O2 reduction by a functional heme/nonheme bis-iron NOR model complex

被引：27

作者：

Collman, James P. ^{[1
]}

Dey, Abhishek ^{[1
]}

Yang, Ying ^{[1
]}

Ghosh, Somdatta ^{[1
]}

Decreau, Richard A. ^{[1
]}

机构：

[1] Stanford Univ, Dept Chem, Stanford, CA 94305 USA

来源：

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA | 2009年 / 106卷 / 26期

基金：

美国国家卫生研究院;

关键词：

electrochemistry; ferryl; NOR functional model; O-2; reductase; PROS; NITRIC-OXIDE REDUCTASE; CYTOCHROME-C-OXIDASE; INTERDIGITATED ARRAY ELECTRODE; RING-DISK ELECTRODE; HEME-PROTEINS; FE-IV=O; OXYGEN; DIOXYGEN; PROTON; MONOLAYERS;

D O I：

10.1073/pnas.0904634106

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

O-2 reactivity of a functional NOR model is investigated by using electrochemistry and spectroscopy. The electrochemical measurements using interdigitated electrodes show very high selectivity for 4e O-2 reduction with minimal production of partially reduced oxygen species (PROS) under both fast and slow electron flux. Intermediates trapped at cryogenic temperatures and characterized by using resonance Raman spectroscopy under single-turnover conditions indicate that an initial bridging peroxide intermediate undergoes homolytic O-O bond cleavage generating a trans heme/nonheme bis-ferryl intermediate. This bis ferryl species can oxygenate 2 equivalents of a reactive substrate.

引用

页码：10528 / 10533

页数：6