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论文中文题名:

 苯乙酰腙类过渡金属配合物的合成、表征和生物活性研究    

姓名:

 丁作成    

学号:

 200905147    

保密级别:

 公开    

学科代码:

 081704    

学科名称:

 应用化学    

学生类型:

 硕士    

学位年度:

 2014    

院系:

 化学与化工学院    

专业:

 应用化学    

第一导师姓名:

 刘向荣    

第二导师姓名:

 杨再文    

论文外文题名:

 Synthesis,characterization and biological activity of transition metal complexes with phenylacetyl hydrazone    

论文中文关键词:

 酰腙 ; 过渡金属 ; 配合物 ; 合成 ; 晶体结构 ; 生物活性    

论文外文关键词:

 Hydrazone ; Transition metal ; Complex ; Synthesis ; Crystal structure ; Biological a    

论文中文摘要:
基于酰腙类化合物强的配位能力、多样的配位形式和良好的生物药理活性,过渡金属在生命体的物质存储和运输及金属离子的转运过程中起着极其重要的作用以及二者配位后可能产生的独特性质,本文合成了两种未见文献报道的新型酰腙及其7种过渡金属配合物。主要进行了以下几个方面的工作: (1) 以苯乙酸甲酯、水合肼和呋喃甲醛为原料,在回流条件下合成了配体2-甲酰基呋喃苯乙酰腙C13H12N2O2,再与六水氯化镍反应,制得新型镍配合物Ni(C13H12N2O2)2•Cl2,并培养出了2-甲酰基呋喃苯乙酰腙及其镍配合物的单晶。2-甲酰基呋喃苯乙酰腙晶体属单斜晶系,P2(1)/c空间群,晶胞参数为: a=11.619(3)Å,b=13.598(3)Å,c=7.9216(19)Å,β=109.307(4)°,V=1181.2(5)Å3,Z=4,F(000)=480,Dc=1.283 g/cm3;2-甲酰基呋喃苯乙酰腙Ni配合物晶体属三斜晶系,P1空间群,晶胞参数为: a=4.557(14) Å,b=10.947(3)Å,c=12.048(19)Å,β=98.302(5)°,V=593.2(3)Å3,Z=1,F(000)=268,Dc=1.422 g/cm3。 (2) 合成2-羟基-1-萘甲醛苯乙酰腙C19H16N2O2及其与6种过渡金属元素(Co、Ni、Cu、Zn、Cd、Pb)的配合物,并培养出2-羟基-1-萘甲醛苯乙酰腙的单晶。2-羟基-1-萘甲醛苯乙酰腙晶体属正交晶系,Pbca空间群,晶胞参数为: a=12.370(3)Å,b=9.704(3)Å,c=25.854(19)Å,β=109.307(4)°,V=1181.2(5)Å3,Z=8,F(000)=480,Dc=1.283 g/cm3。通过元素分析、紫外可见光谱、红外光谱等手段对合成的配合物进行表征,推断出其化学式为:[M(C19H15N2O2)2]•nH2O。 (3) 利用热重技术测试了2-甲酰基呋喃苯乙酰腙和2-羟基-1-萘甲醛苯乙酰腙及7种过渡金属元素的配合物在5.00℃•min-1、10.00℃•min-1和15.00℃•min-1三个不同升温速率下的热分解过程,并通过Kissinger和Ozawa公式计算了主要热分解过程的热动力学参数。热重实验表明2-甲酰基呋喃苯乙酰腙在5.00、10.00、15.00 ℃•min-1的分解峰值分别为285.58、295.30和310.98 ℃; 2-甲酰基呋喃苯乙酰腙Ni配合物在5.00、10.00、15.00 ℃•min-1的分解峰值分别为294.37、 304.25和310.40 ℃; 2-羟基-1-萘甲醛苯乙酰腙在5.00、10.00、15.00 ℃•min-1的分解峰值分别为285.58、295.30和310.98 ℃; 2-羟基-1-萘甲醛苯乙酰腙6种过渡金属配合物(Co、Ni、Cu、ZnCd、Pb)分解峰值在299.23 - 402.60 ℃之间,两种新型配体及其配合物都具有较好的热稳定性,且配合物的热稳定性比相应配体好。 (4) 利用紫外可见光谱和微量热法,初步分析了2-甲酰基呋喃苯乙酰腙及其Ni配合物和2-羟基-1-萘甲醛苯乙酰腙及其6种过渡金属配合物与小牛胸腺DNA的作用行为,结果表明,2-甲酰基呋喃苯乙酰腙与CT-DNA作用放热量为24.70 kJ•mol-1,2-甲酰基呋喃苯乙酰腙Ni配合物与CT-DNA作用放热量为50.10 kJ•mol-1;2-羟基-1-萘甲醛苯乙酰腙与CT-DNA作用放热量为15.50 kJ•mol-1,2-羟基-1-萘甲醛苯乙酰腙6种过渡金属配合物(Co、Ni、Cu、Zn、Cd、Pb)与CT-DNA作用放热量在 28.40 kJ•mol-1 - 89.97 kJ•mol-1之间;实验结果表明两种配体及其配合物与CT-DNA均有一定的相互作用,且配合物与CT-DNA的作用比相应配体更加强烈。
论文外文摘要:
According to multiply coordination forms, strong coordination ability and biological properties of acyl hydrazone compounds, as well as the matter physical storage and transportation of metalions, the complexes of transition metal with acyl hydrazone compounds play an extremdy important role, two novel hydrazones and seven kinds of transition metal complexes have been synthesized, which haven’t been reported. The main contents are as follows: (1) The phenyl-acetic acid furan-2-ylmethylene-hydrazide C13H12N2O2 was synthesized from methyl phenylacetate、hydrazine hydrate and furfural