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Sample records for niii enediolate complex

  1. A Trinuclear Ni(II) Enediolate Complex: Synthesis, Characterization, and O2 Reactivity

    PubMed Central

    Arif, Atta M.; Berreau, Lisa M.

    2009-01-01

    Using a new N4-donor chelate ligand having a mixture of hydrophobic phenyl and hydrogen bond donor appendages, a trinuclear Ni(II) complex of the doubly deprotonated form of 2-hydroxy-1,3-diphenylpropane-1,3-dione was isolated, characterized (X-ray crystallography, elemental analysis, UV-vis, 1H NMR, FTIR, magnetic moment measurement), and evaluated for O2 reactivity. This complex, [(6-NA-6-Ph2TPANi)2(μ-PhC(O)C(O)C(O)Ph)2Ni](ClO4)2 (4), has two terminal pseudo octahedral Ni(II) centers supported by the tetradentate chelate ligand, and a central square planar Ni(II) ion ligated by oxygen atoms of two bridging enediolate ligands. In CH3CN, 4 exhibits a deep orange/brown color and λmax = 463 nm (ε = 16,000 M-1cm-1). The room temperature magnetic moment of 4, determined by Evans method, is μeff = 5.3(2) μB. This is consistent with the presence of two non-interacting high-spin Ni(II) centers, a diamagnetic central Ni(II) ion, and an overall quintet ground state. Exposure of a CH3CN solution of 4 to O2 results in the rapid loss of the orange/brown color to give a green solution. The products identified from this reaction are [(κ3-6-NA-6-Ph2TPA)Ni(O2Ph)(H2O)]ClO4 (5), benzil (PhC(O)C(O)Ph), and CO. Identification of 5 was achieved via its independent synthesis and comparison of its 1H NMR and mass spectral features with those of the 6-NA-6-Ph2TPA-containing product generated upon reaction of 4 with O2. The independently prepared sample of 5 was characterized by X-ray crystallography, elemental analysis, UV-vis, mass spectrometry, and FTIR. The O2 reactivity of 4 has relevance to the active site chemistry of Ni(II)-containing acireductone dioxygenase (Ni(II)-ARD). PMID:18959363

  2. Anticandidal activity of cinnamaldehyde, its ligand and Ni(II) complex: effect of increase in ring and side chain.

    PubMed

    Shreaz, Sheikh; Sheikh, Rayees A; Rimple, Bhatia; Hashmi, Athar Adil; Nikhat, Manzoor; Khan, Luqman A

    2010-09-01

    To increase efficacy of cinnamaldehyde as an antimycotic agent, N, N'- Bis (trans-cinnamadehyde) ethylenediimine [C(20)H(20)N(2)] and Ni(II) complex of the type [Ni(C(40)H(40)N(4))Cl(2)] have been synthesized. The ligand [P] and Ni(II) complex have been characterized on the basis of elemental analysis, FTIR, ESI- MS, IR, (1)H NMR, UV-Vis spectroscopic techniques, conductivity and magnetic measurements. MIC of cinnamaldehyde against clinical isolate of Candida albicans and Candida tropicalis was 400 microg/ml and 500 microg/ml, respectively. Synthesized ligand has markedly reduced MIC; 200 microg/ml and 300 microg/ml whereas Ni(II) complex of ligand displayed MIC of 90 microg/ml and 120 microg/ml. Growth and sensitivity of the organisms were effected by ligand & complex at significantly reduced concentration. Plasma membrane ATPase activity and ergosterol content have been investigated as site of action. Result obtained indicates ergosterol biosynthesis pathway as site of action of cinnamaldehyde, synthesized ligand and its Ni(II) complex.

  3. An unexpected Schiff base-type Ni(II) complex: synthesis, crystal structures, fluorescence, electrochemical property and SOD-like activities.

    PubMed

    Chai, Lan-Qin; Zhang, Hong-Song; Huang, Jiao-Jiao; Zhang, Yu-Li

    2015-02-25

    An unexpected Schiff base-type Ni(II) complex, [Ni(L(2))2]⋅CH3OH (HL(2) = 1-(2-{[(E)-3, 5-dibromo-2-hydroxybenzylidene]amino}phenyl)ethanone oxime), has been synthesized via complexation of Ni(II) acetate tetrahydrate with HL(1) (2-(3,5-dibromo-2-hydroxyphenyl)-4-methyl-1,2-dihydroquinazoline 3-oxide) originally. HL(1) and its corresponding Ni(II) complex were characterized by IR, (1)H NMR spectra, as well as by elemental analysis, UV-Vis and emission spectroscopy, respectively. Crystal structures of the ligand and complex have been determined by single-crystal X-ray diffraction. Each complex links two other molecules into an infinite 1-D chain via intermolecular hydrogen bonding interactions. Moreover, the electrochemical property of the nickle complex was studied by cyclic voltammetry. In addition, SOD-like activities of HL(1) and Ni(II) complex were also investigated.

  4. Nuclease activity and interaction studies of unsymmetrical binuclear Ni(II) complexes with CT-DNA and BSA.

    PubMed

    Poornima, S; Gunasekaran, K; Kandaswamy, M

    2015-10-07

    New unsymmetrical binuclear nickel(II) complexes [Ni2L(1-5)] (ClO4)2 (1-5) were synthesized by using [NiL] [(3-((9E)-(2-((E)-(3-formyl-2-olato-5-methylbenzylideneamino)methyl) phenylimino)methyl)-3-formyl-5-methyl-2-olato)nickel(II)] with various diamines like 1,2-diaminoethane (L(1)), 1,3-diaminopropane (L(2)), 1,4-diaminobutane (L(3)), 1,2-diaminobenzene (L(4)) and 1,8-diaminonaphthalene (L(5)) and characterized by elemental analysis and spectroscopic methods. The molecular structure of binuclear nickel(II) complex 1 is determined by a single crystal X-ray diffraction method. Cyclic voltammograms of binuclear Ni(II) complexes exhibit two quasi-reversible reduction waves in the cathodic region and two oxidation waves in the anodic region. DNA binding, protein binding and DNA cleavage studies were investigated. The interactions of complexes (1-5) with calf thymus DNA were studied by spectroscopic techniques, including absorption and fluorescence methods. The binding affinities of complexes (1-5) with CT-DNA and nuclease activities are in the following order: 5> 4>3 >2>1 . Binuclear Ni(II) complex 1 cleaved the plasmid DNA by a hydrolytic pathway. The hydrolytic cleavage of DNA by the complexes is supported by evidence from free radical quenching and T4 ligase ligation. Binuclear Ni(II) complexes (1-5) displayed significant protein (bovine serum albumin) interactions. The experimental results showed that the interaction between binuclear Ni(II) complexes and BSA was mainly a static quenching process.

  5. Spectroscopic and mycological studies of Co(II), Ni(II) and Cu(II) complexes with 4-aminoantipyrine derivative

    NASA Astrophysics Data System (ADS)

    Sharma, Amit Kumar; Chandra, Sulekh

    2011-10-01

    Complexes of the type [M(L)X 2], where M = Co(II), Ni(II) and Cu(II), have been synthesized with novel NO-donor Schiff's base ligand, 1,4-diformylpiperazine bis(4-imino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one) which is obtained by the acid catalyzed condensation of 1,4-diformylpiperazine with 4-aminoantipyrine. The elemental analyses, molar conductance measurements, magnetic susceptibility measurements, IR, UV, NMR, mass and EPR studies of the compounds led to the conclusion that the ligand acts as tetradentate chelate. The Schiff's base ligand forms hexacoordinated complexes having octahedral geometry for Ni(II) and tetragonal geometry for Co(II) and Cu(II) complexes. The mycological studies of the compounds were examined against the several opportunistic pathogens, i.e., Alternaria brassicae, Aspergillus niger and Fusarium oxysporum. The Cu(II) complexes were found to have most fungicidal behavior.

  6. Synthesis, spectroscopic, anticancer and antibacterial studies of Ni(II) and Cu(II) complexes with 2-carboxybenzaldehyde thiosemicarbazone

    NASA Astrophysics Data System (ADS)

    Chandra, Sulekh; Vandana

    2014-08-01

    Ni(II) and Cu(II) complexes of 2-carboxybenzaldehyde thiosemicarbazone (L) were synthesized and investigated by their spectral and analytical data. These newly synthesized complexes have a composition of M(L)X(H2O)2 (where M = Ni(II), Cu(II) and X = Cl-, NO3-, CH3COO-) and (L) is the tridentate Schiff base ligand. The ligand and its complexes have been characterized on the basis of analytical, molar conductivity, magnetic susceptibility measurements, FT-IR, ESR, 1H NMR and electronic spectral analysis. All the compounds were non-electrolytic in nature. On the basis of spectral studies an octahedral geometry has been assigned for Ni(II) and a tetragonal geometry for Cu(II) complexes. The ligand and its metal complexes were screened for their anticancer studies against human breast cancer cell lines MCF-7 and calculated minimum inhibitory concentration and also for antibacterial activity using Kirby-Bauer single disk susceptibility test.

  7. Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases; Part 1: alkyl halide alkylations.

    PubMed

    Sorochinsky, Alexander E; Aceña, José Luis; Moriwaki, Hiroki; Sato, Tatsunori; Soloshonok, Vadim A

    2013-10-01

    Alkylations of chiral or achiral Ni(II) complexes of glycine Schiff bases constitute a landmark in the development of practical methodology for asymmetric synthesis of α-amino acids. Straightforward, easy preparation as well as high reactivity of these Ni(II) complexes render them ready available and inexpensive glycine equivalents for preparing a wide variety of α-amino acids, in particular on a relatively large scale. In the case of Ni(II) complexes containing benzylproline moiety as a chiral auxiliary, their alkylation proceeds with high thermodynamically controlled diastereoselectivity. Similar type of Ni(II) complexes derived from alanine can also be used for alkylation providing convenient access to quaternary, α,α-disubstituted α-amino acids. Achiral type of Ni(II) complexes can be prepared from picolinic acid or via recently developed modular approach using simple secondary or primary amines. These Ni(II) complexes can be easily mono/bis-alkylated under homogeneous or phase-transfer catalysis conditions. Origin of diastereo-/enantioselectivity in the alkylations reactions, aspects of practicality, generality and limitations of this methodology is critically discussed.

  8. Phosphate ester hydrolysis and DNA binding capacity of two new dinuclear Ni(II) complexes

    NASA Astrophysics Data System (ADS)

    Wang, Y.; Xiao, W.; Mao, J. W.; Zhou, H.; Pan, Z. Q.

    2013-03-01

    Two new dinuclear Ni(II) complexes, [Ni2L1(OAc)2]ClO4 (1) and [Ni2L2(OAc)2] Br·0.5H2O (2) (where HL is the condensation product of 2,6-diformyl-4-X-phenol (X = CH3, Br) and N1-(2-aminoethyl)-N2-(4-nitrobenzyl)ethane-1,2-diamine), were synthesized and characterized. The coordination polyhedron of each metal ion in the complexes can be approximately described as a distorted octahedron. The Ni-Ni distances in 1 and 2 are 3.306 Å and 3.369 Å, respectively. The phosphate hydrolysis promoted by the complexes was examined using 4-nitrophenyl phosphate disodium salt hexahydrate (pNPP) as the substrate. The catalytic rate constants (kcat) are 1.29 × 10-5 s-1 for 1 and 0.47 × 10-5 s-1 for 2 at 25 °C in physiological pH condition. The binding activities of the complexes toward calf thymus (CT-DNA) were analyzed by spectroscopic and voltammetric methods, and the corresponding binding constants are 7.75 × 105 and 6.51 × 104 M-1 for 1 and 8.59 × 105 and 9.18 × 104 M-1 for 2, respectively. The linear Stern-Volmer quenching constants obtained in the fluorescent spectroscopic study of 1 and 2 are 0.7 × 103 and 1.5 × 103 M-1, respectively.

  9. Surface complexation of heavy metal cations on clay edges: insights from first principles molecular dynamics simulation of Ni(II)

    NASA Astrophysics Data System (ADS)

    Zhang, Chi; Liu, Xiandong; Lu, Xiancai; He, Mengjia; Jan Meijer, Evert; Wang, Rucheng

    2017-04-01

    Aiming at an atomistic mechanism of heavy metal cation complexing on clay surfaces, we carried out systematic first principles molecular dynamics (FPMD) simulations to investigate the structures, free energies and acidity constants of Ni(II) complexes formed on edge surfaces of 2:1 phyllosilicates. Three representative complexes were studied, including monodentate complex on the tbnd SiO site, bidentate complex on the tbnd Al(OH)2 site, and tetradentate complex on the octahedral vacancy where Ni(II) fits well into the lattice. The complexes structures were characterized in detail. Computed free energy values indicate that the tetradentate complex is significantly more stable than the other two. The calculated acidity constants indicate that the tetradentate complex can get deprotonated (pKa = 8.4) at the ambient conditions whereas the other two hardly deprotonate due to extremely high pKa values. By comparing with the 2 Site Protolysis Non Electrostatic Surface Complexation and Cation Exchange (2SPNE SC/CE) model, the vacant site has been assigned to the strong site and the other two to the weak site, respectively. Thus a link has been built between atomistic simulations and macroscopic experiments and it is deduced that this should also apply to other heavy metal cations based on additional simulations of Co(II) and Cu(II) and previous simulations of Fe(II) and Cd(II)). This study forms a physical basis for understanding the transport and fixation of heavy metal elements in many geologic environments.

  10. Syntheses, structural characterization, luminescence and optical studies of Ni(II) and Zn(II) complexes containing salophen ligand

    NASA Astrophysics Data System (ADS)

    More, M. S.; Pawal, S. B.; Lolage, S. R.; Chavan, S. S.

    2017-01-01

    Some Ni(II) (1a-d) and Zn(II) (2a-d) salophen complexes were prepared by the treatment of 5-bromosalicylaldehyde, 5-(trimethylsilylethynyl)salicylaldehyde, 5-(4-nitrophenyl)ethynylsalicylaldehyde or 5-(4-methoxyphenyl)ethynylsalicylaldehyde with nickel acetate or zinc acetate followed by addition of 2,3-diamino-5-bromopyridine. All complexes were characterized by elemental analyses, IR, 1H NMR and mass spectral studies. X-ray powder diffraction of representative complexes 1c and 2b and SEM studies of 1b and 2d are used to elucidate the crystal structure and morphology of the complexes. The electrochemical behavior reveals that the redox responses of Ni(II) complexes shifted to more negative potential in order to increase the π-conjugation in the complexes. Room temperature luminescence is observed for all complexes corresponding to π→π* ILCT transition with some MLCT character in DMF and is finely tuned by the degree of extended π-conjugation and variation of the substituent group with different electronic effects in the complexes. The second harmonic generation (SHG) efficiency of the complexes was screened by Kurtz-powder technique indicating that all complexes possesses promising potential for the application as a useful nonlinear optical material.

  11. Spectral studies on Co(II), Ni(II) and Cu(II) complexes with thiosemicarbazone (L1) and semicarbazone (L2) derived from 2-acetyl furan.

    PubMed

    Chandra, Sulekh; Kumar, Anil

    2007-04-01

    Co(II), Ni(II) and Cu(II) complexes are synthesized with thiosemicarbazone (L1) and semicarbazone (L2) derived from 2-acetyl furan. These complexes are characterized by elemental analysis, molar conductance, magnetic susceptibility measurements, mass, IR, electronic and EPR spectral studies. The molar conductance measurements of the complexes in DMSO correspond to non-electrolytic nature except Ni(L)2(NO3)2, which is 1:2 electrolyte. All the complexes are of high-spin type. On the basis of spectral studies an octahedral geometry may be assigned for Co(II) and Ni(II) complexes except nitrato complexes of Ni(II) which is of tetrahedral geometry, whereas tetragonal geometry for Cu(II) complexes.

  12. Synthesis and characterization of Co(II), Ni(II) and Cu(II) complexes involving hydroxy antipyrine azodyes

    NASA Astrophysics Data System (ADS)

    Gaber, M.; Hassanein, A. M.; Lotfalla, A. A.

    2008-03-01

    The complexes formed between some hydroxy antipyrine azodyes and Co(II), Ni(II) and Cu(II) ions were studied spectrophotometrically in solution. The stoichiometry and stability constants of the metal chelates were determined. The spectrophotometric determination of the titled metal ions and titration using EDTA were reported. The chelating behaviour of the azodyes was confirmed by preparing the solid chelates in which their structures are elucidated using molar conductance, elemental, thermogravimetric (TGA) analyses, IR, ESR and electronic spectra as well as the magnetic measurements. Kinetic parameters are computed from the thermal decomposition data. The electrical properties for the metal complexes are measured from which the activation energies are calculated.

  13. Synthesis, biological and comparative DFT studies on Ni(II) complexes of NO and NOS donor ligands.

    PubMed

    Yousef, T A; El-Gammal, O A; Ahmed, Sara F; Abu El-Reash, G M

    2015-01-25

    Three new NOS donor ligands have been prepared by addition ethanolic suspension of 2-hydrazino-2-oxo-N-phenyl-acetamide to phenyl isocyanate (H2PAPS), phenyl isothiocyanate (H2PAPT) and benzoyl isothiocyanate (H2PABT). The Ni(II) complexes prepared from the chloride salt and characterized by conventional techniques. The isolated complexes were assigned the formulaes, [Ni2(PAPS)(H2O)2](H2O)2, [Ni(H2PAPT)Cl2(H2O)](H2O)2 and [(Ni)2(HPABT)2Cl2(H2O)2], respectively. The IR spectra of complexes shows that H2PAPS behaves as a binegative pentadentate via both CO of hydrazide moiety in keto and enol form, enolized CO of cyanate moiety and the CN (azomethine) groups of enolization. H2PAPT behaves as neutral tridentate via both CO of hydrazide moiety and CN (azomethine) group due to SH formation and finally H2PABT behaves as mononegative tetradentate via CO and enolized CO of hydrazide moiety, CO of benzoyl moiety and C=S groups. The experimental IR spectra of ligands are compared with those obtained theoretically from DFT calculations. Also, the bond lengths, bond angles, HOMO (Highest Occupied Molecular Orbitals), LUMO (Lowest Unoccupied Molecular Orbital) and dipole moments have been calculated. The calculated HOMO-LUMO energy gap reveals that charge transfer occurs within the molecule. The theoretical values of binding energies indicate the higher stability of complexes than of ligands. Also, the kinetic and thermodynamic parameters for the different thermal degradation steps of the complexes were determined by Coats-Redfern and Horowitz-Metzger methods. The antibacterial activities were also tested against B. Subtilis and E. coli bacteria. The free ligands showed a higher antibacterial effect than their Ni(II) complexes. The antitumor activities of the Ligands and their Ni(II) complexes have been evaluated against liver (HePG2) and breast (MCF-7) cancer cells. All ligands were found to display cytotoxicity that are better than that of Fluorouracil (5-FU), while Ni(II

  14. Synthesis, biological and comparative DFT studies on Ni(II) complexes of NO and NOS donor ligands

    NASA Astrophysics Data System (ADS)

    Yousef, T. A.; El-Gammal, O. A.; Ahmed, Sara F.; Abu El-Reash, G. M.

    2015-01-01

    Three new NOS donor ligands have been prepared by addition ethanolic suspension of 2-hydrazino-2-oxo-N-phenyl-acetamide to phenyl isocyanate (H2PAPS), phenyl isothiocyanate (H2PAPT) and benzoyl isothiocyanate (H2PABT). The Ni(II) complexes prepared from the chloride salt and characterized by conventional techniques. The isolated complexes were assigned the formulaes, [Ni2(PAPS)(H2O)2](H2O)2, [Ni(H2PAPT)Cl2(H2O)](H2O)2 and [(Ni)2(HPABT)2Cl2(H2O)2], respectively. The IR spectra of complexes shows that H2PAPS behaves as a binegative pentadentate via both CO of hydrazide moiety in keto and enol form, enolized CO of cyanate moiety and the CN (azomethine) groups of enolization. H2PAPT behaves as neutral tridentate via both CO of hydrazide moiety and CN (azomethine) group due to SH formation and finally H2PABT behaves as mononegative tetradentate via CO and enolized CO of hydrazide moiety, CO of benzoyl moiety and Cdbnd S groups. The experimental IR spectra of ligands are compared with those obtained theoretically from DFT calculations. Also, the bond lengths, bond angles, HOMO (Highest Occupied Molecular Orbitals), LUMO (Lowest Unoccupied Molecular Orbital) and dipole moments have been calculated. The calculated HOMO-LUMO energy gap reveals that charge transfer occurs within the molecule. The theoretical values of binding energies indicate the higher stability of complexes than of ligands. Also, the kinetic and thermodynamic parameters for the different thermal degradation steps of the complexes were determined by Coats-Redfern and Horowitz-Metzger methods. The antibacterial activities were also tested against B. Subtilis and E. coli bacteria. The free ligands showed a higher antibacterial effect than their Ni(II) complexes. The antitumor activities of the Ligands and their Ni(II) complexes have been evaluated against liver (HePG2) and breast (MCF-7) cancer cells. All ligands were found to display cytotoxicity that are better than that of Fluorouracil (5-FU), while Ni(II

  15. Synthesis, Structure, and Reactivity of Co(II) and Ni(II) PCP Pincer Borohydride Complexes

    PubMed Central

    2015-01-01

    The 15e square-planar complexes [Co(PCPMe-iPr)Cl] (2a) and [Co(PCP-tBu)Cl] (2b), respectively, react readily with NaBH4 to afford complexes [Co(PCPMe-iPr)(η2-BH4)] (4a) and [Co(PCP-tBu)(η2-BH4)] (4b) in high yields, as confirmed by IR spectroscopy, X-ray crystallography, and elemental analysis. The borohydride ligand is symmetrically bound to the cobalt center in η2-fashion. These compounds are paramagnetic with effective magnetic moments of 2.0(1) and 2.1(1) μB consistent with a d7 low-spin system corresponding to one unpaired electron. None of these complexes reacted with CO2 to give formate complexes. For structural and reactivity comparisons, we prepared the analogous Ni(II) borohydride complex [Ni(PCPMe-iPr)(η2-BH4)] (5) via two different synthetic routes. One utilizes [Ni(PCPMe-iPr)Cl] (3) and NaBH4, the second one makes use of the hydride complex [Ni(PCPMe-iPr)H] (6) and BH3·THF. In both cases, 5 is obtained in high yields. In contrast to 4a and 4b, the borohydride ligand is asymmetrically bound to the nickel center but still in an η2-mode. [Ni(PCPMe-iPr)(η2-BH4)] (5) loses readily BH3 at elevated temperatures in the presence of NEt3 to form 6. Complexes 5 and 6 are both diamagnetic and were characterized by a combination of 1H, 13C{1H}, and 31P{1H} NMR, IR spectroscopy, and elemental analysis. Additionally, the structure of these compounds was established by X-ray crystallography. Complexes 5 and 6 react with CO2 to give the formate complex [Ni(PCPMe-iPr)(OC(C=O)H] (7). The extrusion of BH3 from [Co(PCPMe-iPr)(η2-BH4)] (4a) and [Ni(PCPMe-iPr)(η2-BH4)] (5) with the aid of NH3 to yield the respective hydride complexes [Co(PCPMe-iPr)H] and [Ni(PCPMe-iPr)H] (6) and BH3NH3 was investigated by DFT calculations showing that formation of the Ni hydride is thermodynamically favorable, whereas the formation of the Co(II) hydride, in agreement with the experiment, is unfavorable. The electronic structures and the bonding of the borohydride ligand in [Co

  16. Spectroscopic evaluation of Co(II), Ni(II) and Cu(II) complexes derived from thiosemicarbazone and semicarbazone.

    PubMed

    Chandra, Sulekh; Kumar, Anil

    2007-12-31

    Co(II), Ni(II) and Cu(II) complexes were synthesized with thiosemicarbazone (L(1)) and semicarbazone (L(2)) derived from 2-acetyl furan. These complexes were characterized by elemental analysis, molar conductance, magnetic moment, mass, IR, electronic and EPR spectral studies. The molar conductance measurement of the complexes in DMSO corresponds to non-electrolytic nature. All the complexes are of high-spin type. On the basis of different spectral studies six coordinated geometry may be assigned for all the complexes except Co(L)(2)(SO(4)) and Cu(L)(2)(SO(4)) [where L=L(1) and L(2)] which are of five coordinated square pyramidal geometry.

  17. DNA interaction with octahedral and square planar Ni(II) complexes of aspartic-acid Schiff-bases

    NASA Astrophysics Data System (ADS)

    Sallam, S. A.; Orabi, A. S.; Abbas, A. M.

    2011-12-01

    Ni(II) complexes of (S,E)-2-(2-OHbenzilydene)aspartic acid; (S,E)-2-(2,3-diOHbenzilydene)aspartic acid-; (S,E)-2-(2,4-diOH-benzilydene)aspartic acid; (S,E)-2-(2,5-diOHbenzilydene)aspartic acid and (S,E)-2-((2-OHnaphthalene-1-yl)methylene)aspartic acid Schiff-bases have been synthesized by template method in ethanol or ammonia media. They were characterized by elemental analyses, conductivity measurements, magnetic moment, UV, IR and 1H nmr spectra as well as thermal analysis (TG, DTG, DTA). The Schiff-bases are dibasic tridentate or tetradentate donors and the complexes have square planar and octahedral structures. The complexes decompose in two or three steps where kinetic and thermodynamic parameters of the decomposition steps were computed. The interactions of the formed complexes with FM-DNA were monitored by UV and fluorescence spectroscopy.

  18. Heterodinuclear Ni(ii) and Cu(ii) Schiff base complexes and their activity in oxygen reduction.

    PubMed

    Realista, Sara; Ramgi, Priscila; Cardoso, Bernardo de P; Melato, Ana I; Viana, Ana S; Calhorda, Maria José; Martinho, Paulo N

    2016-10-07

    New Cu(ii)/Ni(ii) heterodinuclear complexes with salphen-type ligands were synthesised via a stepwise template method. DFT studies were performed to understand their electronic properties, showing localisation of the HOMO on the Ni(ii) fragment, while in the oxidised species the spin density was high at some carbon phenolate atoms. These new complexes were potentiodynamically electropolymerised on glassy carbon and platinum. Atomic force microscopy was used to evaluate the influence of the metal centres on the morphology of the polymers, revealing how the presence of Cu(ii) increased the surface roughness. The oxygen reduction reaction was observed on both glassy carbon and platinum modified electrodes in neutral medium.

  19. Antibacterial Co(II), Cu(II), Ni(II) and Zn(II) Complexes of Thiadiazoles Schiff Bases

    PubMed Central

    Jaffery, Maimoon F.; Supuran, Claudiu T.

    2001-01-01

    Schiff bases were obtained by condensation of 2-amino-l,3,4-thiadiazole with 5-substituted-salicylaldehydes which were further used to obtain complexes of the type [M(L)2]Cl2, where M=Co(II), Cu(II), Ni(II) or Zn(II). The new compounds described here have been characterized by physical, spectral and analytical data, and have been screened for antibacterial activity against several bacterial strains such as Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa. The antibacterial potency of these Schiff bases increased upon chelation/complexation, against the tested bacterial species, opening new aproaches in the fight against antibiotic resistant strains. PMID:18475981

  20. Spectral, IR and magnetic studies of Mn(II), Co(II), Ni(II) and Cu(II) complexes with pyrrole-2-carboxyaldehyde thiosemicarbazone (L).

    PubMed

    Chandra, Sulekh; Kumar, Anil

    2007-11-01

    Mn(II), Co(II), Ni(II) and Cu(II) complexes are synthesized with thiosemicarbazone (L) derived from pyrrole-2-carboxyaldehyde. These complexes are characterized by elemental analysis, molar conductance, magnetic susceptibility measurement, mass, IR, electronic and EPR spectral studies. The molar conductance measurement of the complexes in DMSO indicates that the complexes are non-electrolyte except Co(L)2(NO3)2 and Ni(L)2(NO3)2 complexes which are 1:2 electrolyte. All the complexes are of high-spin type. On the basis of spectral studies an octahedral geometry may be assigned for Mn(II), Co(II) and Ni(II) complexes except Co(L)2(NO3)2 and Ni(L)2(NO3)2 which are of tetrahedral geometry. A tetragonal geometry may be suggested for Cu(II) complexes.

  1. Octahedral Ni(II) complex with new NNO donor Schiff base ligand: Synthesis, structure and Hirshfeld surface

    NASA Astrophysics Data System (ADS)

    Jana, Kalyanmoy; Maity, Tithi; Chandra Debnath, Subhas; Samanta, Bidhan Chandra; Seth, Saikat Kumar

    2017-02-01

    A new mononuclear Schiff base octahedral Ni(II) complex of general formula [NiII(L)2] has been synthesized using a new NNO donor Schiff base ligand (HL = 2-[(piperidin-2-ylmethylimino)-methyl]-phenol). The title complex has been characterized by various physical measurements such as elemental analyses, FT-IR, 1H NMR and UV-Vis spectroscopic techniques. The molecular structure of the title complex was determined by single crystal X-ray diffraction technique. The title complex is a mononuclear bis-ligand complex showing distorted octahedral geometry around nickel (II). X-ray crystallography reveals that the complex exhibits extensive supramolecular interactions in the solid-state. Two types of non-covalent interactions namely, π-π and C-H···π interactions are found to govern final solid-state architecture in the complex. The contribution of each interaction to the formation of the self-assembly has been analyzed through Hirshfeld surface calculation which enables quantitative contributions to the crystal packing in a novel visual manner.

  2. Synthesis and studies on Cu(II), Co(II), Ni(II) complexes of Knoevenagel β-diketone ligands.

    PubMed

    Sumathi, S; Tharmaraj, P; Sheela, C D; Anitha, C

    2012-11-01

    Transition metal complexes of various acetylacetone based ligands of the type ML [where M=Cu(II), Ni(II), Co(II); L=3-(aryl)-pentane-2,4-dione] have been synthesized. The structural features have been derived from their elemental analysis, magnetic susceptibility, molar conductance, IR, UV-Vis, (1)H NMR, Mass and ESR spectral studies. Conductivity measurements reveal that all the complexes are non-electrolytic in nature. Spectroscopic and other analytical data of the complexes suggest octahedral geometry for other metal(II) complexes. The redox behavior of the copper(II) complexes have been studied by cyclic voltammetry. The free ligands and their metal complexes have been screened for their in vitro biological activities against the bacteria Pseudomonas aeruginosa, Escherichia coli and Staphylococcus aureus as well as the fungus Candida albicans by well diffusion method. The zone of inhibition value indicates that the most of the metal(II) complexes are found to possess increased activities compared to those of the free ligands. All synthesized compounds may serve as potential photoactive materials as indicated from their characteristic fluorescence properties. The second harmonic generation (SHG) efficiency of the ligands (L1-L3) was found to be considerable effect than that of urea and KDP (potassium dihydrogen phosphate).

  3. Synthesis and studies on Cu(II), Co(II), Ni(II) complexes of Knoevenagel β-diketone ligands

    NASA Astrophysics Data System (ADS)

    Sumathi, S.; Tharmaraj, P.; Sheela, C. D.; Anitha, C.

    2012-11-01

    Transition metal complexes of various acetylacetone based ligands of the type ML [where M = Cu(II), Ni(II), Co(II); L = 3-(aryl)-pentane-2,4-dione] have been synthesized. The structural features have been derived from their elemental analysis, magnetic susceptibility, molar conductance, IR, UV-Vis, 1H NMR, Mass and ESR spectral studies. Conductivity measurements reveal that all the complexes are non-electrolytic in nature. Spectroscopic and other analytical data of the complexes suggest octahedral geometry for other metal(II) complexes. The redox behavior of the copper(II) complexes have been studied by cyclic voltammetry. The free ligands and their metal complexes have been screened for their in vitro biological activities against the bacteria Pseudomonas aeruginosa, Escherichia coli and Staphylococcus aureus as well as the fungus Candida albicans by well diffusion method. The zone of inhibition value indicates that the most of the metal(II) complexes are found to possess increased activities compared to those of the free ligands. All synthesized compounds may serve as potential photoactive materials as indicated from their characteristic fluorescence properties. The second harmonic generation (SHG) efficiency of the ligands (L1-L3) was found to be considerable effect than that of urea and KDP (potassium dihydrogen phosphate).

  4. Synthesis, structural characterization, thermal and electrochemical studies of Mn(II), Co(II), Ni(II) and Cu(II) complexes containing thiazolylazo ligands

    NASA Astrophysics Data System (ADS)

    Chavan, S. S.; Sawant, V. A.

    2010-02-01

    Some thiazolylazo derivatives and their metal complexes of the type [M(L)(H 2O)Cl]; M = Mn(II), Co(II), Ni(II), Cu(II) and L = 6-(2'-thiazolylazo)-2-mercapto-quinazolin-4-one (HL 1), 6-(4'-phenyl-2'-thiazolylazo)-2-mercapto-quinazolin-4-one (HL 2), 6-(2'-thiazolylazo)-2-mercapto-3-( m-tolyl)-quinazolin-4-one (HL 3) and 6-(4'-phenyl-2'-thiazolylazo)-2-mercapto-3-( m-tolyl)-quinazolin-4-one (HL 4) have been prepared. All the complexes were characterized on the basis of elemental analysis, molar conductance, magnetic moment, IR, UV-vis, ESR, TG-DTA and powder X-ray diffraction studies. IR spectra of these complexes reveal that the complex formation occurred through thiazole nitrogen, azo nitrogen, imino nitrogen and sulfur atom of the ligands. On the basis of electronic spectral data and magnetic susceptibility measurement octahedral geometry has been proposed for the Mn(II), Co(II) and Ni(II) complexes and distorted octahedral geometry for the Cu(II) complexes. Electrochemical behavior of Ni(II) complexes exhibit quasireversible oxidation corresponding to Ni(III)/Ni(II) couple along with ligand reduction. X-ray diffraction study is used to elucidate the crystal structure of the complexes.

  5. The Co(II), Ni(II) and Cu(II) complexes with herbicide 2,4-dichlorophenoxyacetic acid - Synthesis and structural studies

    NASA Astrophysics Data System (ADS)

    Drzewiecka-Antonik, Aleksandra; Ferenc, Wiesława; Wolska, Anna; Klepka, Marcin T.; Cristóvão, Beata; Sarzyński, Jan; Rejmak, Paweł; Osypiuk, Dariusz

    2017-01-01

    The Co(II), Ni(II) and Cu(II) complexes with herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) were synthesized and structurally characterized. The geometry of metal-ligand interaction was refined using XAFS and DFT studies. The Co(2,4-D)2·6H2O and Ni(2,4-D)2·4H2O complexes have octahedral geometry with two carboxylate groups of 2,4-D anions and four water molecules in the coordination sphere. The square planar geometry around metal cations formed by the carboxylate groups from two monodentate ligands and two water molecules, is observed for Cu(2,4-D)2·4H2O complex. In the recrystallized Ni(II) complex dinuclear 'Chinese lantern' structures with bridging carboxylate groups of 2,4-D were observed.

  6. Ni(II) and Zn(II) complexes of 2-((thiophen-2-ylmethylene)amino)benzamide: Synthesis, spectroscopic characterization, thermal, DFT and anticancer activities

    NASA Astrophysics Data System (ADS)

    Tyagi, Prateek; Chandra, Sulekh; Saraswat, B. S.

    2015-01-01

    The paper presents the synthesis of Ni(II) and Zn(II) complexes of general composition M(L)X2 and M(L)2X2 (M = Ni(II), Zn(II), X = Cl-1, OAc-1) with Schiff base obtained through the condensation of 2-aminobenzamide with thiophene-2-carbaldehyde. The characterization of newly formed complexes was done by 1H NMR, UV-VIS, TGA, IR, mass spectrophotometry and molar conductivity studies. The thermal studies suggested that the complexes are more stable as compared to ligand. In DFT studies the geometries of Schiff's base and metal complexes were fully optimized with respect to the energy using the 6-31+g(d,p) basis set. On the basis of the spectral studies a distorted octahedral geometry has been assigned for Ni(II) complexes and tetrahedral geometry for Zn(II) complexes. The effect of these complexes on proliferation of human breast cancer cell line (MCF-7) and human hepatocellular liver carcinoma cell line (HepG2) were studied and compared with those of free ligand.

  7. Synthesis, structure, and magnetic properties of (6-9)-nuclear Ni(II) trimethylacetates and their heterospin complexes with nitroxides.

    PubMed

    Ovcharenko, Victor; Fursova, Elena; Romanenko, Galina; Eremenko, Igor; Tretyakov, Evgeny; Ikorskii, Vladimir

    2006-07-10

    New polynuclear nickel trimethylacetates [Ni6(OH)4(C5H9O2)8(C5H10O2)4] (6), [Ni7(OH)7(C5H9O2)7(C5H10O2)6(H2O)] x 0.5 C6H14 x 0.5 H2O (7), [Ni8(OH)4(H2O)2(C5H9O2)12] (8), and [Ni9(OH)6(C5H9O2)12(C5H10O2)4] x C5H10O2 x 3 H2O (9), where C5H9O2 is trimethylacetate and C5H10O2 is trimethylacetic acid, have been found. Their structures were determined by X-ray crystallography. Because of their high solubility in low-polarity organic solvents, compounds 6-9 reacted with stable organic radicals to form the first heterospin compounds based on polynuclear Ni(II) trimethylacetate and nitronyl nitroxides containing pyrazole (L(1)-L(3)), methyl (L(4)), or imidazole (L(5)) substituent groups, respectively, in side chain [Ni7(OH)5(C5H9O2)9(C5H10O2)2(L(1))2(H2O)] x 0.5 C6H14 x H2O (6+1a), [Ni7(OH)5(C5H9O2)9(C5H10O2)2(L2)2(H2O)] x H2O (6+1b), [Ni7(OH)5(C5H9O2)9(C5H10O2)2(L(3))2(H2O)] x H2O (6+1c), [Ni6(OH)3(C5H9O2)9(C5H10O2)4(L(4))] x 1.5 C6H14 (6''), and [Ni4OH)3(C5H9O2)5(C5H10O2)4(L(5))] x 1.5 C7H8 (4). Their structures were also determined by X-ray crystallography. Although Ni(II) trimethylacetates may have varying nuclearity and can change their nuclearity during recrystallization or interactions with nitroxides, this family of compounds is easy to study because of its topological relationship. For any of these complexes, the polynuclear framework may be derived from the [Ni6] polynuclear fragment {Ni6(mu4-OH)2(mu3-OH)2(mu2-C5H9O2-O,O')6(mu2-C5H9O2-O,O)(mu4-C5H9O2-O,O,O',O')(C5H10O2)4}, which is shaped like an open book. On the basis of this fragment, the structure of 7-nuclear compounds (7 and 6+1a-c) is conveniently represented as the result of symmetric addition of other mononuclear fragments to the four Ni(II) ions lying at the vertexes of the [Ni6] open book. The 9-nuclear complex is formed by the addition of trinuclear fragments to two Ni(II) ions lying on one of the lateral edges of the [Ni6] open book. This wing of the 9-nuclear complex preserves its structure in

  8. Thermodynamic functions of Ni(II) complexes with 5-(2-hydroxyphenyl)-pyrazole derivatives. A potentiometric study

    NASA Astrophysics Data System (ADS)

    Deosarkar, S. D.; Narwade, M. L.; Thakre, V. J.

    2013-10-01

    Proton-ligand dissociation constants of five biologically important pyrazole derivatives, viz. [5-(2-hydroxyphenyl)-3-(pyridin-3-yl)-4-benzoyl]-pyrazol (HPPBP), [5-(2-hydroxyphenyl)-3-(3-nitrophenyl)-4-(3-pyridinoyl)]-pyrazol (HPNPPP), [5-(2-hydroxyphenyl)-3-(3-nitrophenyl)-4-benzoyl]-pyrazol (HPNPBP), [5-(2-hydroxyphenyl)-3-phenyl-4-(3-pyridinoyl)]-pyrazol (HPPPP), and [5-(2-hydroxyphenyl)-3-(3-nitrophenyl)-4-(2-furoyl) pyrazol (HPNPFP) and metal ligand stability constants of their Ni(II) complexes in 70% (v/v) dioxane-water and 0.1 M KNO3 were determined at 298.15, 303.15, and 308.15 K by potentiometric method. Thermodynamic functions, such as, free energy change (Δ G ○), enthalpy change (Δ H ○) and entropy (Δ S ○) change for dissociation and complex formation have been estimated form temperature dependence of proton-ligand and metal-ligand stability constants and interpreted in terms of feasibility of these processes.

  9. Electronic structure aspects of the complete O2 transfer reaction between Ni(II) and Mn(II) complexes with cyclam ligands.

    PubMed

    Zapata-Rivera, Jhon; Caballol, Rosa; Calzado, Carmen J

    2015-01-28

    This work explores the electronic structure aspects involving the complete intermolecular O2 transfer between Ni(ii) and Mn(ii) complexes, both containing N-tetramethylated cyclams (TMC). The energy of the low-lying states of reactants, intermediates and products is established at the CASSCF level and also the DDCI level when possible. The orthogonal valence bond analysis of the wave functions obtained from CASSCF and DDCI calculations indicates the dominant superoxide nature of all the adducts participating in the reaction, and consequently that the whole reaction can be described as the transfer of the superoxide O2(-) between Ni(ii) and Mn(ii) complexes, without any additional change in the electronic structure of the fragments.

  10. Magnetic Anisotropy in Pentacoordinate Ni(II) and Co(II) Complexes: Unraveling Electronic and Geometrical Contributions.

    PubMed

    Cahier, Benjamin; Perfetti, Mauro; Zakhia, Georges; Naoufal, Daoud; El-Khatib, Fatima; Guillot, Régis; Rivière, Eric; Sessoli, Roberta; Barra, Anne-Laure; Guihéry, Nathalie; Mallah, Talal

    2017-03-13

    The magnetic properties of the pentacoordinate [M(II) (Me4 cyclam)N3 ](+) (Me4 cyclam=tetramethylcyclam; N3 =azido; M=Ni, Co) complexes were investigated. Magnetization and EPR studies indicate that they have an easy plane of magnetization with axial anisotropy parameters D close to 22 and greater than 30 cm(-1) for the Ni and Co complexes, respectively. Ab initio calculations reproduced the experimental values of the zero-field splitting parameters and allowed the orientation of the anisotropy tensor axes with respect to the molecular frame to be determined. For M=Ni, the principal anisotropy axis lies along the Ni-Nazido direction perpendicular to the Ni(Me4 cyclam) mean plane, whereas for M=Co it lies in the Co(Me4 cyclam) mean plane and thus perpendicular to the Co-Nazido direction. These orientations match one of the possible solutions experimentally provided by single-crystal cantilever torque magnetometry. To rationalize the geometry and its impact on the orientation of the anisotropy tensor axis, calculations were carried out on model complexes [Ni(II) (NCH)5 ](2+) and [Co(II) (NCH)5 ](2+) by varying the geometry between square pyramidal and trigonal bipyramidal. The geometry of the complexes was found to be the result of a compromise between the electronic configuration of the metal ion and the structure-orienting effect of the Me4 cyclam macrocycle. Moreover, the orientation of the anisotropy axes is mainly dependent on the geometry of the complexes.

  11. Adsorption phenomena of cubane-type tetranuclear Ni(II) complexes with neutral, thioether-functionalized ligands on Au(111)

    NASA Astrophysics Data System (ADS)

    Heß, Volkmar; Matthes, Frank; Bürgler, Daniel E.; Monakhov, Kirill Yu.; Besson, Claire; Kögerler, Paul; Ghisolfi, Alessio; Braunstein, Pierre; Schneider, Claus M.

    2015-11-01

    The controlled and intact deposition of molecules with specific properties onto surfaces is an emergent field impacting a wide range of applications including catalysis, molecular electronics, and quantum information processing. One strategy is to introduce grafting groups functionalized to anchor to a specific surface. While thiols and disulfides have proven to be quite effective in combination with gold surfaces, other S-containing groups have received much less attention. Here, we investigate the surface anchoring and organizing capabilities of novel charge-neutral heterocyclic thioether groups as ligands of polynuclear nickel(II) complexes. We report on the deposition of a cubane-type {Ni4} (= [Ni(μ3-Cl)Cl(HL·S)]4) single-molecule magnet from dichloromethane solution on a Au(111) surface, investigated by scanning tunneling microscopy, X-ray photoelectron spectroscopy, and low-energy electron diffraction, both immediately after deposition and after subsequent post-annealing. The results provide strong evidence for partial decomposition of the coordination complex upon deposition on the Au(111) surface that, however, leaves the magnetic {Ni4Cl4n} (n = 1 or 2) core intact. Only post-annealing above 480 K induces further decomposition and fragmentation of the {Ni4Cl4n} core. The detailed insight into the chemisorption-induced decomposition pathway not only provides guidelines for the deposition of thioether-functionalized Ni(II) complexes on metallic surfaces but also reveals opportunities to use multidentate organic ligands decorated with thioether groups as transporters for highly unstable inorganic structures onto conducting surfaces, where they are stabilized retaining appealing electronic and magnetic properties.

  12. The vibrational spectra of the Ni(II) and Cu(II) complexes with oxamic hydrazide

    NASA Astrophysics Data System (ADS)

    Quaeyhaegens, Frank; Hofmans, Hendrik; Desseyn, H. O.

    The infrared-, Raman- and u.v./vis spectra as well as the thermal analysis ofthe Ni(II)and Cu(II) complexes with oxamic hydrazide (H 2NCOCONHNH 2) are discussed. We assume 2/1 planar complexes and a coordination via the four amide nitrogen atoms as visualised in Fig. 1.

  13. Synthesis, spectroscopic, anticancer, antibacterial and antifungal studies of Ni(II) and Cu(II) complexes with hydrazine carboxamide, 2-[3-methyl-2-thienyl methylene

    NASA Astrophysics Data System (ADS)

    Chandra, Sulekh; Vandana; Kumar, Suresh

    2015-01-01

    Schiff's base ligand(L) hydrazine carboxamide, 2-[3-methyl-2-thienyl methylene] and its metal complexes have been synthesized and characterized by elemental analysis, molar conductance, various spectroscopic techniques such as electronic, IR, 1H NMR, mass, EPR. Molar conductance of complexes in DMF solution corresponds to non-electrolyte. Complexes have general composition [M(L)2X2], where M = Ni(II) and Cu(II), X = Cl-, NO3-, CH3COO- and ½SO42-. On the basis of above spectral studies, an octahedral geometry has been assigned for Ni(II) complexes and tetragonal geometry for Cu(II) complexes except [Cu(L)2SO4] which possesses five coordinated trigonal bipyramidal geometry. These metal complexes were also tested for their anticancer, antibacterial and antifungal activities to assess their inhibition potential. Anticancer activity of ligand and its metal complexes were evaluated using SRB fluorometric assay and Adriamycin (ADR) was applied as positive control. Schiff's base ligand and its metal complexes were screened for their antibacterial and antifungal activity against Escherichia coli, Bacillus cereus and Aspergillus niger, Aspergillus flavus, respectively. Kirby-Bauer single disk susceptibility test was used for antibacterial activity and well diffusion method for antifungal activity of the compounds on the used fungi.

  14. Ni(II) and Zn(II) complexes of 2-((thiophen-2-ylmethylene)amino)benzamide: synthesis, spectroscopic characterization, thermal, DFT and anticancer activities.

    PubMed

    Tyagi, Prateek; Chandra, Sulekh; Saraswat, B S

    2015-01-05

    The paper presents the synthesis of Ni(II) and Zn(II) complexes of general composition M(L)X₂ and M(L)₂X₂ (M=Ni(II), Zn(II), X=Cl(-1), OAc(-1)) with Schiff base obtained through the condensation of 2-aminobenzamide with thiophene-2-carbaldehyde. The characterization of newly formed complexes was done by (1)H NMR, UV-VIS, TGA, IR, mass spectrophotometry and molar conductivity studies. The thermal studies suggested that the complexes are more stable as compared to ligand. In DFT studies the geometries of Schiff's base and metal complexes were fully optimized with respect to the energy using the 6-31+g(d,p) basis set. On the basis of the spectral studies a distorted octahedral geometry has been assigned for Ni(II) complexes and tetrahedral geometry for Zn(II) complexes. The effect of these complexes on proliferation of human breast cancer cell line (MCF-7) and human hepatocellular liver carcinoma cell line (HepG2) were studied and compared with those of free ligand.

  15. Investigation of antitumor potential of Ni(II) complexes with tridentate PNO acylhydrazones of 2-(diphenylphosphino)benzaldehyde and monodentate pseudohalides.

    PubMed

    Čobeljić, Božidar; Milenković, Milica; Pevec, Andrej; Turel, Iztok; Vujčić, Miroslava; Janović, Barbara; Gligorijević, Nevenka; Sladić, Dušan; Radulović, Siniša; Jovanović, Katarina; Anđelković, Katarina

    2016-04-01

    Square-planar azido Ni(II) complex with condensation product of 2-(diphenylphosphino)benzaldehyde and Girard's T reagent was synthesized and its crystal structure was determined. Cytotoxic activity of the azido complex and previously synthesized isothiocyanato, cyanato and chlorido Ni(II) complexes with this ligand was examined on six tumor cell lines (HeLa, A549, K562, MDA-MB-453, MDA-MB-361 and LS-174) and two normal cell line (MRC-5 and BEAS-2B). All the investigated nickel(II) complexes were cytotoxic against all tumor cell lines. The newly synthesized azido complex showed selectivity to HeLa and A549 tumor cell lines compared to the normal cells (for A549 IC50 was similar to that of cisplatin). Azido complex interferes with cell cycle phase distribution of A549 and HeLa cells and possesses nuclease activity towards supercoiled DNA. The observed selectivity of the azido complex for some tumor cell lines can be connected with its strong DNA damaging activity.

  16. Transferability of empirical crystal-field parameters of Ni(II) complexes of different symmetries

    NASA Astrophysics Data System (ADS)

    Beltrán, F. Gómez; Sordo, J. A.; Pueyo, L.

    1982-10-01

    A method of systematic linearization of the crystal-field matrices appropriate for obtaining empirical parameters of transition metal complexes of any symmetry is presented and applied to forty complexes of Ni 2+ of Oh and D4 h symmetries. The method is a generalization of that proposed by L. Pueyo, M. Bermejo, and J. W. Richardson ( J. Solid State Chem.31, 217 (1980)) for complexes of Oh symmetry and incorporates the spin-orbit coupling in a very simple manner. Using this method, classical parameters, such as 10 Dq, and punctual quantities, such as the ligand perturbing charges qi, were obtained for these complexes. The former are transferable within 10% if (a) there are not big changes in the metal-ligand distances and (b) the chemical environments of the ligand atoms are comparable. However, the punctual parameters show variations of 20% or more. Electronic repulsion integrals seem to be nicely transferable by means of addition rules based on the hypothesis of isotropic repulsion in the low-symmetry field. Since one of the fitting parameters is a scaling factor of the Rnl( r) metal function, the process of optimization generates an empirical representation, Rnl( λr), of the locally perturbed metallic state.

  17. Synthesis, characterization and quantum chemical ab initio calculations of new dimeric aminocyclodiphosph(V)azane and its Co(II), Ni(II) and Cu(II) complexes.

    PubMed

    Alaghaz, Abdel-Nasser M A; Al-Sehemi, Abdullah G; El-Gogary, Tarek M

    2012-09-01

    The complexes of type [M(2)LCl(2)] in which M=Co(II), Ni(II) and Cu(II) ions and L are 1,3-o-pyridyl-2,4-dioxo-2',4'-bis(3-benzo[d]thiazol-2-yl-2-iminothiophene) cyclodiphosph(V)azane, were prepared and their structures were characterized by different physical techniques (IR, UV-Vis, (1)H NMR, (31)P NMR, mass, TGA, DTA, XRD, SEM, magnetic moment and electrical conductance measurements). Ab initio calculations at the level of DFT B3LYP/6-31G(d) were utilized to find the optimum geometry of the ligand. Spectral characterization of the ligand was simulated using DT-DFT method. Infrared spectra of the complexes indicate deprotonation and coordination of the imine NH. It also confirms that nitrogen atoms of the pyridine group and thiazole group contribute to the complexation. NBO natural charges were computed and discussed in the light of coordination centers. Electronic spectra and magnetic susceptibility measurements as well as quantum chemical calculations reveal square planar geometry for Cu(II) and Ni(II) complexes and tetrahedral geometry for Co(II) complex. The elemental analyses and mass spectral data have justified the M(2)LCl(2) composition of complexes.

  18. Synthesis, molecular docking and evaluation of antifungal activity of Ni(II), Co(II) and Cu(II) complexes of porphyrin core macromolecular ligand.

    PubMed

    Singh, Urvashi; Malla, Ali Mohammad; Bhat, Imtiyaz Ahmad; Ahmad, Ajaz; Bukhari, Mohd Nadeem; Bhat, Sneha; Anayutullah, Syed; Hashmi, Athar Adil

    2016-04-01

    Porphyrin core dendrimeric ligand (L) was synthesized by Rothemund synthetic route in which p-hydroxy benzaldehyde and pyrrole were fused together. The prepared ligand was complexed with Ni(II), Cu(II) and Co(II) ions, separately. Both the ligand and its complexes were characterized by elemental analysis and spectroscopic studies (FT-IR, UV-Vis, (1)HNMR). Square planar geometries were proposed for Cu(II), Ni(II) and Co(II) ions in cobalt, Nickel and copper complexes, respectively on the basis of UV-Vis spectroscopic data. The ligand and its complex were screened on Candida albicans (ATCC 10231), Aspergillus fumigatus (ATCC 1022), Trichophyton mentagrophytes (ATCC 9533) and Pencillium marneffei by determining MICs and inhibition zones. The activity of the ligand and its complexes was found to be in the order: CuL ˃ CoL ≈ NiL ˃ L. Detection of DNA damage at the level of the individual eukaryotic cell was observed by commet assay. Molecular docking technique was used to understand the ligand-DNA interactions. From docking experiment, we conclude that copper complex interacts more strongly than rest two.

  19. Synthesis, characterization and biological activity of Cu(II), Ni(II) and Zn(II) complexes of biopolymeric Schiff bases of salicylaldehydes and chitosan.

    PubMed

    de Araújo, Eliene Leandro; Barbosa, Hellen Franciane Gonçalves; Dockal, Edward Ralph; Cavalheiro, Éder Tadeu Gomes

    2017-02-01

    Schiff bases have been prepared from biopolymer chitosan and salicylaldehyde, 5-methoxysalicylaldehyde, and 5-nitrosalicylaldehyde. Ligands were synthesized in a 1:1.5mol ratio, and their Cu(II), Ni(II) and Zn(II) complexes in a 1:1mol ratio (ligand:metal). Ligands were characterized by (1)H NMR and FTIR, resulting in degrees of substitution from 43.7 to 78.7%. Complexes were characterized using FTIR, electronic spectra, XPRD. The compounds were confirmed by the presence of an imine bond stretching in the 1630-1640cm(-1) and νMetal-N and νMetal-O at <600cm(-1). Electronic spectra revealed that both Cu(II) and Ni(II) complexes present a square plane geometry. The crystallinity values were investigated by X-ray powder diffraction. Thermal behavior of all compounds was evaluated by TGA/DTG and DTA curves with mass losses related to dehydration and decomposition, with characteristic events for ligand and complexes. Schiff base complexes presented lower thermal stability and crystallinity than the starting chitosan. Residues were the metallic oxides as confirmed by XPRD, whose amounts were used in the calculation of the percentage of complexed metal ions. Surface morphologies were analyzed with SEM-EDAX. Preliminary cytotoxicity tests were performed using MTT assay with HeLa cells. Despite the differences in solubility, the free bases presented relatively low toxicity.

  20. Co(II), Ni(II) and Cu(II) complexes with coumarin-8-yl Schiff-bases: Spectroscopic, in vitro antimicrobial, DNA cleavage and fluorescence studies

    NASA Astrophysics Data System (ADS)

    Patil, Sangamesh A.; Unki, Shrishila N.; Kulkarni, Ajaykumar D.; Naik, Vinod H.; Badami, Prema S.

    2011-09-01

    A new series of Co(II), Ni(II) and Cu(II) complexes of the type ML·2H 2O of Schiff-bases derived from m-substituted thiosemicarbazides and 8-acetyl-7-hydroxy-4-methylcoumarin have been synthesized and characterized by spectroscopic studies. Schiff-bases exhibit thiol-thione tautomerism wherein sulphur plays an important role in the coordination. The coordination possibility of the Schiff-bases towards metal ions have been proposed in the light of elemental analyses, spectral (IR, UV-vis, FAB-mass, ESR and fluorescence), magnetic and thermal studies. The low molar conductance values in DMF indicate that, the metal complexes are non-electrolytes. The cyclic voltammetric studies suggested that, the Cu(II) and Ni(II) complexes are of single electron transfer quasi-reversible nature. The Schiff-bases and its metal complexes have been evaluated for their in vitro antibacterial ( Escherichia coli, Staphilococcus aureus, Bascillus subtilis and Salmonella typhi) and antifungal activities ( Candida albicans, Cladosporium and Aspergillus niger) by MIC method. The Schiff-base I and its metal complexes exhibited DNA cleavage activity on isolated DNA of A. niger.

  1. Co(II), Ni(II) and Cu(II) complexes with coumarin-8-yl Schiff-bases: spectroscopic, in vitro antimicrobial, DNA cleavage and fluorescence studies.

    PubMed

    Patil, Sangamesh A; Unki, Shrishila N; Kulkarni, Ajaykumar D; Naik, Vinod H; Badami, Prema S

    2011-09-01

    A new series of Co(II), Ni(II) and Cu(II) complexes of the type ML·2H2O of Schiff-bases derived from m-substituted thiosemicarbazides and 8-acetyl-7-hydroxy-4-methylcoumarin have been synthesized and characterized by spectroscopic studies. Schiff-bases exhibit thiol-thione tautomerism wherein sulphur plays an important role in the coordination. The coordination possibility of the Schiff-bases towards metal ions have been proposed in the light of elemental analyses, spectral (IR, UV-vis, FAB-mass, ESR and fluorescence), magnetic and thermal studies. The low molar conductance values in DMF indicate that, the metal complexes are non-electrolytes. The cyclic voltammetric studies suggested that, the Cu(II) and Ni(II) complexes are of single electron transfer quasi-reversible nature. The Schiff-bases and its metal complexes have been evaluated for their in vitro antibacterial (Escherichia coli, Staphilococcus aureus, Bascillus subtilis and Salmonella typhi) and antifungal activities (Candida albicans, Cladosporium and Aspergillus niger) by MIC method. The Schiff-base I and its metal complexes exhibited DNA cleavage activity on isolated DNA of A. niger.

  2. Cu(II), Ni(II), and Zn(II) Complexes of Salan-Type Ligand Containing Ester Groups: Synthesis, Characterization, Electrochemical Properties, and In Vitro Biological Activities

    PubMed Central

    Jeslin Kanaga Inba, P.; Annaraj, B.; Thalamuthu, S.; Neelakantan, M. A.

    2013-01-01

    A salen ligand on reduction and N-alkylation affords a novel [N2O2] chelating ligand containing ester groups [L = diethyl-2,2′-(propane-1,3-diylbis((2-hydroxy-3-methoxy benzyl)azanediyl))diacetate]. The purity of the ligand was confirmed by NMR and HPLC chromatograms. Its Cu(II), Ni(II), and Zn(II) complexes were synthesized and characterized by a combination of elemental analysis, IR, NMR, UV-Vis, and mass spectral data, and thermogravimetric analysis (TG/DTA). The magnetic moments, UV-Vis, and EPR spectral studies support square planar geometry around the Cu(II) and Ni(II) ions. A tetrahedral geometry is observed in four-coordinate zinc with bulky N-alkylated salan ligand. The redox properties of the copper complex were examined in DMSO by cyclic voltammetry. The voltammograms show quasireversible process. The interaction of metal complexes with CT DNA was investigated by UV-Vis absorption titration, ethidium bromide displacement assay, cyclic voltammetry methods, and agarose gel electrophoresis. The apparent binding constant values suggest moderate intercalative binding modes between the complexes and DNA. The in vitro antioxidant and antimicrobial potentials of the synthesized compounds were also determined. PMID:23983672

  3. DNA cleavage, antibacterial, antifungal and anthelmintic studies of Co(II), Ni(II) and Cu(II) complexes of coumarin Schiff bases: Synthesis and spectral approach

    NASA Astrophysics Data System (ADS)

    Patil, Sangamesh A.; Prabhakara, Chetan T.; Halasangi, Bhimashankar M.; Toragalmath, Shivakumar S.; Badami, Prema S.

    2015-02-01

    The metal complexes of Co(II), Ni(II) and Cu(II) have been synthesized from 6-formyl-7,8-dihydroxy-4-methylcoumarin with o-toluidine/3-aminobenzotrifluoride. The synthesized Schiff bases and their metal complexes were structurally characterized based on IR, 1H NMR, 13C NMR, UV-visible, ESR, magnetic, thermal, fluorescence, mass and ESI-MS studies. The molar conductance values indicate that complexes are non-electrolytic in nature. Elemental analysis reveals ML2·2H2O [M = Co(II), Ni(II) and Cu(II)] stoichiometry, where 'L' stands for a singly deprotonated ligand. The presence of co-ordinated water molecules were confirmed by thermal studies. The spectroscopic studies suggest the octahedral geometry. Redox behavior of the complexes were confirmed by cyclic voltammetry. All the synthesized compounds were screened for their antibacterial (Escherichia coli, Pseudomonas auregenosa, klebsiella, Proteus, Staphylococcus aureus and salmonella) antifungal (Candida, Aspergillus niger and Rhizopus), anthelmintic (Pheretima posthuma) and DNA cleavage (Calf Thymus DNA) activity.

  4. DNA cleavage, antibacterial, antifungal and anthelmintic studies of Co(II), Ni(II) and Cu(II) complexes of coumarin Schiff bases: synthesis and spectral approach.

    PubMed

    Patil, Sangamesh A; Prabhakara, Chetan T; Halasangi, Bhimashankar M; Toragalmath, Shivakumar S; Badami, Prema S

    2015-02-25

    The metal complexes of Co(II), Ni(II) and Cu(II) have been synthesized from 6-formyl-7,8-dihydroxy-4-methylcoumarin with o-toluidine/3-aminobenzotrifluoride. The synthesized Schiff bases and their metal complexes were structurally characterized based on IR, (1)H NMR, (13)C NMR, UV-visible, ESR, magnetic, thermal, fluorescence, mass and ESI-MS studies. The molar conductance values indicate that complexes are non-electrolytic in nature. Elemental analysis reveals ML2·2H2O [M = Co(II), Ni(II) and Cu(II)] stoichiometry, where 'L' stands for a singly deprotonated ligand. The presence of co-ordinated water molecules were confirmed by thermal studies. The spectroscopic studies suggest the octahedral geometry. Redox behavior of the complexes were confirmed by cyclic voltammetry. All the synthesized compounds were screened for their antibacterial (Escherichia coli, Pseudomonas auregenosa, klebsiella, Proteus, Staphylococcus aureus and salmonella) antifungal (Candida, Aspergillus niger and Rhizopus), anthelmintic (Pheretima posthuma) and DNA cleavage (Calf Thymus DNA) activity.

  5. Synthesis, characterization, in vitro antimicrobial and DNA cleavage studies of Co(II), Ni(II) and Cu(II) complexes with ONOO donor coumarin Schiff bases

    NASA Astrophysics Data System (ADS)

    Patil, Sangamesh A.; Unki, Shrishila N.; Kulkarni, Ajaykumar D.; Naik, Vinod H.; Badami, Prema S.

    2011-01-01

    A series of Co(II), Ni(II) and Cu(II) complexes have been synthesized with Schiff bases derived from 2-hydroxy-1-naphthaldehyde and 2-oxo-2H-chromene-3-carbohydrazide/6-bromo-2-oxo-2H-chromene-3-carbohydrazide. The chelation of the complexes has been proposed in the light of analytical, spectral (IR, UV-Vis, 1H NMR, ESR, FAB-mass and fluorescence), magnetic and thermal studies. The measured molar conductance values indicate that, the complexes are non-electrolytic in nature. The redox behavior of the complexes was investigated with electrochemical method by using cyclic voltammetry. The Schiff bases and their metal complexes have been screened for their in vitro antibacterial ( Escherichia coli, Staphylococcus aureus, Bacillus subtilis and Salmonella typhi) and antifungal activities ( Candida albicans, Cladosporium and Aspergillus niger) by MIC method. The DNA cleavage is studied by agarose gel electrophoresis method.

  6. Synthesis and characterization of transition metal 2,6-pyridinedicarboxylic acid derivatives, interactions of Cu(II) and Ni(II) complexes with DNA in vitro

    NASA Astrophysics Data System (ADS)

    Khan, Sadaf; Nami, Shahab A. A.; Siddiqi, K. S.; Husain, Eram; Naseem, Imrana

    2009-03-01

    Mononuclear complexes M(L)Cl 2 where M = Mn(II), Fe(II), Co(II), Ni(II) and Cu(II) and (L = N,N-diethylpiperazinyl,2,6-pyridinedicarboxylate), have been synthesized and characterized by elemental analysis, FT-IR, 1H NMR spectroscopy, UV-vis, magnetic moment, TGA/DSC, cyclic voltammetry and conductivity measurement data. The spectral data suggests that the dipicolinic acid acts as a bidentate ligand and is coordinated to the metal ion through the carboxylate oxygen. The cyclic voltammogram for Cu(L)Cl 2 complex was found to display two reversible Cu(II)/Cu(I) and Cu(II)/Cu(III) redox couple. The ligand exhibits a two-step thermolytic pattern while the complexes decompose in three stages respectively. An octahedral geometry has been proposed for both the complexes. The investigation of the interaction of the complexes with calf thymus DNA has been performed with absorption spectroscopy and fluorescence quenching experiments, which showed that the complexes are avid binders of calf thymus DNA. Also the interaction of the Cu(II) and Ni(II) complexes with plasmid DNA (pUC 19) was studied using agarose gel electrophoresis. The results revealed that these complexes can act as effective DNA cleaving agents resulting in the nicked form of DNA (pUC 19) under physiological conditions. The gel was run both in the absence and presence of an oxidizing agent (H 2O 2). The ligand and its complexes have also been screened against microbes in order to study their antibacterial action. The results revealed that the Cu(II) complex has activity comparable with the reference drugs gentamycin and flucanzole.

  7. Synthesis and characterization of Co(II), Ni(II), Cu(II) and Zn(II) complexes of tridentate Schiff base derived from vanillin and DL-α-aminobutyric acid

    NASA Astrophysics Data System (ADS)

    Nair, M. Sivasankaran; Joseyphus, R. Selwin

    2008-09-01

    Co(II), Ni(II), Cu(II) and Zn(II) complexes of the Schiff base derived from vanillin and DL-α-aminobutyric acid were synthesized and characterized by elemental analysis, IR, electronic spectra, conductance measurements, magnetic measurements, powder XRD and biological activity. The analytical data show the composition of the metal complex to be [ML(H 2O)], where L is the Schiff base ligand. The conductance data indicate that all the complexes are non-electrolytes. IR results demonstrate the tridentate binding of the Schiff base ligand involving azomethine nitrogen, phenolic oxygen and carboxylato oxygen atoms. The IR data also indicate the coordination of a water molecule with the metal ion in the complex. The electronic spectral measurements show that Co(II) and Ni(II) complexes have tetrahedral geometry, while Cu(II) complex has square planar geometry. The powder XRD studies indicate that Co(II) and Cu(II) complexes are amorphous, whereas Ni(II) and Zn(II) complexes are crystalline in nature. Magnetic measurements show that Co(II), Ni(II) and Cu(II) complexes have paramagnetic behaviour. Antibacterial results indicated that the metal complexes are more active than the ligand.

  8. Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases. Part 3: Michael addition reactions and miscellaneous transformations.

    PubMed

    Aceña, José Luis; Sorochinsky, Alexander E; Soloshonok, Vadim

    2014-09-01

    The major goal of this review is a critical discussion of the literature data on asymmetric synthesis of α-amino acids via Michael addition reactions involving Ni(II)-complexes of amino acids. The material covered is divided into two conceptually different groups dealing with applications of: (a) Ni(II)-complexes of glycine as C-nucleophiles and (b) Ni(II)-complexes of dehydroalanine as Michael acceptors. The first group is significantly larger and consequently subdivided into four chapters based on the source of stereocontrolling element. Thus, a chiral auxiliary can be used as a part of nucleophilic glycine Ni(II) complex, Michael acceptor or both, leading to the conditions of matching vs. mismatching stereochemical preferences. The particular focus of the review is made on the practical aspects of the methodology under discussion and mechanistic considerations.

  9. Synthesis, characterization and in vitro antimicrobial studies of Co(II), Ni(II) and Cu(II) complexes derived from macrocyclic compartmental ligand

    NASA Astrophysics Data System (ADS)

    El-Gammal, O. A.; Bekheit, M. M.; El-Brashy, S. A.

    2015-02-01

    New Co(II), Ni(II) and Cu(II) complexes derived from tetradentate macrocyclic nitrogen ligand, (1E,4E,8E,12E)-5,8,13,16-tetramethyl-1,4,9,12-tetrazacyclohexadeca-4,8,12,16-tetraene (EDHDH) have been synthesized. The complexes have been characterized by elemental analysis, spectral (IR, UV-Vis, 1H NMR and ESR (for Cu(II) complex)) mass, and magnetic as well as thermal analysis measurements. The complexes afforded the formulae: [Cu(EDHDH)Cl2]·2EtOH and [M(EDHDH)X2]·nH2O where M = Co(II) and Ni(II), X = Cl- or OH-, n = 1,0, respectively. The data revealed an octahedral arrangement with N4 tetradentate donor sites in addition to two Cl atoms occupying the other two sites. ESR spectrum of Cu2+ complex confirmed the suggested geometry with values of a α2and β2 indicating that the in-plane σ-bonding and in-plane π-bonding are appreciably covalent, and are consistent with very strong σ-in-plane bonding in the complexes. The molecular modeling is drawn and showed the bond length, bond angle, chemical reactivity, energy components (kcal/mol) and binding energy (kcal/mol) for all the title compounds using DFT method. Also, the thermal behavior and the kinetic parameters of degradation were determined using Coats-Redfern and Horowitz-Metzger methods. Moreover, the in vitro antibacterial studies of all compounds screened against pathogenic bacteria (two Gram +ve and two Gram -ve) to assess their inhibiting potential. The assay indicated that the inhibition potential is metal ion dependent. The ligand, EDHDH, Co(II) and Cu(II) complexes exhibited a remarkable antibacterial activity against Streptococcus Pyogenes as Gram +ve and Proteus vulgaris as Gram -ve bacterial strains. On the other hand, Ni(II) complex revealed a moderate antibacterial activity against both Gram +ve organisms and no activity against Gram -ve bacterial strain.

  10. Design, synthesis and characterization of macrocyclic ligand based transition metal complexes of Ni(II), Cu(II) and Co(II) with their antimicrobial and antioxidant evaluation

    NASA Astrophysics Data System (ADS)

    Gull, Parveez; Malik, Manzoor Ahmad; Dar, Ovas Ahmad; Hashmi, Athar Adil

    2017-04-01

    Three new complexes Ni(II), Cu(II) and Co(II) were synthesized of macrocyclic ligand derived from 1, 4-dicarbonyl-phenyl-dihydrazide and O-phthalaldehyde in the ratio of 2:2. The synthesized compounds were characterized by elemental analyses, molar conductance, magnetic susceptibility measurements, FTIR, UV-Vis., Mass and 1H NMR spectral studies. The electronic spectra of the metal complexes indicate a six coordinate octahedral geometry of the central metal ion. These metal complexes and the ligand were evaluated for antimicrobial activity against bacteria (E. coli, B. subtilis, S. aureus) and fungi (A. niger, A. flavus, C. albicans) and compared against standard drugs chloramphenicol and nystatin respectively. In addition, the antioxidant activity of the compounds was also investigated through scavenging effect on DPPH radicals.

  11. Synthesis, characterization, equilibrium study and biological activity of Cu(II), Ni(II) and Co(II) complexes of polydentate Schiff base ligand.

    PubMed

    El-Sherif, Ahmed A; Shehata, Mohamed R; Shoukry, Mohamed M; Barakat, Mohammad H

    2012-10-01

    Schiff base ligand, 1,4-bis[(2-hydroxybenzaldehyde)propyl]piperazine (BHPP), and its Cu(II), Ni(II) and Co(II) metal complexes were synthesized and characterized by elemental analysis, magnetic susceptibility, molar conductance and spectral (IR and UV-vis) studies. The ground state of BHPP ligand was investigated using the BUILDER module of MOE. Metal complexes are formed in the 1:1 (M:L) ratio as found from the elemental analysis and found to have the general formula [ML]·nH(2)O, where M=Co(II), Ni(II) and Cu(II), L=BHPP. In all the studied complexes, the (BHPP) ligand behaves as a hexadentate divalent anion with coordination involving the two azomethine nitrogen's, the two nitrogen atoms of piperazine ring and the two deprotonated phenolic OH-groups. The magnetic and spectral data indicates octahedral geometry of metal(II) complexes. The ligand and their metal chelates have been screened for their antimicrobial activities using the disc diffusion method against the selected bacteria and fungi. They were found to be more active against Gram-positive than Gram-negative bacteria. Protonation constants of (BHPP) ligand and stability constants of its Cu(2+), Co(2+) and Ni(2+) complexes were determined by potentiometric titration method in 50% DMSO-water solution at ionic strength of 0.1 M sodium nitrate. It has been observed that the protonated Schiff base ligand (BHPP) have four protonation constants. The divalent metal ions Cu(2+), Ni(2+) and Co(2+) form 1:1 complexes.

  12. Comparative DNA binding abilities and phosphatase-like activities of mono-, di-, and trinuclear Ni(II) complexes: the influence of ligand denticity, metal-metal distance, and coordinating solvent/anion on kinetics studies.

