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

被引：0
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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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页码：6304 / 6305
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