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Evaluation and Modification of Chemical Functions of Dicopper Proteins

二铜蛋白化学功能的评价和修饰

基本信息

批准号：
15350105
负责人：
ITOH Shinobu
金额：
$ 9.86万
依托单位：
Osaka City University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2004
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15350105/
关键词：
Tyrosinase Dioxygen Activation Dicopper-Dioxygen Complex Phenol Oxidation Reaction Mechanism Copper Protein Peroxo Complex Oxo Complex 酸素反応機構

项目摘要

[1] Evaluation of Enzymatic Activities of Mushroom Tyrosinase:Catalase and peroxygenase activity of mushroom tyrosinase have been investigated kinetically by using amperometric methods. Quantitative analysis on the substituent effects of a series of p-substituted phenols in the peroxygenase activity has demonstrated that the reaction mechanism is the same to that of the phenolase reaction, that is the electrophilic aromatic substitution mechanism by a side-on peroxo dicopper(II) intermediate. The same peroxo intermediate has been imprecated to be involved as an intermediate of catalase activity. Furthermore, catecholase activity has investigated in the same manner to demonstrate that the oxidation of phenols by the side-on peroxo dicopper(II) intermediate involves a similar electrophilic tonic mechanism.[2] Purification of Neurospora crassa Tyrosinase :Neurospora crassa tyrosinase has been isolated and purified in order to examine the catalytic functions and mechanisms of tyrosinase fr … More om different origins.[3] Oxidation Mechanism of Phenols by Dicopper-Dioxygen Complexes :The first systematic study on the oxidation of neutral phenols by the (μ-η^2:η^2-peroxo) dicopper (II) complex and the bis (μ-oxo) dicopper (III) complex. Comparison of the rate-dependences in the oxidation of phenols by the Cu_2/O_2 complexes on the one-electron oxidation potentials of the phenol substrates provides profound insights into the mechanistic basis of the phenol-oxidation as well as the electron-transfer oxidation ability of the Cu_2/O_2 complexes.[4] Ligand Effects on the Copper(I)-Dioxygen Reactivity :Structure, physicochemical properties, and dioxygen-reactivity of copper (I) complexes supported by N, N-bis(6-methyl-2-pyridylmethyl)-2-phenylethylamine tridentate ligands have been compared to those of copper (I) complex 1 of N, N-bis[2-(2-pyridyl)ethyl]-2-phenylethylamine tridentate ligand and copper (I) complex 3 of N, N-bis(2-pyridylmethyl)-2-phenylethylamine tridentate ligand. Oxygenation of 2 at a low temperature gave a side-on peroxo dicopper (II) complex as in the case of 1, but its O-O bond was relatively weakened as compared to that of the peroxo complex derived from 1. On the other hand, 3 reacted with dioxygen very rapidly to give a bis (μ-oxo) dicopper (III) complex. These results can be interpreted by taking account of the difference in electron donor ability of the ligands. Less

[1]蘑菇酪氨酸酶的活性评价：采用安培法研究了蘑菇酪氨酸酶的过氧化氢酶和过氧合酶活性。通过对一系列对位取代酚类化合物在过氧化酶活性中取代基效应的定量分析，证明了其反应机理与酚酶反应相同，即通过一个侧位过氧二铜（II）中间体的亲电芳香取代机理。同样的过氧中间体已被祈求参与作为过氧化氢酶活性的中间体。此外，还以相同的方式研究了儿茶酚酶活性，以证明侧位过氧化二铜（II）中间体对苯酚的氧化涉及类似的亲电紧张机制。[2]粗糙脉孢菌酪氨酸酶的分离纯化：为了研究酪氨酸酶的催化功能和作用机制， ...更多信息不同的起源。[3]二氧合铜（μ-η^2：η^2-过氧）二铜（II）配合物和双（μ-氧代）二铜（III）配合物对中性酚类氧化作用的首次系统研究。通过比较Cu_2/O_2配合物氧化苯酚的速率与底物单电子氧化电位的关系，深入了解了Cu_2/O_2配合物氧化苯酚的机理基础以及配合物的电子转移氧化能力。[4]配体对铜（I）-双氧反应性的影响：将由N，N-双（6-甲基-2-吡啶基甲基）-2-苯乙胺三齿配体支撑的铜（I）配合物的结构、物理化学性质和双氧反应性与N，N-双[2-（2-吡啶基）乙基]-2-苯乙胺三齿配体的铜（I）配合物1和N，N-双（2-吡啶基甲基）-2-苯乙胺三齿配体的铜（I）配合物3的结构、物理化学性质和双氧反应性进行比较。2在低温下的氧化得到侧上的过氧二铜（II）配合物的情况下，1，但其O-O键是相对削弱相比，从1衍生的过氧配合物。另一方面，3与分子氧反应非常迅速，得到双（μ-氧代）二铜（III）配合物。这些结果可以通过考虑配体给电子能力的差异来解释。少

项目成果

期刊论文数量（56）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Quantitative Evaluation of d-t Interaction in Copper (I) Complexes and Control of Copper (I)-Dioxygen Reactivity

铜 (I) 配合物中 d-t 相互作用的定量评估以及铜 (I)-分子氧反应性的控制

DOI：
发表时间：
2004
期刊：
Chem.Eur.J. 10(1)
影响因子：
0
作者：
Takao Osako;Yoshimitsu Tachi;Matsumi Doe;Motoo Shiro;Kei Ohkubo;Shunichi Fukuzumi;Shinobu Itoh
通讯作者：
Shinobu Itoh

S.Itoh, et al.: "Oxidation Mechanism of Phenols by Dicopper-Dioxygen (Cu_2/O_2) Complexes"J.Am.Chem.Soc.. 125・36. 11027-11033 (2003)

S.Itoh等人：“二铜-二氧(Cu_2/O_2)配合物对苯酚的氧化机理” J.Am.Chem.Soc. 125・36 (2003)