一类新型冠醚稀土配合物的合成、表征及与DNA作用研究

Synthesis,Characterization and DNA-Binding of Rare Earth Complexes with A Novel Crown Ether

合成了四种双(N,N′-乙基,苯基)-2,3-萘-二(氧杂乙酰胺)(L=C30H30N2O4)稀土配合物。通过元素分析、红外光谱、差热-热重及摩尔电导值的分析,确定配合物的组成为[RE(pic)3L],RE=Eu(Ⅲ),Tb(Ⅲ),Ce(Ⅲ),Y(Ⅲ)。电化学实验表明:配体无电化学活性,配合物则呈现出一准可逆的氧化还原过程,在10～1000 mV.s-1扫速范围内配合物的氧化还原峰电流与扫描速度的平方根(ν1/2)呈良好的线性关系,表明其在玻碳电极(GCE)上的伏安行为受扩散控制。另外,通过循环伏安法、光谱法及粘度法研究了配合物与DNA的作用方式,结果表明:配合物均以插入方式与DNA作用,并且作用大小次序是Ce(pic)3L>Tb(pic)3L>Y(pic)3L>Eu(pic)3L。在pH=3.0适宜酸度条件下,建立了以Ce(pic)3L为探针定量测定DNA的分析方法。

Four rare earth complexes containing ligand of bis（N,N′-ethyl,phenyl）-2,3-naphthyl-bis（oxaacetamide）（L=C30H30N2O4） were synthesized and characterized by elemental analysis,IR spectra,TG-DTA and molar conductivity.The general formulas of the complexes were [RE（pic）3L],RE=Eu（Ⅲ）,Tb（Ⅲ）,Ce（Ⅲ） and Y（Ⅲ）.The electrochemical experiments showed that the ligand did not have electrochemical activity,while the complexes exhibited a quasi-reversible redox process.In the range of 10～1000 mV·s-1,the redox peak currents were linear with the square root of the scan rate,which showed that the electrochemical behavior of the complex on GCE was controlled by diffusion.In addition,the interaction between the complexes and DNA was studied by means of cyclic voltammetry,spectrometry and viscosity measurements.The results indicated that the interaction modes were intercalation and the interaction strength was Ce（pic）3LTb（pic）3LY（pic）3LEu（pic）3L.To determinate DNA quantitatively,the analytical method was established as the probe of Ce（pic）3L.