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Study On The Microwave Solid State Synthesis And Antibacterial Activities Of Cu, Co, Ni, Zn, Mn Complexes

Posted on:2014-02-21Degree:DoctorType:Dissertation
Country:ChinaCandidate:S P XuFull Text:PDF
GTID:1261330392965054Subject:Chemical processes
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The transition-metal complexes are built by empty d orbitals of transition-metal ionand bidentate ligand. Transition-metal complexes have thermodynamics stability ontransition-metal ion, organic chelate reagent and chelate ring. The transition-metalcomplexes have been widely used in the field of activator, functional material,biologic activities and so on. All of the discoveries brought this field to be a focus inthe coordination chemistry.The especial structure transition-metal complexes are created by Schiff bases ofcontaining N, O bidentate ligand and transition-metal ion. The complexes exhibitsuperior performance in terms of redox, catalyse activity, biologic activity and so on.The steady transition-metal complexes are synthesized by β-diketonates with enolstructure of containing O bidentate ligand and transition-metal ion. The complex has abroad application prospect in the areas of magnetism, fluorescence, chelate extraction,ion exchange, gas storage, molecular carrier, biologic activity and so on. Importantapplications in magnetism, fluorescence, catalyse activity, biologic activity etc. basedon the complexes for Schiff bases and β-diketonates. We conduct halogen substituentsalicylaldehyde Schiff base and β-diketonates transition-metal(Cu, Co, Ni, Zn, Mn)complexes microwave solid-state synthesis, structure characterization and propertiesresearch. All research is divided into following four sections.Firstly, a new synthesis method of3,5-diiodo-salicylaldehyde and5-chloro-salicylaldehyde are presented. Salicylaldehyde, KI and KIO3were dissolvedin the mixture solution of ethanol, glacial acetic acid and phosphoric acid, followed bythe addition of water after stirring for2h at50~70℃. Plentiful yellow color prismcrystals were precipitated.Yield:>80%. Salicylaldehyde, KClO3were dissolved in themixture solution of ethanol, glacial acetic and HCl, followed by the addition of waterafter stirring for1h at the room temperature. Plentiful pale yellow color prismcrystals were precipitated. Yield:44%. On this basis,13kinds of halogen substituentsalicylaldehyde Schiff base ligands were designed and synthesized.Secondly, the synthesis methods of2,4-dihydroxyacetophenone are improved. Theresorcinol, glacial acetic acid, anhydrous zinc chloride mixed together. The mixturewas microwave-irradiated(150W) for a few minutes and than precipitated. Yield:68%.A new synthesis method of3,5-dichloro-2,4-dihydroxyacetophenone was established.The2,4-dihydroxyacetophenone, glacial acetic and HCl were dissolved in the mixture solution of ethanol followed by the addition of KClO3aqueous solution after stirringfor1h at50~60℃. Yield:76%. On this basis,4kinds of β-diketonates ligands weredesigned and synthesized. By infrared spectroscopy, elemental analysis and singlecrystal X ray diffraction analysis and other methods to characterize its structure.Thirdly,65kinds of halogen substituent salicylaldehyde Schiff basestransition-metal complexes and20kinds of β-diketonates transition-metal complexeswere synthesized by halogen substituent salicylaldehyde Schiff bases ligands,β-diketonates ligands and5kinds of transition metal salts(Cu, Co, Ni, Zn, Mn) onmicrowave solid state synthesis, respectively. The32kinds of complexes crystals areproduced. Microwave solid state synthesis conditions transition-metal complexeswere explored. By infrared spectroscopy, elemental analysis and single crystal X raydiffraction analysis and other methods to characterize its structure.Finally, Antibacterial activity of transition-metal complexes was tested against3kinds of Gram-positive bacteria and3kinds of Gram-negative bacteria. Therelationships between the structures and the antibacterial activities have been studied.Have the effect of the central ion, coordination environment of complexes andintramolecular hydrogen bond on Gram bacteria inhibition. Inhibition of coppercomplex is the best. Inhibitory effect of nickel and cobalt complex is medium.Inhibitory effect of zinc and manganese complex is the weakest. The inhibitory effectof four-coordinated complex against Gram bacteria is better than six-coordinatedcomplex. The inhibitory effect of quadrilateral coordination environment complexagainst Gram bacteria is better than tetrahedron coordination environment complex.Antibacterial activity of complexes containing intramolecular hydrogen bond againstGram bacteria is better than does not contain hydrogen bonds. Antibacterial activity ofhalogen substituent salicylaldehyde Schiff bases transition-metal complexes againstGram bacteria is better than β-diketonates transition-metal complexes.103figures,78tables,237referneces.
Keywords/Search Tags:complex, microwave solid state synthesis, crystal structure, antibacterialactivity, halogen substituent salicylaldehyde, Schiff base, β-diketonate
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