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Synthesis,Characterization,Properties Of Strandberg-type Polyoxometalates Appended With Organic Ligands

Posted on:2017-06-22Degree:MasterType:Thesis
Country:ChinaCandidate:Y X TaiFull Text:PDF
GTID:2311330488451216Subject:Chemistry
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Strandberg-type phosphomolybdates(abbreviated as [P2Mo5O236-) seized the attention of chemists due to their unique structures and properties relative to catalysis, medicine, electrochemistry,magnetism and fluorescence, etc. As we all known, the [P2Mo5O236-clusters have a relatively smaller size but higher charge densities compared to other polyoxoanions, which can induce more metal-organic cationic units to enter the crystal structures of the final products. Strandberg-type phosphomolybdates possess good fluorescence and excellent catalytic activity not only in the decolorization of organic dye but also in the esterification reaction. Furthermore, nanoparticles have been widely used for medicine, catalysis and magnetic applications. Both Strandberg-type polyoxometalates and nanoparticles have significant pharmacological activities. Therefore, an effective and low toxicity drug must be developed and it is important to further study the possible application in medicine of POMs-NPs, which have important theoretical and practical significance.In this paper, we studied the synthesis, characterization and properties of compounds 1-9 and hybrid nanoparticles Ag NPsY@6, AgNPsY@7, AgNPs Y@8 and AgNPs Y@9.In chapter 1, reactions of Cu?ClO4?2·6H2O,?Zn?ClO4?2?6H2O, Cd?ClO4?2·6H2O, Co?ClO4?2?6H2O?with pyridine-2-carboxamide?HL1?, NaMoO4·2H2O/?NH4?2Mo7O24·4H2O, HClO4 and concentrated phosphoric acid formed organic-inorganic compounds [Cu?L1?2?H2O?2]H2[Cu?L1?2?P2Mo5O23?]·5H2O?1?,[Cu?L1?2?H2O?2]2H2[P2Mo5O23·2CH3OH?2?, [Zn?L1?2?H2O?2]2H2[P2Mo5O23·2H2O?3?,[Cd?L1?2?H2O?2]2H2[P2Mo5O23·2CH3OH?4? and [Co?L1?2?H2O?2]2[P2Mo5O23·2H2O?5?, respectively.Compounds 1–5 have been characterized by elemental analysis, FT-IR spectroscopy, TG analysis, UV-vis spectroscopy, X-ray powder diffraction and single-crystal X-ray diffraction studies. We evaluate the fluorescence and catalysis of 1–5, and the results reveal that they possess good fluorescence and excellent catalytic activity not only in the decolorization of RhB dye but also in the esterification of n-butyric acid with n-hexanol. 3-?4,5-Dimethylthiazol-2-yl?-2,5-diphenyltetrazolium bromide?MTT? assay was carried out to evaluate cytotoxicity. Pharmacological studies, against human hepatocellular carcinoma HepG2 and human colorectal carcinoma HCT-116 cells, respectively, have shown that compounds 1–5 showdifferences in the cytotoxicity.In chapter 2, the ligands were prepared by boiling a methanol solution of thiosemicarbazide and2-acetylpyridine or 2-acetylpyrazine. Reactions of 2-acetylpyridine thiosemicarbazone?HL2? with Cu?ClO4?2·6H2O/Co?ClO4?2?6H2O), NaMoO4·2H2O and concentrated phosphoric acid formed compounds[Cu?HL2?2]2H2[P2Mo5O23·10H2O?6? and [Co?HL2?2]2{[K?H2O?5]2[P2Mo5O23}·2H2O?7?, respectively.Furthermore, reactions of 2-acetylpyrazine thiosemicarbazone?HL3? with FeCl3·6H2O, NaMo O4·2H2O and concentrated phosphoric acid formed compound [Fe?HL3?2]2[P2Mo5O23·4H2O?8?. Then, we synthesized hybrid nanoparticles AgNPsY@6, AgNPsY@7and AgNPsY@8 based on 6–8. The compounds 6–8 and hybrid nanoparticles have been characterized by elemental analysis, FT-IR spectroscopy, TG analysis, UV-vis spectroscopy, X-ray powder diffraction, single-crystal X-ray diffraction and TEM studies. We evaluate the fluorescence and catalysis of 6–8, and the results reveal that they present good fluorescence. It should be emphasized that 6 and 8 show excellent catalytic activity in the decolorization of Rh B dye.3-?4,5-Dimethylthiazol-2-yl?-2,5-diphenyltetrazolium bromide?MTT? assay was carried out to evaluate cytotoxicity. Pharmacological studies, human hepatocellular carcinoma HepG2 and human normal heptical QSG7701 cells, respectively, have shown that compounds 6, 7, Ag NPsY, AgNPsY@6and AgNPsY@7 show differences in the cytotoxicity.In chapter 3, reactions of pyridine-2-carboxaldehyde?HL4? with Cu?ClO4?2·6H2O,?NH4?2Mo7O24·4H2O, HClO4 and concentrated phosphoric acid formed compound[Cu?L4*?2]2H2[P2Mo5O23·4H2O?9?, and then, we synthesized hybrid nanoparticles AgNPs Y@9 based on 9.The compound 9 and hybrid nanoparticle AgNPs Y@9 have been characterized by elemental analysis, FT-IR spectroscopy, TG analysis, UV-vis spectroscopy, X-ray powder diffraction, single-crystal X-ray diffraction and TEM studies. We evaluate the fluorescence and catalysis of 9, and the results reveal that 9 exhibits good fluorescence and excellent catalytic activity in the decolorization of RhB dye.3-?4,5-Dimethylthiazol-2-yl?-2,5-diphenyltetrazolium bromide?MTT? assay was carried out to evaluate cytotoxicity. Pharmacological studies, human hepatocellular carcinoma HepG2 and human normal heptical QSG7701 cells, respectively, have shown that 9 and Ag NPsY@9 show differences in the cytotoxicity.
Keywords/Search Tags:Strandberg-type, Crystal structure, Hybrid nanoparticles, Catalytic activity, Cytotoxicity
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