Studies On The Metal Complexes With Amino Acids Modified By Bioactivity Groups

The amino acids are the basic structural units of biomacromolecules such as protein, enzyme. Introducing the bioactivity group to the amino acid molecular and studying the influence of bioactivity group to the properties of the metal complexes of amino acids will be of great important in further developing utilization of amino acids and understanding the biological effect of amino acids. In this thesis, the studies of the metal complexes of modified amino acids have been reviewed in detail. The synthetic conditions of ferrocenylformylation amino acid have been explored and a new compound has been synthesized. The compound was characterized by elemetal analysis, IR and 1H NMR. Eight new binary, ternary and tetranary metal complexes of amino acids modified by bioactivity groups have been synthesized. The structures of the complexes were studied by single crystal X-ray diffraction method. These complexes were characterized by IR and elemetal analysis. The antibacterial activity of some complexes was tested. By these ways, the structure features of the synthesized complexes have been studied systematically. Main work is listed as follows: 1. Using ferrocenecarboxylic acid and glycine, we synthesized a new compound (N-ferrocenylformylglycine). The compound was characterized by IR, elemetal analysis, 1H NMR and was proved by the crystal structures of complexes (1) (3). 2. Using N-ferrocenylformylglycine and 2,2′-bipyridine as ligands, we synthesized a one-dimensional chain coordination polymer [Cd(FcCOGly)₂(2,2′-Bipy)(H₂O)]_n·0.25nH₂O (1), (FcCOGly = N-ferrocenylformylglycinate, 2,2′-Biby = 2,2′-bipyridine). It crystallizes in monoclinic space group P2(1)/c with cell parameters a = 19.2337(14) A, b = 20.1215(14) A, c = 8.9404(6) A, α= 90°, β= 98.4030(10)°, γ= 90o, V = 3422.9(4) A³, Z = 4. In the complex (1), the carboxylates of the ligands show two kinds of coordination modes, that is monodentate and bidentate bridging. Every two adjacent cadmium ions are linked by bidentate bridging carboxylate groups to form an infinite chain. 3. Using N-ferrocenylformylglycine, ferrocenecarboxylic acid and 1,10-phenanth-roline as ligands, we synthesized two rare tetranary complexes [Pb2(FcCOO)2(FcCOGly)2 (phen)2]·6H2O (2) and [Cd2(FcCOO)2(FcCOGly)2(phen)2]·2H2O (3) (FcCOO = ferrocene-carboxylato, FcCOGly = N-ferrocenylformylglycinate, phen = 1,10-phenanthroline). They both belong to triclinic system with space group PÄ«. The cell parameters are: (2): a = 11.597(11) A, b = 13.098(13) A, c = 13.171(12 ) A, α= 108.755(15)°, β= 91.749(16)°, γ= 114.270(15)°, V = 1696(3) A³, Z = 2; (3): a = 10.664(4) A, b = 12.771(4) A, c = 13.734(5) ?, α= 67.094(5)°, β= 68.272(6)°, γ= 88.832(6)°, V = 1583.7(9) ?3, Z = 2. In the complex (2), the coordination number of Pb( â…¡) is six and N-ferrocenylformylglycinate acts as a bidentate bridging ligand by carboxylate oxygens. In the complex (3), the coordination number of Cd( â…¡) is seven and N-ferrocenylformylglycinate acts as a tridentate bridging ligand by carboxylate oxygens. 4. Using N-(2-hydroxybenzyl)-DL-alanine and 4,4′-bipyridine as ligands, we synthesized a binuclear complex [Cu2(sala)2(H2O)2(4,4′-bpy)]·3H2O (4) (sala = N-(2-hydroxybenzyl)-DL-alaninate, 4,4′-bpy = 4,4′-bipyridine). It crystallizes in monoclinic space group C2/c with cell parameters a = 42.44(3) ?, b = 10.416(8) ?, c = 15.487(13) ?, α= 90°, β= 97.455(14)°, γ= 90°, V = 6789(9) ?3, Z = 8. The center Cu( â…¡) were linked by 4,4′-bipyridine to form the binuclear structure. 5. Using N-(2-hydroxybenzyl)-L-glutamic acid as ligand, we synthesized a one-dimensional chain coordination polymer [Cu(Hsglu)(H2O)]n·nH2O (Hsglu = N-(2-hydroxybenzyl)-L-glutamate). It crystallizes in monoclinic space group P2(1) with cell parameters a = 5.858(7) ?, b = 10.005(11) ?, c = 11.764(14) ?, α= 90o, β= 94.507(17)°, γ= 90o, V = 687.3(14) ?3, Z = 2. In the complex (5), Every two adjacent Cu(â…¡) are linked by bridging ligand to form an infinite chain. Experiments show that the complex exhibits antibacterial activity against S. aureus, P. aeruginosa, B. subtilis. 6. Using N-(2-hydroxybenzyl)-DL-α-phenylalanine, 2,2′-bipyridine or 1,10-phenanth-roline as ligands, we synthesized three ternary complexes [Cu(Hsphe)(phen)](ClO4)·3H2O (6), [Cu(Hsphe)(2,2′-biby)](ClO4) (7), [Cu(Hsphe)(2,2′-biby)](NO3) (8) (Hsphe = N-(2-hydroxybenzyl)-DL-α-phenylalaninate). Complex (6) crystallizes in monoclinic space group P2(1)/n with cell parameters: a = 11.910(4) ?, b = 13.816(5) ?, c = 17.963(7) ?, α= 90°, β= 99.751(6)°, γ= 90°, V = 2913.1(18) ?3, Z = 4. Both complex (7) and complex (8) belong to monoclinic system with space group P2(1). The cell parameters are: (7): a = 10.885(3) ?, b = 11.193(3) ?, c = 11.560(3) ?, α= 90°, β= 115.314(5)°, γ= 90°, V = 1273.2(6) ?3, Z = 2; (8): a = 10.784(3) ?, b = 11.271(3) ?, c = 10.876(3) ?, α= 90°, β= 115.062(4)°, γ= 90°, V = 1197.5(6)?3, Z = 2. Complexes (6), (7) and (8) are mononuclear structure, Hsphe acts as a tridentate chelate ligand. Experiments show that complex (6) exhibits antibacterial activity against S. aureus, E. coli, P. aeruginosa, S. typhi and B. subtilis, complex (7) exhibits antibacterial activity against S. aureus, P. aeruginosa and B. subtilis, complex (8) exhibits antibacterial activity against S. aureus, P. aeruginosa, S. typhi and B. subtilis.