| 手性铁尧镍席夫碱配合物的合成尧结构及其与DNA相互作用研究 | |
| Synthesis, Structures and DNA-Binding of Enantiomers of Fe(Ⅱ) and Ni(Ⅱ) Schiff Base Complexes | |
| 摘要: 以手性苯乙胺与吡啶醛缩合得到的含双齿或三齿配位基的手性席夫碱（L1、L2）为配体，合成了4对单核铁、镍手性对映体配合物fac-∧-[M（R-L1）3]（ClO4）2·3CH3CN（M=Fe，1R-Fe；M=Ni，1R-Ni），fac-△-[M（S-L1）3]（ClO4）2·3CH3CN（M=Fe，1S-Fe；M=Ni，1S-Ni），[M（R-L2）2]（ClO4）2（M=Fe，2R-Fe；M=Ni，2R-Ni），[M（S-L2）2]（ClO4）2（M=Fe，2S-Fe；M=Ni，2S-Ni）遥利用红外光谱（IR）、核磁共振氢谱（1HNMR）、元素分析（EA）、X-射线单晶衍射等手段对配合物结构进行了表征遥对化合物1R-Fe，1R-Ni，1S-Ni，2R-Fe进行了晶体结构分析，其中1R-Fe，1R-Ni，1S-Ni结晶于P213手性空间群，金属中心与3个二齿配体（L1）提供的6个氮原子配位形成了扭曲变形的八面体结构；R型配体诱导配合物形成fac-∧构型，而S型配体诱导配合物形成fac-△驻构型遥2R-Fe结晶于P212121手性空间群，二价铁离子与2个三齿配体（R-L2）提供的6个氮原子配位形成了扭曲变形的八面体结构遥利用紫外-可见吸收光谱、荧光猝灭光谱、圆二色谱等光谱分析法研究了配合物与DNA的相互作用遥研究结果表明这4对手性配合物均能与小牛胸腺CT-DNA发生不同强度的结合，结合稳定常数从4.41×103L·mol-1到1.88×104L·mol-1遥配合物与DNA的结合模式可能是通过静电作用与DNA骨架发生沟面结合遥金属中心为铁的配合物表现出比相应的镍配合物更强的DNA作用力；而含三齿配体L2的配合物与DNA的作用均比相应的含二齿配体L1的配合物更强；S型配体形成的配合物与DNA的结合能力优于R型配体形成的配合物。 | |
| 关键词: DNA相互作用 手性对映体 配合物 晶体结构 | |
| 基金项目: 国家自然科学基金（No.21101078，21276105）袁新世纪优秀人才计划（NCET-11-0657）以及江苏省自然科学基金（No.BK2011143）资助。 | |
| Abstract: Based on the chiral Schiff base bidentate ligand (L1) and tridentate ligand (L2) condensed by pyridine aldehyde and chiral phenylethylamine, four pairs of Fe(Ⅱ) and Ni(Ⅱ) chiral enantiomers fac-∧-[M(R-L1)3](ClO4)2·(3CH3CN (M=Fe, 1R-Fe; M=Ni, 1R-Ni), fac-∧-[M(S-L1)3](ClO4)2·(3CH3CN (M=Fe, 1R-Fe; M=Ni, 1R-Ni),[M(R-L2)2](ClO4)2 (M=Fe, 2R-Fe; M=Ni,2R-Ni),[M(S-L2)2](ClO4)2 (M=Fe, 2S-Fe; M=Ni, 2S-Ni) were synthesized and characterized by infrared spectra (IR), proton nuclear magnetic resonance (1H NMR), elemental analysis (EA) and the X-ray single crystal diffraction. The X-ray structural analyses of 1R-Fe, 1R-Ni, 1S-Ni revealed that these complexes crystallized in the chiral space groups P213, possessing distorted octahedral coordination geometry for N6 donor atoms by three bidentate ligands (L1). R-enantiomer ligand induces the fac-∧ isomer, while S-enantiomer ligand induces the fac-Δ isomer; 2R-Fe crystallized in the chiral space groups P212121, the Fe(Ⅱ) sitting with N6 donor atoms by two tridentate ligands (L2) formed distorted octahedral geometries. The binding of Fe(Ⅱ) and Ni(Ⅱ) chiral complexes to calf-thymus DNA has been investigated by methods of UV-Vis spectroscopy, fluorescence spectroscopy and circular dichroism spectrometry. The results showed all the complexes could bind to CT-DNA and displayed different DNA-binding affinities with the binding constants ranging from 4.41×103 L·mol -1 to 1.88×104 L·mol -1. The binding mode of complexes with DNA may most likely to bind in the groove of DNA backbone. The factors of metal center, structure and chirality of ligands can influence the DNA binding ability of the complexes. The complexes containing Fe(Ⅱ) metal center showed stronger DNA binding ability with respect to the Ni(Ⅱ) complexes. In addition, the complexes containing tridentate ligand (L2) possessed more efficient DNA interaction than the complexes containing bidentate ligand (L1). Moreover, different enantiomers exhibited discernible differences in the DNA-binding. The complexes with S-ligand showed stronger DNA binding ability than the respective complexes with R-ligand. | |
| Keywords: DNA-binding enantiomers complexes crystal structures | |
| 投稿时间：2014-01-07 修订日期：2014-02-27 | |
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| 包菲菲,徐新新,周文,庞春燕,奚赛飞,顾志国,李在均.手性铁尧镍席夫碱配合物的合成尧结构及其与DNA相互作用研究[J].无机化学学报,2014,30(8):1748-1756. | |
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| Support information: 相关附件： file140017-Supporting Information.doc | |
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