    PubMed

    Bhardwaj, Vimal K; Singh, Ajnesh

    2014-10-06

    Six novel Ni(II) complexes, namely, [Ni2(HL(1))(OAc)2] (1), [Ni3L(1)2]·H2O·2CH3CN (2), [Ni2(L(2))(L(3))(CH3CN)] (3), [Ni2(L(2))2(H2O)2] (4), [Ni2(L(2))2(DMF)2]2·2H2O (5), and [Ni(HL(2))2]·H2O (6), were synthesized by reacting nitrophenol-based tripodal (H3L(1)) and dipodal (H2L(2)) Schiff base ligands with Ni(II) metal salts at ambient conditions. All the complexes were fully characterized with different spectroscopic techniques such as elemental analyses, IR, UV-vis spectroscopy, and electrospray ionization mass spectrometry. The solid-state structures of 2, 3, 5, and 6 were determined using single-crystal X-ray crystallography. The compounds 1, 3, 4, and 5 are dinuclear complexes where the two Ni(II) centers have octahedral geometry with bridging phenoxo groups. Compound 2 is a trinuclear complex with two different types of Ni(II) centers. In compound 3 one of the Ni(II) centers has a coordinated acetonitrile molecule, whereas in compound 4, a water molecule has occupied one coordination site of each Ni(II) center. In complex 5, the coordinated water of complex 4 was displaced by the dimethylformamide (DMF) during its crystallization. Complex 6 is mononuclear with two amine-bis(phenolate) ligands in scissorlike fashion around the Ni(II) metal center. The single crystals of 1 and 4 could not be obtained; however, from the spectroscopic data and physicochemical properties (electronic and redox properties) it was assumed that the structures of these complexes are quite similar to other analogues. DNA binding abilities and phosphatase-like activities of all characterized complexes were also investigated. The ligand denticity, coordinated anions/solvents (such as acetate, acetonitrile, water, and DMF), and cooperative action of two metal centers play a significant role in the phosphate ester bond cleavage of 2-hydroxypropyl-p-nitropenylphosphate by transesterification mechanism. Complex 3 exhibits highest activity among complexes 1-6 with 3.86 × 10(5) times

  13. Conformational change of a chiral Schiff base Ni(II) complex with a binaphthyl moiety: application of vibrational circular dichroism spectroscopy.

    PubMed

    Sato, Hisako; Mori, Yukie; Yamagishi, Akihiko

    2013-05-21

    Vibrational circular dichroism (VCD) spectroscopy was applied to study the structural change of a Ni(II) complex (denoted by [Ni(II)L]) with a chiral Schiff base ligand, (R)- or (S)-2,2'-bis(salicylideneamino)-1,1'-binaphthyl (denoted by H2L), in solution. The major signals in the mid-IR region were assigned on the basis of comparison with the DFT-calculated spectra. The complex transformed reversibly between the square-planar, tetrahedral and octahedral configurations, depending on solvents and temperature. The observed changes in the VCD peaks accompanying the transformation were analyzed in terms of the conformational change of the chiral ligand with a focus on the twisting angle in the Schiff base backbone and the dihedral angle of the binaphthyl group.

  14. Five coordinate M(II)-diphenolate [M = Zn(II), Ni(II), and Cu(II)] Schiff base complexes exhibiting metal- and ligand-based redox chemistry.

    PubMed

    Franks, Mark; Gadzhieva, Anastasia; Ghandhi, Laura; Murrell, David; Blake, Alexander J; Davies, E Stephen; Lewis, William; Moro, Fabrizio; McMaster, Jonathan; Schröder, Martin

    2013-01-18

    Five-coordinate Zn(II), Ni(II), and Cu(II) complexes containing pentadentate N(3)O(2) Schiff base ligands [1A](2-) and [1B](2-) have been synthesized and characterized. X-ray crystallographic studies reveal five coordinate structures in which each metal ion is bound by two imine N-donors, two phenolate O-donors, and a single amine N-donor. Electron paramagnetic resonance (EPR) spectroscopic studies suggest that the N(3)O(2) coordination spheres of [Cu(1A)] and [Cu(1B)] are retained in CH(2)Cl(2) solution and solid-state superconducting quantum interference device (SQUID) magnetometric studies confirm that [Ni(1A)] and [Ni(1B)] adopt high spin (S = 1) configurations. Each complex exhibits two reversible oxidation processes between +0.05 and +0.64 V vs [Fc](+)/[Fc]. The products of one- and two-electron oxidations have been studied by UV/vis spectroelectrochemistry and by EPR spectroscopy which confirm that each oxidation process for the Zn(II) and Cu(II) complexes is ligand-based with sequential formation of mono- and bis-phenoxyl radical species. In contrast, the one-electron oxidation of the Ni(II) complexes generates Ni(III) products. This assignment is supported by spectroelectrochemical and EPR spectroscopic studies, density functional theory (DFT) calculations, and the single crystal X-ray structure of [Ni(1A)][BF(4)] which contains Ni in a five-coordinate distorted trigonal bipyramidal geometry.

  15. Complexation of nitrogen and sulphur donor Schiff's base ligand to Cr(III) and Ni(II) metal ions: Synthesis, spectroscopic and antipathogenic studies

    NASA Astrophysics Data System (ADS)

    Sharma, Amit Kumar; Chandra, Sulekh

    2011-01-01

    2,6-Diacetyl pyridine based ligand was synthesized by the reaction of 2,6-diacetyl pyridine with thiocarbohydrazide in presence of acetic acid. The coordination compounds with Cr(III) and Ni(II) metal ions having [Cr(L)X]X 2 and [Ni(L)X]X compositions (where L = ligand and X = NO 3-, Cl - and CH 3COO -) were synthesized and characterized by physicochemical and spectral studies. The studies like elemental analyses, molar conductance measurements, magnetic susceptibility measurements, IR, UV-Vis, NMR, mass and EPR reveal that the complexes are octahedral. The compounds were examined against the pathogenic fungal and bacterial strains like Alternaria brassicae, Aspergillus niger, Fusarium oxysporum, Xanthomonas compestris and Pseudomonas aeruginosa. A. niger causes the diseases Apergillosis and Otomycosis in humans.

  16. Synthesis, structural characterization and DFT calculation on a square-planar Ni(II) complex of a compartmental Schiff base ligand

    NASA Astrophysics Data System (ADS)

    Biswas, Surajit; Dolai, Malay; Dutta, Arpan; Ali, Mahammad

    2016-12-01

    Reaction of a symmetric compartmental Schiff-base ligand, (H2L) with nickel(II) perchlorate hexahydrate in 1:1 M ratio in methanol gives rise to a mononuclear nickel(II) compound, NiL (1). The compound has been characterized by C, H, N microanalyses and UV-Vis spectra. The single crystal X-ray diffraction studies reveal a square planar geometry around the Ni(II) center. The compound crystallizes in monoclinic system with space group C2/c with a = 21.6425(6), b = 9.9481(3), c = 13.1958(4) Å, β = 107.728(2)°, V = 2706.16(14) Å3 and Z = 4. Ground state DFT optimization and TDDFT calculations on the ligand and complex were performed to get their UV-Vis spectral pattern.

  17. Polymeric Cd(II), trinuclear and mononuclear Ni(II) complexes of 5-methyl-4-phenyl-1,2,4-triazole-3-thione: Synthesis, structural characterization, thermal behaviour, fluorescence properties and antibacterial activity

    NASA Astrophysics Data System (ADS)

    Bharty, M. K.; Paswan, S.; Dani, R. K.; Singh, N. K.; Sharma, V. K.; Kharwar, R. N.; Butcher, R. J.

    2017-02-01

    Syntheses of a polymeric Cd(II) complex, [Cd(mptt)2]n (1), a trinuclear Ni(II) complex, [Ni3(μ-mptt)4(μ-H2O)2(H2O)2(ttfa)2]·3H2O (2) and a mononuclear Ni(II) complex [Ni(mptt)2(en)2] (3) have been performed using the ligand 5-methyl-4-phenyl-1,2,4-triazole-3-thione (Hmptt) and nickel(II)/cadmium(II) salts {ttfa = thenoyltrifluroacetonate). The ligand and the complexes have been characterized by various physicochemical methods in addition to their single crystal X-ray structure. The Cd centre in complex 1 adopts a distorted tetrahedral geometry with one sulfur atom and two mptt ligands provide three nitrogen atoms from three triazole units. The sulfur atom of the ligand binds covalently and overall the ligand acts as uninigative N,S/N,N bidentate moiety. The polymeric structure of complex 1 results from the N atoms of the neighboring triazole units coordinating with the Cd(II) centre. The three Ni(II) centres in the trinuclear Ni(II) complex 2 form a linear arrangement and all have six coordinated arrangements. The middle Ni(II) binds with four deprotonated triazole ring nitrogens and two water molecules form two bridges. The terminal Ni(II) centres bind through two thenoyl oxygens, two triazole nitrogens and water molecules that formed bridges with the middle Ni centre. In complex 3, the nickel(II) centre is covalently bonded through two deprotonated triazole ring nitrogens from two ligand moieties and other four sites are occupied by four nitrogens from two bidentate en ligands. Thermogravimetric analyses (TGA) of the complexes indicated for NiO as the final residue. The bioefficacy of the ligand and complexes 2 and 3 have been examined against the growth of bacteria to evaluate their anti-microbial potential. Complex 2 showed high antibacterial activity as compared to the ligand and complex 3. Complexes 1, 2 and 3 are fluorescent materials with maximum emissions at 425, 421 and 396 nm at an excitation wavelength of 323, 348 and 322 nm, respectively.

  18. Synthesis, characterization, DFT calculation and biological activity of square-planar Ni(II) complexes with tridentate PNO ligands and monodentate pseudohalides. Part II.

    PubMed

    Milenković, Milica; Pevec, Andrej; Turel, Iztok; Vujčić, Miroslava; Milenković, Marina; Jovanović, Katarina; Gligorijević, Nevenka; Radulović, Siniša; Swart, Marcel; Gruden-Pavlović, Maja; Adaila, Kawther; Cobeljić, Božidar; Anđelković, Katarina

    2014-11-24

    Three square-planar complexes of Ni(II) with condensation derivative of 2-(diphenylphosphino)benzaldehyde and 4-phenylsemicarbazide and monodentate pseudohalides have been synthesized and characterized on the basis of the results of X-ray, NMR and IR spectroscopy and elemental analysis. Investigated complexes exhibited moderate antibacterial and cytotoxic activity. The most pronounced cytotoxic activity (in the range of cisplatin) to HeLa cell line was observed for ligand and all the complexes. Azido complex and ligand induced concentration dependent cell cycle arrest in the S phase, as well as decrease of percentage of cells in G1 phase, without significant increase of apoptotic fraction of cells. The interaction of the azido complex and ligand with CT-DNA results in changes in UV-Vis spectra typical for non-covalent bonding. The observed intrinsic binding constant of azido complex-CT-DNA and ligand-CT-DNA were 3.22 × 10(5) M(-1) and 2.79 × 10(5) M(-1). The results of DNA cleavage experiments showed that azido complex nicked supercoiled plasmid DNA.

  19. Electrochemical studies of DNA interaction and antimicrobial activities of MnII, FeIII, CoII and NiII Schiff base tetraazamacrocyclic complexes

    NASA Astrophysics Data System (ADS)

    Kumar, Anuj; Vashistha, Vinod Kumar; Tevatia, Prashant; Singh, Randhir

    2017-04-01

    Tetraazamacrocyclic complexes of MnII, FeIII, CoII and NiII have been synthesized by template method. These tetraazamacrocycles have been analyzed with various techniques like molar conductance, IR, UV-vis, mass spectral and cyclic voltammetric studies. On the basis of all these studies, octahedral geometry has been assigned to these tetraazamacrocyclic complexes. The DNA binding properties of these macrocyclic complexes have been investigated by electronic absorption spectra, fluorescence spectra, cyclic voltammetric and differential pulse voltammetric studies. The cyclic voltammetric data showed that ipc and ipa were effectively decreased in the presence of calf thymus DNA, which is a strong evidence for the interaction of these macrocyclic complexes with the calf thymus DNA (ct-DNA). The heterogeneous electron transfer rate constant found in the order: KCoII > KNiII > KMnII which indicates that CoII macrocyclic complex has formed a strong intercalated intermediate. The Stern-Volmer quenching constant (KSV) and voltammetric binding constant were found in the order KSV(CoII) > KSV(NiII) > KSV(MnII) and K+(CoII) > K+(NiII) > K+(MnII) which shows that CoII macrocyclic complex exhibits the high interaction affinity towards ct-DNA by the intercalation binding. Biological studies of the macrocyclic complexes compared with the standard drug like Gentamycin, have shown antibacterial activities against E. coli, P. aeruginosa, B. cereus, S. aureus and antifungal activity against C. albicans.

  20. Interplay of bifurcated hydrogen bonds in making of inclusion/pseudo-inclusion complexes of Ni(II), Cu(II) and Zn(II) of a salophen type ligand: Crystal structures and spectral aspects

    NASA Astrophysics Data System (ADS)

    Ambili, K. U.; Sithambaresan, M.; Kurup, M. R. Prathapachandra

    2017-04-01

    Three novel photoluminescent materials were synthesized by treating Ni(II), Cu(II) and Zn(II) acetate salts with a Schiff base prepared from 3-ethoxysalicylaldehyde and 2-aminobenzylamine. Among the prepared complexes, Ni(II) and Cu(II) complexes are inclusion compounds while Zn(II) complex is a pseudo-inclusion compound. They were characterized by elemental analysis, IR, UV-visible and EPR spectra. Single crystal XRD studies of these complexes suggest that Ni(II) and Cu(II) are in a distorted square planar environment while the spatial arrangement of donor atoms in Zn(II) complex is best described as distorted square based pyramid although significant distortion towards trigonal bipyramid is noticed. Stabilized crystal packing of the complexes is established via supramolecular interactions. The metal chelate rings as the π system for C-H···π interactions found in Cu(II) and Zn(II) complexes explicit the concept of metalloaromaticity. TG-DTG studies reveal that all the complexes are thermally stable. Both ligand and complexes exhibit intense photoluminescence in near UV region. However, Zn(II) complex giving an intense blue-green emission spectrum at maximum wavelength of 518 nm with shoulder peaks, could be used for optoelectronic applications.

  1. Synthesis, spectral characterization and thermal studies of Co(II), Ni(II), Cu(II) and Zn(II) complexes with 2-amino benzoic acid- and 2-hydroxy benzoic acid thiophen-2-ylmethylene hydrazide

    NASA Astrophysics Data System (ADS)

    Singh, Vinod P.; Singh, Pooja

    2013-03-01

    A series of metal complexes of Co(II), Ni(II), Cu(II) and Zn(II) with 2-amino benzoic acid thiophen-2-ylmethylene hydrazide (Habth) and 2-hydroxy benzoic acid thiophen-2-ylmethylene hydrazide (Hhbth) have been synthesized. The complexes were characterized by elemental analyses, molar conductance, magnetic susceptibility measurements, electronic, IR, NMR, ESR spectra and thermal studies (TGA and DTA). Molecular structure of the Habth ligand was determined by single crystal X-ray diffraction technique. Habth acts as a monobasic bidentate ligand in all its complexes bonding through a deprotonated Csbnd O- and lbond2 Cdbnd Nsbnd groups whereas, Hhbth acts as a monobasic bidentate in its Co(II) and Ni(II) complexes, bonding through a deprotonated Csbnd O- and lbond2 Cdbnd Nsbnd groups and as monobasic tridentate in Cu(II) and Zn(II) complexes bonding through lbond2 Cdbnd O, lbond2 Cdbnd Nsbnd and deprotonated (Csbnd O)- groups with the metal ion. Electronic spectra suggest a square planar geometry for Co(II), Ni(II) and Cu(II) complexes of Habth and Co(II) and Ni(II) complexes of Hhbth. However, the Cu(II) and Zn(II) complexes of Hhbth have octahedral geometry. The ESR spectra of Cu(II) complex of Hhbth in the solid state and in DMSO frozen solution show axial signals and suggest the presence of unpaired electron in d orbital of Cu(II). The Cu(II) complex of Habth in solid state shows isotropic signal, whereas, axial signal in DMSO frozen solution in the range of tetragonally distorted octahedral geometry due to interactions of DMSO molecules at axial positions. Thermal studies of some of the metal complexes show a multi-step decomposition pattern of bonded ligands in the complex.

  2. DNA cleavage, antimicrobial, spectroscopic and fluorescence studies of Co(II), Ni(II) and Cu(II) complexes with SNO donor coumarin Schiff bases

    NASA Astrophysics Data System (ADS)

    Patil, Sangamesh A.; Naik, Vinod H.; Kulkarni, Ajaykumar D.; Badami, Prema S.

    2010-01-01

    A series of Co(II), Ni(II) and Cu(II) complexes of the type ML 2 have been synthesized with Schiff bases derived from methylthiosemicarbazone and 5-formyl-6-hydroxy coumarin/8-formyl-7-Hydroxy-4-methylcoumarin. The complexes are insoluble in common organic solvents but soluble in DMF and DMSO. The measured molar conductance values in DMF indicate that, the complexes are non-electrolytes in nature. In view of analytical, spectral (IR, UV-vis, ESR, FAB-mass and fluorescence), magnetic and thermal studies, it has been concluded that, all the metal complexes possess octahedral geometry in which ligand is coordinated to metal ion through azomethine nitrogen, thione sulphur and phenolic oxygen atom via deprotonation. The redox behavior of the metal complexes was investigated by using cyclic voltammetry. The Schiff bases and their complexes have been screened for their antibacterial ( Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa and Salmonella typhi) and antifungal activities ( Aspergillus niger, Aspergillus flavus and Cladosporium) by Minimum Inhibitory Concentration method. The DNA cleavage is studied by agarose gel electrophoresis method.

  3. Spectroscopic and fluorescence studies on Mn(II), Co(II), Ni(II) and Cu(II) complexes with NO donor fluorescence dyes

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; El-Metwaly, Nashwa M.

    2011-10-01

    The reactions of the two common dyes [2TMPACT and 4PENI] with Mn(II), Co(II), Ni(II) and Cu(II) ions were done. All the isolated complexes have been characterized by physicochemical and spectroscopic techniques. The IR data reflect the bidentate mode of 2TMPACT towards the mononuclear complex [Mn(II)] even its tetradentate in binuclear complexes [Co(II) and Cu(II)]. However, the bidentate mode is the only behavior of 4PENI ligand towards each metal ion in its mononuclear complexes. The UV-vis spectral analysis beside the magnetic moment measurements are proposed different geometries concerning each metal ions with the two ligands under investigation, as the Mn(II)-2TMPACT complex is an octahedral but Mn(II)-4PENI is a tetrahedral geometry. All the synthesized compounds are thermogravimetrically investigated. The proposed thermal decomposition was discussed for each compound with each step as well as, the kinetic parameters were calculated for all preferrible decomposition steps. The mass spectroscopy tool was used to emphasis on the suitable molecular formula proposed and the fragmentation patterns were displayed. The fluorescence properties of the synthesized ligands and their complexes were studied in DMSO at room temperature.

  4. Spectroscopic and fluorescence studies on Mn(II), Co(II), Ni(II) and Cu(II) complexes with NO donor fluorescence dyes.

    PubMed

    Refat, Moamen S; el-Metwaly, Nashwa M

    2011-10-15

    The reactions of the two common dyes [2TMPACT and 4PENI] with Mn(II), Co(II), Ni(II) and Cu(II) ions were done. All the isolated complexes have been characterized by physicochemical and spectroscopic techniques. The IR data reflect the bidentate mode of 2TMPACT towards the mononuclear complex [Mn(II)] even its tetradentate in binuclear complexes [Co(II) and Cu(II)]. However, the bidentate mode is the only behavior of 4PENI ligand towards each metal ion in its mononuclear complexes. The UV-vis spectral analysis beside the magnetic moment measurements are proposed different geometries concerning each metal ions with the two ligands under investigation, as the Mn(II)-2TMPACT complex is an octahedral but Mn(II)-4PENI is a tetrahedral geometry. All the synthesized compounds are thermogravimetrically investigated. The proposed thermal decomposition was discussed for each compound with each step as well as, the kinetic parameters were calculated for all preferrible decomposition steps. The mass spectroscopy tool was used to emphasis on the suitable molecular formula proposed and the fragmentation patterns were displayed. The fluorescence properties of the synthesized ligands and their complexes were studied in DMSO at room temperature.

  5. Synthesis, physico-chemical investigations of Co(II), Ni(II) and Cu(II) complexes and their in vitro microbial, cytotoxic, DNA cleavage studies.

    PubMed

    Bagihalli, Gangadhar B; Patil, Sangamesh A

    2010-06-01

    A series of metal complexes of cobalt(II), nickel(II), and copper(II) have been synthesized with newly derived biologically active ligands. These ligands were synthesized by the condensation of 2-amino-4-phenyl-1,3-thiazole with 8-formyl-7-hydroxy- 4-methylcoumarin. The probable structure of the complexes has been proposed on the basis of analytical and spectroscopic data (IR, UV-Vis, ESR, FAB-mass, and thermoanalytical). Electrochemical study of the complexes is also reported. Elemental analysis of the complexes confined them to stoichiometry of the type ML(2).2H(2)O [M = Co(II), Ni(II), and Cu(II)]. The Schiff base and its metal(II) complexes have been screened for their antibacterial (Escherichia coli, Staphylococcus aureus, Staphylococcus pyogenes, and Pseudomonas aeruginosa) and antifungal activities (Aspergillus niger, Aspergillus flavus, and Cladosporium) by the MIC method. The brine shrimp bioassay was carried out to study their in vitro cytotoxic properties, and also the Schiff base and its metal(II) complexes have been studied for DNA cleavage.

  6. Synthesis, characterization and DNA binding/cleavage, protein binding and cytotoxicity studies of Co(II), Ni(II), Cu(II) and Zn(II) complexes of aminonaphthoquinone.

    PubMed

    Kosiha, A; Parthiban, C; Elango, Kuppanagounder P

    2017-03-01

    The Co(II), Ni(II), Cu(II) and Zn(II) complexes of an aminonaphthoquinone ligand (L) have been prepared and characterized using analytical and spectral techniques. The structures of L and its Zn(II) complex are confirmed by single crystal X-ray diffraction study. The results indicate that Co(II), Ni(II) and Zn(II) complexes possess tetrahedral geometry while Cu(II) complex exhibits square planar structure. The interaction of L and its complexes with CT-DNA reveal that they could interact with CT-DNA through intercalation. The DNA cleavage studies of the L and its complexes indicate that the Cu(II) and Ni(II) complexes cleave the circular form of the DNA relatively to a greater extent than the other complexes. The results of the interaction of these compounds with bovine serum albumin (BSA) indicate that the complexes exhibit a strong binding to BSA over the L. The in vitro anticancer activities indicate that these compounds exhibit substantial activity against human breast (MCF7) and lung cancer (A549) cell lines. The characteristics of apoptosis in cell morphology have been observed using AO/EB and DAPI staining and the results suggest that an apoptotic mode of cell death with these compounds. The overall results and discussion indicate that coordination of metal ions with the ligand enhances the biological activity.

  7. Theoretical and experimental studies on three new coordination complexes of Co(II), Ni(II), and Cu(II) with 2,4-dichloro-6-{(E)-[(5-chloro-2 sulfanylphenyl)imino]methyl}phenol Schiff base ligand.

    PubMed

    Kusmariya, Brajendra S; Mishra, A P

    2015-11-01

    Three mononuclear coordination complexes of Co(II), Ni(II), and Cu(II) have been synthesized from 2,4-dichloro-6-{(E)-[(5-chloro-2-sulfanylphenyl)imino]methyl}phenol ligand (H 2 L) obtained by simple condensation reaction of 3,5-dichloro-2-hydroxybenzaldehyde and 2-amino-4-chlorobenzenethiol and characterized by elemental analysis, spectral (FT-IR, electronic, and (1)H-NMR), molar conductance, thermal, SEM, PXRD, and fluorescence studies. The PXRD analysis and SEM-EDX micrographs show the crystalline nature of complexes. The domain size and the lattice strain of synthesized compounds have been determined according to Williamson-Hall plot. TG of the synthesized complexes illustrates the general decomposition pattern of the complexes. The ligand exhibits an interesting fluorescence property which is suppressed after complex formation. The Co(II) complex adopted a distorted octahedral configuration while Ni(II) and Cu(II) complexes showed square planar geometry around metal center. The geometry optimization, HOMO-LUMO, molecular electrostatic potential map (MEP), and spin density of synthesized compounds have been performed by density functional theory (DFT) method using B3LYP/6-31G and B3LYP/LANL2DZ as basis set. Graphical abstract Three new coordination complexes of Co(II), Ni(II) and Cu(II) with 2,4-dichloro-6-{(E)-[(5-chloro-2 sulfanylphenyl)imino]methyl}phenol Schiff base ligand.

  8. Synthesis, spectroscopic characterization, molecular modeling and antimicrobial activities of Mn(II), Co(II), Ni(II), Cu(II) complexes containing the tetradentate aza Schiff base ligand

    NASA Astrophysics Data System (ADS)

    Chandra, Sulekh; Ruchi

    2013-02-01

    Mn(II), Co(II), Ni(II), and Cu(II) complexes with a tetradentate macrocyclic ligand [1.2.5.6tetraoxo-3,4,7,8tetraaza-(1,2,3,4,5,6,7,8)tetrabenzene(L)] were synthesized and characterized by elemental analysis, molar conductance measurements, mass, nmr, i.r., electronic and e.p.r. spectral studies. All the complexes are non electrolytes in nature and may be formulated as [M(L)X2] [where, M = Mn(II), Co(II), Ni(II), Cu(II) and X = Cl-, CH3COO-]. On the basis of i.r., electronic and e.p.r. spectral studies a distorted octahedral geometry has been assigned for all complexes. The antimicrobial activities and LD50 values of the ligand and its complexes, as growth inhibiting agents, have been screened in vitro against two different species of bacteria and plant pathogenic fungi.

  9. Interaction with biomacromolecules and antiproliferative activities of Mn(II), Ni(II), Zn(II) complexes of demethylcantharate and 2,2'-bipyridine

    NASA Astrophysics Data System (ADS)

    Zhang, Fan; Lin, Qiu-Yue; Hu, Wan-Li; Song, Wen-Ji; Shen, Shu-Ting; Gui, Pan

    2013-06-01

    Three new transition metal complexes [Mn2(DCA)2(bipy)2]·5H2O (1), [M2(DCA)2(bipy)2(H2O)]·10H2O(M = Ni(II)(2);Zn(II)(3)), (DCA = demethylcantharate, 7-oxabicyclo[2,2,1]heptane-2,3-dicarboxylate, C8H8O5) were synthesized and characterized by elemental analysis, molar conductance, infrared spectra and X-ray diffraction techniques. Each metal ion was six-coordinated in complexes. Complex 1 has a Mn2O2 center. Complexes 2 and 3 have asymmetric binuclear structure. Great amount of intermolecular hydrogen-bonding and π-π* stacking interactions were formed in these complex structures. The DNA-binding properties of complexes were investigated by electronic absorption spectra and viscosity measurements. The DNA binding constants Kb/(L mol-1) were 1.71 × 104 (1), 2.62 × 104 (2) and 1.59 × 104 (3) at 298 K. The complexes could quench the intrinsic fluorescence of bovine serum albumin (BSA) strongly through static quenching. The protein binding constants Ka/(L mol-1) were 7.27 × 104 (1), 4.55 × 104 (2) and 7.87 × 104 L mol-1 (3) and binding site was one. The complexes bind more tightly with DNA and BSA than with ligands. Complexes 1 and 3 had stronger inhibition ratios than Na2(DCA) against human hepatoma cells (SMMC-7721) lines and human gastric cancer cells (MGC80-3) lines in vitro. Complex 3 showed the strongest antiproliferative activity against SMMC-7721 (IC50 = 29.46 ± 2.12 μmol L-1) and MGC80-3 (IC50 = 27.02 ± 2.38 μmol L-1), which shows potential in anti-cancer drug development.

  10. Molecular structure and spectroscopic studies on novel complexes of coumarin-3-carboxylic acid with Ni(II), Co(II), Zn(II) and Mn(II) ions based on density functional theory

    NASA Astrophysics Data System (ADS)

    Creaven, B. S.; Devereux, M.; Georgieva, I.; Karcz, D.; McCann, M.; Trendafilova, N.; Walsh, M.

    2011-12-01

    Novel Ni(II), Co(II), Zn(II) and Mn(II) complexes of coumarin-3-carboxylic acid (HCCA) were studied at experimental and theoretical levels. The complexes were characterised by elemental analyses, FT-IR, 1H NMR, 13C NMR and UV-Vis spectroscopy and by magnetic susceptibility measurements. The binding modes of the ligand and the spin states of the metal complexes were established by means of molecular modelling of the complexes studied and calculation of their IR, NMR and absorption spectra at DFT(TDDFT)/B3LYP level. The experimental and calculated data verified high spin Ni(II), Co(II) and Mn(II) complexes and a bidentate binding through the carboxylic oxygen atoms (CCA2). The model calculations predicted pseudo octahedral trans-[M(CCA2) 2(H 2O) 2] structures for the Zn(II), Ni(II) and Co(II) complexes and a binuclear [Mn 2(CCA2) 4(H 2O) 2] structure. Experimental and calculated 1H, 13C NMR, IR and UV-Vis data were used to distinguish the two possible bidentate binding modes (CCA1 and CCA2) as well as mononuclear and binuclear structures of the metal complexes.

  11. Molecular structure and spectroscopic studies on novel complexes of coumarin-3-carboxylic acid with Ni(II), Co(II), Zn(II) and Mn(II) ions based on density functional theory.

    PubMed

    Creaven, B S; Devereux, M; Georgieva, I; Karcz, D; McCann, M; Trendafilova, N; Walsh, M

    2011-12-15

    Novel Ni(II), Co(II), Zn(II) and Mn(II) complexes of coumarin-3-carboxylic acid (HCCA) were studied at experimental and theoretical levels. The complexes were characterised by elemental analyses, FT-IR, (1)H NMR, (13)C NMR and UV-Vis spectroscopy and by magnetic susceptibility measurements. The binding modes of the ligand and the spin states of the metal complexes were established by means of molecular modelling of the complexes studied and calculation of their IR, NMR and absorption spectra at DFT(TDDFT)/B3LYP level. The experimental and calculated data verified high spin Ni(II), Co(II) and Mn(II) complexes and a bidentate binding through the carboxylic oxygen atoms (CCA2). The model calculations predicted pseudo octahedral trans-[M(CCA2)(2)(H(2)O)(2)] structures for the Zn(II), Ni(II) and Co(II) complexes and a binuclear [Mn(2)(CCA2)(4)(H(2)O)(2)] structure. Experimental and calculated (1)H, (13)C NMR, IR and UV-Vis data were used to distinguish the two possible bidentate binding modes (CCA1 and CCA2) as well as mononuclear and binuclear structures of the metal complexes.

  12. Spectroscopic, magnetic and thermal studies of Co(II), Ni(II), Cu(II) and Zn(II) complexes of 3-acetylcoumarin-isonicotinoylhydrazone and their antimicrobial and anti-tubercular activity evaluation

    NASA Astrophysics Data System (ADS)

    Hunoor, Rekha S.; Patil, Basavaraj R.; Badiger, Dayananda S.; Vadavi, Ramesh S.; Gudasi, Kalagouda B.; Chandrashekhar, V. M.; Muchchandi, I. S.

    2010-11-01

    Co(II), Ni(II), Cu(II) and Zn(II) complexes with a new heterocyclic Schiff base derived by the condensation of isonicotinoylhydrazide and 3-acetylcoumarin have been synthesized. 1H, 13C and 2D HETCOR NMR analyses confirm the formation of title compound and existence of the same in two isomeric forms. The metal complexes were characterized on the basis of various spectroscopic techniques like electronic, EPR, IR, 1H and 13C NMR studies, elemental analysis, magnetic properties and thermogravimetric analysis, and also by the aid of molar conductivity measurements. It is found that the Schiff base behaves as a monobasic tridentate ligand coordinating in the imidol form with 1:1 metal to ligand stoichiometry. Trigonal bipyramidal geometry has been assigned for Ni(II) and Cu(II) complexes, while tetrahedral for Co(II) and Zn(II) complexes. The compounds were subjected to antimicrobial and anti-tubercular activity screening using serial broth dilution method and Minimum Inhibitory Concentration (MIC) is determined. Zn(II) complex has shown significant antifungal activity with an MIC of 6.25 μg/mL while Cu(II) complex is noticeable for antibacterial activity at the same concentration. Anti-TB activity of the ligand has enhanced on complexation with Co(II) and Ni(II) ions.

  13. Theoretical investigations of the structures and electronic spectra of Zn(II) and Ni(II) complexes with cyclohexylamine-N-dithiocarbamate

    NASA Astrophysics Data System (ADS)

    Yu, Xiaohan; Wang, Na; He, Hongqing; Wang, Li

    2014-03-01

    The ground-state structures of two ligands cyclohexylamine-N-dithiocarbamate (L) and PPh3 and four complexes [Zn(L)2] (A), [Ni(L)2] (B), [Zn(L)2PPh3] (C), and [Ni(L)2PPh3] (D) are optimized by M06, B3LYP, and B3PW91 methods with the same mixed basis set. As compared with the experimental data of other complexes containing the Ni-P bond, the result obtained by M06/6-31+G(d)-LANL2DZ method is finally regarded as accurate and reliable for this project. Based on the optimized geometries, the compositions of molecular orbitals are analyzed and the absorption spectra are simulated. When one more ligand PPh3 is coordinated, the lowest-lying transition energy presents red-shift; while it shows blue-shift when the metal coordination center change from Ni to Zn with the same ligands. The detailed transition characters related with the absorption spectrum are assigned. In all the key transitions, it is hard to find the contribution from Zn atom. On the contrary, the d orbital of Ni atom contributes a lot for the HOMO and LUMO of complexes B and D. Consequently, the transition characters of Zn(II) and Ni(II) complexes are different.

  14. Synthesis, crystal structure, DFT study and photocatalytic property of a new Ni(II) complex of a symmetric N2O4-donor bis-Schiff base ligand

    NASA Astrophysics Data System (ADS)

    Wang, Hu; Meng, Xiangmin; Fan, Chuanbin; Fan, Yuhua; Bi, Caifeng

    2016-03-01

    A new complex, Ni(C22H26N2O10S2)·2CH3OH, with a sexidentate (N2O4) symmetric bis-Schiff base ligand (C22H26N2O10S2 = 1,2-bis(2-methoxy-6-formylphenoxy)ethane-2-aminoethane-sulfonic acid) has been synthesized and characterized by physico-chemical and spectroscopic methods. The X-ray crystal structure shows that the Ni(II) atom of the complex is six-coordinated by two nitrogens from Cdbnd N groups, two oxygens from ether groups and two hydroxyl oxygens from sulfonic acid groups in the mono-ligand, forming a distorted octahedral geometry. Theoretical study of the complex is carried out by density functional theory (DFT) method and the B3LYP method employing the 6-3l+G* basis set. Moreover, the complex proved to be good candidate for the photocatalytic degradation of methylene blue.

  15. Synthesis, antimicrobial activity, structural and spectral characterization and DFT calculations of Co(II), Ni(II), Cu(II) and Pd(II) complexes of 4-amino-5-pyrimidinecarbonitrile.

    PubMed

    Mohamed, Tarek A; Shaaban, Ibrahim A; Farag, Rabei S; Zoghaib, Wajdi M; Afifi, Mahmoud S

    2015-01-25

    Co(II), Ni(II), Cu(II) and Pd(II) complexes of 4-amino-5-pyrimidinecarbonitrile (APC) have been synthesized and characterized using elemental analysis, magnetic susceptibility, mass spectrometry, infrared (4000-200 cm(-1)), UV-Visible (200-1100 nm), (1)H NMR and ESR spectroscopy as well as TGA analysis. The molar conductance measurements in DMSO imply non-electrolytic complexes, formulated as [M(APC)2Cl2] where M=Co(II), Ni(II), Cu(II) and Pd(II). The infrared spectra of Co(II), Ni(II) and Cu(II) complexes indicate a bidentate type of bonding for APC through the exocyclic amino and adjacent pyrimidine nitrogen as donors whereas APC coordinated to Pd(II) ion as a monodentated ligand via a pyrimidine nitrogen donor. The magnetic measurements and the electronic absorption spectra support distorted octahedral geometries for Co(II), Ni(II) and Cu(II) complexes however a square planar complex was favored for the Pd(II) complex (C2h skeleton symmetry). In addition, we carried out B3LYP and ω-B97XD geometry optimization at 6-31G(d) basis set except for Pd(II) where we implemented LanL2DZ/6-31G(d) combined basis set. The computational results favor all trans geometrical isomers where amino N, pyrimidine N and Cl are trans to each other (structure 1). Finally, APC and its divalent metal ion complexes were screened for their antibacterial activity, and the synthesized complexes were found to be more potent antimicrobial agents than APC against one or more microbial species.

  16. Synthesis, antimicrobial activity, structural and spectral characterization and DFT calculations of Co(II), Ni(II), Cu(II) and Pd(II) complexes of 4-amino-5-pyrimidinecarbonitrile

    NASA Astrophysics Data System (ADS)

    Mohamed, Tarek A.; Shaaban, Ibrahim A.; Farag, Rabei S.; Zoghaib, Wajdi M.; Afifi, Mahmoud S.

    2015-01-01

    Co(II), Ni(II), Cu(II) and Pd(II) complexes of 4-amino-5-pyrimidinecarbonitrile (APC) have been synthesized and characterized using elemental analysis, magnetic susceptibility, mass spectrometry, infrared (4000-200 cm-1), UV-Visible (200-1100 nm), 1H NMR and ESR spectroscopy as well as TGA analysis. The molar conductance measurements in DMSO imply non-electrolytic complexes, formulated as [M(APC)2Cl2] where M = Co(II), Ni(II), Cu(II) and Pd(II). The infrared spectra of Co(II), Ni(II) and Cu(II) complexes indicate a bidentate type of bonding for APC through the exocyclic amino and adjacent pyrimidine nitrogen as donors whereas APC coordinated to Pd(II) ion as a monodentated ligand via a pyrimidine nitrogen donor. The magnetic measurements and the electronic absorption spectra support distorted octahedral geometries for Co(II), Ni(II) and Cu(II) complexes however a square planar complex was favored for the Pd(II) complex (C2h skeleton symmetry). In addition, we carried out B3LYP and ω-B97XD geometry optimization at 6-31G(d) basis set except for Pd(II) where we implemented LanL2DZ/6-31G(d) combined basis set. The computational results favor all trans geometrical isomers where amino N, pyrimidine N and Cl are trans to each other (structure 1). Finally, APC and its divalent metal ion complexes were screened for their antibacterial activity, and the synthesized complexes were found to be more potent antimicrobial agents than APC against one or more microbial species.

  17. Synthesis, characterization, DFT and biological studies of (Z)-N‧-(2-oxoindolin-3-ylidene)picolinohydrazide and its Co(II), Ni(II) and Cu(II) complexes

    NASA Astrophysics Data System (ADS)

    Rakha, T. H.; El-Gammal, O. A.; Metwally, H. M.; Abu El-Reash, G. M.

    2014-03-01

    The picolinohydrazide derivative: (Z)-N‧-(2-oxoindolin-3-ylidene)picolinohydrazide (H2IPH) and its Co(II), Ni(II) and Cu(II) complexes have been synthesized and investigated by using the modern spectroscopic and physicochemical techniques viz. IR, 1H NMR, UV-Vis spectrometric methods and magnetic moment measurements. The investigation study revealed that the ligand acts as monobasic tri- and tetradentate in Co(II) and Ni(II) complex, respectively and as neutral tridentate in Cu(II) complex. On the basis of magnetic moment and spectral studies, a six coordinated octahedral geometry is assigned for all complexes. The molecular modeling are drawn and showed the bond length, bond angle, chemical reactivity, energy components (kcal/mol) and binding energy (kcal/mol) for all the title compounds and also NLO for the ligand is shown. The energy gap between the HOMO and LUMO for Ni(II) complex is (-7 eV) which indicates that these compound is a promising structure for photovoltaic devices such as solar cells. A comparison of the experimental and theoretical spectra can be very useful in making correct assignments and understanding the basic chemical shift. The thermal behavior and the kinetic parameters of degradation were determined using Coats-Redfern and Horowitz-Metzger methods. The in vitro antibacterial studies of these complexes screened against pathogenic bacteria proved them as growth inhibiting agents. Antitumor activity, carried out in vitro on human mammary gland (breast) MCF7, have shown that the Co(II) complex exhibited potent activity followed by the ligand, Cu(II) and Ni(II) complexes.

  18. Ni(II) complexes with 2,2-dipyridylamine and salicylaldehydes: Synthesis, crystal structure and interaction with calf-thymus DNA and albumins.

    PubMed

    Zianna, Ariadni; Psomas, George; Hatzidimitriou, Antonis; Lalia-Kantouri, Maria

    2016-10-01

    The synthesis of four cationic mixed-ligand Ni(II) complexes with 2,2'-dipyridylamine (dpamH) and substituted salicylaldehydes (X-saloH) was undertaken in an effort to discover new biologically active compounds. The complexes with the general formula [Ni(dpamH)2(X-salo)]Cl, 3-6, namely [Ni(dpamH)2(5-Cl-salo)]Cl, 3, [Ni(dpamH)2(5-Br-salo)]Cl, 4, [Ni(dpamH)2(5-CH3-salo)]Cl, 5, and [Ni(dpamH)2(3-OCH3-salo)]Cl·CH3OH, 6, were characterized by elemental analyses, FT-IR and UV-vis spectroscopy, magnetic and conductivity measurements. In addition, two analogous nickel-salicylaldehydato complexes in the absence of dpamH were prepared and characterized as [Ni(5-Cl-salo)2(CH3OH)2], 1 and [Ni(5-Br-salo)2(CH3OH)2], 2. The structures of complexes 1-6 were determined by X-ray crystallography revealing octahedral coordination of nickel (II) and monomeric nature of the compounds. Spectroscopic (UV-vis), electrochemical (cyclic voltammetry) and physicochemical (viscosity measurements) techniques were employed in order to study the binding mode and strength of the complexes to calf-thymus (CT) DNA, while competitive studies with ethidium bromide (EB), performed by fluorescence spectroscopy, revealed the ability of the complexes to displace the DNA-bound EB. The complexes bind to DNA probably via intercalation exhibiting high DNA-binding constants. For the cationic complexes 3-6, the coexistence of an electrostatic interaction with CT DNA may be also suggested. The interaction of the complexes with serum albumins was studied by fluorescence emission spectroscopy and the determined binding constants exhibit relative high values.

  19. Synthesis, spectral, antitumor, antioxidant and antimicrobial studies on Cu(II), Ni(II) and Co(II) complexes of 4-[(1H-Benzoimidazol-2-ylimino)-methyl]-benzene-1,3-diol

    NASA Astrophysics Data System (ADS)

    El-wakiel, Nadia; El-keiy, Mai; Gaber, Mohamed

    2015-08-01

    A new Schiff base of 2-aminobenzimidazole with 2,4-dihydroybezaldehyde (H3L), and its Cu(II), Ni(II) and Co(II) complexes have been synthesized and characterized by elemental analyses, molar conductance, thermal analysis (TGA), inductive coupled plasma (ICP), magnetic moment measurements, IR, EI-mass, UV-Vis. and ESR spectral studies. On the basis of spectral studies and analytical data, it is evident that the Schiff base acts as dibasic tridentate ligand coordinating via deprotonated OH, NH and azomethine nitrogen atom. The results showed that Co(II) and Ni(II) complexes have tetrahedral structure while Cu(II) complexes has octahedral geometry. The kinetic and thermodynamic parameters of the thermal decomposition stages have been evaluated. The studied complexes were tested for their in vitro antimicrobial activities against some bacterial strains. The anticancer activity of the ligand and its metal complexes is evaluated against human liver Carcinoma (HEPG2) cell. These compounds exhibited a moderate and weak activity against the tested HEPG2 cell lines with IC50 of 9.08, 18.2 and 19.7 μg/ml for ligand, Cu(II) and Ni(II) complexes, respectively. In vitro antioxidant activity of the newly synthesized compounds has also been evaluated.

  20. Novel Ni(II) and Zn(II) complexes coordinated by 2-arylaminomethyl-1H-benzimidazole: molecular structures, spectral, DFT studies and evaluation of biological activity.

    PubMed

    Abdel-Ghani, Nour T; Abo El-Ghar, Maha F; Mansour, Ahmed M

    2013-03-01

    [NiL(1,2)Cl(2)(OH(2))(3)]·zH(2)O and [ZnL(1,2)(CH(3)CO(2))(2)] (L(1)=(1H-benzimidazol-2-ylmethyl)-N-phenyl amine, z=0 and L(2)=2-[(1H-Benzimidazol-2-ylmethyl)-amino]-benzoic acid methyl ester, z=1) complexes have been synthesized and characterized by a variety of physico-chemical techniques. The central Ni(II) ion is coordinated by only the pyridine-type nitrogen (N(py)) of benzimidazole ring, three water molecules and two chlorido ligands forming a distorted octahedral geometry. Five coordinated zinc complexes were obtained, where the coordination sphere of zinc ion is made up of secondary amino group (NH(sec)), N(py) and two acetate groups, one acts as a unidentate and the other as a bidentate. A theoretical DFT/UB3LYP method combined with LANL2DZ basis set shows that all the metal-ligand bonds are of the L→M type. Electronic structures have been calculated using TD-DFT method. The antibacterial activity of NiL(2) complexes decreases by the introduction of COOCH(3) group in the ortho-position of the aniline moiety.

  1. Synthesis and characterization of Cu(II), Co(II) and Ni(II) complexes of a number of sulfadrug azodyes and their application for wastewater treatment.

    PubMed

    El-Baradie, K; El-Sharkawy, R; El-Ghamry, H; Sakai, K

    2014-01-01

    The azodye ligand (HL(1)) was synthesized from the coupling of sulfaguanidine diazonium salt with 2,4-dihydroxy-benzaldehyde while the two ligands, HL(2) and HL(3), were prepared by the coupling of sulfadiazine diazonium salt with salicylaldehyde (HL(2)) and 2,4-dihydroxy-benzaldehyde (HL(3)). The prepared ligands were characterized by elemental analysis, IR, (1)H NMR and mass spectra. Cu(II), Co(II) and Ni(II) complexes of the prepared ligands have been synthesized and characterized by various spectroscopic techniques like IR, UV-Visible as well as magnetic and thermal (TG and DTA) measurements. It was found that all the ligands behave as a monobasic bidentate which coordinated to the metal center through the azo nitrogen and α-hydroxy oxygen atoms in the case of HL(1) and HL(3). HL(2) coordinated to the metal center through sulfonamide oxygen and pyrimidine nitrogen. The applications of the prepared complexes in the oxidative degradation of indigo carmine dye exhibited good catalytic activity in the presence of H2O2 as an oxidant. The reactions followed first-order kinetics and the rate constants were determined. The degradation reaction involved the catalytic action of the azo-dye complexes toward H2O2 decomposition, which can lead to the generation of HO radicals as a highly efficient oxidant attacking the target dye. The detailed kinetic studies and the mechanism of these catalytic reactions are under consideration in our group.

  2. Synthesis, characterization, antibacterial activities and carbonic anhydrase enzyme inhibitor effects of new arylsulfonylhydrazone and their Ni(II), Co(II) complexes.

    PubMed

    Ozdemir, Ummühan Ozmen; Arslan, Fatma; Hamurcu, Fatma

    2010-01-01

    Ethane sulfonic acide hydrazide (esh: CH(3)CH(2)SO(2)NHNH(2)) derivatives as 5-methylsalicyl-aldehydeethanesulfonylhydrazone (5msalesh), 5-methyl-2-hydroxyacetophenoneethane sulfonylhydrazone (5mafesh) and their Ni(II), Co(II) complexes have been synthesized for the first time. The structure of these compounds has been investigated by elemental analysis, FT-IR, (1)H NMR, (13)C NMR, LC/MS, UV-vis spectrophotometric method, magnetic susceptibility, thermal studies and conductivity measurements. The antibacterial activities of synthesized compounds were studied against Gram positive bacteria; Staphylococcus aureus, Bacillus subtilis, Bacillus magaterium and Gram negative bacteria; Salmonella enteritidis, Escherichia coli by using the microdilution broth method. The biological activity screening showed that ligands have more activity than complexes against the tested bacteria. The inhibition activities of these compounds on carbonic anhydrase II (CA II) have been investigated by comparing IC(50) and K(i) values and it has been found that 5msalesh and its complexes have more enzyme inhibition efficiency than other compounds.

  3. Synthesis, characterization, antibacterial activities and carbonic anhydrase enzyme inhibitor effects of new arylsulfonylhydrazone and their Ni(II), Co(II) complexes

    NASA Astrophysics Data System (ADS)

    Özdemir, Ümmühan Özmen; Arslan, Fatma; Hamurcu, Fatma

    2010-01-01

    Ethane sulfonic acide hydrazide ( esh: CH 3CH 2SO 2NHNH 2) derivatives as 5-methylsalicyl-aldehydeethanesulfonylhydrazone ( 5msalesh), 5-methyl-2-hydroxyacetophenoneethane sulfonylhydrazone ( 5mafesh) and their Ni(II), Co(II) complexes have been synthesized for the first time. The structure of these compounds has been investigated by elemental analysis, FT-IR, 1H NMR, 13C NMR, LC/MS, UV-vis spectrophotometric method, magnetic susceptibility, thermal studies and conductivity measurements. The antibacterial activities of synthesized compounds were studied against Gram positive bacteria; Staphylococcus aureus, Bacillus subtilis, Bacillus magaterium and Gram negative bacteria; Salmonella enteritidis, Escherichia coli by using the microdilution broth method. The biological activity screening showed that ligands have more activity than complexes against the tested bacteria. The inhibition activities of these compounds on carbonic anhydrase II (CA II) have been investigated by comparing IC 50 and Ki values and it has been found that 5msalesh and its complexes have more enzyme inhibition efficiency than other compounds.

  4. Supramolecular complexes of Co(II), Ni(II) and Zn(II) p-hydroxybenzoates with caffeine: Synthesis, spectral characterization and crystal structure

    NASA Astrophysics Data System (ADS)

    Taşdemir, Erdal; Özbek, Füreya Elif; Sertçelik, Mustafa; Hökelek, Tuncer; Çelik, Raziye Çatak; Necefoğlu, Hacali

    2016-09-01

    Three novel complexes Co(II), Ni(II) and Zn(II) containing p-hydroxybenzoates and caffeine ligands were synthesized and characterized by elemental analysis, FT-IR and UV-vis Spectroscopy, molar conductivity and single crystal X-ray diffraction methods. The thermal properties of the synthesized complexes were investigated by TGA/DTA. The general formula of the complexes is [M(HOC6H4COO)2(H2O)4]·2(C8H10N4O2)·8H2O (where: M: Co, Ni and Zn). The IR studies showed that carboxylate groups of p-hydroxybenzoate ligands have monodentate coordination mode. The M2+ ions are octahedrally coordinated by two p-hydroxybenzoate ligands, four water molecules leading to an overall MO6 coordination environment. The medium-strength hydrogen bondings involving the uncoordinated caffeine ligands and water molecules, coordinated and uncoordinated water molecules and p-hydroxybenzoate ligands lead to three-dimensional supramolecular networks in the crystal structures.

  5. Synthesis and characterization of Cu(II), Co(II) and Ni(II) complexes of a number of sulfadrug azodyes and their application for wastewater treatment

    NASA Astrophysics Data System (ADS)

    El-Baradie, K.; El-Sharkawy, R.; El-Ghamry, H.; Sakai, K.

    2014-03-01

    The azodye ligand (HL1) was synthesized from the coupling of sulfaguanidine diazonium salt with 2,4-dihydroxy-benzaldehyde while the two ligands, HL2 and HL3, were prepared by the coupling of sulfadiazine diazonium salt with salicylaldehyde (HL2) and 2,4-dihydroxy-benzaldehyde (HL3). The prepared ligands were characterized by elemental analysis, IR, 1H NMR and mass spectra. Cu(II), Co(II) and Ni(II) complexes of the prepared ligands have been synthesized and characterized by various spectroscopic techniques like IR, UV-Visible as well as magnetic and thermal (TG and DTA) measurements. It was found that all the ligands behave as a monobasic bidentate which coordinated to the metal center through the azo nitrogen and α-hydroxy oxygen atoms in the case of HL1 and HL3. HL2 coordinated to the metal center through sulfonamide oxygen and pyrimidine nitrogen. The applications of the prepared complexes in the oxidative degradation of indigo carmine dye exhibited good catalytic activity in the presence of H2O2 as an oxidant. The reactions followed first-order kinetics and the rate constants were determined. The degradation reaction involved the catalytic action of the azo-dye complexes toward H2O2 decomposition, which can lead to the generation of HOrad radicals as a highly efficient oxidant attacking the target dye. The detailed kinetic studies and the mechanism of these catalytic reactions are under consideration in our group.

  6. Synthesis, characterization and in vitro anticancer activity of 18-membered octaazamacrocyclic complexes of Co(II), Ni(II), Cd(II) and Sn(II)

    NASA Astrophysics Data System (ADS)

    Kareem, Abdul; Zafar, Hina; Sherwani, Asif; Mohammad, Owais; Khan, Tahir Ali

    2014-10-01

    An effective series of 18 membered octaazamacrocyclic complexes of the type [MLX2], where X = Cl or NO3 have been synthesized by template condensation reaction of oxalyl dihydrazide with dibenzoylmethane and metal salt in 2:2:1 molar ratio. The formation of macrocyclic framework, stereochemistry and their overall geometry have been characterized by various physico-chemical studies viz., elemental analysis, electron spray ionization-mass spectrometry (ESI-MS), I.R, UV-Vis, 1H NMR, 13C NMR spectroscopy, X-ray diffraction (XRD) and TGA/DTA studies. These studies suggest formation of octahedral macrocyclic complexes of Co(II), Ni(II), Cd(II) and Sn(II). The molar conductance values suggest nonelectrolytic nature for all the complexes. Thermogravimatric analysis shows that all the complexes are stable up to 600 °C. All these complexes have been tested against different human cancer cell lines i.e. human hepatocellular carcinoma (Hep3B), human cervical carcinoma (HeLa), human breast adenocarcinoma (MCF7) and normal cells (PBMC). The newly synthesized 18-membered octaazamacrocyclic complexes during in vitro anticancer evaluation, displayed moderate to good cytotoxicity on liver (Hep3B), cervical (HeLa) and breast (MCF7) cancer cell lines, respectively. The most effective anticancer cadmium complex (C34H28N10CdO10) was found to be active with IC50 values, 2.44 ± 1.500, 3.55 ± 1.600 and 4.82 ± 1.400 in micro-molar on liver, cervical and breast cancer cell lines, respectively.

  7. Synthesis, spectral, thermal and magnetic studies of Mn(II), Ni(II) and Cu(II) complexes with some benzopyran-4-one Schiff bases.

    PubMed

    el-Ansary, Aida L; Abdel-Fattah, Hussein M; Abdel-Kader, Nora S

    2011-08-01

    The Schiff bases of N(2)O(2) dibasic ligands, H(2)La and H(2)Lb are prepared by the condensation of ethylenediamine (a) and trimethylenediamine (b) with 6-formyl-7-hydroxy-5-methoxy-2-methylbenzopyran-4-one. Also tetra basic ligands, H(4)La and H(4)Lb are prepared by the condensation of aliphatic amines (a) and (b) with 6-formyl-5,7-dihydroxy-2-methylbenzopyran-4-one. New complexes of H(4)La and H(4)Lb with metal ions Mn(II), Ni(II) and Cu(II) are synthesized, in addition Mn(II) complexes with ligands H(2)La and H(2)Lb are also synthesized. Elemental and thermal analyses, infrared, ultraviolet-visible as well as conductivity and magnetic susceptibility measurements are used to elucidate the structure of the newly prepared metal complexes. The structures of copper(II) complexes are also assigned based upon ESR spectra study. All the complexes separated with the stoichiometric ratio (1:1) (M:L) except Mn-H(4)La and Mn-H(4)Lb with (2:1) (M:L) molar ratio. In metal chelates of the type 1:1 (M:L), the Schiff bases behave as a dinegative N(2)O(2) tetradentate ligands. Moreover in 2:1 (M:L) complexes, the Schiff base molecules act as mono negative bidentate ligand and binuclear complex is then formed. The Schiff bases were assayed by the disc diffusion method for antibacterial activity against Staphylococcus aureus and Escherichia coli. The antifungal activity of the Schiff bases was also evaluated against the fungi Aspergillus flavus and Candida albicans.

  8. Ni(II) and Fe(II) complexes based on bis(imino)aryl pincer ligands: synthesis, structural characterization and catalytic activities.

    PubMed

    Zhang, Jingshun; Gao, Wei; Lang, Xiaomei; Wu, Qiaolin; Zhang, Lei; Mu, Ying

    2012-08-28

    Bis(imino)aryl NCN pincer Ni(II) complexes 2,6-(ArN=CH)(2)C(6)H(3)NiBr (1: Ar = 2,6-Me(2)C(6)H(3); 2: Ar = 2,6-Et(2)C(6)H(3); 3: Ar = 2,6-(i)Pr(2)C(6)H(3)) were prepared via the oxidative-addition of Ni(0)(Ph(3)P)(4) with bis(N-aryl)-2-bromoisophthalaldimine. These nickel complexes were characterized by NMR and elemental analyses. Their solid molecular structures were established by X-ray diffraction analyses. The nickel metal centers adopt distorted square planar geometries with the bromine atoms acting as one coordinate ligands. The NCN pincer Fe(II) complexes 2,6-(ArN=CH)(2)C(6)H(3)Fe(μ-Cl)(2)Li(THF)(2) (4: Ar = 2,6-Me(2)C(6)H(3); 5: Ar = 2,6-Et(2)C(6)H(3); 6: Ar = 2,6-(i)Pr(2)C(6)H(3)) were synthesized by lithium salt metathesis reactions of the ligand lithium salts with FeCl(2). X-ray structure analyses of 4 and 5 revealed that the Fe(II) complexes are hetero-dinuclear with the iron atoms in trigonal bipyramidal environments. When activated with MAO, the nickel complexes are active for norbornene vinyl polymerization but are inert for butadiene polymerization. The Fe(II) complexes show moderate activities in butadiene polymerization when activated with alkylaluminium, affording the cis-1,4 enriched polymer.

  9. Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases. Part 2: aldol, Mannich addition reactions, deracemization and (S) to (R) interconversion of α-amino acids.

    PubMed

    Sorochinsky, Alexander E; Aceña, José Luis; Moriwaki, Hiroki; Sato, Tatsunori; Soloshonok, Vadim

    2013-11-01

    This review provides a comprehensive treatment of literature data dealing with asymmetric synthesis of α-amino-β-hydroxy and α,β-diamino acids via homologation of chiral Ni(II) complexes of glycine Schiff bases using aldol and Mannich-type reactions. These reactions proceed with synthetically useful chemical yields and thermodynamically controlled stereoselectivity and allow direct introduction of two stereogenic centers in a single operation with predictable stereochemical outcome. Furthermore, new application of Ni(II) complexes of α-amino acids Schiff bases for deracemization of racemic α-amino acids and (S) to (R) interconversion providing additional synthetic opportunities for preparation of enantiomerically pure α-amino acids, is also reviewed. Origin of observed diastereo-/enantioselectivity in the aldol, Mannich-type and deracemization reactions, generality and limitations of these methodologies are critically discussed.

  10. Effect of the competition of Cu(II) and Ni(II) on the kinetic and thermodynamic stabilities of Cr(III)-organic ligand complexes using competitive ligand exchange (EDTA).

    PubMed

    Cunha, Graziele da Costa; Goveia, Danielle; Romão, Luciane Pimenta Cruz; de Oliveira, Luciana Camargo

    2015-05-01

    The effect of competition of Cu(II) and Ni(II) on the kinetic stability of Cr(III) complexed with natural organic matter (NOM) was characterized using EDTA exchange with single-stage tangential-flow ultrafiltration. For a water sample from Serra de Itabaiana, 3% of spiked Cr(III) was exchanged, while for a sample from the Itapanhaú River, 7, 10, 10, and 21% was exchanged in experiments using Cr(III) alone and in combination with Cu(II), Ni(II), or Cu(II) + Ni(II), respectively. Times required to reach exchange equilibrium with EDTA were less than 360 min. The influence of competition from Ni(II) and Cu(II) on the availability of complexed Cr(III) was low, demonstrating preference of the ligand sites for Cr(III). This was correlated with sample humification, as confirmed by EPR and (13)C NMR analyses. Exchange efficiency was in the order Cu > Ni > Cr, and the process could be readily described by first order kinetics, with average rate constants of 0.35-0.37 h(-1).

  11. Bonding analyses, formation energies, and vibrational properties of M-R2dtc complexes (M=Ag(I), Ni(II), Cu(II), or Zn(II)).

    PubMed

    Georgieva, I; Trendafilova, N

    2007-12-20

    Detailed theoretical studies based on density functional theory (DFT)/B3LYP calculations of dimethyl- and diethyldithiocarbamate complexes of Ni(II), Cu(II), Zn(II), and Ag(I) are performed to characterize the metal-ligand bonding type as well as the metal-ligand bonding strength depending on the metal and the dialkyl substituent. The metal-ligand interactions in the studied complexes are investigated by means of charge decomposition analysis, energy partitioning analysis (EPA), and natural bond orbital analysis. According to the EPA calculations, the electrostatic attraction is the dominant contribution to the M-S2(R2dtc) (dtc=dithiocarbamate) bonding. The electrostatic and the orbital energies follow the order of the total binding energy, and hence both contributions are responsible for the binding energy order of M(R2dtc)2 complexes. The stability of the M(R2dtc)2 complexes is estimated by means of calculated formation reaction energies in the gas phase and solution, and it decreases in the order Ni(R2dtc)2>Cu(R2dtc)2>Zn(R2dtc)2. Larger formation reaction energies are found for M(Et2dtc)2 than for M(Me2dtc)2 complexes. The calculations predict stabilization of M(II)(R2dtc)2 complexes going from the gas phase to a polar solvent and destabilization of the bidentate AgR2dtc complex in a polar solvent. Gas-phase frequency calculations of all possible bonding types, symmetrical, asymmetrical, and uni- and bidentate, predict one band due to the nu(CS) IR absorption, and therefore the number of the bands in the 1060-920 cm(-1) region could not be used to discern the metal-ligand bonding type. Periodic DFT frequency calculations for Cu(Et2dtc)2 reveal that the splitting observed in the solid-state spectra of the complexes arises from the nonplanar MS4 fragment and intermolecular contacts but not from asymmetrical bonding. The calculations suggest that the important vibrational characteristic that can be used to discern uni- and bidentate bonding is the Raman activity of

  12. Characterization and electrochemical studies of Mn(II), Co(II), Ni(II) and Cu(II) complexes with 2-mercapto-3-substituted-quinazolin-4-one and 1,10-phenanthroline or ethylenediamine as ligands

    NASA Astrophysics Data System (ADS)

    Sawant, V. A.; Gotpagar, S. N.; Yamgar, B. A.; Sawant, S. K.; Kankariya, R. D.; Chavan, S. S.

    2009-04-01

    Some mixed ligand complexes of the type [M(L 1 or L 2)( phen or en)(H 2O)Cl], where M = Mn(II), Co(II), Ni(II) and Cu(II); HL 1 = 2-mercapto-quinazolin-4-one; HL 2 = 2-mercapto-3-phenyl-quinazolin-4-one; phen = 1,10-phenanthroline; en = ethylenediamine have been prepared. All complexes were characterized on the basis of elemental analysis, molar conductance, magnetic susceptibility measurements, IR, UV-vis, ESR and powder X-ray diffraction studies. IR spectra of these complexes reveal that the complex formation occurred through both nitrogen and sulphur atoms. On the basis of electronic spectral data and magnetic susceptibility measurement octahedral geometry has been proposed for the complexes. The ESR spectral data of the Cu(II) complexes showed that the metal-ligand bonds have considerable covalent character. X-ray diffraction studies of Cu(II) complexes are used to elucidate the crystal structure. The electrochemical behaviour of mixed ligand Ni(II) complexes was studied which showed that complexes of phen appear at more positive potential as compared to those for corresponding en complexes.

  13. Characterization and electrochemical studies of Mn(II), Co(II), Ni(II) and Cu(II) complexes with 2-mercapto-3-substituted-quinazolin-4-one and 1,10-phenanthroline or ethylenediamine as ligands.

    PubMed

    Sawant, V A; Gotpagar, S N; Yamgar, B A; Sawant, S K; Kankariya, R D; Chavan, S S

    2009-04-01

    Some mixed ligand complexes of the type [M(L(1) or L(2))(phen or en)(H(2)O)Cl], where M=Mn(II), Co(II), Ni(II) and Cu(II); HL(1)=2-mercapto-quinazolin-4-one; HL(2)=2-mercapto-3-phenyl-quinazolin-4-one; phen=1,10-phenanthroline; en=ethylenediamine have been prepared. All complexes were characterized on the basis of elemental analysis, molar conductance, magnetic susceptibility measurements, IR, UV-vis, ESR and powder X-ray diffraction studies. IR spectra of these complexes reveal that the complex formation occurred through both nitrogen and sulphur atoms. On the basis of electronic spectral data and magnetic susceptibility measurement octahedral geometry has been proposed for the complexes. The ESR spectral data of the Cu(II) complexes showed that the metal-ligand bonds have considerable covalent character. X-ray diffraction studies of Cu(II) complexes are used to elucidate the crystal structure. The electrochemical behaviour of mixed ligand Ni(II) complexes was studied which showed that complexes of phen appear at more positive potential as compared to those for corresponding en complexes.

  14. Ni(II), Pd(II) and Pt(II) complexes of (1H-1,2,4-triazole-3-ylimino)methyl]naphthalene-2-ol. Structural, spectroscopic, biological, cytotoxicity, antioxidant and DNA binding

    NASA Astrophysics Data System (ADS)

    Gaber, M.; El-Ghamry, H. A.; Fathalla, S. K.

    2015-03-01

    Metal complexes of the general formula [ML(H2O)Cl]nH2O; n = 1 for M = Ni and Pt and n = 2 for M = Pd, L = Schiff base (HL) derived from the condensation of 3-amino-1,2,4-triazole and 2-hydroxy-1-naphthaldehyde, were prepared. The synthesized ligand and its metal complexes were characterized on the basis of elemental analyses, spectral and magnetic studies as well as thermal analysis. The IR spectra revealed that the ligand is coordinated to the metal ions in bidentate manner via the N-atom of the azomethine group and the phenolic OH group. Square planar geometry was proposed for Pd(II) and Pt(II) complexes and tetrahedral for Ni(II) complex. The ligand and its metal complexes were screened against the sensitive organisms Escherichia coli as Gram-negative bacteria, Staphylococcus aureus as Gram-positive bacteria, Aspergillus flavus and Candida albicans as fungi. Moreover, the anticancer activity of the ligand and its metal complexes was evaluated in liver carcinoma (HEPG2) cell line. The results obtained indicated that the Schiff base ligand is more effective than its metal complexes towards the tested cell line. Ni(II), Pd(II) and Pt(II) complexes as well as the free Schiff base ligand were tested for their antioxidant activities. The DNA-binding properties of the studied complexes have been investigated by electronic absorption and viscosity measurements.

  15. Ni(II), Pd(II) and Pt(II) complexes of (1H-1,2,4-triazole-3-ylimino)methyl]naphthalene-2-ol. Structural, spectroscopic, biological, cytotoxicity, antioxidant and DNA binding.

    PubMed

    Gaber, M; El-Ghamry, H A; Fathalla, S K

    2015-03-15

    Metal complexes of the general formula [ML(H2O)Cl]nH2O; n=1 for M=Ni and Pt and n=2 for M=Pd, L=Schiff base (HL) derived from the condensation of 3-amino-1,2,4-triazole and 2-hydroxy-1-naphthaldehyde, were prepared. The synthesized ligand and its metal complexes were characterized on the basis of elemental analyses, spectral and magnetic studies as well as thermal analysis. The IR spectra revealed that the ligand is coordinated to the metal ions in bidentate manner via the N-atom of the azomethine group and the phenolic OH group. Square planar geometry was proposed for Pd(II) and Pt(II) complexes and tetrahedral for Ni(II) complex. The ligand and its metal complexes were screened against the sensitive organisms Escherichia coli as Gram-negative bacteria, Staphylococcus aureus as Gram-positive bacteria, Aspergillus flavus and Candida albicans as fungi. Moreover, the anticancer activity of the ligand and its metal complexes was evaluated in liver carcinoma (HEPG2) cell line. The results obtained indicated that the Schiff base ligand is more effective than its metal complexes towards the tested cell line. Ni(II), Pd(II) and Pt(II) complexes as well as the free Schiff base ligand were tested for their antioxidant activities. The DNA-binding properties of the studied complexes have been investigated by electronic absorption and viscosity measurements.

  16. Coordination behavior of tetraaza [N4] ligand towards Co(II), Ni(II), Cu(II), Cu(I) and Pd(II) complexes: Synthesis, spectroscopic characterization and anticancer activity

    NASA Astrophysics Data System (ADS)

    El-Boraey, Hanaa A.

    2012-11-01

    Novel eight Co(II), Ni(II), Cu(II), Cu(I) and Pd(II) complexes with [N4] ligand (L) i.e. 2-amino-N-{2-[(2-aminobenzoyl)amino]ethyl}benzamide have been synthesized and structurally characterized by elemental analysis, spectral, thermal (TG/DTG), magnetic, and molar conductivity measurements. On the basis of IR, mass, electronic and EPR spectral studies an octahedral geometry has been proposed for Co(II), Ni(II) complexes and Cu(II) chloride complex, square-pyramidal for Cu(I) bromide complex. For Cu(II) nitrate complex (6), Pd(II) complex (8) square planar geometry was proposed. The EPR data of Cu(II) complexes in powdered form indicate dx2-y2 ground state of Cu(II) ion. The antitumor activity of the synthesized ligand and some selected metal complexes has been studied. The palladium(II) complex (8) was found to display cytotoxicity (IC50 = 25.6 and 41 μM) against human breast cancer cell line MCF-7 and human hepatocarcinoma HEPG2 cell line.

  17. Determining enediol compounds in tea using surface-assisted laser desorption/ionization mass spectrometry with titanium dioxide nanoparticle matrices.

    PubMed

    Lee, Kun-Hong; Chiang, Cheng-Kang; Lin, Zong-Hong; Chang, Huan-Tsung

    2007-01-01

    We describe the use of titanium dioxide nanoparticles (TiO2 NPs) as selective probes and matrices for the determination of catechins using surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS). The interactions between the enediol compounds and TiO2 NPs were evident by the change in color of the TiO2 NP solution from milky white to orange. Through these interactions, the TiO2 NPs could be used to concentrate enediol compounds, including catechins and ascorbic acid. The limits of detection (LODs) for three catechins--catechin, (-)-epigallocatechin, and (-)-epigallocatechin gallate--at a signal-to-noise ratio of 3 were 0.45, 1.85 and 0.65 microM, respectively. The TiO2 NP matrices provide a number of advantages over conventional organic matrices (e.g. 2',4',6'-trihydroxyacetophenone), including ease of sample preparation, less background noise in the low-mass region, and high repeatability. The applicability of this method was confirmed through the high reproducibility of the determination of the two catechins in tea samples that had not been subjected to any sample preparation procedures (shot-to-shot variation: <10%).

  18. Structural studies on some dithiophosphonato complexes of Ni(II), Cd(II), Hg(II) and theoretical studies on a dithiophosphonato Ni(II) complex using density functional theory

    NASA Astrophysics Data System (ADS)

    Sağlam, Ertuğrul Gazi; Ebinç, Ahmet; Zeyrek, Celal Tuğrul; Ünver, Hüseyin; Hökelek, Tuncer

    2015-11-01

    In this study, three dithiophosphonic acid complexes, namely, trans-bis-[O-3-methylbutyl (4-methoxyphenyl)dithiophosphonato]nickel(II), Ni(L)2; bis-{bis-[O-3-phenylpropyl (4-methoxyphenyl)dithiophosphonato]cadmium(II)}, [Cd(L)2]2 and bis-{bis-[O-3-methylbutyl (4-methoxyphenyl)dithiophosphonato]mercury(II)}, [Hg(L)2]2 were prepared. The compounds were characterized by elemental analysis; MS; FTIR and Raman spectroscopies and were also investigated by 1H-, 13C- and 31P- NMR. The Ni(L)2 complex was elucidated by X-ray crystallography, molecular characterization and density functional modelling studies. The molecular structure obtained from X-ray single-crystal analysis of the Ni(L)2 complex in the ground state has been compared using density functional theory (DFT), B3LYP functional with 6-311G(d,p) basis set. In addition to the optimized geometrical structures, atomic charges and nonlinear optical (NLO) effects have been investigated by using DFT. The experimental (spectroscopic) and calculated vibrational frequencies (using DFT) of the Ni(L)2 have been compared. There exists a good correlation between experimental and theoretical data for the Ni(L)2 complex.

  19. Synthesis, spectral and theoretical studies of Ni(II), Pd(II) and Pt(II) complexes of 5-mercapto-1,2,4-triazole-3-imine-2'-hydroxynaphthaline.

    PubMed

    Gaber, Mohamed; El-Ghamry, Hoda; Atlam, Faten; Fathalla, Shaimaa

    2015-02-25

    Ni(II), Pd(II) and Pt(II) complexes of 5-mercapto-1,2,4-triazole-3-imine-2'-hydroxynaphthaline have been isolated and characterized by elemental analysis, IR, (1)H NMR, EI-mass, UV-vis, molar conductance, magnetic moment measurements and thermogravimetric analysis. The molar conductance values indicated that the complexes are non-electrolytes. The magnetic moment values of the complexes displayed diamagnetic behavior for Pd(II) and Pt(II) complexes and tetrahedral geometrical structure for Ni(II) complex. From the bioinorganic applications point of view, the interaction of the ligand and its metal complexes with CT-DNA was investigated using absorption and viscosity titration techniques. The Schiff-base ligand and its metal complexes have also been screened for their antimicrobial and antitumor activities. Also, theoretical investigation of molecular and electronic structures of the studied ligand and its metal complexes has been carried out. Molecular orbital calculations were performed using DFT (density functional theory) at B3LYP level with standard 6-31G(d,p) and LANL2DZ basis sets to access reliable results to the experimental values. The calculations were performed to obtain the optimized molecular geometry, charge density distribution, extent of distortion from regular geometry, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), Mulliken atomic charges, reactivity index (ΔE), dipole moment (D), global hardness (η), softness (σ), electrophilicity index (ω), chemical potential and Mulliken electronegativity (χ).

