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双核 Cu(II) --salophen/salen 配合物的合成、表征及与 DNA 的结合与切割性质。

Synthesis, characterization, and DNA-binding and -cleavage properties of dinuclear Cu(II) --salophen/salen complexes.

机构信息

Department of Chemistry, Osmania University, Hyderabad-500 007, India.

出版信息

Chem Biodivers. 2011 Jul;8(7):1245-65. doi: 10.1002/cbdv.201000153.

Abstract

Dinuclear Cu(II) complexes, [Cu(2) (salophen)(2) ] (1) and [Cu(2) (salen)(2) ] (2), with Schiff bases derived from salicylaldehyde and o-phenylenediamine (ophen) or ethylenediamine (en) were synthesized and characterized. They exhibit square-planar geometry with CuN(2) O(2) coordination, where the dianionic Schiff base acts as a tetradentate N(2) O(2) donor ligand. Calf thymus (CT)-DNA Binding studies revealed that the complexes possess good binding propensities (K(b) =3.13×10(5) for 1 and K(b) =2.99×10(5)  M(-1) for 2). They show good DNA-cleavage abilities under oxidative and hydrolytic conditions. Complex 1 binds and cleaves DNA more efficiently as compared to 2 due to the presence of an extended aromatic phenyl ring which might be involved in an additional stacking interaction with DNA bases. From the kinetic experiments, hydrolytic DNA-cleavage rate constants were determined as 1.54 for 1 and 0.72 h(-1) for 2. The nuclease activities of 1 and 2 are significant, giving rise to (2.03-2.88)×10(7) -fold rate enhancement compared to non-catalyzed DNA cleavage.

摘要

双核 Cu(II) 配合物 [Cu(2) (salophen)(2)] (1) 和 [Cu(2) (salen)(2)] (2) 是由水杨醛和邻苯二胺 (ophen) 或乙二胺 (en) 衍生的席夫碱合成并进行了表征。它们具有正方形平面几何形状,CuN(2)O(2) 配位,其中二价阴离子席夫碱作为四齿 N(2)O(2) 供体配体。小牛胸腺 (CT)-DNA 结合研究表明,这些配合物具有良好的结合倾向(K(b)=3.13×10(5) 对于 1 和 K(b)=2.99×10(5)  M(-1) 对于 2)。它们在氧化和水解条件下具有良好的 DNA 切割能力。与 2 相比,1 由于存在扩展的芳基苯环,可能涉及与 DNA 碱基的额外堆积相互作用,因此具有更好的 DNA 结合和切割能力。从动力学实验中,确定了水解 DNA 切割速率常数为 1.54 对于 1 和 0.72 h(-1) 对于 2。1 和 2 的核酸酶活性显著,与非催化 DNA 切割相比,产生了 (2.03-2.88)×10(7) 倍的速率增强。

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