节点文献
一种新型三齿仲胺配体及其配合物的合成、表征及性能研究
Synthesis, Characterization and Property Study of a Novel Tridentate Secondary and Its Amine Complexes
【作者】 戴雪芹;
【导师】 张岐;
【作者基本信息】 海南大学 , 应用化学, 2011, 硕士
【摘要】 近年来,希夫碱及其过渡金属配合物因功能多样性而备受关注。如:1)过渡金属配合物与DNA作用。DNA是生物体遗传信息的载体,是生命体的重要物质,与生物的生长、发育和繁殖等正常生命活动及癌变等异常生命活动息息相关。因此,研究配合物与DNA作用是探索和开发新核酸探针的基础,有助于从分子水平上了解药物的作用机理,为临床上设计有效的药物提供理论指导。2)希夫碱在有机光电和信息功能材料领域也有广泛地应用,设计合成能将化学信号、光信号或电信号转变为可测的输出信号的有机分子逻辑系统是希夫碱的另一功能性质。希夫碱中-C=N-键转动不灵活的特点可能阻碍其与金属小分子或DNA等生物活性大分子的相互作用。为了提高希夫碱与金属离子或生物活性分子相互作用的能力,我们尝试把具有亚胺基的希夫碱还原为仲胺类配体。研究发现还原后仲胺配体中的C-N单键可以自由旋转,分子柔韧性和稳定性都有所提高。基于这种思路,我们设计并合成新的三齿配体L,N-(4-甲基苯)-N’-(2-(4-甲基苯氨基)乙烷基)乙烷-1,2-二胺,以及其过渡金属配合物,并探索这类配合物与DNA相互作用方式及配体的荧光分子逻辑门特性,本论文分为五大部分:第一章:介绍了配位化学和希夫碱的研究进展。配合物和DNA作用的机理,晶体培养和研究方法,以及配体的阳离子识别和荧光分子逻辑门特性等。第二章:以对甲基苯甲醛和二乙烯三胺为原料合成希夫碱,经硼氢化钾还原得到三齿仲胺配体L。利用核磁、元素分析、红外和摩尔电导等表征了该三齿仲胺配体L及其与CuⅡ, CoⅡ, NiⅡ, ZnⅡ的氯化盐和硝酸盐形成的八种金属配合物。通过结构表征发现,硝酸盐配合物中,硝酸盐与配体L以1:1配位,且硝酸盐中的两个硝酸根离子都参与配位,是一个非电解质配合物。氯化盐配合物中,氯化盐与配体也是以1:1形成配位,但是氯化盐中的两个氯离子只有一个参与配位,另一个以游离的形式存在,是一个1:1型电解质配合物。第三章:对硝酸镍、硝酸锌和氯化镍三个金属配合物通过X-ray单晶衍射仪测定并解析出其晶体结构,解析结果进一步证实了硝酸盐配合物是一个配体和金属盐以1:1配位的非电解质配合物,而氯化盐则是与配体以1:1配位形成1:1型电解质配合物。第四章:配合物与DNA相互作用的研究。采用紫外光谱和荧光光谱法研究配合物与DNA的作用机制,探讨它们之间的作用方式。结果发现随着配合物的加入,DNA紫外光谱的最大吸收峰有减色效应。同时配合物也能较大程度的猝灭DNA-EB体系的荧光,配合物可能通过静电作用与DNA结合。计算配合物对DNA-EB体现的猝灭常数研究配合物与DNA结合的强弱。结果表明,硝酸盐配合物与DNA作用比氯化盐强,铜配合物比其它金属配合物与DNA作用强。第五章:考察了过渡金属及碱土金属对配体的荧光发射光谱的影响,结果发现加入Cu2+和Fe3+后受体分子的荧光有明显的猝灭,在此基础上,我们以Cu2+和Fe3+为两化学输入,研究发现配体L可构建一个“或”(OR)分子逻辑门。
【Abstract】 In recent years, Schiff base and its transition metal complexes have attracted much attention because of functional diversity. Such as:1) The interaction of transition metal complexes and DNA, DNA is the carrier of genetic information in organism and an essential material in life. It is closely related to normal life activities such as growth, development, propagation and abnormal vital movements such as carcinogenesis. Therefore, Researching the interaction of complexes with DNA is the basis of new nucleic acid probe development, DNA-binding properties was studied from the molecular level and providing an effective theoretical guidance for clinical drug design.2) Schiff bases were widely used in organic optoelectronic and information functional materials, organic molecular which can change chemical signals, optical signals or electrical signals into measurable output signals was designed and synthesised is the other functional properties of schiff bases. The rotation of-C=N-bond in Schiff base is not flexible may hinder it interact with small metal molecule or big biological molecule. We try to reduct the imine Schiff base into secondary amine ligand to enhance the ability of Schiff base interacted with metal ions or biological moleculars. Examination found that-C-N-single bond in secondary amine ligand can rotate freely, and molecular flexibility and stability has been increased.We design and synthesis a novel tridentate ligand (L), N-(4-methylbenzyl)-N’-(2-(4-methylbenzylamino)ethyl) ethane-1,2-diamine and its transition metal complexes,the interaction mode of DNA with small molecules and fluorescent molecular logic gate properties of ligand were studied. This dissertation consists of five chapters:Chapter 1:A brief review of the research of the coordination chemistry and Schiff base. Mechanism of crystal growth and research methods of complexes interacte with DNA, as well as the characteristics of ligand recognition and fluorescent molecular logic gate.Chapter2:N-(4-methylbenzyl)-N’-(2-(4-methylbenzylamino)ethyl) ethane-1,2-diamine a novel tridentate ligand (L)and its transition metal complexes (M=CuⅡ, CoⅡ, NiⅡ,ZnⅡ) have been synthesized. Their compositions and structures were characterized by elemental analysis,1H NMR, FT-IR and molar conductance. The structural characterization showed that the nitrate complexs were coordinated by nitrate and ligand in 1:1,and the two nitrate ions were all in coordination, there were non-electrolyte complexes. Chloride salt complexs were coordinated by chloride salt and ligand in 1:1,only one chlorine ion was in coordination,the other was free.There were 1:1 electrolyte.Chapter 3:The crystal structure of the nickel nitrate, zinc nitrate and nickel chloride complexs were characterized by X-ray single crystal diffraction, the results showed that the nitrate complexs were coordinated by nitrate and ligand in 1:1,and the two nitrate ions were all in coordination, there were non-electrolyte complexes. Chloride salt complexs were coordinated by chloride salt and ligand in 1:1,only one Chlorine ion was in coordination,the other was free.There were 1:1 electrolyte.Chapter 4:The interaction of the complexes with calf thymus DNA was investigated by UV spectroscopy and fluorescence spectroscopy, and the results illustrated that the absorption intensity of DNA solution have hypochromic effect and the emission intensity of DNA-EB system decreases with the concentration of the complex increasing. This phenomenon indicates that the complexes may bind to DNA by electrostatic interaction mode. Through the binding constants we known that the interaction of nitrate complexes with DNA stronger than chloride salt.copper complex effects stronger than other metal complexes.Chapter 5:The effects of transition metal and alkaline earth metal on ligand fluorescence emission spectra were researched.The results showed that the receptor exhibited a fluorescence emission which was quenched upon addition of Cu2+ or Fe3+.Interestingly, the receptor offers an’OR’logic gate property to Cu2+ and Fe3+. Keywords:transition metal complexes crystal structure DNA biological activity fluorescence logic gate
【Key words】 transition metal complexes; crystal structure; DNA; biological activity fluorescence; logic gate;