Facultatea de Chimie şi Tehnologie Chimică / Faculty of Chemistry and Chemical Technology
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Item EFECTUL ANTIBACTERIAN AL UNOR COMPUŞI ORGANICI NOI DIN RÂNDUL SULFANILAMIDELOR(2009) Prisacari, Viorel; Buraciova, Svetlana; Țapcov, Victor; Gulea, AurelianStudiul dat se referă la un grup de substanţe sintetice noi din rândul sulfanilamidelor, care manifestă activitate antibacteriană pronunţată faţă de bacteriile grampozitive şi gramnegative şi, totodată, toxicitate joasă.Item SYNTHESIS, STRUCTURE AND PROPERTIES OF COMPLEX COMPOUNDS OF COBALT, NICKEL, COPPER AND ZINC WITH 2-FORMYLPYRIDINE SEMICARBAZONE(2009) Gulea, Aurelian; Gînju, Dumitru; Bairac, Natalia; Poirier, Donald; Țapcov, Victor2-Formylpyridine semicarbazone L reacts with cobalt, nickel, copper and zinc chlorides, nitrates and perchlorites to form coordination compounds of compositions ML2X2•nH2O (M=Co, Ni, Cu, Zn; X = Cl, NO3, ClO4; L = NC5H 4-CH=N-NH-C(O)-NH2; n = 0, 1) and CuLX2• nH2O (X = Cl, Br, NO3; n = 0-0.5). Complex CuL(NO 3)2 has polynuclear, CuLX2•0.5H 2O (X = Cl, Br), binuclear, and other compounds, mononuclear structures. Azomethine L behaves in them as tridental N,N,O-ligand. Thermolysis of these complexes proceeds through such stages as dehydration (80-95°C), deactivation (145-155°C) and complete theral degradation (170-590°C). Complexes CuLX2•nH2O (X = Cl, NO3; n = 0-0.5) were established to inhibit in vitro the growth and reproduction of 100% of cancer cells of human mieloid leukaemia HL-60 at 10-4 M concentration. At 10-5 M concentration they inhibit only 10% of cells, and at 10-6 M concentration they do not possess anticancer activity.Item SULFANYLAMIDE-CONTAINING COORDINATION COMPOUNDS OF 3d-ELEMENTS WITH 2,4-PENTANEDIONE BIS-THIOSEMICARBAZONE AND BIS-4-PHENYLTHIOSEMICARBAZONE(2008) Gulea, Aurelian; Spînu, S.; Țapcov, Victor; Poirier, DonaldThiosemicarbazide and 4-phenylthiosemicarbazide react in ethanol with 2,4-pentanedione in the presence of manganese, cobalt, nickel, copper, and zinc acetates hydrates and streptamin (Sf1), sulfaethidole (Sf 2), and sulfadimidine (Sf3) to form coordination compounds of the composition M(Sf1-3)(L1-2)·nH2O (M = Mn, Co, Ni, Cu, Zn; H2L1 is 2,4-pentanedione bis-thiosemicarbazone, H2L2 is 2,4-pentanedione bis-4-phenylthiosemicarbazone; n = 0-6). All the complexes synthesized are monomeric. Thiosemicarbazones (H2L1 and H 2L2) behave as twice deprotonated S,N,N,S-tetradentate ligands, while sulfanylamides (Sf1-3) act as monodentate ones. Thermolysis of these substances proceeds through the stages of dehydration (65-95°C) and complete thermal decomposition (430-560°C). It is found that the complex [Cu(Sf2)(L1)]·4H2O in the concentration 10-5 M inhibits the growth and fission of 100% cancer cells of the human myeloid leukemia (HL-60).Item COORDINATION COMPOUNDS OF COBALT, NICKEL, COPPER, AND ZINC WITH 2-BROMO-3-PHENYLPROPENAL BENZOYLHYDRAZONE AND THIOSEMICARBAZONE(2009) Samusi, Nina; Ciumacov, Iurie; Țapcov, Victor; Bocelli, Gabrielle; Simonov, Iurie; Gulea, AurelianBy X-ray structural analysis the crystal structure of 2-bromo-3- phenylpropenal benzoylhydrazone (HL) was determined. The molecule is not flat. In the crystal the HL molecules form infinite chains with reciprocal van der Waals interaction. 