| Polyoxometalates?POMs?,as early transition metal-oxygen clusters,have been attracting great attention owing to the diversity of structural and compositional and manifold potential applications in magnetism,catalysis,electrochemistry,photochemistry,material,biology and medicine.Strandberg-type polyoxometalates have higher charge density and smaller size than other polyacid anions.In order to obtain compounds with superior biological activity,higher physiological stability and lower toxicity,many efforts have been made to modify POMs through altering their structure,polarity,charge and composition.There are many potential applications of nanomaterials in the fields of photochemistry,heat,electrochemistry,magnetism,mechanics,catalysis and medicine.Polyoxometalates/nanoparticles?POMs/NPs?,which based on polyoxometalates and nanoparticles have attracted considerable interests due to the unique properties resulting from the combination of the polyoxometalates and the nanoparticles.The adsorption property and drug activity of this kind of material were improved by its interaction,and the work in this field was studied.In the present paper,we describe the synthesis and chemical characterization of five Strandberg-type inorganic-organic hybrid compounds,[Cu?HL1?2]2H2[P2Mo5O23]·IOH2O?1?,[Ni?HL'?2]2H2[P2Mo5O23]·4H2O?2?,?H2L1?SH[P2Mo5O23]·12H2O?3?,[Ni?HL2?2]2H2[P2Mo5O23]·2H2O?4?,[Zn?HL2?2]2H2[P2Mo5O23]·2H2O?5?.The POMs/NPs Fe3O4?1?Fe3O4@2?Fe3O4?3?Fe3O4@4?and Fe3O4@5 were synthesized by ultrasonic dispersion technique.At the same time,they were characterized and their properties were studied.In addition,the adsorption properties and in vitro cytotoxicity of these complexes to organic dyes were also studied.In chapter 1?the ligands were prepared by the condensation reaction of thiosemicarbazide and 2-acetylpyridine.Reactions of 2-acetylpyridine thiosemicarbazone?HL1?with Cu?ClO4?2·6H2O/Ni?ClO4?2·6H2O/Sm?NO3?3·6H2O,NaMoO4·2H2O and concentrated phosphoric acid as raw materials formed compounds[Cu?HL1?2]2H2[P2Mo5O23]·10H2O?1?,[Ni?HL1?2]2H2[P2Mo5O23]·4H2O?2?,?H2L,?5H[P2MO5O23]·12H2O?3?,respectively.Then,we synthesized hybrid nanoparticles Fe3O4@1,Fe3O4@2 and Fe3O4@3 based on 1-3.Compounds 1-3 were characterized by elemental analysis,FT-IR spectroscopy,TG analysis,fluorescence spectrometry,X-ray diffraction and XRD powder diffraction.Three POMs/NPs Fe3O4@1,Fe3O4@2 and Fe3O4@3 were characterized by FT-IR spectroscopy,XRD powder diffraction,vibrating sample magnetometer?VSM?transmission electron microscopy and?TEM,including high-resolution TEM?.The adsorption properties and in vitro cytotoxicity of 1-3,Fe3O4@1,Fe3O4@2 and Fe3O4@3 were studied.The adsorption activity of the as-prepared 1-3,Fe3O4@1,Fe3O4@2 and Fe3O4@3 are investigated by photometrically monitoring the removing of methylene blue?MB?,rhodamine B?RhB?,safranine T?T?,gentian violet?GV?,fuchsin basic?FB?and methyl orange?MO?from aqueous solutions.The results showed that 1-3,Fe3O4@1,Fe3O4@2 and Fe3O4@3 have a good selective adsorption for cationic dyes,but had no adsorption effect on anionic dyes.It has potential application in purification and treatment of wastewater.3-?4,5-Dimethylthiazol-2-yl?-2,5-diphenyltetrazolium bromide?MTT?assay was carried out to evaluate the cytotoxicity.In vitro cytotoxicity tests were carried out on both SMMC-7721 human hepatoma cells and HL-7702 human hepatocytes by MTT method for 1-3,Fe3O4@1,Fe3O4@2 and Fe3O4@3.Pharmacological studies have shown that compounds 1 and 3 show goods cytotoxicity against SMMC-7721 human hepatoma cells and HL-7702 human hepatocytes.The Fe3O4@3 was selective to SMMC-7721 human hepatoma cells.In chapter 2,the ligands were prepared by the condensation reaction of thiosemicarbazide and 2-acetylpyrazine.2-acetylpyrazine thiosemicarbazone?HL2?with Ni?ClO4?2 · 6H2O/Zn?ClO4?2·6H2O,NaMo4-2H2O and concentrated phosphoric acid were as raw materials to form compounds[Ni?HL2?2]2H2[P2Mo5O23]·2H2O?4?,[Zn?HL2?2]2H2[P2Mo5O23]·2H2O?5?,respectively.Then,we synthesized hybrid nanoparticles Fe3O4@4 and Fe3O4@5 based on 4-5.Compounds 4-5 were characterized by elemental analysis,FT-IR spectroscopy,TG analysis,fluorescence spectrometry,X-ray diffraction and X-ray powder diffraction.Two POMs/NPs Fe3O4@4 and Fe3O4@5 were characterized by spectroscopic analysis FT-IR spectroscopy,XRD powder diffraction,vibrating sample magnetometer?VSM?and transmission electron microscopy?TEM,including high-resolution TEM?.The adsorption properties and in vitro cytotoxicity of 4-5,Fe3O4@4 and Fe3O4@5 were studied.The adsorption activity of the as-prepared 4-5,Fe3O4@4 and Fe3O4@5 are investigated by photometrically monitoring the removing of MB,RhB,T,GV,FB and MO from aqueous solutions.The results showed that 4-5,Fe3O4@4 and Fe3O4@5 have a good selective adsorption for cationic dyes,but had no adsorption effect on anionic dyes.It has potential application in purification and treatment of wastewater.In vitro cytotoxicity tests were carried out on both SMMC-7721 human hepatoma cells and HL-7702 human hepatocytes by MTT method for 4-5,Fe3O4@4 and Fe3O4@5.Pharmacological studies have shown that 5 and Fe3O4@5 show goods cytotoxicity against SMMC-7721 human hepatoma cells and HL-7702 human hepatocytes. |
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