A Dinuclear Copper(II) Complex with Adeninate Bridge Ligands and Prominent DNA Cleavage Activity. Structural and Spectroscopic Characterization and Magnetic Properties
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- 作者：José ; Luis Garcí ; a-Gimé ; nez ; Gloria Alzuet ; Marta Gonzá ; lez-Á ; lvarez ; Alfonso Castiñ ; eiras ; Malva Liu-Gonzá ; lez ; Joaquí ; n Borrá ; s
- 刊名：Inorganic Chemistry
- 出版年：2007
- 出版时间：August 20, 2007
- 年：2007
- 卷：46
- 期：17
- 页码：7178 - 7188
- 全文大小：385K
- 年卷期：v.46,no.17(August 20, 2007)
- ISSN：1520-510X
文摘
A new dinuclear copper(II) complex has been synthesized and structurally characterized: [Cu(
ntities/mgr.gif">-ade)(tolSO3)(phen)]2·2H2O (Hade = adenine, tolSO3- = toluenesulfonate anion). Its magnetic properties and electronicparamagnetic resonance (EPR) spectra have been studied in detail. The compound has two metal centers bridgedby two adeninate NCN groups. The coordination geometry of the copper(II) ions in the dinuclear entity is distortedsquare pyramidal, with the four equatorial positions occupied by two phenanthroline N atoms and two N atomsfrom different adenine molecules. The axial position is occupied by one sulfonate O atom. Magnetic susceptibilitydata show antiferromagnetic behavior with an estimated exchange constant of -2J = 65 cm-1. The EPR spectrumhas been obtained at both X- and Q-band frequencies; a study at different temperatures has been carried out atthe latter. Above 20 K, the Q-band spectra are characteristic of S = 1 species with a small zero-field splittingparameter (D = 0.0970 cm-1). A detailed study of the DNA-complex interaction has been performed. The titlecomplex efficiently cleaves the pUC18 plasmid in the presence of reducing agents. Both the kinetics and themechanism of the cleavage reaction are examined and described herein.
ntities/mgr.gif">-ade)(tolSO3)(phen)]2·2H2O (Hade = adenine, tolSO3- = toluenesulfonate anion). Its magnetic properties and electronicparamagnetic resonance (EPR) spectra have been studied in detail. The compound has two metal centers bridgedby two adeninate NCN groups. The coordination geometry of the copper(II) ions in the dinuclear entity is distortedsquare pyramidal, with the four equatorial positions occupied by two phenanthroline N atoms and two N atomsfrom different adenine molecules. The axial position is occupied by one sulfonate O atom. Magnetic susceptibilitydata show antiferromagnetic behavior with an estimated exchange constant of -2J = 65 cm-1. The EPR spectrumhas been obtained at both X- and Q-band frequencies; a study at different temperatures has been carried out atthe latter. Above 20 K, the Q-band spectra are characteristic of S = 1 species with a small zero-field splittingparameter (D = 0.0970 cm-1). A detailed study of the DNA-complex interaction has been performed. The titlecomplex efficiently cleaves the pUC18 plasmid in the presence of reducing agents. Both the kinetics and themechanism of the cleavage reaction are examined and described herein.