  20. Synthesis, spectral and theoretical studies of Ni(II), Pd(II) and Pt(II) complexes of 5-mercapto-1,2,4-triazole-3-imine-2‧-hydroxynaphyhaline

    NASA Astrophysics Data System (ADS)

    Gaber, Mohamed; El-Ghamry, Hoda; Atlam, Faten; Fathalla, Shaimaa

    2015-02-01

    Ni(II), Pd(II) and Pt(II) complexes of 5-mercapto-1,2,4-triazole-3-imine-2‧-hydroxynaphthaline have been isolated and characterized by elemental analysis, IR, 1H NMR, EI-mass, UV-vis, molar conductance, magnetic moment measurements and thermogravimetric analysis. The molar conductance values indicated that the complexes are non-electrolytes. The magnetic moment values of the complexes displayed diamagnetic behavior for Pd(II) and Pt(II) complexes and tetrahedral geometrical structure for Ni(II) complex. From the bioinorganic applications point of view, the interaction of the ligand and its metal complexes with CT-DNA was investigated using absorption and viscosity titration techniques. The Schiff-base ligand and its metal complexes have also been screened for their antimicrobial and antitumor activities. Also, theoretical investigation of molecular and electronic structures of the studied ligand and its metal complexes has been carried out. Molecular orbital calculations were performed using DFT (density functional theory) at B3LYP level with standard 6-31G(d,p) and LANL2DZ basis sets to access reliable results to the experimental values. The calculations were performed to obtain the optimized molecular geometry, charge density distribution, extent of distortion from regular geometry, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), Mulliken atomic charges, reactivity index (ΔE), dipole moment (D), global hardness (η), softness (σ), electrophilicity index (ω), chemical potential and Mulliken electronegativity (χ).

  1. Spectroscopic evaluation for VO(II), Ni(II), Pd(II) and Cu(II) complexes derived from thiosemicarbazide: A special emphasis on EPR study and DNA cleavage

    NASA Astrophysics Data System (ADS)

    El-Metwally, Nashwa M.; Al-Hazmi, Gamil A. A.

    2013-04-01

    Some thiosemicarbazide complexes were prepared and deliberately investigated by all allowed tools. The ligand coordinates as a mono negative bidentate towards VO(II) and Ni(II) as well as a neutral bidentate towards Pd(II) and Cu(II) ions. Electronic spectral data beside the magnetic measurements facilitate the structural geometry proposal. EPR spectra of Cu(II) and VO(II) complexes were recorded in their solid state. Spin Hamiltonian parameters and molecular orbital coefficient for Cu(II) and VO(II) complexes were calculated and supporting the octahedral geometry of Cu(II) complex and a square pyramidal for VO(II) one. The biological activity investigation was studied by the use of all prepared compounds. The VO(II) and Cu(II) complexes display the susceptible biotoxicity against a gram-positive bacterium. Also, Cu(II) complex displays the same toxicity against gram-negative bacteria used. The effect of all compounds on DNA were photographed. A successive degradation for the DNA target was observed with Pd(II) and Ni(II) complexes beside their original ligand.

  2. Synthesis, spectral, and thermal characterizations of Ni(II) and Cu(II) β-diketone complexes with thenoyltrifluoroacetone ligand

    NASA Astrophysics Data System (ADS)

    Chen, Zhimin; Wu, Yiqun; Huang, Fuxin; Gu, Donghong; Gan, Fuxi

    2007-04-01

    Two kinds of nickel(II) and copper(II) β-diketone complexes derived from thenoyltrifluoroacetone ligand with blue-violet light absorption were synthesized by reacting free ligand and different metal(II) ions in sodium methoxide solution. Their structures were postulated based on elemental analysis, ESI-MS, FT-IR spectra and UV-vis electronic absorption spectra. Smooth films on K9 glass substrates were prepared using the spin-coating method. Their solubility in organic solvents, absorption properties of thin film and thermal stability of these complexes were evaluated.

  3. Synthesis, spectral, and thermal characterizations of Ni(II) and Cu(II) beta-diketone complexes with thenoyltrifluoroacetone ligand.

    PubMed

    Chen, Zhimin; Wu, Yiqun; Huang, Fuxin; Gu, Donghong; Gan, Fuxi

    2007-04-01

    Two kinds of nickel(II) and copper(II) beta-diketone complexes derived from thenoyltrifluoroacetone ligand with blue-violet light absorption were synthesized by reacting free ligand and different metal(II) ions in sodium methoxide solution. Their structures were postulated based on elemental analysis, ESI-MS, FT-IR spectra and UV-vis electronic absorption spectra. Smooth films on K9 glass substrates were prepared using the spin-coating method. Their solubility in organic solvents, absorption properties of thin film and thermal stability of these complexes were evaluated.

  4. A rapid synthesis of 2-substituted 1,2,3- triazole-1-oxide derivative starting from 4-(methyl)isonitrosoacetophenone and its Ni(II) complex: Characterization, DNA binding and cleavage properties

    NASA Astrophysics Data System (ADS)

    Gup, Ramazan; Erer, Oktay; Dilek, Nefise

    2017-02-01

    An efficient route, not including any metal salt as a catalyst, for the synthesis of a new 2-substituted 1,2,3- triazole-1-oxide is reported in this paper. The title compound has been synthesized via reacting 4-(methyl)isonitrosoacetophenone with hydrazine hydrate and dipyridyl ketone in high yield under mild reaction condition. The structure of the new 1,2,3-triazole-1-oxide has been characterized via single crystal X-ray and spectral studies. The 1:1 ratio reaction of the 1,2,3-triazole 1-oxide ligand with nickel(II) chloride gives the mononuclear complex [Ni(L)(DMF)(Cl)2] which is hexa-coordinated within an octahedral geometry. Characterization of the 1,2,3-triazole compound and its Ni(II) complex with FTIR, 1H and 13C NMR, UV-vis, TGA and elemental analysis also confirm the proposed structures for the compounds. The interactions of the compounds with Calf thymus DNA (CT-DNA) have been investigated via UV-visible spectra and viscosity measurements. The results suggested that both ligand and Ni(II) complex bind to DNA in electrostatic interaction and/or groove binding with a slight partial intercalation. DNA cleavage experiments have been also investigated by agarose gel electrophoresis in the presence and absence of an oxidative agent (H2O2). Both 1,2,3-triazole 1-oxide ligand and nickel(II) complex show nuclease activity, which significantly depends on concentrations of the compounds, both in the presence and absence of an oxidative agent. DNA binding and cleavage affinities of the Ni(II) complex is stronger than that of the 1,2,3-triazole 1-oxide ligand.

  5. Synthesis, DNA-binding, DNA-photonuclease profiling and antimicrobial activity of novel tetra-aza macrocyclic Ni(II), Co(II) and Cu(II) complexes constrained by thiadiazole

    NASA Astrophysics Data System (ADS)

    Vinay Kumar, B.; Bhojya Naik, H. S.; Girija, D.; Sharath, N.; Pradeepa, S. M.; Joy Hoskeri, H.; Prabhakara, M. C.

    A new tetra-aza macrocyclic ligand, L (C24H16N12O2S4) and its complexes of type, [MLCl2] and [CuL]Cl2 (where M = Ni(II), Co(II); L = N,N'-(benzene-1,3-diyldi-1,3,4-thiadiazole-5,2-diyl)bis{2-[(5-benzene-1,3-diyl-1,3,4-thiadiazol-2-yl)amino]acetamide}) were synthesized and characterized by the spectral and analytical techniques. An octahedral geometry has been proposed for Ni(II) and Co(II) complexes while Cu(II) complex exhibit a square planar geometry. All the synthesized metal complexes were screened for their in vitro antimicrobial activity against selected species of pathogenic bacteria and fungi. The binding property of the complexes with CT-DNA was studied by absorption spectral analysis, followed by viscosity measurement and thermal denaturation studies. The photo induced cleavage studies revealed that the complexes possess photonuclease property against pUC19 DNA under UV-visible irradiation.

  6. Synthesis, spectroscopic characterization, molecular modeling and potentiometric studies of Co(II), Ni(II), Cu(II) and Zn(II) complexes with 1,1-diaminobutane-Schiff base

    NASA Astrophysics Data System (ADS)

    Alaghaz, Abdel-Nasser M. A.

    2014-08-01

    Complexes of cobalt(II), nickel(II), copper(II) and zinc(II) of general composition [M(L)(H2O)2]·2H2O have been synthesized [L = N,N";-bis(2-hydroxybenzylidene)-1,1-diaminobutane]. The elemental analysis, molar conductance measurements, magnetic susceptibility measurements, mass, IR, UV, NMR, SEM, EDX, thermal and EPR spectral studies of the compounds led to the conclusion that the ligand acts as a tetradentate manner. The molar conductance of the complexes in fresh solution of DMSO lies in the range of 7.46-9.13 Ω-1 cm2 mol-1 indicating their non-electrolytic behavior. On the basis of analytical and spectroscopic techniques, octahedral geometry of the complexes was proposed. The Schiff base acts as tetradentate ligand, coordinated through deprotonated phenolic oxygen and azomethine nitrogen atoms. The ligand field parameters were calculated for Co(II), Ni(II) and Cu(II) complexes and their values were found in the range reported for a octahedral structure. The molecular parameters of the ligand and its Co(II), Ni(II), Cu(II) and Zn(II) complexes have been calculated. Protonation constants of Schiff base and stability constants of their binary metal complexes have been determined potentiometrically in 50% DMSO-water media at 25 °C and ionic strength 0.10 M sodium perchlorate.

  7. Synthesis, spectral characterization and microbiological studies of Co(II), Ni(II) and Cu(II) complexes with some novel 20-membered macrocyclic hydrazino-1,2,4-triazole Schiff bases.

    PubMed

    Avaji, Prakash Gouda; Patil, Sangamesh Amarappa

    2009-02-01

    A series of Co(II), Ni(II) and Cu(II) complexes have been synthesized by template condensation of 2,6-diformyl-4-methylphenol and 3-substituted-4-amino-5-hydrazino-1,2,4-triazole with CoCl(2).6H(2)O, NiCl(2).6H(2)O and CuCl(2).2H(2)O chlorides in 2 + 2+2 molar ratio in ethanol. These complexes were characterized by elemental analyses, magnetic susceptibility, molar conductance, spectral (IR, Uv-Vis, ESR, (1)H NMR and FAB-mass), thermal, fluorescence and solid-state DC electrical conductivity studies. The observed molar conductance values indicate that they are non-electrolytes. Elemental analyses suggest the complexes to have 2:1 stoichiometry of the type [M(2)LX(2)] 2H(2)O (M = Co(II) & Cu(II), L = L(I)-L(IV) and X = Cl) and [Ni(2)LX(2)2H(2)O] 2H(2)O. The solid state DC electrical conductivity showed that the complexes were semiconducting. All the Schiff bases and their Co(II), Ni(II) and Cu(II) complexes were evaluated for their microbiological properties and some compounds showed promising results.

  8. Synthesis, characterization and biological activity of some new VO(IV), Co(II), Ni(II), Cu(II) and Zn(II) complexes of chromone based NNO Schiff base derived from 2-aminothiazole

    NASA Astrophysics Data System (ADS)

    Kalanithi, M.; Kodimunthiri, D.; Rajarajan, M.; Tharmaraj, P.

    2011-11-01

    Coordination compounds of VO(IV), Co(II), Ni(II), Cu(II) and Zn(II) with the Schiff base obtained through the condensation of 2-aminothiazole with 3-formyl chromone were synthesized. The compounds were characterized by 1H, 13C NMR, UV-Vis, IR, Mass, EPR, molar conductance and magnetic susceptibility measurements. The Cu(II) complex possesses tetrahedrally distorted square planar geometry whereas Co(II), Ni(II), and Zn(II) show distorted tetrahedral geometry. The VO(IV) complex shows square pyramidal geometry. The cyclic voltammogram of Cu (II) complex showed a well defined redox couple Cu(II)/Cu(I) with quasireversible nature. The antimicrobial activity against the species Pseudomonas aeruginosa, Escherichia coli, Staphylococcus aureus, Bacillus subtilis, Candida albigans and Aspergillus niger was screened and compared to the activity of the ligand. Emission spectrum was recorded for the ligand and the metal(II) complexes. The second harmonic generation (SHG) efficiency was measured and found to have one fourth of the activity of urea. The SEM image of the copper(II) complex implies that the size of the particles is 2 μm.

  9. Synthesis, spectroscopic, antimicrobial and DNA cleavage studies of new Co(II), Ni(II), Cu(II), Cd(II), Zn(II) and Hg(II) complexes with naphthofuran-2-carbohydrazide Schiff base

    NASA Astrophysics Data System (ADS)

    Halli, Madappa B.; Sumathi, R. B.

    2012-08-01

    A series of Co(II), Ni(II), Cu(II), Cd(II), Zn(II) and Hg(II) complexes have been synthesized with newly synthesized Schiff base derived from naphthofuran-2-carbohydrazide and cinnamaldehyde. The elemental analyses of the complexes are confined to the stoichiometry of the type MLCl2 [M = Co(II) and Cu(II)], ML2Cl2 [M = Ni(II), Cd(II), Zn(II) and Hg(II)] respectively, where L is Schiff base ligand. Structures have been proposed from elemental analyses, IR, electronic, mass, 1H NMR, ESR spectral data, magnetic, and thermal studies. The measured low molar conductance values in DMF indicate that the complexes are non-electrolytes. Spectroscopic studies suggest coordination occurs through azomethine nitrogen and carbonyl oxygen of the ligand with the metal ions. The Schiff base and its complexes have been screened for their antibacterial (Escherichia coli, Staphylococcus aureus, Bacillus subtilis and Salmonella typhi) and antifungal (Aspergillus niger, Aspergillus flavus, Cladosporium and Candida albicans) activities by minimum inhibitory concentration (MIC) method. The DNA cleavage studies by agarose gel electrophoresis method was studied for all the complexes.

  10. Thermodynamic Modeling of Poorly Complexing Metals in Concentrated Electrolyte Solutions: An X-Ray Absorption and UV-Vis Spectroscopic Study of Ni(II) in the NiCl2-MgCl2-H2O System

    PubMed Central

    Zhang, Ning; Brugger, Joël; Etschmann, Barbara; Ngothai, Yung; Zeng, Dewen

    2015-01-01

    Knowledge of the structure and speciation of aqueous Ni(II)-chloride complexes is important for understanding Ni behavior in hydrometallurgical extraction. The effect of concentration on the first-shell structure of Ni(II) in aqueous NiCl2 and NiCl2-MgCl2 solutions was investigated by Ni K edge X-ray absorption (XAS) and UV-Vis spectroscopy at ambient conditions. Both techniques show that no large structural change (e.g., transition from octahedral to tetrahedral-like configuration) occurs. Both methods confirm that the Ni(II) aqua ion (with six coordinated water molecules at RNi-O = 2.07(2) Å) is the dominant species over the whole NiCl2 concentration range. However, XANES, EXAFS and UV-Vis data show subtle changes at high salinity (> 2 mol∙kg-1 NiCl2), which are consistent with the formation of small amounts of the NiCl+ complex (up to 0.44(23) Cl at a Ni-Cl distance of 2.35(2) Å in 5.05 mol∙kg-1 NiCl2) in the pure NiCl2 solutions. At high Cl:Ni ratio in the NiCl2-MgCl2-H2O solutions, small amounts of [NiCl2]0 are also present. We developed a speciation-based mixed-solvent electrolyte (MSE) model to describe activity-composition relationships in NiCl2-MgCl2-H2O solutions, and at the same time predict Ni(II) speciation that is consistent with our XAS and UV-Vis data and with existing literature data up to the solubility limit, resolving a long-standing uncertainty about the role of chloride complexing in this system. PMID:25885410

  11. Thermodynamic modeling of poorly complexing metals in concentrated electrolyte solutions: an X-ray absorption and UV-Vis spectroscopic study of Ni(II) in the NiCl2-MgCl2-H2O system.

    PubMed

    Zhang, Ning; Brugger, Joël; Etschmann, Barbara; Ngothai, Yung; Zeng, Dewen

    2015-01-01

    Knowledge of the structure and speciation of aqueous Ni(II)-chloride complexes is important for understanding Ni behavior in hydrometallurgical extraction. The effect of concentration on the first-shell structure of Ni(II) in aqueous NiCl2 and NiCl2-MgCl2 solutions was investigated by Ni K edge X-ray absorption (XAS) and UV-Vis spectroscopy at ambient conditions. Both techniques show that no large structural change (e.g., transition from octahedral to tetrahedral-like configuration) occurs. Both methods confirm that the Ni(II) aqua ion (with six coordinated water molecules at RNi-O = 2.07(2) Å) is the dominant species over the whole NiCl2 concentration range. However, XANES, EXAFS and UV-Vis data show subtle changes at high salinity (> 2 mol∙kg(-1) NiCl2), which are consistent with the formation of small amounts of the NiCl+ complex (up to 0.44(23) Cl at a Ni-Cl distance of 2.35(2) Å in 5.05 mol∙kg(-1) NiCl2) in the pure NiCl2 solutions. At high Cl:Ni ratio in the NiCl2-MgCl2-H2O solutions, small amounts of [NiCl2]0 are also present. We developed a speciation-based mixed-solvent electrolyte (MSE) model to describe activity-composition relationships in NiCl2-MgCl2-H2O solutions, and at the same time predict Ni(II) speciation that is consistent with our XAS and UV-Vis data and with existing literature data up to the solubility limit, resolving a long-standing uncertainty about the role of chloride complexing in this system.

  12. Synthesis, structural characterization, thermal and electrochemical studies of the N,N'-bis[(3,4-dichlorophenyl)methylidene]cyclohexane-1,4-diamine and its Cu(II), Co(II) and Ni(II) metal complexes.

    PubMed

    Dolaz, Mustafa; McKee, Vickie; Gölcü, Ayşegül; Tümer, Mehmet

    2009-01-01

    In this study, N,N'-bis[(3,4-dichlorophenyl)methylidene]cyclohexane-1,4-diamine (L) and its Cu(II), Co(II) and Ni(II) complexes were prepared and characterized by the analytical and spectroscopic methods. The analytical data show the composition of the metal complex to be [M(2)L(Cl)(4)(H(2)O)(2)], where L is the Schiff base ligand. The conductance data indicate that all the complexes are non-electrolytes. The compound (L) behaves as a monodentate ligand. But, obtained complexes have binuclear nature. The electrochemical properties of the metal complexes are dependent on reversible, irreversible and quasi-reversible redox waves in the anodic and cathodic regions due to oxidation and reduction of the metal ions. The single crystal of the ligand (L) was obtained from CH(3)CN solution. Space group and crystal system of the ligand are P2(1)/C and monoclinic, respectively.

  13. Synthesis, spectral and thermal studies of Co(II), Ni(II) and Cu(II) complexes 1-(4,6-dimethyl-pyrimidin-2-ylazo)-naphthalen-2-ol.

    PubMed

    Gaber, M; Ayad, M M; El-Sayed, Y S Y

    2005-11-01

    The electronic absorption spectra of 1-(4,6-dimethyl-pyrimidin-2-ylazo)-naphthalen-2-ol is studied in organic solvents of different polarity as well as in buffer solutions of varying pH values at different temperatures and different ratios of methanol. The probable structure of the azodye has been assigned on the basis of spectral studies (IR and (1)H NMR). The effect of Co(II), Ni(II) and Cu(II) ions on the emission spectrum of the free azodye is also assigned. The stoichiometry of the metal complexes is determined spectrophotometrically and conductometrically. Novel complexes of Co(II), Ni(II) and Cu(II) with the pyrimidine azodye have been synthesized and characterized on the basis of elemental analyses, molar conductance, magnetic susceptibility measurements, IR, electronic as well as ESR spectral studies The thermal decomposition of the metal complexes is studied by TGA and DTA techniques. The kinetic parameters like activation energy, pre-exponential factor and entropy of activation are estimated.

  14. Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) new complexes of 5-aminosalicylic acid: Spectroscopic, thermal characterization and biological activity studies

    NASA Astrophysics Data System (ADS)

    Soliman, Madiha H.; Mohamed, Gehad G.

    2013-04-01

    The complexing behavior of mesalazine (5-aminosalicylic acid; 5-ASA) towards the transition metal ions namely, Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) have been examined by elemental analyses, magnetic measurements, electronic, IR and 1H NMR. Thermal properties and decomposition kinetics of all complexes are investigated. The interpretation, mathematical analyses and evaluation of kinetic parameters of all thermal decomposition stages have been evaluated using Coats-Redfern equation. The free ligand and its metal complexes have been tested in vitro against Aspergillus fumigatus and Candida albicans fungi and Pseudomonas aeruginosa, Escherichia coli, Bacillis subtilies and Staphylococcus aureus bacteria in order to assess their antimicrobial potential. The results indicate that the metal complexes are also found to have more antimicrobial activity than the parent 5-ASA drug.

  15. Synthesis and characterization of binary and ternary complexes of Co(II), Ni(II), Cu(II) and Zn(II) ions based on 4-aminotoluene-3-sulfonic acid

    NASA Astrophysics Data System (ADS)

    Faheim, Abeer A.; Abdou, Safaa N.; Abd El-Wahab, Zeinab H.

    2013-03-01

    Salicylidene (4-aminotoluene-3-sulfonic acid) Schiff base ligand H2L, and its binary and ternary Co(II), Ni(II), Cu(II) and Zn(II) complexes using 8-hydroxyquinoline (8-HOqu) and 2-aminopyridine (2-Ampy) as secondary ligands have been synthesised and characterized via elemental analysis, spectral data (IR, 1H NMR, mass and solid reflectance), molar conductance, magnetic moment, TG-DSC measurements and XRPD analysis. Correlation of all spectroscopic data suggest that H2L ligand acts as monoanionic terdentate ligand with ONO sites coordinating to the metal ions via deprotonated phenolic-O, azomethine-N and sulfonate-O while 2-Ampy behaves as a neutral monodentate ligand via amino group-N and 8-HOqu behaves as a monoanionic bidentate ligand through the ring-N and deprotonated phenolic-O. The thermal behavior of these complexes shows that the coordinated water molecules were eliminated from the complexes at relatively higher temperatures than the hydrated water and there are two routes in removal of coordinated water molecules. All complexes have mononuclear structure and the tetrahedral, square planar or an octahedral geometry have been proposed. The ligand and its complexes have been screened for their antimicrobial activity against Staphylococcus aureus, Bacillus subtilis, Escherichia coli, Salmonella typhimurium, Candida albicans and Aspergillus fumigatus. Among the synthesised compounds, the binary and ternary Ni(II) complexes, (2, 8 and 10) and ternary Zn(II) complex, (12) were found to be very effective against Candida albicans and Bacillus subtilis than all other complexes with MICs of 2 and 8 μg/mL, respectively.

  16. Synthesis and characterization of binary and ternary complexes of Co(II), Ni(II), Cu(II) and Zn(II) ions based on 4-aminotoluene-3-sulfonic acid.

    PubMed

    Faheim, Abeer A; Abdou, Safaa N; Abd El-Wahab, Zeinab H

    2013-03-15

    Salicylidene (4-aminotoluene-3-sulfonic acid) Schiff base ligand H(2)L, and its binary and ternary Co(II), Ni(II), Cu(II) and Zn(II) complexes using 8-hydroxyquinoline (8-HOqu) and 2-aminopyridine (2-Ampy) as secondary ligands have been synthesised and characterized via elemental analysis, spectral data (IR, (1)H NMR, mass and solid reflectance), molar conductance, magnetic moment, TG-DSC measurements and XRPD analysis. Correlation of all spectroscopic data suggest that H(2)L ligand acts as monoanionic terdentate ligand with ONO sites coordinating to the metal ions via deprotonated phenolic-O, azomethine-N and sulfonate-O while 2-Ampy behaves as a neutral monodentate ligand via amino group-N and 8-HOqu behaves as a monoanionic bidentate ligand through the ring-N and deprotonated phenolic-O. The thermal behavior of these complexes shows that the coordinated water molecules were eliminated from the complexes at relatively higher temperatures than the hydrated water and there are two routes in removal of coordinated water molecules. All complexes have mononuclear structure and the tetrahedral, square planar or an octahedral geometry have been proposed. The ligand and its complexes have been screened for their antimicrobial activity against Staphylococcus aureus, Bacillus subtilis, Escherichia coli, Salmonella typhimurium, Candida albicans and Aspergillus fumigatus. Among the synthesised compounds, the binary and ternary Ni(II) complexes, (2, 8 and 10) and ternary Zn(II) complex, (12) were found to be very effective against Candida albicans and Bacillus subtilis than all other complexes with MICs of 2 and 8 μg/mL, respectively.

  17. Characterization of Ni(II) complexes of Schiff bases of amino acids and (S)-N-(2-benzoylphenyl)-1-benzylpyrrolidine-2-carboxamide using ion trap and QqTOF electrospray ionization tandem mass spectrometry.

    PubMed

    Jirásko, Robert; Holcapek, Michal; Kolárová, Lenka; Nádvorník, Milan; Popkov, Alexander

    2008-09-01

    This work demonstrates the application of electrospray ionization mass spectrometry (ESI-MS) using two different mass analyzers, ion trap and hybrid quadrupole time-of-flight (QqTOF) mass analyzer, for the structural characterization of Ni(II) complexes of Schiff bases of (S)-N-(2-benzoylphenyl)-1-benzylpyrrolidine-2-carboxamide with different amino acids. ESI enables the determination of molecular weight on the basis of rather simple positive-ion ESI mass spectra containing only protonated molecules and adducts with sodium or potassium ions. Fragmentation patterns are characterized by tandem mass spectrometric experiments, where both tandem mass analyzers provide complementary information. QqTOF data are used for the determination of elemental composition of individual ions due to mass accuracies always better than 3 ppm with the external calibration, while multistage tandem mass spectra obtained by the ion trap are suitable for studying the fragmentation paths. The novel aspect of our approach is the combination of mass accuracies and relative abundances of all isotopic peaks in isotopic clusters providing more powerful data for the structural characterization of organometallic compounds containing polyisotopic elements. The benefit of relative and absolute mean mass accuracies is demonstrated on the example of studied Ni(II) complexes.

  18. Spectroscopic and thermal degradation behavior of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) complexes with thiopental sodium anesthesia drug

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.

    2013-04-01

    A new series of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) complexes have been synthesized with thiopental sodium anesthesia drug. The elemental analyses of the complexes are confined to stoichiometry of the formulas [M(TPL)3]ṡnH2O (M = Cr(III) or Fe(III); n = 6 or 5), [M(TPL)2(H2O)2]ṡnH2O (M = Mn(II), Co(II) or Ni(II); n = 0 or 4), and [M(TPL)2] (M = Cu(II) or Zn(II); n = 2 or 0) respectively, where TPL is thiopental chelating agent. Structures have been discussed and suggested upon elemental analyses, infrared, Raman, electronic, electron spin resonance, 1H NMR spectral data and magnetic studies. The X-ray powder diffraction (XRD) was performed of metal complexes. The XRD patterns indicate crystalline nature for the complexes. The measured low molar conductance values in dimethylsulfoxide indicate that the complexes are non-electrolyte nature. Spectroscopic discussion refer that coordination take place through three types: Cdbnd N (pyrimidine moiety) nitrogen and C2sbnd S (2-thiolate group) for Cr(III), Mn(II) and Fe(III), C6dbnd O (amido group) oxygen and C2sbnd S (2-thiolate group) for Co(II) and Ni(II), and Cu(II) and Zn(II) ions coordinated via Cdbnd N (pyrimidine moiety) nitrogen, C2dbnd S (2-thiolate group) and C6dbnd O (amido group) oxygen, respectively. The thermal behavior (TG/DTG/DTA) of the complexes was studied and kinetic parameters were determined by Horowitz-Metzger and Coats-Redfern methods. The thiopental and its complexes have been screened for their antimicrobial (G+ and G-) bacteria (Escherichia coli, Staphylococcus aureus, Bacillus subtilis and Pseudomonas aeruginosa) and fungi (Aspergillus flavus and Candida albicans) activities by minimum inhibitory concentration (MIC) method.

  19. Preparation, characterization and biological activity of Fe(III), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and UO 2(II) complexes of new cyclodiphosph(V)azane of sulfaguanidine

    NASA Astrophysics Data System (ADS)

    Sharaby, Carmen M.

    2005-11-01

    Novel hexachlorocyclodiphosph(V)azane of sulfaguanidine, H 4L, l,3-[ N'-amidino-sulfanilamide]-2,2,2,4,4,4-hexachlorocyclodiphosph(V)azane was prepared and its coordination behaviour towards the transition metal ions Fe(III), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and UO 2(II) was studied. The structures of the isolated products are proposed based on elemental analyses, IR, UV-vis, 1H NMR, mass spectra, reflectance, magnetic susceptibility measurements and thermogravimetric analysis (TGA). The hyperfine interactions in the isolated complex compounds were studied using 14.4 keV γ-ray from radioactive 57Co (Mössbauer spectroscopy). The data show that the ligand are coordinated to the metal ions via the sulfonamide O and deprotonated NH atoms in an octahedral manner. The H 4L ligand forms complexes of the general formulae [(MX z) 2(H 2L)H 2O) n] and [(FeSO 4) 2 (H 4L) (H 2O) 4], where X = NO 3 in case of UO 2(II) and Cl in case of Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II). The molar conductance data show that the complexes are non-electrolytes. The thermal behaviour of the complexes was studied and different thermodynamic parameters were calculated using Coats-Redfern method. Most of the prepared complexes showed high bactericidal activity and some of the complexes show more activity compared with the ligand and standards.

  20. NiII, CuII and ZnII complexes with a sterically hindered scorpionate ligand (TpmsPh) and catalytic application in the diasteroselective nitroaldol (Henry) reaction.

    PubMed

    Rocha, Bruno G M; Mac Leod, Tatiana C O; Guedes da Silva, M Fátima C; Luzyanin, Konstantin V; Martins, Luísa M D R S; Pombeiro, Armando J L

    2014-10-28

    The Ni(II) and Zn(II) complexes [MCl(Tpms(Ph))] (Tpms(Ph) = SO3C(pz(Ph))3, pz = pyrazolyl; M = Ni 2 or Zn 3) and the Cu(II) complex [CuCl(Tpms(Ph))(H2O)] (4) have been prepared by treatment of the lithium salt of the sterically demanding and coordination flexible tris(3-phenyl-1-pyrazolyl)methanesulfonate (Tpms(Ph))(-) (1) with the respective metal chlorides. The (Tpms(Ph))(-) ligand shows the N3 or N2O coordination modes in 2 and 3 or in 4, respectively. Upon reaction of 2 and 3 with Ag(CF3SO3) in acetonitrile the complexes [M(Tpms(Ph))(MeCN)](CF3SO3) (M = Ni 5 or Zn 6, respectively) were formed. The compounds were obtained in good yields and characterized by analytic and spectral (IR, (1)H and (13)C{(1)H} NMR, ESI-MS) data, density functional theory (DFT) methods and {for 4 and [(n)Bu4N](Tpms(Ph)) (7), the latter obtained upon Li(+) replacement by [(n)Bu4N](+) in Li(Tpms(Ph))} by single crystal X-ray diffraction analysis. The Zn(II) and Cu(II) complexes (3 and 4, respectively) act as efficient catalyst precursors for the diastereoselective nitroaldol reaction of benzaldehydes and nitroethane to the corresponding β-nitroalkanols (up to 99% yield, at room temperature) with diastereoselectivity towards the formation of the anti isomer, whereas the Ni(II) complex 2 only shows a modest catalytic activity.

  1. Theoretical and experimental studies of two Co(II) and Ni(II) coordination complex with N,O donor 2-chloro-6-{[(4-hydroxy-3-methoxyphenyl)methylidene]amino}-4 nitrophenol ligand

    NASA Astrophysics Data System (ADS)

    Kusmariya, Brajendra S.; Tiwari, Sandeep; Tiwari, Anjali; Mishra, A. P.; Naikoo, Gowhar Ahmad; Pandit, Umar J.

    2016-07-01

    Here we report two mononuclear Co(II) and Ni(II) complexes of general formula [M(L)2(H2O)].2H2O; {M = CoII & NiII} derived from bidentate 2-chloro-6-{[(4-hydroxy-3-methoxyphenyl)methylidene]amino}-4 nitrophenol ligand (HL). These compounds were characterized by elemental analysis, spectral (FT-IR, electronic and 1H-NMR), molar conductance, thermal, PXRD, SEM and electrochemical studies. Distorted octahedral geometry was proposed around the metal center with ligand (HL). The PXRD and SEM analysis shows the crystalline nature of complexes. The broadening of diffraction peaks were explained in terms of domain size and the lattice strain according to Scherrer and Williamson-Hall method. TG of the synthesized complexes illustrates their general decomposition pattern and thermal stability. The kinetic and thermodynamic parameters viz. activation energy (E∗), pre-exponential factor (Z), entropy of activation (ΔS∗), enthalpy of activation (ΔH∗) and free energy of activation (ΔG∗) of degradation process were also evaluated using Coats-Redfern (C-R), Piloyan-Novikova (P-N) and Horowitz-Metzger (H-M) methods for both complexes assuming first order degradation. The optical band gap values of complexes were found to be in good agreement with calculated HOMO-LUMO energy gap (ΔE) and lie in semiconducting range. The cyclic voltammetric studies of synthesized compounds were carried out in order to examine their electrochemical behavior. In addition theoretical calculations by means of DFT at B3LYP level were incorporated to support the experimental findings.

  2. Synthesis, characterization, and antioxidant/cytotoxic activity of new chromone Schiff base nano-complexes of Zn(II), Cu(II), Ni(II) and Co(II)

    NASA Astrophysics Data System (ADS)

    Saif, M.; El-Shafiy, Hoda F.; Mashaly, Mahmoud M.; Eid, Mohamed F.; Nabeel, A. I.; Fouad, R.

    2016-08-01

    A chromone Schiff base complexes of Zn(II) (1), Cu(II) (2), Ni(II) (3) and Co(II) (4) were successfully prepared in nano domain with crystalline or amorphous structures. The spectroscopic data revealed that the Schiff base ligand behaves as a monoanionic tridentate ligand. The metal complexes exhibited octahedral geometry. Transmission electron microscope (TEM) analysis showed that Cu(II) complex have aggregated nanospheres morphology. The obtained nano-complexes were tested as antioxidant and antitumor agents. The H2L and its Cu(II) complex (2) were found to be more potent antioxidant (IC50(H2L) = 0.93 μM; IC50(Cu(II) complex) = 1.1 μM than standard ascorbic acid (IC50 = 2.1 μM) as evaluated by DPPH• method. The H2L and its complexes (1-4) were tested for their in vitro cytotoxicity against Ehrlich Ascites Carcinoma cell line (EAC). The Cu(II) nano-complex (2) effectively inhibited EAC growth with IC50 value of 47 μM in comparison with its parent compound and other prepared complexes. The high antioxidant activity and antitumor activity of Cu(II) nano-complex (2) were attributed to their chemical structure, Cu(II) reducing capacity, and nanosize property. The toxicity test on mice showed that Zn(II) (1) and Cu(II) (2) nano-complex have lower toxicity than the standard cis-platin.

  3. Synthesis, characterization and electrochemical study of synthesis of a new Schiff base (H₂cddi(t)butsalen) ligand and their two asymmetric Schiff base complexes of Ni(II) and Cu(II) with NN'OS coordination spheres.

    PubMed

    Menati, Saeid; Azadbakht, Azadeh; Taeb, Abbas; Kakanejadifard, Ali; Khavasi, Hamid Reza

    2012-11-01

    A novel Schiff base (H(2)cddi(t)butsalen) ligand was prepared via condensation of Methyl-2-{N-(2'-aminoethane)}-amino-1-cyclopentenedithiocarboxylate(Hcden) and 3,5-di-tert-butyl-2-hydroxybenzaldehyde. The ligand and Ni(II) and Cu(II) complexes were characterized based on elemental analysis, IR, (1)H NMR, (13)C NMR, UV-Vis spectrometry and cyclic voltammetry. The structure of copper{methyl-2-{N-[2-(3,5-di-tert-butyl-2-hydroxyphenyl)methylidynenitrilo]ethyl}amino-1-cyclopentedithiocarboxylate has been determined by X-ray crystallography. The X-ray results confirm that the geometry of the complex is slightly distorted square-planar structure. The copper(II) ion coordinates to two nitrogen atoms from the imine moiety of the ligand, a sulfur atom the methyl dithiocarboxylate moiety and phenolic oxygen atom.

  4. Syntheses, spectroscopic characterization, thermal study, molecular modeling, and biological evaluation of novel Schiff's base benzil bis(5-amino-1,3,4-thiadiazole-2-thiol) with Ni(II), and Cu(II) metal complexes.

    PubMed

    Chandra, Sulekh; Gautam, Seema; Rajor, Hament Kumar; Bhatia, Rohit

    2015-02-25

    Novel Schiff's base ligand, benzil bis(5-amino-1,3,4-thiadiazole-2-thiol) was synthesized by the condensation of benzil and 5-amino-1,3,4-thiadiazole-2-thiol in 1:2 ratio. The structure of ligand was determined on the basis of elemental analyses, IR, (1)H NMR, mass, and molecular modeling studies. Synthesized ligand behaved as tetradentate and coordinated to metal ion through sulfur atoms of thiol ring and nitrogen atoms of imine group. Ni(II), and Cu(II) complexes were synthesized with this nitrogen-sulfur donor (N2S2) ligand. Metal complexes were characterized by elemental analyses, molar conductance, magnetic susceptibility measurements, IR, electronic spectra, EPR, thermal, and molecular modeling studies. All the complexes showed molar conductance corresponding to non-electrolytic nature, expect [Ni(L)](NO3)2 complex, which was 1:2 electrolyte in nature. [Cu(L)(SO4)] complex may possessed square pyramidal geometry, [Ni(L)](NO3)2 complex tetrahedral and rest of the complexes six coordinated octahedral/tetragonal geometry. Newly synthesized ligand and its metal complexes were examined against the opportunistic pathogens. Results suggested that metal complexes were more biological sensitive than free ligand.

  5. Synthesis and characterization of VO(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes of chromone based azo-linked Schiff base ligand

    NASA Astrophysics Data System (ADS)

    Anitha, C.; Sheela, C. D.; Tharmaraj, P.; Johnson Raja, S.

    2012-12-01

    Azo-Schiff-base complexes of VO(II), Co(II), Ni(II), Cu(II) and Zn(II) have been synthesized and characterized by elemental analysis, IR, UV-Vis, 1H NMR, mass spectra, molar conductance, magnetic susceptibility measurement, electron spin resonance (EPR), CV, fluorescence, NLO and SEM. The conductance data indicate the nonelectrolytic nature of the complexes, except VO(II) complex which is electrolytic in nature. On the basis of electronic spectra and magnetic susceptibility octahedral geometry has been proposed for the complexes. The EPR spectra of copper and oxovanadium complexes in DMSO at 300 and 77 K were recorded and its salient features are reported. The redox behavior of the copper(II) complex was studied using cyclic voltammetry. The in vitro antimicrobial activity against Staphylococcus aureus, Escherichia coli, Salmonella enterica typhi, Bacillus subtilis and Candida strains was studied and compared with that of free ligand by well-diffusion technique. The azo Schiff base exhibited fluorescence properties originating from intraligand (π-π∗) transitions and metal-mediated enhancement is observed on complexation and so the synthesized complexes can serve as potential photoactive materials as indicated from their characteristic fluorescence properties. On the basis of the optimized structures, the second-order nonlinear optical properties (NLO) are calculated by using second-harmonic generation (SHG) and also the surface morphology of the complexes was studied by SEM.

  6. Synthesis, spectroscopic characterization, DNA interaction and biological activities of Mn(II), Co(II), Ni(II) and Cu(II) complexes with [(1H-1,2,4-triazole-3-ylimino)methyl]naphthalene-2-ol

    NASA Astrophysics Data System (ADS)

    Gaber, Mohamed; El-Wakiel, Nadia A.; El-Ghamry, Hoda; Fathalla, Shaimaa K.

    2014-11-01

    Manganese(II), cobalt(II), nickel(II) and copper(II) complexes of [(1H-1,2,4-triazole-3-ylimino)methyl]naphthalene-2-ol have been synthesized. The structure of complexes have been characterized by elemental analysis, molar conductance, magnetic moment measurements and spectral (IR, 1H NMR, EI-mass, UV-Vis and ESR), and thermal studies. The results showed that the chloro and nitrato Cu(II) complexes have octahedral geometry while Ni(II), Co(II) and Mn(II) complexes in addition to acetato Cu(II) complex have tetrahedral geometry. The possible structures of the metal complexes have been computed using the molecular mechanic calculations using the hyper chem. 8.03 molecular modeling program to confirm the proposed structures. The kinetic and thermodynamic parameters of the thermal decomposition steps were calculated from the TG curves. The binding modes of the complexes with DNA have been investigated by UV-Vis absorption titration. The results showed that the mode of binding of the complexes to DNA is intercalative or non-intercalative binding modes. Schiff base and its metal complexes have been screened for their in vitro antimicrobial activities against Gram positive bacteria (Staphylococcus aureus), Gram negative bacteria (Escherichia coli and Pesudomonas aeruginosa), fungi (Asperigllus flavus and Mucer) and yeast (Candida albicans and Malassezia furfur).

  7. N-((5-chloropyridin-2-yl)carbamothioyl)furan-2-carboxamide and its Co(II), Ni(II) and Cu(II) complexes: Synthesis, characterization, DFT computations, thermal decomposition, antioxidant and antitumor activity

    NASA Astrophysics Data System (ADS)

    Yeşilkaynak, Tuncay; Özpınar, Celal; Emen, Fatih Mehmet; Ateş, Burhan; Kaya, Kerem

    2017-02-01

    N-((5-chloropyridin-2-yl)carbamothioyl)furan-2-carboxamide (HL: C11H8ClN3O2S) and its Co(II), Ni(II) and Cu(II) complexes have been synthesized and characterized by elemental analysis, FT-IR,1H NMR and HR-MS methods. The HL was characterized by single crystal X-ray diffraction technique. It crystallizes in the monoclinic system. The HL has the space group P 1 21/c 1, Z = 4, and its unit cell parameters are a = 4.5437(5) Å, b = 22.4550(3) Å, c = 11.8947(14) Å. The ligand coordinates the metal ions as bidentate and thus essentially yields neutral complexes of the [ML2] type. ML2 complex structures were optimized using B97D/TZVP level. Molecular orbitals of both HL ligand were calculated at the same level. Thermal decomposition of the complexes has been investigated by thermogravimetry. The complexes were screened for their anticancer and antioxidant activities. Antioxidant activity of the complexes was determined by using the DPPH and ABTS assays. The anticancer activity of the complexes was studied by using MTT assay in MCF-7 breast cancer cells.

  8. Synthesis, structural, spectral (FT-IR, FT-Ra, and UV-Vis), thermal, and density functional studies on p-methylaniline complexes of Mn(II), Co(II), and Ni(II) bromides

    NASA Astrophysics Data System (ADS)

    Bardakçı, Tayyibe; Altun, Ahmet; Golcuk, Kurtulus; Kumru, Mustafa

    2015-11-01

    Transition metal complexes of the form MBr2L2, where M = Mn(II), Co(II) and Ni(II); L = p-methylaniline, were prepared and characterized by elemental and thermogravimetric analyses, magnetic moment measurements, and UV-vis, FT-IR and FT-Raman spectral studies. Geometries, spin-state energetics, and vibrational spectra of the complexes were obtained at the B3LYP/def2-TZVP level. The present experimental and theoretical data suggest 5-coordinate polymeric bromide bridged structure for the Mn complex, distorted tetrahedral structure for the Co complex, and distorted octahedral coordination site for the Ni complex. The experimental FT-IR and FT-Raman bands of the complexes were assigned based on the computational results expressed in terms of internal coordinates with percent potential energy distributions. The vibrational spectra suggest that the coordination occurs via nitrogen atom of p-methylaniline. The thermal characteristics of the complexes indicate that their decompositions start through p-methylaniline.

  9. Antimicrobial, spectral, magnetic and thermal studies of Cu(II), Ni(II), Co(II), UO(2)(VI) and Fe(III) complexes of the Schiff base derived from oxalylhydrazide.

    PubMed

    Melha, Khlood Abou

    2008-04-01

    The Schiff base ligand, oxalyl [( 2 - hydroxybenzylidene) hydrazone] [corrected].H(2)L, and its Cu(II), Ni(II), Co(II), UO(2)(VI) and Fe(III) complexes were prepared and tested as antibacterial agents. The Schiff base acts as a dibasic tetra- or hexadentate ligand with metal cations in molar ratio 1:1 or 2:1 (M:L) to yield either mono- or binuclear complexes, respectively. The ligand and its metal complexes were characterized by elemental analyses, IR, (1)H NMR, Mass, and UV-Visible spectra and the magnetic moments and electrical conductance of the complexes were also determined. For binuclear complexes, the magnetic moments are quite low compared to the calculated value for two metal ions complexes and this shows antiferromagnetic interactions between the two adjacent metal ions. The ligand and its metal complexes were tested against a Gram + ve bacteria (Staphylococcus aureus), a Gram -ve bacteria (Escherichia coli), and a fungi (Candida albicans). The tested compounds exhibited high antibacterial activities.

  10. Synthesis, spectral characterization and biological evaluation of Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes with thiosemicarbazone ending by pyrazole and pyridyl rings

    NASA Astrophysics Data System (ADS)

    Yousef, T. A.; Abu El-Reash, G. M.; Al-Jahdali, M.; El-Rakhawy, El-Bastawesy R.

    2014-08-01

    Here we present the synthesis of the new Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes with chelating ligand (Z)-(2-((1,3-diphenyl-1H-pyrazol-4-yl)methylene) hydrazinyl)(pyridin-2-ylamino)methanethiol. All the complexes were characterized by elemental analysis, IR, 1H NMR, UV-vis, magnetic susceptibility measurements and EPR spectral studies. IR spectra of complexes showed that the ligand behaves as NN neutral bidentate, NSN mononegative tridentate and NSNN mononegative tetradentate. The electronic spectra and the magnetic measurements suggested the octahedral geometry for all complexes as well as the EPR confirmed the tetragonal distorted octahedral for Cu(II) complex. Cd(II) complex showed the highest inhibitory antioxidant activity either using ABTS method. The SOD-like activity exhibited those Cd(II) and Zn(II) complexes have strong antioxidative properties. We tested the synthesized compounds for antitumor activity and showed that the ability to kill liver (HePG2) and breast (MCF-7) cancer cells definitely.

  11. Synthesis, DNA-binding, DNA-photonuclease profiling and antimicrobial activity of novel tetra-aza macrocyclic Ni(II), Co(II) and Cu(II) complexes constrained by thiadiazole.

    PubMed

    Vinay Kumar, B; Bhojya Naik, H S; Girija, D; Sharath, N; Pradeepa, S M; Joy Hoskeri, H; Prabhakara, M C

    2012-08-01

    A new tetra-aza macrocyclic ligand, L (C(24)H(16)N(12)O(2)S(4)) and its complexes of type, [MLCl(2)] and [CuL]Cl(2) (where M=Ni(II), Co(II); L=N,N'-(benzene-1,3-diyldi-1,3,4-thiadiazole-5,2-diyl)bis{2-[(5-benzene-1,3-diyl-1,3,4-thiadiazol-2-yl)amino]acetamide}) were synthesized and characterized by the spectral and analytical techniques. An octahedral geometry has been proposed for Ni(II) and Co(II) complexes while Cu(II) complex exhibit a square planar geometry. All the synthesized metal complexes were screened for their in vitro antimicrobial activity against selected species of pathogenic bacteria and fungi. The binding property of the complexes with CT-DNA was studied by absorption spectral analysis, followed by viscosity measurement and thermal denaturation studies. The photo induced cleavage studies revealed that the complexes possess photonuclease property against pUC19 DNA under UV-visible irradiation.

  12. Self-assembled Cu(II) and Ni(II) metallamacrocycles formed from 3,3,3',3'-tetrabenzyl-1,1'-aroylbis(thiourea) ligands: DNA and protein binding studies, and cytotoxicity of trinuclear complexes.

    PubMed

    Selvakumaran, Nagamani; Bhuvanesh, Nattamai S P; Karvembu, Ramasamy

    2014-11-21

    Self-assembled metallamacrocyclic Cu(II) and Ni(II) complexes of the types [Cu(L1-O,S)]3 (1), [Ni(L1-O,S)]3 (2), [Cu(L2-O,S)]2 (3) and [Ni(L2-O,S)]2 (4) [H2L1 = 3,3,3',3'-tetrabenzyl-1,1'-terephthaloylbis(thiourea) and H2L2 = 3,3,3',3'-tetrabenzyl-1,1'-isophthaloylbis(thiourea)] were synthesized and characterized by analytical, spectroscopic (UV-Vis, FT-IR, mass, (1)H & (13)C NMR and EPR) and single crystal X-ray diffraction techniques. The crystal structures of [Ni(L1-O,S)]3 and [Cu(L2-O,S)(Py)]2 showed the formation of self-assembled 3:3 and 2:2 metallamacrocyclic Cu(II) and Ni(II) complexes respectively. The binding affinity and binding mode of the trinuclear complexes toward CT DNA were determined by UV-Vis spectrophotometric titrations and the fluorescent indicator displacement (FID) assay. The interaction of the ligand (H2L1) and the complexes (1 and 2) with BSA was investigated using UV-Vis and fluorescence spectroscopic methods. Absorption and emission spectral studies indicate that the complexes 1 and 2 interact with CT DNA and BSA protein more strongly than their parent ligand. Both the complexes (1 and 2) cleaved the pBR 322 plasmid DNA in the absence of an external agent. Complex 1 [IC50 = 22.36 (A549) and 10 μM (MCF7)] exhibited higher cytotoxicity than cyclophosphamide against A549 and MCF7 cancer cell lines. The IC50 value of 2 (29.24) is lower in the A549 cell line and slightly higher (18.04) in the MCF7 cell line than that of cyclophosphamide [IC50 = 41.84 (A549) and 11.89 μM (MCF7)].

  13. Co(II), Ni(II), Cu(II) and Zn(II) complexes of tridentate ONO donor Schiff base ligand: Synthesis, characterization, thermal, non-isothermal kinetics and DFT calculations

    NASA Astrophysics Data System (ADS)

    Kusmariya, Brajendra S.; Mishra, A. P.

    2017-02-01

    We report here four mononuclear Co(II), Ni(II), Cu(II) and Zn(II) coordination compounds of general formula [M(L)2] {L = dcp; M = CoII, CuII & ZnII} and [M(L)(H2O)]·H2O {L = dcp; M = NiII} derived from tridentate 2,4-dichloro-6-{[(3-chloro-2-hydroxy-5-nitrophenyl)imino]methyl}phenol (dcp) ligand. These compounds were synthesized and characterized by elemental analysis, FT-IR, uv-vis, 1H NMR, molar conductance, magnetic moment, thermal, PXRD and SEM-EDX. The Powder X-ray Diffraction patterns and SEM analyses showed the crystalline nature of synthesized compounds. The peak broadening was explained in terms of crystallite size and the lattice strain using Scherrer and Williamson-Hall method. Thermogravimetric analysis was performed to determine the thermal stability of synthesized compounds under nitrogen atmosphere up to 820 K at 10 Kmin-1 heating rate. The kinetic and thermodynamic parameters of thermal decomposition were calculated using Coats-Redfern (C-R), Piloyan-Novikova (P-N) and Horowitz-Metzger (H-M) methods assuming first order degradation. The calculated optical band gap values of complexes were found to be in semiconducting range. To support the experimental findings, and derive some fruitful information viz. frequency calculations, HOMO-LUMO, energy gap (ΔE), molecular electrostatic potential (MEP), spin density, absorption spectra etc.; theoretical calculations by means of DFT and TD-DFT at B3LYP level were incorporated.

  14. Synthesis, Spectroscopic Characterization, and In Vitro Antimicrobial Studies of Pyridine-2-Carboxylic Acid N′-(4-Chloro-Benzoyl)-Hydrazide and Its Co(II), Ni(II), and Cu(II) Complexes

    PubMed Central

    Singh, Jagvir; Singh, Prashant

    2012-01-01

    N-substituted pyridine hydrazide (pyridine-2-carbonyl chloride and 4-chloro-benzoic acid hydrazide) undergoes hydrazide formation of the iminic carbon nitrogen double bond through its reaction with cobalt(II), nickel(II), and copper(II) metal salts in ethanol which are reported and characterized based on elemental analyses, IR, solid reflectance, magnetic moment, molar conductance, and thermal analysis (TG). From the elemental analyses data, 1 : 2 metal complexes are formed having the general formulae [MCl2(HL)2] ·yH2O (where M = Co(II), Ni(II), and Cu(II), y = 1–3). The important infrared (IR) spectral bands corresponding to the active groups in the ligand and the solid complexes under investigation were studied. IR spectra show that ligand is coordinated to the metal ions in a neutral bidentate manner with ON donor sites. The solid complexes have been synthesized and studied by thermogravimetric analysis. All the metal chelates are found to be nonelectrolytes. From the magnetic and solid reflectance spectra, the complexes (cobalt(II), nickel(II), and copper(II)) have octahedral and square planner geometry, respectively. The antibacterial and antifungal activity's data show that the metal complexes have a promising biological activity comparable with the parent ligand against bacterial and fungal species. PMID:23125560

  15. Synthesis, Spectroscopic Characterization, and In Vitro Antimicrobial Studies of Pyridine-2-Carboxylic Acid N'-(4-Chloro-Benzoyl)-Hydrazide and Its Co(II), Ni(II), and Cu(II) Complexes.

    PubMed

    Singh, Jagvir; Singh, Prashant

    2012-01-01

    N-substituted pyridine hydrazide (pyridine-2-carbonyl chloride and 4-chloro-benzoic acid hydrazide) undergoes hydrazide formation of the iminic carbon nitrogen double bond through its reaction with cobalt(II), nickel(II), and copper(II) metal salts in ethanol which are reported and characterized based on elemental analyses, IR, solid reflectance, magnetic moment, molar conductance, and thermal analysis (TG). From the elemental analyses data, 1 : 2 metal complexes are formed having the general formulae [MCl(2)(HL)(2)] ·yH(2)O (where M = Co(II), Ni(II), and Cu(II), y = 1-3). The important infrared (IR) spectral bands corresponding to the active groups in the ligand and the solid complexes under investigation were studied. IR spectra show that ligand is coordinated to the metal ions in a neutral bidentate manner with ON donor sites. The solid complexes have been synthesized and studied by thermogravimetric analysis. All the metal chelates are found to be nonelectrolytes. From the magnetic and solid reflectance spectra, the complexes (cobalt(II), nickel(II), and copper(II)) have octahedral and square planner geometry, respectively. The antibacterial and antifungal activity's data show that the metal complexes have a promising biological activity comparable with the parent ligand against bacterial and fungal species.

  16. Synthesis, characterization, thermal study and biological evaluation of Cu(II), Co(II), Ni(II) and Zn(II) complexes of Schiff base ligand containing thiazole moiety

    NASA Astrophysics Data System (ADS)

    Nagesh, G. Y.; Mahendra Raj, K.; Mruthyunjayaswamy, B. H. M.

    2015-01-01

    The novel Schiff base ligand 2-(4-(dimethylamino)benzylidene)-N-(4-phenylthiazol-2-yl)hydrazinecarboxamide (L) obtained by the condensation of N-(4-phenylthiazol-2-yl)hydrazinecarboxamide with 4-dimethylaminobenzaldehyde and its newly synthesized Cu(II), Co(II), Ni(II) and Zn(II) complexes have been characterized by microanalysis, magnetic susceptibility, molar conductance, thermal analysis, FT-IR, 1H NMR, ESI mass, UV-Visible, ESR spectroscopy and powder X-ray diffraction data. The newly synthesized ligand behaves as a bidentate ON donor. The IR results confirmed the bidentate binding of the ligand involving oxygen atom of amide carbonyl and azomethine nitrogen. 1H NMR spectral data of the ligand (L) and its Zn(II) complex agreed well with the proposed structures. In order to evaluate the effect of antimicrobial activity of metal ions upon chelation, the newly synthesized ligand and its metal complexes were screened for their antibacterial and antifungal activities by minimum inhibitory concentration (MIC) method. The DNA cleavage activities were studied using plasmid DNA pBR322 as a target molecule by agarose gel electrophoresis method. The brine shrimp bioassay was also carried out to study the in vitro cytotoxicity properties of all the compounds against Artemia salina. Furthermore, the antioxidant activity of the ligand (L) and its metal complexes were determined in vitro by reduction of 1,1-diphenyl-2-picryl hydrazyl (DPPH), the ligand exhibited potent in vitro - antioxidant activity than its metal complexes.

  17. A mononuclear Ni(II) complex with 5,6-diphenyl-3-(2-pyridyl)-1,2,4-triazine: DNA- and BSA-binding and anticancer activity against human breast carcinoma cells

    NASA Astrophysics Data System (ADS)

    Anjomshoa, Marzieh; Hadadzadeh, Hassan; Fatemi, Seyed Jamilaldin; Torkzadeh-Mahani, Masoud

    2015-02-01

    DNA- and BSA-binding properties of a mononuclear Ni(II) complex, [Ni(dppt)2Cl2] (dppt = 5,6-diphenyl-3-(2-pyridyl)-1,2,4-triazine), have been investigated under physiological conditions. The interaction of the complex with the fish sperm DNA (FS-DNA) has been studied by UV-Vis absorption, thermal denaturation, viscosity measurement, competitive DNA-binding studies with ethidium bromide (EB) by fluorescence, and gel electrophoresis technique. The experimental results indicate that the complex interacts with DNA by intercalative binding mode. The competitive study with ethidium bromide (EB) shows that the complex competes for the DNA-binding sites with EB and displaces the DNA-bound EB molecule. The interactions of the dppt ligand and the complex with BSA have been studied by UV-Vis absorption and fluorescence spectroscopic techniques. The values of Kb for the BSA-dppt and the BSA-complex systems at room temperature were calculated to be 0.14 × 104 M-1 and 0.32 × 105 M-1, respectively, indicating that the complex has stronger tendency to bind with BSA than the dppt ligand. The quenching constants (Ksv), binding constants (Kbin), and number of binding sites (n) at different temperatures, as well as the binding distance (r) and thermodynamic parameters (ΔH°, ΔS° and ΔG°) have been calculated for the BSA-dppt and the BSA-complex systems. The cytotoxicities of the dppt ligand and the complex have been also tested against the human breast adenocarcinoma (MCF-7) cell line using the MTT assay. The results indicate that the dppt ligand and the complex display cytotoxicity against human breast cancer cell lines (MCF-7) with the IC50 values of 17.35 μM and 13.00 μM, respectively. It is remarkable that the complex can introduce as a potential anticancer drug.

  18. Synthesis, spectral and electrochemical studies of Cu(II) and Ni(II) complexes with new N 2O 2 ligands: A new precursor capable of depositing copper nanoparticles using thermal reduction

    NASA Astrophysics Data System (ADS)

    Habibi, Mohammad Hossein; Mokhtari, Reza; Mikhak, Maryam; Amirnasr, Mehdi; Amiri, Ahmad

    2011-09-01

    Cu(II) and Ni(II) complexes of the general type [M(N 2O 2)] are described. The N 2O 2 ligands used are [N,N'-bis(2-hydroxy-6-methoxybenzylidene)propane-1,3-diamine] (HOMeSalpn) and [N,N'-bis(2-hydroxy-6-methoxybenzylidene)propane-1,2-diamine (HOMeSalpr). These complexes have been characterized by IR, UV-vis, CV, TG-DTA and 1H NMR spectroscopy. The electrochemical behavior of these complexes at a glassy carbon electrode in acetonitrile solution indicates that the first reduction process corresponding to Cu(II)-Cu(I) and Ni(II)-Ni(I) is electrochemically irreversible. The new copper complexes have been applied for the preparation of copper nanoparticles using non-ionic surfactant (Triton X-100) by thermal reduction. The copper nanoparticles with average size of 48 nm were formed by thermal reduction of [N,N'-bis(2-hydroxy-6-methoxybenzylidene)propane-1,3-diamine]copper(II) in the presence of triphenylphosphine thus releasing the reduced copper and affording the high-purity copper nanoparticles.

  19. Synthesis, characterization and equilibrium studies of some potential antimicrobial and antitumor complexes of Cu(II), Ni(II), Zn(II) and Cd(II) ions involving 2-aminomethylbenzimidazole and glycine

    NASA Astrophysics Data System (ADS)

    Aljahdali, M.

    2013-08-01

    The ternary complexes of Cu(II), Zn(II), Ni(II) and Cd(II) with 2-aminomethylbenzimidazole (AMBI) and glycine as a representative example of amino acids have been isolated and characterized by elemental analyses, IR, ESR, UV-vis, magnetic moment, molar conductance and 1H NMR spectra. AMBI behaves as neutral bidentate ligands with coordination through imidazole and amino group nitrogens while the glycine amino acid behaves as a monodenate anion with coordination involving the amino group and carboxylate oxygen after deprotonation. The magnetic and spectral data indicates a square planar geometry for both Cu2+ and Ni2+ complexes and a tetrahedral geometry for both Zn2+ and Cd2+ complexes. The isolated chelates have been screened for their antifungal and antibacterial activities using the disc diffusion method. A cytotoxicity of the compounds against colon (HCT116) and larynx (HEP2) cancer cells have been studied. The stability constants of ternary M-AMBI-Gly complexes were determined potentiometrically in aqueous solution at I = 0.1 mol dm-3 NaCl.

  20. Synthesis, spectral and electrochemical studies of Cu(II) and Ni(II) complexes with new N2O2 ligands: a new precursor capable of depositing copper nanoparticles using thermal reduction.

    PubMed

    Habibi, Mohammad Hossein; Mokhtari, Reza; Mikhak, Maryam; Amirnasr, Mehdi; Amiri, Ahmad

    2011-09-01

    Cu(II) and Ni(II) complexes of the general type [M(N2O2)] are described. The N2O2 ligands used are [N,N'-bis(2-hydroxy-6-methoxybenzylidene)propane-1,3-diamine] (HOMeSalpn) and [N,N'-bis(2-hydroxy-6-methoxybenzylidene)propane-1,2-diamine (HOMeSalpr). These complexes have been characterized by IR, UV-vis, CV, TG-DTA and 1H NMR spectroscopy. The electrochemical behavior of these complexes at a glassy carbon electrode in acetonitrile solution indicates that the first reduction process corresponding to Cu(II)-Cu(I) and Ni(II)-Ni(I) is electrochemically irreversible. The new copper complexes have been applied for the preparation of copper nanoparticles using non-ionic surfactant (Triton X-100) by thermal reduction. The copper nanoparticles with average size of 48nm were formed by thermal reduction of [N,N'-bis(2-hydroxy-6-methoxybenzylidene)propane-1,3-diamine]copper(II) in the presence of triphenylphosphine thus releasing the reduced copper and affording the high-purity copper nanoparticles.

  1. Synthesis, crystal structures, DFT studies, molecular docking and urease inhibition studies of three Ni(II) complexes with a sexidentate N2O4-donor bis-Schiff base ligand.

    PubMed

    Wang, Hu; Lan, Tianxiang; Zhang, Xia; Zhang, Dongmei; Bi, Caifeng; Fan, Yuhua

    2016-12-01

    Three Ni(II) complexes with a sexidentate N2O4-donor bis-Schiff base ligand, namely Ni(C36H34N2O8)·2CH3OH (1), Ni(C28H34N2O8S2)·H2O (2) and Ni(C40H36N4O8)·3CH3OH (3) (C36H34N2O8=1,2-bis(2-methoxy-6-formylphenoxy)ethane-l-phenylalanine; C28H34N2O8S2=1,2-bis(2-methoxy-6-formylphenoxy)ethane-l-methionine; C40H36N4O8=1,2-bis(2-methoxy-6-formylphenoxy)ethane-l-tryptophan) were synthesized and structurally characterized. Theoretical studies of the three complexes were carried out by density functional theory (DFT) Becke's three-parameter hybrid (B3LYP) method employing the 6-31G basis set. Moreover, the inhibitory activities were tested in vitro against jack bean urease. At the same time, molecular docking was investigated to determine the probable binding mode by inserting the complexes into the active site of jack bean urease. The experimental values and docking simulation exhibited that complex 3 showed strong inhibitory activity (IC50=11.27±2.08μM) compared with the positive reference acetohydroxamic acid. Their structure-activity relationships were further discussed.

  2. Spectrophotometric, conductometric and thermal studies of Co(II), Ni(II) and Cu(II) complexes with 2-(2-hydroxynaphthylazo)-4-hydroxy-6-methyl-1,3-pyrimidine

    NASA Astrophysics Data System (ADS)

    Gaber, Mohamed; Mansour, Ikhlas A.; El-Sayed, Yousif S. Y.

    2007-10-01

    The electronic absorption spectra of 2-(2-hydroxynaphthylazo)-4-hydroxy-6-methyl-1,3-pyrimidine in pure organic solvents of different polarities and in buffer solutions of varying pH are studied. The important bands in the IR and the main signals in the 1H NMR spectra are assigned. The observed UV-vis absorption bands are assigned to the corresponding electronic transitions. The molecular stoichiometry, stability constant, absorption maximum, molar absorptivity and Sandell's sensitivity of the complexes are calculated. Obeyence to Beer's law and Ringbom optimum concentration ranges are also determined. The ability of using the titled azodye as metalochromic indicator in complexometric titrations was also studied. The effect of Co(II), Ni(II) and Cu(II) ions on the fluorescence of the azodye is also considered. The solid Cu(II) complexes of the titled azodye have been prepared and characterized by elemental, IR, UV-vis spectra as well as by conductometric and magnetic measurements. The data suggest square planar geometry for 1:1 and 1:2 (M:L) complexes. The thermal behaviour of the complexes has been studied. The kinetic parameters ( n, E, A, Δ H, Δ S and Δ G) of the thermal decomposition steps are computed using Coats-Redfern equations.

  3. Synthesis, spectral characterization, solution equilibria, in vitro antibacterial and cytotoxic activities of Cu(II), Ni(II), Mn(II), Co(II) and Zn(II) complexes with Schiff base derived from 5-bromosalicylaldehyde and 2-aminomethylthiophene

    NASA Astrophysics Data System (ADS)

    El-Sherif, Ahmed A.; Eldebss, Taha M. A.

    2011-09-01

    Schiff base namely 2-aminomethylthiophenyl-4-bromosalicylaldehyde (ATS)(4-bromo-2-(thiophen-2-yl-imino)methylphenol) and its metal complexes have been synthesized and characterized by elemental analyses, IR, 1H NMR, solid reflectance, magnetic moment, molar conductance, mass spectra, ESR and thermal analysis (TGA). The analytical data of the complexes show the formation of 1:2 [M:L] ratio of the formula [ML 2], where M represents Ni(II), Zn(II) and Cu(II) ions, while L represents the deprotonated Schiff base. IR spectra show that ATS is coordinated to the metal ions in a bidentate manner through azomethine-N and phenolic-oxygen groups. The ligand and their metal chelates have been screened for their antimicrobial activities using the disc diffusion method against the selected bacteria. A cytotoxicity of the compounds against colon (HCT116) and larynx (HEP2) cancer cells have been studied. Protonation constants of (ATS) ligand and stability constants of its Cu 2+, Co 2+, Mn 2+, Zn 2+ and Ni 2+ complexes were determined by potentiometric titration method in 50% (v/v) DMSO-water solution at ionic strength of 0.1 M NaNO 3.

  4. Experimental and computational study on 2,2'-[(1E,2E)-hydrazine-1,2-diylidenedi(1E)eth-1-yl-1-ylidene]diphenol and its Ni(II), Pt(II), Pd(II) complexes.

    PubMed

    Alyar, Saliha; Özbek, Neslihan; Yıldırım, Sema Öztürk; Ide, Semra; Butcher, Ray J

    2014-09-15

    2,2'-[(1E,2E)-hydrazine-1,2-diylidenedi(1E)eth-1-yl-1-ylidene]diphenol and its dimeric, binuclear Ni(II), Pd(II) and Pt(II) metal complexes were synthesized. Hydrazine derivative and its complexes were characterized by elemental analyses, LC-MS, IR, electronic spectra, (1)H and (13)C NMR spectra, conductivity and magnetic measurements. 1H and 13C shielding tensors for crystal structure were calculated with GIAO/DFT/B3LYP/6-311++G(d,p) methods in CDCl3. The vibrational band assignments were performed at B3LYP/6-311++G(d,p) theory level combined with scaled quantum mechanics force field (SQMFF) methodology. The antibacterial activities of synthesized compounds were studied against some Gram-positive and Gram-negative bacteria by using the microdilution and disk diffusion method. As the antibacterial activity results evidently show, the compound possessed a broad spectrum of activity against the tested bacteria.

  5. Proton/metal-ligand stability constants of complexes of Ni(II), Cu(II), and Co(II) with diethyl 4-(substituted-phenyl)-2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate in 70% dioxane-water mixture

    NASA Astrophysics Data System (ADS)

    Tekade, Pradip V.; Bajaj, Sonal D.; Thool, Seemita

    2015-12-01

    Physico-chemical properties viz proton-ligand and metal-ligand stability constants of complexes of diethyl 4-(substituted-phenyl)-2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate with Ni(II), Cu(II), and Co(II) were determined in mixed solvents (70% dioxane). Presence of OH/NH group(s) in these compounds was confirmed at 0.1 M ionic strength in 70% dioxane-water mixture pH-metrically. It is observed that Ni(II), Cu(II), and Co(II) metal ions formed 1: 1 and 1: 2 complex with all the three ligands. The results show that the ratio of log K 1/log K 2 is positive in all cases. This implies that there is little or no steric hindrance to the addition of secondary molecules.

  6. Crystal structures of two nickel compounds comprising neutral NiII hydrazone complexes and di­carb­oxy­lic acids

    PubMed Central

    Nakanishi, Takumi; Sato, Osamu

    2017-01-01

    Two isostructural NiII compounds, bis­{N-[1-(pyridin-2-yl-κN)eth­ylidene]pyridine-4-carbohydrazonato-κ2 N′,O}nickel(II)–2,5-di­chloro­terephthalic acid (1/1), [Ni(C13H11N4O)2](C8H4Cl2O4), and bis­{N-[1-(pyridin-2-yl-κN)eth­ylidene]pyridine-4-carbohydrazonato-κ2 N′,O}nickel(II)–2,5-di­bromo­terephthalic acid (1/1), [Ni(C13H11N4O)2](C8H4Br2O4), were synthesized and their crystal structures determined. The pair of N,N′,O-tridentate N-[1-(pyridin-2-yl-κN)eth­yl]pyridine-4-carbohydrazonate L ligands result in a cis-NiO2N4 octa­hedral coordination sphere for the metal ions. The asymmetric units consist of two half-mol­ecules of the di­carb­oxy­lic acids, which are completed by crystallographic inversion symmetry. In the respective crystals, the 2,5-di­chloro­terephthalic acid (H2Cl2TPA, 1-Cl) mol­ecules form zigzag hydrogen-bonded chains with the [Ni(L)2] mol­ecules, with the hydrogen-bond distances in 1-Br slightly longer than those in 1-Cl. The packing is consolidated by aromatic π–π stacking between the di­carb­oxy­lic acid mol­ecules and terminal pyridine rings in [Ni(L)2] and short halogen–halogen inter­actions are also observed. The qualitative prediction of the H-atom position from the C—N—C angles of the terminal pyridine rings in L and the C—O distances in the carboxyl groups show that 1-Cl and 1-Br are co-crystals rather than salts. PMID:28217320

  7. Solvent-induced structural diversity in tetranuclear Ni(ii) Schiff-base complexes: the first Ni4 single-molecule magnet with a defective dicubane-like topology.

    PubMed

    Herchel, Radovan; Nemec, Ivan; Machata, Marek; Trávníček, Zdeněk

    2016-11-22

    Two tetranuclear Ni(II) complexes, namely [Ni4(L)4(CH3OH)3(H2O)]·CH3OH (1) and (Pr3NH)2[Ni4(L)4(CH3COO)2] (2, Pr3N = tripropylamine), were synthesized from a tridentate Schiff base ligand H2L (2-[(E)-(2-hydroxybenzylidene)amino]phenol) and Ni(CH3COO)2·4H2O, using different solvents and their ratios (CH3OH and/or CH2Cl2). The prepared Ni4 complexes are of different structural types, involving an Ni4O4 cubane-like core (1) and Ni4O6 defective dicubane-like core (2), with all the Ni atoms hexacoordinated. The complexes were characterized by elemental analysis, FT-IR spectroscopy, variable temperature and field magnetic measurements, and single crystal X-ray analysis. The DFT and CASSCF/NEVPT2 theoretical calculations were utilized to reveal information about the isotropic exchange parameters (Jij) and single-ion zero-field splitting parameters (Di, Ei). The variable temperature magnetic data suggested the competition of the antiferromagnetic and ferromagnetic intracluster interactions in compound 1, which is in contrast to compound 2, where all intracluster interactions are ferromagnetic resulting in the ground spin state S = 4 with an easy-axis type of anisotropy quantified by the axial zero-field splitting parameter D = -0.81 cm(-1). This resulted in the observation of a field-induced slow-relaxation of magnetization (U = 3.3-6.7 K), which means that the complex 2 represents the first Ni4 single-molecule magnet with the defective dicubane-like topology.

  8. Cytosolic Ni(II) sensor in cyanobacterium: nickel detection follows nickel affinity across four families of metal sensors.