2-Bromo-3-phenylpropenal hydrazone (HL) and thiosemicarbazone (HL') react with cobalt, nickel, copper and zinc chlorides, nitrates and acetates to form coordination compounds of the composition Cu(HL)(L)2 [HL = C6H5-CH=CBr-CH=N-NH-C(O)-C6H 5], MX2•2 HL'•nH2O [M = Co, Ni, Cu, Zn; X = Cl, NO3, HL' = C6H5-CH=CBr-CH=N-NH-C(S) -NH2; n = 0-3], MX2•HL•n H2O [M = Ni, Cu; n = 0, 1], and ML'2•nH2O [M = Co, Ni, Zn; n = 0-3]. The same reactions in the presence of amines (A = C5H 5N, 2-CH3C5H4N, 3-CH 3C5H4N, 4-CH3C5H 4N) afford complexes of the composition CuALCl and MALX•n H 2O [M = Cu, Ni; X = Cl, NO3; n = 0-2]. Structure of the coordination node in the amine-containing copper derivatives is polynuclear, in complexes Cu(HL)(L)2 is octahedral, in other compounds it is tetrahedral. The azomethines (HL and HL') in these complexes behave as bidentate N,O and N,S ligands. Thermolysis of the complexes includes a step of dehydration (60-90°C) and complete thermal decomposition (430-590°C).Item COBALT, NICKEL, AND COPPER COORDINATION COMPOUNDS WITH 3-PHENYLPROPENAL BENZOYLHYDRAZONE(2006) Samusi, Nina; Gulea, Aurelian; Țapcov, Victor3-Phenylpropenal benzoylhydrazone (HL) reacts with cobalt, nickel, and copper chlorides, nitrates, and acetates to give coordination compounds MX 2 • nH2O [M = Co, Ni, Cu; X = Cl, NO3, HL = C6H5CH=CHCH=NNHC(O)C6H5; n = 0, 2] and ML2 • nH2O (M = Co, Ni, Cu; n = 1-3). Complexes MALCI (M = Co, Ni, Cu) were obtained by these reactions in the presence of amines (A = C5H5N, 2-CH3C5H 4N, 3-CH3C5H4N, 4-CH 3C5H4N). All the compounds have a monomeric structure. Azomethine (HL) in them behaves as a bidentate N,O-ligand. Thermolysis of the complexes involves the stages of dehydration (70-90°C), deaquation (145-155°C) or deamination (145-185°C), and complete thermal decomposition (330-490°C).Item SULFANILAMIDE-CONTAINING COORDINATION COMPOUNDS OF Cu (II) WITH ISATIN AND N-METHYLISATIN THIOSEMICARBAZONES(2006) Gulea, Aurelian; Spînu, S.; Țapcov, Victor; Poirier, Donald; Roy, JennyIsatin (L1) and N-methylisatin (L2) β-thiosemicarbazones react in ethanol with Cu(II) chloride and bromide in the presence of sulfanilamide (Streptocid, Sf1), N′- acetylsulfanilamide (Sulfacyl, Sf2), Norsulfazole (Sf3), Aethazolum (Sf4), and Sulfadimesine (Sf5) to form coordination compounds Cu(Sf1-5)L1-2X2· nH2O (X = Cl, Br; n = 2-5). All the complexes have a monomeric structure. Thiosemicarbazones L1 and L2 in these complexes are tridentate O,N,S ligands, and sulfanilamides Sf1-5 are monodentate ligands. Thermolysis of the substances involves the steps of dehydration (70-95°C) and complete decomposition (410-530°C).Item COORDINATION COMPOUNDS OF COBALT, NICKEL, COPPER AND ZINC WITH THIOSEMICARBAZONE AND 3-PHENYLPROPENAL SEMICARBAZONE(2006) Samusi, Nina; Gulea, Aurelian; Țapcov, Victor; Ciumacov, Iurie; Roșu, TudorHydrates of 3-phenylpropenal thiosemicarbazone (HL•H2O) and semicarbazone (HL'•H2O) react in methanol with cobalt, nickel, copper, and zinc chlorides, nitrates, and acetates to form coordination compounds MX2•2HL•nSolv [M = Co, Ni, Cu, Zn; X = Cl, NO3; HL = C6H5CH=CH-CH=N-NHC(O)NH2; n = 0-3; Solv = H2O, CH3OH], CuX2•HL• nH2O [M = Ni, Cu; n = 0, 1], ML2•nH2O and ML'•nH2O [M = Co, Ni, Zn; HL' = C6H 5CH=CH-CH=N-NHC(O)NH2; n = 0-3]. In the presence of amines (A = C5H5N, 2-CH3C5H4N, 3-CH3C5H4N, and 4-CH3C 5H4N) these reactions yield the complexes Cu(A)LCl•CH3OH and M(A)LX•nH2O [M = Cu, Ni; X = Cl, NO3; n = 0-2]. The copper complexes with the amine ligands are of polynuclear structure, and other complexes are monomeric. Carbazones (HL and HL') are included in the complexes as bidentate N,S-and N,O-ligands. The thermolysis of the complexes involves the stages of removing solvent crystallization molecules (70-90°C), deaquation (150-170°C), and full thermal decomposition (500-580°C).Item COORDINATION COMPOUNDS OF COPPER(II), NICKEL(II), AND COBALT(II) WITH β-THIOSEMICARBAZONES OF ISATIN AND N-METHYLISATIN(2004) Samusi, Nina; Țapcov, Victor; Gulea, AurelianIsatin thiosemicarbazone (HL) reacts in aquoeus-ethanolic medium with copper(II) chloride and bromide (pH 7-7.5, ethanolic KOH) to give coordination compounds CuLX·nH2O (X = Cl, Br; n = 3, 4). In the presence of amines (A = C5H5N, 3-CH3C5H 4N, and 4-CH3C5H4N), complexes CuALX·2H2O and CuA2LX·H2O (X = Cl, Br) are formed. With nickel(II) or cobalt(II) chlorides, thiosemicarbazone HL, and