Role of a distal pocket in the catalytic O2 reduction by cytochrome c oxidase models immobilized on interdigitated array electrodes

被引：55

作者：

Collman, James P. ^{[1
]}

Decreau, Richard A. ^{[1
]}

Lin, Hengwei ^{[1
]}

Hosseini, Ali ^{[1
]}

Yang, Ying ^{[1
]}

Dey, Abhishek ^{[1
]}

Eberspacher, Todd 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 / 18期

基金：

美国国家卫生研究院;

关键词：

electron transfer rate; oxygen binding rates; water cluster; oxygen complex stabilization; partially reduced oxygen species; DIOXYGEN REDUCTION; HEMOPROTEIN MODELS; CLICK CHEMISTRY; PICKET FENCE; WATER; SUPEROXIDE; MYOGLOBIN; PORPHYRINS; SURFACES; CLUSTERS;

D O I：

10.1073/pnas.0902285106

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：

070301 [无机化学]; 070403 [天体物理学]; 070507 [自然资源与国土空间规划学]; 090105 [作物生产系统与生态工程];

摘要：

Five iron porphyrins with different superstructures were immobilized on self-assembled-monolayer (SAM)-coated interdigitated-array (IDAs) gold-platinum electrodes. The selectivity of the catalysts i.e., limited formation of partially reduced oxygen species (PROS) in the electrocatalytic reduction of dioxygen, is a function of 2 rates: (i) the rate of electron transfer from the electrode to the catalyst, which is controlled by the length, and conjugation of the linker from the catalyst to the electrode and (ii) the rate of bound oxygen (superoxide) hydrolysis, which correlates with the presence of a water cluster in the gas-binding pocket influencing the rate of oxygen binding; these factors are controlled by the nature of the porphyrin superstructure. The structurally biomimetic Trisimidazole model is the most selective.

引用

页码：7320 / 7323

页数：4

共 36 条

[1]

Interaction of superoxide O2- with water hexamer clusters [J].