Synthesis And Properties Investigation Of Tripodal Phosphorus Ligands Centered On The Nitrogen Atom And Their Rare Earth Complexes

On the purpose of further understanding the coordination characteristics of tripod ligands centered on the Nitrogen atom and study some properties of the rare earth coordination complexes which formed by this kind of ligands, we have designed and synthesized an series of phosphate-containing soluble tripod ligands L:-L3 and their corresponding rare earth complexes(Eu(III), Tb(Ⅲ),Nd(Ⅲ)) in this thesis.At the same time, various testing methods were used to analyze and characterized the structure of the ligands and the complexes. During this period, we have researched the interaction between DNA and this series of rare earth coordination complexes by using the method of UV spectra and cyclic voltammetry. The result that this series of rare earth coordination complexes were electroactive was treated as the basis of the research towards the DNA Electrochemical sensor which had chosen the coordination complexes above as the hybridization probes. The results of the work are mainly reflected in the following points:1.The possible structure of the ligands was commonly confirmed by the data of IR spectra, elemental analysis,1HNMR and 13CNMR, and the GaussianO3 program was used to calculate the ligands by full-optimized molecular geometry. In the following work, the structure of the rare earth complexes were characterized by using the continuous variation method of mole ratio, elemental analysis, TG-DSC and IR spectra. The result tells that the ligands have formed 1:1 compounds RE(pic)3L1-3 with the rare earth atoms (Eu(Ⅲ),Tb(Ⅲ),Nd(Ⅲ)).2.In the terms of the research about the interaction between DNA and rare earth complexes Re(pic)3L1-3,the consequences of UV spectra and cyclic voltammetry proved that the series of rare earth complexes interacted with DNA by the insert form. In addition, the rare earth complexes were confirmed a kind of electrochemical activity compound in the specific voltage range. Based on the complexes’nature of electrically neutral, it will harvest good results when using the complexes in electrochemical testing.3.When the series of rare earth complexes RE(pic)3L1-3 were regarded as DNA hybridization probe used in the study of DNA electrochemical sensor, it was found that there was no obvious electrochemical signal response when the complexes were under the effect of modified electrodes single-strand DNA testing. However, in contrast to the phenomenon mentioned above, obvious electrochemical signal response was caught when under the effect of double-stranded DNA testing. When the surface of glassy carbon electrode was modified by single-base mismatch sequence, electrochemical signal response which had been caught will be stronger than the electrochemical signal response which was caught when the glassy carbon electrode was modified by three-base mismatch sequence, but it will be weaker than the electrochemical signal response when the glassy carbon electrode was modified by complementary sequence. This indicated that the biosensor could well discriminate the complementary sequences from the base-mismatched and the non-complementary sequences.