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Palladium (ii) Mixed Ligand Complexes Of Weak Interaction And Its Biological Activity Study

Posted on:2004-12-07Degree:DoctorType:Dissertation
Country:ChinaCandidate:E J GaoFull Text:PDF
GTID:1111360122966293Subject:Inorganic Chemistry
Abstract/Summary:PDF Full Text Request
Palladium is one of the most important rare metal with characterized square-planar structure of its bivalent cation in its mixed ligand complex PdAB (where A B are two different ligands), the interaction of different ligand can cause many intermolecular and intramolecular interactions ,which have important effect on the property of complex ,such as the feedback donation hydrogen bonds . hydrophobic interaction and aromatic ring stacking et al. These weak interaction usually are the key factors inducing formation of supermolecule, even cause important influence on its biological activities. In this paper, we synthesized more than 20 complexes according to the combination of different ligands, the interaction of intermolecular and intramolecular interaction of complexes were studied based on their crystal structures and stability in solution, the inhibition activity of these complex were determined in vitro. Their interaction with DNA were determined by many experimental methods. There are seven sections in this paper: Part 1 is introduction and the significance of the paper. Part 2 is the synthesis and characterization of mixed ligand complexes. Part 3 is the determination of crystal structure in which weak intermolecular or intramolecular interaction was discussed in terms of molecular structure and crystal structure. Part 4 is the determination of stability in solution. The weak interactions was further discussed on the basis of the characterizaton constant in solution and the crystal data in Part 3. Part 5 is the determination of antitumor activity. Part 6 studied the action rule and mode of complex with DNA. Part 7 is the conclusion of this paper.The main research in this paper includes:1 The 22 mixed ligand complexes were synthesized in which bipyridine(bipy)-, phenanthroline(phen) 5-nitrophenanthroline(Nphen) , phenanthroline- 5,6-dikentone (Dphen) and biquinoline(biqu) are the first ligand and chlorine ion (Cl-) phenylalanine(phe~), tyosine(tyr") asparagic radical(asp-) 2.6-diaminocaproic radical(lys-) tryptophan(trp-) , histidine(his-) malonate(mal2-) benzyl malonate (bmal2-) phenethtyl malonate (pmal2-) are the second ligand. There are 6 mixed ligand single crystal and 1 mono-ligand crystal were synthesized and determined by single crystal X-ray diffraction.The results showed that combination of different ligand affect molecular and crystal structure greatly and can influence weak intermolecular and intramolecular interaction directly. Based on the above reasons, the supermolecule is formed.2 The stability constant and characterization constant of the complex in solution were determined by pH potentiometric titration. The possible weak intermolecular interaction of complex in solution can be inferred from the compare of characterization constant and determined constant. When combined with the structural data in crystal , the weak intramolecular interaction were fully discussed.3 The inhibition activity of 16 complexes against lung cancer AGZY-83a were determined in vitro. At the same time, screening were also done by fluorescence methods. These data were compared with cis-platin. The results showed that some complexes have anticancer activity against lung cancer cell, seven of them have better activity corresponding to others and their activity have relation with weak intramolecular interaction . 4 The action rule of complex with sperm DNA were determined by fluorescence spectra-, UV spectra and CD spectra. The mobility ratio of some specific complex with pBR322 plasid DNA were determined by gel electrophoresis and binding constants of dichelate palladium complex with DNA were calculated. Based on the above results, the possible mechanism of complex with DNA were discussed. In order to further discuss the mechanism of interaction of complex with DNA, two single crystal of palladium coordinated by bipy/phen as the first ligand while adenine as the target molecule were synthesized, its corresponding hydrolysis reaction rate constants were determined, too. Their covalent combinatio...
Keywords/Search Tags:Palladium(II), mixed ligand complex, weak interaction, DNA, crystal structure, stability
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