in anhydrous alcohol, and then reacts with six water nickel chloride,the crystal of a new complex [Ni(C13H12N2O2)2]•Cl2 was obtained. The restlt of X-ray crystal diffraction show that the crystal of C13H12N2O2 is monoclinic, P2(1)/n space group with a=11.619(3)Å,b=13.598(3)Å,c=7.9216(19)Å,β=109.307(4)°,V=1181.2(5)Å3,Z=4,F(000)=480,Dc=1.283 g/cm3;that the crystal of Ni(C13H12N2O2)2•Cl2 is triclinic, P1 space group with a=4.557(14) Å,b=10.947(3)Å,c=12.048(19)Å,β=98.302(5)°,V=593.2(3)Å3,Z=1,F(000)=268,Dc=1.422 g/cm3。 (2) 2-hydroxy-1-naphthaldehyde phenylacetyl hydrazone single crystals and its six complexes were synthesized and a single crystal of 2-hydroxy-1-naphthaldehyde phenylacetyl hydrazone was obtained. The crystal of 2-hydroxy-1-naphthaldehyde phenylacetyl hydrazone single crystals is orthorhombic, pbca space group, cell parameters: a=12.370(3)Å,b=9.704(3)Å,c=25.854(19)Å,β=109.307(4)°,V=1181.2(5)Å3,Z=8,F(000)=480,Dc=1.283 g/cm3. Synthetic hydrazones and its complexes are characterized by elemental analysis, UV-Vis spectra and FT-IR. It was found that the possible structure of the complexes is [M(C19H15N2O2)2]•nH2O. (3) The thermal decomposition of the C13H12N2O2、C19H16N2O2 and their seven complexes were carried out by TG-DTG analysis at 5.00℃•min-1、10.00℃•min-1 and 15.00℃•min-1 respectively. Their apparent activation energies were calculated by Kissinger’s and Ozawa’s equations. The results showed that the decomposition peaks of C13H12N2O2 at the heating rates of 5.00、10.00、15.00 ℃•min-1, were 285.58、295.30 and 310.98 ℃, the decomposition peaks of [Ni(C13H12N2O2)2]•Cl2 at the heating rate of 5.00、10.00、15.00 ℃•min-1 were 294.37、304.25 and 310.40 ℃; the decomposition peaks of C19H16N2O2 at the heating rates of 5.00、10.00、15.00 ℃•min-1 were 285.58、295.30 and 310.98 ℃; the decomposition peaks of six kinds of transition metal complexes (Co、Ni、Cu、Zn、Cd and Pb) with C19H16N2O2 range from 299.23 to 402.60 ℃. Thermal stabilities of two new ligands and their complexes have good thermal stability, which are better than the corresponding ligand. (4) The ability of C13H12N2O2 and its Ni complexes、C19H16N2O2 and its six complexes(Ni、Cu、Zn、Cd、Co and Pb) binding to CT-DNA were investigated by UV-Vis spectra and microcalorimetry. The interaction heat of C13H12N2O2 and its Ni complexes with CT-DNA are 24.70 kJ•mol-1 and 50.10 kJ•mol-1. The heat of C19H16N2O2 with CT-DNA is 15.50 kJ•mol-1,the heat of six kinds of transition metal complexes with CT-DNA range from 28.40 kJ•mol-1 to kJ•mol-1. It is show that the two ligands and their complexes with CT-DNA have certain interaction, and the interactions of complexes with CT-DNA are stronger than the corresponding ligands.
中图分类号:

 O641.4    

开放日期:

 2014-06-19    

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