Theoretical Study on Catalytic Mechanism of Metalloenzyme including Manganese Ions at Active Site

含锰离子金属酶活性位点催化机理的理论研究

• 批准号: 22550010
• 负责人: YOSHIOKA Yasunori
• 金额: $ 2.83万
• 依托单位: Mie University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2010
• 资助国家: 日本
• 起止时间: 2010 至 2012
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-22550010/
• 关键词: 生物物理科学; 金属酵素; マンガンイオン; 酸素発生複合体; Mn/Fe２核系; 光化学系II; ホスファターゼ; B3LYP; 自然軌道解析; Mn/Fe2核系; リボヌクレオチド還元酵素; 光科学系II

Oxygen-Evolving Complex (OEC), which is one of metalloenzymes including manganese ions at active site, catalyzes four-electron oxidation of two water molecules to give oxygen. The catalytic mechanism of OEC is unclear and has been investigated intensively based on theoretical and experimental viewpoints. We have determined the molecular and electronic structures of five oxidative states, S0, S1, S2, S3,and S4 proposed as Kok cycle using theoretical study. We have also proposed the catalyticmechanism. It is expected that our results will be basis to develop a new unit producing oxygen and hydrogen as next-generation energy.

氧演化配合物（OEC）是一种活性位点含有锰离子的金属酶，它催化两个水分子的四电子氧化生成氧气。OEC的催化机理尚不清楚，从理论和实验的角度对其进行了深入的研究。我们通过理论研究确定了5种氧化态S0、S1、S2、S3和S4作为Kok循环的分子和电子结构。我们还提出了催化机理。我们的研究结果将为开发新一代能源氢氧联产装置奠定基础。

项目成果

OECのS2からS3状態遷移での一電子酸化およびプロトン移動に関する理論的研究

OEC S2到S3态转变过程中单电子氧化和质子转移的理论研究

• 发表时间: 2013
• 作者: 市野智也;三谷昌輝;吉岡泰規
• 通讯作者: 吉岡泰規

A B3LYP Study on Electronic structures of [(X)mMn(-oxo)2Mn(Y)n]q+ (X, Y = H2O, OH and O) as a Mn cluster model of OEC

[(X)mMn( 电子结构的 B3LYP 研究

• 发表时间: 2012
• 期刊: J. Biophys. Chem.
• 作者: M. Katsuda;E. Hishikawa;M. Mitani and Y. Yoshioka
• 通讯作者: M. Mitani and Y. Yoshioka

B3LYP Study on reduction mechanisms from O_2 to H_2O at the active site of fully reduced and mixed-valence bovine cytochrome c oxidase

B3LYP 全还原混合价牛细胞色素c氧化酶活性位点O_2还原为H_2O机制研究

• 发表时间: 2010
• 期刊: Bioinorg.Chem.Appl.
• 作者: Y.Yoshioka;M.Mitani
• 通讯作者: M.Mitani

Development of Broken Symmetry Methods-Application to the CaMn_4O_5 Cluster at OEC of PSII Refined to 1.9 Å X-Ray Resolution

破缺对称方法的发展-应用于细化至 1.9 Å X 射线分辨率的 PSII OEC 处的 CaMn_4O_5 团簇

• 发表时间: 2011
• 作者: K.Kanda;S.Yamanaka;T.Saito;Y.Umena;K.Kawakami;J.R.Shen;N.Kamiya;M.Okumura;Y.Yoshioka;K.Yamaguchi
• 通讯作者: K.Yamaguchi

Theoretical Study on the Mechanism of Dioxygen Evolution in Photosystem II. I. Molecular and Electronic Structures at the S0, S1, and S2 States of Oxygen-Evolving Complex

光系统析氧机理的理论研究II。

• DOI: 10.1246/bcsj.20120223
• 发表时间: 2013
• 期刊: Bull. Chem. Soc. Jpn
• 作者: H. Sakagami;T. Johzaki;A. Sunahara;and H. Nagatomo;T. Ichino and Y. Yoshioka
• 通讯作者: T. Ichino and Y. Yoshioka