Synthesis, Structure And Interactions With DNA And Bsa Of Nickle Complexs With Amino Acid And Aromatic Aldetydic Schiff Base

In recent years, transition metal complexes are concerned. Nickel is one of thenecessary trace elements in organisms. What’s more, nickel could not only promote theabsorption of iron ion, the growth of RBC and the synthesis of amino enzyme, be a kind ofDNA and RNA structure stabilizer, but also it was a component of the urease. Schiff base iscompound that primary amine (–NH2) and carbonyl (C=O) compounds synthesized withmethylene amino. Its coordination ability of N atom is very strong and it is also a kind ofexcellent organic ligand. There are many different types of Ni complexes. Structure ofamino Schiff base metal complexes is very steady and rich and is widely used many fields.The interaction of small molecular compounds with deoxyribonucleic acid (DNA) andserum albumin has been important subject of bioinorganic chemistry. DNA is a carrier andpasser of genetic information, and is the main targets of some anticancer and antiviral.Serum albumin directly affects the distribution, storage, transshipment, pharmacokinetics,drug metabolism and toxic and side effects in biological body. So studing the interaction ofamion acid Schiff base nickel complexes with DNA and BSA could help to design andsynthesize useful anti–cancer and anti–tumor drugs. It is of great significance in the lifeprocess, drugs mechanism of action and drug molecular design.Based on these advantages, we designed and synthesized11kinds of amino acidSchiff base1,10–phenanthroline nickel complexes in this thesis. They have beensynthesized and then characterized by elemental analysis, IR spectra and X–ray singlecrystal diffraction. Meanwhile, UV–Vis spectra, fluorescence spectra and circulardichroism spectra mesurements have been used to investigate the properties of interacrionsbetween CT–DNA, BSA and11nickle complexes. The main contents are as follows:1. Three L–alanine Schiff base phenanthroline nickel complexes[Ni(Sal–L–Ala)(Phen)(CH3OH)](1),[Ni(Naph–L–Ala)(Phen)(CH3OH)]·(CH3OH)(2) and[Ni2(o–Van–L–Ala)2(Phen)2](3)(Sal=salicylaldehyde, Naph=2–hydroxy–1–napthaldehyde,o–Van=o–vanillin, L–Ala=L–alanine, Phen=1,10–phenanthroline) have been synthesized and characterized by elemental analysis, IR spectra and X–ray single crystal diffraction.The results shown that the three complexes are six–coordinated with Ni(Ⅱ) centers andshow distorted octahedral configuration. In their srystal structure, three dimensional spacestructure has been formed by hydrogen bonds from between neighboring molecules.What’s more, UV–Vis spectra, fluorescence spectra and CD spectra mesurements havebeen used to investigate the properties of interacrions between CT–DNA or BSA and thesecomplexes. The results displayed that the complexes could bind to DNA in an interalationmode and the binding constants calculated are Kb1=4.0×103L·mol1, Kb2=1.4×104L·mol1and Kb3=4.6×103L·mol1, respectively. The three complexes could well binding affinity toBSA protein and then quench their intrinsic fluorescence efficiently.2. Two L–methionine Schiff base phenanthroline nickel complexes[Ni(Sal–L–Met)(Phen)(CH3OH)](4) and [Ni(Naph–L–Met)(Phen)(CH3OH)](5)(Sal=salicylaldehyde, Naph=2–hydroxy–1–napthaldehyde, L–Met=L–methionine,Phen=1,10–phenanthroline) have been synthesized and characterized by elemental analysis,IR spectra and X–ray single crystal diffraction. In addition, UV–Vis spectra, fluorescencespectra and CD spectra mesurements have been used to investigate the properties ofinteracrions between CT–DNA or BSA and these complexes. The results displayed thenickle(Ⅱ) complexes could bind to DNA in an interalation mode. The quenching constantKq4is4.7×1012L·mol1·s1and Kq5is1.2×1013L·mol1·s1, while the apparent quenchingconstant of bimolecular fluorescence Kb4is1.5×105mol·L1and Kb5is2.9×108mol·L1; thenumber (n) of the binding sites per BSA n4is1.1and n5is1.8.3. Two L–phenylalanine Schiff base phenanthroline nickel complexes[Ni(Sal–L–Phe)(Phen)(CH3OH)](6) and3[Ni(o–Van–L–Phe)(Phen)(CH3OH)]·5H2O (7)(Sal=salicylaldehyde, Naph=2–hydroxy–1–napthaldehyde, L–Phe=L–phenylalanine,Phen=1,10–phenanthroline) have