A Mechanistic Study of the Copper(II)-Peptide-Cataly zed Superoxide Dismutation. A Pulse Radiolysis Study

Sara Goldstein; Gidon Czapski; Dan Meyerstein

doi:10.1021/ja00174a006

A Mechanistic Study of the Copper(II)-Peptide-Cataly zed Superoxide Dismutation. A Pulse Radiolysis Study

Sara Goldstein, Gidon Czapski, Dan Meyerstein

Department of Chemistry

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61 Scopus citations

Abstract

The reactivity of O₂^- toward Cu(II)-peptides containing glycine and histidine for which E°cu(III)/Cu(II) ≤ 108 V was investigated by the pulse radiolysis technique. It has been found that the ability of the various complexes to catalyze O₂^- dismutation depends inversely on the redox potential of the couple Cu(III)/Cu(II). The Cu(II)-peptides containing histidine, which have higher redox potentials than that of the couple O₂^-/H₂O₂, do not catalyze the reaction at all. Although no direct evidence was found for the formation of Cu(III)-peptide, the results suggest that the mechanism of the catalysis of Of dismutation proceeds via alternate oxidation and reduction of the metal by O₂^-. Furthermore, this mechanism is supported by indirect observations, which are discussed in detail.

Original language	English
Pages (from-to)	6489-6492
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	112
Issue number	18
DOIs	https://doi.org/10.1021/ja00174a006
State	Published - 1 Jan 1990

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "A Mechanistic Study of the Copper(II)-Peptide-Cataly zed Superoxide Dismutation. A Pulse Radiolysis Study",

abstract = "The reactivity of O2- toward Cu(II)-peptides containing glycine and histidine for which E°cu(III)/Cu(II) ≤ 108 V was investigated by the pulse radiolysis technique. It has been found that the ability of the various complexes to catalyze O2- dismutation depends inversely on the redox potential of the couple Cu(III)/Cu(II). The Cu(II)-peptides containing histidine, which have higher redox potentials than that of the couple O2-/H2O2, do not catalyze the reaction at all. Although no direct evidence was found for the formation of Cu(III)-peptide, the results suggest that the mechanism of the catalysis of Of dismutation proceeds via alternate oxidation and reduction of the metal by O2-. Furthermore, this mechanism is supported by indirect observations, which are discussed in detail.",

author = "Sara Goldstein and Gidon Czapski and Dan Meyerstein",

year = "1990",

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doi = "10.1021/ja00174a006",

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T1 - A Mechanistic Study of the Copper(II)-Peptide-Cataly zed Superoxide Dismutation. A Pulse Radiolysis Study

AU - Goldstein, Sara

AU - Czapski, Gidon

AU - Meyerstein, Dan

PY - 1990/1/1

Y1 - 1990/1/1

N2 - The reactivity of O2- toward Cu(II)-peptides containing glycine and histidine for which E°cu(III)/Cu(II) ≤ 108 V was investigated by the pulse radiolysis technique. It has been found that the ability of the various complexes to catalyze O2- dismutation depends inversely on the redox potential of the couple Cu(III)/Cu(II). The Cu(II)-peptides containing histidine, which have higher redox potentials than that of the couple O2-/H2O2, do not catalyze the reaction at all. Although no direct evidence was found for the formation of Cu(III)-peptide, the results suggest that the mechanism of the catalysis of Of dismutation proceeds via alternate oxidation and reduction of the metal by O2-. Furthermore, this mechanism is supported by indirect observations, which are discussed in detail.

AB - The reactivity of O2- toward Cu(II)-peptides containing glycine and histidine for which E°cu(III)/Cu(II) ≤ 108 V was investigated by the pulse radiolysis technique. It has been found that the ability of the various complexes to catalyze O2- dismutation depends inversely on the redox potential of the couple Cu(III)/Cu(II). The Cu(II)-peptides containing histidine, which have higher redox potentials than that of the couple O2-/H2O2, do not catalyze the reaction at all. Although no direct evidence was found for the formation of Cu(III)-peptide, the results suggest that the mechanism of the catalysis of Of dismutation proceeds via alternate oxidation and reduction of the metal by O2-. Furthermore, this mechanism is supported by indirect observations, which are discussed in detail.

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DO - 10.1021/ja00174a006

M3 - Article

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ER -

A Mechanistic Study of the Copper(II)-Peptide-Cataly zed Superoxide Dismutation. A Pulse Radiolysis Study

Abstract

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