    PubMed

    Foster, Andrew W; Patterson, Carl J; Pernil, Rafael; Hess, Corinna R; Robinson, Nigel J

    2012-04-06

    Efflux of surplus Ni(II) across the outer and inner membranes of Synechocystis PCC 6803 is mediated by the Nrs system under the control of a sensor of periplasmic Ni(II), NrsS. Here, we show that the product of ORF sll0176, which encodes a CsoR/RcnR-like protein now designated InrS (for internal nickel-responsive sensor), represses nrsD (NrsD is deduced to efflux Ni(II) across the inner membrane) from a cryptic promoter between the final two ORFs in the nrs operon. Transcripts initiated from the newly identified nrsD promoter accumulate in response to nickel or cobalt but not copper, and recombinant InrS forms specific, Ni(II)-inhibited complexes with the nrsD promoter region. Metal-dependent difference spectra of Ni(II)- and Cu(I)-InrS are similar to Cu(I)-sensing CsoR and dissimilar to Ni(II)/Co(II)-sensing RcnR, consistent with factors beyond the primary coordination sphere switching metal selectivity. Competition with chelators mag-fura-2, nitrilotriacetic acid, EDTA, and EGTA estimate K(D) Ni(II) for the tightest site of InrS as 2.05 (±1.5) × 10(-14) m, and weaker K(D) Ni(II) for the cells' metal sensors of other types: Zn(II) co-repressor Zur, Co(II) activator CoaR, and Zn(II) derepressor ZiaR. Ni(II) transfer to InrS occurs upon addition to Ni(II) forms of each other sensor. InrS binds Ni(II) sufficiently tightly to derepress Ni(II) export at concentrations below K(D) Ni(II) of the other sensors.

  9. Structural consequences of spin conversion in a sterically encumbered Ni(II) porphyrin

    SciTech Connect

    Barkigia, K.M.; Nelson, N.Y.; Renner, M.W.; Smith, K.M.; Fajer, J.

    1999-10-14

    The crystal structure of a pyridine-ligated, high-spin Ni(II) complex of 2,3,7,8,12,13,17,18-octabromo-5, 15-bis(isopropyl)-10,20-bis(isopropylidenyl) porphyrin, is reported and compared to the unligated, low-spin Ni(II) complex previously reported. The results demonstrate that conversion to high-spin Ni(II) in nonplanar, sterically encumbered porphyrins induces a significant core expansion about the Ni while nonplanarity is still retained. The expansion of the core parameters (Ni-N, Ct-C{alpha}, Ct-Cmexo) and the Ni-N{sub axial} distances are characteristic of the d{sub x{sup 2}{minus}y{sup 2}} orbital occupancies in high-spin Ni(II) porphyrins and document the structural consequences of the spin conversion in severely nonplanar Ni(II) porphyrins. The stereochemical results are particularly relevant to ligation effects in nonplanar Ni biomolecules and synthetic porphyrins increasingly used as biomimetic models of conformational effects in chromophores and prosthetic groups in vivo, and to the remarkably wide range of lifetimes observed for excited (d,d) states in nonplanar, sterically constrained Ni(II) porphyrins in which the d{sub x{sup 2}{minus}y{sup 2}} and d{sub z{sup 2}} orbitals are also populated.

  10. Metal-Based Antibacterial and Antifungal Agents: Synthesis, Characterization, and In Vitro Biological Evaluation of Co(II), Cu(II), Ni(II), and Zn(II) Complexes With Amino Acid-Derived Compounds

    PubMed Central

    Chohan, Zahid H.; Arif, M.; Akhtar, Muhammad A.; Supuran, Claudiu T.

    2006-01-01

    A series of antibacterial and antifungal amino acid-derived compounds and their cobalt(II), copper(II), nickel(II), and zinc(II) metal complexes have been synthesized and characterized by their elemental analyses, molar conductances, magnetic moments, and IR, and electronic spectral measurements. Ligands (L1)−(L5) were derived by condensation of β-diketones with glycine, phenylalanine, valine, and histidine and act as bidentate towards metal ions (cobalt, copper, nickel, and zinc) via the azomethine-N and deprotonated-O of the respective amino acid. The stoichiometric reaction between the metal(II) ion and synthesized ligands in molar ratio of M : L (1 : 1) resulted in the formation of the metal complexes of type [M(L)(H2O)4]Cl (where M = Co(II), Cu(II), and Zn(II)) and of M : L (1 : 2) of type [M(L)2(H2O)2] (where M = Co(II), Cu(II), Ni(II), and Zn(II)). The magnetic moment data suggested for the complexes to have an octahedral geometry around the central metal atom. The electronic spectral data also supported the same octahedral geometry of the complexes. Elemental analyses and NMR spectral data of the ligands and their metal(II) complexes agree with their proposed structures. The synthesized ligands, along with their metal(II) complexes, were screened for their in vitro antibacterial activity against four Gram-negative (Escherichia coli, Shigella flexeneri, Pseudomonas aeruginosa, and Salmonella typhi) and two Gram-positive (Bacillus subtilis and Staphylococcus aureus) bacterial strains and for in vitro antifungal activity against Trichophyton longifusus, Candida albicans, Aspergillus flavus, Microsporum canis, Fusarium solani, and Candida glaberata. The results of these studies show the metal(II) complexes to be more antibacterial/antifungal against one or more species as compared to the uncomplexed ligands. The brine shrimp bioassay was also carried out to study their in vitro cytotoxic properties. Five compounds, (3), (7), (10), (11), and (22), displayed

  11. Reactivity of phosphonodithioato-dppt Ni(II) mixed ligand complexes with halogens: first example of a metal-coordinating tribromide anion.

    PubMed

    Aragoni, M Carla; Arca, Massimiliano; Coles, Susanne L; Devillanova, Francesco A; Hursthouse, Michael B; Isaia, Francesco; Lippolis, Vito

    2012-06-14

    The first example of a metal complex containing a tribromide anion is presented and characterised by X-ray diffraction. Hybrid DFT calculations were used to investigate the nature of the bond in coordinating trihalides and the differences with the corresponding mono-halide complexes.

  12. Synthesis and characterization of Ni(II) complex with 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-7,14-dienium bromide

    SciTech Connect

    Yusoff, Latifah M.; Yusoff, Siti Fairus M.; Ismail, Wafiuddin; Yamin, Bohari M.

    2014-09-03

    Nickel(II) complex have been synthesized by treating a 14-membered ring tetraaza macrocyclic compound, 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-7,14-dienium, bromide (Me{sub 6}N{sub 4}H{sub 4})Br{sub 2} with nickel acetate in metanol. The complex was characterized using elemental analysis, Fourier Transform Infrared (FTIR), Ultraviolet-Visible (UV-Vis), and single crystal diffraction (X-ray). The nickel atom coordinates through four nitrogen atoms in the ligand. Square planar geometry has been proposed for this complex.

  13. Ni(II) and Pd(II) complexes with new N,O donor thiophene appended Schiff base ligand: Synthesis, electrochemistry, X-ray structure and DFT calculation

    NASA Astrophysics Data System (ADS)

    Kundu, Subhankar; Pramanik, Ajoy Kumar; Mondal, Apurba Sau; Mondal, Tapan Kumar

    2016-07-01

    The thiophene appended Schiff's base ligand, 1-(2-(thiophen-2-yl)ethylimino)methyl)naphthalene-2-ol (HL) with N,O donor sites has been synthesized by the condensation between 2-hydroxy-1-naphthaldehyde and thiophene-2-ethylamine. The square planar 1:2 complexes of HL having general formula [M(L)2] (M = Ni(1) and Pd(2)) with nickel(II) and palladium(II) have been synthesized and characterized by several spectroscopic techniques. The geometry has been confirmed by single crystal X-ray study for complex 1. The electronic structure and spectral properties of the complexes are interpreted by DFT and TDDFT studies.

  14. Phenoxide bridged tetranuclear Co(II), Ni(II), Cu(II) and Zn(II) complexes: Electrochemical, magnetic and antimicrobial studies

    NASA Astrophysics Data System (ADS)

    Kamath, Anupama; Kulkarni, Naveen V.; Netalkar, Priya P.; Revankar, Vidyanand K.

    2011-09-01

    Phenoxide bridged later first row transition metal(II) complexes have been prepared by the interaction of later 3d transition metal(II) chlorides with tetranucleating compartmental Schiff base ligand system derived from 2,6-diformyl-4-methylphenol, p-phenylenediamine and 2-hydrazinobenzothiazole. Ligand and complexes were characterized by analytical, spectral (IR, UV-visible, ESR, FAB-mass and fluorescence), magnetic and thermal studies. All complexes are found to have octahedral geometry. The mutual influence of metal centres in terms of cooperative effect on the electronic, magnetic, electrochemical and structural properties was investigated. The Schiff base and its complexes have been screened for their antibacterial (against Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa) and antifungal activities (against Aspergillus niger, and Candida albicans).

  15. Phenoxide bridged tetranuclear Co(II), Ni(II), Cu(II) and Zn(II) complexes: electrochemical, magnetic and antimicrobial studies.

    PubMed

    Kamath, Anupama; Kulkarni, Naveen V; Netalkar, Priya P; Revankar, Vidyanand K

    2011-09-01

    Phenoxide bridged later first row transition metal(II) complexes have been prepared by the interaction of later 3d transition metal(II) chlorides with tetranucleating compartmental Schiff base ligand system derived from 2,6-diformyl-4-methylphenol, p-phenylenediamine and 2-hydrazinobenzothiazole. Ligand and complexes were characterized by analytical, spectral (IR, UV-visible, ESR, FAB-mass and fluorescence), magnetic and thermal studies. All complexes are found to have octahedral geometry. The mutual influence of metal centres in terms of cooperative effect on the electronic, magnetic, electrochemical and structural properties was investigated. The Schiff base and its complexes have been screened for their antibacterial (against Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa) and antifungal activities (against Aspergillus niger, and Candida albicans).

  16. Synthesis, structural and biochemical activity studies of a new hexadentate Schiff base ligand and its Cu(II), Ni(II), and Co(II) complexes

    NASA Astrophysics Data System (ADS)

    Ekmekcioglu, Pinar; Karabocek, Nevin; Karabocek, Serdar; Emirik, Mustafa

    2015-11-01

    A new Schiff base ligand (H2L) and its metal complexes have been prepared and characterized by elemental analysis, magnetic moment and spectral studies. The comparative in-vitro antimicrobial activities against various pathogens with reference to known antibiotics activity under the standard control of different concentrations revealed that the metal complexes (6-8) showed enhanced antimicrobial activities in general as compared to free ligand. As an exception, the free ligand showed better activity against Trichoderma. The antifungal activity experiments were performed in triplicate. The order of biochemical activity for metal complexes were observed as in the following. CuL > CoL > NiL, which is exactly same as the order of stability constants of these complexes. Additionally, we performed DFT and TD-DFT calculation for free ligand and Cu(II) complex to support the experimental data. The geometries of the Cu(II) complex have been optimized using the B3LYP level of theory. The theoretical calculations confirm that the copper (II) center exhibits a distorted square pyramidal geometry which is favored by experimental results.

  17. Effect of substitution and planarity of the ligand on DNA/BSA interaction, free radical scavenging and cytotoxicity of diamagnetic Ni(II) complexes: a systematic investigation.

    PubMed

    Sathyadevi, Palanisamy; Krishnamoorthy, Paramasivam; Butorac, Rachel R; Cowley, Alan H; Bhuvanesh, Nattamai S P; Dharmaraj, Nallasamy

    2011-10-14

    Four new bivalent nickel hydrazone complexes have been synthesised from the reactions of [NiCl(2)(PPh(3))(2)] with H(2)L {L = dianion of the hydrazones derived from the condensation of salicylaldehyde or o-hydroxy acetophenone with p-toluic acid hydrazide (H(2)L(1)) (1), (H(2)L(2)) (2) and o-hydroxy acetophenone or o-hydroxy naphthaldehyde with benzhydrazide (H(2)L(3)) (3) and (H(2)L(4)) (4)} and formulated as [Ni(L(1))(PPh(3))] (5), [Ni(L(2))(PPh(3))] (6), [Ni(L(3))(PPh(3))] (7) and [Ni(L(4))(PPh(3))] (8). Structural characterization of complexes 5-8 were accomplished by using various physico-chemical techniques. In order to study the influence of substitution in the ligand and its planarity on the biological activity of complexes 5-8 containing them, suitable hydrazone ligands 1-4 have been selected in this study. Single crystal diffraction data of complexes 5, 7 and 8 proved the geometry of the complexes to be distorted square planar with a 1 : 1 ratio between the metal ion and the coordinated hydrazones. To provide more insight on the mode of action of complexes 5-8 under biological conditions, additional experiments involving their interaction with calf thymus DNA (CT DNA) and bovine serum albumin (BSA) were monitored by UV-visible and fluorescence titrations respectively. Further, the ligands 1-4 and corresponding nickel(ii) chelates 5-8 have been tested for their scavenging effect towards OH and O(2)(-) radicals. The effect of complexes 5-8 to arrest the growth of HeLa and Hep-2 tumour cell lines has been studied along with the cell viability against the non-cancerous NIH 3T3 cells under in vitro conditions.

  18. Template synthesis of square-planar Ni(II) complexes with new thiophene appended Schiff base ligands: Characterization, X-ray structure and DFT calculation

    NASA Astrophysics Data System (ADS)

    Kundu, Subhankar; Biswas, Sujan; Mondal, Apurba Sau; Roy, Puspendu; Mondal, Tapan Kumar

    2015-11-01

    The square planar nickel(II) complexes have been synthesized by the reaction of nickel(II) chloride hexahydrate and the in situ condensed thiophene appended Schiff base ligands of thiophene-2-ethylamine with 3,5-dimethyl-2-hydroxybenzaldehyde or 3,5-dichloro-2-hydroxybenzaldehyde for [Ni(L1)2] (1) and [Ni(L2)2] (2) respectively. The complexes have been characterized by several spectroscopic techniques, viz. FT-IR, 1H NMR, absorption and emission spectroscopy. The complexes crystallize in monoclinic crystal system with C2/c space group for 1 and triclinic crystal system with P-1 space group for 2. In complex 1 the nickel sits on an inversion centre with symmetry -x, 2-y, -z. Cyclic voltammgrams of the complexes show quasi-reversible NiII/NiIII oxidation couple along with irreversible NiII/NiI reduction. Electronic structure and spectral properties are well interpreted by DFT and TDDFT calculations.

  19. [Studies on the mechanism of the interaction between hydrazide-podophyllic Ni(II), Co(II), Zn(II) metal complexes and DNA].

    PubMed

    Wang, Ping-Hong; Zhang, Qi; Yuan, Wen-Bing; Wang, Liu-Fang; Song, Yu-Min; Liu, Hui-Hong

    2006-07-01

    The mechanism of the interaction between hydrazide-podophyllic (HDPP) metal (Me) complexes and calf thymus (ct) DNA in Tris buffer (pH 7.08) was studied by viscosity measurements, electronic absorption, gel electrophoresis, and ethidium bromide (EB) fluorescence spectroscopy. The results from varied experiments show that the intensity of the maximal absorption peaks from absorption spectra is weakened in the presence of DNA compared with that in the absence of DNA. Meanwhile, DNA can remarkably quench the emission intensity of the complex Me-HDPP system. The Me-HDPP complexes can increase the viscosity of ct DNA slightly and catalyze the cleavage of super coiled pBR322 DNA to the nicked form. The complexes of Ni-HDPP and Co-HDPP can be bound to ct DNA mainly by interaction, while the partial interaction of Zn-HDPP and ct DNA is the major modes. The binding constant of Me-HDPP complexes with ct DNA was determined.

  20. One-pot synthesis, structural characterization, UV-Vis and electrochemical analyses of new Schiff base complexes of Fe(III), Ni(II) and Cu(II)

    NASA Astrophysics Data System (ADS)

    Back, Davi Fernando; de Oliveira, Gelson Manzoni; Fontana, Liniquer Andre; Ramão, Brenda Fiorin; Roman, Daiane; Iglesias, Bernardo Almeida

    2015-11-01

    The complexes [Ni(Pyr2tetam-2H)]·2H2O (1) (Pyr2tetam = (pyridoxyl)2-N1,N4-triethylenetetramine), [Fe(Pyr2tetam-2H)](ClO4)·H2O (2) and [Cu(Pyrtetam-H)](ClO4) (3) (Pyrtetam = pyridoxyl-N1-triethylenetetramine) were obtained through one pot reactions of triethylenetetramine, pyridoxal chloridrate, triethylamine and the metal salts Ni(ClO4)2·6H2O, Fe(ClO4)2·6H2O and Cu(ClO4)2·6H2O. In complexes 1 and 2 the metal centers present a distorted octahedral coordination, while complex 3 shows a square pyramidal configuration. The structures were characterized through X-ray diffractometry, IR and UV-Vis spectra. Cyclic voltammograms of the title compounds are also presented and discussed.

  1. Synthesis, crystal structures and theoretical studies of dinuclear Mn(II) and Ni(II) complexes of phenol-based "end-off" compartmental ligand

    NASA Astrophysics Data System (ADS)

    Jana, Atanu; Das, Kinsuk; Konar, Saugata; Dhara, Anamika; Biswas, Sujan; Chatterjee, Sudipta; Mondal, Tapan Kumar

    2015-11-01

    Two novel complexes [Mn2(phmp)2](ClO4)2 (1) and [Ni2(phmp)(μ-H2O)(H2O)4](NO3)3 (2) were synthesized using an "end-off" compartmental ligand [H-phmp = 4-Methyl-2,6-bis-(pyridin-2-yl-hydrazonomethyl)-phenol] with Mn(II)-perchlorate and Ni(II)-nitrate salts as metal precursors. Both these complexes were characterized by spectroscopic (IR, UV-Vis) and X-ray crystal structure analysis. The ligand, H-phmp acts as a pentadentate NNONN donor for both the metal complexes and the geometry of the complexes 1 and 2 is distorted octahedral. The DFT optimized bond distances and angles are well correlate to the X-ray structure bond parameters. For complex 1 the transitions at 435 nm and 428 nm have mixed MLCT (dπ(Mn) → π*(L)) and ILCT (π(L) → π*(L)) character whereas other transitions correspond to intra-ligand charge transfer transitions (ILCT). For complex 2, weak transitions at 464 and 405 nm correspond to ligand to metal charge transfer transitions (LMCT) (π(L) → dπ(Ni)) and most of the other transitions have ILCT character. As anticipated, various weak forces, i.e. anion-π/π-anion/anion-π/π-NH interactions as well as C-H/π interaction, play a key role in stabilizing the self-assembly process observed for both compounds.

  2. Synthesis, spectral characterization, structural investigation and antimicrobial studies of mononuclear Cu(II), Ni(II), Co(II), Zn(II) and Cd(II) complexes of a new potentially hexadentate N2O4 Schiff base ligand derived from salicylaldehyde

    NASA Astrophysics Data System (ADS)

    Keypour, Hassan; Shayesteh, Maryam; Rezaeivala, Majid; Chalabian, Firoozeh; Elerman, Yalcin; Buyukgungor, Orhan

    2013-01-01

    A new potentially hexadentate N2O4 Schiff base ligand, H2L derived from condensation reaction of an aromatic diamine and salicylaldehyde, and its metal complexes were characterized by elemental analyses, IR, UV-Vis, EI-MS, 1H and 13C NMR spectra, as well as conductance measurements. It has been originated that the Schiff base ligand with Cu(II), Ni(II), Co(II), Cd(II) and Zn(II) ions form mononuclear complexes on 1:1 (metal:ligand) stoichiometry. The conductivity data confirm the non-electrolytic nature of the complexes. Also the crystal structures of the complexes [ZnL] and [CoL] have also been determined by using X-ray crystallographic technique. The Zn(II) and Co(II) complexes show a tetrahedral configuration. Electronic absorption spectra of the Cu(II) and Ni(II) complexes suggest a square-planar geometry around the central metal ion. The synthesized compounds have antibacterial activity against the three Gram-positive bacteria: Bacillus cereus, Enterococcus faecalis and Listeria monocytogenes and also against the three Gram-negative bacteria: Salmonella paraB, Citrobacter freundii and Enterobacter aerogenes. The results showed that in some cases the antibacterial activity of complexes were more than nalidixic acid and amoxicillin as standards.

  3. Structures and spectroscopic properties of Ni(II) and Mn(II) complexes based on 5-(3‧, 5‧-dicarboxylphenyl) picolinic acid ligand

    NASA Astrophysics Data System (ADS)

    Ma, Qi; Song, Jin-Ping; Su, Feng; Guo, Jun-Mei; Guo, Yong; Dong, Chuan

    2016-05-01

    Two novel complexes including [Ni(Hdcppa)(H2O)4] (1) and {[Mn3(dcppa)2(H2O)6]·2H2O}n (2) have been synthesized and characterized by single crystal X-ray structure analysis and elemental analysis. Results show that 1 is a mononuclear nickel(II) compound with octahedron coordination geometry, while 2 is a stairs-like 2D layer structure consisting of the trinuclear MnII units linked through dcppa3-. Spectroscopic and electrochemical properties of the complexes 1-2 have also been studied in dimethyl sulfoxide solution at room temperature.

  4. Mechanistic information from volume profiles for water exchange and complex-formation reactions of aquated Ni(II). pH, buffer and medium effects.

    PubMed

    Gazzaz, Hanaa Asaad; Ember, Erika; Zahl, Achim; van Eldik, Rudi

    2009-11-21

    Rate and activation parameters for the complex-formation reaction of Ni(2+) with 4-(2-pyridylazo)-N,N-dimethyl aniline (PADA) were studied as a function of pH in different buffers in both aqueous and sodium dodecyl sulfate (SDS) micelle solutions. In aqueous Tris buffer solution, the forward and backward rate constants increased with increasing pH, while the complex-formation constant decreased due to a larger increase in the backward rate constant. The activation entropy, DeltaS(#), and activation volume, DeltaV(#), changed with increasing pH from positive to negative values, suggesting an apparent changeover from a dissociative to a more associative mechanism. Complex-formation reactions with 2,2'-bipyridine in Tris buffer showed almost no increase in the forward and backward rate constants on increasing the pH, but the DeltaS(#) and DeltaV(#) values became more negative. N-ethylmorpholine buffer showed no pH effect on the rate constants and activation parameters. Water exchange reactions of aquated Ni(2+) were also studied as a function of pH under the same conditions. The reported rate and activation parameters for water exchange in Tris and N-ethylmorpholine buffers are consistent with those found for the complex-formation reactions of Ni(2+) with PADA. The observed pH and buffer effects for both the complex-formation and water exchange reactions of aquated Ni(2+) can be accounted for in terms of the formation of a Ni(2+)-Tris complex in Tris buffer and general base catalysis by the buffer components. In SDS micelle solution, the complex-formation reaction with PADA was much faster than in aqueous solution, but the increase in rate constant with increasing pH was less significant, while DeltaS(#) and DeltaV(#) became more positive, pointing to a more dissociative mechanism. For SDS micelle solutions there was no effect on the water exchange rate constant or activation volume. Mechanistic interpretations are offered for all observed pH, buffer and medium

  5. Synthesis, crystal structure, spectroscopic, thermogravimetric and theoretical characterization of Ni(II) and Zn(II) complexes with 4-chloro-2-nitrobenzenesulfonamide

    NASA Astrophysics Data System (ADS)

    Estiu, G.; Chacón Villalba, M. E.; Camí, G. E.; Echeverria, G. A.; Soria, D. B.

    2014-03-01

    Two new complexes of Ni and Zn with 4-chloro-2-nitrobenzenesulfonamide (ClNbsa) have been synthesized and characterized. The structure of the [Ni(ClNbsa)2(NH3)4] complex was determined by X-ray diffraction methods. It crystallizes in the monoclinic P21/c space group with a = 12.8679(3) Å, b = 7.7254(1) Å, c = 12.2478(2) Å, β = 109.899(2)°, V = 1144.85 (4)Å3 and Z = 4 molecules per unit cell. The coordination geometry of the Nickel (II) ion in the complex can be described as a distorted octahedron with two N-sulfonamide and four NH3 groups in opposite vertices. Due to the poor solubility of the Zn(II) complex, their cell parameters were determined by indexing the powder X-ray pattern using the successive dichotomy method implemented in the Fullprof Suite software package. A triclinic cell was determined with cell parameters a = 18.3724(1) Å, b = 7.9468(8) Å, c = 10.2212(9) Å α = 63.061(6) β = 108.754(6) γ = 109.153(6) and V = 1229.97(2)Å3. Nuclear magnetic resonance (NMR) spectroscopy of 1H and 13C have been used for support the structure of the Zn complex. Vibrational and electronic spectroscopy have been used to characterize the compounds, using theoretical calculations for the assignment of the experimental bands. The thermal behavior was investigated by thermogravimetric analyses (TG) and differential thermal analysis (DT).

  6. Zn(II), Ni(II), Cu(II) and Pb(II) complexes of tridentate asymmetrical Schiff base ligands: Synthesis, characterization, properties and biological activity

    NASA Astrophysics Data System (ADS)

    Şahin, Mustafa; Koçak, Nuriye; Erdenay, Damla; Arslan, Uğur

    2013-02-01

    New asymmetrical tridentate Schiff base ligands were synthesized using 1,2-phenylenediamine, 4-methyl-1,2-phenylenediamine, 2-hydroxy-1-napthaldehyde, 9-anthracenecarboxaldehyde. Schiff base ligands and their metal complexes were synthesised and characterized by using FT-IR, 1H NMR, 13C NMR, UV-Vis, XRD, ESR, elemental analysis and fluorescence studies. The antimicrobial activity of the ligands and their metal complexes were studied against Staphylococcus aureus ATCC 29213, S. aureus ATCC 25923, Streptococcus mutans RSHM 676, Enterococcus faecalis ATCC 29212, Escherichia coli ATCC 25922, Pseudomonas aeruginosa ATCC 27853. The determination of the antibacterial activity was done using the broth microdilution methods. In general, it has been determined that the studied compounds have MIC values similar to Gram-positive and Gram-negative bacteria. It has been found that Ni, Pb, Zn derivatives of HL1A and ZnL2A has lower MIC values than ampicillin for P. aeruginosa ATCC 27853 strain.

  7. Zn(II), Ni(II), Cu(II) and Pb(II) complexes of tridentate asymmetrical Schiff base ligands: synthesis, characterization, properties and biological activity.

    PubMed

    Şahin, Mustafa; Koçak, Nuriye; Erdenay, Damla; Arslan, Uğur

    2013-02-15

    New asymmetrical tridentate Schiff base ligands were synthesized using 1,2-phenylenediamine, 4-methyl-1,2-phenylenediamine, 2-hydroxy-1-napthaldehyde, 9-anthracenecarboxaldehyde. Schiff base ligands and their metal complexes were synthesised and characterized by using FT-IR, (1)H NMR, (13)C NMR, UV-Vis, XRD, ESR, elemental analysis and fluorescence studies. The antimicrobial activity of the ligands and their metal complexes were studied against Staphylococcus aureus ATCC 29213, S. aureus ATCC 25923, Streptococcus mutans RSHM 676, Enterococcus faecalis ATCC 29212, Escherichia coli ATCC 25922, Pseudomonas aeruginosa ATCC 27853. The determination of the antibacterial activity was done using the broth microdilution methods. In general, it has been determined that the studied compounds have MIC values similar to Gram-positive and Gram-negative bacteria. It has been found that Ni, Pb, Zn derivatives of HL1A and ZnL(2)A has lower MIC values than ampicillin for P. aeruginosa ATCC 27853 strain.

  8. Design, spectral characterization, thermal, DFT studies and anticancer cell line activities of Co(II), Ni(II) and Cu(II) complexes of Schiff bases derived from 4-amino-5-(pyridin-4-yl)-4H-1,2,4-triazole-3-thiol

    NASA Astrophysics Data System (ADS)

    Tyagi, Prateek; Chandra, Sulekh; Saraswat, B. S.; Yadav, Deepak

    2015-06-01

    A series of two biologically active Schiff base ligands L1, L2 have been synthesized in equimolar reaction of 4-amino-5-(pyridin-4-yl)-4H-1,2,4-triazole-3-thiol with thiophene-2-carbaldehyde and furan-2-carbaldehyde. The synthesized Schiff bases were used for complexation with different metal ions like Co(II), Ni(II) and Cu(II) by using a molar ratio of ligand: metal as 1:1 and 2:1. The characterization of Schiff bases and metal complexes was done by 1H NMR, UV-Vis, TGA, IR, mass spectrometry and molar conductivity studies. The in DFT studies the geometries of Schiff bases and metal complexes were fully optimized with respect to the energy using the 6-31+g(d,p) basis set. On the basis of the spectral studies an octahedral geometry has been assigned for Co(II), Ni(II) and Cu(II) complexes. The effect of these complexes on proliferation of human breast cancer cell line (MCF-7) and human hepatocellular liver carcinoma cell line (Hep-G2) were studied and compared with those of free ligand. The anticancer cell line results reveal that all metal complexes show moderate to significant % cytotoxicity on cell line HepG2 and MCF-7.

  9. Design, spectral characterization, thermal, DFT studies and anticancer cell line activities of Co(II), Ni(II) and Cu(II) complexes of Schiff bases derived from 4-amino-5-(pyridin-4-yl)-4H-1,2,4-triazole-3-thiol.

    PubMed

    Tyagi, Prateek; Chandra, Sulekh; Saraswat, B S; Yadav, Deepak

    2015-06-15

    A series of two biologically active Schiff base ligands L(1), L(2) have been synthesized in equimolar reaction of 4-amino-5-(pyridin-4-yl)-4H-1,2,4-triazole-3-thiol with thiophene-2-carbaldehyde and furan-2-carbaldehyde. The synthesized Schiff bases were used for complexation with different metal ions like Co(II), Ni(II) and Cu(II) by using a molar ratio of ligand: metal as 1:1 and 2:1. The characterization of Schiff bases and metal complexes was done by (1)H NMR, UV-Vis, TGA, IR, mass spectrometry and molar conductivity studies. The in DFT studies the geometries of Schiff bases and metal complexes were fully optimized with respect to the energy using the 6-31+g(d,p) basis set. On the basis of the spectral studies an octahedral geometry has been assigned for Co(II), Ni(II) and Cu(II) complexes. The effect of these complexes on proliferation of human breast cancer cell line (MCF-7) and human hepatocellular liver carcinoma cell line (Hep-G2) were studied and compared with those of free ligand. The anticancer cell line results reveal that all metal complexes show moderate to significant % cytotoxicity on cell line HepG2 and MCF-7.

  10. Structure of the Ni(II) complex of Escherichia coli peptide deformylase and suggestions on deformylase activities depending on different metal(II) centres.

    PubMed

    Yen, Ngo Thi Hai; Bogdanović, Xenia; Palm, Gottfried J; Kühl, Olaf; Hinrichs, Winfried

    2010-02-01

    Crystal structures of polypeptide deformylase (PDF) of Escherichia coli with nickel(II) replacing the native iron(II) have been solved with chloride and formate as metal ligands. The chloro complex is a model for the correct protonation state of the hydrolytic hydroxo ligand and the protonated status of the Glu133 side chain as part of the hydrolytic mechanism. The ambiguity that recently some PDFs have been identified with Zn(2+) ion as the active-site centre whereas others are only active with Fe(2+) (or Co(2+), Ni(2+) is discussed with respect to Lewis acid criteria of the metal ion and substrate activation by the CD loop.

  11. Molecular tectonics: homochiral coordination networks based on combinations of a chiral neutral tecton with Hg(II), Cu(II) or Ni(II) neutral complexes as metallatectons.

    PubMed

    Larpent, Patrick; Jouaiti, Abdelaziz; Kyritsakas, Nathalie; Hosseini, Mir Wais

    2014-02-07

    The use of compound 1 as an enantiomerically pure neutral and rigid organic linear tecton bearing two divergently oriented monodentate coordinating sites appended with two chiral centres of the same (S) configuration leads, in the presence of neutral metal complexes behaving either as a linear (Cu(hfac)2, Cu(OAc)2) or a V-shaped (HgCl2) 2-connecting node or a 4-connecting square node (NiCl2), to the formation of four homochiral 1- and 2-D coordination polymers.

  12. Spectroscopic and theoretical study of Cu(II), Zn(II), Ni(II), Co(II) and Cd(II) complexes of glyoxilic acid oxime

    NASA Astrophysics Data System (ADS)

    Georgieva, Ivelina; Trendafilova, Natasha; Bauer, Günther

    2006-02-01

    The paper presents a detailed experimental and theoretical study of five metal complexes of glyoxilic acid oxime (gaoH 2), Cu(gaoH) 2(H 2O) 2 ( 1), Zn(gaoH) 2(H 2O) 2 ( 2), Co(gaoH) 2(H 2O) 2 ( 3), Ni(gaoH) 2(H 2O) 2 ( 4) and [Cd(gaoH) 2(H 2O) 2]·H 2O ( 5). The electronic and vibrational spectra were measured and discussed as to the most sensitive to the M-L binding bands. Two different types of coordination were considered for gaoH - ligand: bidentate through the carboxylic oxygen and oxime nitrogen in 1- 4 and mixed bidentate and bridging through the COO group in 5. It is shown that the spectral behavior of the ν(COO) modes can be used to predict bridging ligand coordination. DFT(B3LYP/6-31++G(d,p)) calculations on model compounds: neutral, anionic and radical forms of gao and Cu(gaoH) 2, have been carried out to correlate geometries, electronic and vibrational structures. The results obtained were used to assist the electronic and vibrational analysis of the complexes studied. The effect of the metal-ligand interactions (electrostatic and covalent) on the geometry structure of the ligand was investigated.

  13. Spectroscopic and theoretical study of Cu(II), Zn(II), Ni(II), Co(II) and Cd(II) complexes of glyoxilic acid oxime.

    PubMed

    Georgieva, Ivelina; Trendafilova, Natasha; Bauer, Günther

    2006-02-01

    The paper presents a detailed experimental and theoretical study of five metal complexes of glyoxilic acid oxime (gaoH2), Cu(gaoH)2(H2O)2 (1), Zn(gaoH)2(H2O)2 (2), Co(gaoH)2(H2O)2 (3), Ni(gaoH)2(H2O)2 (4) and [Cd(gaoH)2(H2O)2].H2O (5). The electronic and vibrational spectra were measured and discussed as to the most sensitive to the M-L binding bands. Two different types of coordination were considered for gaoH- ligand: bidentate through the carboxylic oxygen and oxime nitrogen in 1-4 and mixed bidentate and bridging through the COO group in 5. It is shown that the spectral behavior of the nu(COO) modes can be used to predict bridging ligand coordination. DFT(B3LYP/6-31++G(d,p)) calculations on model compounds: neutral, anionic and radical forms of gao and Cu(gaoH)2, have been carried out to correlate geometries, electronic and vibrational structures. The results obtained were used to assist the electronic and vibrational analysis of the complexes studied. The effect of the metal-ligand interactions (electrostatic and covalent) on the geometry structure of the ligand was investigated.

  14. Synthesis, Characterization, Electrochemical Studies, and In Vitro Antibacterial Activity of Novel Thiosemicarbazone and Its Cu(II), Ni(II), and Co(II) Complexes

    PubMed Central

    Khan, Salman A.; Asiri, Abdullah M.; Al-Amry, Khalid; Malik, Maqsood Ahmad

    2014-01-01

    Metal complexes were prepared by the reaction of thiosemicarbazone with CuCl2, NiCl2, CoCl2, Cu(OAc)2, Ni(OAc)2, and Co(OAc)2. The thiosemicarbazone coordinates to metal through the thionic sulfur and the azomethine nitrogen. The thiosemicarbazone was obtained by the thiosemicarbazide with 3-acetyl-2,5-dimethylthiophene. The identities of these compounds were elucidated by IR, 1H, 13C-NMR, and GC-MS spectroscopic methods and elemental analyses. The antibacterial activity of these compounds was first tested in vitro by the disc diffusion assay against two Gram-positive and two Gram-negative bacteria, and then the minimum inhibitory concentration (MIC) was determined by using chloramphenicol as reference drug. The results showed that compound 1.1 is better inhibitor of both types of tested bacteria as compared to chloramphenicol. PMID:24523641

  15. Co(II), Ni(II) and Cu(II) complexes of methyl-5-(Phenylthio) benzimidazole-2-carbamate: Molecular structures, spectral and DFT calculations

    NASA Astrophysics Data System (ADS)

    Mansour, Ahmed M.; El Bakry, Eslam M.; Abdel-Ghani, Nour T.

    2016-05-01

    [Co(FBZ)2(H2O)]·2NO3·0.5H2O (1), [Ni(FBZ)2X2]·zH2O (X = Cl​-, z = 0.5 (2) and X = CH3COO-, z = 1 (3)) and [Cu(FBZ)2(H2O) (NO3)]·NO3·1.5H2O (4) (FBZ = methyl-5-(Phenylthio) benzimidazole-2-carbamate; Fenbendazole) complexes were synthesized and characterized by elemental analysis, thermal, IR, EPR, UV-Vis, magnetic and conductance measurements. Geometry optimization, molecular electrostatic potential maps and natural bond orbital analysis were carried out at DFT/B3LYP/6-31G∗ level of theory. FBZ behaves as a neutral bidentate ligand via the pyridine-type nitrogen of the benzimidazole moiety and the carbamate group. Three-step ionization with pKa values of 3.38, 4.06 and 10.07 were reported for FBZ. The coordination of FBZ to the metal ions led to an increase in the antibacterial activity against the tested Staphylococcus aureus and Escherichia coli bacteria.

  16. Wheel-like Mn(II)6 and Ni(II)6 complexes from the use of 2-pyridinealdoxime and carboxylates.

    PubMed

    Zhang, Suyun; Zhen, Lina; Xu, Bin; Inglis, Ross; Li, Kai; Chen, Wenqian; Zhang, Yong; Konidaris, Konstantis F; Perlepes, Spyros P; Brechin, Euan K; Li, Yahong

    2010-04-21

    The employment of 2-pyridinealdoxime, (py)C(H)NOH, in nickel(II) and manganese(II) carboxylate chemistry under solvothermal conditions is reported. The syntheses, crystal structures and magnetochemical characterization (for two representative compounds) are described for [Ni(6)(O(2)CMe)(6){(py)C(H)NO}(6)].H(2)O (1.H(2)O), [Ni(6)(O(2)CPh)(6){(py)C(H)NO}(6)].2EtOH (2.2EtOH), [Ni(6){(4-Cl)O(2)CPh}(6){(py)C(H)NO}(6)].2EtOH (3.2EtOH) and [Mn(6)(O(2)CMe)(6){(py)C(H)NO}(6)].H(2)O (4.H(2)O), where (4-Cl)PhCO(2)(-) is 4-chlorobenzoate. The reactions of M(O(2)CMe)(2).4H(2)O (M = Ni, Mn) with one equivalent of (py)C(H)NOH in EtOH at 120 degrees C under autogenous pressure give isostructural 1.H(2)O and 4.H(2)O. Complexes 2.2EtOH and 3.2EtOH were obtained from the 1 : 1 : 1 Ni(O(2)CMe)(2).4H(2)O/{(py)C(H)NOH/(X)PhCO(2)H reaction mixtures in EtOH under solvothermal conditions (X = H, 4-Cl). The structurally similar clusters 1-4 have a wheel-like topology with the six metal ions in a chair conformation. Each metal site is bound to four oxygen and two nitrogen atoms; the donor atoms come from two carboxylate oxygens, two oximate oxygens, one pyridyl nitrogen and one oximate nitrogen atom. The carboxylate ligands show the syn, syn eta(1):eta(1):mu mode, while the (py)C(H)NO(-) ions behave as eta(1):eta(1):eta(2):mu(3) ligands. Each metal...metal vector is bridged by one carboxylate group, one mu-O derived from a (py)C(H)NO(-) ligand and by one diatomic oximate-NO- group from an adjacent (py)C(H)NO(-) group. The IR spectra of the complexes are discussed in terms of the coordination modes of the ligands. Variable-temperature, solid-state dc magnetic susceptibility studies were carried out on polycrystalline samples of 1 and 4. The data in the 2.0-300 K range have been fit to a model with one J value revealing moderate (1) or weak (2) antiferromagnetic M(II)...M(II) exchange interactions. This work demonstrates the synthetic potential of combining (py)C(H)NOH with carboxylate ligands

  17. Dehydrogenation of ammonia-borane by cationic Pd(II) and Ni(II) complexes in a nitromethane medium: hydrogen release and spent fuel characterization.

    PubMed

    Kim, Sung-Kwan; Hong, Sung-Ahn; Son, Ho-Jin; Han, Won-Sik; Michalak, Artur; Hwang, Son-Jong; Kang, Sang Ook

    2015-04-28

    A highly electrophilic cationic Pd(II) complex, [Pd(MeCN)4][BF4]2 (1), brings about the preferential activation of the B-H bond in ammonia-borane (NH3·BH3, AB). At room temperature, the reaction between 1 in CH3NO2 and AB in tetraglyme leads to Pd nanoparticles and formation of spent fuels of the general formula MeNHxBOy as reaction byproducts, while 2 equiv. of H2 is efficiently released per AB equiv. at room temperature within 60 seconds. For a mechanistic understanding of dehydrogenation by 1, the chemical structures of spent fuels were intensely characterized by a series of analyses such as elemental analysis (EA), X-ray photoelectron spectroscopy (XPS), solid state magic-angle-spinning (MAS) NMR spectra ((2)H, (13)C, (15)N, and (11)B), and cross polarization (CP) MAS methods. During AB dehydrogenation, the involvement of MeNO2 in the spent fuels showed that the mechanism of dehydrogenation catalyzed by 1 is different from that found in the previously reported results. This AB dehydrogenation derived from MeNO2 is supported by a subsequent digestion experiment of the AB spent fuel: B(OMe)3 and N-methylhydroxylamine ([Me(OH)N]2CH2), which are formed by the methanolysis of the AB spent fuel (MeNHxBOy), were identified by means of (11)B NMR and single crystal structural analysis, respectively. A similar catalytic behavior was also observed in the AB dehydrogenation catalyzed by a nickel catalyst, [Ni(MeCN)6][BF4]2 (2).

  18. Syntheses, spectroscopic and thermal analyses of cyanide bridged heteronuclear polymeric complexes: [M(L)2Ni(CN)4]n (Ldbnd N-methylethylenediamine or N-ethylethylenediamine; Mdbnd Ni(II), Cu(II), Zn(II) or Cd(II))

    NASA Astrophysics Data System (ADS)

    Karaağaç, Dursun; Kürkçüoğlu, Güneş Süheyla

    2016-02-01

    Polymeric tetracyanonickelate(II) complexes of the type [M(L)2Ni(CN)4]n (Ldbnd N-methylethylenediamine (men) or N-ethylethylenediamine (neen); Mdbnd Ni(II), Cu(II), Zn(II) or Cd(II)) have been prepared and characterized by FT-IR, Raman spectroscopy, thermal and elemental analysis techniques. Additionally, FT-IR and Raman spectral analyses of men and neen have experimentally and theoretically investigated in the range of 4000-250 cm-1. The corresponding vibration assignments of men and neen are performed by using B3LYP density functional theory (DFT) method together with 6-31 G(d) basis set. The spectral features of the complexes suggest that the coordination environment of the M(II) ions are surrounded by the two symmetry related men and neen ligands and the two symmetry related N atom of cyanide groups, whereas the Ni(II) atoms are coordinated with a square-planar to four C atoms of the cyanide groups. Polymeric structures of the complexes consist of one dimensional alternative chains of [M(L)2]2+ and [Ni(CN)4]2- moieties. The thermal decompositions in the temperature range 30-700 °C of the complexes were investigated in the static air atmosphere.

  19. Adsorption characteristics of Ni(II) onto MA-DTPA/PVDF chelating membrane.

    PubMed

    Zhao, Xiaodan; Song, Laizhou; Fu, Jie; Tang, Pei; Liu, Feng

    2011-05-30

    The melamine-diethylenetriaminepentaacetic acid/polyvinylidene fluoride (MA-DTPA/PVDF) chelating membrane bearing polyaminecarboxylate groups was prepared for the removal of Ni(II) from wastewater effluents. The membrane was characterized by SEM, (13)C NMR and FTIR techniques. Quantitative adsorption experiments were performed in view of pH, contact time, temperature, the presence of Ca(II) and lactic acid as the controlling parameters. Adsorption kinetics and equilibrium were examined regarding the single Ni(II) system, binary Ni(II) and Ca(II) system and nickel-lactic acid complexes system. The desorption efficiency was also evaluated, and the adsorption mechanism was suggested based on experimental data. The results show that the sorption kinetics fit well to Lagergren second-order equation and the isotherms can be well described by Langmuir model. At 298 K, the second-order rate constant is calculated to be 4.171, 11.39, 6.203 cm(2)/(mg min) and the equilibrium uptake is 0.0264, 0.0211 and 0.0216 mg/cm(2) in the aforementioned three systems. The distribution coefficient of Ni(II) slowly decreases from 4.27 to 2.72, and the separation factor (f(Ni(II)/Ca(II))) increases from 3.10 to 8.46 when the initial Ca(II) concentration varies from 20 to 200mg/L. This reveals the chelating membrane shows more affinity for Ni(II) than Ca(II) ions. In the studied range of lactic acid concentration, Ni(II) uptake decreases with the maximum ratio of 10%. Chemical bonding (chelation) dominates in the adsorption process, and the negative ΔG° and ΔH° indicate the spontaneous and exothermic nature of adsorption.

  20. Spectroscopic and structural study of some 2,5-hexanedione bis(salicyloylhydrazone) complexes: Crystal structures of its Ni(II) and Cu(II) complexes and N-(2,5-dimethyl-1H-pyrrol-1-yl)-2-hydroxy-benzamide

    NASA Astrophysics Data System (ADS)

    Jeragh, Bakir; El-Asmy, Ahmed A.

    2014-08-01

    The reaction between 2,5-hexanedione and salicylic acid hydrazide produced two compounds: 2,5-hexanedione bis(salicyloylhydrazone) [HDSH] (ethanol insoluble) and N-(2,5-dimethyl-1H-pyrrol-1-yl)-2-hydroxybenzamide [DPH] (ethanol soluble). HDSH formed complexes with Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II) and Pd(II) which are characterized by elemental analyses, spectra (IR, 1H NMR, ESR and MS), thermal and magnetic measurements. The crystals of [Ni(HDSH-2H)(EtOH)(H2O)] and [Cu(HDSH-2H)] were solved having octahedral and square-planar geometries, respectively. The other complexes have the formulae [Co(HDSH-2H)(H2O)2], [Cu(HDSH-H)2], [Zn(HDSH-2H)(H2O)2], [Cd2(HDSH-4H)(H2O)4], [Cd2(HDSH-2H)(H2O)4Cl2]; [Hg(HDSH-2H)] and [Pd2(HDSH-4H)(H2O)4]. The obtained complexes are stable in air and non-hygroscopic. The magnetic moments and electronic spectra of the complexes provide different geometries. The ESR spectra support the mononuclear geometry for [Cu(HDSH-2H)] and [Cu(HDSH-H)2]. The thermal decomposition of the complexes revealed the coordinated waters as well as the end product which is in most cases the metal oxide. The crystal structure of N-(2,5-dimethyl-1H-pyrrol-1-yl)-2-hydroxybenzamide is solved by X-ray technique.

  1. Spectroscopic and structural study of some 2,5-hexanedione bis(salicyloylhydrazone) complexes: crystal structures of its Ni(II) and Cu(II) complexes and N-(2,5-dimethyl-1H-pyrrol-1-yl)-2-hydroxy-benzamide.

    PubMed

    Jeragh, Bakir; El-Asmy, Ahmed A

    2014-08-14

    The reaction between 2,5-hexanedione and salicylic acid hydrazide produced two compounds: 2,5-hexanedione bis(salicyloylhydrazone) [HDSH] (ethanol insoluble) and N-(2,5-dimethyl-1H-pyrrol-1-yl)-2-hydroxybenzamide [DPH] (ethanol soluble). HDSH formed complexes with Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II) and Pd(II) which are characterized by elemental analyses, spectra (IR, (1)H NMR, ESR and MS), thermal and magnetic measurements. The crystals of [Ni(HDSH-2H)(EtOH)(H2O)] and [Cu(HDSH-2H)] were solved having octahedral and square-planar geometries, respectively. The other complexes have the formulae [Co(HDSH-2H)(H2O)2], [Cu(HDSH-H)2], [Zn(HDSH-2H)(H2O)2], [Cd2(HDSH-4H)(H2O)4], [Cd2(HDSH-2H)(H2O)4Cl2]; [Hg(HDSH-2H)] and [Pd2(HDSH-4H)(H2O)4]. The obtained complexes are stable in air and non-hygroscopic. The magnetic moments and electronic spectra of the complexes provide different geometries. The ESR spectra support the mononuclear geometry for [Cu(HDSH-2H)] and [Cu(HDSH-H)2]. The thermal decomposition of the complexes revealed the coordinated waters as well as the end product which is in most cases the metal oxide. The crystal structure of N-(2,5-dimethyl-1H-pyrrol-1-yl)-2-hydroxybenzamide is solved by X-ray technique.

  2. Synthesis, spectral and quantum chemical studies and use of (E)-3-[(3,5-bis(trifluoromethyl)phenylimino)methyl]benzene-1,2-diol and its Ni(II) and Cu(II) complexes as an anion sensor, DNA binding, DNA cleavage, anti-microbial, anti-mutagenic and anti-cancer agent

    NASA Astrophysics Data System (ADS)

    Ünver, Hüseyin; Boyacıoğlu, Bahadır; Zeyrek, Celal Tuğrul; Yıldız, Mustafa; Demir, Neslihan; Yıldırım, Nuray; Karaosmanoğlu, Oğuzhan; Sivas, Hülya; Elmalı, Ayhan

    2016-12-01

    We report the synthesis of a novel Schiff base (E)-3-[(3,5-bis(trifluoromethyl) phenylimino)methyl] benzene-1,2-diol from the reaction of 2,3-dihydroxybenzaldehyde with 3,5-bis(trifluoromethyl)aniline, and its Ni(II) and Cu(II) complexes. The molecular structure of the Schiff base was experimentally determined using X-ray single-crystal data and was compared to the structure predicted by theoretical calculations using density functional theory (DFT), Hartree-Fock (HF) and Möller-Plesset second-order perturbation (MP2). In addition, nonlinear optical (NLO) effects of the compound was predicted using DFT. The antimicrobial activities of the compounds were investigated for their minimum inhibitory concentration. UV-Vis spectroscopy studies of the interactions between the compounds and calf thymus DNA (CT-DNA) showed that the compounds interacts with CT-DNA via intercalative binding. A DNA cleavage study showed that the Cu(II) complex cleaved DNA without any external agents. The compounds inhibited the base pair mutation in the absence of S9 with high inhibition rate. In addition, in vitro cytotoxicity of the Ni(II) complex towards HepG2 cell line was assayed by the MTT method. Also, the colorimetric response of the Schiff base in DMSO to the addition of equivalent amount of anions (F-, Br-, I-, CN-, SCN-, ClO4-, HSO4-, AcO-, H2PO4-, N3- and OH-) was investigated. In this regard, while the addition of F-, CN-, AcO- and OH- anions into the solution containing Schiff base resulted in a significant color change, the addition of Br-, I-, SCN-, ClO4-, HSO4-, H2PO4- and N3- anions resulted in no color change. The most discernable color change in the Schiff base was caused by CN-, which demonstrated that the ligand can be used to selectively detect CN-.

  3. Ternary complexes metal [Co(II), Ni(II), Cu(II) and Zn(II)]--ortho-iodohippurate (I-hip)--acyclovir. X-ray characterization of isostructural [(Co, Ni or Zn)(I-hip)(2)(ACV)(H(2)O)(3)] with stacking as a recognition factor.

    PubMed

    Barceló-Oliver, M; Terrón, A; García-Raso, A; Fiol, J J; Molins, E; Miravitlles, C

    2004-11-01

    Four ternary metal--ortho-iodohippurate (I-hip)--acyclovir (ACV) complexes, [M(I-hip)(2)(ACV)(H(2)O)(3)] where M is Co(II) (1), Ni(II) (2), Cu (3) and Zn(II) have been obtained by reaction between the corresponding binary complexes M(II)(I-hip)(2)xnH(2)O and ACV. Three ternary complexes (M=Co, Ni and Zn) and the corresponding Zn(II)--ortho-iodohippurate binary derivative have been structurally characterized by X-ray diffraction: The studies show these three ternary complexes are isostructural and present, in solid state, an interesting stacking between the nucleobase and the aryl ring of the hippurate moiety, which probably promotes the formation of ternary complexes. Moreover, the two different ligands interact between them by means of ancillary hydrogen bonds with water molecules coordinated to the metal ion. It must be mentioned that these two recognition factors, hydrogen bonds plus stacking, could explain the reason for the isostructurality of these ternary derivatives with so different three metal ions, with diverses trends in coordination numbers and geometries. In solid state, there are two enantiomeric molecules that are related by an inversion center as the crystal-building unit (as a translational motif) for the ternary complexes.

  4. Template Synthesis of Co(II), Ni(II) and Cu(II) Complexes Derived From Oxamide Ligand and the Reactivity of Cu(II) Complex Towards Human Serum Albumin

    PubMed Central

    Mohani, Bhawana; Arjmand, Farukh

    2004-01-01

    A new oxamide ligand 2,2'-(oxalydimino)bis(diacetic acid)[C10H11O10N2],[L] has been synthesized by the condensation reaction of Iminodiacetic acid and Diethyloxalate. This ligand [L] was further allowed to interact with triethylene-tetraamine metal complexes [C16H26N6O8M]Cl2 (where M=Co11, Ni11 and Cu11) to yield the new N4 macrocyclic complexes 3, 3', 6, 6' tetraazadodeca 1-1' diimino N N tetraacetic acid M) chloride ([C16H26N6O8Co]Cl2, [C16H26N6O8Ni]Cl2 and [C16H26N6O8Cu]Cl2). These complexes were characterized by elemental analyses, i.r., n.m.r., e.p.r, and u.v.-vis spectroscopy. All the complexes show square planar geometry and are ionic in nature. The kinetic studies of the Cu(lI) complex were ascertained spectrophotometrically by observing the absorbance changes in presence of protein Human Serum Albumin (HSA) in phosphate buffer at different pH's at 300C. The absorbance changes were monitored at 278 nm (λmax of HSA) with respect to time and pseudo-first-order rate constants, kobs, were obtained from the slope of the straight line using the least squares regression method. The electrochemical behaviour of the Cu(ll) complex was monitored by cyclic voltammetry in a phosphate buffer. The Ep values-0.730 and-0.560 V respectively, were obtained at the scan rate of 0.1 Vs-1. The interaction of the Cu(II) complex with the HSA was studied at the same scan rate, which reveals weak binding as the E0 values do not shift considerably. The cyclic voltammogram of the Cu(II) complex bound to HSA was recorded at different pH's also (6.5 to 7.4). The pH-rate profile data reveals that the reactions are pH dependent. PMID:18365078

  5. Cu(II), Co(II), Ni(II), Mn(II), and Fe(II) metal complexes containing N,N'-(3,4-diaminobenzophenon)-3,5-Bu t2-salicylaldimine ligand: Synthesis, structural characterization, thermal properties, electrochemistry, and spectroelectrochemistry

    NASA Astrophysics Data System (ADS)

    Tas, E.; Kilic, A.; Durgun, M.; Küpecik, L.; Yilmaz, I.; Arslan, S.

    2010-02-01

    The synthesis, structure, spectroscopic and electro-spectrochemical properties of steric hindered Schiff-base ligand [ N,N'-(3,4-benzophenon)-3,5-Bu t2-salicylaldimine (LH 2)] and its mononuclear Cu(II), Co(II), Ni(II), Mn(II) and Fe(II) complexes are described in this work. The new dissymmetric steric hindered Schiff-base ligand containing a donor set of NONO was prepared through reaction of 3,4-diaminobenzophenon with 3,5-Bu t2-salicylaldehyde. Certain metal complexes of this ligand were synthesized by treating an ethanolic solution of the ligand with an equimolar amount of metal salts. The ligand and its complexes were characterized by FT-IR, UV-vis, 1H NMR, elemental analysis, molar conductivity and thermal analysis methods in addition to magnetic susceptibility, electrochemistry and spectroelectrochemistry techniques. The tetradentate and mononuclear metal complexes were obtained by reacting N,N'-(3,4-benzophenon)-3,5-Bu t2-salicylaldimine (LH 2) with some metal acetate in a 1:1 mole ratio. The molar conductance data suggest metal complexes to be non-electrolytes.

  6. Pharmacologically significant complexes of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) of novel Schiff base ligand, (E)-N-(furan-2-yl methylene) quinolin-8-amine: Synthesis, spectral, XRD, SEM, antimicrobial, antioxidant and in vitro cytotoxic studies

    NASA Astrophysics Data System (ADS)

    Shakir, M.; Hanif, Summaiya; Sherwani, Mohd. Asif; Mohammad, Owais; Al-Resayes, Saud I.

    2015-07-01

    A novel series of metal complexes of the types, [ML2(H2O)2]Cl2 and [ML2]Cl2 [M = Mn(II), 1; Co(II), 2; Ni(II), 3; Cu(II), 4; and Zn(II), 5] were synthesized by the interaction of ligand, L (E)-N-(furan-2-yl methylene) quinolin-8-amine, derived from the condensation of 2-furaldehyde and 8-aminoquinoline. The synthesized ligand and its metal complexes were characterized on the basis of results obtained from elemental analysis, ESI-MS, XRD, SEM, TGA/DTA, FT-IR, UV-Vis, magnetic moment and 1H and 13C NMR spectroscopic studies. EPR parameters were recorded in case of complex 4. The comparative in-vitro antimicrobial activities against various pathogens with reference to known antibiotics and antioxidant activity against standard control at variable concentrations revealed that the metal complexes show enhanced antimicrobial and free radical scavenging activities in general as compared to free ligand. However, the complexes 1 and 5 have shown best antioxidant activity among all the metal complexes. Furthermore, comparative in-vitro antiproliferative activity on ligand and its metal chelates performed on MDA-MB-231 (breast carcinoma), KCL22 (blood lymphoid carcinoma), HeLa (cervical carcinoma) cell lines and normal cells (PBMC) revealed that metal chelates show moderate to good activity as compared to ligand where as complex 1 seems to be the most promising one possessing a broad spectrum of activity against all the selected cancer cell lines with IC50 < 2.10 μM.

  7. Unexpected Ni(II) and Cu(II) polynuclear assemblies--a balance between ligand and metal ion coordination preferences.

    PubMed

    Shuvaev, Kontantin V; Tandon, Santokh S; Dawe, Louise N; Thompson, Laurence K

    2010-07-14

    Polytopic ligand design involves matching the coordination pocket composition with the metal ion coordination 'algorithm', but despite targeting [4 x 4] grids as the final outcome, metal ion preferences and ligand control can lead to widely varying complexes in the self-assembly process with Ni(II) and Cu(II).

  8. Synthesis, Characterization, and Biological Activity of N (')-[(Z)-(3-Methyl-5-oxo-1-phenyl-1,5-dihydro-4H-pyrazol-4-ylidene)(phenyl)methyl]benzohydrazide and Its Co(II), Ni(II), and Cu(II) Complexes.

    PubMed

    Asegbeloyin, Jonnie N; Ujam, Oguejiofo T; Okafor, Emmanuel C; Babahan, Ilknur; Coban, Esin Poyrazoglu; Ozmen, Ali; Biyik, Halil

    2014-01-01

    Reaction of 1-phenyl-3-methyl-4-benzoyl-pyrazol-5-one and benzoyl hydrazide in refluxing ethanol gave N (')-[(Z)-(3-methyl-5-oxo-1-phenyl-1,5-dihydro-4H-pyrazol-4-ylidene)(phenyl)methyl]benzohydrazide (HL(1)), which was characterized by NMR spectroscopy and single-crystal X-ray structure study. X-ray diffraction analyses of the crystals revealed a nonplanar molecule, existing in the keto-amine form, with intermolecular hydrogen bonding forming a seven-membered ring system. The reaction of HL(1) with Co(II), Ni(II), and Cu(II) halides gave the corresponding complexes, which were characterized by elemental analysis, molar conductance, magnetic measurements, and infrared and electronic spectral studies. The compounds were screened for their in vitro cytotoxic activity against HL-60 human promyelocytic leukemia cells and antimicrobial activity against some bacteria and yeasts. Results showed that the compounds are potent against HL-60 cells with the IC50 value ≤5 μM, while some of the compounds were active against few studied Gram-positive bacteria.

  9. Another step toward DNA selective targeting: NiII and CuII complexes of a Schiff base ligand able to bind gene promoter G-quadruplexes† †Electronic supplementary information (ESI) available. CCDC 1451694–1451696. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6dt00648e Click here for additional data file. Click here for additional data file.

    PubMed Central

    Lötsch, Daniela; van Schoonhoven, Sushilla; Roller, Alexander; Kowol, Christian R.; Berger, Walter; Keppler, Bernhard K.

    2016-01-01

    DNA G-rich sequences are able to form four-stranded structures organized in stacked guanine tetrads. These structures, called G-quadruplexes, were found to have an important role in the regulation of oncogenes expression and became, for such a reason, appealing targets for anticancer drugs. Aiming at finding selective G-quadruplex binders, we have designed, synthesized and characterized a new water soluble Salen-like Schiff base ligand and its NiII and CuII metal complexes. UV-Vis, circular dichroism and FRET measurements indicated that the nickel complex can stabilize oncogene promoter G-quadruplexes with high selectivity, presenting no interactions with duplex DNA at all. The same compound exhibited dose-dependent cytotoxic activity in MCF-7 breast cancer cells when combined with lipofectamine as lipophilic carrier. PMID:27054617

  10. Substitutional impact on biological activity of new water soluble Ni(II) complexes: Preparation, spectral characterization, X-ray crystallography, DNA/protein binding, antibacterial activity and in vitro cytotoxicity.

    PubMed

    Umadevi, C; Kalaivani, P; Puschmann, H; Murugan, S; Mohan, P S; Prabhakaran, R

    2017-02-01

    A series of new water soluble nickel(II) complexes containing triphenylphosphine and 4-methoxysalicylaldehyde-4(N)-substituted thiosemicarbazones were synthesized and characterized. Crystallographic investigations confirmed the structure of the complexes (1-4) having the general structure [Ni(4-Msal-Rtsc)(PPh3)] (Where R=H (1); CH3 (2); C2H5 (3); C6H5 (4)) which showed that thiosemicarbazone ligands coordinated to nickel(II) ion as ONS tridentate bibasic donor. DNA/BSA protein binding ability of the ligands and their new complexes were studied by taking calf-thymus DNA (CT-DNA) and Bovine serum albumin (BSA) through absorption and emission titrations. Ethidium bromide (EB) displacement study showed the intercalative binding trend of the complexes to DNA. From the albumin binding studies, the mechanism of quenching was found as static and the alterations in the secondary structure of BSA by the compounds were confirmed with synchronous spectral studies. The binding affinity of the complexes to CT-DNA and BSA has the order of [Ni(4-Msal-etsc)(PPh3)] (3) >[Ni(4-Msal-mtsc)(PPh3)] (2) >[Ni(4-Msal-tsc)(PPh3)] (1) >[Ni(4-Msal-ptsc)(PPh3)] (4). In vitro cytotoxicity of the complexes was tested on human lung cancer cells (A549), human cervical cancer cells (HeLa), human liver carcinoma cells (Hep G2). All the complexes exhibited significant activity against three cancer cells. Among them, complex 4 exhibited almost 2.5 fold activity than cisplatin in A549 and HepG2 cell lines. In HeLa cell line, the complexes exhibited significant activity which is less than cisplatin. While comparing the activity of the complexes in A549 and HepG2 cell lines it falls in the order 4>1>2>3>cisplatin. The results obtained from DNA, protein binding and cytotoxicity studies, it is concluded that the cytotoxicity of the complexes as determined by MTT assay were not unduly influenced by the complexes having different binding efficiency with DNA and protein. The complexes exhibited good spectrum

  11. Synthesis and X-ray structural studies of Cd(II) and Ni(II) complexes of 5-(4-methoxy phenyl), 5-(2-pyridyl) and 5-(2-methoxy phenyl)-1,3,4-oxadiazole-2-thione

    NASA Astrophysics Data System (ADS)

    Bharty, M. K.; Bharti, A.; Dani, R. K.; Dulare, R.; Bharati, P.; Singh, N. K.

    2012-03-01

    Three new mixed ligand complexes [Cd(en)2(4-mpot)2] (1) [Ni(2-pytone)2(en)2] (2) and [Ni(2-mpot)2(en)2] (3) {4-mpot = 5-(4-methoxy-phenyl)-1,3,4-oxadiazole-2-thione, 2-pytone = 5-(2-pyridyl)-1,3,4-oxadiazole-2-thione, 2-mpot = 5-(2-methoxy-phenyl)-1,3,4-oxadiazole-2-thione} have been prepared containing en as co-ligand. Potassium N-(4-methoxy benzoyl)-hydrazinecarbodithioate cyclized to 5-(4-methoxy-phenyl)-1,3,4-oxadiazole-2-thiol on addition of tetrabutylammonium bromide which then reacted with Cd(OAc)2·2H2O and ethylenediamine to form complex 1, whereas potassium N-(2-methoxy benzoyl/pyridine-2-carbonyl)-hydrazinecarbodithioates (RCONHNHCSSK) underwent cyclization during complexation in the presence of en to give the complexes of the corresponding 5-aryl-1,3,4-oxadiazole-2-thiones. The complexes have been characterized by physicochemical techniques and single crystal X-ray structure determination. In the complexes the metal center has a six coordinate octahedral arrangement coordinated by 4N atoms of two en and two covalently bonded N atoms of the oxadiazole-2-thione anions. All the complexes contain extended hydrogen bonding providing supramolecular framework.

  12. Synthesis, spectroscopic characterization and antimicrobial studies of Co(II), Ni(II), Cu(II) and Zn(II) complexes with Schiff bases derived from 5-bromo-salicylaldehyde

    NASA Astrophysics Data System (ADS)

    Kursunlu, Ahmed Nuri; Guler, Ersin; Sevgi, Fatih; Ozkalp, Birol

    2013-09-01

    In this study, the new Schiff base ligands derived from condensation of amine and 5-bromo-salicylaldehyde were characterized. All compounds, the Schiff bases and the metal complexes, were characterized by elemental analyzes, FT-IR, 1H NMR, 13C NMR and magnetic susceptibility measurements. The synthesized ligands, along with their metal (II) complexes, were screened for their in vitro antibacterial activity against four Gram-negative (Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa and Salmonella enteritidis) and four Gram-positive (Streptococcus pyogones, Bacillus cereus, Staphylococcus aureus and Methicillin-resistant S. aureus) bacterial strains by using disc diffusion and broth microdilution techniques.

  13. Synthesis, spectral characterization, in vitro antibacterial, antifungal and cytotoxic activities of Co(II), Ni(II) and Cu(II) complexes with 1,2,4-triazole Schiff bases.

    PubMed

    Bagihalli, Gangadhar B; Avaji, Prakash Gouda; Patil, Sangamesh A; Badami, Prema S

    2008-12-01

    A series of metal complexes of cobalt(II), nickel(II) and copper(II) have been synthesized with newly synthesized biologically active 1,2,4-triazole Schiff bases derived from the condensation of 3-substituted-4-amino-5-mercapto-1,2,4-triazole and 8-formyl-7-hydroxy-4-methylcoumarin, which have been characterized by elemental analyses, spectroscopic measurements (IR, UV-vis, fluorescence, ESR), magnetic measurements and thermal studies. Electrochemical study of the complexes is also reported. All the complexes are soluble to limited extent in common organic solvents but soluble to larger extent in DMF and DMSO and are non-electrolytes in DMF and DMSO. All these Schiff bases and their complexes have also been screened for their antibacterial (Escherichia coli, Staphylococcus aureus, Streptococcus pyogenes, Pseudomonas aeruginosa and Salmonella typhi) and antifungal activities (Aspergillus niger, Aspergillus flavus and Cladosporium) by MIC method. The brine shrimp bioassay was also carried out to study their in vitro cytotoxic properties.

  14. Synthesis, characterization and anticancer studies of Ni(II), Pd(II) and Pt(II) complexes with Schiff base derived from N-methylhydrazinecarbothioamide and 2-hydroxy-5-methoxy-3-nitrobenzaldehyde

    NASA Astrophysics Data System (ADS)

    Arafath, Md. Azharul; Adam, Farook; Razali, Mohd. R.; Ahmed Hassan, Loiy E.; Ahamed, Mohamed B. Khadeer; Majid, Amin Malik S. A.

    2017-02-01

    A carbothioamide NSO tridentate Schiff base ligand (HL) and its square planar complexes Na[NiLOAc], Na[PdLOAc] and [PtLdmso] have been synthesized and characterized on the basis of melting point, elemental analysis, FT-IR, 1H NMR, 13C NMR, UV-Vis spectra. The structure of HL was elucidated with X-ray diffraction analysis. In the present study, the synthesized compounds were evaluated for their anticancer properties against three human cancer cell lines breast cancer (MCF-7), cervical (Hela), and colon (HCT-116). In addition, the cytotoxicity of the synthesized compounds was tested on a normal human cell line (human endothelial cell line EA.hy926). Among the tested compounds, the complex [NiLOAc] excelled in halting proliferation of the cervical and colon cancer cells with median inhibitory concentration (IC50) values of 28.33 and 34.4 μM, respectively. The complex, [PdLOAc] demonstrated selective cytotoxicity against breast cancer line MCF-7 with IC50 = 47.5 μM, while HL showed inhibitory effect against colon cancer cell line (HCT-116) with IC50 = 55.66 μM. The complex, [PtLdmso] showed mild activity against breast cancer (MCF-7) and cervical cancer (Hela) cells with IC50 = 64.44 and 68.3 μM, respectively, whereas, it displayed insignificant cytotoxicity against human endothelial cells (EA.hy926) with IC50 > 200 μM. Cancer cells treated with [NiLOAc] showed apoptotic features such as membrane blebbing and DNA condensation. Thus, the findings of the present study demonstrated that the series of metal complexes of HL could form the new lead for development of cancer chemotherapies to treat human cervical, breast and colon malignancies.

  15. Syntheses, structures, and magnetic properties of acetato- and diphenolato-bridged 3d-4f binuclear complexes [M(3-MeOsaltn)(MeOH)x(ac)Ln(hfac)2] (M = Zn(II), Cu(II), Ni(II), Co(II); Ln = La(III), Gd(III), Tb(III), Dy(III); 3-MeOsaltn = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato; ac = acetato; hfac = hexafluoroacetylacetonato; x = 0 or 1).

    PubMed

    Towatari, Masaaki; Nishi, Koshiro; Fujinami, Takeshi; Matsumoto, Naohide; Sunatsuki, Yukinari; Kojima, Masaaki; Mochida, Naotaka; Ishida, Takayuki; Re, Nazzareno; Mrozinski, Jerzy

    2013-05-20

    A series of 3d-4f binuclear complexes, [M(3-MeOsaltn)(MeOH)x(ac)Ln(hfac)2] (x = 0 for M = Cu(II), Zn(II); x = 1 for M = Co(II), Ni(II); Ln = Gd(III), Tb(III), Dy(III), La(III)), have been synthesized and characterized, where 3-MeOsaltn, ac, and hfac denote N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato, acetato, and hexafluoroacetylacetonato, respectively. The X-ray analyses demonstrated that all the complexes have an acetato- and diphenolato-bridged M(II)-Ln(III) binuclear structure. The Cu(II)-Ln(III) and Zn(II)-Ln(III) complexes are crystallized in an isomorphous triclinic space group P1, where the Cu(II) or Zn(II) ion has square pyramidal coordination geometry with N2O2 donor atoms of 3-MeOsaltn at the equatorial coordination sites and one oxygen atom of the bridging acetato ion at the axial site. The Co(II)-Ln(III) and Ni(II)-Ln(III) complexes are crystallized in an isomorphous monoclinic space group P2(1)/c, where the Co(II) or Ni(II) ion at the high-spin state has an octahedral coordination environment with N2O2 donor atoms of 3-MeOsaltn at the equatorial sites, and one oxygen atom of the bridged acetato and a methanol oxygen atom at the two axial sites. Each Ln(III) ion for all the complexes is coordinated by four oxygen atoms of two phenolato and two methoxy oxygen atoms of "ligand-complex" M(3-MeOsaltn), four oxygen atoms of two hfac(-), and one oxygen atom of the bridging acetato ion; thus, the coordination number is nine. The temperature dependent magnetic susceptibilities from 1.9 to 300 K and the field-dependent magnetization up to 5 T at 1.9 K were measured. Due to the important orbital contributions of the Ln(III) (Tb(III), Dy(III)) and to a lesser extent the M(II) (Ni(II), Co(II)) components, the magnetic interaction between M(II) and Ln(III) ions were investigated by an empirical approach based on a comparison of the magnetic properties of the M(II)-Ln(III), Zn(II)-Ln(III), and M(II)-La(III) complexes. The differences of χ(M)T and M

  16. Ni(II) Tol-BINAP-catalyzed enantioselective Michael reactions of beta-ketoesters and unsaturated N-acylthiazolidinethiones.

    PubMed

    Evans, David A; Thomson, Regan J; Franco, Francisco

    2005-08-10

    The enantioselective addition of beta-ketoesters to unsaturated N-acylthiazolidinethiones catalyzed by Ni(II) Tol-BINAP Lewis acid complexes is reported. Notable features of this reaction are its operation simplicity, the obviated need for the addition of an external base, and the ease with which the adducts are converted into a range of potentially useful derivatives. In particular, the dihydropyrone adducts are versatile scaffolds for further stereoselective elaboration.

  17. Competitive sorption of Pb(II), Cu(II) and Ni(II) on carbonaceous nanofibers: A spectroscopic and modeling approach.

    PubMed

    Ding, Congcong; Cheng, Wencai; Wang, Xiangxue; Wu, Zhen-Yu; Sun, Yubing; Chen, Changlun; Wang, Xiangke; Yu, Shu-Hong

    2016-08-05

    The competitive sorption of Pb(II), Cu(II) and Ni(II) on the uniform carbonaceous nanofibers (CNFs) was investigated in binary/ternary-metal systems. The pH-dependent sorption of Pb(II), Cu(II) and Ni(II) on CNFs was independent of ionic strength, indicating that inner-sphere surface complexation dominated sorption Pb(II), Cu(II) and Ni(II) on CNFs. The maximum sorption capacities of Pb(II), Cu(II) and Ni(II) on CNFs in single-metal systems at a pH 5.5±0.2 and 25±1°C were 3.84 (795.65mg/g), 3.21 (204.00mg/g) and 2.67 (156.70mg/g)mmol/g, respectively. In equimolar binary/ternary-metal systems, Pb(II) exhibited greater inhibition of the sorption of Cu(II) and Ni(II), demonstrating the stronger affinity of CNFs for Pb(II). The competitive sorption of heavy metals in ternary-metal systems was predicted quite well by surface complexation modeling derived from single-metal data. According to FTIR, XPS and EXAFS analyses, Pb(II), Cu(II) and Ni(II) were specifically adsorbed on CNFs via covalent bonding. These observations should provide an essential start in simultaneous removal of multiple heavy metals from aquatic environments by CNFs, and open the doorways for the application of CNFs.