been synthesized and characterized by elemental analysis,IR spectra and X–ray single crystal diffraction. Furthermore, UV–Vis spectra, fluorescencespectra and CD spectra mesurements have been used to investigate the properties ofinteracrions between CT–DNA or BSA and these complexes. By the UV spectrum analysisthe binding constants Kb6=1.4×104L·mol1and Kb7=1.9×104L·mol1could be calculated. The quenching constants Ksq6is1.9and Ksq7is3.0according to the fluorescence spectrumanalysis. It is shown the complex with o–vanillin Schiff base ligand to bind to DNA ismore stronger and the results should be related to both complexes structure. The bothcomplexes could well bind to BSA and then quench their intrinsic fluorescence efficiently.4. A novel L–glycine Schiff base phenanthroline nickel complex[Ni(Naph–L–Gly)(Phen)(CH3OH)]·CH3OH (8)(Naph=2–hydroxy–1–napthaldehyde,L–Gly=L–glycine, Phen=1,10–phenanthroline) has been synthesized and characterized byelemental analysis, IR spectra and X–ray single crystal diffraction. It shown bycrystallographic data that the new complex was six–coordinated with Ni(Ⅱ) centers andshow distorted octahedral configuration. Three dimensional space structure has beenformed by O–H···O and C–H···O hydrogen bonds from between neighboring molecules.What’s more, UV–Vis spectra, fluorescence spectra and CD spectra mesurements havebeen used to investigate the properties of interacrions between CT–DNA and the complex.The results exhibited that the Ni(Ⅱ) complex could bind to DNA in an interalation mode.By spectra mesurements to study the properties of interactions between BSA and thecomplex, the results shown that the complex could well bind to BSA and then make BSAconformation changed.5. A new L–serine Schiff base phenanthroline nickel complex[Ni(Naph–L–Ser)(Phen)(CH3OH)](9)(Naph=2–hydroxy–1–napthaldehyde,L–Ser=L–serine, Phen=1,10–phenanthroline) has been synthesized and characterized byelemental analysis, IR spectra and X–ray single crystal diffraction. The results shown bycrystallographic data that the crystal belongs to monoclinic system; P2(1)/c space group;crystal cell parameters of a=15.0499(7), b=14.4575(5), c=11.5689(5),=90o,=96.1650(10)o,=90o, V=2502.65(18)3, Z=4, Dc=1.402Mg·m–3, F(000)=1096,R1=0.0755, wR2=0.2127. In addition, UV–Vis spectra, fluorescence spectra and CD spectramesurements have been used to investigate the properties of interacrions betweenCT–DNA or BSA and the complex. The results displayed this complex could bind to DNAin an interalation mode but the intensity is not strong. The complex could well bind affinityto BSA and then quench their intrinsic fluorescence efficiently. 6. A novel L–valine Schiff base phenanthroline nickel complex[Ni(o–Van–L–Val)(Phen)(CH3OH)]·3CH3OH (10)(o–Van=o–vanillin, L–Val=L–valine,Phen=1,10–phenanthroline) have been synthesized and characterized by elemental analysis,IR spectra and X–ray single crystal diffraction. Furthermore, UV–Vis spectra, fluorescencespectra and CD spectra mesurements have been used to investigate the properties ofinteracrions between CT–DNA or BSA and the complex. The results shown by UV–Visspectra that the binding constants Kb10calculated is7.6×103L·mol1and the quenchconstants calculated is1.3. By fluorescence spectra the quench constants of Kq10is about9.0×1012L·mol1·s1, and is considerably larger than the maximum value for the diffusioncontrolled quenching of biological macromolecules. The complex could quench theirintrinsic fluorescence efficiently.7. A L–tyrosine Schiff base phenanthroline nickel complex[Ni(o–Van–L–Tyr)(Phen)(CH3OH)]·CH3OH(11)(o–Van=o–vanillin, L–Tyr=L–tyrosine,Phen=1,10–phenanthroline) has been synthesized and characterized by elemental analysis,IR spectra and X–ray single crystal diffraction. The crystal is monoclinic system and P2(1)/n space group. What’s more, UV–Vis spectra, fluorescence spectra and CD spectramesurements have been used to investigate the properties of interacrions betweenCT–DNA or BSA and the complex. The results shown this Ni(Ⅱ) complex could bind toDNA in an interalation mode and well bind to BSA. And the complex could induce aconformational change with loss of–helical stability of protein.