Iijima;M.Kojima;N.Re;F.Dahan;J.-P.Tuchagues;Z.Zhu 他;M.Yamada 他;Y.Shimazaki et al.;Y.Shimazaki et al.;Y.Shimazaki et al.;J.Nakazawa et al.;J.Nakazawa et al.;J.Nakazawa et al.;J.Nakazawa et al.;K.Shimojo et al.;J.Nakazawa et al.;J.Nakazawa et al.;T.Chishiro et al.;J.Nakazawa et al.;J.- G.Liu et al.
  • 通讯作者:
    J.- G.Liu et al.
Size-selective and reversible encapsulation of single small hydrocarbon molecules by a cavitand-pophyrin species
空穴卟啉对单个小烃分子的尺寸选择性和可逆封装
  • DOI:
  • 发表时间:
    2005
  • 期刊:
  • 影响因子:
    0
  • 作者:
    M.Yamada;E.Fukumoto;M.Ooidemizu;N.Brefuel;N.Matsumoto;S.Iijima;M.Kojima;N.Re;F.Dahan;J.-P.Tuchagues;Z.Zhu 他;M.Yamada 他;Y.Shimazaki et al.;Y.Shimazaki et al.;Y.Shimazaki et al.;J.Nakazawa et al.;J.Nakazawa et al.;J.Nakazawa et al.;J.Nakazawa et al.;K.Shimojo et al.;J.Nakazawa et al.;J.Nakazawa et al.;T.Chishiro et al.;J.Nakazawa et al.
  • 通讯作者:
    J.Nakazawa et al.
Syntheses, Crystal Structures, and Single Small Molecule Encapsulation Properties of Cavitand-Porphyrins
  • DOI:
    10.1246/bcsj.79.1431
  • 发表时间:
    2006-09
  • 期刊:
  • 影响因子:
    4
  • 作者:
    J. Nakazawa;Maki Mizuki;J. Hagiwara;Y. Shimazaki;F. Tani;Y. Naruta
  • 通讯作者:
    J. Nakazawa;Maki Mizuki;J. Hagiwara;Y. Shimazaki;F. Tani;Y. Naruta
Selective formation of a stable μ-peroxo ferric heme-CuII complex from the corresponding μ-oxo FeIII-CuII species with hydrogen peroxide
  • DOI:
    10.1039/b413275k
  • 发表时间:
    2005-02-28
  • 期刊:
  • 影响因子:
    4.9
  • 作者:
    Chishiro, T;Shimazaki, Y;Naruta, Y
  • 通讯作者:
    Naruta, Y
Syntheses and electronic structures of one-electron-oxidized group 10 metal(II)-(disalicylidene)diamine complexes (Metal = Ni, Pd, Pt)
  • DOI:
    10.1021/ja067022r
  • 发表时间:
    2007-03-07
  • 期刊:
  • 影响因子:
    15
  • 作者:
    Shimazaki, Yuichi;Yajima, Tatsuo;Yamauchi, Osamu
  • 通讯作者:
    Yamauchi, Osamu
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TANI Fumito其他文献

Carboxymethylated-cellulose Nanofibers May Confer Physiological Functions Compatible to the Gastrointestinal Tract?
羧甲基化纤维素纳米纤维可以赋予与胃肠道相容的生理功能吗?
  • DOI:
  • 发表时间:
    2020
  • 期刊:
  • 影响因子:
    0
  • 作者:
    YAMANOUE Miki;POPUANG Nuntanut;MAEKAWA Kazuki;OGAWA Takenobu;MASUDA Tetsuya;TANI Fumito
  • 通讯作者:
    TANI Fumito

TANI Fumito的其他文献

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{{ truncateString('TANI Fumito', 18)}}的其他基金

Biological roles of heat shock proteins in the regulation of mucosal homeostasis for mutual symbiosis
热休克蛋白在调节粘膜稳态相互共生中的生物学作用
  • 批准号:
    25292060
  • 财政年份:
    2013
  • 资助金额:
    $ 9.66万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
Studies on the mechanoreception of the gastrointestinal cells in response to fluid shear stress produced by food hydrocolloids
胃肠细胞对食物水胶体产生的流体剪切应力的机械感受研究
  • 批准号:
    25660105
  • 财政年份:
    2013
  • 资助金额:
    $ 9.66万
  • 项目类别:
    Grant-in-Aid for Challenging Exploratory Research
Studies on the Molecular Mechanism of Species-specific Recognition in Biological Diversity
生物多样性物种特异性识别的分子机制研究
  • 批准号:
    19580395
  • 财政年份:
    2007
  • 资助金额:
    $ 9.66万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Sphingoglycolipid as a candidate receptor for stress signal to innate immunity
鞘糖脂作为先天免疫应激信号的候选受体
  • 批准号:
    12660076
  • 财政年份:
    2000
  • 资助金额:
    $ 9.66万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)

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Development of mid-infrared femtosecond pulse laser using transition metal ion doped chalcogenides
过渡金属离子掺杂硫族化物中红外飞秒脉冲激光器的研制
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    21J13586
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Modeling Transition Metal Ion Binding to Proteins
模拟过渡金属离子与蛋白质的结合
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Modeling Transition Metal Ion Binding to Proteins
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Study on the control of luminescence wavelength of transition metal ion doped phosphors for wideband near-infrared LEDs
宽带近红外LED过渡金属离子掺杂荧光粉发光波长控制研究
  • 批准号:
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Selective synthesis of transition metal ion nanoclusters embedded in zeolites for methane oxidation at low temperatures
选择性合成嵌入沸石中的过渡金属离子纳米团簇用于低温氧化甲烷
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迈向新一代抗生素:过渡金属离子催化硫代酰胺裂解反应的机理研究
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Toward a new generation of antibiotics: Mechanistic investigations into transition metal ion-catalyzed thioamide cleavage reactions
迈向新一代抗生素:过渡金属离子催化硫代酰胺裂解反应的机理研究
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IDENTIFICATION OF TRANSITION METAL ION COMPOUNDS BY ESR SPECTROSCOPY
ESR 光谱法鉴定过渡金属离子化合物
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