Synthesis And Properties Of Tripodal Phosphorus Ligands And Their Rare Earth Complexes

In this thesis, we synthesized an phosphate-containing soluble tripod ligand L1～L3 and its rare earth picrate (Eu(Ⅲ),Tb(Ⅲ), La(Ⅲ),Y(Ⅲ)) complexes. At the same time, the ligands and the complexes of synthesized were analyzed and characterized by different methods. The interaction of complexes with DNA and BSA has been studied by fluorescence spectrum, UV spectra and cyclic voltammetry. Using Eu (pic)3L1·3H2O and Eu (pic)3L2·3H2O as electro chemical probes was studied systematic and complete.At the same time, the widely used many fields of Eu (pic)3L’·3H2O and Eu (pic)3L2·3H2O as electro chemical probes in electrochemical DNA Biosensor was also investigated. The main contents are as follows:1. Ligand L1～L3and its rare earth picrate complexes were synthesized and characterized by1H NMR,13CNMR,IR spectra and elemental analysis.At the same time, the ligand were calculated by full-optimized molecular geometry with Gaussian09 program. By using the method of continuous molar ratio,elemental analysis, IR spectra, UV spectra and TG-DSC, the structure of complexes were characterized. The experimental results show that ligand formed 1:1complexes Re (pic)3L’·3H2O (Re= Eu(Ⅲ). Y(Ⅲ))、Eu(pic)3L2·3H2O and Re(pic)3L3(Re=Eu(Ⅲ),2. The interaction of Eu (pic)3L’·3H2O、Eu (pic)3L2·3H2O and Eu (pic)3L3 and bovine serum albumin and bovine serum albumin (BSA) was studied by fluorescence spectrometry at different temperatures. The results indicate that the complex can markedly quench the intrinsic fluorescence of BSA via a static quenching process. The complexes and BSA may have dipole-dipole no radiation energy transfer. The binding constant, binding point numbers and thermodynamic parameters (△H>0, △S>0, △G<0) at three temperature levels, for example,293,303 and 313 K were calculated by the double logarithm regression equation and van der Waals forces, and the results revealed that there exists a strong combination action between complexes and BSA, the primary binding pattern between Eu (pic)3L1·3H2O and BSA was interpreted as hydrophobic interaction, however Eu (pic)3L2-3H2O and Eu (pic)3L3 with BSA were hydrogen bond and van der Waals force. The effects of metal ions Cu2+and Fe3+on the interactions between BSA and complex was investigated and the results indicated that there was a big influences between Eu(pic)3L and BSA Under the Cu2+and Fe3+mediated,which is quite helpful for us to comprehensivly interpret the mechanism of action and exportation of the complexes as drugs.3. The UV-Vis spectroscopy、Fluorescence Spectrometry and cyclic voltammetry were adopted to investigate the interaction between calf thymus DNA and Eu (pic)3L1·3H2O、Eu (pic)3L2·3H2O and Eu (pic)3L3.The results indicated that there are intercalation interaction between calf thymus DNA and complexes, complexes are electrochemically active substance in the specific voltage range and the mechanism of the intercalation between the complexes and DNA, complexes are electrochemically active substance in the specific voltage range. The complexes will harvest good results when using the complexes in electrochemical testing. When Eu (pic)3L1·3H2O and Eu (pic)3L2·3H2O were utilized as a hybridization indicator for the detection of CaMV35S promoter gene fragments, no electrochemical response was observed on the probe of DNA modified electrode. While the obvious electrochemical response was investigated for the double-stranded DNA. So Eu (pic)3L1·3H2O and Eu (pic)3L2·3H2O could be well used as the biosensor to discriminate the complementary sequences from the base-mismatched and the non-complementary sequences.