Dataset Information

Electrocatalytic O2 reduction by covalently immobilized mononuclear copper(I) complexes: evidence for a binuclear Cu2O2 intermediate.

ABSTRACT: A Cu(I) complex of 3-ethynyl-phenanthroline covalently immobilized onto an azide-modified glassy carbon surface is an active electrocatalyst for the four-electron (4-e) reduction of O(2) to H(2)O. The rate of O(2) reduction is second-order in Cu coverage at moderate overpotential, suggesting that two Cu(I) species are necessary for efficient 4-e reduction of O(2). Mechanisms for O(2) reduction are proposed that are consistent with the observations for this covalently immobilized system and previously reported results for a similar physisorbed Cu(I) system.

SUBMITTER: McCrory CC

PROVIDER: S-EPMC3077299 | biostudies-literature | 2011 Mar

REPOSITORIES: biostudies-literature

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Publications

Electrocatalytic O2 reduction by covalently immobilized mononuclear copper(I) complexes: evidence for a binuclear Cu2O2 intermediate.

McCrory Charles C L CC Devadoss Anando A Ottenwaelder Xavier X Lowe Randall D RD Stack T Daniel P TD Chidsey Christopher E D CE

Journal of the American Chemical Society 20110302 11

A Cu(I) complex of 3-ethynyl-phenanthroline covalently immobilized onto an azide-modified glassy carbon surface is an active electrocatalyst for the four-electron (4-e) reduction of O(2) to H(2)O. The rate of O(2) reduction is second-order in Cu coverage at moderate overpotential, suggesting that two Cu(I) species are necessary for efficient 4-e reduction of O(2). Mechanisms for O(2) reduction are proposed that are consistent with the observations for this covalently immobilized system and previ ...[more]

PMID: 21366244

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Project description:Cu(A) is a binuclear electron transfer (ET) center found in cytochrome c oxidases (CcOs), nitrous oxide reductases (N₂ORs), and nitric oxide reductase (NOR). In these proteins, the Cu(A) centers facilitate efficient ET (kET > 10⁴s⁻¹) under low thermodynamic driving forces (10-90 mV). While the structure and functional properties of Cu(A) are well understood, a detailed mechanism of the incorporation of copper into the protein and the identity of the intermediates formed during the Cu(A) maturation process are still lacking. Previous studies of the Cu(A) assembly mechanism in vitro using a biosynthetic model Cu(A) center in azurin (Cu(A)Az) identified a novel intermediate X (Ix) during reconstitution of the binuclear site. However, because of the instability of Ix and the coexistence of other Cu centers, such as Cu(A)' and type 1 copper centers, the identity of this intermediate could not be established. Here, we report the mechanism of Cu(A) assembly using variants of Glu114XCuAAz (X = Gly, Ala, Leu, or Gln), the backbone carbonyl of which acts as a ligand to the Cu(A) site, with a major focus on characterization of the novel intermediate Ix. We show that Cu(A) assembly in these variants proceeds through several types of Cu centers, such as mononuclear red type 2 Cu, the novel intermediate Ix, and blue type 1 Cu. Our results show that the backbone flexibility of the Glu114 residue is an important factor in determining the rates of T2Cu → Ix formation, suggesting that Cu(A) formation is facilitated by swinging of the ligand loop, which internalizes the T2Cu capture complex to the protein interior. The kinetic data further suggest that the nature of the Glu114 side chain influences the time scales on which these intermediates are formed, the wavelengths of the absorption peaks, and how cleanly one intermediate is converted to another. Through careful understanding of these mechanisms and optimization of the conditions, we have obtained Ix in ∼80-85% population in these variants, which allowed us to employ ultraviolet-visible, electron paramagnetic resonance, and extended X-ray absorption fine structure spectroscopic techniques to identify the Ix as a mononuclear Cu(Cys)(2)(His) complex. Because some of the intermediates have been proposed to be involved in the assembly of native Cu(A), these results shed light on the structural features of the important intermediates and mechanism of Cu(A) formation.

Dataset Information

Electrocatalytic O2 reduction by covalently immobilized mononuclear copper(I) complexes: evidence for a binuclear Cu2O2 intermediate.

Publications

Electrocatalytic O2 reduction by covalently immobilized mononuclear copper(I) complexes: evidence for a binuclear Cu2O2 intermediate.

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