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单、二和多核镧系元素与双(N-水杨醛)-3-氧杂戊烷-1,5-二胺配合物的合成、晶体结构、抗氧化及DNA结合研究

Study on synthesis, crystal structure, antioxidant and DNA-binding of mono-, di- and poly-nuclear lanthanides complexes with bis(N-salicylidene)-3-oxapentane-1,5-diamine.

作者信息

Wu Huilu, Pan Guolong, Bai Yuchen, Zhang Yanhui, Wang Hua, Shi Furong, Wang Xiaoli, Kong Jin

机构信息

School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, PR China.

School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, PR China.

出版信息

J Photochem Photobiol B. 2014 Jun 5;135:33-43. doi: 10.1016/j.jphotobiol.2014.04.005. Epub 2014 Apr 18.

Abstract

A Schiff base ligand bis(N-salicylidene)-3-oxapentane-1,5-diamine H2L have been prepared. Reaction of the shape-specific designed ligand with Ln(NO3)3⋅6H2O afforded three novel complexes, namely, Sm(L)(NO3)(DMF)(H2O) 1, [Eu(H2L)2(NO3)3]n2 and Tb2(L)2(NO3)23. The ligand and complexes were characterized by elemental analysis, UV-Vis, IR, NMR spectroscopy and X-ray crystallography. It is noteworthy that the complexes demonstrate three different types of the structure which changed according to the charge density and acidity of the lanthanide. Complex 1 is a discrete mononuclear species that Sm(III) ion is nine-coordinated in the structure and forming a distorted tricapped trigonal prism geometry. Complex 2 is possessed a 1-D ribbon framework constructed from an extended array of ten-coordinated Eu(3+) centers and the Schiff base ligands. Complex 3 is revealed as a centrosymmetric binuclear neutral entity, in which Tb(III) ion is eight-coordinated with the coordination surround of distorted square antiprism geometry. In order to explore the relationship between the structure and biological properties, the DNA-binding properties have been investigated by electronic absorption, fluorescence, and viscosity measurements. The results suggest that the ligand and complexes bind to DNA via groove modes. The intrinsic binding constants Kb of the complexes 1-3 are (1.19±0.112)×10(5), (4.22±0.086)×10(4) and (3.89±0.104)×10(4) M(-)(1) respectively. Moreover, the antioxidant activity experiments show that these compounds also exhibit good antioxidant activities against OH· and O2(-·) in vitro studies.

摘要

已制备出一种席夫碱配体双(N-水杨醛)-3-氧杂戊烷-1,5-二胺H₂L。将这种形状特异性设计的配体与Ln(NO₃)₃·6H₂O反应,得到了三种新型配合物,即Sm(L)(NO₃)(DMF)(H₂O) 1、[Eu(H₂L)₂(NO₃)₃]ₙ 2和Tb₂(L)₂(NO₃)₂ 3。通过元素分析、紫外可见光谱、红外光谱、核磁共振光谱和X射线晶体学对配体和配合物进行了表征。值得注意的是,这些配合物呈现出三种不同类型的结构,它们根据镧系元素的电荷密度和酸度而变化。配合物1是一种离散的单核物种,其中Sm(III)离子在结构中为九配位,形成扭曲的三帽三棱柱几何构型。配合物2具有由十配位的Eu(3+)中心和席夫碱配体的扩展阵列构建而成的一维带状框架。配合物3被揭示为一种中心对称的双核中性实体,其中Tb(III)离子为八配位,具有扭曲的方形反棱柱几何构型的配位环境。为了探索结构与生物学性质之间的关系,通过电子吸收、荧光和粘度测量研究了DNA结合性质。结果表明,配体和配合物通过沟槽模式与DNA结合。配合物1-3的固有结合常数Kb分别为(1.19±0.112)×10⁵、(4.22±0.086)×10⁴和(3.89±0.104)×10⁴ M⁻¹。此外,抗氧化活性实验表明,在体外研究中,这些化合物对OH·和O₂⁻·也表现出良好的抗氧化活性。

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