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三元氨基酸席夫碱-苯并咪唑/联吡啶 Cu(II)配合物的合成、结构、DNA 键合与切割性质。

Synthesis, structure, DNA binding and cleavage properties of ternary amino acid Schiff base-phen/bipy Cu(II) complexes.

机构信息

Department of Chemistry, Osmania University, Hyderabad, India.

出版信息

J Inorg Biochem. 2011 Dec;105(12):1603-12. doi: 10.1016/j.jinorgbio.2011.08.022. Epub 2011 Sep 14.

Abstract

Ternary Cu(II) complexes [Cu(II)(saltrp)(B)] (1,2), (saltrp=salicylidene tryptophan, B=1,10 phenathroline (1) or 2,2' bipyridine (2)) were synthesized and characterized. Complex 2 was structurally characterized by single crystal X-ray crystallography. The molecular structure shows a distorted square pyramidal coordination geometry (CuN(3)O(2)) in which the ONO donor Schiff base is bonded to the Cu(II) in the basal plane. The N,N donor heterocyclic base displays an axial-equatorial binding mode. CT-DNA binding studies revealed that the complexes show good binding propensity (Intrinsic binding constant, K(b)=3.32×10(5) M(-1) for 1 and K(b)=3.10×10(5) M(-1) for 2). The catalytic role of these complexes in the oxidative and hydrolytic cleavage of DNA was studied in detail. Complex 1 binds and cleaves DNA more efficiently as compared to 2. From the kinetic experiments, rate constants for the hydrolysis of phosphodiester bond of DNA backbone were determined as 1.94 h(-1) and 1.05 h(-1) for 1 and 2 respectively. It amounts to (2.93-5.41)×10(7) fold rate enhancement compared to uncatalyzed double stranded DNA, which is impressive as compared to related Cu(II) Schiff base complexes.

摘要

三核铜(II)配合物[Cu(II)(saltrp)(B)](1、2)(saltrp=水杨醛色氨酸,B=1,10 菲啰啉(1)或 2,2'联吡啶(2))被合成并进行了表征。配合物 2 的结构通过单晶 X 射线晶体学进行了表征。分子结构显示出扭曲的四方锥配位几何形状(CuN(3)O(2)),其中 ONO 供体席夫碱在基底平面中与 Cu(II)键合。N,N 供体杂环碱基呈现轴向-赤道结合模式。CT-DNA 结合研究表明,这些配合物具有良好的结合倾向(固有结合常数,K(b)=3.32×10(5) M(-1)对于 1 和 K(b)=3.10×10(5) M(-1)对于 2)。这些配合物在 DNA 的氧化和水解断裂中的催化作用进行了详细研究。与 2 相比,配合物 1 具有更强的结合和切割 DNA 的能力。从动力学实验中,确定了 DNA 骨架磷酸二酯键水解的速率常数分别为 1.94 h(-1)和 1.05 h(-1)对于 1 和 2。与未催化的双链 DNA 相比,这相当于 2.93-5.41 倍的速率增强,与相关的 Cu(II)席夫碱配合物相比,这是令人印象深刻的。

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