Synthesis And Properties Of Some Tripodal Phosphorus Ligands And Their Function Complexes

In this thesis, we designed and synthesized an phosphate-containing soluble tripod ligand L1-L4and its rare earth picrate complexes. The tripod ligand derivatives was characterized by1HNMR,13CNMR, elemental analysis, IR spectra and the ligand were calculated by full-optimized molecular geometry with GaussianO3program. By using the method of continuous molar ratio,elemental analysis, TG-DSC and IR spectra, the structure of complexes were characterized. The results of experiments showed that the four ligands and its rare earth (Eu (Ⅲ) and Tb (Ⅲ)) picrate had formed a1:1complex (Eu (pic)3L1～4and Tb(pic)3L1～4).The characteristics of the intercalation of the series rare earth picrate complexes (Eu (pic)3L1～4) with BSA were studied by UV spectra, fluorescent spectra and cyclic voltammetry. From the study of the UV spectra we found that the Eu (pic)3L1～4with BSA can formed new Eu(pic)3L1～4-BSA complexes through a strong interaction. Separately, the binding constants between them are:4.11×105L·mol-1,3.28×105L·mol-1,2.59×104L·mol-1,4.53×104L·mol-1; From the study of the cyclic voltammetry we found that the Eu (pic)3L’-4with BSA had formed a kind of1:1complexes Eu (pic)3L1～4-BSA, KEu(Ⅱ)/K Eu(Ⅲ)>1, indicated that the binding capacity of Eu (Ⅱ) complexes with BSA are stronger than Eu (Ⅲ) complexes; The study of the fluorescence spectroscopy showed that Eu (pic)3L1～4with BSA had formed a non-fluorescent complexes Eu (pic)3L’-4-BSA, and the fluorescence quenching method is static quenching. However, the binding constants decreased as the temperature increased. There was one binding site between the complexe and BSA. The thermodynamic parameters of the Eu(pic)3L1～4and BSA showed that reaction are spontaneous exothermic process, the forces are hydrogen bonds and van der Waals. The interaction of the Fe3+and Cu2+with complexes and BSA was studied by UV spectra and fluorescence spectra, the consequences showed that the presence of Fe3+and Cu2+could enhance the situation of the Eu(pic)3L1～4and BSA but couldn’t change its binding sites, indicating that Cu2+and Fe3+can enhance the stability of the Eu(pic)3L1～4-BSA complexes through the metal bridge by the metal ions-Eu(pic)3L1～4.The characteristics of the Eu(pic)3L1～4with ct-DNA were examined by UV spectra and cyclic voltammetry, we found that Eu(pic)3L1～4are electrochemically active substance in-0.6v～0.6v, The electrochemical redox processes of Eu(pic)3L1～4on glassy carbon electrode is a reversible process controlled by diffusion. The binding mode of the complexes with DNA were insert mode, the binding constants were1.21×106L·mol-1,4.81×105L·mol-1,5.34×105L·mol-1,5.51×105L·mol-1. The coordination reaction of6-furfurylaminopurine, DNA and Eu (pic)3L1～4were studied by UV spectra, the results proved that Eu(pic)3L1～4can form1:1complexes (6furfurylaminopurine-Eu (pic)3L1～4) with6-furfurylaminopurine, Eu (pic)3L1～4, DNA and6furfurylaminopurine can self-assemble to form a6-furfurylaminopurine-DNA-Eu(pic)3L1～4supramolecular. It was calculated by Scatchard that the binding constants of the system were:2.24×105L·mol-1,1.41×105L·mol-1.2.1×105L·mol-1’and2.82×105L·mol-1, which is smaller than the binding constant of Eu(pic)3L’-4-DNA. The study of Eu(pic)3L3DNA-based chemical sensor, showed that Eu(pic)3L3have a good recognition of the DNA complementary sequence and mismatch sequence. Accordingly, the Eu(pic)3L3can be used as a DNA electrochemically active probes to effectively identify the hybridization of the DNA bases sequence at the electrode surface.