  18. Effective removal of Ni(II) from aqueous solutions by modification of nano particles of clinoptilolite with dimethylglyoxime.

    PubMed

    Nezamzadeh-Ejhieh, Alireza; Kabiri-Samani, Mehdi

    2013-09-15

    In this work an Iranian natural clinoptilolite tuff was pre-treated and changed to the micro (MCP) and nano (NCP) particles by mechanical method. Modification of micro and nano particles and also their Ni-exchanged forms were done by dimethylglyoxime (DMG). The raw and modified samples were characterized by XRD, FT-IR, SEM, BET, TG-DTG and energy dispersive analysis X-ray spectroscopy (EDAX). Removal of Ni(II) by modified and unmodified samples was investigated in batch procedure. It was found that NCP-DMG has higher capacity for removal of Ni(II). The effects of analytical parameters such as pH, dose of DMG, concentration of nickel solution, contact time and selectivity were studied and the optimal operation parameters were found as follows: pHPZC: 7.6, CNi(II): 0.01 M, contact time: 360 min and DMG dosage: 5mM. The results of selectivity experiments showed that the modified zeolite has a good selectivity for nickel in the presence of different multivalent cations. Langmuir and Freundlich isotherm models were adopted to describe the adsorption isotherms. Adsorption isotherms of Ni(II) ions could be best modelled by Langmuir equation, that indicate the monolayer sorption of Ni(II). Comparison of two kinetic models indicates that the adsorption kinetic can be well described by the pseudo-second-order rate equation that indicates that the rate limiting step for the process involves chemical reaction. The negative ΔH and ΔG indicate an exothermic and spontaneously process. The negative ΔS indicates that the adsorption of nickel cations from solution occurs with lower amount ion replacement, thus chemisorptions due to complex formation are dominant process in nickel removal.

  19. Competitive sorption and selective sequence of Cu(II) and Ni(II) on montmorillonite: Batch, modeling, EPR and XAS studies

    NASA Astrophysics Data System (ADS)

    Yang, Shitong; Ren, Xuemei; Zhao, Guixia; Shi, Weiqun; Montavon, Gilles; Grambow, Bernd; Wang, Xiangke

    2015-10-01

    Heavy metal ions that leach from various industrial and agricultural processes are simultaneously present in the contaminated soil and water systems. The competitive sorption of these toxic metal ions on the natural soil components and sediments significantly influences their migration, bioavailability and ecotoxicity in the geochemical environment. In this study, the competitive sorption and selectivity order of Cu(II) and Ni(II) on montmorillonite are investigated by combining the batch experiments, X-ray diffraction (XRD), electron paramagnetic resonance (EPR), surface complexation modeling and X-ray Absorption Spectroscopy (XAS). The batch experimental data show that the coexisting Ni(II) exhibits a negligible influence on the sorption behavior of Cu(II), whereas the coexisting Cu(II) reduces the Ni(II) sorption percentage and changes the shape of the Ni(II) sorption isotherm. The sorption species of Cu(II) and Ni(II) on montmorillonite over the acidic and near-neutral pH range are well simulated by the surface complexation modeling. However, this model cannot identify the occurrence of surface nucleation and the co-precipitation processes at a highly alkaline pH. Based on the results of the EPR and XAS analyses, the microstructures of Cu(II) on montmorillonite are identified as the hydrated free Cu(II) ions at pH 5.0, inner-sphere surface complexes at pH 6.0 and the surface dimers/Cu(OH)2(s) precipitate at pH 8.0 in the single-solute and the binary-solute systems. For the Ni(II) sorption in the single-solute system, the formed microstructure varies from the hydrated free Ni(II) ions at the pH values of 5.0 and 6.0 to the inner-sphere surface complexes at pH 8.0. For the Ni(II) sorption in the binary-solute system, the coexisting Cu(II) induces the formation of the inner-sphere complexes at pH 6.0. In contrast, Ni(II) is adsorbed on montmorillonite via the formation of Ni phyllosilicate co-precipitate/α-Ni(OH)2(s) precipitate at pH 8.0. The selective sequence

  20. DFT investigation of Ni(II) adsorption onto MA-DTPA/PVDF chelating membrane in the presence of coexistent cations and organic acids.

    PubMed

    Song, Laizhou; Zhao, Xiaodan; Fu, Jie; Wang, Xiuli; Sheng, Yiping; Liu, Xiaowei

    2012-01-15

    Melamine-diethylenetriaminepentaacetic acid/polyvinylidene fluoride (MA-DTPA/PVDF) chelating membrane bearing polyaminecarboxylate groups was used to remove Ni(II) from nickel plating effluents. Adsorption experiments were conducted to study the adsorption of the membrane towards Ni(II) in Ni(II)-Ca(II), Ni(II)-NH(4)(+), Ni(II)-Fe(III) binary systems, and Ni(II)-lactic acid, Ni(II)-succinic acid and Ni(II)-citric acid complex systems. For the ternary nickel plating processes, the effects of 3d transition metals including Fe(II), Co(II), Cu(II) and Zn(II) on Ni(II) adsorption were evaluated. The influences of the aforementioned coexistent cations and organic acids were elucidated by the continuum solvation model (COSMO)-corrected density functional theory (DFT) method. Geometries and complexation energies were analyzed for metal-MA-DTPA and Ni(II)-organic acid complexes. DFT results accord with the experimental data, indicating that DFT is helpful to evaluate the complexation between the membrane and metal cations. The coexistent Ca(II) tends to form more stable complex with MA-DTPA ligand than NH(4)(+) and Fe(III), and can interfere with the formation of Ni(II)-MA-DTPA complex. The complexing sequence of 3d metals with MA-DTPA ligand is Zn(II)Ni(II). The stabilities of Ni(II)-organic acid complexes follow the order of lactic acidcomplex.

  1. Elaborated studies for the ligitional behavior of thiouracil derivative towards Ni(II), Pd(II), Pt(IV), Cu(II) and UO2 ² ions.

    PubMed

    Abou-Melha, Khlood Saad

    2012-11-01

    A synthesis of new thiouracil derivative was carried out and deliberately investigated. A new series of complexes was prepared using Ni(II), Pd(II), Pt(IV), Cu(II) and UO(2)(+2) ions. IR spectral data proposed the coordination mod of the ligand towards each metal ion and displays the binegative pentadentate mod as the maximum mod of coordination obtained with Ni(II) and Cu(II) complexes. (1)HNMR spectrum of UO(2)(+2) complex in comparing with the free ligand spectrum supports the binegative appearance of the coordinated ligand through the ionization of CO and CS groups. The electronic spectral data as well as the magnetic moment measurements are coincide with each others to propose the square-planar geometry with Ni(II), Pd(II) and Cu(II) complexes and octahedral geometry with the others. ESR spectrum of Cu(II) complex displays axially symmetric g tensor parameters with g(11)>g(⊥)>2.0023 indicating that the [Formula: see text] orbital as a ground state with the square-planar geometry. The TG analysis for all isolated complexes were carried out to assert about the presence of water molecules physically or chemically attached with the central atom. The biological study was carried out against different microorganisms as gram negative, gram positive and fungi. The comparable data display the relative priority of Ni(II) complex in comparing with others against all organisms but, the other complexes display activity by the same with the free ligand.

  2. XAFS and crystallographic studies of Ni(II) porphyrins in single crystals and in solution

    SciTech Connect

    Renner, M.W.; Furenlid, L.R.; Barkigia, K.M.; Fajer, J.

    1996-09-01

    Abstract. Nickel porphyrins serve as models for the active sites of several biological processes. Crystallographic and EXAFS results for a Ni meso-tetrapropyl porphyrin (NiTPrP) yield different Ni-N distances in solution and in the solid state. The Ni-N distances determined by single crystal polarized XAS and X-ray diffraction agree well. Polarized XANES experiments further establish that the pre-edge feature observed in square planar Ni(II) complexes is a ls-4pz transition. The single crystal and solution EXAFS results demonstrate that conformational variations of the porphyrin macrocycle can readily be imposed by environmental and/or packing forces and can thereby modulate the chemical and physical properties of porphyrinic chromophores and prosthetic groups.

  3. Using a first-derivative spectrophotometric method for simultaneous determination of Fe(II) and Ni(II) in mineral vitamins by interaction with 2,4-diamino-5-(2-hydroxy-5-nitrophenylazo)benzenesulfonic acid sodium salt in the presence of Tween 20.

    PubMed

    Hashem, Elham Y; Seleim, Mohamed M; El-Zohry, Ahmed M

    2010-01-01

    A highly selective and sensitive derivative spectrophotometric method has been developed for the determination of Fe(II) and Ni(II) in different mineral vitamins. The method is based on the formation of binary complexes of Fe(II) and Ni(II) with 2,4-diamino-5-(2-hydroxy-5-nitrophenylazo) benzenesulfonic acid sodium salt (Mordant Brown 33) at pH 5.6 with Tween 20. At lambda(max) 512 and 493 nm, the molar absorbtivity was 2.09 x 10(4) and 0.58 x 10(4) L/mol cm for Fe(II) and Ni(II), respectively. Fe(II) can be determined in the range 0.55-2.79 microg/mL in the presence of 2.92 microg/mL Ni, and Ni(II) can be determined in the range 1.17-3.5 microg/mL in the presence of 2.79 microg/mL Fe(II) in the presence of Tween 20 (4%). The detection limits were 9.0 and 15.0 ng/mL for Fe(II) and Ni(II), respectively. The effect of foreign ions was elucidated. The RSD values were, in all instances, less than 1.3%. The proposed method was successfully applied for the simultaneous determination of Fe(II) and Ni(II) in different mineral vitamins.

  4. Arene C(sp(2))-H Metalation at Ni(II) Modeled with a Reactive PONCPh Ligand.

    PubMed

    Jongbloed, Linda S; García-López, Diego; van Heck, Richard; Siegler, Maxime A; Carbó, Jorge J; van der Vlugt, Jarl Ivar

    2016-08-15

    Coordination of the reactive phosphinitopyridylphenyl PONCPh ligand L(H) to NiBr2 initially yields paramagnetic brown NiBr2(L(H)) (1), but addition of triethylamine results in fast and facile cyclometalation at Ni(II), giving NiBr(κ(3)-P,N,C-L) (2) as well-defined species. This is a rare example of direct cyclometalation at Ni(II) from a C-H bond in a ligand structure other than encumbering ligands (e.g., ECE pincers). Diamagnetic yellow complex 2 reacts instantaneously with HBF4 to give purple [NiBr(κ(3)-P,N-L(H))]BF4 (3). A very unusual (an)agostic Ni(CPh-H) interaction in the solid-state structure of 3 was unequivocally demonstrated using single-crystal X-ray crystallography and was interpreted by density functional theory calculations (quantum theory of atoms in molecules and electron localization function analysis). These compounds may be viewed as models for key intermediates in the Ni-catalyzed C-H functionalization of arenes.

  5. Selective and sensitized spectrophotometric determination of trace amounts of Ni(II) ion using α-benzyl dioxime in surfactant media

    NASA Astrophysics Data System (ADS)

    Ghaedi, Mehrorang

    2007-02-01

    Highly sensitive and interference-free sensitized spectrophotometric method for the determination of Ni(II) ions is described. The method is based on the reaction between Ni(II) ion and benzyl dioxime in micellar media in the presence of sodium dodecyl sulfate (SDS). The absorbance is linear from 0.1 up to 25.0 μg mL -1 in aqueous solution with repeatability (RSD) of 1.0% at a concentration of 1 μg mL -1 and a detection limit of 0.12 ng mL -1 and molar absorption coefficient of 68,600 L mol -1 cm -1. The influence of reaction variables including type and amount of surfactant, pH, and amount of ligand and complexation time and the effect of interfering ions are investigated. The proposed procedure was applied to the determination of trace amounts of Ni(II) ion in tap water, river water, chocolate and vegetable without separation or organic solvent extraction.

  6. The analysis of the immobilization mechanism of Ni(II) on Bacillus cereus.

    PubMed

    Pan, Xiaohong; Chen, Zhi; Cheng, Yangjian; Pan, Danmei; Yin, Shungao; Huang, Feng; Guan, Xiong; Lin, Zhang

    2011-04-01

    This work focused on the identification of biosorption mechanism of Ni(II) by living Bacillus cereus (B. cereus) based on batch experiments and a variety of microscopic equipments. The adsorption equilibrium reached rapidly in 2 h and the maximum nickel adsorption capability of B. cereus was 17.7 mg x g(-1) (dry weight). Atomic force microscopy (AFM) analysis showed that the bacterial surface roughness increased from 7.9 +/- 0.5 nm to 12.6 +/- 1.6 nm during this process. Scanning electron microscopy (SEM) observation confirmed that there was Ni(II) on the bacterial surface. However, transmission electron microscopy (TEM) thin section analysis coupled with energy dispersive X-ray spectroscopy (EDS) revealed that Ni(II) could also be found in the inner portions of the bacteria. Inductive coupled plasma emission spectrometer (ICP-OES) quantitative analysis elucidated that over 70% of the immobilized Ni(II) was binding on the surface of bacteria. X-ray diffraction (XRD) analysis showed that the Ni(II) collected by the bacteria was amorphous. Fourier transform infrared (FT-IR) analysis indicated that amides and carboxylation functional groups might be involved in the coordination of Ni(II).

  7. Biosorption of Ni(II) from aqueous solutions by Litchi chinensis seeds.

    PubMed

    Flores-Garnica, Jonathan Gonzalo; Morales-Barrera, Liliana; Pineda-Camacho, Gabriela; Cristiani-Urbina, Eliseo

    2013-05-01

    The potential of Litchi chinensis seeds (LCS) for biosorption of Ni(II) ions from aqueous solutions was investigated in batch systems in terms of kinetics, equilibrium and thermodynamics. Experimental data showed that the biosorption capacity of LCS was dependent on operating variables such as solution pH, initial Ni(II) concentration, contact time, and temperature. The optimum pH value for Ni(II) biosorption was 7.5. Significant enhancement of Ni(II) biosorption was observed by increasing initial metal concentration and temperature. Modeling of sorption kinetics showed good agreement of experimental data with the pseudo-second-order kinetic model. Langmuir model exhibited the best fit to experimental data. According to this isotherm model, the maximum Ni(II) biosorption capacity of LCS is 66.62 mg g(-1). The calculated thermodynamic parameters showed that the biosorption of Ni(II) ions is an endothermic and non-spontaneous process. Results indicate that LCS can be used as an effective and environmentally friendly biosorbent to detoxify Ni(II)-polluted wastewaters.

  8. Ten metal complexes of vitamin B3/niacin: Spectroscopic, thermal, antibacterial, antifungal, cytotoxicity and antitumor studies of Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Pd(II), Cd(II), Pt(IV) and Au(III) complexes

    NASA Astrophysics Data System (ADS)

    Al-Saif, Foziah A.; Refat, Moamen S.

    2012-08-01

    Ten coordination compounds, namely Mn(NA)2Cl2·4H2O (1), Fe(NA)Cl3(H2O)2 (2), Co(NA)2(NO3)2·6H2O (3), Ni(NA)Cl2·5H2O (4), Cu(NA)Cl2·3H2O (5), Zn(NA)(NO3)2·H2O (6), Pd(NA)2Cl2·H2O (7), Cd(NA)Cl2·H2O (8), Pt(NA)2Cl4·5H2O (9) and Au(NA)Cl3 (10) were obtained by the reactions of the corresponding transition metal salts with vitamin B3/niacin (NA) in the presence of 1:4 (v:v) distilled water: methanol solvent at 70 °C for about 30 min, and their suggested structures were determined by elemental analyses, molar conductivity, (infrared, UV-vis) spectra, effective magnetic moment in Bohr magnetons, electron spin resonance (ESR), thermal analysis (TG), X-ray powder diffraction (XRD) as well as scanning electron microscopy (SEM). The results revealed that in complexes 1, 3, 7, and 9 both of two NA ligand coordinates one metal ion to form four or six coordinated structures, while in compound 10, one NA ligand coordinate to Au+++ ion to form a square-planar geometry with N-bonded pyridine ligand is suggested, and (2, 4, 5, 6 and, 8) complexes have 1:1 structures. Antimicrobial and antitumor activities were assessment against some kind of (G+ and G-) bacteria, fungi and breast carcinoma cells (MCF-7-cell line).

  9. Electrochemical hydrogenation of a homogeneous nickel complex to form a surface adsorbed hydrogen-evolving species.

    PubMed

    Martin, Daniel J; McCarthy, Brian D; Donley, Carrie L; Dempsey, Jillian L

    2015-03-28

    A Ni(II) complex degrades electrochemically in the presence of acid in acetonitrile to form an electrode adsorbed film that catalytically evolves hydrogen. Comparison with a similar compound permitted investigation of the degradation mechanism.

  10. Crystal Structures of the Iron–Sulfur Cluster-Dependent Quinolinate Synthase in Complex with Dihydroxyacetone Phosphate, Iminoaspartate Analogues, and Quinolinate

    SciTech Connect

    Fenwick, Michael K.; Ealick, Steven E.

    2016-07-12

    The quinolinate synthase of prokaryotes and photosynthetic eukaryotes, NadA, contains a [4Fe-4S] cluster with unknown function. We report crystal structures of Pyrococcus horikoshii NadA in complex with dihydroxyacetone phosphate (DHAP), iminoaspartate analogues, and quinolinate. DHAP adopts a nearly planar conformation and chelates the [4Fe-4S] cluster via its keto and hydroxyl groups. The active site architecture suggests that the cluster acts as a Lewis acid in enediolate formation, like zinc in class II aldolases. The DHAP and putative iminoaspartate structures suggest a model for a condensed intermediate. The ensemble of structures suggests a two-state system, which may be exploited in early steps.

  11. Relationship between Ni(II) and Zn(II) Coordination and Nucleotide Binding by the Helicobacter pylori [NiFe]-Hydrogenase and Urease Maturation Factor HypB*

    PubMed Central

    Sydor, Andrew M.; Lebrette, Hugo; Ariyakumaran, Rishikesh; Cavazza, Christine; Zamble, Deborah B.

    2014-01-01

    The pathogen Helicobacter pylori requires two nickel-containing enzymes, urease and [NiFe]-hydrogenase, for efficient colonization of the human gastric mucosa. These enzymes possess complex metallocenters that are assembled by teams of proteins in multistep pathways. One essential accessory protein is the GTPase HypB, which is required for Ni(II) delivery to [NiFe]-hydrogenase and participates in urease maturation. Ni(II) or Zn(II) binding to a site embedded in the GTPase domain of HypB modulates the enzymatic activity, suggesting a mechanism of regulation. In this study, biochemical and structural analyses of H. pylori HypB (HpHypB) revealed an intricate link between nucleotide and metal binding. HpHypB nickel coordination, stoichiometry, and affinity were modulated by GTP and GDP, an effect not observed for zinc, and biochemical evidence suggests that His-107 coordination to nickel toggles on and off in a nucleotide-dependent manner. These results are consistent with the crystal structure of HpHypB loaded with Ni(II), GDP, and Pi, which reveals a nickel site distinct from that of zinc-loaded Methanocaldococcus jannaschii HypB as well as subtle changes to the protein structure. Furthermore, Cys-142, a metal ligand from the Switch II GTPase motif, was identified as a key component of the signal transduction between metal binding and the enzymatic activity. Finally, potassium accelerated the enzymatic activity of HpHypB but had no effect on the other biochemical properties of the protein. Altogether, this molecular level information about HpHypB provides insight into its cellular function and illuminates a possible mechanism of metal ion discrimination. PMID:24338018

  12. Remarkable Features of the McMurry Reaction Conditions in Dimerization of Formyl- and 2-Formylvinylpurpurinimides. Electrochemistry of Monomeric Ni(II) Purpurinimide and the Corresponding Dyads

    PubMed Central

    Goswami, Lalit N.; Ethirajan, Manivannan; Dobhal, Mahabeer P.; Zhang, Min; Missert, Joseph R.; Shibata, Masayuki; Kadish, Karl M.; Pandey, Ravindra K.

    2009-01-01

    To investigate the electrochemical properties of purpurinimide dyads and electron transfer sites for their reduction and oxidation, a series of dimers with variable C-C linkages were synthesized. For the preparation of these novel structures, the formyl and 2-formylvinyl substituents were regioselectively introduced at positions-3 and 20 of Ni(II) purpurinimides by the Vilsmeier reaction. The Ni(II) complexes were then subjected to the McMurry reaction under two different conditions with unexpected results being obtained. For example, the reaction of formyl purpurinimides with TiCl3(DME)1.5 failed to produce the desired C-C dimers and the starting compounds were recovered almost quantitatively. Under similar reaction conditions, the 20-(2-formylvinyl)purpurinimide also did not dimerize but gave instead unexpected benzoisobacteriochlorins via an intramolecular cyclization. However, treatment of the 3-formyl- and 20-formyl-purpurinimides with TiCl4/Zn gave the corresponding dimers linked with one double bond (trans-) in modest yields. Under similar conditions, Ni(II) purpurinimides containing a 2-formylvinyl substituent either at position-3 or position-20 afforded the respective C-C dimers, where the purpurinimide moieties were joined with a trans-trans-trans- hexatriene linker. Molecular modeling data suggest that the nature of the conformational energy difference found in all trans- vs. trans-cis-trans- conformers of the dimers connected by a hexatriene linker at the meso- or β-position of the macrocycle is not due to the intrinsic conformational energy difference of the linker region, which is identical for both dimers. PMID:19072690

  13. Direct C-N Coupling in an in Situ Ligand Transformation and the Self-Assembly of a Tetrametallic [Ni(II)4] Staircase.

    PubMed

    Ghosh, Aloke Kumar; Singha Mahapatra, Tufan; Clérac, Rodolphe; Mathonière, Corine; Bertolasi, Valerio; Ray, Debashis

    2015-06-01

    A [Ni(II)4] staircase complex was serendipitously prepared from the reaction of the binucleating Schiff base proligand 2,6-bis[[(3-hydroxypropyl)imino]methyl]-4-methylphenol (H3L2) and 3,5-dimethylpyrazole (Me2pzH) with nickel(II) nitrate in a reaction at room temperature, initially aimed to yield a dinuclear complex. From a room temperature metal ion/ligand reaction, the proligand H3L2 in situ transformed to modified forms HL3(2-) and HL4(2-), allowing the [Ni4] formation. Variable-temperature magnetic behavior of a [Ni4] complex reveals antiferromagnetic interactions with stabilization of a diamagnetic ground state (ST = 0).

  14. Synthesis, crystal structure and spectral properties of a supramolecular trinuclear nickel(II) complex with 5-methoxy-4'-bromo-2,2'-[ethylenedioxybis(nitrilomethylidyne)]diphenol.

    PubMed

    Dong, Wen-Kui; Du, Wei; Zhang, Xin-Ying; Li, Gang; Dong, Xiu-Yan

    2014-11-11

    A novel trinuclear Ni(II) complex [{NiL(n-PrOH)(μ-OAc)}2Ni]·n-PrOH·H2O with an asymmetric Salamo-type ligand, 5-methoxy-4'-bromo-2,2'-[ethylenedioxybis(nitrilomethylidyne)]diphenol (H2L), has been synthesized and characterized by elemental analyses, IR, UV/Vis and fluorescence spectra and molar conductance measurement. The crystal structure of the Ni(II) complex has been determined by single-crystal X-ray diffraction. Two acetate groups coordinating to three Ni(II) ions through NiOCONi bridges and four μ-phenoxo oxygen atoms from two [NiL(n-PrOH)] units also coordinating to Ni(II) ions. In the Ni(II) complex, two n-propanol molecules are coordinated to the two terminal Ni(II) ions having slightly distorted octahedral coordination geometries and form a trinuclear structure, There are also one non-coordinated n-propanol and one non-coordinated water molecule. In the crystal structure, the Ni(II) complex is linked by intermolecular hydrogen bonds into an infinite 1D supramolecular chain-like structure.

  15. Iminodiacetic acid functionalized cation exchange resin for adsorptive removal of Cr(VI), Cd(II), Ni(II) and Pb(II) from their aqueous solutions.

    PubMed

    Misra, R K; Jain, S K; Khatri, P K

    2011-01-30

    Iminodiacetic acid functionality has been introduced on styrene-divinyl benzene co-polymeric beads and characterized by FT-IR in order to develop weak acid based cation exchange resin. This resin was evaluated for the removal of different heavy metal ions namely Cd(II), Cr(VI), Ni(II) and Pb(II) from their aqueous solutions. The results showed greater affinity of resin towards Cr(VI) for which 99.7% removal achieved in optimal conditions following the order Ni(II)>Pb(II)>Cd(II) with 65%, 59% and 28% removal. Experiments were also directed towards kinetic studies of adsorption and found to follow first order reversible kinetic model with the overall rate constants 0.3250, 0.2393, 0.4290 and 0.2968 for Cr(VI), Ni(II), Pb(II) and Cd(II) removal respectively. Detailed studies of Cr(VI) removal has been carried out to see the effect of pH, resin dose and metal ion concentration on adsorption and concluded that complexation enhanced the chromium removal efficacy of resin drastically, which is strongly pH dependent. The findings were also supported by the comparison of FT-IR spectra of neat resin with the chromium-adsorbed resin.

  16. A study on the inhibition kinetics of bioaccumulation of Cu(II) and Ni(II) ions using Rhizopus delemar.

    PubMed

    Açikel, Unsal; Alp, Tuğba

    2009-09-15

    The microbial growth and simultaneous bioaccumulation of Cu(II) and Ni(II) ions during the growth of Rhizopus delemar in molasses medium was investigated in a batch system. The level of Cu(II) and Ni(II) bioaccumulation and microbial growth was dependent on pH, molasses sucrose concentration and initial Cu(II) and Ni(II) ion concentrations. An increase in initial total metal ion concentration inhibited both the growth rate of fungus and the bioaccumulation capacity. Lineweaver-Burk plot of Monod equation was used to study the inhibition kinetics of bioaccumulation of Cu(II) and Ni(II) and the intrinsic and apparent model parameters were evaluated in metals-free and metals-contaminated fermentation media. The maximum specific growth rate (micro(m)) and the Monod constant (K(s)) of microorganism in metals-free media were found as 0.405 L/h and 3.977 g/L, respectively. As micro(m) remained constant in the presence of increasing concentrations of Cu(II) and Ni(II) ions, the combined inhibition of Cu(II) and Ni(II) ions on the growth rate of R. delemar was found to be a competitive inhibition. The inhibition constants for Cu(II) and Ni(II) ions were determined as 56.71 mg Cu(II)/L and 47.44 mg Ni(II)/L. As the bioaccumulation of Cu(II) and Ni(II) ions was reduced by the presence of increasing concentrations of the other metal ion, compared with the single-metal systems, the individual action of Cu(II) and Ni(II) ions on the bioaccumulation of R. delemar was generally found to be antagonistic. On the other hand, the total combined effects of Cu(II) and Ni(II) ions on the bioaccumulation of R. delemar are thought to be synergistic since the total bioaccumulated metal ion quantities per unit mass of biomass were higher than those obtained in the growth media containing Cu(II) and Ni(II) ions alone at the same concentrations.

  17. Removal of Cu(II) and Ni(II) from aqueous solution by lignite-based humic acids

    SciTech Connect

    Arslan, G.; Cetin, S.; Pehlivan, E.

    2007-07-01

    The removal of Cu(II) and Ni(II) metal ions from an aqueous solution were investigated by using humic acids (HAs) in a batch arrangement. HAs were prepared by using alkaline extraction, following sedimentation and acidic precipitation from three Turkish lignites: Ilgin, Beysehir, and Ermenek. The interactions of Cu(II) and Ni(II) with solid HAs and influence of three parameters (initial metal concentration, solution pH and temperature) on the removal of metals were studied. Adsorption equilibrium was achieved in about 120 min for Cu(II) and Ni(II) ions. The sorption of Cu(II) and Ni(II) on the surface of HAs depended strongly on the pH, and increased with increasing pH and the initial concentration of metal. The sorption of Cu(II) was higher than that of Ni(II) for HAs. The equilibrium relationship between adsorbent and adsorbate is described by adsorption isotherms at a fixed temperature 35 {sup o}C, at pH about 4.0. The Langmuir adsorption isotherm was used to describe observed sorption phenomena. Adsorption isotherms and kinetics data of Cu(II) and Ni(II) ions removed by HAs are presented and discussed.

  18. Saturation magnetization of Ni(II) in metalloproteins and model compounds

    SciTech Connect

    Sendova, M.; Day, E.P.; Kiick, K.; Johnson, M.; Ma, L.; Scott, B.; Hausinger, R.; Todd, M.; Peterson, J. Univ. of Georgia, Athens Michigan State Univ., East Lansing Univ. of Alabama, Tuscaloosa )

    1992-01-01

    The Ni(II) sites of urease (from Klebsiella aerogenes and jack bean), coenzyme F[sub 430] (from Methanobacterium thermoautotrophicum), and several model compounds having octahedral symmetry have been studied using the saturation megnetization technique. Data were collected at four fixed fields over the temperature range from 2 - 200K. Theoretical curves calculated from the spin Hamiltonian were used to fit the experimentally obtained magnetization curves. The following parameters were determined: the spine state (S), the amount of the sample in this spin state ([S]), the gyromagnetic ratio (g), and the zero field splitting parameters (D, E/D). The amount of S=1 paramagnetism of the Ni(II) sites was found to depend on the pH of the buffer and on the concentration of the protein in D[sub 2]O (for coenzyme F[sub 430]). The relationship of the strength of the ligand field to the zero field splitting parameter was studied for the model compounds. There was no evidence for exchange coupling between the two Ni(II) ions at the active sites of either plant or bacterial urease.

  19. Dual shell-like magnetic clusters containing Ni(II) and Ln(III) (Ln = La, Pr, and Nd) ions.

    PubMed

    Kong, Xiang-Jian; Ren, Yan-Ping; Long, La-Sheng; Zheng, Zhiping; Nichol, Gary; Huang, Rong-Bin; Zheng, Lan-Sun

    2008-04-07

    Dual shell-like nanoscopic magnetic clusters featuring a polynuclear nickel(II) framework encapsulating that of lanthanide ions (Ln = La, Pr, and Nd) were synthesized using Ni(NO3)(2).6H2O, Ln(NO3)(3).6H2O, and iminodiacetic acid (IDA) under hydrothermal conditions. Structurally established by crystallographic studies, these clusters are [La20Ni30(IDA)30(CO3)6(NO3)6(OH)30(H2O)12](CO3)(6).72H2O (1), [Ln20Ni21(C4H5NO4)21(OH)24(C2H2O3)6(C2O4)3(NO3)9(H2O)12](NO3)9.nH2O [C2H2O3 is the alkoxide form of glycolate; Ln = Pr (2), n = 42; Nd (3), n = 50], and {[La4Ni5Na(IDA)5(CO3)(NO3)4(OH)5(H2O)5][CO3].10H2O} infinity (4). Carbonate, oxalate, and glycolate are products of hydrothermal decomposition of IDA. Compositions of these compounds were confirmed by satisfactory elemental analyses. It has been found that the cluster structure is dependent on the identity of the lanthanide ion as well as the starting Ln/Ni/IDA ratio. The cationic cluster of 1 features a core of the Keplerate type with an outer icosidodecahedron of Ni(II) ions encaging a dodecahedral kernel of La(III). Clusters 2 and 3, distinctly different from 1, are isostructural, possessing a core of an outer shell of 21 Ni(II) ions encapsulating an inner shell of 20 Ln(III) ions. Complex 4 is a three-dimensional assembly of cluster building blocks connected by units of Na(NO3)/La(NO3)3; the structure of the building block resembles closely that of 1, with a hydrated La(III) ion internalized in the decanuclear cage being an extra feature. Magnetic studies indicated ferromagnetic interactions in 1, while overall antiferromagnetic interactions were revealed for 2 and 3. The polymeric, three-dimensional cluster network 4 displayed interesting ferrimagnetic interactions.

  20. Process optimization for Ni(II) removal from wastewater by calcined oyster shell powders using Taguchi method.

    PubMed

    Yen, Hsing Yuan; Li, Jun Yan

    2015-09-15

    Waste oyster shells cause great environmental concerns and nickel is a harmful heavy metal. Therefore, we applied the Taguchi method to take care of both issues by optimizing the controllable factors for Ni(II) removal by calcined oyster shell powders (OSP), including the pH (P), OSP calcined temperature (T), Ni(II) concentration (C), OSP dose (D), and contact time (t). The results show that their percentage contribution in descending order is P (64.3%) > T (18.9%) > C (8.8%) > D (5.1%) > t (1.7%). The optimum condition is pH of 10 and OSP calcined temperature of 900 °C. Under the optimum condition, the Ni(II) can be removed almost completely; the higher the pH, the more the precipitation; the higher the calcined temperature, the more the adsorption. The latter is due to the large number of porosities created at the calcination temperature of 900 °C. The porosities generate a large amount of cavities which significantly increase the surface area for adsorption. A multiple linear regression equation obtained to correlate Ni(II) removal with the controllable factors is: Ni(II) removal(%) = 10.35 × P + 0.045 × T - 1.29 × C + 19.33 × D + 0.09 × t - 59.83. This equation predicts Ni(II) removal well and can be used for estimating Ni(II) removal during the design stage of Ni(II) removal by calcined OSP. Thus, OSP can be used to remove nickel effectively and the formula for removal prediction is developed for practical applications.

  1. Enneanuclear [Ni6Ln3] Cages: [Ln(III)3] Triangles Capping [Ni(II)6] Trigonal Prisms Including a [Ni6Dy3] Single-Molecule Magnet.

    PubMed

    Canaj, Angelos B; Tzimopoulos, Demetrios I; Siczek, Milosz; Lis, Tadeusz; Inglis, Ross; Milios, Constantinos J

    2015-07-20

    The use of (2-(β-naphthalideneamino)-2-hydroxymethyl-1-propanol) ligand, H3L, in Ni/Ln chemistry has led to the isolation of three new isostructural [Ni(II)6Ln(III)3] metallic cages. More specifically, the reaction of Ni(ClO4)2·6H2O, the corresponding lanthanide nitrate salt, and H3L in MeCN, under solvothermal conditions in the presence of NEt3, led to the isolation of three complexes with the formulas [Ni6Gd3(OH)6(HL)6(NO3)3]·5.75MeCN·2Et2O·1.5H2O (1·5.75MeCN·2Et2O·1.5H2O), [Ni6Dy3(OH)6(HL)6(NO3)3]·2MeCN·2.7Et2O·2.4H2O (2·2MeCN·2.7Et2O·2.4H2O), and [Ni6Er3(OH)6(HL)6(NO3)3]·5.75MeCN·2Et2O·1.5H2O (3·5.75MeCN·2Et2O·1.5H2O). The structure of all three clusters describes a [Ln(III)3] triangle capping a [Ni(II)6] trigonal prism. Direct current magnetic susceptibility studies in the 5-300 K range for complexes 1-3 reveal the different nature of the magnetic interactions within the clusters: dominant antiferromagnetic exchange interactions for the Dy(III) and Er(III) analogues and dominant ferromagnetic interactions for the Gd(III) example. Alternating current magnetic susceptibility measurements under zero external dc field displayed fully formed temperature- and frequency-dependent out-of-phase peaks for the [Ni(II)6Dy(III)3] analogue, establishing its single molecule magnetism behavior with Ueff = 24 K.

  2. Cu(II), Ni(II) and Co(II) co-ordination properties and tautomerism of 1,8-bis-phenylazo-2,7-dihydroxy naphthalene. A spectroscopic and semiempirical AM1/PM3 study

    NASA Astrophysics Data System (ADS)

    Arancibia, J. A.; Olivieri, A. C.; Escandar, G. M.

    2000-04-01

    As a continuation of a study on the prototropic properties of aromatic α,α'-dihydroxy-bis-azocompounds, 1,8-bis-phenylazo-2,7-dihydroxynaphthalene (PHADN) has been studied through 1H and 13C nuclear magnetic resonance experiments, electronic absorption and semiempirical molecular orbital methods. In addition, the metal binding properties of this compound were evaluated and related with its tautomeric forms. The equilibrium constants for Cu(II), Ni(II) and Co(II)-PHADN complexes were spectrophotometrically determined in dioxane-water 50% v/v solutions. The structures of the evaluated chelates were proposed on the basis of spectral analysis and PM3 semiempirical calculations.

  3. Changes in spectrochemical and catalytic properties of biopolymer anchored Cu(II) and Ni(II) catalysts by electron beam irradiation.

    PubMed

    Antony, R; Suja Pon Mini, P S; Theodore David Manickam, S; Sanjeev, Ganesh; Mitu, Liviu; Balakumar, S

    2015-01-01

    Chitosan (a biopolymer) anchored Cu(II) and Ni(II) Schiff base complexes, [M(OIAC)Cl2] (M: Cu/Ni and OIAC: ([2-oxo-1H-indol-3-ylidene]amino)chitosan) were electron beam irradiated by different doses (100 Gy, 1 kGy and 10 kGy). The electron beam has shown potential impact on biopolymer's support, in detail chain linking and chain scissoring, as evidenced by viscosity studies, FT-IR and X-ray diffraction spectroscopic techniques. Due to these structural changes, thermal properties of the complexes were found to be changed. The surface of these heterogeneous complexes was also effectually altered by electron beam. As a consequence, pores and holes were created as probed by SEM technique. The catalytic activity of both non-irradiated and irradiated complexes was investigated in the aerobic oxidation of cyclohexane using hydrogen peroxide oxidant. The catalytic ability of the complexes was enhanced significantly after irradiation as the result of surface changes. The reusability of the complexes was also greatly affected because of the structural variations in polymeric support. In terms of both better catalytic activity along with the reusability, 1 kGy is suggested as the best dose to attain adequate increase in catalytic activity and good reusability.

  4. Benzimidazole based ratiometric and colourimetric chemosensor for Ni(II)

    NASA Astrophysics Data System (ADS)

    Sarkar, Deblina; Pramanik, Ajoy Kumar; Mondal, Tapan Kumar

    2016-01-01

    A highly sensitive and selective benzimidazole based colourimetric chemosensor (HL) for the efficient detection of Ni2 + has been reported. The synthesized chemosensor HL is highly efficient in detecting Ni2 + over other metal ions that commonly coexist with Ni2 + in physiological and environmental samples. HL also shows distinct color change from orange yellow to blue visible under the naked eye due to specific binding with Ni2 +. This color change corresponds to a large red shift of the UV-Vis spectrum from 403 nm to 600 nm with a distinct isosbestic point at around 500 nm. The cation sensing property of the receptor HL has been examined by UV-Vis spectroscopy. Electronic structure of the HL-Ni2 + complex and sensing mechanism has been interpreted by DFT and TDDFT calculations.

  5. Benzimidazole based ratiometric and colourimetric chemosensor for Ni(II).

    PubMed

    Sarkar, Deblina; Pramanik, Ajoy Kumar; Mondal, Tapan Kumar

    2016-01-15

    A highly sensitive and selective benzimidazole based colourimetric chemosensor (HL) for the efficient detection of Ni(2+) has been reported. The synthesized chemosensor HL is highly efficient in detecting Ni(2+) over other metal ions that commonly coexist with Ni(2+) in physiological and environmental samples. HL also shows distinct color change from orange yellow to blue visible under the naked eye due to specific binding with Ni(2+). This color change corresponds to a large red shift of the UV-Vis spectrum from 403 nm to 600 nm with a distinct isosbestic point at around 500 nm. The cation sensing property of the receptor HL has been examined by UV-Vis spectroscopy. Electronic structure of the HL-Ni(2+) complex and sensing mechanism has been interpreted by DFT and TDDFT calculations.

  6. Characterizing Ni(II) hydration in aqueous solution using DFT and EXAFS.

    PubMed

    Liu, H Y; Fang, C H; Fang, Y; Zhou, Y Q; Ge, H W; Zhu, F Y; Sun, P C; Miao, J T

    2016-01-01

    In the present work, a detailed investigation of Ni(II) hydration in water solutions was carried out using density functional theory (DFT) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The hydrated characteristics of [Ni(H2O)n](2+) clusters, such as energy parameters, atomic charge distributions, and bond parameters, were explored using DFT with Becke's three-parameter exchange potential and the Lee-Yang-Parr correlation functional (B3LYP). DFT calculations indicated that the preferred structure of the first hydration shell of Ni(II) generally has a coordination number of six and is almost unaffected by the water molecules in the outer solvation shell, whereas the structure of the second solvation shell varies as the hydration proceeds. EXAFS measurements are reported for aqueous NiSO4 and Ni(NO3)2 solutions and the Ni(NO3)2·6H2O crystal. Analysis of the EXAFS spectra of these three systems using a multiparameter fitting procedure showed that, in each case, the first coordination shell consists of six water molecules with a Ni-O coordination distance of 2.04 Å, and that there is no Ni-S or Ni-N coordination in the first shell. There was no evidence of outer-shell SO4(2-) or NO3(-) ions substituting inner-sphere water molecules in NiSO4 and Ni(NO3)2. The characteristics of Ni(II) hydration obtained from DFT calculations agreed well with those obtained experimentally using EXAFS.

  7. Aromatic versus heteroradialene character in extended thiophloroglucinol ligands and their trinuclear nickel(II) complexes.

    PubMed

    Feldscher, Bastian; Stammler, Anja; Bögge, Hartmut; Glaser, Thorsten

    2014-08-01

    Extended phloroglucinol ligands and complexes are best described as nonaromatic heteroradialenes. Herein, the electronic structures of extended thiophloroglucinol ligands and their Ni(II) 3 complexes are evaluated by comparison to their phloroglucinol analogs by means of NMR, FTIR, UV/Vis, and structural parameters. To provide a full set of compounds for this comparison of S versus O substitution, a new triplesalen ligand, its Ni(II) 3 complex, and a new thiophloroglucinol were synthesized. (1) H and (15) N NMR chemical shifts and coupling constants prove that the thiophloroglucinol ligands exist as the N-protonated and not the O-protonated tautomer. (13) C and (15) N NMR chemical shifts and structural parameters further demonstrated that the extended thiophloroglucinol ligands must be described with a predominant thione-enamine (heteroradialene) character despite the participation of a CS double bond. In the Ni(II) 3 complexes, this heteroradialene character is reduced but still predominant.

  8. Nickel(II) and copper(II) complexes with humic acid anions and their derivatives

    SciTech Connect

    Ryabova, I.N.

    2008-01-15

    Complexation of Ni(II) and Cu(II) in aqueous solutions with anions of humic acids, extracted from naturally oxidized coal, and with their hydroxymethyl derivatives is studied spectrophotometrically and potentiometrically. The complexation stoichiometry and the stability constants of the complexes are determined.

  9. 4,2-Ribbon like ferromagnetic cyano-bridged Fe(III)2Ni(II) chains: a magneto-structural study.

    PubMed

    Toma, Luminita Marilena; Lescouëzec, Rodrigue; Uriel, Santiago; Llusar, Rosa; Ruiz-Pérez, Catalina; Vaissermann, Jacqueline; Lloret, Francesc; Julve, Miguel

    2007-09-07

    The low-spin iron(III) complex AsPh(4)[Fe(III)(bpy)(CN)(4)].CH(3)CN (1) [AsPh(4) = tetraphenylarsonium cation] and the heterobimetallic chains [{Fe(III)(L)(CN)(4)}(2)Ni(II)(H(2)O)(2)].4H(2)O with L = bpy (2) and phen (3) [bpy = 2,2'-bipyridine and phen = 1,10-phenanthroline] have been prepared and their structures determined by X-ray diffraction methods. The structure of 1 consists of mononuclear [Fe(bpy)(CN)(4)](-) anions, tetraphenylarsonium cations and acetonitrile molecules of crystallization. The iron(III) is hexacoordinated with two nitrogen atoms of the bidentate bpy and four carbon atoms of four terminal cyanide groups building a distorted octahedral surrounding around the metal atom. 2 and 3 are isomorphous compounds whose structure is made up of neutral 4,2-ribbon like bimetallic chains of formula [{Fe(III)(L)(CN)(4)}(2)Ni(II)(H(2)O)(2)] where the [Fe(III)(L)(CN)(4)](-) unit acts as a bis-monodentate bridging ligand toward the trans-diaquanickel(II) units through two of its four cyanide groups in cis positions. The chains exhibit two orientations in the unit cell and they interact with each other through hydrogen bonds involving the coordination and crystallization water molecules together with the uncoordinated cyanide nitrogen atoms of the [Fe(L)(CN)(4)](-) units. Compounds 2 and 3 behave as ferromagnetic Fe(III)(2)Ni(II) chains which interact ferromagnetically at very low temperatures in the case of 2, whereas metamagnetic-like behaviour is observed for with a critical field (H(c)) around 200 G. For H > H(c) the ferromagnetic Fe(III)(2)Ni(II) chains of 3 exhibit a frequency dependence of the out-of-phase ac susceptibility signal at T < 3.5 K.

  10. Metal-ion exchange induced structural transformation as a way of forming novel Ni(II)- and Cu(II)-salicylaldimine structures

    NASA Astrophysics Data System (ADS)

    Wu, Jing-Yun; Tsai, Chi-Jou; Chang, Ching-Yun; Wu, Yung-Yuan

    2017-02-01

    A Zn(II)-salicylaldimine complex [Zn(Lsalpyca)(H2O)]n (1, where H2Lsalpyca=4-hydroxy-3-(((pyridin-2-yl)methylimino)methyl)benzoic acid), with a one-dimensional (1D) chain structure, has been successfully converted to a discrete Ni(II)-salicylaldimine complex [Ni(Lsalpyca)(H2O)3] (2) and an infinite Cu(II)-salicylaldimine complex {[Cu(Lsalpyca)]·3H2O}n (3) through a metal-ion exchange induced structural transformation process. However, such processes do not worked by Mn(II) and Co(II) ions. Solid-state structure analyses reveal that complexes 1-3 form comparable coordinative or supramolecular zigzag chains running along the crystallographic [201] direction. In addition, replacing Zn(II) ion by Ni(II) and Cu(II) ions caused changes in coordination environment and sphere of metal centers, from a 5-coordinate intermediate geometry of square pyramidal and trigonal bipyramidal in 1 to a 6-coordinate octahedral geometry in 2, and to a 4-coordiante square planar geometry in 3. This study shows that metal-ion exchange serves as a very efficient way of forming new coordination complexes that may not be obtained through direct synthesis.

  11. The coordination structure of the extracted nickel(ii) complex with a synergistic mixture containing dinonylnaphthalene sulfonic acid and 2-ethylhexyl 4-pyridinecarboxylate ester.

    PubMed

    Li, Jiyuan; Hu, Huiping; Zhu, Shan; Hu, Fang; Wang, Yongxi

    2017-01-24

    In this paper, a synergist complex of Ni(ii) with naphthalene-2-sulfonic acid (HNS) and n-hexyl 4-pyridinecarboxylate ester (L(I)), which are corresponding short chain analogues of active synergistic extractants dinonylnaphthalene sulfonic acid (HDNNS) and 2-ethylhexyl 4-pyridinecarboxylate ester (4PC, L(II)), was prepared and characterized by Nuclear Magnetic Resonance ((1)H-NMR), elemental analyses, Fourier Transform Infrared Spectroscopy (FT-IR) and Electrospray Ionization Mass Spectrometry (ESI-MS) spectroscopic studies. Single crystals of the nickel synergist complex have been grown from a methanol/water (10/1) solution and analyzed by single crystal X-ray diffraction. The crystal structure of the nickel synergist complex shows that Ni(ii) is coordinated by four water molecules and two monodentate L(I) ligands and there is no direct interaction of the Ni(ii) with sulfonic oxygen atoms of naphthalene-2-sulfonic acid anions, while hydrogen-bonded interactions of the coordinated water molecules with sulfonic oxygen atoms of naphthalene-2-sulphate anions were observed. In addition, in order to provide parallels to solvent extraction, the extracted Ni(ii) complex with HDNNS and 4PC is also prepared and studied using FT-IR and ESI-MS technology. Compared with their corresponding free ligand, similar shifts assigned to the stretching vibration of the pyridine ring and S[double bond, length as m-dash]O in both the nickel synergist complex and the extracted Ni(ii) complex suggest that in the non-polar organic phase, Ni(ii) is also coordinated by L(II) ligands, while the sulfonic oxygen atoms of dinonylnaphthalene sulfonate anions not directly bonded to Ni(ii) form hydrogen bonds with water molecules (coordinated with Ni(ii) or/and solubilized in the non-polar organic phase). For the ESI-MS spectrum of the extracted Ni(ii) complex in non-polar organic phase, there exists a peak at m/z values of 1058.76, which indicates that the extracted Ni(ii) complex in the non

  12. Complexity.

    PubMed

    Gómez-Hernández, J Jaime

    2006-01-01

    It is difficult to define complexity in modeling. Complexity is often associated with uncertainty since modeling uncertainty is an intrinsically difficult task. However, modeling uncertainty does not require, necessarily, complex models, in the sense of a model requiring an unmanageable number of degrees of freedom to characterize the aquifer. The relationship between complexity, uncertainty, heterogeneity, and stochastic modeling is not simple. Aquifer models should be able to quantify the uncertainty of their predictions, which can be done using stochastic models that produce heterogeneous realizations of aquifer parameters. This is the type of complexity addressed in this article.

  13. Adsorption of Cu(II), Ni(II) and Zn(II) on modified jute fibres.

    PubMed

    Shukla, S R; Pai, Roshan S

    2005-09-01

    The potential of a lignocellulosic fibre, jute, was assessed for adsorption of heavy metal ions like Cu(II), Ni(II) and Zn(II) from their aqueous solutions. The fibre was also used as adsorbent after chemically modifying it by two different techniques viz, loading of a dye with specific structure, C.I. Reactive Orange 13, and oxidising with hydrogen peroxide. Both the modified jute fibres gave higher metal ion adsorption. Thus, the dye loaded jute fibres showed metal ion uptake values of 8.4, 5.26 and 5.95 mg/g for Cu(II), Ni(II) and Zn(II), respectively, while the corresponding values for oxidised jute fibres were 7.73, 5.57 and 8.02 mg/g, as against 4.23, 3.37 and 3.55 mg/g for unmodified jute fibres. Adsorption isotherm models indicated best fit for Langmuir model for the modified jute fibres. The adsorption values decreased with lowering of pH. The desorption efficiency, regenerative and reuse capacity of these adsorbents were also assessed for three successive adsorption-desorption cycles. The adsorptive capacity was retained only when the caustic soda regeneration is carried out as an intermediate step after desorption. Possible mechanism has been given.

  14. A new approach for simultaneous determination of Co(II), Ni(II), Cu(II) and Pd(II) using 2-thiophenaldehyde-3-thiosemicarbazone as reagent by solid phase microextraction-high performance liquid chromatography.

    PubMed

    Kaur, Varinder; Aulakh, Jatinder Singh; Malik, Ashok Kumar

    2007-11-05

    A new method is proposed herein for the sorption, separation and simultaneous determination of Co(II), Ni(II), Cu(II) and Pd(II) using 2-thiophenaldehyde-3-thiosemicarbazone (TPTS) as a reagent by solid phase microextraction-high performance liquid chromatography-UV detection. The method is based upon the sorption of metal complexes on polydimethylsiloxane (PDMS) fiber from aqueous solution followed by desorption in the desorption chamber of solid phase microextraction-high performance liquid chromatography (SPME-HPLC) interface. Reversed phase high performance liquid chromatography using acetonitrile:water (65:35) as an eluent on a C18 column has been used to achieve the separation. The effects of agitation, addition of salts, extraction time and desorption time are examined to obtain optimized conditions. The detection limits for Co(II), Ni(II), Cu(II) and Pd(II) are 9, 6, 1 and 7 ng L(-1) based on 3sigma of blank response. The precision is calculated to be less than 3.5% (R.S.D.) for all species. A 10 time enhancement in the signal is observed for SPME when compared with direct analysis. The method is successfully applied to several synthetic mixtures without interference from other common metal ions such as Mo(VI), V(V), Ag(I), Sn(IV), Cd(II), Zn(II), Pb(II), Cr(III) and Cr(VI). The proposed method is tested for the determination of Co(II), Ni(II), Cu(II) and Pd(II) in alloys and water samples spiked with these metal ions.

  15. A new chelating resin for preconcentration and determination of Mn(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(II) by flame atomic absorption spectrometry.

    PubMed

    Maheswari, Mohan A; Subramanian, Mandakolathur S

    2003-01-01

    A new polychelatogen, AXAD-16-1,2-diphenylethanolamine, was developed by chemically modifying Amberlite XAD-16 with 1,2-diphenylethanolamine to produce an effective metal-chelating functionality for the preconcentration of Mn(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(II) and their determination by flame atomic absorption spectrometry. Various physiochemical parameters that influence the quantitative preconcentration and recovery of metal were optimized by both static and dynamic techniques. The resin showed superior extraction efficiency with high-metal loading capacity values of 0.73, 0.80, 0.77, 0.87, 0.74, and 0.81 mmol/g for Mn(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(II), respectively. The system also showed rapid metal-ion extraction and stripping, with complete saturation in the sorbent phase within 15 min for all the metal ions. The optimum condition for effective metal-ion extraction was found to be a neutral pH, which is a great advantage in the preconcentration of trace metal ions from natural water samples without any chemical pretreatment of the sample. The resin also demonstrated exclusive ion selectivity toward targeted metal ions by showing greater resistivity to various complexing species and more common metal ions during analyte concentration, which ultimately led to high preconcentration factors of 700 for Cu(II); 600 for Mn(II), Ni(II), and Zn(II); and 500 for Cd(II) and Pb(II), arising from a larger sample breakthrough volume. The lower limits of metal-ion detection were 7 ng/mL for Mn(II) and Ni(II); 5 ng/mL for Cu(II), Zn(II), and Cd(II), and 10 ng/mL for Pb(II). The developed resin was successful in preconcentrating metal ions from synthetic and real water samples, multivitamin-multimineral tablets, and curry leaves (Murraya koenigii) with relative standard deviations of < or = 3.0% for all analytical measurements, which demonstrated its practical utility.

  16. Rapid and direct electrochemical determination of Ni(II) in industrial discharge water.

    PubMed

    Ferancová, Adriana; Hattuniemi, Maarit K; Sesay, Adama M; Räty, Jarkko P; Virtanen, Vesa T

    2016-04-05

    Industrial water contains a number of contaminants, such as organic pollutants and heavy metals, which can significantly affect the quality of soil, ground and environmental waters. We have successfully optimized and tested an electrochemical method and sensor modified with dimethylglyoxime for monitoring of nickel(II). The detection limit was 0.03mg/L and determination limit was 0.09mg/L. Linear concentration range was observed from 0.06 to 0.5mg/L Ni(II) and it is suitable for the analysis of environmental waters. The effect of all parameters important for on-site measurements (such as interferences, presence of dissolved oxygen, temperature) was investigated and considered in the analysis of mine discharge water. Water samples were analyzed without any pretreatment or filtration. A low level of error (5.6%) was observed for analysis demonstrating the usability of the optimized sensor and method for on-site measurements.

  17. New hexadentate macrocyclic ligand and their copper(II) and nickel(II) complexes: Spectral, magnetic, electrochemical, thermal, molecular modeling and antimicrobial studies

    NASA Astrophysics Data System (ADS)

    Chandra, Sulekh; Ruchi; Qanungo, Kushal; Sharma, Saroj. K.

    Ni(II) and Cu(II) complexes were synthesized with a hexadentate macrocyclic ligand [3,4,8,9tetraoxo-2,5,7,10tetraaza-1,6dithio-(3,4,8,9) dipyridinedodecane(L)] and characterized by elemental analysis, molar conductance measurements, mass, NMR, IR, electronic, EPR spectral, thermal and molecular modeling studies. All the complexes are 1:2 electrolytes in nature and may be formulated as [M(L)]X2 [where, M = Ni(II) and Cu(II) and X = Cl-, NO3-, ½SO42-, CH3COO-]. On the basis of IR, electronic and EPR spectral studies an octahedral geometry has been assigned for Ni(II) complexes and tetragonal geometry for Cu(II) complexes. The antimicrobial activities and LD50 values of the ligand and its complexes, as growth inhibiting agents, have been screened in vitro against two different species of bacteria and plant pathogenic fungi.

  18. Modification of humic acid by ether functional group as biosorbent to Au(III) adsorption in the presence of Sn(II) and Ni(II)

    NASA Astrophysics Data System (ADS)

    Yanti, Ika; Winata, Wahyu Fajar; Sudiono, Sri; Triyono

    2017-03-01

    Modification of humic acid on the phenolic functional group with dimethylsulfate (DMS) for adsorption Au(III) in the presence of Sn(II) and Ni(II) have been conducted. Ash content was analyzed and characterized by Fourier-Transform Infrared (FTIR). Determination of Au(III) adsorption in the presence of Sn(II) and Ni(II) was conducted by Atomic Adsorption Spectroscopy (AAS). The isolated humic acid has 19.8% ash content and after purification has 0.6% ash content, etherified humic acid (EHAs) has 1.4% ash content. Adsorption percentage of Au(III) in the presence of Sn(II) and Ni(II) by EHAs decreased until 4.936% and 41.782% respectively. The addition of Sn(II) and Ni(II) as competitors of Au(III) in the Au(III) adsorption by using EHAs, were affect the percentage of Au(III) adsorption.

  19. p53 activation by Ni(II) is a HIF-1α independent response causing caspases 9/3-mediated apoptosis in human lung cells

    SciTech Connect

    Wong, Victor C.; Morse, Jessica L.; Zhitkovich, Anatoly

    2013-06-15

    Hypoxia mimic nickel(II) is a human respiratory carcinogen with a suspected epigenetic mode of action. We examined whether Ni(II) elicits a toxicologically significant activation of the tumor suppressor p53, which is typically associated with genotoxic responses. We found that treatments of H460 human lung epithelial cells with NiCl{sub 2} caused activating phosphorylation at p53-Ser15, accumulation of p53 protein and depletion of its inhibitor MDM4 (HDMX). Confirming the activation of p53, its knockdown suppressed the ability of Ni(II) to upregulate MDM2 and p21 (CDKN1A). Unlike DNA damage, induction of GADD45A by Ni(II) was p53-independent. Ni(II) also increased p53-Ser15 phosphorylation and p21 expression in normal human lung fibroblasts. Although Ni(II)-induced stabilization of HIF-1α occurred earlier, it had no effect on p53 accumulation and Ser15 phosphorylation. Ni(II)-treated H460 cells showed no evidence of necrosis and their apoptosis and clonogenic death were suppressed by p53 knockdown. The apoptotic role of p53 involved a transcription-dependent program triggering the initiator caspase 9 and its downstream executioner caspase 3. Two most prominently upregulated proapoptotic genes by Ni(II) were PUMA and NOXA but only PUMA induction required p53. Knockdown of p53 also led to derepression of antiapoptotic MCL1 in Ni(II)-treated cells. Overall, our results indicate that p53 plays a major role in apoptotic death of human lung cells by Ni(II). Chronic exposure to Ni(II) may promote selection of resistant cells with inactivated p53, providing an explanation for the origin of p53 mutations by this epigenetic carcinogen. - Highlights: • Ni(II) is a strong activator of the transcription factor p53. • Apoptosis is a principal form of death by Ni(II) in human lung epithelial cells. • Ni(II)-activated p53 triggers caspases 9/3-mediated apoptotic program. • NOXA and PUMA are two main proapoptotic genes induced by Ni(II). • HIF-1α and p53 are independent

  20. Synthesis, structural and electrochemical properties of nickel(II) sulfamethazine complex with diethylenetriamine ligand.

    PubMed

    Bulut, İclal; Öztürk, Filiz; Bulut, Ahmet

    2015-03-05

    In this study, [Ni(dien)2]⋅smz2⋅(Hsmz: sulfamethazine and dien: diethylenetriamine) complex has been synthesized and its crystal structure has been determined by X-ray diffraction technique. The title complex crystallizes in orthorhombic system with space group Pbnb [a=8.556(5), b=16.228(5), c=28.209(5)Å, V=3917(3)Å(3) and Z=4]. The nickel(II) ion has distorted octahedral coordination geometry. The metal atom, which rides on a crystallographic center of symmetry, is coordinated by six nitrogen atoms of two dien ligands to form a discrete [Ni(dien)2](2+) unit, which captures two sulfamethazine ions, each through intermolecular hydrogen bonds. The powder EPR spectrum of Cu(2+) doped Ni(II) complex was recorded at room temperature. The vibrational investigation has been carried out by considering the characteristic bands related to the functional groups of the complex. The electrochemical behavior of Ni(II) ions in the presence and in the absence of smz and dien were studied by square wave and cyclic voltammetry. A well-defined irreversible peak at -1.112V different from those of the Ni(II)-smz (-0.876V) and the Ni(II)-dien complex (-1.064V) was observed in the solution containing Ni(II) ions, which was attributed to the formation of the new mixed ligand complex of Ni(II) with smz and dien.

  1. Potentiometric and spectrophotometric study of a new dipodal ligand N, N'-bis{2-[(2-hydroxybenzylidine)amino]ethyl}malonamide with Co(II), Ni(II), Cu(II) and Zn(II)

    NASA Astrophysics Data System (ADS)

    Sahoo, Suban K.; Muthu, S. E.; Baral, Minati; Kanungo, B. K.

    2006-03-01

    A new dipodal ligand, N, N'-bis{2-[(2-hydroxybenzylidine)amino]ethyl}malonamide (BHAEM) was synthesized by Schiff base condensation of N, N'-bis(2-aminoethyl)malonamide with two equivalent of salicylaldehyde and characterized on the basis of elemental analyses and various spectral (UV-vis, IR, 1H NMR and 13C NMR) data. The complexation reaction of the ligand with H +, Co(II), Ni(II), Cu(II) and Zn(II) in solution was investigated by spectrophotometric and potentiometric method. Two protonation constants of BHAEM assigned for two hydroxyl groups of aromatic ring were determined and its hydrolysis mechanism was proposed through potentiometric result. In presence of metal ions, BHAEM shows different coordination properties. All metal ions form ML type complex where the ligand coordinates to the metal ion through two N-amine and two O-phenolate groups. In addition, Ni(II) and Cu(II) form additional complex species of the type MLH -1 and MLH -2, respectively due to ionization of amide protons. The molecular geometry of BHAEM was examined theoretically using the molecular mechanics MM3 force field followed by semi-empirical PM3 method and various spectral data UV-vis, IR and 1H NMR were calculated from the energy-minimized structure applying semi-empirical ZINDO, PM3 and TNDO/2 method, respectively and compared with the experimental data. The probable structure of metal complexes in solution were proposed through calculated minimum strain energy by applying molecular mechanics MM + force field coupled with molecular dynamics simulation. Further the proposed structure of Cu(BHAEM) was refined through semi-empirical AM1/d method.

  2. Synthesis, characterization and antimicrobial studies of Schiff base complexes

    NASA Astrophysics Data System (ADS)

    Zafar, Hina; Ahmad, Anis; Khan, Asad U.; Khan, Tahir Ali

    2015-10-01

    The Schiff base complexes, MLCl2 [M = Fe(II), Co(II), Ni(II), Cu(II) and Zn(II)] have been synthesized by the template reaction of respective metal ions with 2-acetylpyrrole and 1,3-diaminopropane in 1:2:1 M ratio. The complexes have been characterized by elemental analyses, ESI - mass, NMR (1H and 13C), IR, XRD, electronic and EPR spectral studies, magnetic susceptibility and molar conductance measurements. These studies show that all the complexes have octahedral arrangement around the metal ions. The molar conductance measurements of all the complexes in DMSO indicate their non-electrolytic nature. The complexes were screened for their antibacterial activity in vitro against Gram-positive (Streptococcus pyogenes) and Gram-negative (Klebsiella pneumoniae) bacteria. Among the metal complexes studied the copper complex [CuLCl2], showed highest antibacterial activity nearly equal to standard drug ciprofloxacin. Other complexes also showed considerable antibacterial activity. The relative order of activity against S. Pyogenes is as Cu(II) > Zn(II) > Co(II) = Fe(II) > Ni(II) and with K. Pneumonia is as Cu(II) > Co(II) > Zn(II) > Fe(II) > Ni(II).

  3. Synthesis, spectroscopic (electronic, IR, NMR and ESR) and theoretical studies of transition metal complexes with some unsymmetrical Schiff bases

    NASA Astrophysics Data System (ADS)

    Singh, Vinod P.; Singh, Shweta; Singh, Divya P.; Tiwari, K.; Mishra, Monika

    2014-01-01

    Two unsymmetrical Schiff bases, glyoxal salicylaldehyde oxalic acid dihydrazone (gsodh) and glyoxal salicylaldehyde malonic acid dihydrazone (gsmdh) and their Co(II), Ni(II), Cu(II) and Zn(II) complexes have been synthesized. The structures of metal complexes are elucidated on the basis of elemental analyses, molar conductance, magnetic susceptibility measurements, electronic, ESR, IR and NMR (1H and 13C) spectral studies. Both ligands show monobasic tetra-dentate behaviour, bonding through CO, two CN and a phenolate group. The electronic spectral studies in solid state indicate a square planar geometry for Ni(II) and Cu(II) complexes and a tetrahedral geometry for Co(II) complexes. However, Co(II) and Cu(II) complexes adopt octahedral geometry in DMSO solution. The ESR spectra of Cu(II) complexes in DMSO solution at 77 K predict an elongated tetragonal distorted octahedral geometry around metal ion and presence of unpaired electron in d orbital. Further, the structures of ligands and their Ni(II) complexes have been satisfactorily modelled by calculations based on density functional theory (DFT). The electronic spectra of Ni(II) complexes are also analyzed in depth with the help of time dependent-DFT (TD-DFT). The theoretical analyses of electronic structure and molecular orbitals have demonstrated that the high-energy absorption bands are M → L charge transfer and low energy transitions are d-d transitions.

  4. EPR, UV-vis, magnetic, spectral studies and electrochemical behaviour of mononuclear transition metal complexes derived from novel hexa-aza-macrotricyclic ligand

    NASA Astrophysics Data System (ADS)

    Chandra, Sulekh; Gupta, Nidhi; Gupta, Rachna; Bawa, Sukhwant Singh

    2005-11-01

    Aza-macrocyclic complexes have gained importance because of their pharmacological properties [N.K. Singh, Srivastava, Trans. Met. Chem. 25 (2000) 133]. Hexa-aza-macrocyles containing glutarimide efficiently coordinate as hexa-dentate ligand, to give complexes of Cu(II) possessing tetragonal structure and Mn(II), Co(II) and Ni(II) metal ions that are essentially octahedral. Spectroscopic, and chemical characterizations of these systems are presented in this article. For Ni(II) complexes results on electron transfer processes measured by cyclic voltammetry and colourimetry have been studied.

  5. Covalent attachment of diphosphine ligands to glassy carbon electrodes via Cu-catalyzed alkyne-azide cycloaddition. Metallation with Ni(II).

    PubMed

    Das, Atanu K; Engelhard, Mark H; Lense, Sheri; Roberts, John A S; Bullock, R Morris

    2015-07-21

    Covalent tethering of P(Ph)2N(C6H4C≡CH)2 ligands (P(Ph)2N(C6H4C≡CH)2 = 1,5-di-(4-ethynylphenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) to planar, azide-terminated glassy carbon electrode surfaces has been accomplished using a Cu(I)-catalyzed alkyne-azide cycloaddition (CuAAC) coupling reaction, using a BH3←P protection-deprotection strategy. Deprotected, surface-confined ligands were metallated using [Ni(II)(MeCN)6](BF4)2. X-ray photoelectron spectroscopic measurements demonstrate that metallation introduced 1.3 equivalents Ni(II) per diphosphine onto the electrode surface. Exposure of the surface to a second diphosphine ligand, P(Ph)2N(Ph)2, resulted in the removal of Ni from the surface. Protection, coupling, deprotection, and metallation conditions were optimized using solution-phase model systems, with benzyl azide as a model for the azide-terminated carbon surface; these reactions generate a [Ni(II)(diphosphine)2](2+) complex.

  6. Adsorptive removal of Cu(II) and Ni(II) from single-metal, binary-metal, and industrial wastewater systems by surfactant-modified alumina.

    PubMed

    Khobragade, Moni U; Pal, Anjali

    2015-01-01

    Batch adsorption was carried out to investigate the possibility of utilizing surfactant-modified alumina (SMA) as an adsorbent for the removal of Cu(II) and Ni(II) from single-metal and binary-metal solutions. Scanning electron microscopic (SEM) images of SMA before and after metal removal from single-metal matrix, showed no significant changes, whereas energy dispersive X-ray (EDX) studies confirmed the incorporation of Cu(II) (∼ 0.74 atomic%) and Ni(II) (∼ 0.64 atomic%) on the adsorbent surface. The removal of Cu(II) and Ni(II), using SMA depends on contact time, adsorbent dose and medium pH. The sorption kinetics followed pseudo-second-order model for Cu(II). However, for Ni(II), either pseudo-first-order or pseudo-second-order model is applicable. The batch experimental data were fitted to Langmuir and Freundlich isotherm, and based on the correlation coefficient value (R(2)), the adsorption could be described more precisely by the Freundlich isotherm. The maximum adsorption capacity from Langmuir isotherm of Cu(II) was 9.34 mg g(-1) and for Ni(II) 6.87 mg g(-1). In a synthetic binary mixture of Cu(II) and Ni(II), having a concentration of 10 mg L(-1) each, removal of Cu(II) was better. The treatment method was further applied to real wastewater from an electroplating industry. The batch experiment results showed that SMA was effective in the simultaneous removal of Cu(II) and Ni(II) to a significant extent, with additional improvement of water quality of the industrial effluent considered.

  7. Adsorption of Cd(II), Cu(II) and Ni(II) ions by cross-linking chitosan/rectorite nano-hybrid composite microspheres.

    PubMed

    Zeng, Lixuan; Chen, Yufei; Zhang, Qiuyun; Guo, Xingmei; Peng, Yanni; Xiao, Huijuan; Chen, Xiaocheng; Luo, Jiwen

    2015-10-05

    Chitosan/rectorie (CTS/REC) nano-hybrid composite microsphere was prepared by changing the proportion of CTS/REC with 2:1, 3:1 and 4:1. Compared with the pure cross-linking chitosan microsphere, the nano-hybrid composite microsphere was proved to have better sorption capacity of Cd(II), Cu(II) and Ni(II), especially 2:1(CTS/REC-1). The adsorption behavior of the microsphere of Cd(II), Cu(II) and Ni(II) was investigated in single and binary metal systems. In single system, the equilibrium studies showed that the adsorption of Cd(II), Cu(II) and Ni(II) followed the Langmuir model and the pseudo-second-order kinetic model. The negative values of (ΔG) suggested that the adsorption process was spontaneous. In binary system, the combined action of the metals was found to be antagonistic and the metal sorption followed the order of Cu(II)>Cd(II)>Ni(II). The regeneration studies indicated that EDTA desorbed Cd(II), Cu(II) and Ni(II) from cross-linking microspheres better than HCl. The FT-IR and XPS spectra showed that coordination bonds were formed between Cd(II), Cu(II) and Ni(II) and the nitrogen atoms of cross-linking CTS/REC nano-hybrid composite microspheres.

  8. Synthesis and characterization of hydroxyapatite nanoparticles impregnated on apple pomace to enhanced adsorption of Pb(II), Cd(II), and Ni(II) ions from aqueous solution.

    PubMed

    Chand, Piar; Pakade, Yogesh B

    2015-07-01

    Hydroxyapatite nanoparticles were synthesized, characterized, and impregnated onto apple pomace surface (HANP@AP) for efficient removal of Pb(II), Cd(II), and Ni(II) ions from water. HANP@AP was characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), transmission electron microscope (TEM), X-ray diffraction (XRD), and surface area analysis. Batch sorption studies were carried out to investigate the influence of different parameters as amount of dose (g), pH, time (min), and initial concentration (mg L(-1)) on adsorption process. Experimental kinetic data followed pseudo-second-order model and equilibrium data well fitted to Langmuir adsorption model with maximum adsorption capacities of 303, 250, and 100 mg g(-1) for Pb(II), Cd(II), and Ni(II) ions, respectively. Competitive adsorption of Pb(II), Cd(II), and Ni(II) ions in presences of each other was studied to evaluate the removal efficiency of HANP@AP against multi metal-loaded water. HANP@AP was successfully applied to real industrial wastewater with 100 % removal of all three metal ions even at high concentration. HANP@AP could be recycled for four, four, and three cycles in case of Pb(II), Cd(II) and Ni(II), respectively. The study showed that HANP@AP is fast, cost effective, and environmental friendly adsorbent for removal of Pb(II), Cd(II), and Ni(II) ions from real industrial wastewater.

  9. A new one-dimensional NiII coordination polymer with a two-dimensional supra­molecular architecture

    PubMed Central

    Zhong, Kai-Long

    2017-01-01

    A new one-dimensional NiII coordination polymer of 1,3,5-tris­(imidazol-1-ylmeth­yl)benzene, namely catena-poly[[aqua­(sulfato-κO)hemi(μ-ethane-1,2-diol-κ2 O:O′)[μ3-1,3,5-tris­(1H-imidazol-1-ylmeth­yl)benzene-κ3 N 3,N 3′,N 3′′]nickel(II)] ethane-1,2-diol monosolvate monohydrate], {[Ni(SO4)(C18H18N6)(C2H6O2)0.5(H2O)]·C2H6O2·H2O}n, was synthesized and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. The NiII cation is coordinated by three N atoms of three different 1,3,5-tris­(imidazol-1-ylmeth­yl)benzene ligands, one O atom of an ethane-1,2-diol mol­ecule, by a sulfate anion and a water mol­ecule, forming a distorted octa­hedral NiN3O3 coordination geometry. The tripodal 1,3,5-tris­(imidazol-1-ylmeth­yl)benzene ligands link the NiII cations, generating metal–organic chains running along the [100] direction. Adjacent chains are further connected by O—H⋯O hydrogen bonds, resulting in a two-dimensional supermolecular architecture running parallel to the (001) plane. Another water mol­ecule and a second ethane-1,2-diol mol­ecule are non-coordinating and are linked to the coordinating sulfate ions via O—H⋯O hydrogen bonds. PMID:28217340

  10. Adsorption of Cu(II), Hg(II), and Ni(II) ions by modified natural wool chelating fibers.

    PubMed

    Monier, M; Ayad, D M; Sarhan, A A

    2010-04-15

    The graft copolymerization of ethyl acrylate (EA) onto natural wool fibers initiated by potassium persulphate and Mohr's salt redox initiator system in limited aqueous medium was carried out in heterogeneous media. Ester groups of the grafted copolymers were partially converted into hydrazide function groups followed by hydrazone formation through reaction with isatin. Also the application of the modified fibers for metal ion uptake was studied using Cu(II), Hg(II) and Ni(II). The modified chelating fibers were characterized using FTIR spectroscopy, SEM and X-ray diffraction.

