Hydrogen peroxide and dioxygen activation by dinuclear copper complexes in aqueous solution: Hydroxyl radical production initiated by internal electron transfer

被引：0

作者：

Zhu, Qing ^{[1
]}

Lian, Yuxiang ^{[2
]}

Thyagarajan, Sunita ^{[2
]}

Rokita, Steven E. ^{[1
]}

Karlin, Kenneth D. ^{[2
]}

Blough, Neil V. ^{[1
]}

机构：

[1] Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742, United States

[2] Department of Chemistry, Johns Hopkins University, Baltimore, MD 21218, United States

来源：

Journal of the American Chemical Society | 2008年 / 130卷 / 20期

关键词：

Dinuclear Cu(II) complexes; CuII2Nn; (n; 4; or; 5); were recently found to specifically cleave DNA in the presence of a reducing thiol and O2 or in the presence of H2O2 alone. However; CuII2N3 and a closely related mononuclear Cu(II) complex exhibited no selective reaction under either condition. Spectroscopic studies indicate an intermediate is generated from CuII2Nn (n = 4 or 5) and mononuclear Cu(II) solutions in the presence of H2O2 or from CuI2Nn (n = 4 or 5) in the presence of O2. This intermediate decays to generate OH radicals and ligand degradation products at room temperature. The lack of reactivity of the intermediate with a series of added electron donors suggests the intermediate discharges through a rate-limiting intramolecular electron transfer from the ligand to the metal peroxo center to produce an OH radical and a ligand-based radical. These results imply that DNA cleavage does not result from direct reaction with a metal-peroxo intermediate but instead arises from reaction with either OH radicals or ligand-based radicals. Copyright © 2008 American Chemical Society;

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摘要：

Journal article (JA)

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页码：6304 / 6305