pyridine (1:1:3) as starting compounds, compounds MPy 2LCl·H2O (M = Ni, Co) are isolated. Under similar conditions, N-methylisatin β-thiosemicarbazone (HL') reacts with chlorides of the above-noted metals in the presence of pyridine to give complexes MPy 2L'Cl·H2O (M = Cu, Ni, Co). All the complexes are monomeric and have a pseudooctahedral structure of the coordination unit. Thiosemicarbazones HL and HL1 in these complexes behave as tridentate monodeprotonated O,N,S-ligands. Thermolysis of these substances passes through the stages of dehydration (60-90°C), deaquation (135-140°C) or deamination (160-215°C), and complete thermal decomposition (560-670°C).Item CRYSTAL STRUCTURE OF COPPER SULFATE AND THIOCYANATE COMPLEXES WITH 5-BROMO-AND 5-NITROSALICYLALDEHYDE THIOSEMICARBAZONES(2008) Ciumacov, Iurie; Jeanneau, Erwann; Bejenari, Natalia; Țapcov, Victor; Gulea, AurelianThe crystal structures of (5-bromosalicylidenethiosemicarbazido) aquacopper(II) sulfato(5-bromosalicylidenethiosemicarbazido)aquacuprate(II) tetrahydrate (I), (5-nitrosalicylidenethiosemicarbazido) dimethylsulfoxide(methanol)copper(II) sulfate (II), and catena(μ-thiocyanato) (5-nitrosalicylidenethiosemicarbazido)copper(II) (III) were determined. In structure I, the independent part of the unit cell contains four water molecules of crystallization and the cation-anion complex [Cu(H2O)(L)] [Cu(H2O)(L)(SO4)] containing two nonequivalent copper complexes (A and B). In these, the metal atom coordinates monodeprotonated 5-bromosalicylaldehyde thiosemicarbazone (HL) and water molecules, and in anion B also a sulfate ion. In complex ions A and B, sulfur, azomethine nitrogen, and phenolic oxygen of the salicylidene thiosemicarbazone fragment, and also water molecule form a distorted planar square around the metal atom. The axial vertex of the pyramid in anion B is occupied by the oxygen atom of the monodentate sulfate anion. In structure II, the independent part of the unit cell contains the (5-nitrosalicylidenethiosemicarbazido)dimethylsulfoxide(methanol)copper(II) complex cation and the sulfate anion. The coordination polyhedron of the central atom is a slightly distorted tetragonal pyramid whose base is formed by sulfur, azomethine nitrogen, phenolic oxygen of thiosemicarbazone, and dimethyl sulfoxide oxygen. The axial position is occupied by the methanol oxygen atom. In structure III, the copper atom coordinates 5-nitrosalicylaldehyde thiosemicarbazone and the thiocyanate ion, which combines complexes into infinite polymer chains along the [010] direction. The copper coordination polyhedron in III is a slightly distorted tetragonal pyramid whose base is formed by sulfur, azomethine nitrogen, phenolic oxygen of thiosemicarbazone, and nitrogen of thiocyanate ion, the axial vertex is occupied by sulfur of thiocyanate ion of the neighboring complex.Item HETEROMETALLIC COMPOUNDS WITH THE BINUCLEAR COMPLEX ANION [CR2 (OH)(AC)(NTA)2 ]2– : SYNTHESIS AND STRUCTURE(2009) Ciornea, Victor; Șova, Sergiu; Novițchi, Ghenadie; Ganju, Dumitru; Cajeva, Olga; Gulea, Aurelian; Simonov, IurieHeterometallic compounds BaCr2(OH)(Ac)(Nta)2 • 4H2O (I) and [Fe(L)3][Cr2(OH)(Ac)(Nta) 2] • nH2O (L is Bipy (II) and Phen (III); Bipy is, αα′-bipyridine, Phen is o,o′-phenanthroline, Ac - is acetate ion, Nta is nitrilotriacetate ion; n = 8 (II) and 6.25 (III)) are synthesized. According to the X-ray diffraction data, compounds II and III have ionic structures built of the isolated complex cations [Fe(L) 3]2+, binuclear complex anions [Cr2(OH)(Ac) (Nta)2]2-, and crystallization water molecules. The magnetic properties of compounds II and III in the interval from 2 to 300 K confirm assumptions on the diamagnetic character of [Fe(L)3] 2+ and indicate the antiferromagnetic interaction between the chromium atoms in the dimeric fragment [Cr2(OH)(Ac)(Nta) 2]2-.