  11. Immobilization of Pb(II), Cd(II) and Ni(II) ions on kaolinite and montmorillonite surfaces from aqueous medium.

    PubMed

    Sen Gupta, Susmita; Bhattacharyya, Krishna G

    2008-04-01

    The present study investigates the immobilization of Pb(II), Cd(II) and Ni(II) on clays (kaolinite and montmorillonite) in aqueous medium through the process of adsorption under a set of variables (concentration of metal ion, amount of clay, pH, time and temperature of interaction). Increasing pH favours the removal of metal ions till they are precipitated as the insoluble hydroxides. The uptake is rapid with maximum adsorption being observed within 180 min for Pb(II) and Ni(II) and 240 min for Cd(II). A number of available models like the Lagergren pseudo first-order kinetics, second-order kinetics, Elovich equation, liquid film diffusion and intra-particle diffusion are utilized to evaluate the kinetics and the mechanism of the immobilization interactions. Two isotherm equations due to Langmuir and Freundlich showed good fits with the experimental data. Kaolinite and montmorillonite have considerable Langmuir monolayer capacity with respect to Pb(II), Cd(II) and Ni(II), the values being in the range of 6.8-11.5mg/g (kaolinite) and 21.1-31.1mg/g (montmorillonite). The Freundlich adsorption capacity follows a similar order. The thermodynamics of the immobilization process indicates the same to be exothermic with Pb(II) and Ni(II), but endothermic with Cd(II). The interactions with Pb(II) and Ni(II) are accompanied by decrease in entropy and Gibbs energy while the endothermic immobilization of Cd(II) is supported by an increase in entropy and an appreciable decrease in Gibbs energy. The results have established good potentiality for kaolinite and montmorillonite to remove heavy metals like Pb(II), Cd(II) and Ni(II) from aqueous medium through adsorption-mediated immobilization.

  12. Adsorption of Ni(II) and Cd(II) from water by novel chelating sponge and the effect of alkali-earth metal ions on the adsorption.

    PubMed

    Cheng, Cheng; Wang, Jinnan; Yang, Xin; Li, Aimin; Philippe, Corvini

    2014-01-15

    Novel chelating sponge (PVA-M-H) was prepared with polyvinyl alcohol by graft polymerization and nucleophilic substitution. E.A, SEM, FT-IR, (13)CNMR, and XPS analyses were used to characterize PVA-M-H. The equilibrium adsorption capacities of PVA-M-H for Ni(II) and Cd(II) were 65.39 and 125.11mgg(-1), respectively. Within the range of 278-308K, the adsorption enthalpy changes of Ni(II) and Cd(II) on PVA-M-H were about 36.39-37.72kJmol(-1), and the free energy were about -13.27 to -1.7kJmol(-1). Both pseudo-first- and -second-order equations fit the adsorption kinetic curves well, and the initial adsorption rates of Ni(II) and Cd(II) onto PVA-M-H were 17.83 and 34.81mg (gmin)(-1), respectively. Although the presence of alkali-earth metal ions in solution decreased Ni(II) and Cd(II) removal, PVA-M-H still retained more than 60 and 80% of its adsorption capacity even as the concentration of Ca(2+) and Mg(2+) was up to 10mmolL(-1), respectively. Both 0.1M HCl and 0.1M EDTA solution could desorb Ni(II) and Cd(II) from PVA-M-H effectively, and the adsorption capacity of PVA-M-H for Ni(II) and Cd(II) could still maintain more than 90% level without any obvious decrease at the fifth cycle.

  13. Kinetic and thermodynamic studies of the Co(II) and Ni(II) ions removal from aqueous solutions by Ca-Mg phosphates.

    PubMed

    Ivanets, A I; Srivastava, V; Kitikova, N V; Shashkova, I L; Sillanpää, M

    2017-03-01

    The aim of this work was to study the sorption kinetics and thermodynamics of Co(II) and Ni(II) from aqueous solutions by sorbents on the basis of hydrogen (PD-1) and tertiary (PD-2) Ca-Mg phosphates depending on the solution temperature and sorbents chemical composition. Kinetic studies of adsorption of Co(II) and Ni(II) ions onto samples of phosphate sorbents were performed in batch experiment at the temperatures 288, 303, 318 and 333 K. The sorbent dose was fixed at 10 g L(-1), initial pH value 2.6, and contact time varied from 5 to 600 min. The kinetics of Co(II) and Ni(II) adsorption were analyzed by using pseudo-first order, pseudo-second order and intraparticle diffusion models. Thermodynamic parameters (ΔG°, ΔH° and ΔS°) for the sorption of Co(II) and Ni(II) were determined using the Gibbs-Helmholtz equation. The calculated kinetic parameters and corresponding correlation coefficients revealed that Co(II) and Ni(II) uptake process followed the pseudo-second order rate expression. Thermodynamic studies confirmed the spontaneous and endothermic nature of removal process which indicate that sorption of Co(II) and Ni(II) ions onto both phosphate sorbents is favoured at higher temperatures and has the chemisorptive mechanism. The data thus obtained would be useful for practical application of the low cost and highly effective Ca-Mg phosphate sorbents.

  14. A multi-approach study of the interaction of the Cu(II) and Ni(II) ions with alanylglycylhistamine, a mimicking pseudopeptide of the serum albumine N-terminal residue.

    PubMed

    Gizzi, P; Henry, B; Rubini, P; Giroux, S; Wenger, E

    2005-05-01

    The protonation equilibria of alanylglycylhistamine (Ala-Gly-Ha) and the complexation of this ligand with Cu(II) and Ni(II) have been studied by pH-potentiometry, 1H and 14N NMR spectroscopy, electrospray ionization mass spectrometry (ESI-MS), circular dichroism (CD), UV-Vis spectrophotometry and electron paramagnetic resonance (EPR). From pH approximately 2-12, the following complexes: MLH, MLH(-1), MLH(-2) and MLH(-3) are successively formed in aqueous solutions, the ligand under its neutral form being noted L. At physiological pH, the MLH(-2) complex is predominant. The coordination in this complex is assumed by one amino, two deprotonated peptide and one imidazole nitrogen atoms. The ESI-MS study confirmed the formation of the MLH(-1), MLH(-2) and MLH(-3) complexes. The structure of MLH(-2) was determined by single crystal X-ray analysis. CD and UV-Vis techniques allowed us to propose that the imidazole-N3 nitrogen acts as the anchor group for the coordination to the metal(II) ions rather than the amino group. At high pH values, the further deprotonation of the N-H imidazole group, leading to the formation of MLH(-3), occurs, as revealed by 1H NMR spectroscopy.

  15. Synthesis, characterization, electrochemical and biological studies on some metal(II) Schiff base complexes containing quinoxaline moiety.

    PubMed

    Dhanaraj, Chellaian Justin; Johnson, Jijo

    2014-01-24

    Novel Co(II), Ni(II), Cu(II) and Zn(II) complexes of Schiff base derived from quinoxaline-2,3-(1,4H)-dione and 4-aminoantipyrine (QDAAP) were synthesized. The ligand and its complexes were characterized by elemental analyses, molar conductance, magnetic susceptibility measurements, FTIR, UV-Vis., mass and (1)H NMR spectral studies. The X band ESR spectrum of the Cu(II) complex at 300 and 77K were also recorded. Thermal studies of the ligand and its complexes show the presence of coordinated water in the Ni(II) and Zn(II) complexes. The coordination behavior of QDAAP is also discussed. All the complexes are mono nuclear and tetrahedral geometry was found for Co(II) complex. For the Ni(II) and Zn(II) complexes, octahedral geometry was assigned and for the Cu(II) complex, square planar geometry has been suggested. The grain size of the complexes was estimated using powder XRD. The surface morphology of the compounds was studied using SEM analysis. Electrochemical behavior of the synthesized complexes in DMF at room temperature was investigated by cyclic voltammetry. The in vitro biological screening of QDAAP and its metal complexes were tested against bacterial species Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa. The fungal species include Aspergillus niger, Aspergillus flavus and Candida albicans. The DNA cleavage activity of QDAAP and its complexes were also discussed.

  16. Synthesis, characterization, electrochemical and biological studies on some metal(II) Schiff base complexes containing quinoxaline moiety

    NASA Astrophysics Data System (ADS)

    Justin Dhanaraj, Chellaian; Johnson, Jijo

    2014-01-01

    Novel Co(II), Ni(II), Cu(II) and Zn(II) complexes of Schiff base derived from quinoxaline-2,3-(1,4H)-dione and 4-aminoantipyrine (QDAAP) were synthesized. The ligand and its complexes were characterized by elemental analyses, molar conductance, magnetic susceptibility measurements, FTIR, UV-Vis., mass and 1H NMR spectral studies. The X band ESR spectrum of the Cu(II) complex at 300 and 77 K were also recorded. Thermal studies of the ligand and its complexes show the presence of coordinated water in the Ni(II) and Zn(II) complexes. The coordination behavior of QDAAP is also discussed. All the complexes are mono nuclear and tetrahedral geometry was found for Co(II) complex. For the Ni(II) and Zn(II) complexes, octahedral geometry was assigned and for the Cu(II) complex, square planar geometry has been suggested. The grain size of the complexes was estimated using powder XRD. The surface morphology of the compounds was studied using SEM analysis. Electrochemical behavior of the synthesized complexes in DMF at room temperature was investigated by cyclic voltammetry. The in vitro biological screening of QDAAP and its metal complexes were tested against bacterial species Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa. The fungal species include Aspergillus niger, Aspergillus flavus and Candida albicans. The DNA cleavage activity of QDAAP and its complexes were also discussed.

  17. Trinuclear nickel complexes with triplesalen ligands: simultaneous occurrence of mixed valence and valence tautomerism in the oxidized species.

    PubMed

    Glaser, Thorsten; Heidemeier, Maik; Fröhlich, Roland; Hildebrandt, Peter; Bothe, Eberhart; Bill, Eckhard

    2005-07-25

    The coordination chemistries of the triple tetradentate triplesalen ligands H(6)talen, H(6)talen(t)(-)(Bu)(2), and H(6)talen(NO)(2) have been investigated with nickel(II). These triplesalen ligands provide three salen-like coordination environments bridged in a meta-phenylene arrangement by a phloroglucinol backbone. The structures of the complexes [(talen)Ni(II)(3)], [(talen(t)(-)(Bu)(2)Ni(II)(3)], and [(talen(NO)(2)Ni(II)(3)] have been determined by single-crystal X-ray diffraction. All three compounds are composed of neutral trinuclear complexes with square-planar coordinated Ni(II) ions in a salen-like coordination environment. Whereas the overall molecular structure of [(talen(NO)(2)Ni(II)(3)] is nearly planar, the structures of [(talen)Ni(II)(3)] and [(talen(t)(-)(Bu)(2)Ni(II)(3)] are bowl-shaped as a result of ligand folding. The strongest ligand folding occurs at the central nickel-phenolate bond of [(talen(t)(-)(Bu)(2)Ni(II)(3)], resulting in the formation of a chiral hemispherical pocket. The dependence of the physical properties by the substituents on the terminal phenolates has been studied by FTIR, resonance Raman, UV-vis-NIR absorption, and electrochemistry. The three nickel-salen subunits are electronically interacting via the pi system of the bridging phloroglucinol backbone. The strength of this interaction is mediated by two opposing effects: the electron density at the terminal phenolates and the folding of the ligand at the central phenolates. The parent complex [(talen)Ni(II)(3)] is irreversibly oxidized at 0.32 V versus ferrocenium/ferrocene (Fc(+)/Fc), whereas [(talen(t)(-)(Bu)2)Ni(II)(3)] and [(talen(NO)(2)Ni(II)(3)] exhibit reversible oxidations at 0.22 V versus Fc(+)/Fc and 0.52 V versus Fc(+)/Fc, respectively. The oxidized species [(talen(t)(-)(Bu)(2)Ni(3)](+) and [(talen(NO)(2)Ni(3)](+) undergo a valence-tautomeric transformation involving a Ni(III) and a phenoxyl radical species, as observed by EPR spectroscopy. Thus, these oxidized

  18. Synthesis, structural characterization and antimicrobial activity evaluation of metal complexes of sparfloxacin

    NASA Astrophysics Data System (ADS)

    El-Gamel, Nadia E. A.; Zayed, M. A.

    2011-11-01

    The synthesis and characterization of binary Cu(II)- ( 1), Co(II)- ( 2), Ni(II)- ( 3), Mn(II)- ( 4), Cr(III)- ( 5), Fe(III)- ( 6), La(III)- ( 7), UO 2(VI)- ( 8) complexes with sparfloxacin ( HL1) and ternary Cu(II)- ( 9), Co(II)- ( 10), Ni(II)- ( 11), Mn(II)- ( 12), Cr(III)- ( 13), Fe(III)- ( 14), La(III)- ( 15), UO 2(VI)- ( 16) complexes with sparfloxacin ( HL1) and DL-alanine ( H2L2) complexes are reported using elemental analysis, molar conductance, magnetic susceptibility, IR, UV-Vis, thermal analysis and 1H-NMR spectral studies. The molar conductance measurements of all the complexes in DMF solution correspond to non-electrolytic nature. All complexes were of the high-spin type and found to have six-coordinate octahedral geometry except the Cu(II) complexes which were four coordinate, square planar and U- and La-atoms in the uranyl and lanthanide have a pentagonal bipyramidal coordination sphere. The antimicrobial activity of these complexes has been screened against two Gram-positive and two Gram-negative bacteria. Antifungal activity against two different fungi has been evaluated and compared with reference drug sparfloxacin. All the binary and ternary complexes showed remarkable potential antimicrobial activity higher than the recommended standard agents. Ni(II)- and Mn(II) complexes exhibited higher potency as compared to the parent drug against Gram-negative bacteria.

  19. Stability Constants of Mixed Ligand Complexes of Nickel(II) with Adenine and Some Amino Acids

    PubMed Central

    Türkel, Naciye

    2015-01-01

    Nickel is one of the essential trace elements found in biological systems. It is mostly found in nickel-based enzymes as an essential cofactor. It forms coordination complexes with amino acids within enzymes. Nickel is also present in nucleic acids, though its function in DNA or RNA is still not clearly understood. In this study, complex formation tendencies of Ni(II) with adenine and certain L-amino acids such as aspartic acid, glutamic acid, asparagine, leucine, phenylalanine, and tryptophan were investigated in an aqueous medium. Potentiometric equilibrium measurements showed that both binary and ternary complexes of Ni(II) form with adenine and the above-mentioned L-amino acids. Ternary complexes of Ni(II)-adenine-L-amino acids are formed by stepwise mechanisms. Relative stabilities of the ternary complexes are compared with those of the corresponding binary complexes in terms of Δlog10⁡K, log10⁡X, and % RS values. It was shown that the most stable ternary complex is Ni(II):Ade:L-Asn while the weakest one is Ni(II):Ade:L-Phe in aqueous solution used in this research. In addition, results of this research clearly show that various binary and ternary type Ni(II) complexes are formed in different concentrations as a function of pH in aqueous solution. PMID:26843852

  20. Removal of Cu(II) and Ni(II) ions from an aqueous solution using α-Fe₂O₃nanoparticle-coated volcanic rocks.

    PubMed

    Zhu, Xianfang; Song, Tiehong; Lv, Zhuo; Ji, Guodong

    2015-01-01

    An adsorbent, volcanic rocks coated with α-Fe₂O₃nanoparticles, was prepared and utilized for the removal of Cu(II) and Ni(II) ions from an aqueous solution. Characterization of the coated volcanic rocks indicated that the α-Fe₂O₃nanoparticles were successfully and homogeneously distributed on the volcanic rocks, including penetration into rock pores. Batch experiments were conducted to investigate adsorption performance. The adsorption behavior of both ions was found to best fit a pseudo second-order model and Langmuir isotherm. The maximum adsorption capacities of Cu(II) and Ni(II) ions were 58.14 mg g⁻¹ and 56.50 mg g⁻¹ at 293 K, respectively, and increased with rising temperature. The loaded α-Fe₂O₃nanoparticles onto volcanic rock significantly increased removal of Cu(II) and Ni(II) ions. The adsorption process was combined control of film diffusion and intra-particle diffusion. Adsorption thermodynamics indicated the adsorption process was spontaneous and occurred mainly through chemisorption. The results confirmed that the volcanic rocks coated with α-Fe₂O₃nanoparticles acted as a high-efficiency and low-cost absorbent, and effectively removed Cu(II) and Ni(II) from wastewater.

  1. Reductive nitrosylation of nickel(ii) complex by nitric oxide followed by nitrous oxide release.

    PubMed

    Ghosh, Somnath; Deka, Hemanta; Dangat, Yuvraj B; Saha, Soumen; Gogoi, Kuldeep; Vanka, Kumar; Mondal, Biplab

    2016-06-21

    Ni(ii) complex of ligand ( = bis(2-ethyl-4-methylimidazol-5-yl)methane) in methanol solution reacts with an equivalent amount of NO resulting in a corresponding Ni(i) complex. Adding further NO equivalent affords a Ni(i)-nitrosyl intermediate with the {NiNO}(10) configuration. This nitrosyl intermediate upon subsequent reaction with additional NO results in the release of N2O and formation of a Ni(ii)-nitrito complex. Crystallographic characterization of the nitrito complex revealed a symmetric η(2)-O,O-nitrito bonding to the metal ion. This study demonstrates the reductive nitrosylation of a Ni(ii) center followed by N2O release in the presence of excess NO.

  2. Mass-dependent and -independent fractionation of isotopes in Ni and Pb chelate complex formation reactions

    NASA Astrophysics Data System (ADS)

    Nomura, Masao; Kudo, Takashi; Adachi, Atsuhiko; Aida, Masao; Fujii, Yasuhiko

    2013-11-01

    Mass independent fractionation (MIF) has been a very interesting topic in the field of inorganic isotope chemistry, in particular, geo- and cosmo- chemistry. In the present work, we studied the isotope fractionation of Ni(II) and Pb(II) ions in complex formation with chelating reagent EDTA. To obtain clear results on the mass dependence of the isotope fractionation, we have conducted long-distance ion exchange chromatography of Ni(II) and Pb(II), using chelate complex reagent EDTA. The results apparently show that the isotope fractionation in Ni complex formation system is governed by the mass dependent rule. On the other hand the isotope fractionation in the Pb complex system is governed by the mass independent rule or the nuclear volume effect.

  3. Mass-dependent and -independent fractionation of isotopes in Ni and Pb chelate complex formation reactions

    SciTech Connect

    Nomura, Masao; Kudo, Takashi; Adachi, Atsuhiko; Aida, Masao; Fujii, Yasuhiko

    2013-11-13

    Mass independent fractionation (MIF) has been a very interesting topic in the field of inorganic isotope chemistry, in particular, geo- and cosmo- chemistry. In the present work, we studied the isotope fractionation of Ni(II) and Pb(II) ions in complex formation with chelating reagent EDTA. To obtain clear results on the mass dependence of the isotope fractionation, we have conducted long-distance ion exchange chromatography of Ni(II) and Pb(II), using chelate complex reagent EDTA. The results apparently show that the isotope fractionation in Ni complex formation system is governed by the mass dependent rule. On the other hand the isotope fractionation in the Pb complex system is governed by the mass independent rule or the nuclear volume effect.

  4. Design and synthesis of novel complexes containing N-phenyl-1H-pyrazole moiety: Ni complex as potential antifungal and antiproliferative compound

    NASA Astrophysics Data System (ADS)

    El-Gamel, Nadia E. A.; Farghaly, Thoraya A.

    2013-11-01

    Cu(II) (1), Ni(II) (2), Cr(III) (3) and Fe(III) (4) complexes with 3-acetyl-4-benzoyl-1-phenyl-1H-pyrazole (L1) were prepared and structurally characterized. Usual coordination of L1 was achieved through nitrogen of pyrazole moiety and carbonyl acetyl group. Electronic spectra of the complexes indicate that the geometry of the metal center was six coordinate octahedral. In vitro antimicrobial activity of the ligand and complex compounds was screened in terms of antibacterial effect on Staphylococcus aureus (Gram-positive), Escherichia coli (Gram-negative) and antifungal effect on the fungi Aspergillus flavus and candida albicans using the modified Kirby-Bauer disc diffusion and minimum inhibitory concentrations (MIC) methods. Ni(II) complex (2) exhibited remarkable antifungal inhibition against Candida albicans equal to the standard antifungal agent. To continue our study some structural modifications are formed by adding 4-fluoro-benzoyl moiety to L1 in different forms to produce different ligands, 3-acetyl-4-(4-flourobenzoyl)-1-phenyl-1H-pyrazole (L2) and 3-[(3-acetyl-1-phenyl-1H-4-pyrazolyl)carbonyl]-1-phenyl-4-(4-flourobenzoyl)-1H-pyrazole (L3), Ni complexes (5 and 6) are prepared and comparable in vitro antimicrobial study is evaluated. In vitro cytotoxicity of the Ni(II) complex (2) is studied using MTT assay. The analysis of the cell test showed that (2) displayed quite small cytotoxic response at the higher concentration level which indeed would further enable us for more opportunities in therapeutic and biomedical challenges. Both of the capability as a potent in vitro antifungal agent and the cell test analysis show Ni(II) complex (2) as a promising material in the translation of observed in vitro biological phenomenon into clinical therapies settings.

  5. Design and synthesis of novel complexes containing N-phenyl-1H-pyrazole moiety: Ni complex as potential antifungal and antiproliferative compound.

    PubMed

    El-Gamel, Nadia E A; Farghaly, Thoraya A

    2013-11-01

    Cu(II) (1), Ni(II) (2), Cr(III) (3) and Fe(III) (4) complexes with 3-acetyl-4-benzoyl-1-phenyl-1H-pyrazole (L1) were prepared and structurally characterized. Usual coordination of L1 was achieved through nitrogen of pyrazole moiety and carbonyl acetyl group. Electronic spectra of the complexes indicate that the geometry of the metal center was six coordinate octahedral. In vitro antimicrobial activity of the ligand and complex compounds was screened in terms of antibacterial effect on Staphylococcus aureus (Gram-positive), Escherichia coli (Gram-negative) and antifungal effect on the fungi Aspergillus flavus and candida albicans using the modified Kirby-Bauer disc diffusion and minimum inhibitory concentrations (MIC) methods. Ni(II) complex (2) exhibited remarkable antifungal inhibition against Candida albicans equal to the standard antifungal agent. To continue our study some structural modifications are formed by adding 4-fluoro-benzoyl moiety to L1 in different forms to produce different ligands, 3-acetyl-4-(4-flourobenzoyl)-1-phenyl-1H-pyrazole (L2) and 3-[(3-acetyl-1-phenyl-1H-4-pyrazolyl)carbonyl]-1-phenyl-4-(4-flourobenzoyl)-1H-pyrazole (L3), Ni complexes (5 and 6) are prepared and comparable in vitro antimicrobial study is evaluated. In vitro cytotoxicity of the Ni(II) complex (2) is studied using MTT assay. The analysis of the cell test showed that (2) displayed quite small cytotoxic response at the higher concentration level which indeed would further enable us for more opportunities in therapeutic and biomedical challenges. Both of the capability as a potent in vitro antifungal agent and the cell test analysis show Ni(II) complex (2) as a promising material in the translation of observed in vitro biological phenomenon into clinical therapies settings.

  6. Preparation and Reactions of the 1,1-Dithiolato Complexes of Ni(II). An Undergraduate Coordination Chemistry Experiment.

    ERIC Educational Resources Information Center

    Ballester, L.; Perpinan, M. F.

    1988-01-01

    Described is an undergraduate coordination chemistry experiment that enables students to relate concepts developed in class about the stereochemistry and coordination numbers to the interpretation of the electronic and infrared spectra and their magnetic behavior. Indicates that thermal decomposition and x-ray diffraction studies can also be…

  7. Synthesis, characterization, and reactivity of pentamethylcyclopentadienyl complexes of divalent cobalt and nickel

    SciTech Connect

    Smith, Michael Edward

    1993-10-01

    The thesis is divided into the following 4 chapters: synthesis, characterization, and reactivity of trinuclear pentamethylcyclopentadienyl cobalt and nickel clusters with triply-bridging methylidyne groups; chemical and physical properties of pentamethylcyclopentadienyl acetylacetonate complexes of Co(II) and Ni(II); synthesis, characterization, and reactivity of pentamethylcyclopentadienyl halide complexes of Co and Ni; and crystallographic studies of distortions in metallocenes with C5-symmetrical cyclopentadienyl rings.

  8. Complexation of 1-hexadecyl-4-aza-1-azoniabicyclo[2.2.2]octane bromide with nickel nitrate in acetone

    NASA Astrophysics Data System (ADS)

    Zhiltsova, E. P.; Lukashenko, S. S.; Ibatullina, M. R.; Kutyreva, M. P.; Zakharova, L. Ya.

    2016-07-01

    The complexation of 1-hexadecyl-4-aza-1-azoniabicyclo[2.2.2]octane bromide with Ni(II) nitrate in acetone is studied by means of spectrophotometry (the Job-Ostromisslensky technique and molar ratios). The formation of 3: 1 and 1: 1 ligand: metal complexes is established and confirmed by mathematical modeling. The stability constants of the complexes and the change in the Gibbs free energy are determined.

  9. Interaction of Co(II), Ni(II) and Cu(II) with dibenzo-substituted macrocyclic ligands incorporating both symmetrically and unsymmetrically arranged N, O and S donors.

    PubMed

    Vasilescu, I M; Baldwin, D S; Bourne, D J; Clegg, J K; Li, F; Lindoy, L F; Meehan, G V

    2011-09-14

    The synthesis and characterisation of four 17-membered, dibenzo-substituted macrocyclic ligands incorporating unsymmetrical arrangements of their N(3)S(2), N(3)O(2) and N(3)OS (two ligands) donor atoms are described; these rings complete the matrix of related macrocyclic systems incorporating both symmetric and unsymmetric donor sets reported previously. The X-ray structures of three of the new macrocycles are reported. In two of the Cu(II) structures only three of the possible five donor atoms present in the corresponding macrocyclic ligand bind to the Cu(II) site, whereas all five donors are coordinated in each of the remaining complexes. The interaction of Co(II), Ni(II) and Cu(II) with the unsymmetric macrocycle series has been investigated by potentiometric (pH) titration in 95% methanol; X-ray structures of two nickel and three copper complexes of these ligands, each exhibiting 1:1 (M:L) ratios, have been obtained. The results are discussed in the context of previous results for these metals with the analogous 17-membered ring systems incorporating symmetrical arrangements of their donor atoms, with emphasis being given to both the influence of the donor atom set, as well as the donor atom sequence, on the nature of the resulting complexes.

  10. Nickel(II) complexes of N-CH2CF3 cyclam derivatives as contrast agents for (19)F magnetic resonance imaging.

    PubMed

    Blahut, Jan; Hermann, Petr; Gálisová, Andrea; Herynek, Vít; Císařová, Ivana; Tošner, Zdeněk; Kotek, Jan

    2016-01-14

    Kinetically inert Ni(ii) complexes of N(1),N(8)-bis(2,2,2-trifluoroethyl)cyclams with hydrogen atoms or phosphonic acid groups in the N(4),N(11)-positions show significant (19)F NMR relaxation rate enhancement useful for 19-fluorine MRI imaging.

  11. Asymmetric self-assembly with atmospheric CO2 fixation of a pentanuclear carbonate NiI) complex based on dissimilar building blocks.

    PubMed

    Fondo, Matilde; García-Deibe, Ana M; Ocampo, Noelia; Sanmartín, Jesús; Bermejo, Manuel R

    2007-01-28

    Formation in basic solution of an asymmetric pentanuclear carbonate Ni(II) complex with a compartmental ligand involves atmospheric CO(2) uptake, either by reaction of two slightly different dinuclear precursors that yield its di- and trinuclear "building blocks", or directly, by spontaneous self-organization of metal and ligand starting reactants.

  12. Energetic changes in the surface of activated carbons and relationship with Ni(II) adsorption from aqueous solution

    NASA Astrophysics Data System (ADS)

    Rodríguez-Estupiñan, Paola; Giraldo, Liliana; Moreno-Piraján, Juan Carlos

    2013-12-01

    This study investigated Ni(II) ion adsorption from aqueous solution on activated carbons obtained by chemically modifying the surface with the oxidizing agents nitric acid and hydrogen peroxide (CAGoxP and CAGoxN, respectively). The activated carbons were characterized by total acidity and basicity, pH at the point of charge zero determination and IR spectroscopy. Textural parameters such as the BET area and pore volumes were evaluated by gas adsorption. The BET area of the materials was between 816 and 876 m2 g-1. Additionally, the immersion enthalpies of the activated carbons in water and benzene were determined. The experimental results on adsorption in solution were adjusted to the Langmuir and Freundlich models, obtaining values for the monolayer capacity between 29.68 and 50.97 mg g-1, which indicates that the adsorption capacity depends largely on solid surface chemistry.

  13. Batch and dynamic sorption of Ni(II) ions by activated carbon based on a native lignocellulosic precursor.

    PubMed

    Nabarlatz, Debora; de Celis, Jorge; Bonelli, Pablo; Cukierman, Ana Lea

    2012-04-30

    Vinal-derived Activated Carbon (VAC) developed by phosphoric acid activation of sawdust from Prosopis ruscifolia native wood was tested for the adsorption of Ni(II) ions from dilute solutions in both batch and dynamic modes, comparing it with a Commercial Activated Carbon (CAC). Batch experiments were performed to determine adsorption kinetics and equilibrium isotherms for both carbons. It was possible to remove near 6.55 mg Ni g(-1) VAC and 7.65 mg Ni g(-1) CAC after 5 h and 10 h contact time, respectively. A pseudo second order equation fitted well with the kinetics of the process, and Langmuir adsorption model was used to adjust the experimental results concerning the adsorption isotherm. The parameters obtained indicate a stronger interaction between sorbent and sorbate for VAC (K = 26.56 L mmol(-1)) than for CAC (K = 19.54 L mmol(-1)). Continuous experiments were performed in a fixed-bed column packed with the investigated carbons, evaluating the influence of operational parameters such as flow rate, bed height and feed concentration on the breakthrough curves obtained. The breakthrough occurred more slowly for low concentrations of the metal ion in the feed, low flow rates and high bed height. The breakthrough curves were properly represented by Hall's model for both carbon types. Regeneration of the vinal activated carbon in column was tested, obtaining the same breakthrough curve in a new cycle of use. Finally, vinal-derived activated carbon can effectively be used to treat wastewater having until 30 ppm Ni(II).

  14. Synthesis, characterization and antibacterial activity of new sulfonyl hydrazone derivatives and their nickel(II) complexes

    NASA Astrophysics Data System (ADS)

    Özmen, Ümmühan Özdemir; Olgun, Gülçin

    2008-08-01

    Prophane sulfonic acid hydrazide (psh: CH 3CH 2CH 2SO 2NHNH 2) derivatives as salicylaldehydeprophanesulfonylhydrazone (salpsh), 5-methylsalicylaldehydeprophanesulfonylhydrazone (5-msalpsh), 2-hydroxyacetophenoneprophanesulfonylhydrazone (afpsh), 5-methyl-2-hydroxyacetophenoneprophanesulfonylhydrazone (5-mafpsh) and their Ni(II) complexes have been synthesized. The structure of these compounds has been investigated by using elemental analysis, FTIR, 1H NMR, LC/MS, UV-vis spectrophotometric method, magnetic susceptibility and conductivity measurements. The complexes were found to have general compositions [NiL2]. Square-planer structures are proposed for the Ni(II) complexes on the basis of magnetic evidence, electronic spectra and TGA data. Bacterial activities of sulfonyl hydrazone compounds were studied against gram-positive bacteria: Staphylococcus aureus, Bacillus subtilis, Bacillus magaterium and gram-negative bacteria: Salmonella enteritidis, Escherichia coli by using minimum inhibitory concentrations (MICs) method.

  15. Synthesis, characterization and antibacterial activity of new sulfonyl hydrazone derivatives and their nickel(II) complexes.

    PubMed

    Ozmen, Ummühan Ozdemir; Olgun, Gülçin

    2008-08-01

    Prophane sulfonic acid hydrazide (psh: CH(3)CH(2)CH(2)SO(2)NHNH(2)) derivatives as salicylaldehydeprophanesulfonylhydrazone (salpsh), 5-methylsalicylaldehydeprophanesulfonylhydrazone (5-msalpsh), 2-hydroxyacetophenoneprophanesulfonylhydrazone (afpsh), 5-methyl-2-hydroxyacetophenoneprophanesulfonylhydrazone (5-mafpsh) and their Ni(II) complexes have been synthesized. The structure of these compounds has been investigated by using elemental analysis, FTIR, (1)H NMR, LC/MS, UV-vis spectrophotometric method, magnetic susceptibility and conductivity measurements. The complexes were found to have general compositions [NiL2]. Square-planer structures are proposed for the Ni(II) complexes on the basis of magnetic evidence, electronic spectra and TGA data. Bacterial activities of sulfonyl hydrazone compounds were studied against gram-positive bacteria: Staphylococcus aureus, Bacillus subtilis, Bacillus magaterium and gram-negative bacteria: Salmonella enteritidis, Escherichia coli by using minimum inhibitory concentrations (MICs) method.

  16. Copper(II) and nickel(II) complexes of benzyloxybenzaldehyde-4-phenyl-3-thiosemicarbazone: Synthesis, characterization and biological activity

    NASA Astrophysics Data System (ADS)

    Prathima, B.; Subba Rao, Y.; Adinarayana Reddy, S.; Reddy, Y. P.; Varada Reddy, A.

    2010-09-01

    Benzyloxybenzaldehyde-4-phenyl-3-thiosemicarbazone ligand (L) has been synthesized from benzyloxybenzaldehyde and 4-phenyl-3-thiosemicarbazide. Complexes of this ligand with chlorides of Cu(II) and Ni(II) have been prepared. The structure of the ligand (L) is proposed based on elemental analysis, IR and 1H NMR spectra. Its complexes with Cu(II) and Ni(II) ions are characterized from the studies of electronic as well as EPR spectra. On the basis of electronic and EPR studies, rhombically distorted octahedral structure has been proposed for Cu(II) complex while the Ni(II) complex has been found to acquire an octahedral structure. The ligand and their metal complexes have been tested in vitro for their biological effects. Their antibacterial activities against Gram-negative bacteria ( Escherichia coli and Klebsiella pneumoniae) and Gram-positive bacteria ( Staphylococcus aureus and Bacillus subtilis) have been investigated. The prepared metal complexes exhibit higher antibacterial activities than the parent ligand. The in vitro antioxidant activity of free ligand and its metal(II) complexes have also been investigated and the results however reveal that the ligand exhibits greater antioxidant activity than its complexes.

  17. Copper(II) and nickel(II) complexes of benzyloxybenzaldehyde-4-phenyl-3-thiosemicarbazone: Synthesis, characterization and biological activity.

    PubMed

    Prathima, B; Subba Rao, Y; Adinarayana Reddy, S; Reddy, Y P; Varada Reddy, A

    2010-09-15

    Benzyloxybenzaldehyde-4-phenyl-3-thiosemicarbazone ligand (L) has been synthesized from benzyloxybenzaldehyde and 4-phenyl-3-thiosemicarbazide. Complexes of this ligand with chlorides of Cu(II) and Ni(II) have been prepared. The structure of the ligand (L) is proposed based on elemental analysis, IR and (1)H NMR spectra. Its complexes with Cu(II) and Ni(II) ions are characterized from the studies of electronic as well as EPR spectra. On the basis of electronic and EPR studies, rhombically distorted octahedral structure has been proposed for Cu(II) complex while the Ni(II) complex has been found to acquire an octahedral structure. The ligand and their metal complexes have been tested in vitro for their biological effects. Their antibacterial activities against Gram-negative bacteria (Escherichia coli and Klebsiella pneumoniae) and Gram-positive bacteria (Staphylococcus aureus and Bacillus subtilis) have been investigated. The prepared metal complexes exhibit higher antibacterial activities than the parent ligand. The in vitro antioxidant activity of free ligand and its metal(II) complexes have also been investigated and the results however reveal that the ligand exhibits greater antioxidant activity than its complexes.

  18. Solid-phase extraction of Mn(II), Co(II), Ni(II), Cu(II), Cd(II) and Pb(II) ions from environmental samples by flame atomic absorption spectrometry (FAAS).

    PubMed

    Duran, Celal; Gundogdu, Ali; Bulut, Volkan Numan; Soylak, Mustafa; Elci, Latif; Sentürk, Hasan Basri; Tüfekci, Mehmet

    2007-07-19

    A new method using a column packed with Amberlite XAD-2010 resin as a solid-phase extractant has been developed for the multi-element preconcentration of Mn(II), Co(II), Ni(II), Cu(II), Cd(II), and Pb(II) ions based on their complex formation with the sodium diethyldithiocarbamate (Na-DDTC) prior to flame atomic absorption spectrometric (FAAS) determinations. Metal complexes sorbed on the resin were eluted by 1 mol L(-1) HNO3 in acetone. Effects of the analytical conditions over the preconcentration yields of the metal ions, such as pH, quantity of Na-DDTC, eluent type, sample volume and flow rate, foreign ions etc. have been investigated. The limits of detection (LOD) of the analytes were found in the range 0.08-0.26 microg L(-1). The method was validated by analyzing three certified reference materials. The method has been applied for the determination of trace elements in some environmental samples.

  19. Importance of reduced sulfur for the equilibrium chemistry and kinetics of Fe(II), Co(II) and Ni(II) supplemented to semi-continuous stirred tank biogas reactors fed with stillage.

    PubMed

    Shakeri Yekta, Sepehr; Lindmark, Amanda; Skyllberg, Ulf; Danielsson, Asa; Svensson, Bo H

    2014-03-30

    The objective of the present study was to assess major chemical reactions and chemical forms contributing to solubility and speciation of Fe(II), Co(II), and Ni(II) during anaerobic digestion of sulfur (S)-rich stillage in semi-continuous stirred tank biogas reactors (SCSTR). These metals are essential supplements for efficient and stable performance of stillage-fed SCSTR. In particular, the influence of reduced inorganic and organic S species on kinetics and thermodynamics of the metals and their partitioning between aqueous and solid phases were investigated. Solid phase S speciation was determined by use of S K-edge X-ray absorption near-edge spectroscopy. Results demonstrated that the solubility and speciation of supplemented Fe were controlled by precipitation of FeS(s) and formation of the aqueous complexes of Fe-sulfide and Fe-thiol. The relatively high solubility of Co (∼ 20% of total Co content) was attributed to the formation of compounds other than Co-sulfide and Co-thiol, presumably of microbial origin. Nickel had lower solubility than Co and its speciation was regulated by interactions with FeS(s) (e.g. co-precipitation, adsorption, and ion substitution) in addition to precipitation/dissolution of discrete NiS(s) phase and formation of aqueous Ni-sulfide complexes.

  20. Structural and biological evaluation of some metal complexes of vanillin-4N-(2-pyridyl) thiosemicarbazone

    NASA Astrophysics Data System (ADS)

    Yousef, T. A.; Abu El-Reash, G. M.; Al-Jahdali, M.; El-Rakhawy, El-Bastawesy R.

    2013-12-01

    The synthesis and characterization of Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II) and U(VI)O2 complexes of vanillin-4N-(2-pyridyl) thiosemicarbazone (H2PVT) are reported. Theoretical calculations have been performed to obtain IR spectra of ligand and its complexes using AM1, Zindo/1, MM+ and PM3, methods. The Schiff base and its metal complexes have been screened for antibacterial Pseudomonas aeruginosa, Escherichia coli, Bacillus subtilis and Staphylococcus saprophyticus. H2VPT shows no apparent digestion effect on the egg albumin while Mn(II), Hg(II) and Cu(II) complexes exhibited a considerable digestion effect following the order Cu(II) > Mn(II) > Hg(II). Moreover, Ni(II) and Co(II) complexes revealed strong digestion effect. Fe(II), Mn(II), Cu(II), Zn(II) and Ni(II) acted as metal co- SOD enzyme factors, which are located in different compartments of the cell.

  1. Design, synthesis, and carbon-heteroatom coupling reactions of organometallic nickel(IV) complexes.

    PubMed

    Camasso, Nicole M; Sanford, Melanie S

    2015-03-13

    Homogeneous nickel catalysis is used for the synthesis of pharmaceuticals, natural products, and polymers. These reactions generally proceed via nickel intermediates in the Ni(0), Ni(I), Ni(II), and/or Ni(III) oxidation states. In contrast, Ni(IV) intermediates are rarely accessible. We report herein the design, synthesis, and characterization of a series of organometallic Ni(IV) complexes, accessed by the reaction of Ni(II) precursors with the widely used oxidant S-(trifluoromethyl)dibenzothiophenium triflate. These Ni(IV) complexes undergo highly selective carbon(sp(3))-oxygen, carbon(sp(3))-nitrogen, and carbon(sp(3))-sulfur coupling reactions with exogenous nucleophiles. The observed reactivity has the potential for direct applications in the development of nickel-catalyzed carbon-heteroatom coupling reactions.

  2. Biosorption of Cu(II), Zn(II), Ni(II) and Pb(II) ions by cross-linked metal-imprinted chitosans with epichlorohydrin.

    PubMed

    Chen, Chia-Yun; Yang, Cheng-Yu; Chen, Arh-Hwang

    2011-03-01

    Cross-linked metal-imprinted chitosan microparticles were prepared from chitosan, using four metals (Cu(II), Zn(II), Ni(II), and Pb(II)) as templates, and epichlorohydrin as the cross-linker. The microparticles were characterized by Fourier transform infrared spectroscopy, solid state (13)C nuclear magnetic resonance spectroscopy, and energy-dispersive X-ray spectroscopy. They were used for comparative biosorption of Cu(II), Zn(II), Ni(II) and Pb(II) ions in an aqueous solution. The results showed that the sorption capacities of Cu(II), Zn(II), Ni(II), and Pb(II) on the templated microparticles increased from 25 to 74%, 13 to 46%, 41 to 57%, and 12 to 43%, respectively, as compared to the microparticles without metal ion templates. The dynamic study showed that the sorption process followed the second-order kinetic equation. Three sorption models, Langmuir, Freundlich, and Dubinin-Radushkevich, were applied to the equilibrium isotherm data. The result showed that the Langmuir isotherm equation best fitted for monolayer sorption processes. Furthermore, the microparticles can be regenerated and reused for the metal removal.

  3. Synthesis, spectral characterization, computational calculations and biological activity of complexes designed from NNO donor Schiff-base ligand

    NASA Astrophysics Data System (ADS)

    El-Gammal, Ola A.; El-Reash, G. M. Abu; Yousef, T. A.; Mefreh, M.

    2015-07-01

    A new series of Co(II), Ni(II) and Cu(II) complexes of (Z)-2-oxo-2-(phenylamino)-N‧-(1-(pyridin-2-yl)ethylidene)acetohydrazide (H2OPPAH) have been prepared and characterized by conventional techniques. The spectral data indicated that the ligand acts as neutral or mononegative NNO tridentate. On the basis of magnetic and electronic spectral data an octahedral geometry for Ni(II) and Cu(II) complexes and a tetrahedral geometry for Co(II) complex have been proposed. The molecular modeling using DFT method are drawn showing the bond length, bond angle, chemical reactivity, energy components (kcal/mol) and binding energy (kcal/mol) for all title compounds. The Kinetic parameters were determined for each thermal degradation stages of the ligand and its complexes using Coats-Redfern and Horowitz-Metzger methods. Also, the compounds were screened for antioxidant activity using ABTS free radical, anti-hemolytic, and in vitro cytotoxic assay. H2OPPAH showed the potent antioxidant activity followed by Co(II) and Cu(II) complexes. On the other hand Ni(II) complex exhibited weak antioxidant activity using ABTS free radical and Erlich and strong erythrocyte hemolysis activity.

  4. Synthesis, spectral characterization, computational calculations and biological activity of complexes designed from NNO donor Schiff-base ligand.

    PubMed

    El-Gammal, Ola A; Abu El-Reash, G M; Yousef, T A; Mefreh, M

    2015-07-05

    A new series of Co(II), Ni(II) and Cu(II) complexes of (Z)-2-oxo-2-(phenylamino)-N'-(1-(pyridin-2-yl)ethylidene)acetohydrazide (H2OPPAH) have been prepared and characterized by conventional techniques. The spectral data indicated that the ligand acts as neutral or mononegative NNO tridentate. On the basis of magnetic and electronic spectral data an octahedral geometry for Ni(II) and Cu(II) complexes and a tetrahedral geometry for Co(II) complex have been proposed. The molecular modeling using DFT method are drawn showing the bond length, bond angle, chemical reactivity, energy components (kcal/mol) and binding energy (kcal/mol) for all title compounds. The Kinetic parameters were determined for each thermal degradation stages of the ligand and its complexes using Coats-Redfern and Horowitz-Metzger methods. Also, the compounds were screened for antioxidant activity using ABTS free radical, anti-hemolytic, and in vitro cytotoxic assay. H2OPPAH showed the potent antioxidant activity followed by Co(II) and Cu(II) complexes. On the other hand Ni(II) complex exhibited weak antioxidant activity using ABTS free radical and Erlich and strong erythrocyte hemolysis activity.

  5. Spectroscopic and structural studies of the Schiff base 3-methoxy-N-salicylidene-o-amino phenol complexes with some transition metal ions and their antibacterial, antifungal activities

    NASA Astrophysics Data System (ADS)

    Abo-Aly, M. M.; Salem, A. M.; Sayed, M. A.; Abdel Aziz, A. A.

    2015-02-01

    Spectroscopic (IR, Raman, NMR, UV-visible, and ESR), and structural studies of the ligand 3-methoxy-N-salicylidene-o-amino phenol (H2L) and its synthesized complexes with some transition metal ions (Mn(II), Co(II), Ni(II)), Cu(II) and Zn(II)) were recorded and analyzed. The magnetic properties and thermal gravimetric analysis (TGA and DTA) were also measured for the complexes. The metal complexes were found to have The structural formula MLṡH2O and the metal ions Mn(II), Co(II), Ni(II)) and Zn(II) were found to form tetrahedral complexes with the ligand whereas Cu(II) formed a square planar one. Antimicrobial activity of the ligand and its complexes were also investigated and discussed.

  6. Spectroscopic and structural studies of the Schiff base 3-methoxy-N-salicylidene-o-amino phenol complexes with some transition metal ions and their antibacterial, antifungal activities.

    PubMed

    Abo-Aly, M M; Salem, A M; Sayed, M A; Abdel Aziz, A A

    2015-02-05

    Spectroscopic (IR, Raman, NMR, UV-visible, and ESR), and structural studies of the ligand 3-methoxy-N-salicylidene-o-amino phenol (H2L) and its synthesized complexes with some transition metal ions (Mn(II), Co(II), Ni(II)), Cu(II) and Zn(II)) were recorded and analyzed. The magnetic properties and thermal gravimetric analysis (TGA and DTA) were also measured for the complexes. The metal complexes were found to have The structural formula ML⋅H2O and the metal ions Mn(II), Co(II), Ni(II)) and Zn(II) were found to form tetrahedral complexes with the ligand whereas Cu(II) formed a square planar one. Antimicrobial activity of the ligand and its complexes were also investigated and discussed.

  7. Antifungal activity of α-methyl trans cinnamaldehyde, its ligand and metal complexes: promising growth and ergosterol inhibitors.

    PubMed

    Shreaz, Sheikh; Sheikh, Rayees A; Bhatia, Rimple; Neelofar, Khan; Imran, Sheikh; Hashmi, Athar A; Manzoor, Nikhat; Basir, Seemi F; Khan, Luqman A

    2011-10-01

    Antifungal effectivity and utility of cinnamaldehyde is limited because of its high MIC and skin sensitivity. In this study, α-methyl trans cinnamaldehyde, a less irritating derivative, have been self coupled and complexed with Co(II) and Ni(II) to generate N, N'-Bis (α-methyl trans cinnamadehyde) ethylenediimine [C(22)H(24)N(2)], [Co(C(44)H(48)N(4))Cl(2)] and [Ni(C(44)H(48)N(4))Cl(2)]. Ligand and complexes were characterized on the basis of FTIR, ESI-MS, IR and (1)HNMR techniques. Synthesized ligand [L] and complexes were investigated for their MICs, inhibition of ergosterol biosynthesis and H(+) extrusion against three strains of Candida: C. albicans 44829, C. tropicalis 750 and C. krusei 6258. Average of three species MIC of methyl cinnamaldehyde is 317 μg/ml (2168 μM). Compared to methyl cinnamaldehyde ligand [L], Co(II) and Ni(II) complex are found to be 4.48, 17.78 and 21.46 times more effective in liquid medium and 2.73, 8.93 and 10.38 times more effective in solid medium. At their respective MIC(90) average inhibition of ergosterol biosynthesis caused by methyl cinnamaldehyde, ligand [L], Co(II) and Ni(II) complex, respectively was 80, 78, 90 and 93%. H(+) extrusion was also significantly inhibited but did not co-relate well with MIC(90). Results indicate ergosterol biosynthesis as site of action of α-methyl cinnamaldehyde, synthesized ligand and complexes. α-methyl cinnamaldehyde and ligand did not show any toxicity against H9c2 rat cardiac myoblast cell, whereas Co(II) and Ni(II) complexes on an average produced 19% cellular toxicity.

  8. X-ray crystal structure of phenylglycine hydrazide: Synthesis and spectroscopic studies of its transition metal complexes

    NASA Astrophysics Data System (ADS)

    Gudasi, Kalagouda B.; Patil, Manjula S.; Vadavi, Ramesh S.; Shenoy, Rashmi V.; Patil, Siddappa A.; Nethaji, M.

    2007-05-01

    Phenylglycine hydrazide was synthesized and investigated by X-ray crystallography. It crystallizes in the monoclinic space group P121/ c with cell parameters a = 5.9459 (18) Å, b = 5.1940 (16) Å, c = 26.7793 (83) Å and Z = 2. Its conformational changes, on complexation with transition metal ions Cu(II), Co(II), Ni(II), Mn(II) and Zn(II) has been studied on the basis of elemental analysis, magnetic moment and spectral (IR, 1H NMR, UV-vis) studies. The bidentate nature of the ligand was confirmed on the basis of a comparative IR and NMR spectral studies. The trigonal bipyramidal geometries were observed for Cu(II), Ni(II) and Co(II) complexes, while it is octahedral for the remaining complexes. The conductivity data suggest them to be non-electrolytes.

  9. X-ray crystal structure of phenylglycine hydrazide: synthesis and spectroscopic studies of its transition metal complexes.

    PubMed

    Gudasi, Kalagouda B; Patil, Manjula S; Vadavi, Ramesh S; Shenoy, Rashmi V; Patil, Siddappa A; Nethaji, M

    2007-05-01

    Phenylglycine hydrazide was synthesized and investigated by X-ray crystallography. It crystallizes in the monoclinic space group P121/c with cell parameters a=5.9459 (18) Angstrom, b=5.1940 (16) Angstrom, c=26.7793 (83) Angstrom and Z=2. Its conformational changes, on complexation with transition metal ions Cu(II), Co(II), Ni(II), Mn(II) and Zn(II) has been studied on the basis of elemental analysis, magnetic moment and spectral (IR, (1)H NMR, UV-vis) studies. The bidentate nature of the ligand was confirmed on the basis of a comparative IR and NMR spectral studies. The trigonal bipyramidal geometries were observed for Cu(II), Ni(II) and Co(II) complexes, while it is octahedral for the remaining complexes. The conductivity data suggest them to be non-electrolytes.

  10. Sonochemical synthesis, DNA binding, antimicrobial evaluation and in vitro anticancer activity of three new nano-sized Cu(II), Co(II) and Ni(II) chelates based on tri-dentate NOO imine ligands as precursors for metal oxides.

    PubMed

    Abdel-Rahman, Laila H; Abu-Dief, Ahmed M; El-Khatib, Rafat M; Abdel-Fatah, Shimaa Mahdy

    2016-09-01

    Three new nano sized Cu(II), Co(II) and Ni(II) complexes of imine ligand derived from the condensation of 2-amino-3-hydroxypyridine and 3-methoxysalicylaldehyde have been prepared and investigated using various chemical techniques such as NMR, elemental analysis, molar conductance, IR, electronic spectra, TGA and magnetic moment measurements. The obtained chemical analysis data showed that the synthesis of 1:1 (metal:ligand) ratio and octahedral geometry was proposed on the basis of magnetic moment and spectral data studies except the Cu(II) complex which is tetrahedral geometry. Nano-sized particles of the investigated complexes were prepared by sonochemistry method. Furthermore, metal oxides nanoparticles were gained by calcination of the prepared corresponding complexes at 500°C and their structures were characterized by powder x-ray and transmittance electron microscopy. Moreover, the free ligand, its complexes and their metal oxides have been checked in vitro against a number of bacteria and fungi in order to assess their antimicrobial activities. In addition to that, DNA binding of the prepared complexes was tested by many routes such as electronic spectra, viscosity and gel electrophoresis. The results showed that the investigated complexes could bind to DNA via an intercalative mode. The cytotoxicity of the Schiff base complexes on human colon carcinoma cells, (HCT-116 cell line) and Breast carcinoma cells, (MCF-7 cell line) showed potent cytotoxicity effect against growth of carcinoma cells compared to the clinically used Vinblastine standard.

  11. Theoretical investigation of polymer chain stability in the metal coordinated azorubine and cyclam complex

    NASA Astrophysics Data System (ADS)

    Vlassa, Mihaela; Bende, Attila

    2015-08-01

    Theoretical investigations have been performed for unit systems with Ni(II) and Zn(II) coordination between azorubine and 1,4,8,11-tetraazacyclotetradecane (cyclam) complexes using the conventional DFT and the DFT-based tight binding (DFTB) methods. Two different geometries (short and long) and spin states (singlet and triplet) of the model system built by two mesylate groups and the cyclam ring together with Ni(II) and Zn(II) ions were energetically characterized. For the Ni(II) coordination complex the triplet geometry is preferred, but one could not exclude also the presence of the singlet spin configuration due to the huge energy barrier defined by the intersystem crossing. The intersystem crossing geometry of the singlet-triplet transition was studied in details and the corresponding spin-orbit couplings were discussed. For the Zn(II) coordination complex only the singlet state was found. Polymer chain build up from four unit systems presents irregular forms with strong coordination bonds between units.

  12. Computational simulation and biological studies on 3-(2-(2-hydroxybenzoyl)hydrazono)-N-(pyridine-2-yl)butanamide complexes

    NASA Astrophysics Data System (ADS)

    Ibrahim, K. M.; Zaky, R. R.; Gomaa, E. A.; Yasin, L. A.

    2015-12-01

    A number of Cu(II), Co(II), Ni(II), Cd(II) and Hg complexes with 3-(2-(2-hydroxybenzoyl)hydrazono)-N-(pyridine-2-yl)butanamide were synthesized. The structures were elucidated by elemental and thermal analysis, as well as spectroscopic techniques (1H NMR, IR, UV-visible, MS) and physical measurements (magnetic susceptibility and molar conductance). The IR and 1H NMR data suggested that H2SHAH acted as a tridentate and/or tetradentate ligand. The electronic spectrum plus magnetic moments suggesting octahedral geometry of all isolated complexes except [Cu(HSHAH)Cl] complex has square planner structure. The kinetic and thermodynamic parameters of the Ni(II) and Cu(II) complexes were measured using the Coats-Redfern approach. The DFT used to confirm the geometry of the isolated compounds. Also, the association and formation constants of Ni(II), Co(II) and Cu(II) ions in mixed solvent at 298.15 K were intended by employing electrical conductance. The biological activity (antimicrobial, antioxidant & cytotoxic) were carried out on the prepared compounds. The Cd(II) complex has the most potent biological activity among all the other compounds.

  13. Tren centered tris-macrocycles as polytopic ligands for Cu(II) and Ni(II).

    PubMed

    Siegfried, Liselotte; McMahon, C Niamh; Kaden, Thomas A; Palivan, Cornelia; Gescheidt, Georg

    2004-07-21

    Two novel symmetric polytopic ligands L(1) and L(2) have been synthesized. They are composed of three 1,4,8,11-tetraazacyclotetradecane macrocycles which are connected to a central tren moiety via an ethylene and a trimethylene bridge, respectively. The complexation potential and the speciation diagrams of L(1) and L(2) towards Cu(2+) and Ni(2+) were determined by spectrophotometric and potentiometric titrations. Insight into the geometry of the Cu(2+) complexes is provided by UV-VIS and EPR spectroscopy. The simplified ligands L(3) and L(4) are utilized as references for an aminoethyl- and a tren-substituted tetraaza macrocycle to help assign the EPR spectra of the polytopic ligands L(1) and L(2). At a metal-to-ligand ratio of 3 : 1, the metal cations are preferentially bound to the tetraaza macrocycles of L(1) and L(2) in a square planar geometry. At high pH values, a nitrogen atom of the tren moiety in L(1) serves as an additional ligand in an axial position leading to a square pyramidal coordination around Cu(2+), whereas in L(2) no such geometry change is observed. At a metal-to-ligand ratio of 4 : 1, the additional metal cation resides in the central tren moiety of L(1) and L(2). However, in contrast to the typical trigonal bipyramidal geometry found in the [Cutren](2+) complex, the fourth Cu(2+) has a square pyramidal coordination caused by the interaction with the Cu(2+) cations in the macrocycles (as evidenced by EPR spectra). Since the sequence of metal complexation is such that the first three metal ions always bind to the three macrocycles of L(1) and L(2) and the fourth to the tren unit, it is possible to prepare heteronuclear complexes such as [Cu(3)NiL](8+) or [Ni(3)CuL](8+), which can be unambiguously identified by their spectral properties.

  14. Synthesis and characterization of two new hydroxamic acids derivatives and their metal complexes. An investigation on the keto/enol, E/Z and hydroxamate/hydroximate forms

    NASA Astrophysics Data System (ADS)

    Adiguzel, Ekrem; Yilmaz, Fatih; Emirik, Mustafa; Ozil, Musa

    2017-01-01

    2-phenylbenzimidazole-N-acetohydroxamic acid (HL1), 2-phenylbenzimidazole-N-butanohydroxamic acid (HL2) and Ni(II), Cu(II), Zn(II) and Cd(II) metal complexes have been synthesized and characterized by elemental analyses, 1H NMR, 13C NMR, FT-IR spectrometry, LC-MS (ESI+) and thermal analyses. The results of NMR spectra and theoretical calculations showed that the hydroxamic acids were in the keto-E and keto-Z conformations. The elemental analysis and thermal analysis indicated that M:L ratio of the complexes are 1:1 and the spectral analysis confirmed that hydroxamate groups are keto form in the Ni(II) and Zn(II) complexes of 2-phenylbenzimidazole-N-butanohydroxamic acid and enol form in the other complexes.

  15. Aryl Amination using Ligand-Free Ni(II) Salts and Photoredox Catalysis

    PubMed Central

    Corcoran, Emily B.; Pirnot, Michael T.; Lin, Shishi; Dreher, Spencer D.; DiRocco, Daniel A.; Davies, Ian W.; Buchwald, Stephen L.; MacMillan, David W. C.

    2016-01-01

    Over the past two decades, there have been major developments in transition metal-catalyzed aminations of aryl halides to form anilines, a common structure found in drug agents, natural product isolates, and fine chemicals. Many of these approaches have enabled highly efficient and selective coupling through the design of specialized ligands, which facilitate reductive elimination from a destabilized metal center. We postulated that a general and complementary method for C–N bond formation could be developed through the destabilization of a metal amido complex via photoredox catalysis, thus providing an alternative approach to the use of structurally complex ligand systems. Herein, we report the development of a distinct mechanistic paradigm for aryl amination using ligand-free nickel(II) salts, in which facile reductive elimination from the nickel metal center is induced via a photoredox-catalyzed electron-transfer event. PMID:27338703

  16. Synthesis, Spectroscopic Characterization, and Biological Evaluation Studies of 5-Bromo-3-(((hydroxy-2-methylquinolin-7-yl)methylene)hydrazono)indolin-2-one and Its Metal (II) Complexes

    PubMed Central

    Siddappa, Kuruba; Mayana, Nabiya Sultana

    2014-01-01

    The Schiff base ligand 5-bromo-3-(((8-hydroxy-2-methylquinolin-7-yl)methylene)hydrazono)indolin-2-one (BHMQMHI) was prepared via condensation of 5-bromo-3-hydrazonoindolin-2-one and 7-formyl-8-hydroxy-2-methylquinoline and its Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Hg(II) complexes have been synthesized and characterized by elemental analysis, conductance data, magnetic susceptibility measurements, IR, UV-Vis, mass spectrometry, 1H NMR, ESR, XRD, and thermal studies. By these spectral studies it is found that Co(II), Ni(II), and Cu(II) complexes have exhibited octahedral geometry whereas the Zn(II), Cd(II), and Hg(II) complexes have exhibited tetrahedral geometry. Potentiometric studies have been carried out on complexes of Schiff base (BHMQMHI) with Cu(II), Co(II), and Ni(II). Calvin-Bjerrum pH-titration technique as used by Irving and Rossotti has been applied to determine stability constants in mixed solvents at 25 ± 1°C. The present study reports the protonation constants of this ligand and stability constants of its metal complexes in dioxane-water (50%, v/v) mixtures. Metal-ligand stability constants fall in the order of Cu(II) > Co(II) > Ni(II) which is in agreement with those reported by Irving stability order. The Schiff base (BHMQMHI) and its metal complexes have been screened for their in vitro antibacterial and antifungal activities by minimum inhibitory concentration (MIC) method. The DNA cleavage activities of all the complexes were studied by agarose gel electrophoresis method. In addition, the free ligand along with its complexes has been studied for their antioxidant activity. PMID:25371658

  17. Synthesis, characterization and biological activities of Cu(II), Co(II), Mn(II), Fe(II), and UO2(VI) complexes with a new Schiff Base hydrazone: O-hydroxyacetophenone-7-chloro-4-quinoline hydrazone.

    PubMed

    Al-Shaalan, Nora H

    2011-10-13

    The Schiff base hydrazone ligand HL was prepared by the condensation reaction of 7-chloro-4-quinoline with o-hydroxyacetophenone. The ligand behaves either as monobasic bidentate or dibasic tridentate and contain ONN coordination sites. This was accounted for be the presence in the ligand of a phenolic azomethine and imine groups. It reacts with Cu(II), Ni(II), Co(II), Mn(II), UO(2) (VI) and Fe(II) to form either mono- or binuclear complexes. The ligand and its metal complexes were characterized by elemental analyses, IR, NMR, Mass, and UV-Visible spectra. The magnetic moments and electrical conductance of the complexes were also determined. The Co(II), Ni(II) and UO(2) (VI) complexes are mononuclear and coordinated to NO sites of two ligand molecules. The Cu(II) complex has a square-planar geometry distorted towards tetrahedral, the Ni(II) complex is octahedral while the UO(2) (VI) complex has its favoured heptacoordination. The Co(II), Mn(II) complexes and also other Ni(II) and Fe(III) complexes, which were obtained in the presence of Li(OH) as deprotonating agent, are binuclear and coordinated via the NNNO sites of two ligand molecules. All the binuclear complexes have octahedral geometries and their magnetic moments are quite low compared to the calculated value for two metal ions complexes and thus antiferromagnetic interactions between the two adjacent metal ions. The ligand HL and metal complexes were tested against a strain of Gram +ve bacteria (Staphylococcus aureus), Gram -ve bacteria (Escherichia coli), and fungi (Candida albicans). The tested compounds exhibited high antibacterial activities.

  18. Extraction of nickel from edible oils with a complexing agent prior to determination by FAAS.

    PubMed

    Tokay, Feyzullah; Bağdat, Sema

    2016-04-15

    In the present work, a new extraction method for separation of nickel from edible oils and determination by FAAS is reported. This method is based on extraction of Ni(II) ions from the oil to aqueous phase with N,N'-bis(4-methoxysalicylidene) ethylenediamine (MSE) and determination by FAAS. Properties of the complex formed between MSE and Ni(II) were investigated spectrophotometrically. Central composite design (CCD) was utilized for optimization of MSE to oil, stirring time and temperature, which were 0.97 mL g(-1), 15.4 min, and 29.7°C, respectively. The developed method was tested with an oil-based metal standard and the recovery was 93.8±3.9%. The proposed method was applied with five different edible oils.

  19. Trinuclear nickel coordination complexes of phenanthrene-9,10-dione dioxime.

    PubMed

    Williams, Owen M; Cowley, Alan H

    2016-04-01

    A trinuclear nickel complex of phenanthrene-9,10-dione dioxime (H2pqd), namely bis-[μ2-9,10-bis-(oxido-imino)-phenanthrene]-bis-[μ2-10-(oxido-imino)phenanthrene-9-one oxime](phenanthrene-9,10-dione dioxime)trinickel(II) toluene disolvate, [Ni3(C14H8N2O2)2(C14H9N2O2)2(C14H10N2O2)]·2C7H8, has been isolated and its crystal structure determined. This complex features three independent Ni(II) atoms that are arranged in a triangular fashion along with five supporting ligands. There are two square-planar Ni(II) atoms and a third pseudo-octa-hedral Ni(II) atom. While the square-planar Ni(II) atoms are stacked, there are no ligand bridges between them. Each square-planar Ni(II) atom, however, bridges with the pseudo-octa--hedral Ni(II) atom through Ni-N-O-Ni and Ni-O-Ni bonds. A fluorido-bor-ation reaction of the proton-bridged species gave the analogous complex bis-(μ2-bis-{[10-(oxido-imino)-9,10-di-hydro-phenanthren-9-yl-idene]amino}di-fluorido-borato)(phenanthrene-9,10-dione dioxime)trinickel(II) dichloromethane trisolvate, [Ni3(C28H16BF2N4O2)4(C14H10N2O2)]·3CH2Cl2, which shows the same binding structure, but features a widened Ni-Ni inter-action between the square-planar Ni(II) atoms. The proton-bridged complex completes the macrocyclic coordination around the square-planar Ni(II) atoms by means of an O-H⋯O hydrogen bond. Both compounds feature O-H⋯N hydrogen bonds between the oxime and the N atoms attached to square-planar nickel atom. The nickel units show no direct inter-action with their nearest neighbors in the extended lattice. Two π-stacking inter-actions between adjacent mol-ecules are found: one with a centroid-centroid distance of 3.886 (2) Å and the other with a centroid-centroid distance of 4.256 (3) Å. In the latter case, although not aromatic, the distance to the centroid of the central phenanthrene ring is shorter, with a distance of 3.528 (3) Å. Toluene mol-ecules occupy the solvent channels that are oriented along the c axis. In

  20. Trinuclear nickel coordination complexes of phenanthrene-9,10-dione dioxime

    PubMed Central

    Williams, Owen M.; Cowley, Alan H.

    2016-01-01

    A trinuclear nickel complex of phenanthrene-9,10-dione dioxime (H2pqd), namely bis­[μ2-9,10-bis­(oxido­imino)­phenanthrene]­bis­[μ2-10-(oxido­imino)phenanthrene-9-one oxime](phenanthrene-9,10-dione dioxime)trinickel(II) toluene disolvate, [Ni3(C14H8N2O2)2(C14H9N2O2)2(C14H10N2O2)]·2C7H8, has been isolated and its crystal structure determined. This complex features three independent NiII atoms that are arranged in a triangular fashion along with five supporting ligands. There are two square-planar NiII atoms and a third pseudo-octa­hedral NiII atom. While the square-planar NiII atoms are stacked, there are no ligand bridges between them. Each square-planar NiII atom, however, bridges with the pseudo-octa­­hedral NiII atom through Ni—N—O—Ni and Ni—O—Ni bonds. A fluorido­bor­ation reaction of the proton-bridged species gave the analogous complex bis­(μ2-bis­{[10-(oxido­imino)-9,10-di­hydro­phenanthren-9-yl­idene]amino}di­fluorido­borato)(phenanthrene-9,10-dione dioxime)trinickel(II) dichloromethane trisolvate, [Ni3(C28H16BF2N4O2)4(C14H10N2O2)]·3CH2Cl2, which shows the same binding structure, but features a widened Ni—Ni inter­action between the square-planar NiII atoms. The proton-bridged complex completes the macrocyclic coordination around the square-planar NiII atoms by means of an O—H⋯O hydrogen bond. Both compounds feature O—H⋯N hydrogen bonds between the oxime and the N atoms attached to square-planar nickel atom. The nickel units show no direct inter­action with their nearest neighbors in the extended lattice. Two π-stacking inter­actions between adjacent mol­ecules are found: one with a centroid–centroid distance of 3.886 (2) Å and the other with a centroid–centroid distance of 4.256 (3) Å. In the latter case, although not aromatic, the distance to the centroid of the central phenanthrene ring is shorter, with a distance of 3.528 (3) Å. Toluene mol­ecules occupy the solvent channels that are

  1. Synthesis, spectral characterization, molecular modeling and in vitro antibacterial activity of complexes designed from O2, NO and NO donor Schiff-base ligand

    NASA Astrophysics Data System (ADS)

    El-Gammal, Ola A.; Abu El-Reash, G.; Ahmed, S. F.

    2015-01-01

    A new chelating agent, N‧-(4-methoxybenzylidene)-2-oxo-2-(phenylamino)acetohydrazide (H2OMPH) and its complexes with Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Hg(II) and U(IV)O22+ ions have been prepared and characterized by conventional techniques. The spectral data indicated that the ligand coordinates as neutral bidentate with Cu(II), Mn(II), U(IV)O22+ and Hg(II), neutral tridentate with Ni(II), mononegative tridentate with Co(II) and binegative tetradentate with Zn(II) ions. On basis of magnetic and electronic spectral data an octahedral geometry for Mn(II), Co(II) and Ni(II) complexes and a square planar geometry for Cu(II) complex have been proposed and confirmed by applying geometry optimization and conformational analysis. The protonation constants of H2OMPH and the stepwise stability constants of its complexes are calculated at 298, 308 and 318 k as well as their thermodynamic parameters. Also, the Kinetic parameters (Ea, A, ΔH*, ΔS* and ΔG*) were determined for each thermal degradation stage of some complexes using Coats-Redfern and Horowitz-Metzger methods. Moreover, the ligand and some complexes were screened for in vitro antibacterial activity against Staphylococcus epidermalies (St. epid); Streptococcus pyagenies (Strp. py.) as Gram +ve bacteria and Escherichia coli (E. coli); Klebsiella spp. (kleb. spp.) as Gram -ve bacteria using inhibition zone diameter.

  2. Removal of Ni(II), Zn(II) and Pb(II) ions from single metal aqueous solution using rice husk-based activated carbon

    SciTech Connect

    Taha, Mohd F. Shaharun, Maizatul S.; Shuib, Anis Suhaila Borhan, Azry

    2014-10-24

    An attempt was made to investigate the potential of rice husk-based activated carbon as an alternative low-cost adsorbent for the removal of Ni(II), Zn(II) and Pb(II) ions from single aqueous solution. Rice husk-based activated carbon was prepared via treatment of rice husk with NaOH followed by the carbonization process at 400°C for 2 hours. Three samples, i.e. raw rice husk, rice husk treated with NaOH and rice husk-based activated carbon, were analyzed for their morphological characteristics using field-emission scanning electron microscope/energy dispersive X-ray (FESEM/EDX). These samples were also analyzed for their carbon, hydrogen, nitrogen, oxygen and silica contents using CHN elemental analyzer and FESEM/EDX. The porous properties of rice husk-based activated carbon were determined by Brunauer-Emmett-Teller (BET) surface area analyzer, and its surface area and pore volume were 255 m{sup 2}/g and 0.17 cm{sup 2}/g, respectively. The adsorption studies for the removal of Ni(II), Zn(II) and Pb(II) ions from single metal aqueous solution were carried out at a fixed initial concentration of metal ion (150 ppm) with variation amount of adsorbent (rice husk-based activated carbon) as a function of varied contact time at room temperature. The concentration of each metal ion was analyzed using atomic absorption spectrophotometer (AAS). The results obtained from adsorption studies indicate the potential of rice husk as an economically promising precursor for the preparation of activated carbon for removal of Ni(II), Zn(II) and Pb(II) ions from single aqueous solution. Isotherm and kinetic model analyses suggested that the experimental data of adsorption studies fitted well with Langmuir, Freundlich and second-order kinetic models.

  3. Removal of Ni(II), Zn(II) and Pb(II) ions from single metal aqueous solution using rice husk-based activated carbon

    NASA Astrophysics Data System (ADS)

    Taha, Mohd F.; Shuib, Anis Suhaila; Shaharun, Maizatul S.; Borhan, Azry

    2014-10-01

    An attempt was made to investigate the potential of rice husk-based activated carbon as an alternative low-cost adsorbent for the removal of Ni(II), Zn(II) and Pb(II) ions from single aqueous solution. Rice husk-based activated carbon was prepared via treatment of rice husk with NaOH followed by the carbonization process at 400°C for 2 hours. Three samples, i.e. raw rice husk, rice husk treated with NaOH and rice husk-based activated carbon, were analyzed for their morphological characteristics using field-emission scanning electron microscope/energy dispersive X-ray (FESEM/EDX). These samples were also analyzed for their carbon, hydrogen, nitrogen, oxygen and silica contents using CHN elemental analyzer and FESEM/EDX. The porous properties of rice husk-based activated carbon were determined by Brunauer-Emmett-Teller (BET) surface area analyzer, and its surface area and pore volume were 255 m2/g and 0.17 cm2/g, respectively. The adsorption studies for the removal of Ni(II), Zn(II) and Pb(II) ions from single metal aqueous solution were carried out at a fixed initial concentration of metal ion (150 ppm) with variation amount of adsorbent (rice husk-based activated carbon) as a function of varied contact time at room temperature. The concentration of each metal ion was analyzed using atomic absorption spectrophotometer (AAS). The results obtained from adsorption studies indicate the potential of rice husk as an economically promising precursor for the preparation of activated carbon for removal of Ni(II), Zn(II) and Pb(II) ions from single aqueous solution. Isotherm and kinetic model analyses suggested that the experimental data of adsorption studies fitted well with Langmuir, Freundlich and second-order kinetic models.

