| Since its discovery,polyoxometalate(POM)has been widely used in many fields including catalysis,biotechnology,medicine,macromolecular crystallography and molecular magnetism due to its rich structure and unique properties.Organic nitrogen heterocycles have been used as ideal ligand to construct POM based organic inorganic hybrid materials,because of their rich types,diversified coordination modes,and excellent coordination ability.Furthermore,nitrogen heterocycles are common in nature,and they are key motifs in a variety of natural products and biologically active compounds.In this thesis,nitrogen heterocyclic ligands in electron deficient are combined with polyoxometalate in electron rich to synthesize organic-inorganic hybrid materials,and it is expected that nitrogen heterocyclic ligands can affect the electronic behavior of polyoxometalate,resulting in unique functionality.The combination of POM and nitrogen heterocyclic organic ligands can not only construct stable heterogeneous catalyst materials,but also control the properties of POM in biomedicine,laying a foundation for the development of POM-based biomedical materials.We constructed thirteen POM-based organic-inorganic hybrid materials under hydrothermal conditions,characterized their structures,and studied the properties of some compounds.(HL1)2(H3O)(PW12O40)·?10H2O(1)(HL2)3(PW12O40)·3H2O(2){Ag(HL2)2(H2O)}(PMo12O40)(3){Ag6(L2)5(H2O)2}(PMo12O40)2·4H2O(4)(HL2)2(Ag4(L2)4)(PW12O40)2·4H2O(5){Ag2(L2)(HL2)4}(PW12O40)2·3H2O(6)Ag(HL3)2(PMo12O40)·4H2O(7)Ag(HL3)2(PW12O40)(8){Cu2(L2)4}{Cu(L2)(H2O)2(PMo12O40)2}·4H2O(9)[Cu3(L2)3(H2O)2](PW12O40)·2H2O(10)(H3O){Cu6(L3)6Cl4(H2O)2}(PW12O40)·H2O(11)(HL3)(Cu(L3)2)(PMo12O40)·H2O(12){Cu(L2)2(H3O)}(PW12O40)·H2O(13)The performance research part is as follows:(1)Under hydrothermal conditions,synthesize two examples of nitrogen heterocyclic ligand-polyoxometalate adducts(1,2).There are obvious hydrogen bonds and anion-?interactions between the nitrogen heterocyclic ligands and the polyoxometalate anions.These weak forces enhance the stability of the compounds.The catalytic performance of the two compounds were evaluated and the results show that the two compounds have good activity in the selective oxidation of aniline to nitrosobenzene.Under the optimal conditions,the conversion rate of aniline reaches 91%,and the selectivity of nitrosobenzene reaches 79%with compound 1 as catalyst;the conversion rate of aniline reaches 88%,and the selectivity of nitrosobenzene reaches 69%with compound 2 as catalyst.(2)By changing the nitrogen heterocyclic ligands(2-(1H-1,2,4-triazol-3-yl)pyridine and 2-(1H-pyrazol-3-yl)pyridine),reaction time,reaction temperature and molar ratio of reactants,a series of silver-containing POM-based organic-inorganic hybrid materials(3-8)were obtained.The disc diffusion test for these compounds were observed with B.pumilus(B.pumilus),Bacillus subtilis(B.subtilis),Staphylococcus aureus(S.aureus),Escherichia coli(E.coli)and Candida albicans(C.albicans)as probe strains,and the antibacterial activities of compounds 3,4,and 5 were studied.The results showed that the inhibitory radius of compound 3 against B.pumilus was 10.7 mm;the inhibitory radius against B.subtilis was 9.30 mm;the inhibitory radius against S.aureus was 10.7 mm;the inhibitory radius against E.coli was 11.0 mm;the inhibitory radius of C.albicans is 11.0mm.The inhibitory radius of compound 4 against B.pumilus is 11.3mm;the inhibitory radius against B.subtilis is 8.00 mm;the inhibitory radius against S.aureus is 5.70 mm;the inhibitory radius against E.coli is 8.70 mm;The inhibitory radius of C.albican is6.70 mm.The inhibitory radius of compound 5 against B.pumilus is 11.3 mm;the inhibitory radius against B.subtilis is 9.30 mm;the inhibitory radius against S.aureus is8.30 mm;the inhibitory radius against E.coli is 10.7 mm;The inhibitory radius of C.albicans is 8.00 mm.(3)By changing the nitrogen heterocyclic ligands(2-(1H-1,2,4-triazol-3-yl)pyridine and 2-(1H-pyrazol-3-yl)pyridine),reaction time,reaction temperature and reactant molar ratio,a series of copper-containing POM-based organic-inorganic hybrid materials(9-13)were obtained,and the antibacterial activity of compounds 10 and 11 were studied.The results showed that for compound 10 the radius of inhibiton bacteriostatic for B pumilus is 5.70 mm;the radius for B.subtilis is 11.7 mm;the radius for S.aureus is 7.00 mm;the radius for E.coli is 10.3 mm;the radius for C.albicans is 8.30 mm.The inhibitory radius of compound 11 against B.pumilus is 12.7 mm;the inhibitory radius against for B.subtilis is 10.0 mm;the inhibitory radius against S.aureus is 7.70 mm;the inhibitory radius against E.coli is 10.7 mm;the inhibitory radius of C.albicans is 12.3 mm. |
PDF Full Text Request