  4. Synthesis and Characterization of a Tetramethyl Furanone Functionalized Diiminedioxime, A Potential Ligand for 64Cu Radiopharmaceuticals, and its Copper(II) and Nickel(II) Complexes

    PubMed Central

    Kiani, Salma; Staples, Richard J.; Treves, S. Ted; Packard, Alan B.

    2009-01-01

    As part of our on-going effort to develop 64Cu-based radiopharmaceuticals for PET (positron emission tomography) imaging of multidrug resistance in cancer, we prepared a tetramethylfuranone-functionalized diiminedioxime ligand, TMFPreH (TMFPreH = 4-[3-(4-Hydroxyimino-2,2,5,5-dimethyl-dihydro-furan-3-ylideneamino)-propylimino]-2,2,5,5-tetramethyl-dihydro-furan-3-one oxime) and its Cu(II) and Ni(II) complexes. When the copper(II) complex was prepared from Cu(ClO4)2 in ethanol, it was isolated as a Cu(II)-bridged dimer, but when it was prepared from Cu(OAc)2 and heated in acetone, an unusual example of an acetone adduct of the ligand is formed by reduction of one of the imine double bonds by the solvent. The Ni(II) complex is square pyramidal with the perchlorate counterion at the apex. PMID:20161333

  5. Bio-important antipyrine derived Schiff bases and their transition metal complexes: Synthesis, spectroscopic characterization, antimicrobial, anthelmintic and DNA cleavage investigation

    NASA Astrophysics Data System (ADS)

    Manjunath, M.; Kulkarni, Ajaykumar D.; Bagihalli, Gangadhar B.; Malladi, Shridhar; Patil, Sangamesh A.

    2017-01-01

    Spectroscopic (IR, NMR, UV-vis, ESR, ESI-mass), magnetic and TGA studies suggests octahedral geometry for all the CoII, NiII and CuII complexes of the Schiff bases, derived from 4-aminoantipyrine and 8-formyl-7-Hydroxy-4-methylcoumarin/5-formyl-6-hydroxycoumarin, coordinated through ONO donor sites. Antibacterial (Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa and Salmonella typhi), antifungal (Aspergillus niger, Aspergillus flavus and Cladosporium) and DNA cleavage properties of the metal complexes are investigated. The results suggested that some of the synthesized compounds are potential antimicrobials. The synthesized compounds tested for their anthelmintic activities and it was found that CoII and NiII complexes exhibited good anthelmintic properties.

  6. Synthesis characterization and antimicrobial activity studies of some transition metal complexes derived from 3-chloro-N'-[(1E)-(2-hydroxy phenyl)methylene]-6-methoxy-1-benzothiophene-2-carbohydrazide.

    PubMed

    Biradar, Vivekanand D; Mruthyunjayaswamy, B H M

    2013-01-01

    A series of new coordination complexes of Cu(II), Co(II), Ni(II), Zn(II), Hg(II), Mn(II), and Fe(III) with the Schiff base 3-chloro-N'-[(1E)-(2-hydroxy phenyl)methylene]-6-methoxy-1-benzothiophene-2-carbohydrazide (HL) have been synthesized and characterized by elemental analysis, electrical conductivity measurements, IR spectra, (1)H NMR, mass spectral data, electronic spectra, magnetic susceptibility, ESR spectra, TGA, and Powder XRD data. The Schiff base behaves as tridentate ONO donor ligand and forms the complexes of the type ML2 (metal-ligand) stoichiometry for Cu(II), Co(II), Ni(II), and Mn(II) complexes and ML stoichiometry for Zn(II), Hg(II), and Fe(III) complexes. All the complexes are colored and nonelectrolytes. It is found that Cu(II), Co(II), Ni(II), Mn(II) and Fe(III) complexes have exhibited octahedral geometry whereas Zn(II) and Hg(II) complexes exhibited tetrahedral geometry. The ligand and its metal complexes have been screened for their antibacterial activity against E. coli and S. aureus and antifungal activity against A. niger and A. flavus.

  7. Synthesis Characterization and Antimicrobial Activity Studies of Some Transition Metal Complexes Derived from 3-Chloro-N′-[(1E)-(2-hydroxy phenyl)methylene]-6-methoxy-1-benzothiophene-2-carbohydrazide

    PubMed Central

    Biradar, Vivekanand D.; Mruthyunjayaswamy, B. H. M.

    2013-01-01

    A series of new coordination complexes of Cu(II), Co(II), Ni(II), Zn(II), Hg(II), Mn(II), and Fe(III) with the Schiff base 3-chloro-N′-[(1E)-(2-hydroxy phenyl)methylene]-6-methoxy-1-benzothiophene-2-carbohydrazide (HL) have been synthesized and characterized by elemental analysis, electrical conductivity measurements, IR spectra, 1H NMR, mass spectral data, electronic spectra, magnetic susceptibility, ESR spectra, TGA, and Powder XRD data. The Schiff base behaves as tridentate ONO donor ligand and forms the complexes of the type ML2 (metal-ligand) stoichiometry for Cu(II), Co(II), Ni(II), and Mn(II) complexes and ML stoichiometry for Zn(II), Hg(II), and Fe(III) complexes. All the complexes are colored and nonelectrolytes. It is found that Cu(II), Co(II), Ni(II), Mn(II) and Fe(III) complexes have exhibited octahedral geometry whereas Zn(II) and Hg(II) complexes exhibited tetrahedral geometry. The ligand and its metal complexes have been screened for their antibacterial activity against E. coli and S. aureus and antifungal activity against A. niger and A. flavus. PMID:24453851

  8. Transition Metal(II) Complexes with Cefotaxime-Derived Schiff Base: Synthesis, Characterization, and Antimicrobial Studies

    PubMed Central

    Amzoiu, Emilia; Spînu, Cezar Ionuţ

    2014-01-01

    New [ML2(H2O)2] complexes, where M = Co(II), Ni(II), Cu(II), and Zn(II) while L corresponds to the Schiff base ligand, were synthesized by condensation of cefotaxime with salicylaldehyde in situ in the presence of divalent metal salts in ethanolic medium. The complexes were characterized by elemental analyses, conductance, and magnetic measurements, as well as by IR and UV-Vis spectroscopy. The low values of the molar conductance indicate nonelectrolyte type of complexes. Based on spectral data and magnetic moments, an octahedral geometry may be proposed for Co(II), Ni(II), and Zn(II) complexes while a tetragonal geometry for Cu(II) complex. Molecular structure of the Schiff base ligand and its complexes were studied using programs dedicated to chemical modeling and quantomolecular calculation of chemical properties. All the synthesized complexes were tested for in vitro antibacterial activity against some pathogenic bacterial strains, namely Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa, Bacillus subtilis, and Staphylococcus aureus. The MIC values shown by the complexes against these bacterial strains revealed that the metal complexes possess superior antibacterial activity than the Schiff base. PMID:24688454

  9. 2,4-Dinitrophenylhydrazine functionalized sodium dodecyl sulfate-coated magnetite nanoparticles for effective removal of Cd(II) and Ni(II) ions from water samples.

    PubMed

    Sobhanardakani, Soheil; Zandipak, Raziyeh

    2015-07-01

    2,4-Dinitrophenylhydrazine immobilized on sodium dodecyl sulfate (SDS)-coated magnetite and was used for removal of Cd(II) and Ni(II) ions from aqueous solution. The prepared product was characterized by X-ray diffraction (XRD) analysis, Fourier transform infrared spectroscopy (FT-IR), and scanning electron microscopy (SEM). The size of the nanoparticles according to SEM was obtained around 20-35 nm. In batch tests, the effects of pH, contact time, initial metal concentration, and temperature were studied. The kinetic and equilibrium data were modeled with recently developed models. The adsorption kinetics and isotherms were well fitted by the fractal-like pseudo-second-order model and Langmuir-Freundlich model, respectively. Maximum adsorption capacity by this adsorbent is 255.1 mg g(-1) for Cd(II) ion and 319.6 mg g(-1) for Ni(II) ion at pH 7.0 and 25 °C. The method was successfully applied to the removal of metal cations in real samples (tap water, river water, and petrochemical wastewater).

  10. Competitive adsorption of Cd(II), Zn(II) and Ni(II) from their binary and ternary acidic systems using tourmaline.

    PubMed

    Liu, Haibin; Wang, Cuiping; Liu, Jingting; Wang, Baolin; Sun, Hongwen

    2013-10-15

    The adsorption of Cd(II), Zn(II) and Ni(II) from aqueous solutions in binary and ternary component systems by tourmaline was investigated. Kinetic data were accurately fitted to pseudo-second order and internal diffusion models, which indicated that the adsorption of heavy metals occurred on the interior surface of the sorbent and internal diffusion was the controlling mechanism during heavy metal ion adsorption but was not the only rate-controlling step. Additionally, tourmaline had a very good adsorption capacity for Cd(II), Zn(II) and Ni(II) in multi-component aqueous solutions at strongly acidic pH values (in contrast to industrial wastewater pH values). This good adsorption capacity is attributed to the fact that tourmaline can automatically adjust the pH values of acidic (except pH 2.0 and 3.0), neutral or alkaline aqueous solutions to 6.0. Adsorption isotherms and separation factors showed that tourmaline displays a high selectivity toward one metal in a two-component or a three-component system with an affinity order of Cd(II) > Zn(II) > Ni(II). Thermodynamic parameters indicated that heavy metal adsorption was feasible, spontaneous, and endothermic. Therefore, tourmaline should be explored as a material for removing pollutants from the strongly acidic wastewater.

  11. Importance of nanoparticle size in colorimetric and SERS-based multimodal trace detection of Ni(II) ions with functional gold nanoparticles.

    PubMed

    Krpetić, Zeljka; Guerrini, Luca; Larmour, Iain A; Reglinski, John; Faulds, Karen; Graham, Duncan

    2012-03-12

    Colorimetric detection of analytes using gold nanoparticles along with surface-enhanced Raman spectroscopy (SERS) are areas of intense research activity since they both offer sensing of very low concentrations of target species. Multimodal detection promotes the simultaneous detection of a sample by a combination of different techniques; consequently, surface chemistry design in the development of multimodal nanosensors is important for rapid and sensitive evaluation of the analytes by diverse analytical methods. Herein it is shown that nanoparticle size plays an important role in the design of functional nanoparticles for colorimetric and SERS-based sensing applications, allowing controlled nanoparticle assembly and tunable sensor response. The design and preparation of robust nanoparticle systems and their assembly is reported for trace detection of Ni(II) ions as a model system in an aqueous solution. The combination of covalently attached nitrilotriacetic acid moieties along with the L-carnosine dipeptide on the nanoparticle surface represents a highly sensitive platform for rapid and selective detection of Ni(II) ions. This systematic study demonstrates that significantly lower detection limits can be achieved by finely tuning the assembly of gold nanoparticles of different core sizes. The results clearly demonstrate the feasibility and usefulness of a multimodal approach.

  12. Tetranuclear nickel complex of dimethylene bridged diiminedioxime containing different hybridizations of nickel (II)

    NASA Astrophysics Data System (ADS)

    Achiwawanich, Supakit; Duangthongyou, Tanwawan; Kitiphaisalnont, Panana; Siripaisarnpipat, Sutatip

    2014-08-01

    The reaction of ligand 3,3";-(1,4-ethanediyldinitrilo)bis(2-butanone)dioxime (EnH2) with Ni(ClO4)2 yields [Ni(Ni(En))3](ClO4)2 (1). Complex 1 crystallizes in an R-centered trigonal cell with the space group R3bar. The structure consists of an octahedral [Ni(Ni(En))3]2+ cation containing four Ni(II) ions with different hybridizations (dsp2 and sp3d2) and two perchlorate anions. Three dsp2 Ni(II) ions coordinate to three EnH2 ligands via imine nitrogens and oxime nitrogens and the fourth Ni(II) ion octahedrally coordinates to six oxime oxygens of the coordinated EnH2. Accordingly, a three-bladed propeller-like structure is observed. Two kinds of νCdbnd N relating to imine and oxime groups are observed at 1623 and 1488 cm-1 respectively. The μeff is 3.47 BM. Bands at 413 and 541 nm are assigned to d-d transitions in octahedral field and weak band at 477 nm is assigned to d-d transition in square planar field. The emission spectrum under the excitation wavelength 305 nm shows a broad band with maximum emission wavelength at 350 nm.

  13. Synthesis, structural elucidation, biological, antioxidant and nuclease activities of some 5-Fluorouracil-amino acid mixed ligand complexes

    NASA Astrophysics Data System (ADS)

    Shobana, Sutha; Subramaniam, Perumal; Mitu, Liviu; Dharmaraja, Jeyaprakash; Arvind Narayan, Sundaram

    2015-01-01

    Some biologically active mixed ligand complexes (1-9) have been synthesized from 5-Fluorouracil (5-FU; A) and amino acids (B) such as glycine (gly), L-alanine (ala) and L-valine (val) with Ni(II), Cu(II) and Zn(II) ions. The synthesized mixed ligand complexes (1-9) were characterized by various physico-chemical, spectral, thermal and morphological studies. 5-Fluorouracil and its mixed ligand complexes have been tested for their in vitro biological activities against some pathogenic bacterial and fungal species by the agar well diffusion method. The in vitro antioxidant activities of 5-Fluorouracil and its complexes have also been investigated by using the DPPH assay method. The results demonstrate that Cu(II) mixed ligand complexes (4-6) exhibit potent biological as well as antioxidant activities compared to 5-Fluorouracil and Ni(II) (1-3) and Zn(II) (7-9) mixed ligand complexes. Further, the cleaving activities of CT DNA under aerobic conditions show moderate activity with the synthesized Cu(II) and Ni(II) mixed ligand complexes (1-6) while no activity is seen with Zn(II) complexes (7-9). Binding studies of CT DNA with these complexes show a decrease in intensity of the charge transfer band to the extent of 5-15% along with a minor red shift. The free energy change values (Δ‡G) calculated from intrinsic binding constants indicate that the interaction between mixed ligand complex and DNA is spontaneous.

  14. Synthesis, structural elucidation, biological, antioxidant and nuclease activities of some 5-Fluorouracil-amino acid mixed ligand complexes.

    PubMed

    Shobana, Sutha; Subramaniam, Perumal; Mitu, Liviu; Dharmaraja, Jeyaprakash; Arvind Narayan, Sundaram

    2015-01-05

    Some biologically active mixed ligand complexes (1-9) have been synthesized from 5-Fluorouracil (5-FU; A) and amino acids (B) such as glycine (gly), L-alanine (ala) and L-valine (val) with Ni(II), Cu(II) and Zn(II) ions. The synthesized mixed ligand complexes (1-9) were characterized by various physico-chemical, spectral, thermal and morphological studies. 5-Fluorouracil and its mixed ligand complexes have been tested for their in vitro biological activities against some pathogenic bacterial and fungal species by the agar well diffusion method. The in vitro antioxidant activities of 5-Fluorouracil and its complexes have also been investigated by using the DPPH assay method. The results demonstrate that Cu(II) mixed ligand complexes (4-6) exhibit potent biological as well as antioxidant activities compared to 5-Fluorouracil and Ni(II) (1-3) and Zn(II) (7-9) mixed ligand complexes. Further, the cleaving activities of CT DNA under aerobic conditions show moderate activity with the synthesized Cu(II) and Ni(II) mixed ligand complexes (1-6) while no activity is seen with Zn(II) complexes (7-9). Binding studies of CT DNA with these complexes show a decrease in intensity of the charge transfer band to the extent of 5-15% along with a minor red shift. The free energy change values (Δ(‡)G) calculated from intrinsic binding constants indicate that the interaction between mixed ligand complex and DNA is spontaneous.

  15. Synthesis, characterisation, spectral, thermal, XRD, molecular modelling and potential antibacterial study of metal complexes containing octadentate azodye ligands

    NASA Astrophysics Data System (ADS)

    Mahapatra, Bipin Bihari; Chaulia, Satyanarayan; Sarangi, Ashish Kumar; Dehury, Satyanarayan; Panda, Jnyanaranjan

    2015-05-01

    Twelve tetrametallic complexes of Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) with two new octadentate azodye ligands, 4,4‧-bis(2‧,4‧-dihydroxy-5‧carboxyphenylazo) diphenylether (LH6) and 4,4‧-bis(2‧,4‧-dihydroxy-5‧-acylphenylazo) diphenylether (L‧H4) have been synthesised. The structural elucidation of the complexes was made basing upon analytical, conductance, magnetic susceptibility, IR, electronic spectra, ESR, NMR, ESI-MS, TG, DTG, DTA and X-ray diffraction (powder pattern) data. The cobalt (II) and nickel (II) complexes are found to be octahedral, copper (II) complexes are distorted octahedral and a tetrahedral stereochemistry has been suggested to zinc (II), cadmium (II) and mercury (II) complexes. The thermal analysis data provided the kinetic parameters as order of decomposition reaction, activation energy and frequency factor. The geometry of the ligands and their Co(II), Ni(II), Cu(II) and Zn(II) complexes were optimised and their physicochemical properties were calculated by using molecular modelling procedure. The ESI-MS determination supports the molecular formula and molecular weight of the ligands and the complexes. The Ni(II) complex is found to have a triclinic crystal system. The potential antibacterial study of the two ligands and eight metal complexes was made by cup-plate method against one gram positive and one gram negative bacteria. The results showed increase in the activity of some metal complexes as compare with azodye ligands.

  16. Two novel macroacyclic schiff bases containing bis-N 2O 2 donor set and their binuclear complexes: synthesis, spectroscopic and magnetic properties

    NASA Astrophysics Data System (ADS)

    Karaoglu, Kaan; Baran, Talat; Serbest, Kerim; Er, Mustafa; Degirmencioglu, Ismail

    2009-03-01

    Herein, we report two novel macroacyclic Schiff bases derived from tetranaphthaldehyde derivative compound and their binuclear Mn(II), Ni(II), Cu(II) and Zn(II) complexes. The structures of the compounds have been proposed by elemental analyses, spectroscopic data i.e. IR, 1H and 13C NMR, UV-Vis, electrospray ionisation mass spectra, molar conductivities and magnetic susceptibility measurements. The stoichiometries of the complexes derived from mass and elemental analysis correspond to the general formula [M 2L(ClO 4) n](ClO 4) 4-n, (where M is Mn(II), Ni(II), Cu(II), Zn(II) and L represents the Schiff base ligands).

  17. Synthesis, spectral studies and biological evaluation of 2-aminonicotinic acid metal complexes

    NASA Astrophysics Data System (ADS)

    Nawaz, Muhammad; Abbasi, Muhammad Waseem; Hisaindee, Soleiman; Zaki, Muhammad Javed; Abbas, Hira Fatima; Mengting, Hu; Ahmed, M. Arif

    2016-05-01

    We synthesized 2-aminonicotinic acid (2-ANA) complexes with metals such as Co(II), Fe(III), Ni(II), Mn(II), Zn(II), Ag(I),Cr(III), Cd(II) and Cu(II) in aqueous media. The complexes were characterized and elucidated using FT-IR, UV-Vis, a fluorescence spectrophotometer and thermo gravimetric analysis (TGA). TGA data showed that the stoichiometry of complexes was 1:2 metal/ligand except for Ag(I) and Mn(II) where the ratio was 1:1. The metal complexes showed varied antibacterial, fungicidal and nematicidal activities. The silver and zinc complexes showed highest activity against Bacillus subtilis and Bacillus licheniformis respectively. Fusarium oxysporum was highly susceptible to nickel and copper complexes whereas Macrophomina phaseolina was completely inert to the complexes. The silver and cadmium complexes were effective against the root-knot nematode Meloidogyne javanica.

  18. Synthesis, spectroscopic characterization, DNA interaction and antibacterial study of metal complexes of tetraazamacrocyclic Schiff base

    NASA Astrophysics Data System (ADS)

    Shakir, Mohammad; Khanam, Sadiqa; Firdaus, Farha; Latif, Abdul; Aatif, Mohammad; Al-Resayes, Saud I.

    The template condensation reaction between benzil and 3,4-diaminotoulene resulted mononuclear 12-membered tetraimine macrocyclic complexes of the type, [MLCl2] [M = Co(II), Ni(II), Cu(II) and Zn(II)]. The synthesized complexes have been characterized on the basis of the results of elemental analysis, molar conductance, magnetic susceptibility measurements and spectroscopic studies viz. FT-IR, 1H and 13C NMR, FAB mass, UV-vis and EPR. An octahedral geometry has been envisaged for all these complexes, while a distorted octahedral geometry has been noticed for Cu(II) complex. Low conductivity data of all these complexes suggest their non-ionic nature. The interactive studies of these complexes with calf thymus DNA showed that the complexes are avid binders of calf thymus DNA. The in vitro antibacterial studies of these complexes screened against pathogenic bacteria proved them as growth inhibiting agents.

  19. Preparation and Characterization of Bi-metallic and Tri-metallic Metal Organic Frameworks Based on Trimesic Acid and Co(II), Ni(II), and Cu(II) Ions

    NASA Astrophysics Data System (ADS)

    Sahiner, Nurettin; Demirci, Sahin; Yildiz, Mustafa

    2017-02-01

    Trimesic acid-M1(II):M2(II) (M1,2(II)=M(II)=Co(II), Ni(II) and Cu(II)) bi-metallic or tri-metallic organic frameworks (MOFs) were synthesized by the reaction of trimesic acid (H3BTC) ligand with the corresponding MCl2nH2O aqueous solutions. Here, bi- and tri-metallic MOF preparations were demonstrated by using H3BTC as an organic linker, with dual metal ion mixtures at different mole ratios such as Co(II):Ni(II), Ni(II):Cu(II), and Cu(II):Co(II) as metal ion sources in the synthesis of bi-metallic MOFs, and the triple metal ion mixture of Co(II):Ni(II):Cu(II) as the metal ion source in the synthesis of tri-metallic MOFs. The bi- or tri-metallic MOFs were characterized via the Brunauer-Emmett-Teller method, thermogravimetric analyzer (TGA), and magnetic susceptibility measurements with the Gouy method, FT-IR spectroscopy, and electronic spectral studies. The results revealed that the H3BTC MOFs have octahedral and distorted octahedral arrangement around the metal ions, and the d-d transition was not observed in the complex. It was further found that all the prepared MOFs contain water molecules confirmed by Fourier transform infrared (FT-IR) and TGA analyses. The FT-IR spectra of the MOF complexes were characterized by the appearance of a broad band in the region of 3454-3300 cm-1 due to the ν(-OH) of the coordinated water; therefore, the location of the two water molecules was assumed to be inside the complex structure. Remarkably, the synthesized bi-metallic MOFs had unique and distinct colors depending on the amounts of metal ions used in the feed, implying that these bi-metallic MOFs with tunable M1(II) and M2(II) ratios offer great potential in the design of color-coded materials for use as sensors.

  20. Coordination of Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II), Pd(II) and Pt(II) with 2,5-hexanedione bis(thiosemicarbazone), HBTS: Crystal structure of cis-[Pd(HBTS)]Cl2 and 1-(2,5-dimethyl-1H-pyrrol-yl)-thiourea

    NASA Astrophysics Data System (ADS)

    Jeragh, Bakir; El-Asmy, Ahmed A.

    2014-09-01

    Metal complexes of Fe3+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Hg2+, Pd2+ or Pt2+ with 2,5-hexanedione bis(thiosemicarbazone), HBTS; have been prepared and spectroscopically investigated. The empirical formulae of the complexes were suggested based on the elemental analysis. Single crystal of Pd(II) has been solved to be cis-form of square-planar geometry by the X-ray crystallography. 1H and 13C NMR spectra have been recorded for HBTS, Zn(II), Cd(II), Hg(II), Pd(II) and Pt(II) complexes, in DMSO-d6, showing the mode of chelation. The ligand acts as a neutral or a binegative tetradentate (N2S2) or neutral bidentate on the basis of FT-IR. The magnetic moments and electronic spectra provide information about the geometry of the complexes which supported by calculating the ligand field parameters for the Co(II) and Fe(III) complexes. The Ni(II) complex has subnormal magnetic moment (0.71 BM) indicative of a mixed stereochemistry of square-planar and tetrahedral structure. [Cu(HBTS-2H)] measured 0.93 BM indicating high interaction between the copper centers. The ligand may be ordered at the top of the spectrochemical series which giving high ligand field splitting energy (10Dq = 17,900 cm-1 for Co2+ complex). The mass spectra of some complexes proved their stable chemical formulae while the TGA depicts the degradation steps and the final residue. In evaporating the mother liquor during the preparation of HBTS, new compound is obtained naming 1-(2,5-dimethyl-1H-pyrrol-yl)thiourea and its crystal was solved.

  1. Synthesis, characterization and antifungal activities of 3d-transition metal complexes of 1-acetylpiperazinyldithioc arbamate, M(acpdtc) 2

    NASA Astrophysics Data System (ADS)

    Mohammad, Ali; Varshney, Charu; Nami, Shahab A. A.

    2009-07-01

    A series of mononuclear 3d-transition metal complexes of the type M(acpdtc) 2 have been synthesized (where acpdtc = 1-acetylpiperazinyldithiocarbamate, M = Mn(II), Fe(II), Co(II), Ni(II) and Cu(II)). The ligand and its complexes have been characterized by micro analysis (CHNS), TG/DSC, FT-IR, UV-vis, 1H NMR, magnetic susceptibility and conductance measurements. On the basis IR spectroscopy a symmetrical bidentate coordination has been observed for the 1-acetylpiperazinyldithiocarbamate moiety in all the complexes. On the basis of UV-vis spectra and magnetic susceptibility measurement a square-planar geometry has been proposed for the Ni(II) and Cu(II) complexes while the other complexes have been found to acquire a distorted-tetrahedral structure. The thermogravimetric and differential scanning calorimetric profile of the ligand indicates a two-step decomposition pattern while the complexes exhibit a three-stage thermogram forming metal sulfide as the eventual end product. The molar conductivity data of 1 mM solution in DMSO of the complexes is in close accord to their non-electrolytic behaviour. The ligand and its 3d-transition metal complexes have also been tested for their antifungicidal activity by agar well diffusion method using Fusarium sp. and Sclerotina sp. The maximum activity has been observed in case of Mn(II) and Fe(II) complexes.

  2. Synthesis of two nickel (II) complexes bearing pyrrolide-imine ligand and their catalytic effects on thermal decomposition of ammonium perchlorate

    NASA Astrophysics Data System (ADS)

    Zhuo, Ji-Bin; Ma, Zai-He; Lin, Cai-Xia; Xie, Li-Li; Bai, Sha; Yuan, Yao-Feng

    2015-04-01

    Two pyrrolide-imine chelating Ni(II) complexes {[2-(2-CH3O-C6H4-NCH)C4H3N]2Ni (2a) and [(Fc-NCH)]C4H3N]2Ni (2b, Fc = ferrocenyl)} were prepared via treating corresponding Schiff base with 0.5 equiv. NiCl2·6H2O in moderate yields. The crystal structures of 2a and 2b were determined by single-crystal X-ray diffraction. Atom Ni(II) of 2a was coordinated by two pyrrolide-imine ligands in trans position to display a twisted octahedral coordination geometry. Ni(II) of 2b had a distorted square-planar geometry, bonded with two ferrocenyl pyrrole-imine ligands, each ferrocene and pyrrole of ligands adopting a trans conformation. The UV-vis spectroscopy and electrochemical measurements were investigated. The catalytic efficiency of the complexes on the thermal decomposition of ammonium perchlorate (AP) was studied by differential scanning calorimetry (DSC) and thermogravimetry (TG). Compared with the thermal decomposition of pure AP, the decomposition temperatures were decreased by 27 °C, 77 °C, 88 °C and 172 °C, respectively when 1a, 1b, 2a and 2b were added in AP. The results indicated that the Ni(II) complex 2b bearing ferrocene-based pyrrolide-imine N,N-chelate ligand displayed an excellent catalytic efficiency on the thermal decomposition of AP.

  3. Characterization and application of expanded graphite modified with phosphoric acid and glucose for the removal of Ni(II) from aqueous solution

    NASA Astrophysics Data System (ADS)

    Jiang, Li; Zhang, Jian; Xu, Xiaoli; Zhang, Jie; Liu, Hai; Guo, Zizhang; Kang, Yan; Li, Yiran; Xu, Jingtao

    2015-12-01

    Three kinds of modified expanded graphite (EG), impregnated with phosphoric acid (H3PO4) (P-EG), impregnated with glucose (G-EG), and impregnated with H3PO4 and glucose (G-P-EG), were prepared under a low temperature (150 °C). The adsorption capacity of G-P-EG (Qm = 7.016 mg/g) is much higher than original expanded graphite (EG Qm = 0.423 mg/g) and other two kinds of modified expanded graphite (P-EG Qm = 0.770 mg/g; G-EG Qm = 0.507 mg/g). The physicochemical properties of EG and G-P-EG were characterized by N2 adsorption/desorption, Boehm's titration and X-ray photoelectron spectroscopy (XPS). EG exhibited higher values of BET surface area (11.357 m2/g) and total pore volume (0.0303 cm3/g) than that of G-P-EG (4.808 m3/g and 0.0109 cm3/g). However, the results of Bohm's titration and XPS showed that G-P-EG contained more surface oxygen-containing functional groups. The Ni(II) adsorption equilibrium data agreed well with the Langmuir model. And the experimental data of EG and G-P-EG fitted better by pseudo-second order model. Based on the results of batch adsorption experiments and XPS analysis, there were several possible mechanisms for Ni(II) adsorption on the G-P-EG, including chemical adsorption, cation exchange, electrostatic attraction and surface complication.

  4. Ni(ii) ions cleave and inactivate human alpha-1 antitrypsin hydrolytically, implicating nickel exposure as a contributing factor in pathologies related to antitrypsin deficiency.

    PubMed

    Wezynfeld, Nina Ewa; Bonna, Arkadiusz; Bal, Wojciech; Frączyk, Tomasz

    2015-04-01

    Human alpha-1 antitrypsin (AAT) is an abundant serum protein present at a concentration of 1.0-1.5 g L(-1). AAT deficiency is a genetic disease that manifests with emphysema and liver cirrhosis due to the accumulation of a misfolded AAT mutant in hepatocytes. Lung AAT amount is inversely correlated with chronic obstructive pulmonary disease (COPD), a serious and often deadly condition, with increasing frequency in the aging population. Exposure to cigarette smoke and products of fossil fuel combustion aggravates AAT deficiency and COPD according to mechanisms that are not fully understood. Taking into account that these fumes contain particles that can release nickel to human airways and skin, we decided to investigate interactions of AAT with Ni(ii) ions within the paradigm of Ni(ii)-dependent peptide bond hydrolysis. We studied AAT protein derived from human blood using HPLC, SDS-PAGE, and mass spectrometry. These studies were aided by spectroscopic experiments on model peptides. As a result, we identified three hydrolysis sites in AAT. Two of them are present in the N-terminal part of the molecule next to each other (before Thr-13 and Ser-14 residues) and effectively form one N-terminal cleavage site. The single C-terminal cleavage site is located before Ser-285. The N-terminal hydrolysis was more efficient than the C-terminal one, but both abolished the ability of AAT to inhibit trypsin in an additive manner. Nickel ions bound to hydrolysis products demonstrated an ability to generate ROS. These results implicate Ni(ii) exposure as a contributing factor in AAT-related pathologies.

  5. In situ ligand generation for novel Mn(II) and Ni(II) coordination polymers with disulfide ligand: Solvothermal syntheses, structures and magnetic properties

    SciTech Connect

    Han, Yinfeng Wang, Chang'an; Zheng, Zebao; Sun, Jiafeng; Nie, Kun; Zuo, Jian; Zhang, Jianping

    2015-07-15

    Two coordination polymers, ([Mn{sub 2}(L1){sub 2}(μ{sub 2}-H{sub 2}O)(H{sub 2}O){sub 4}]·5H{sub 2}O){sub n}1 and ([Ni(L1)(H{sub 2}O){sub 2}]·2H{sub 2}O){sub n}2 (H{sub 2}L1=2,2′-dithiobisnicotinic acid), were prepared by the solvothermal reactions of the Mn(II) or Ni(II) ions with 2-mercaptonanicotinic acid. In 1, the [Mn{sub 2}(COO){sub 4}] units are connected by the 2,2′-dithiobisnicotinic dianion to form a two-dimensional (4,4)-connected network. In 2, the adjacent Ni(II) ions are connected by the carboxyl groups of the 2,2′-dithiobisnicotinic dianion to form an one-dimensional inorganic rod-shaped chain [Ni(COO){sub 2}]{sub n}, which are further interconnected by the 2,2′-dithiobisnicotinic ligand, giving rise to a two-dimensional framework. Variable-temperature magnetic susceptibilities of 1 and 2 exhibit overall weak antiferromagnetic coupling between the adjacent metal ions. - Graphical abstract: Two 2D coordination polymers were synthesized by transition-metal/in-situ oxidation of 2-mercaptonicotinic acid. The compounds pack into 2D frameworks by the carboxyl groups of 2,2′-dithiobisnicotinic dianion and exhibit overall weak antiferromagnetic coupling. - Highlights: • Two 2D coordination polymers containing 2,2′-dithiobisnicotinic dianion. • In situ oxidation and dehydro coupling reaction of 2-mercaptonbenzoic acid. • Two compounds display weak antiferromagnetic exchanges.

  6. Unsymmetrical Schiff base (ON) ligand on complexation with some transition metal ions: Synthesis, spectral characterization, antibacterial, fluorescence and thermal studies

    NASA Astrophysics Data System (ADS)

    Ali, Omyma A. M.; El-Medani, Samir M.; Abu Serea, Maha R.; Sayed, Abeer S. S.

    2015-02-01

    A series of eight metal Schiff base complexes were synthesized by the thermal reaction of Cu(II), Ni(II), Fe(III), Co(II), Zn(II), Hg(II), La(III) or Sm(III) with a Schiff base "L" produced by the condensation of furfuraldehyde and 1,2-diaminobenzene. These compounds were characterized by elemental analysis, UV-Vis, FT-IR, molar conductance, mass spectrometry, thermal and fluorescence studies. The studies suggested the coordination of the ligand L to metal through azomethine imine nitrogen and furan oxygen atoms of Schiff base moiety. Thermogravimetric (TG/DTG) analyses data were studied and indicated high stability for all complexes and suggested the presence of lattice and/or coordinated water molecules in the complexes. Coats-Redfern method has been used to calculate the kinetic and thermodynamic parameters of the metal complexes. The spectral and thermal analysis reveal that all complexes have octahedral geometry except Cu(II) and Ni(II) complexes which can attain a square planner arrangements. The ligand and its complexes exhibited intraligand (π-π∗) fluorescence and can potentially serve as photoactive materials. Both the ligand and its complexes have been screened for antibacterial activities.

  7. The crucial role of polyatomic anions in molecular architecture: structural and magnetic versatility of five nickel(II) complexes derived from A N,N,O-donor Schiff base ligand.

    PubMed

    Mukherjee, Pampa; Drew, Michael G B; Gómez-García, Carlos J; Ghosh, Ashutosh

    2009-07-06

    Five new nickel(II) complexes [Ni(2)L(2)(N(3))(2)(H(2)O)(2)] (1), [Ni(2)L(2)(NO(3))(2)] (2), [Ni(2)L(2)(O(2)CPh)(CH(3)OH)(2)]ClO(4).0.5CH(3)OH (3), [Ni(3)L(2)(O(2)CPh)(4)] (4), and [Ni(2)L(2)(NO(2))(2)](n) (5) have been synthesized by using a tridentate Schiff base ligand, HL (2-[(3-Methylamino-propylimino)-methyl]-phenol), and the polyatomic monoanions N(3)(-), NO(3)(-), PhCOO(-), or NO(2)(-). The complexes have been structurally and magnetically characterized. The structural analysis reveals that in all five complexes, the Ni(II) ions possess a distorted octahedral geometry. Complexes 1 and 2 are dinuclear with di-mu-1,1-azido and di-mu(2)-phenoxo bridges, respectively. Complex 3 is also a di-mu(2)-phenoxo-bridged dinuclear Ni(II) complex but has an additional syn-syn benzoate bridge. Compound 4 possesses a linear trinuclear structure with the tridentate Schiff base ligand coordinated to the terminal nickel atoms which are linked to the central Ni(II) by phenoxo and carboxylate bridges. Complex 5 consists of a dinuclear entity, bridged by di-mu(2)-phenoxo together with a cis-(mu-nitrito-1kappaO:2kappaN) nitrite ion. The dinuclear units are linked each other by another bridging trans-(mu-nitrito-1kappaO:2kappaN) nitrite to form a Ni(II) chain that shows the presence of unprecedented alternating cis- and trans-N,O bridging mode of the nitrite anion. Variable-temperature magnetic susceptibility measurements of complex 1 indicate the presence of ferromagnetic exchange interactions within the dimer (J = 23.5(3) cm(-1)) together with antiferromagnetic interdimer interactions (J' = -0.513(3) cm(-1)), whereas compounds 2 and 3 show intradimer antiferromagnetic interactions (J = -24.27(6) and -16.48(4) cm(-1), respectively). Ferromagnetic coupling (J = 6.14(2) cm(-1)) is observed in complex 4 for the linear centro-symmetric Ni(II) trimer, whereas complex 5 shows an alternating intra-chain antiferromagnetic coupling (J(1) = -32.1(1) cm(-1) and J(2) = -3.2(1) cm(-1)).

  8. Magnetic interactions in CuII-LnIII cyclic tetranuclear complexes: is it possible to explain the occurrence of SMM behavior in CuII-TbIII and CuII-DyIII complexes?

    PubMed

    Hamamatsu, Takefumi; Yabe, Kazuya; Towatari, Masaaki; Osa, Shutaro; Matsumoto, Naohide; Re, Nazzareno; Pochaba, Andrzej; Mrozinski, Jerzy; Gallani, Jean-Louis; Barla, Alessandro; Imperia, Paolo; Paulsen, Carley; Kappler, Jean-Paul

    2007-05-28

    An extensive series of tetranuclear CuII2LnIII2 complexes [CuIILLnIII(hfac)2]2 (with LnIII being all lanthanide(III) ions except for the radioactive PmIII) has been prepared in order to investigate the nature of the CuII-LnIII magnetic interactions and to try to answer the following question: What makes the CuII2TbIII2 and CuII2DyIII2 complexes single molecule magnets while the other complexes are not? All the complexes within this series possess a similar cyclic tetranuclear structure, in which the CuII and LnIII ions are arrayed alternately via bridges of ligand complex (CuIIL). Regular SQUID magnetometry measurements have been performed on the series. The temperature-dependent magnetic susceptibilities from 2 to 300 K and the field-dependent magnetizations from 0 to 5 T at 2 K have been measured for the CuII2LnIII2 and NiII2LnIII2 complexes, with the NiII2LnIII2 complex containing diamagnetic NiII ions being used as a reference for the evaluation of the CuII-LnIII magnetic interactions. These measurements have revealed that the interactions between CuII and LnIII ions are very weakly antiferromagnetic if Ln=Ce, Nd, Sm, Yb, ferromagnetic if Ln=Gd, Tb, Dy, Ho, Er, Tm, and negligible if Ln=La, Eu, Pr, Lu. With the same goal of better understanding the evolution of the intramolecular magnetic interactions, X-ray magnetic circular dichroism (XMCD) has also been measured on CuII2TbIII2, CuII2DyIII2, and NiII2TbIII2 complexes, either at the L- and M-edges of the metal ions or at the K-edge of the N and O atoms. Last, the CuII2TbIII2 complex exhibiting SMM behavior has received a closer examination of its low temperature magnetic properties down to 0.1 K. These particular measurements have revealed the unusual very slow setting-up of a 3D order below 0.6 K.

  9. Spectral and thermal characterization of 3-acetyl-5-azophenyl-4-hydroxy-6-methyl-pyran-2-one and its metal complexes

    NASA Astrophysics Data System (ADS)

    Seth, Susannah; Aravindakshan, K. K.

    2013-08-01

    Five chelates of 3-acetyl-5-azophenyl-4-hydroxy-6-methyl-pyran-2-one (phenylazo dehydroacetic acid) with Cr(III), Fe(III), Ni(II), Cu(II) and Zn(II) have been synthesized and characterized by elemental analysis, magnetic susceptibility measurements, electronic, 1H NMR, FAB mass, IR-spectral and thermal (TG/DTG) analytical techniques. In the present work it has been found that oxygen of the deprotonated sbnd OH group and one of the azo-nitrogens of the ligand take part in coordination. The Cr(III), Fe(III) and Ni(II) complexes were found to be having octahedral geometry and the Cu(II) and Zn(II) tetrahedral.

  10. Crystal structure of D-psicose 3-epimerase from Agrobacterium tumefaciens and its complex with true substrate D-fructose: a pivotal role of metal in catalysis, an active site for the non-phosphorylated substrate, and its conformational changes.

    PubMed

    Kim, Kwangsoo; Kim, Hye-Jung; Oh, Deok-Kun; Cha, Sun-Shin; Rhee, Sangkee

    2006-09-01

    D-psicose, a rare sugar produced by the enzymatic reaction of D-tagatose 3-epimerase (DTEase), has been used extensively for the bioproduction of various rare carbohydrates. Recently characterized D-psicose 3-epimerase (DPEase) from Agrobacterium tumefaciens was found to belong to the DTEase family and to catalyze the interconversion of D-fructose and D-psicose by epimerizing the C-3 position, with marked efficiency for D-psicose. The crystal structures of DPEase and its complex with the true substrate D-fructose were determined; DPEase is a tetramer and each monomer belongs to a TIM-barrel fold. The active site in each subunit is distinct from that of other TIM-barrel enzymes, which use phosphorylated ligands as the substrate. It contains a metal ion with octahedral coordination to two water molecules and four residues that are absolutely conserved across the DTEase family. Upon binding of D-fructose, the substrate displaces water molecules in the active site, with a conformation mimicking the intermediate cis-enediolate. Subsequently, Trp112 and Pro113 in the beta4-alpha4 loop undergo significant structural changes, sealing off the active site. Structural evidence and site-directed mutagenesis of the putative catalytic residues suggest that the metal ion plays a pivotal role in catalysis by anchoring the bound D-fructose, and Glu150 and Glu244 carry out an epimerization reaction at the C-3 position.

  11. Dinuclear Metallacycles with Single M-X-M Bridges (X = Cl(-), Br(-); M = Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II)): Strong Antiferromagnetic Superexchange Interactions.

    PubMed

    Reger, Daniel L; Pascui, Andrea E; Foley, Elizabeth A; Smith, Mark D; Jezierska, Julia; Wojciechowska, Agnieszka; Stoian, Sebastian A; Ozarowski, Andrew

    2017-03-06

    A series of monochloride-bridged, dinuclear metallacycles of the general formula [M2(μ-Cl)(μ-L)2](ClO4)3 have been prepared using the third-generation, ditopic bis(pyrazolyl)methane ligands L = m-bis[bis(1-pyrazolyl)methyl]benzene (Lm), M = Cu(II), Zn(II), and L = m-bis[bis(3,5-dimethyl-1-pyrazolyl)methyl]benzene (Lm*), M = Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II). These complexes were synthesized from the direct reactions of M(ClO4)2·6H2O, MCl2, and the ligand, Lm or Lm*, in the appropriate stoichiometric amounts. Three analogous complexes of the formula [M2(μ-Cl)(μ-L)2](BF4)3, L = Lm, M = Cu(II), and L = Lm*, M = Co(II), Cu(II), were prepared from the reaction of [M2(μ-F)(μ-L)2](BF4)3 and (CH3)3SiCl. The bromide-bridged complex [Cu2(μ-Br)(μ-Lm*)2](ClO4)3 was prepared by the first method. Three acyclic complexes, [Co2(μ-Lm)μ-Cl4], [Co2(μ-Lm*)Cl4], and [Co2(μ-Lm*)Br4], were also prepared. The structures of all [M2(μ-X)(μ-L)2](3+) (X = Cl(-), Br(-)) complexes have two ditopic bis(pyrazolyl)methane ligands bridging two metals in a metallacyclic arrangement. The fifth coordination site of the distorted trigonal bipyramidal metal centers is filled by a bridging halide ligand that has an unusual linear or nearly linear M-X-M angle. The NMR spectra of [Zn2(μ-Cl)(μ-Lm*)2](ClO4)3 and especially [Cd2(μ-Cl)(μ-Lm*)2](ClO4)3 demonstrate that the metallacycle structure is maintained in solution. Solid state magnetic susceptibility data for the copper(II) compounds show very strong antiferromagnetic exchange interactions, with -J values of 536 cm(-1) for [Cu2(μ-Cl)(μ-Lm)2](ClO4)3·xCH3CN, 720 cm(-1) for [Cu2(μ-Cl)(μ-Lm*)2](ClO4)3, and 945 cm(-1) for [Cu2(μ-Br)(μ-Lm*)2](ClO4)3·2CH3CN. Smaller but still substantial antiferromagnetic interactions are observed with other first row transition metals, with -J values of 98 cm(-1) for [Ni2(μ-Cl)(μ-Lm*)2](ClO4)3, 55 cm(-1) for [Co2(μ-Cl)(μ-Lm*)2](ClO4)3, and 34 cm(-1) for [Fe2(μ-Cl)(μ-Lm*)2](ClO4

  12. Nickel-quinolones interaction. Part 5-Biological evaluation of nickel(II) complexes with first-, second- and third-generation quinolones.

    PubMed

    Skyrianou, Kalliopi C; Perdih, Franc; Papadopoulos, Athanasios N; Turel, Iztok; Kessissoglou, Dimitris P; Psomas, George

    2011-10-01

    The nickel(II) complexes with the quinolone antibacterial agents oxolinic acid, flumequine, enrofloxacin and sparfloxacin in the presence of the N,N'-donor heterocyclic ligand 2,2'-bipyridylamine have been synthesized and characterized. The quinolones act as bidentate ligands coordinated to Ni(II) ion through the pyridone oxygen and a carboxylato oxygen. The crystal structure of [(2,2'-bipyridylamine)bis(sparfloxacinato)nickel(II)] has been determined by X-ray crystallography. UV study of the interaction of the complexes with calf-thymus DNA (CT DNA) has shown that they bind to CT DNA with [(2,2'-bipyridylamine)bis(flumequinato)nickel(II)] exhibiting the highest binding constant to CT DNA. The cyclic voltammograms of the complexes have shown that in the presence of CT DNA the complexes can bind to CT DNA by the intercalative binding mode which has also been verified by DNA solution viscosity measurements. Competitive study with ethidium bromide (EB) has shown that the complexes can displace the DNA-bound EB indicating that they bind to DNA in strong competition with EB. The complexes exhibit good binding propensity to human or bovine serum albumin protein having relatively high binding constant values. The biological properties of the [Ni(quinolonato)(2)(2,2'-bipyridylamine)] complexes have been evaluated in comparison to the previously reported Ni(II) quinolone complexes [Ni(quinolonato)(2)(H(2)O)(2)], [Ni(quinolonato)(2)(2,2'-bipyridine)] and [Ni(quinolonato)(2)(1,10-phenanthroline)]. The quinolones and their Ni(II) complexes have been tested for their antioxidant and free radical scavenging activity. They have been also tested in vitro for their inhibitory activity against soybean lipoxygenase.

  13. Synthesis, Characterization, Antibacterial and Anti-Inflammatory Activities of Enoxacin Metal Complexes

    PubMed Central

    Arayne, Saeed; Sultana, Najma; Haroon, Urooj; Mesaik, M. Ahmed

    2009-01-01

    The present work comprises the synthesis of enoxacin (Heno) complexes with various transition metals. Two types of complexes [M(eno)2(H2O)2]3H2O(M = CuII, NiII or MnII) and [M(eno)(H2O)2]Cl · 4H2O (M = FeIII) were obtained. The complexes were characterized by different physicochemical, spectroscopic, and elemental analysis. Results suggest that enoxacin interacts with the metals as a monoanionic bidentate ligand. These complexes were also tested for their antibacterial activity against eleven (11) different microorganisms, and the results were compared with the parent drug. Moreover all the metal complexes were also tested for their ability to scavenge reactive oxygen species where by MnII and CuII complexes exhibited potential to mediate anti-inflammatory response. PMID:19657456

  14. Synthesis, Spectral Characterization, SEM, Antimicrobial, Antioxidative Activity Evaluation, DNA Binding and DNA Cleavage Investigation of Transition Metal(II) Complexes Derived from a tetradentate Schiff base bearing thiophene moiety.

    PubMed

    Abdel Aziz, Ayman A; Seda, Sabry H

    2017-03-01

    A novel series of Co(II), Ni(II), Cu(II) and Zn(II) mononuclear complexes have been synthesized involving a potentially tetradentate Schiff base ligand, which was obtained by condensation of 2-aminophenol with 2,5-thiophene-dicarboxaldehyde. The complexes were synthesized via reflux reaction of methanolic solution of the appropriate Schiff base ligand with one equivalent of corresponding metal acetate salt. Based on different techniques including micro analysis, FT-IR, NMR, UV-Vis, ESR, ESI-mass and conductivity measurements, four-coordinated geometry was assigned for all complexes. Spectroscopic data have shown that, the reported Schiff base coordinated to metal ions as a dibasic tetradentate ligand through the phenolic oxygen and the azomethine nitrogen. The antimicrobial activities of the parent ligand and its complexes were investigated by using the agar disk diffusion method. Antioxidation properties of the novel complexes were investigated and it was found that all the complexes have good radical scavenging properties. The binding of complexes to calf thymus DNA (CT-DNA) was investigated by absorption, emission and viscosity measurements. Binding studies have shown that all the complexes interacted with CT-DNA via intercalation mode and the binding affinity varies with relative order as Cu(II) complex > Co(II) complex > Zn(II) complex > Ni(II) complex. Furthermore, DNA cleavage properties of the metal complexes were also investigated. The results suggested the possible utilization of novel complexes for pharmaceutical applications.

  15. Ligational behaviour of lomefloxacin drug towards Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Th(IV) and UO(2)(VI) ions: synthesis, structural characterization and biological activity studies.

    PubMed

    Abd el-Halim, Hanan F; Mohamed, Gehad G; el-Dessouky, Maher M I; Mahmoud, Walaa H

    2011-11-01

    Nine new mononuclear Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Th(IV) and UO(2)(VI) complexes of lomefloxacin drug were synthesized. The structures of these complexes were elucidated by elemental analyses, IR, XRD, UV-vis, (1)H NMR as well as conductivity and magnetic susceptibility measurements and thermal analyses. The dissociation constants of lomefloxacin and stability constants of its binary complexes have been determined spectrophotometrically in aqueous solution at 25±1°C and at 0.1 M KNO(3) ionic strength. The discussion of the outcome data of the prepared complexes indicate that the lomefloxacin ligand behaves as a neutral bidentate ligand through OO coordination sites and coordinated to the metal ions via the carbonyl oxygen and protonated carboxylic oxygen with 1:1 (metal:ligand) stoichiometry for all complexes. The molar conductance measurements proved that the complexes are electrolytes. The powder XRD study reflects the crystalline nature for the investigated ligand and its complexes except Mn(II), Zn(II) and UO(2)(II). The geometrical structures of these complexes are found to be octahedral. The thermal behaviour of these chelates is studied where the hydrated complexes lose water molecules of hydration in the first steps followed by decomposition of the anions, coordinated water and ligand molecules in the subsequent steps. The activation thermodynamic parameters are calculated using Coats-Redfern and Horowitz-Metzger methods. A comparative study of the inhibition zones of the ligand and its metal complexes indicates that metal complexes exhibit higher antibacterial effect against one or more bacterial species than the free LFX ligand. The antifungal and anticancer activities were also tested. The antifungal effect of almost metal complexes is higher than the free ligand. LFX, [Co(LFX)(H(2)O)(4)]·Cl(2) and [Zn(LFX)(H(2)O)(4)]·Cl(2) were found to be very active with IC50 values 14, 11.2 and 43.1, respectively. While, other

  16. Ligational behaviour of lomefloxacin drug towards Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Th(IV) and UO 2(VI) ions: Synthesis, structural characterization and biological activity studies

    NASA Astrophysics Data System (ADS)

    El-Halim, Hanan F. Abd; Mohamed, Gehad G.; El-Dessouky, Maher M. I.; Mahmoud, Walaa H.

    2011-11-01

    Nine new mononuclear Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Th(IV) and UO 2(VI) complexes of lomefloxacin drug were synthesized. The structures of these complexes were elucidated by elemental analyses, IR, XRD, UV-vis, 1H NMR as well as conductivity and magnetic susceptibility measurements and thermal analyses. The dissociation constants of lomefloxacin and stability constants of its binary complexes have been determined spectrophotometrically in aqueous solution at 25 ± 1 °C and at 0.1 M KNO 3 ionic strength. The discussion of the outcome data of the prepared complexes indicate that the lomefloxacin ligand behaves as a neutral bidentate ligand through OO coordination sites and coordinated to the metal ions via the carbonyl oxygen and protonated carboxylic oxygen with 1:1 (metal:ligand) stoichiometry for all complexes. The molar conductance measurements proved that the complexes are electrolytes. The powder XRD study reflects the crystalline nature for the investigated ligand and its complexes except Mn(II), Zn(II) and UO 2(II). The geometrical structures of these complexes are found to be octahedral. The thermal behaviour of these chelates is studied where the hydrated complexes lose water molecules of hydration in the first steps followed by decomposition of the anions, coordinated water and ligand molecules in the subsequent steps. The activation thermodynamic parameters are calculated using Coats-Redfern and Horowitz-Metzger methods. A comparative study of the inhibition zones of the ligand and its metal complexes indicates that metal complexes exhibit higher antibacterial effect against one or more bacterial species than the free LFX ligand. The antifungal and anticancer activities were also tested. The antifungal effect of almost metal complexes is higher than the free ligand. LFX, [Co(LFX)(H 2O) 4]·Cl 2 and [Zn(LFX)(H 2O) 4]·Cl 2 were found to be very active with IC50 values 14, 11.2 and 43.1, respectively. While, other complexes had

  17. Spectrophotometric sequential injection determination of D-penicillamine based on a complexation reaction with nickel ion.

    PubMed

    Martinović-Bevanda, Anita; Radić, Njegomir

    2013-01-01

    A simple and sensitive spectrophotometric method, based on reaction between Ni(II) ion and D-penicillamine (PEN), was developed. The proposed SIA system enhanced the analytical applicability of the reaction of complexation, and allowed the determination of PEN in the concentration range of 3.0 × 10(-6) - 2.0 × 10(-4) mol L(-1) with a sampling rate of 200 h(-1). With the proposed SIA system, PEN could be accurately determinated up to 0.9 nmol quantity. The method was successfully applied to the determination of PEN in laboratory samples and pharmaceuticals.

  18. Multiporphyrin coordination arrays based on complexation of magnesium(II) porphyrins with porphyrinylphosphine oxides.

    PubMed

    Atefi, Farzad; McMurtrie, John C; Arnold, Dennis P

    2007-06-07

    Di- and triporphyrin arrays consisting of 5,15-diphenylporphyrinatomagnesium(II) (MgDPP) coordinated to free-base and Ni(II) porphyrinyl mono- and bis-phosphine oxides, as well as the self-coordinating diphenyl[10,20-diphenylporphyrinatomagnesium(II)-5-yl]phosphine oxide [MgDPP(Ph(2)PO)], were synthesised in excellent yields and characterised by various spectroscopic techniques. Phosphine oxides stabilise Mg(II) coordination to porphyrins and the resulting complexes have convenient solubilities, while the Ni(II) complexes exhibit interesting intramolecular fluorescence quenching behaviour. The binding constant of MgDPP to triphenylphosphine oxide (5.3 +/- 0.1 x 10(5) M(-1)) and the very high self-association constant of [MgDPP(Ph(2)PO)] (5.5 +/- 0.5 x 10(8) M(-1)) demonstrate the strong affinity of phosphine oxides towards Mg(II) porphyrins. These complexes are the first strongly bound synthetic Mg(II) multiporphyrin complexes and could potentially mimic the "special pair" in the photosynthetic reaction centre.

  19. Two new heterodinuclear Schiff base complexes: synthesis, crystal structure and thermal studies.

    PubMed

    Yardan, Alper; Hopa, Cigdem; Yahsi, Yasemin; Karahan, Ahmet; Kara, Hulya; Kurtaran, Raif

    2015-02-25

    Two new heterodinuclear Schiff base complexes, [Hg(L)NiCl2(DMF)2] 1, and [Zn(L)NiCl2(DMF)2] 2, where H2L = N,N'-bis(salicylidene)-1,3-diaminopropane and DMF = dimethylformamide have been synthesized and characterized using elemental analysis, IR spectroscopy, thermal analysis and X-ray diffraction. Structural studies on 1 and 2 reveal the presence of a heterodinuclear [Ni(II)Hg(II)] unit and [Zn(II)Ni(II)] in which the central metal ions are connected to each other by two phenolate oxygen bridges. For complex 1 the Ni(II) ion adopts an elongated octahedral geometry (NiN2O4) while the Hg(II) ion assumes a distorted tetrahedral arrangement (HgO2Cl2) whereas for complex 2 the Zn(II) ion adopts an elongated octahedral geometry (ZnN2O4) while the Ni(II) ion assumes a distorted tetrahedral arrangement (NiO2Cl2). There are intermolecular C-H···Cl-M interactions among the dinuclear complexes which are interconnected for 1 and 2. These intermolecular interactions result in the formation of a three dimensional structure for 1 and one dimensional zig-zag chains for 2.

  20. Spectrophotometric determination of molybdenum by extraction of its thiosulphate complex.

    PubMed

    Yatirajam, V; Ram, J

    1974-12-01

    A simple and rapid spectrophotometric determination of molybdenum is described. The molybdenum thiosulphate complex is extracted into isoamyl alcohol from 1.0-1.5M hydrochloric acid containing 36-40 mg of Na(2)S(2)O(3).5H(2)O per ml. The absorbance at lambda(max) = 475 nm obeys Beer's law over the range 0-32 microg of Mo per ml of solvent phase. Up to 5 mg/ml of Ti(IV), V(V), Cr(VI), Fe(III), Co(II), Ni(II), U(VI), W(VI), Sb(III), 1 mg/ml of Cu(II), Sn(II), Bi(V) and 10 microg/ml of Pt(IV) and Pd(II) do not interfere. Large amounts of complexing agents interfere. The method has been applied to analysis of synthetic and industrial samples.

  1. Spectroscopic and antibacterial studies of new octaazamacrocyclic complexes derived from carbohydrazide and isatin

    NASA Astrophysics Data System (ADS)

    Kumar, Krishan; Kamboj, Monika; Jain, Kiran; Singh, D. P.

    2014-07-01

    A novel series of the macrocyclic complexes of the type: [M(C18H14N10O2)X2], where M = Co(II), Ni(II), Cu(II) and Zn(II); X = Cl-, NO3- and CH3COO-, has been synthesized by template condensation of carbohydrazide and isatin in methanolic medium. The complexes were characterized by various physico-chemical techniques, such as elemental analyses, molar conductance measurements, magnetic measurements, and electronic, NMR, IR and EPR spectral studies. The low value of molar conductance indicates them to be non-electrolytes. Based on various studies, a distorted octahedral geometry was proposed for all the metal complexes. Metal complexes were tested for their in vitro antibacterial activities against some pathogenic bacterial strains and compared with standard antibiotic, Ciprofloxacin. Some of the tested complexes was found effective against Gram-positive bacterial strains.

  2. Synthesis, physico-chemical characterization and antimicrobial activities of 3-methoxysalicylaldehyde-2-aminobenzoylhydrazone and its transition metal complexes

    NASA Astrophysics Data System (ADS)

    Badiger, Dayananda S.; Hunoor, Rekha S.; Patil, Basavaraj R.; Vadavi, Ramesh S.; Mangannavar, Chandrashekhar V.; Muchchandi, Iranna S.; Gudasi, Kalagouda B.

    2012-07-01

    The transition metal complexes of 3-methoxysalicylaldehyde-2-aminobenzhydrazone (H2L) were synthesized and characterized by various spectroscopic (IR, NMR, UV-Vis, mass), thermal and other physicochemical methods. The ligand acts both in monobasic as well as dibasic manner and coordinates in tridentate fashion with carbonyl oxygen, azomethine nitrogen and phenolic oxygen via deprotonation except in Cu(II) complex where the ligand coordinates via enolization and deprotonation of amide proton. An octahedral geometry was assigned for Mn(II), Co(II), Ni(II) and Zn(II) complexes and square planar for Cu(II) complex. The ligand and its metal complexes have been screened for their in vitro antimicrobial activities using serial dilution method. Metal complexes in general have exhibited better antibacterial and antifungal activity than the free ligand. The Cu(II) complex exhibited highest antimicrobial activity among the compounds tested.

  3. Quinoxaline based bio-active mixed ligand transition metal complexes: Synthesis, characterization, electrochemical, antimicrobial, DNA binding, cleavage, antioxidant and molecular docking studies.

    PubMed

    Dhanaraj, C Justin; Johnson, Jijo

    2015-10-01

    Co(II), Ni(II), Cu(II) and Zn(II) mixed ligand complexes have been synthesized from N(2), N(3)-bis(4-nitrophenyl)quinoxaline-2,3-diamine and 1,10-phenanthroline. The compounds were characterized by elemental analyses, molar conductance, magnetic susceptibility, IR, UV-Vis., (1)H NMR, mass and ESR spectra. Octahedral geometry has been assigned for Co(II), Ni(II) and Zn(II) complexes and distorted octahedral geometry for Cu(II) complex. Electrochemical behavior of the synthesized complexes was studied using cyclic voltammetry. Grain size and surface morphologies of the complexes were determined by powder XRD and SEM analyses. The mixed ligand metal complexes were screened for antimicrobial activity against bacterial species Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa and Staphylococcus aureus; fungal species Aspergillus niger, and Candida albicans by disc diffusion method. The DNA binding and DNA cleavage activities of the compounds were determined using electronic absorption titration and agarose gel electrophoresis respectively. The superoxide radical scavenging and free radical scavenging activities of the Cu(II) complex was also evaluated. Molecular docking studies of the synthesized mixed ligand metal complexes were carried out against B-DNA dodecamer and the protein Plasmodium falciparum dihydrofolate reductase (pf DHFR).

  4. Removal of Cu(II) and Ni(II) using cellulose extracted from sisal fiber and cellulose-g-acrylic acid copolymer.

    PubMed

    Hajeeth, T; Vijayalakshmi, K; Gomathi, T; Sudha, P N

    2013-11-01

    The extraction of cellulose from sisal fiber was done initially using the steam explosion method. The batch adsorption studies were conducted using the cellulose extracted from the sisal fiber and cellulose-g-acrylic acid as an adsorbent for the removal of Cu(II) and Ni(II) metal ions from aqueous solution. The effect of sorbent amount, agitation period and pH of solution that influence sorption capacity were investigated. From the observed results, it was evident that the adsorption of metal ions increases with the increase in contact time and adsorbent dosage. The optimum pH was found to be 5.0 for the removal of copper(II) and nickel(II) for both the extracted cellulose and cellulose-g-acrylic acid copolymer. The adsorption data were modeled using Langmuir and Freundlich isotherms. The experimental results of the Langmuir, Freundlich isotherms revealed that the adsorption of Cu(II) and nickel(II) ion onto cellulose extracted from the sisal fiber and cellulose-g-acrylic acid copolymer was found to fit well with Freundlich isotherm. The kinetics studies show that the adsorption follows the pseudo-second-order kinetics. From the above results, it was concluded that the cellulose-g-acrylic acid copolymer was found to be an efficient adsorbent.

  5. Simultaneous removal of Ni(II), As(III), and Sb(III) from spiked mine effluent with metakaolin and blast-furnace-slag geopolymers.

    PubMed

    Luukkonen, Tero; Runtti, Hanna; Niskanen, Mikko; Tolonen, Emma-Tuulia; Sarkkinen, Minna; Kemppainen, Kimmo; Rämö, Jaakko; Lassi, Ulla

    2016-01-15

    The mining industry is a major contributor of various toxic metals and metalloids to the aquatic environment. Efficient and economical water treatment methods are therefore of paramount importance. The application of natural or low-cost sorbents has attracted a great deal of interest due to the simplicity of its process and its potential effectiveness. Geopolymers represent an emerging group of sorbents. In this study, blast-furnace-slag and metakaolin geopolymers and their raw materials were tested for simultaneous removal of Ni(II), As(III) and Sb(III) from spiked mine effluent. Blast-furnace-slag geopolymer proved to be the most efficient of the studied materials: the experimental maximum sorption capacities for Ni, As and, Sb were 3.74 mg/g, 0.52 mg/g, and 0.34 mg/g, respectively. Although the capacities were relatively low due to the difficult water matrix, 90-100% removal of Ni, As, and Sb was achieved when the dose of sorbent was increased appropriately. Removal kinetics fitted well with the pseudo-second-order model. Our results indicate that geopolymer technology could offer a simple and effective way to turn blast-furnace slag to an effective sorbent with a specific utilization prospect in the mining industry.

  6. Batch sorption dynamics, kinetics and equilibrium studies of Cr(VI), Ni(II) and Cu(II) from aqueous phase using agricultural residues

    NASA Astrophysics Data System (ADS)

    Kaur, Rajvinder; Singh, Joginder; Khare, Rajshree; Cameotra, Swaranjit Singh; Ali, Amjad

    2013-03-01

    In the present study, the agricultural residues viz., Syzygium cumini and Populus deltoides leaves powder have been used for the biosorption of Cu(II), Ni(II), and Cr(VI) from aqueous solutions. FTIR and SEM analysis of the biosorbents were performed to explore the type of functional groups available for metal binding and to study the surface morphology. Various physico-chemical parameters such as pH, adsorbent dosage, initial metal ion concentration, and equilibrium contact time were studied. Thermodynamic studies were carried out and the results demonstrated the spontaneous and endothermic nature of the biosorption process. The equilibrium data were tested using four isotherm models—Langmuir, Freundlich, Temkin and Dubinin-Radushkevich and the maximum biosorption capacities were evaluated. The Pseudo-first-order, pseudo-second-order, Elovich and intraparticle diffusion models were applied to study the reaction kinetics with pseudo-second order model giving the best fit ( R 2 = 0.99) to the experimental data.

  7. Synthesis of high surface area, mesoporous MgO nanosheets with excellent adsorption capability for Ni(II) via a distillation treating.

    PubMed

    Feng, Jing; Zou, Linyi; Wang, Yuting; Li, Bowen; He, Xiaofeng; Fan, Zhuangjun; Ren, Yueming; Lv, Yanzhuo; Zhang, Milin; Chen, Dan

    2015-01-15

    Hexagonal mesoporous MgO nanosheets with a side length of 250 nm and specific surface area of 181.692 m(2)/g were fabricated by a three-step process. Firstly, MgO powders were obtained by sintered Mg5(OH)2(CO3)4⋅4H2O, which was synthesized by a wet precipitation process using ammonium hydrogen carbonate as precipitants. Secondly, the above-MgO were distilled 2 h in a three-necked bottle with condenser device. Lastly, we annealed the distilled-MgO at 500-800 °C to form mesoporous MgO nanosheets. We found the pore size distribution and the thicknesses of nanosheets were determined by the distillation process in step 2 and annealed temperature in step 3. By optimizing the experimental parameters, the mesoporous dis-MgO annealed at 600 °C displayed uniform hexagonal structure with the largest pore volume (0.875 cm(3)/g) and highest BET surface area (181.692 m(2)/g), as well as the maximum adsorption capability of 1684.25 mg/g for Ni(II).

  8. Spectroscopic characterization and biological activity of dihydrazone transition metal complexes: Crystal structure of 2,3-butanedione bis(isonicotinylhydrazone)

    NASA Astrophysics Data System (ADS)

    El-Sayed, Ahmed E. M.; Al-Fulaij, O. A.; Elaasar, A. A.; El-Defrawy, M. M.; El-Asmy, A. A.

    2015-01-01

    Metal complexes of the chloride, nitrate and acetate salts of Co(II), Ni(II) Cu(II), Zn(II), Cd(II) or Hg(II) with 2,3-butanedione bis(isonicotinylhydrazone) [BBINH] have been synthesized and structurally characterized. The crystal of BBINH was solved to crystallize as monoclinic system with space group of P121/c14. The formulae of the complexes were assigned based on the elemental analysis and mass spectra. The formation of BBINH complexes depend on the metal anion used. All complexes are nonelectrolytes except for the complexes 2, 3, 4 are (1:1) and 13 and 14 which are 1:2 electrolytes. BBINH behaves as a neutral tetradentate (N2O2) in the chloride complexes of Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II). In [Co2(BBINH)(H2O)Cl3]ClṡH2O, BBINH has the same dentate but with the two Co(II) ions. In the acetate complexes, [Ni2(BBINH-2H)(H2O)2(OAc)2]ṡ3H2O and [Cu2(BBINH-2H)(OAc)2]ṡ5H2O, BBINH acts as a binegative tetradentate with the two metal ions. The ligand in the nitrate complexes acts as a neutral bidentate via the two hydrazone azomethine Cdbnd NHy; the nitrate ions are ionic in the Cd(II) and Zn(II) complexes and covalent in the Ni(II) complex. The data are supported by NMR (1H and 13C) spectra. The magnetic moments and electronic spectra of all complexes provide tetrahedral, square planar and/or octahedral structure. The decomposition of the complexes revealed the outer and inner solvents as well as the remaining residue based on TGA. The complexes have variable activities against some bacteria and fungi. The ligand is inactive against all tested organisms. The activity of Cd(II) and Hg(II) may be related to the geometry of the complexes.

  9. Synthesis, characterization and biological activity of transition metal complexes with Schiff bases derived from 2-nitrobenzaldehyde with glycine and methionine

    NASA Astrophysics Data System (ADS)

    Singh, Bibhesh K.; Rajour, Hemant K.; Prakash, Anant

    Schiff bases derived from 2-nitrobenzaldehyde with amino acids (glycine, methionine) and their Co(II), Ni(II) and Cu(II) complexes have been synthesized and characterized by various physico-chemical techniques. From spectral studies, it has been concluded that the ligands acts as bidentate molecule, coordinates metal through azomethine nitrogen and carboxylate oxygen. Mass spectrum explains the successive degradation of the molecular species in solution and justifies ML2 complexes. X-ray powder diffraction helps to determine the cell parameters of the complexes. Molecular structure of the complexes has been optimized by MM2 calculations and suggests a square planar geometry. The ligands and their metal complexes have been tested in vitro against Streptococcus, Staph, Staphylococcus aureus and Escherchia coli bacteria in order to assess their antibacterial potential. The results indicate that the biological activity increases on complexation.

  10. Trithiocyanurate complexes of iron, manganese and nickel and their anticholinesterase activity.

    PubMed

    Kopel, Pavel; Dolezal, Karel; Langer, Vratislav; Jun, Daniel; Adam, Vojtech; Kuca, Kamil; Kizek, Rene

    2014-04-08

    The complexes of Fe(II), Mn(II) and Ni(II) with a combination of a Schiff base, nitrogen-donor ligand or macrocyclic ligand and trithiocyanuric acid (ttcH3) were prepared and characterized by elemental analysis and spectroscopies. Crystal and molecular structures of the iron complex of composition [Fe(L1)](ttcH2)(ClO4)·EtOH·H2O (1), where L1 is Schiff base derived from tris(2-aminoethyl)amine and 2-pyridinecarboxaldehyde, were solved. It was found that the Schiff base is coordinated to the central iron atom by six nitrogens forming deformed octahedral arrangement, whereas trithiocyanurate(1-) anion, perchlorate and solvent molecules are not coordinated. The X-ray structure of the Schiff base sodium salt is also presented and compared with the iron complex. The anticholinesterase activity of the complexes was also studied.

  11. Bio-sensitive activities of coordination compounds containing 1,10-phenanthroline as co-ligand: Synthesis, structural elucidation and DNA binding properties of metal(II) complexes

    NASA Astrophysics Data System (ADS)

    Raman, Natarajan; Mahalakshmi, Rajkumar; Mitu, Liviu

    2014-10-01

    Present work reports the DNA binding and cleavage characteristics of a series of mixed-ligand complexes having the composition [M(L)(phen)2]Cl2 (where M = Cu(II), Ni(II), Co(II) and Zn(II) and phen as co-ligand) in detail. Their structural features and other properties have been deduced from their elemental analyses, magnetic susceptibility and molar conductivity as well as from IR, UV-Vis, 1H NMR and EPR spectral studies. The UV-Vis, magnetic susceptibility and EPR spectral data of metal complexes suggest an octahedral geometry. The binding properties of these complexes with calf thymus DNA (CT-DNA) have been explored using electronic absorption spectroscopy, viscosity measurement, cyclic voltammetry and differential pulse voltammetry. The DNA-binding constants for Cu(II), Ni(II), Co(II), and Zn(II) complexes are 6.14 × 105 M-1, 1.8 × 105 M-1, 6.7 × 104 M-1 and 2.5 × 104 M-1 respectively. Detailed analysis reveals that these complexes interact with DNA through intercalation binding. Nuclease activity has also been investigated by gel electrophoresis. Moreover, the synthesized Schiff base and its mixed-ligand complexes have been screened for antibacterial and antifungal activities. The data reveal that the complexes exhibit higher activity than the parent ligand.

  12. Synthesis, Characterization, Antimicrobial, DNA Cleavage, and Antioxidant Studies of Some Metal Complexes Derived from Schiff Base Containing Indole and Quinoline Moieties

    PubMed Central

    Karekal, Mahendra Raj; Biradar, Vivekanand; Bennikallu Hire Mathada, Mruthyunjayaswamy

    2013-01-01

    A new Schiff base of 5-chloro-3-phenyl-1H-indole-2-carboxyhydrazide and 3-formyl-2-hydroxy-1H-quinoline (HL), and its Cu(II), Co(II), Ni(II), Zn(II), Cd(II), and Hg(II) complexes have been synthesized and characterized in the light of microanalytical, IR, H1 NMR, UV-Vis, FAB-mass, ESR, XRD, and TGA spectral studies. The magnetic susceptibility measurements and low conductivity data provide evidence for monomeric and neutral nature of the complexes. On the basis of spectral studies and analytical data, it is evident that the Schiff base acts as tridentate ligand. The Cu(II), Co(II), and Ni(II) complexes were octahedral, whereas Zn(II), Cd(II), and Hg(II) complexes were tetrahedral in nature. The redox behavior of the Cu(II) complex was investigated by electrochemical method using cyclic voltammetry. In order to evaluate the effect of metal ions upon chelation, both the ligand and its metal complexes were screened for their antibacterial and antifungal activities by minimum inhibitory concentration (MIC) method. The DNA cleavage experiment performed using agarose gel electrophoresis method showed the cleavage of DNA by all the metal complexes. The free radical scavenging activity of newly synthesized compounds has been determined at a different concentration range by means of their interaction with the stable free radical 1,1-diphenyl-2-picrylhydrazyl (DPPH). PMID:24194692

  13. Synthesis, spectroscopic characterization, electrochemical behaviour, reactivity and antibacterial activity of some transition metal complexes with 2-( N-salicylideneamino)-3-carboxyethyl-4,5-dimethylthiophene

    NASA Astrophysics Data System (ADS)

    Daniel, Varughese P.; Murukan, B.; Kumari, B. Sindhu; Mohanan, K.

    2008-07-01

    Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes with a potentially tridentate Schiff base, formed by condensation of 2-amino-3-carboxyethyl-4,5-dimethylthiophene with salicylaldehyde were synthesized and characterized on the basis of elemental analyses, molar conductance values, magnetic susceptibility measurements, UV-vis, IR, EPR and NMR spectral data, wherever possible and applicable. Spectral studies reveal that the free ligand exists in a bifunctionally hydrogen bonded manner and coordinates to the metal ion in a tridentate fashion through the deprotonated phenolate oxygen, azomethine nitrogen and ester carbonyl group. On the basis of electronic spectral data and magnetic susceptibility measurements, suitable geometry has been proposed for each complex. The EPR spectral data of the Cu(II) complex showed that the metal-ligand bonds have considerable covalent character. The Ni(II) complex has undergone facile transesterification reaction when refluxed in methanol for a lengthy period. X-ray diffraction studies of Cu(II) complex showed that the complex has an orthorhombic crystal lattice. In view of the biological activity of thiophene derivatives, the ligand and the complexes were subjected to antibacterial screening. It has been observed that the antibacterial activity of the ligand increased on chelation with metal ion.

  14. Design, spectral characterization, DFT and biological studies of transition metal complexes of Schiff base derived from 2-aminobenzamide, pyrrole and furan aldehyde.

    PubMed

    Tyagi, Prateek; Chandra, Sulekh; Saraswat, B S; Sharma, Deepansh

    2015-05-15

    A series of two biologically active Schiff base ligands L(1), L(2) have been synthesized in equimolar reaction of 2-aminobenzamide with pyrrol-2-carboxaldehyde and furan-2-carboxaldehyde. The synthesized Schiff bases were used for complexation with different metal ions like Co(II), Ni(II) and Cu(II) by using a molar ratio of ligand: metal as 2:1. The characterization of newly formed complexes was done by (1)H NMR, UV-Vis, TGA, IR, mass spectrophotometry, EPR and molar conductivity studies. The thermal studies suggested that the complexes are more stable as compared to ligand. In DFT studies the geometries of Schiff bases and metal complexes were fully optimized with respect to the energy using the 6-31+g(d,p) basis set. On the basis of the spectral studies an octahedral geometry has been assigned for Co(II) and Ni(II) complexes and distorted octahedral geometry for Cu(II) complexes. All the synthesized compounds, were studied for their in vitro antimicrobial activities, against four bacterial strains and two fungal strains by using serial dilution method. The data also revealed that the metal complexes showed better activity than the ligands due to chelation/coordination.

  15. Design, spectral characterization, DFT and biological studies of transition metal complexes of Schiff base derived from 2-aminobenzamide, pyrrole and furan aldehyde

    NASA Astrophysics Data System (ADS)

    Tyagi, Prateek; Chandra, Sulekh; Saraswat, B. S.; Sharma, Deepansh

    2015-05-01

    A series of two biologically active Schiff base ligands L1, L2 have been synthesized in equimolar reaction of 2-aminobenzamide with pyrrol-2-carboxaldehyde and furan-2-carboxaldehyde. The synthesized Schiff bases were used for complexation with different metal ions like Co(II), Ni(II) and Cu(II) by using a molar ratio of ligand: metal as 2:1. The characterization of newly formed complexes was done by 1H NMR, UV-Vis, TGA, IR, mass spectrophotometry, EPR and molar conductivity studies. The thermal studies suggested that the complexes are more stable as compared to ligand. In DFT studies the geometries of Schiff bases and metal complexes were fully optimized with respect to the energy using the 6-31+g(d,p) basis set. On the basis of the spectral studies an octahedral geometry has been assigned for Co(II) and Ni(II) complexes and distorted octahedral geometry for Cu(II) complexes. All the synthesized compounds, were studied for their in vitro antimicrobial activities, against four bacterial strains and two fungal strains by using serial dilution method. The data also revealed that the metal complexes showed better activity than the ligands due to chelation/coordination.

  16. Bio-sensitive activities of coordination compounds containing 1,10-phenanthroline as co-ligand: synthesis, structural elucidation and dna binding properties of metal(II) complexes.

    PubMed

    Raman, Natarajan; Mahalakshmi, Rajkumar; Mitu, Liviu

    2014-10-15

    Present work reports the DNA binding and cleavage characteristics of a series of mixed-ligand complexes having the composition [M(L)(phen)2]Cl2 (where M=Cu(II), Ni(II), Co(II) and Zn(II) and phen as co-ligand) in detail. Their structural features and other properties have been deduced from their elemental analyses, magnetic susceptibility and molar conductivity as well as from IR, UV-Vis, (1)H NMR and EPR spectral studies. The UV-Vis, magnetic susceptibility and EPR spectral data of metal complexes suggest an octahedral geometry. The binding properties of these complexes with calf thymus DNA (CT-DNA) have been explored using electronic absorption spectroscopy, viscosity measurement, cyclic voltammetry and differential pulse voltammetry. The DNA-binding constants for Cu(II), Ni(II), Co(II), and Zn(II) complexes are 6.14×10(5)M(-1), 1.8×10(5)M(-1), 6.7×10(4)M(-1) and 2.5×10(4)M(-1) respectively. Detailed analysis reveals that these complexes interact with DNA through intercalation binding. Nuclease activity has also been investigated by gel electrophoresis. Moreover, the synthesized Schiff base and its mixed-ligand complexes have been screened for antibacterial and antifungal activities. The data reveal that the complexes exhibit higher activity than the parent ligand.

  17. Mononuclear thiocyanate containing nickel(II) and binuclear azido bridged nickel(II) complexes of N4-coordinate pyrazole based ligand: Syntheses, structures and magnetic properties

    NASA Astrophysics Data System (ADS)

    Solanki, Ankita; Monfort, Montserrat; Kumar, Sujit Baran

    2013-10-01

    Two mononuclear nickel(II) complexes [NiL1(NCS)2] (1) and [NiL2(NCS)2] (2) and two azido bridged binuclear nickel(II) complexes [Ni(()2()2] (3) and [Ni(()2()2] (4), where L1, L2, L1‧ and L2‧ are N,N-diethyl-N‧,N‧-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)ethane-1,2-diamine (L1), N,N-bis((1H-pyrazol-1-yl)methyl)-N‧,N‧-diethylethane-1,2-diamine (L2), N,N-diethyl-N‧-((3,5-dimethyl-1H-pyrazol-1-yl)methyl)ethane-1,2-diamine (L1‧) and N-((1H-pyrazol-1-yl)methyl)-N‧,N‧-diethylethane-1,2-diamine (L2‧) have been synthesized and characterized by microanalyses and physico-chemical methods. Single crystal X-ray diffraction analyses revealed that complexes 1 and 2 are mononuclear NCS- containing Ni(II) complex with octahedral geometry and complexes 3 and 4 are end-on (μ-1,1) azido bridged binuclear Ni(II) complexes with distorted octahedral geometry. Variable temperature magnetic studies of the complexes 3 and 4 display ferromagnetic interaction with J values 19 and 32 cm-1, respectively.

  18. Transition metal complexes of isonicotinic acid (2-hydroxybenzylidene)hydrazide

    NASA Astrophysics Data System (ADS)

    Abou-Melha, Khlood S.

    2008-06-01

    A new series of transition metal complexes of Schiff base isonicotinic acid (2-hydroxybenzylidene)hydrazide, HL, have been synthesized. The Schiff base reacted with Cu(II), Ni(II), Co(II), Mn(II), Fe(III) and UO 2(II) ions as monobasic tridentate ligand to yield mononuclear complexes of 1:2 (metal:ligand) except that of Cu(II) which form complex of 1:1 (metal:ligand). The ligand and its metal complexes were characterized by elemental analyses, IR, UV-vis, mass and 1H NMR spectra, as well as magnetic moment, conductance measurements, and thermal analyses. All complexes have octahedral configurations except Cu(II) complex which has an extra square planar geometry distorted towards tetrahedral. While, the UO 2(II) complex has its favour hepta-coordination. The ligand and its metal complexes were tested against one strain Gram +ve bacteria ( Staphylococcus aureus), Gram -ve bacteria (Escherichia coli) , and Fungi ( Candida albicans). The tested compounds exhibited higher antibacterial activities.

  19. Transition metal complexes of isonicotinic acid (2-hydroxybenzylidene)hydrazide.

    PubMed

    Abou-Melha, Khlood S

    2008-06-01

    A new series of transition metal complexes of Schiff base isonicotinic acid (2-hydroxybenzylidene)hydrazide, HL, have been synthesized. The Schiff base reacted with Cu(II), Ni(II), Co(II), Mn(II), Fe(III) and UO2(II) ions as monobasic tridentate ligand to yield mononuclear complexes of 1:2 (metal:ligand) except that of Cu(II) which form complex of 1:1 (metal:ligand). The ligand and its metal complexes were characterized by elemental analyses, IR, UV-vis, mass and 1H NMR spectra, as well as magnetic moment, conductance measurements, and thermal analyses. All complexes have octahedral configurations except Cu(II) complex which has an extra square planar geometry distorted towards tetrahedral. While, the UO2(II) complex has its favour hepta-coordination. The ligand and its metal complexes were tested against one strain Gram +ve bacteria (Staphylococcus aureus), Gram -ve bacteria (Escherichia coli), and Fungi (Candida albicans). The tested compounds exhibited higher antibacterial activities.

  20. Metal complexes derived from hydrazoneoxime ligands: V. Spectral and structural studies on diacetylmonoxime n-alkanoylhydrazones and their nickel(II) and copper(II) complexes

    NASA Astrophysics Data System (ADS)

    Salem, Nahed M. H.; El Sayed, Laila; Haase, Wolfgang; Iskander, Magdi F.

    2015-01-01

    A series of diacetylmonoxime n-alkanoylhydrazones (H2Ln, n = 4, 5, 6, 12 and 16) were prepared by the condensation of diacetylmonoxime with the corresponding n-alkanoylhydrazine in ethanol. The X-ray crystal structure of diacetylmonoxime octadecanoyl hydrazone has been solved and its molecular and supramolecular structures have been discussed. Both neutral dinuclear Cu(II) and Ni(II) complexes, [{M(Ln)}2] (M = Cu, Ni and n = 4, 5, 6, 12 and 16) as well as cationic dinuclear Cu(II) complexes, [Cu2(Ln)(HLn)]NO3 (n = 12 and 16) have been also prepared and characterized by elemental analyses, FD- and ESI-mass spectra as well as IR, UV-Vis, 1H NMR, 13C NMR spectra. Variable temperature magnetic susceptibility measurements for dinuclear Cu(II) complexes have been also discussed.

  1. Metal complexes derived from hydrazoneoxime ligands: V. Spectral and structural studies on diacetylmonoxime n-alkanoylhydrazones and their nickel(II) and copper(II) complexes.

    PubMed

    Salem, Nahed M H; El Sayed, Laila; Haase, Wolfgang; Iskander, Magdi F

    2015-01-05

    A series of diacetylmonoxime n-alkanoylhydrazones (H₂L(n), n=4, 5, 6, 12 and 16) were prepared by the condensation of diacetylmonoxime with the corresponding n-alkanoylhydrazine in ethanol. The X-ray crystal structure of diacetylmonoxime octadecanoyl hydrazone has been solved and its molecular and supramolecular structures have been discussed. Both neutral dinuclear Cu(II) and Ni(II) complexes, [{M(L(n))}₂] (M=Cu, Ni and n=4, 5, 6, 12 and 16) as well as cationic dinuclear Cu(II) complexes, [Cu₂(L(n))(HL(n))]NO₃ (n=12 and 16) have been also prepared and characterized by elemental analyses, FD- and ESI-mass spectra as well as IR, UV-Vis, (1)H NMR, (13)C NMR spectra. Variable temperature magnetic susceptibility measurements for dinuclear Cu(II) complexes have been also discussed.

  2. Acireductone dioxygenase- (ARD-) type reactivity of a nickel(II) complex having monoanionic coordination of a model substrate: product identification and comparisons to unreactive analogues.

    PubMed

    Szajna-Fuller, Ewa; Rudzka, Katarzyna; Arif, Atta M; Berreau, Lisa M

    2007-07-09

    A mononuclear Ni(II) complex ([(6-Ph2TPA)Ni(PhC(O)C(OH)C(O)Ph)]ClO4 (1)), supported by the 6-Ph2TPA chelate ligand (6-Ph2TPA = N,N-bis((6-phenyl-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine) and containing a cis-beta-keto-enolate ligand having a C2 hydroxyl substituent, undergoes reaction with O2 to produce a Ni(II) monobenzoate complex ([(6-Ph2TPA)Ni(O2CPh)]ClO4 (3)), CO, benzil (PhC(O)C(O)Ph), benzoic acid, and other minor unidentified phenyl-containing products. Complex 3 has been identified through independent synthesis and was characterized by X-ray crystallography, 1H NMR, FAB-MS, FTIR, and elemental analysis. A series of cis-beta-keto-enolate Ni(II) complexes supported by the 6-Ph2TPA ligand ([(6-Ph2TPA)Ni(PhC(O)CHC(O)Ph)]ClO4 (4), [(6-Ph2TPA)Ni(CH3C(O)CHC(O)CH3)]ClO4 (5), and [(6-Ph2TPA)Ni(PhC(O)CHC(O)C(O)Ph) (6)) have been prepared and characterized. While these complexes exhibit structural and/or spectroscopic similarity to 1, all are unreactive with O2. The results of this study are discussed in terms of relevance to Ni(II)-containing acireductone dioxygenase enzymes, as well as in the context of recently reported cofactor-free, quercetin, and beta-diketone dioxygenases.

  3. Synthesis, characterization and application of enrofloxacin complexes as thermal stabilizers for rigid poly(vinyl chloride).

    PubMed

    el-Gamel, Nadia E A; Mohamed, Riham R; Zayed, M A

    2012-02-14

    Synthesis and characterization of both binary Co(II)- (1), Ni(II)- (2) complexes with enrofloxacin drug (HL(1)) and ternary Co(II)- (3), Ni(II)- (4) complexes in presence of DL-alanine (H(2)L(2)) are reported using physico-chemical techniques. The antimicrobial activity of these complexes has been screened against two gram-positive and two gram-negative bacteria. Antifungal activity against two different fungi has been evaluated and compared with reference drug. All the binary and ternary complexes showed remarkable potential antimicrobial activity higher than the recommended standard agents. Ni(II)-complexes exhibited higher potency as compared to the parent drug against bacterial and fungal strain. In addition, it was of interest to investigate the reported complexes as thermal stabilizers and co-stabilizers for rigid PVC in air at 180 °C. Their high stabilizing efficiency is detected by their high induction period values (T(s)) compared with some of the common reference stabilizers used industrially, such as dibasic lead carbonate (DBLC) and calcium-zinc soap. Blending these complexes with some of the reference stabilizers in different ratios had a synergistic effect on both induction period as it gave better thermal stability and lower extent of discoloration. The stabilizing efficiency is attributed at least partially to the ability of the metal complex stabilizer to be incorporated in the polymeric chains, thus disrupting the chain degradation and replace the labile chlorine atoms on PVC chains by a relatively more s moiety of the inorganic stabilizer. Their amenability to use as a biomedical additives for PVC, has afforded them great potential for various medical applications.

  4. Quadrupole ion trap studies of the structure and reactivity of transition metal ion pair complexes

    PubMed

    Vachet; Callahan

    2000-03-01

    Ion pairs are common species observed in the electrospray mass spectra of transition metal coordination complexes. To understand the nature of these ion pairs, a systematic study of the gas-phase chemistry of these species using ion-molecule reactions and collision-induced dissociation (CID) was carried out. Ion pair complexes of the type MLnX+ (where M is Mn(II), Fe(II), Co(II), Ni(II), Cu(II) or Zn(II), L is 1,10-phenanthroline, 2,2'-bipyridine, ethylenediamine, diethylenetriamine or 1,4,8,11-tetraazacyclotetradecane and X is Cl-, NO3-, acetylacetonate, ClO4-, acetate or SCN-) were studied. Ion-molecule reactions can distinguish whether the counterion in an ion pair is an inner- or outer-sphere ligand and can determine the coordination mode of the counterion. In addition, CID and ion-molecule reactions reveal some interesting chemistry of these complexes and unique coordination modes for some of the anions studied here were inferred from the ion-molecule reactions. For example, the thiocyanate ion is found to coordinate in a bidentate fashion in Zn(II) and Ni(II) complexes, contrasting behavior typically observed in solution. Also, certain Co(II) and Fe(II) ion pair complexes undergo oxidation reactions in which species such as dioxygen and nitric oxide from the counterions ClO4- and NO3- are transferred to the Co(II) and Fe(II) complexes, showing the inherent affinity of these metals for these molecules. These complexes were also studied by ion-molecule reactions and CID. Dioxygen in complexes formed by CID is demonstrated to be bidentate, suggesting the formation of a peroxo ligand with concurrent oxidation of the metal.

  5. Binuclear copper(II), cobalt(II) and nickel(II) complexes of N1-ethyl-N2-(pyridin-2-yl) hydrazine-1,2-bis(carbothioamide): structural, spectral, pH-metric and biological studies.

    PubMed

    El-Gammal, O A; Abu El-Reash, G M; El-Gamil, M M

    2012-10-01

    Binuclear Cu(II), Co(II) and Ni(II) complexes derived from N(1)-ethyl-N(2)-(pyridin-2-yl) hydrazine-1,2-bis(carbothioamide) (H(2)PET) have been prepared and characterized by elemental analysis, spectral (IR, UV-vis, EI mass, ESR and (1)HNMR) and magnetic measurements. The isolated complexes assigned the general formula, [M(HPET)(H(2)O)(n)Cl](2)·xH(2)O where M=Cu(II), Co(II) and Ni(II), n=2, 1, 0 and x=0, 0.5 and 0, respectively. IR data revealed that the ligand behaves as monobasic tridentate through (CN)(py), (C-S) and new azomethine, (NC)(∗) groups in the Co(II) complex but in Cu(II) complex, the ligand coordinate via both (CS) groups, one of them in thiol form as well as the new azomethine group. In Ni(II) complex, H(2)PET acts as NSNS monobasic tetradente via (CN)(py), (C-S), (CS) and the new azomethine, (NC)(∗) groups. An octahedral geometry is proposed for all complexes. pH- metric titration was carried out in 50% dioxane-water mixture at 298, 308 and 318 °K, respectively and the dissociation constant of the ligand as well as the stability constants of its complexes were evaluated. Also the kinetic and thermodynamic parameters for the different thermal decomposition steps of the complexes were determined by Coats-Redfern and Horowitz-Metzger methods. Moreover, the anti-oxidant, anti-hemolytic, and cytotoxic activities of the compounds have been tested.

  6. Synthesis, spectroscopic, thermal and DFT calculations of 2-(3-amino-2-hydrazono-4-oxothiazolidin-5-yl) acetic acid binuclear metal complexes

    NASA Astrophysics Data System (ADS)

    Hassan, Walid M. I.; Badawy, M. A.; Mohamed, Gehad G.; Moustafa, H.; Elramly, Salwa

    2013-07-01

    The binuclear complexes of 2-(3-amino-2-hydrazono-4-oxothiazolidin-5-yl) acetic acid ligand (HL) with Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) ions were prepared and their stoichiometry was determined by elemental analysis. The stereochemistry of the studied series of metal complexes was established by analyzing their infrared, 1H NMR spectra and the magnetic moment measurements. According to the elemental analysis data, the complexes were found to have the formulae [Fe2L(H2O)8]Cl5 and [M2L(H2O)8]Cl3 (M = Co(II), Ni(II), Cu(II) and Zn(II)). The present analyses demonstrate that all metal ions coordinated to the ligand via O(9), O(11), N(16) and N(18) atoms. Thermal decomposition studies of the ligand-metal complexes have been performed to verify the status of water molecules present in these metal complexes and their general decomposition pattern. Density Functional Theory (DFT) calculations at the B3LYP/6-31G* level of theory have been carried out to investigate the equilibrium geometry of the ligand and complexes. Moreover, charge density distribution, extent of distortion from regular geometry, dipole moment and orientation have been performed and discussed.

  7. Structural, spectral, thermal and biological studies on (E)-2-(1-(4-hydroxyphenyl)ethylidene)-N-(pyridin-2-yl)hydrazinecarbothioamide and its metal complexes

    NASA Astrophysics Data System (ADS)

    Yousef, T. A.; Abu El-Reash, G. M.; El-Rakhawy, E. R.

    2014-12-01

    Schiff base complexes of Mn(II), Co(II), Ni(II), Cu(II), Cd(II), Hg(II) and U(VI)O2 with (E)-2-(1-(4-hydroxyphenyl)ethylidene)-N-(pyridin-2-yl)hydrazinecarbothioamide (H2PHAT) were synthesized and characterized by different physicochemical methods, elemental analysis, (UV-vis, IR and 1H NMR spectra) and thermal analysis (TG and DTG) techniques. Spectral data showed that H2PHAT behaves as a NS bidentate ligand through both thione sulphur or thiol sulphur and the nitrogen of the pyridine ring or azomethine nitrogen, NSN tridentate ligand through both thione sulphur or thiol sulphur, the nitrogen of the pyridine ring and azomethine nitrogen. ESR spectrum data for Cu(II) solid complex confirms the square planar state is the most fitted one for the coordinated structure. The kinetic parameters were determined for each thermal degradation stage of the complexes using Coats-Redfern and Horowitz-Metzger methods. From modeling studies, the bond length, bond angle, HOMO, LUMO and dipole moment had been calculated to confirm the geometry of the ligand and their investigated complexes. The biological activity was tested against DNA showing that Cd(II), U(VI)O2, Ni(II) and Mn(II) complexes had powerful and complete degradation effect. Also, the ligand and its complexes were screened against Bacillus thuringiensis as Gram-positive bacteria and Pseudomonas aeuroginosa as Gram-negative bacteria using the inhibitory zone diameter.

  8. Synthesis, spectral and thermal studies of some transition metal mixed ligand complexes: Modeling of equilibrium composition and biological activity

    NASA Astrophysics Data System (ADS)

    Neelakantan, M. A.; Sundaram, M.; Nair, M. Sivasankaran

    2011-09-01

    Several mixed ligand Ni(II), Cu(II) and Zn(II) complexes of 2-amino-3-hydroxypyridine (AHP) and imidazoles viz., imidazole (him), benzimidazole (bim), histamine (hist) and L-histidine (his) have been synthesized and characterized by elemental and spectral (vibrational, electronic, 1H NMR and EPR) data as well as by magnetic moment values. On the basis of elemental analysis and molar conductance values, all the complexes can be formulated as [MAB]Cl except histidine complexes as MAB. Thermogravimetric studies reveal the presence of coordinated water molecules in most of the complexes. From the magnetic measurements and electronic spectral data, octahedral structure was proposed for Ni(II) and Cu(II)-AHP-his, tetrahedral for Cu(II)-AHP-him/bim/hist, but square planar for the Cu(II)-AHP complex. The g∥/ A∥ calculated supports tetrahedral environment around the Cu(II) in Cu(II)-AHP-him/bim/hist and distorted octahedral for Cu(II)-AHP-his complexes. The morphology of the reported metal complexes was investigated by scanning electron micrographs (SEM). The potentiometric study has been performed in aqueous solution at 37 °C and I = 0.15 mol dm -3 NaClO 4. MABH, MAB and MAB 2 species has been identified in the present systems. Proton dissociation constants of AHP and stability constants of metal complexes were determined using MINIQUAD-75. The most probable structure of the mixed ligand species is discussed based upon their stability constants. The in vitro biological activity of the complexes was tested against the Gram positive and Gram negative bacteria, fungus and yeast. The oxidative DNA cleavage studies of the complexes were performed using gel electrophoresis method. Cu(II) complexes have been found to promote DNA cleavage in presence of biological reductant such as ascorbate and oxidant like hydrogen peroxide.

  9. Hydrothermal Syntheses and Crystal Structures of Ni(II), Co(II), and Cu(II), Bis( trans-4-pyridylacrylate) Interpenetration Networks

    NASA Astrophysics Data System (ADS)

    Liu, Yen-Hsiang; Lin, Chia-Shiang; Chen, Shiang-Ying; Tsai, Hui-Lien; Ueng, Chuen-Her; Lu, Kuang-Lieh

    2001-02-01

    Three metal-organic polymeric networks, Ni(C8H6NO2)2(H2O)2 (1), Co(C8H6NO2)2 (2), and Cu(C8H6NO2)2(H2O)2 (3), were synthesized by the hydrothermal method. Single-crystal X-ray analysis revealed that within these compounds metal centers are linked through trans-4-pyridylacrylate ligands to form interpenetrating infinite networks. The Ni(II) and Cu(II) compounds possess an overlay of interpenetrating square grid layers, whereas the Co(II) compound possesses interpenetrating diamondoid networks. Comparing these three compounds, the formation of cavities potentially for guest molecule inclusion within the interpenetrating networks could be achieved by taking advantage of the coordination nature of metals. Crystal structures of all three compounds were determined by single-crystal X-ray diffraction methods and solved by direct method. Crystal data for 1: orthorhombic, space group Pbcn, a=13.735(3) Å, b=6.995(2) Å, c=16.723(3) Å, V=1606.7(6) Å3, Z=4, final refinement (I>2σ(I)): R1=0.0296, wR2=0.0843. Crystal data for 2: monoclinic, space group Cc, a=11.5717(9) Å, b=21.2838(16) Å, c=8.5504(7) Å, β=130.5210(10)°, V=1600.8(2) Å3, Z=4, final refinement (I>2σ(I)): R1=0.0347, wR2=0.0879. Crystal data for 3: orthorhombic, space group Pbcn, a=13.6844(13) Å, b=7.5053(8) Å, c=15.929(4) Å, V=1636.0(5) Å3, Z=4, final refinement (I>2σ(I)), R1=0.0299, wR2=0.0787.

  10. Immobilization of heavy metal ions (CuII, CdII, NiII, and PbII) by broiler litter-derived biochars in water and soil.

    PubMed

    Uchimiya, Minori; Lima, Isabel M; Thomas Klasson, K; Chang, SeChin; Wartelle, Lynda H; Rodgers, James E

    2010-05-12

    Chars, a form of environmental black carbon resulting from incomplete burning of biomass, can immobilize organic contaminants by both surface adsorption and partitioning mechanisms. The predominance of each sorption mechanism depends upon the proportion of organic to carbonized fractions comprising the sorbent. Information is currently lacking in the effectiveness of char amendment for heavy metal immobilization in contaminated (e.g., urban and arms range) soils where several metal contaminants coexist. The present study employed sorbents of a common biomass origin (broiler litter manure) that underwent various degrees of carbonization (chars formed by pyrolysis at 350 and 700 degrees C and steam-activated analogues) for heavy metal (Cd(II), Cu(II), Ni(II), and Pb(II)) immobilization in water and soil. ATR-FTIR, (1)H NMR, and Boehm titration results suggested that higher pyrolysis temperature and activation lead to the disappearance (e.g., aliphatic -CH(2) and -CH(3)) and the formation (e.g., C-O) of certain surface functional groups, portions of which are leachable. Both in water and in soil, pH increase by the addition of basic char enhanced the immobilization of heavy metals. Heavy metal immobilization resulted in nonstoichiometric release of protons, that is, several orders of magnitude greater total metal concentration immobilized than protons released. The results suggest that with higher carbonized fractions and loading of chars, heavy metal immobilization by cation exchange becomes increasingly outweighed by other controlling factors such as the coordination by pi electrons (C=C) of carbon and precipitation.

  11. Spectroscopic and density functional theory investigation of novel Schiff base complexes

    NASA Astrophysics Data System (ADS)

    Hassan, Walid M. I.; Zayed, Ehab M.; Elkholy, Asmaa K.; Moustafa, H.; Mohamed, Gehad G.

    2013-02-01

    Novel Schiff base (H2L, 1,2-bis[(2-(2-mercaptophenylimino)methyl)phenoxy] ethane) derived from condensation of bisaldehyde and 2-aminothiophenol was prepared in a molar ratio 1:2. The ligand and its metal complexes are fully characterized with analytical and spectroscopic techniques. The metal complexes with Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and Th(IV) have been prepared and characterized by elemental analyses, IR and 1H-NMR spectroscopy, thermal and magnetic measurements. The results suggested that the Schiff base is a bivalent anion with hexadentate OONNSS donors derived from the etheric oxygen (O, O'), azomethine nitrogen (N, N') and thiophenolic sulphur (S, S'). The formulae of the complexes were found to be [ML]·xH2O (M = Mn(II) (x = 0), Co(II) (x = 1), Ni(II), (x = 1), Cu(II) (x = 2) and Zn(II) (x = 0)) and [ML]·nCl (M = Cr(III) (n = 1), Fe(III) (n = 1) and Th(IV) (n = 2)). The thermogravimetric analysis of the complexes shows metal oxide remaining as the final product at 700-1000 °C. Density functional theory at the B3LYP/6-31G* level of theory was used to investigate molecular geometry, Mulliken atomic charges and energetics. The synclinal-conformer was found to be responsible for complex formation. The calculation showed that ligand has weak field. Structural deformation and the dihedral angles rotation during complexation were investigated. The binding energy of each complex was calculated. The calculated results are in good agreement with experimental data.

  12. Spin crossover iron(II) coordination polymer chains: syntheses, structures, and magnetic characterizations of [Fe(aqin)2(μ2-M(CN)4)] (M = Ni(II), Pt(II), aqin = quinolin-8-amine).

    PubMed

    Setifi, Fatima; Milin, Eric; Charles, Catherine; Thétiot, Franck; Triki, Smail; Gómez-García, Carlos J

    2014-01-06

    New Fe(II) coordination polymeric neutral chains of formula [Fe(aqin)2(μ2-M(CN)4)] (M = Ni(II) (1) and Pt(II) (2)) (aqin = Quinolin-8-amine) have been synthesized and characterized by infrared spectroscopy, X-ray diffraction, and magnetic measurements. The crystal structure determinations of 1-2 reveal in both cases a one-dimensional structure in which the planar [M(CN)4](2-) (M = Ni(II) (1) and Pt(II) (2)) anion acts as a μ2-bridging ligand, and the two aqin molecules as chelating coligands. Examination of the intermolecular contacts in the two compounds reveals that the main contacts are ascribed to hydrogen bonding interactions involving the amine groups of the aqin chelating ligands and the nitrogen atoms of the two non bridging CN groups of the [M(CN)4](2-) (M = Ni(II) (1) and Pt(II) (2)) anion. The average values of the six Fe-N distances observed respectively at room temperature (293 K) and low temperature (120 K), that is, 2.142(3) and 2.035(2) Å for 1, and 2.178(3) and 1.990(2) Å for 2, and the thermal variation of the cell parameters (performed on 2) are indicative of the presence of an abrupt HS-LS spin crossover (SCO) transition in both compounds. The thermal dependence of the product of the molar magnetic susceptibility times the temperature (χmT), in cooling and warming modes, confirms the SCO behavior at about 145 and 133 K in 1 and 2, respectively, and reveals the presence of a small thermal hysteresis of about 2 K for each compound.

  13. Microwave Assisted Synthesis, Spectral and Antifungal Studies of 2-Phenyl-N,N′-bis(pyridin-4-ylcarbonyl)butanediamide Ligand and Its Metal Complexes

    PubMed Central

    Shiekh, Rayees Ahmad; Malik, Maqsood Ahmad; Al-Thabaiti, Shaeel Ahmed; Nabi, Arshid

    2014-01-01

    2-Phenyl-N,N′-bis(pyridin-4-ylcarbonyl)butanediamide ligand with a series of transition metal complexes has been synthesized via two routes: microwave irradiation and conventional heating method. Microwave irritation method happened to be the efficient and versatile route for the synthesis of these metal complexes. These complexes were found to have the general composition M(L)Cl2/M(L)(CH3COO)2 (where M = Cu(II), Co(II), Ni(II), and L = ligand). Different physical and spectroscopic techniques were used to investigate the structural features of the synthesized compounds, which supported an octahedral geometry for these complexes. In vitro antifungal activity of the ligand and its metal complexes revealed that the metal complexes are highly active compared to the standard drug. Metal complexes showed enhanced activity compared to the ligand, which is an important step towards the designing of antifungal drug candidates. PMID:24772018

  14. Synthesis, spectroscopic characterization and biological evaluation studies of Schiff's base derived from naphthofuran-2-carbohydrazide with 8-formyl-7-hydroxy-4-methyl coumarin and its metal complexes

    NASA Astrophysics Data System (ADS)

    Halli, M. B.; Sumathi, R. B.; Kinni, Mallikarjun

    2012-12-01

    Metal complexes of the type ML2, where M = Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II) and L = Schiff's base derived from the condensation of naphthofuran-2-carbohydrazide with 8-formyl-7-hydroxy-4-methyl coumarin have been synthesized. The chelation of the complexes have been elucidated in the light of analytical, IR, UV-vis, 1H NMR, mass, ESR spectral data, thermal and magnetic studies. The measured molar conductance values indicate that, the complexes are non-electrolytic in nature. The redox behavior of one of the synthesized metal complexes was investigated by cyclic voltammetry. The Schiff's base and its metal complexes have been screened for their in vitro antibacterial and antifungal activities by MIC method. The DNA cleavage activities of all the complexes were studied by agarose gel electrophoresis method. In addition, the free ligand along with its complexes has been studied for their antioxidant activity.

  15. Regioselective synthesis and photophysical and electrochemical studies of 20-substituted cyanine dye-purpurinimide conjugates: incorporation of Ni(II) into the conjugate enhances its tumor-uptake and fluorescence-imaging ability.

    PubMed

    Ethirajan, Manivannan; Chen, Ping; Ohulchanskyy, Tymish Y; Goswami, Lalit N; Gupta, Anurag; Srivatsan, Avinash; Dobhal, Mahabeer P; Missert, Joseph R; Prasad, Paras N; Kadish, Karl M; Pandey, Ravindra K

    2013-05-17

    We report herein a simple and efficient approach to the synthesis of a variety of meso-substituted purpurinimides. The reaction of meso-substituted purpurinimide with N-bromosuccinimide regioselectively introduced a bromo functionality at the 20-position, which on further reaction with a variety of boronic acids under Suzuki reaction conditions yielded the corresponding meso-substituted analogues. Interestingly, the free base and the metalated analogues showed remarkable differences in photosensitizing efficacy (PDT) and tumor-imaging ability. For example, the free-base conjugate showed significant in vitro PDT efficacy, but limited tumor avidity in mice bearing tumors, whereas the corresponding Ni(II) derivative did not produce any cell kill, but showed excellent tumor-imaging ability at a dose of 0.3 μmol kg(-1) at 24, 48, and 72 h post-injection. The limited PDT efficacy of the Ni(II) analogue could be due to its inability to produce singlet oxygen, a key cytotoxic agent required for cell kill in PDT. Based on electrochemical and spectroelectrochemical data in DMSO, the first one-electron oxidation (0.52 V vs. SCE) and the first one-electron reduction (-0.57-0.67 V vs. SCE) of both the free base and the corresponding Ni(II) conjugates are centered on the cyanine dye, whereas the second one-electron reduction (-0.81 V vs. SCE) of the two conjugates is assigned to the purpurinimide part of the molecule. Reduction of the cyanine dye unit is facile and occurs prior to reduction of the purpurinimide group, which suggests that the cyanine dye unit as an oxidant could be the driving force for quenching of the excited triplet state of the molecules. An interaction between the cyanine dye and the purpurinimide group is clearly observed in the free-base conjugate, which compares with a negligible interaction between the two functional groups in the Ni(II) conjugate. As a result, the larger HOMO-LUMO gap of the free-base conjugate and the corresponding smaller

  16. Structure, Spectra, and DFT Simulation of Nickel Benzazolate Complexes with Tris(2-aminoethyl)amine Ligand.

    PubMed

    Cerezo, Javier; Requena, Alberto; Zúñiga, José; Piernas, María José; Santana, M Dolores; Pérez, José; García, Luís

    2017-03-20

    Benzazolate complexes of Ni(II), [Ni(pbz)(tren)]ClO4 (pbz = 2-(2'-hydroxyphenyl)-benzimidazole (pbm), 1, 2-(2'-hydroxyphenyl)-benzoxazole (pbx), 2, 2-(2'-hydroxyphenyl)-benzothiazole (pbt), 3; tren = tris(2-aminoethyl)amine), are prepared by self-assembly reaction and structurally characterized. Theoretical DFT simulations are carried out to reproduce the features of their crystal structures and their spectroscopic and photophysic properties. The three complexes are moderately luminescent at room temperature both in acetonitrile solution and in the solid state. The simulations indicate that the absorption spectrum is dominated by two well-defined transitions, and the electronic density concentrates in three MOs around the benzazole ligands. The Stokes shifts of the emission spectra of complexes 1-3 are determined by optimizing the electronic excited state.

  17. Synthesis, physico-chemical studies of manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) complexes with some p-substituted acetophenone benzoylhydrazones and their antimicrobial activity.

    PubMed

    Singh, Vinod P; Singh, Shweta; Katiyar, Anshu

    2009-04-01

    Complexes of the type [M(pabh)(H2O)Cl], [M(pcbh)(H2O)Cl] and [M(Hpabh)(H2O)2 (SO4)] where, M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II); Hpabh = p-amino acetophenone benzoyl hydrazone and Hpcbh = p-chloro acetophenone benzoyl hydrazone have been synthesized and characterized with the help of elemental analyses, electrical conductance, magnetic susceptibility measurements, electronic, ESR and IR spectra, thermal (TGA & DTA) and X-ray diffraction studies. Co(II), Ni(II) and Cu(II) chloride complexes are square planar, whereas their sulfate complexes have spin-free octahedral geometry. ESR spectra of Cu(II) complexes with Hpabh are axial and suggest d(x(2)-y(2) as the ground state. The ligand is bidentate bonding through > C = N--and deprotonated enolate group in all the chloro complexes, whereas, >C = N and >C = O groups in all the sulfato complexes. Thermal studies (TGA & DTA) on [Cu(Hpabh)(H2O)2(SO4)] indicate a multistep decomposition pattern, which are both exothermic and endothermic in nature. X-ray powder diffraction parameters for [Co(pabh)(H2O)Cl] and [Ni(Hpabh)(H2O)2(SO4)] correspond to tetragonal and orthorhombic crystal lattices, respectively. The ligands as well as their complexes show a significant antifungal and antibacterial activity. The metal complexes are more active than the ligand.

  18. Synthesis and Reactivity of Four- and Five-Coordinate Low-Spin Cobalt(II) PCP Pincer Complexes and Some Nickel(II) Analogues.

    PubMed

    Murugesan, Sathiyamoorthy; Stöger, Berthold; Carvalho, Maria Deus; Ferreira, Liliana P; Pittenauer, Ernst; Allmaier, Günter; Veiros, Luis F; Kirchner, Karl

    2014-11-10

    Anhydrous CoCl2 or [NiCl2(DME)] reacts with the ligand PCP(Me)-iPr (1) in the presence of nBuLi to afford the 15e and 16e square planar complexes [Co(PCP(Me)-iPr)Cl] (2) and [Ni(PCP(Me)-iPr)Cl] (3), respectively. Complex 2 is a paramagnetic d(7) low-spin complex, which is a useful precursor for a series of Co(I), Co(II), and Co(III) PCP complexes. Complex 2 reacts readily with CO and pyridine to afford the five-coordinate square-pyramidal 17e complexes [Co(PCP(Me)-iPr)(CO)Cl] (4) and [Co(PCP(Me)-iPr)(py)Cl] (5), respectively, while in the presence of Ag(+) and CO the cationic complex [Co(PCP(Me)-iPr)(CO)2](+) (6) is afforded. The effective magnetic moments μeff of all Co(II) complexes were derived from the temperature dependence of the inverse molar magnetic susceptibility by SQUID measurements and are in the range 1.9 to 2.4 μB. This is consistent with a d(7) low-spin configuration with some degree of spin-orbit coupling. Oxidation of 2 with CuCl2 affords the paramagnetic Co(III) PCP complex [Co(PCP(Me)-iPr)Cl2] (7), while the synthesis of the diamagnetic Co(I) complex [Co(PCP(Me)-iPr)(CO)2] (8) was achieved by stirring 2 in toluene with KC8 in the presence of CO. Finally, the cationic 16e Ni(II) PCP complex [Ni(PCP(Me)-iPr)(CO)](+) (10) was obtained by reacting complex 3 with 1 equiv of AgSbF6 in the presence of CO. The reactivity of CO addition to Co(I), Co(II), and Ni(II) PCP square planar complexes of the type [M(PCP(Me)-iPr)(CO)] (n) (n = +1, 0) was investigated by DFT calculations, showing that formation of the Co species, 6 and 8, is thermodynamically favorable, while Ni(II) maintains the 16e configuration since CO addition is unfavorable in this case. X-ray structures of most complexes are provided and discussed. A structural feature of interest is that the apical CO ligand in 4 deviates significantly from linearity, with a Co-C-O angle of 170.0(1)°. The DFT-calculated value is 172°, clearly showing that this is not a packing but an electronic effect.

  19. Synthesis, characterization and light harvesting properties of nickel(II) diimine dithiolate complexes.

    PubMed

    Kumar, Abhinav; Auvinen, Sami; Trivedi, Manoj; Chauhan, Ratna; Alatalo, Matti

    2013-11-01

    Four Ni(II) diimine dithiolato complexes viz. [Ni{(S2C2Ph2)(1,10-Phenanthroline)}] (2), [Ni{(S2C2Ph2)(3,3'-dicarboxy-2,2'-bipyridyl)}] (3), [Ni{(S2C2Ph2)(4,4'-dicarboxy-2,2'-bipyridyl)}] (4) [Ni{(S2C2Ph2)(2,2'-bipyridyl)}] (5) have been prepared from [Ni(S2C2Ph2)2] (1) and characterized by microanalyses, UV-Vis, IR, (1)H and (13)C NMR. Attempts have been made to explain the nature of charge transfer in these molecules through quantum chemical calculations. The light harvesting properties of all the compounds have been studied using these compounds as photosensitizers in TiO2-based DSSC. The change in position of anchoring group on diimine derivative leads to different structural, electronic and light harvesting properties about the Ni(II) diimine dithiolate dyes.

  20. Synthesis, spectroscopic characterization, electrochemistry and biological evaluation of some binuclear transition metal complexes of bicompartmental ONO donor ligands containing benzo[b]thiophene moiety

    NASA Astrophysics Data System (ADS)

    Mahendra Raj, K.; Vivekanand, B.; Nagesh, G. Y.; Mruthyunjayaswamy, B. H. M.

    2014-02-01

    A series of new binucleating Cu(II), Co(II), Ni(II) and Zn(II) complexes of bicompartmental ligands with ONO donor were synthesized. The ligands were obtained by the condensation of 3-chloro-6-substituted benzo[b]thiophene-2-carbohydrazides and 4,6-diacetylresorcinol. The synthesized ligands and their complexes were characterized by elemental analysis and various spectroscopic techniques. Elemental analysis, IR, 1H NMR, ESI-mass, UV-Visible, TG-DTA, magnetic measurements, molar conductance and powder-XRD data has been used to elucidate their structures. The bonding sites are the oxygen atom of amide carbonyl, azomethine nitrogen and phenolic oxygen for ligands 1 and 2. The binuclear nature of the complexes was confirmed by ESR spectral data. TG-DTA studies for some complexes showed the presence of coordinated water molecules and the final product is the metal oxide. All the complexes were investigated for their electrochemical activity, only the Cu(II) complexes showed the redox property. Cu(II) complexes were square planar, whereas Co(II), Ni(II) and Zn(II) complexes were octahedral. Powder-XRD pattern have been studied in order to test the degree of crystallinity of the complexes and unit cell calculations were made. In order to evaluate the effect of antimicrobial activity of metal ions upon chelation, both the ligands and their metal complexes were screened for their antibacterial and antifungal activities by minimum inhibitory concentration (MIC) method. The results showed that the metal complexes were found to be more active than free ligands. The DNA cleaving capacities of all the complexes were analyzed by agarose gel electrophoresis method against supercoiled plasmid DNA. Among the compounds tested for antioxidant capacity, ligand 1 displayed excellent activity than its metal complexes.

  1. Metal-Based Biologically Active Compounds: Synthesis, Spectral, and Antimicrobial Studies of Cobalt, Nickel, Copper, and Zinc Complexes of Triazole-Derived Schiff Bases

    PubMed Central

    Singh, Kiran; Kumar, Yogender; Puri, Parvesh; Sharma, Chetan; Aneja, Kamal Rai

    2011-01-01

    A series of cobalt, nickel, copper, and zinc complexes of bidentate Schiff bases derived from the condensation reaction of 4-amino-5-mercapto-3-methyl/ethyl-1,2,4-triazole with 2,4-dichlorobenzaldehyde were synthesized and tested as antimicrobial agents. The synthesized Schiff bases and their metal complexes were characterized with the aid of elemental analyses, magnetic moment measurements, spectroscopic and thermogravimetric techniques. The presence of coordinated water in metal complexes was supported by infrared and thermal gravimetric studies. A square planar geometry was suggested for Cu(II) and octahedral geometry proposed for Co(II), Ni(II), and Zn(II) complexes. The Schiff bases and their metal complexes have been screened for antibacterial (Pseudomonas aeruginosa, Bacillus subtilis) and antifungal activities (Aspergillus niger, A. flavus). The metal complexes exhibited significantly enhanced antibacterial and antifungal activity as compared to their simple Schiff bases. PMID:22216017

  2. Syntheses, characterizations and structures of NO donor Schiff base ligands and nickel(II) and copper(II) complexes

    NASA Astrophysics Data System (ADS)

    Şenol, Cemal; Hayvali, Zeliha; Dal, Hakan; Hökelek, Tuncer

    2011-06-01

    New Schiff base derivatives ( L 1 and L 2) were prepared by the condensation of 2-hydroxy-3-methoxybenzaldehyde ( o-vanillin) and 3-hydroxy-4-methoxybenzaldehyde ( iso-vanillin) with 5-methylfurfurylamine. Two new complexes [Ni(L 1) 2] and [Cu(L 1) 2] have been synthesized with bidentate NO donor Schiff base ligand ( L 1). The Ni(II) and Cu(II) atoms in each complex are four coordinated in a square planar geometry. Schiff bases ( L 1 and L 2) and complexes [Ni(L 1) 2] and [Cu(L 1) 2] were characterized by elemental analyses, FT-IR, UV-vis, mass and 1H, 13C NMR spectroscopies. The crystal structures of the ligand ( L 2) and complexes [Ni(L 1) 2] and [Cu(L 1) 2] have also been determined by using X-ray crystallographic technique.

  3. Synthesis, spectral characterization and 3D molecular modeling of some novel nickel(II) complexes derived from 4-aminoantipyrine

    NASA Astrophysics Data System (ADS)

    Nair, M. L. Harikumaran; Lalitha, K. P.

    2014-10-01

    Some novel Ni(II) complexes with the ligand (z)-4-((2-hydroxy-4-methoxyphenyl)diazenyl)-1,5-dimethyl-2-phenyl-1H-pyrazole-3(2H)-one, 3-methoxy phenol azoantipyrine, L having the formulae [Ni(L)2X2] and [Ni(L)2(Y)Cl] where X = 450 Cl-/NO3; Y = NCS- were synthesized and characterized by elemental analysis, molar conductance measurements, magnetic susceptibility measurements, spectral (IR, UV-Visible, EPR, FAB-mass) studies, thermo gravimetric analysis and by TEM image. Energy minimized configuration of the complex [Ni(L)2Cl2] was made with CHEM Bio 3D Ultra 11.0 and the respective parameters were computed. The ligand and the complex [Ni(L)2(Y)Cl] were screened for their antibacterial activities. An octahedral structure is tentatively proposed for the complexes.

  4. Synthesis, characterization of 1,2,4-triazole Schiff base derived 3d-metal complexes: Induces cytotoxicity in HepG2, MCF-7 cell line, BSA binding fluorescence and DFT study

    NASA Astrophysics Data System (ADS)

    Tyagi, Prateek; Tyagi, Monika; Agrawal, Swati; Chandra, Sulekh; Ojha, Himanshu; Pathak, Mallika

    2017-01-01

    Two novel Schiff base ligands H2L1 and H2L2 have been synthesized by condensation reaction of amine derivative of 1,2,4-triazole moiety with 2-hydroxy-4-methoxybenzaldehyde. Co(II), Ni(II), Cu(II) and Zn(II) of the synthesized Schiff bases were prepared by using a molar ratio of ligand:metal as 1:1. The structure of the Schiff bases and synthesized metal complexes were established by 1H NMR, UV-Vis, IR, Mass spectrometry and molar conductivity. The thermal stability of the complexes was study by TGA. Fluorescence quenching mechanism of metal complexes 1-4 show that Zn(II) and Cu(II) complex binds more strongly to BSA. In DFT studies the geometries of Schiff bases and metal complexes were fully optimized with respect to the energy using the 6-31 + g(d,p) basis set. The spectral data shows that the ligands behaves as binegative tridentate. On the basis of the spectral studies, TGA and DFT data an octahedral geometry has been assigned for Co(II), Ni(II), square planar for Cu(II) and tetrahedral for Zn(II) complexes. The anticancer activity were screened against human breast cancer cell line (MCF-7) and human hepatocellular liver carcinoma cell line (Hep-G2). Result indicates that metal complexes shows increase cytotoxicity in proliferation to cell lines as compared to free ligand.

  5. Structural, spectral, thermal and biological studies on 2-oxo-N‧-((4-oxo-4H-chromen-3-yl)methylene)-2-(phenylamino)acetohydrazide (H2L) and its metal complexes

    NASA Astrophysics Data System (ADS)

    El-Gammal, Ola A.; El-Reash, Gaber Abu; Ahmed, Sara F.

    2012-01-01

    A new series of metal complexes formed by the reaction of 2-oxo-N'-((4-oxo-4H-chromen-3-yl)methylene)-2-(phenylamino)acetohydrazide(H 2L) and Cu(II), Co(II), Ni(II), Cd(II), Zn(II), Hg(II) and U(VI) O22+ ions. The isolated complexes have been characterized by elemental analyses, spectral (IR, UV-visible and 1H NMR) as well as magnetic and thermal measurements. The data revealed that the ligand acts as neutral ON or ONO as well as mononegative ONO. On the basis of magnetic and electronic spectral data an octahedral geometry for the Co(II), Cu(II) and U(VI)O 2 complexes, a tetrahedral structure for the Ni(II), Cd(II), Zn(II) and Hg(II) complexes have been proposed. The bond length, bond angle, HOMO, LUMO, dipole moment and charges on the atoms have been calculated to confirm the geometry of the ligand and the investigated complexes. Also, kinetic parameters were determined for each thermal degradation stage of some complexes using Coats-Redfern and Horowitz-Metzger methods. Moreover, the ligand and its complexes were screened against Bacillus thuringiensis ( Bt) as Gram positive bacteria and Pseudomonas aeuroginosa ( Pa) Gram negative bacteria using the inhibitory zone diameter.

  6. Synthesis, characterization of 1,2,4-triazole Schiff base derived 3d-metal complexes: Induces cytotoxicity in HepG2, MCF-7 cell line, BSA binding fluorescence and DFT study.

    PubMed

    Tyagi, Prateek; Tyagi, Monika; Agrawal, Swati; Chandra, Sulekh; Ojha, Himanshu; Pathak, Mallika

    2017-01-15

    Two novel Schiff base ligands H2L(1) and H2L(2) have been synthesized by condensation reaction of amine derivative of 1,2,4-triazole moiety with 2-hydroxy-4-methoxybenzaldehyde. Co(II), Ni(II), Cu(II) and Zn(II) of the synthesized Schiff bases were prepared by using a molar ratio of ligand:metal as 1:1. The structure of the Schiff bases and synthesized metal complexes were established by (1)H NMR, UV-Vis, IR, Mass spectrometry and molar conductivity. The thermal stability of the complexes was study by TGA. Fluorescence quenching mechanism of metal complexes 1-4 show that Zn(II) and Cu(II) complex binds more strongly to BSA. In DFT studies the geometries of Schiff bases and metal complexes were fully optimized with respect to the energy using the 6-31+g(d,p) basis set. The spectral data shows that the ligands behaves as binegative tridentate. On the basis of the spectral studies, TGA and DFT data an octahedral geometry has been assigned for Co(II), Ni(II), square planar for Cu(II) and tetrahedral for Zn(II) complexes. The anticancer activity were screened against human breast cancer cell line (MCF-7) and human hepatocellular liver carcinoma cell line (Hep-G2). Result indicates that metal complexes shows increase cytotoxicity in proliferation to cell lines as compared to free ligand.

  7. Complexation of desferricoprogen with trivalent Fe, Al, Ga, In and divalent Fe, Ni, Cu, Zn metal ions: effects of the linking chain structure on the metal binding ability of hydroxamate based siderophores.

    PubMed

    Enyedy, Eva A; Pócsi, István; Farkas, Etelka

    2004-11-01

    Complexes of the natural siderophore, desferricoprogen (DFC), with several trivalent and divalent metal ions in aqueous solution were studied by pH-potentiometry, UV-Vis spectrophotometry and cyclic voltammetry. DFC was found to be an effective metal binding ligand, which, in addition to Fe(III), forms complexes of high stability with Ga(III), Al(III), In(III), Cu(II), Ni(II) and Zn(II). Fe(II), however, is oxidized by DFC under anaerobic conditions and Fe(III) complexes are formed. By comparing the results with those of desferrioxamine B (DFB), it can be concluded that the conjugated beta-double bond slightly increases the stability of the hydroxamate chelates, consequently increases the stability of mono-chelated complexes of DFC. Any steric effect by the connecting chains arises only in the bis- and tris-chelated complexes. With metal ions possessing a relatively big ionic radius (Cu(II), Ni(II), Zn(II), In(III)) DFC, containing a bit longer chains than DFB, forms slightly more stable complexes. With smaller metal ions the trend is the opposite. Also a notable difference is that stable trinuclear complex, [Cu(3)L(2)], is formed with DFC but not with DFB. Possible bio-relevance of the Fe(II)/Fe(III) results is also discussed in the paper.

  8. A New Chelating Reagent: Its Synthesis/Characterization and Application for the Determination of Cd(II) and Ni(II) in Various Food and Make-Up Product Samples by FAAS Using Simultaneous Microextraction Sampling.

    PubMed

    Saçmacı, Şerife; Saçmacı, Mustafa

    2016-07-01

    A new and simple dispersive liquid-liquid simultaneous microextraction procedure was developed for the rapid separation and simultaneous extraction/preconcentration of Cd(II) and Ni(II) at ultratrace amounts. Microextraction of the analytes was carried out in the presence of 2-methyl-5-[(Z)-pyridin-4-yldiazenyl]quinolin-8-ol as the chelating reagent. Chloroform and ethanol were used as the extraction and dispersive solvents. Various parameters that influence the microextraction procedure's efficiency-such as pH, centrifugation rate and time, reagent concentration, and sampling volume on the recovery of analytes-were examined. The calibration curves were linear in the range of 0.01-1.25 and 0.075-5 mg/L with LODs of 0.25 and 0.84 μg/L, and with a preconcentration factor of 94, for Cd(II) and Ni(II), respectively. Precision was >1.0%. The accuracy of the method was confirmed by analyzing the Certified Standard Reference Material (CWW-TMD: Certified wastewater-Trace metals, wastewater). The results show that the dispersive liquid-liquid simultaneous microextraction pretreatment is a sensitive, rapid, simple, green, and safe method for the separation/preconcentration of cadmium and nickel.

  9. Synthesis of amino functionalized magnetic graphenes composite material and its application to remove Cr(VI), Pb(II), Hg(II), Cd(II) and Ni(II) from contaminated water.

    PubMed

    Guo, Xiaoyao; Du, Bin; Wei, Qin; Yang, Jian; Hu, Lihua; Yan, Liangguo; Xu, Weiying

    2014-08-15

    In the present study, a kind of graphenes magnetic material (Fe3O4-GS) was prepared by compositing graphene sheet with ferroferric oxide, and shown to be effective for removing Cr(VI), Pb(II), Hg(II), Cd(II) and Ni(II) ions from aqueous solution. The synthesized sorbent was characterized by SEM, TEM, FTIR, XRD, XPS and BET, respectively. The pHZPC value of the sorbent was estimated to be 3.5 by alkaline-titration methods. Fe3O4-GS can be simply recovered from water with magnetic separation at low magnetic field within one minute. The sorption capacities of the metals were 17.29, 27.95, 23.03, 27.83 and 22.07 mg g(-1) for Cr(VI), Pb(II), Hg(II), Cd(II) and Ni(II), respectively. Kinetic data showed good correlation with pseudo-second-order equation and the Freundlich model was found to fit for the isotherm data of all the heavy metal ions. It was found that the metals sorption was accomplished mainly via chelation or ion exchange. The results of thermodynamic studies illustrate that the adsorption process was endothermic and spontaneous in nature.

  10. Synthesis, spectroscopic, cytotoxic aspects and computational study of N-(pyridine-2-ylmethylene)benzo[d]thiazol-2-amine Schiff base and some of its transition metal complexes

    NASA Astrophysics Data System (ADS)

    Abd El-Aziz, Dina M.; Etaiw, Safaa Eldin H.; Ali, Elham A.

    2013-09-01

    N-(pyridine-2-ylmethylene)benzo[d]thiazol-2-amine Schiff base (L) and its Cu(II), Fe(III), Co(II), Ni(II) and Zn(II) complexes were synthesized and characterized by a set of chemical and spectroscopic measurements using elemental analysis, electrical conductance, mass spectra, magnetic susceptibility and spectral techniques (IR, UV-Vis, 1H NMR). Elemental and mass spectrometric data are consistent with the proposed formula. IR spectra confirm the bidentate nature of the Schiff base ligand. The octahedral geometry around Cu(II), Fe(III), Ni(II) and Zn(II) as well as tetrahedral geometry around Co(II) were suggested by UV-Vis spectra and magnetic moment data. The thermal degradation behavior of the Schiff base and its complexes was investigated by thermogravimetric analysis. The structure of the Schiff base and its transition metal complexes was also theoretically studied using molecular mechanics (MM+). The obtained structures were minimized with a semi-empirical (PM3) method. The in vitro antitumor activity of the synthesized compounds was studied. The Zn-complex exhibits significant decrease in surviving fraction of breast carcinoma (MCF 7), liver carcinoma (HEPG2), colon carcinoma (HCT116) and larynx carcinoma (HEP2) cell lines human cancer.

  11. Designing a heterotrinuclear Cu(II)-Ni(II)-Cu(II) complex from a mononuclear Cu(II) Schiff base precursor with dicyanamide as a coligand: synthesis, crystal structure, thermal and photoluminescence properties.

    PubMed

    Hopa, Cigdem; Cokay, Ismail

    2016-08-01

    Schiff bases are considered `versatile ligands' in coordination chemistry. The design of polynuclear complexes has become of interest due to their facile preparations and varied synthetic, structural and magnetic properties. The reaction of the `ligand complex' [CuL] {H2L is 2,2'-[propane-1,3-diylbis(nitrilomethanylylidene)]diphenol} with Ni(OAc)2·4H2O (OAc is acetate) in the presence of dicyanamide (dca) leads to the formation of bis(dicyanamido-1κN(1))bis(dimethyl sulfoxide)-2κO,3κO-bis{μ-2,2'-[propane-1,3-diylbis(nitrilomethanylylidene)]diphenolato}-1:2κ(6)O,O':O,N,N',O';1:3κ(6)O,O':O,N,N',O'-dicopper(II)nickel(II), [Cu2Ni(C17H16N2O2)2(C2N3)2(C2H6OS)2]. The complex shows strong absorption bands in the frequency region 2155-2269 cm(-1), which clearly proves the presence of terminal bonding dca groups. A single-crystal X-ray study revealed that two [CuL] units coordinate to an Ni(II) atom through the phenolate O atoms, with double phenolate bridges between Cu(II) and Ni(II) atoms. Two terminal dca groups complete the distorted octahedral geometry around the central Ni(II) atom. According to differential thermal analysis-thermogravimetric analysis (DTA-TGA), the title complex is stable up to 423 K and thermal decomposition starts with the release of two coordinated dimethyl sulfoxide molecules. Free H2L exhibits photoluminescence properties originating from intraligand (π-π*) transitions and fluorescence quenching is observed on complexation of H2L with Cu(II).

  12. Studies on some metal complexes of quinoxaline based unsymmetric ligand: Synthesis, spectral characterization, in vitro biological and molecular modeling studies.

    PubMed

    Dhanaraj, Chellaian Justin; Johnson, Jijo

    2016-08-01

    Mononuclear Co(II), Ni(II), Cu(II) and Zn(II) complexes of an unsymmetric Schiff base ligand, 3-(-(3-(-3,5-dichloro-2-hydroxybenzylideneamino)propylimino)methyl)quinoxalin-2(1H) -one (L) were synthesized and characterized by various analytical and spectral techniques. The molar conductance values of metal complexes indicate non-electrolytic behavior of the metal complexes. The Schiff base act as tetra dentate ONNO donor ligand in Co(II), Ni(II), Zn(II) complexes and tridentate NNO donor in Cu(II) complex. Thermal stabilities of the newly synthesized compounds were determined by thermal analysis. Crystallinity, average grain size and unit cell parameters were determined from powder X-ray diffraction study. Electrochemical behaviors of the compounds were examined by cyclic voltammetry technique. The Schiff base and its complexes have been screened for their in vitro antimicrobial activities against some bacterial and fungal strains by disc diffusion method. The interaction of the compounds with calf thymus DNA (CT DNA) has been investigated by electronic absorption spectral titration and viscosity measurement (hydrodynamic) methods. Furthermore, the pUC18 DNA cleavage activities of the complexes have been explored. The compounds were also subjected to in vitro antioxidant, anticancer activity screening, druglikeness and bioactivity predictions using Molinspiration software. Molecular docking studies of the present compounds were carried out against B-DNA dodecamer d(CGCGAATTCGCG)2 and vascular endothelial growth factor receptor (VEGFR-2) kinase. Quantum chemical calculations were done with DFT method to determine the optimum geometry of the ligand and its metal complexes. From the quantum chemical parameters, the reactivity parameters of the compounds were established.

  13. New non-toxic transition metal nanocomplexes and Zn complex-silica xerogel nanohybrid: Synthesis, spectral studies, antibacterial, and antitumor activities

    NASA Astrophysics Data System (ADS)

    Shebl, Magdy; Saif, M.; Nabeel, Asmaa I.; Shokry, R.

    2016-08-01

    A new chromone Schiff base and its complexes of Cu(II), Ni(II), Co(II), Fe(III), Zn(II), Cd(II), and UO2(VI) as well as Zn(II) complex-silica xerogel nanohybrid were successfully prepared in a nano domain with crystalline or amorphous structures. Structures of the Schiff base and its complexes were investigated by elemental and thermal analyses, IR, 1H NMR, electronic, ESR, mass spectra, XRD, and TEM, as well as conductivity and magnetic susceptibility measurements. The spectroscopic data revealed that the Schiff base ligand behaves as a monobasic tridentate ligand. The coordination sites with metal ions are γ-pyrone oxygen, azomethine nitrogen, and oxygen of the carboxylic group. The metal complexes exhibited octahedral geometry, except Cu(II) complex, which has a square planar geometry and UO2(VI) complex, in which uranium ion is hepta-coordinated. Transmission electron microscope (TEM) analysis showed that Ni(II) and Zn(II) complexes have aggregated spheres and rod morphologies, respectively. TEM images of Zn(II) complex-silica xerogel nanohybrid showed a nanosheet morphology with 46 nm average size and confirmed that the complex was uniformly distributed into the silica pores. The obtained nanocomplexes were tested as antimicrobial and antitumor agents. The results showed that Zn(II) nanocomplex and Zn(II) complex-silica xerogel nanohybrid have high activity. The toxicity test on mice showed that Zn(II) complex and Zn(II) complex-silica xerogel nanohybrid have lower toxicity than cisplatin.

  14. Spectral, electrical conductivity and biological activity properties of some new azopyrimidine derivatives and their complexes.

    PubMed

    Masoud, Mamdouh S; Khalil, Ekram A; Ramadan, Ahmed M; Gohar, Yousry M; Sweyllam, Amr

    2007-07-01

    The electronic absorption spectra of 5-(o-substituted phenylazo)-6-amino-2-thiouracils and 6-(o-substituted phenylazo)-5-aminouracils containing different substituents are studied at different pH's. The dissociation constants are evaluated and discussed. Phenomenon of tautomerism is more supported by (1)H NMR and (13)C NMR spectra. The electrical conductivity of some ligands and their Co(II), Ni(II) and Cu(II) complexes in the temperature range 293-150K favoured their semiconducting properties where the metal ion forms a bridge to facilitate the flow of the current. The biological activity of some ligands and their complexes are tested against a number of Gram-positive and Gram-negative bacteria. The results showed that some of the compounds have a well considerable activity against some of the organisms.

  15. Interaction of Carbon Dioxide with Transition-Metal-Substituted Heteropolyanions in Nonpolar Solvents. Spectroscopic Evidence for Complex Formation.

    PubMed

    Szczepankiewicz, Steven H.; Ippolito, Calogero M.; Santora, Brian P.; Van De Ven, Thomas J.; Ippolito, Giuseppe A.; Fronckowiak, Louise; Wiatrowski, Fred; Power, Tom; Kozik, Mariusz

    1998-08-24

    Tetraheptylammonium salts of various transition-metal-substituted heteropolyanions with alpha-Keggin ([XW(11)O(39)M](n)()(-)), alpha-Wells-Dawson ([P(2)W(17)O(61)M](m)(-)), and Weakley and Finke structures ([P(2)W(18)O(68)Co(4)](10)(-)) were investigated with respect to their reactivity with CO(2) in nonpolar solvents. It was found that copper(II)- and manganese(III)-substituted heteropolyanions do not react with CO(2). Germano- and silicotungstates with the alpha-Keggin structure do form complexes with CO(2) when substituted with Co(II), Ni(II), and Mn(II). In contrast, boro- and phosphotungstates substituted with Co(II), Ni(II), and Mn(II) are unreactive. The alpha(2) isomers of Wells-Dawson phosphotungstates show reactivity similar to that of alpha-Keggin silicotungstates-i.e., Co(II), Ni(II), and Mn(II) derivatives do react with CO(2). On the other hand, the alpha(1) isomer of the Co(II)-substituted Wells-Dawson anion does not react with CO(2), and neither does the Weakley and Finke cobaltotungstate. When reactions do occur, they are completely reversible. An excess of water decomposes the complexes. Traces of water are, however, necessary for the reactions to take place. The CO(2) adducts were characterized by UV/vis, IR, and (13)C NMR. The IR data could be explained as originating either from CO(2) complexes with a direct eta(1) metal-carbon bond or from bicarbonato complexes. IR spectra with isotopically enriched (13)CO(2) and C(18)O(2) support the presence of a eta(1) metal-carbon bond. The (13)C NMR spectra indicate the presence of two different kinds of paramagnetic CO(2) complexes after the reaction of alpha-[SiW(11)O(39)Co](6)(-) with CO(2) (chemical shifts 792 and 596 ppm at 26 degrees C). The variable-temperature experiments are consistent with the chemical exchange between these two species. UV/vis, IR, and NMR studies in the presence of controlled amounts of water or ethanol suggest the existence of H-bonding in the CO(2) complexes, similar to that

  16. Spectral, thermal, kinetic, molecular modeling and eukaryotic DNA degradation studies for a new series of albendazole (HABZ) complexes

    NASA Astrophysics Data System (ADS)

    El-Metwaly, Nashwa M.; Refat, Moamen S.

    2011-01-01

    This work represents the elaborated investigation for the ligational behavior of the albendazole ligand through its coordination with, Cu(II), Mn(II), Ni(II), Co(II) and Cr(III) ions. Elemental analysis, molar conductance, magnetic moment, spectral studies (IR, UV-Vis and ESR) and thermogravimetric analysis (TG and DTG) have been used to characterize the isolated complexes. A deliberate comparison for the IR spectra reveals that the ligand coordinated with all mentioned metal ions by the same manner as a neutral bidentate through carbonyl of ester moiety and NH groups. The proposed chelation form for such complexes is expected through out the preparation conditions in a relatively acidic medium. The powder XRD study reflects the amorphous nature for the investigated complexes except Mn(II). The conductivity measurements reflect the non-electrolytic feature for all complexes. In comparing with the constants for the magnetic measurements as well as the electronic spectral data, the octahedral structure was proposed strongly for Cr(III) and Ni(II), the tetrahedral for Co(II) and Mn(II) complexes but the square-pyramidal for the Cu(II) one. The thermogravimetric analysis confirms the presence or absence of water molecules by any type of attachments. Also, the kinetic parameters are estimated from DTG and TG curves. ESR spectrum data for Cu(II) solid complex confirms the square-pyramidal state is the most fitted one for the coordinated structure. The albendazole ligand and its complexes are biologically investigated against two bacteria as well as their effective effect on degradation of calf thymus DNA.

  17. Herbo-mineral based Schiff base ligand and its metal complexes: Synthesis, characterization, catalytic potential and biological applications.

    PubMed

    Kareem, Abdul; Laxmi; Arshad, Mohammad; Nami, Shahab A A; Nishat, Nahid

    2016-07-01

    Schiff base ligand, (L), derived from condensation reaction of 1,7-bis-(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione, (curcumin), with pyridine-3-carboxamide, (nicotinamide), and its complexes of Co(II), Ni(II) and Cu(II) ions, containing 1,10-phenanthroline as auxiliary ligand were synthesized and characterized by various physico-chemical techniques. From the micro analytical data, the stoichiometry of the complexes 1:1 (metal: ligand) was ascertained. The Co(II) and Cu(II) forms octahedral complexes, while the geometric structure around Ni(II) atom can be described as square planar. The catalytic potential of the metal complexes have been evaluated by recording the rate of decomposition of hydrogen peroxide. The results reveal that the percent decomposition of H2O2increases with time and the highest value (50.50%) was recorded for Co(II) complex. The ligand and its complexes were also screened for their in vitro antibacterial activity against Escherichia coli, Staphylococcus aureus, Klebsiella pneumoniae, Streptococcus pyogenes and Pseudomonas aeruginosa. The relative order of antibacterial activity against S. Pyogenes, S. aureus and E. coli is Cu(II)>Ni(II)>Co(II)>(L); while with P. aeruginosa, K. pneumoniae the order of activity is Cu(II)>Co(II)>Ni(II)>(L). The anthelmintic screening was performed using Pheretima posthuma. The order of anthelmintic activity of ligand and its complexes is [(Phen)CuLCl2]>[(Phen)CoLCl2]>[(Phen)NiL]Cl2>(L).

  18. Preparation, spectroscopic investigation and antiproliferative capacity of new metal complexes of (3E)-2-(hydroxyimino)-N-P-Tolyl-3-(P-tolylimino) butanamide

    NASA Astrophysics Data System (ADS)

    El-Tabl, Abdou Saad; Abd El-wahed, Moshira Mohamed; Abd El-Razek, Samar Ebrahim

    2013-03-01

    Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Sr(II), Hg(II), Tl(I), UO2(II) and ZrO(II) complexes of (3E)-2-(hydroxyimino)-N-P-Tolyl-3-(P-tolylimino) butanamide have been prepared and characterized by elemental analyses, IR, UV-Vis spectra, magnetic moments, conductances, 1H NMR and mass spectra (ligand and its Zn(II) complex), thermal analyses (DTA and TGA) and ESR measurements. The IR data show that, the ligand behaves as monobasic bidentate or neutral bidentate. Molar conductances in DMF indicate that, the complexes are non-electrolytes. ESR spectra of solid Cu(II) complexes at room temperature show axial type (dx2-y2) with covalent bond character in an octahedral environment. Complexes showed inhibitory activity against hepatocellular carcinoma (HepG-2 cell line).

  19. Spectral and in vitro antimicrobial properties of 2-oxo-4-phenyl-6-styryl-1,2,3,4-tetrahydro-pyrimidine-5-carboxylic acid transition metal complexes

    NASA Astrophysics Data System (ADS)

    Dhankar, Raksha P.; Rahatgaonkar, Anjali M.; Chorghade, Mukund S.; Tiwari, Ashutosh

    2-oxo-4-phenyl-6-styryl-1,2,3,4-tetrahydro-pyrimidine-5-carboxylic acid (ADP) was complexed with acetates of Mn(II), Ni(II), Cu(II) and Zn(II). The structures of the ligand and its metal complexes were characterized by microanalysis, IR, NMR, UV-vis spectroscopy, magnetic susceptibility and TGA-DTA analyses. Octahedral and square planar geometries were suggested for the complexes in which the central metal ion coordinated with sbnd O donors of ligand and acetate ions. Each ligand binds the metal using carboxylate oxygens. The ligand and complexes were evaluated for their antimicrobial activities against different species of pathogenic bacteria and fungi. The present novel pyrimidine containing complexes could constitute a new group of antibacterial and antifungal agents.

  20. In search of molecules displaying ferromagnetic exchange: multiple-decker Ni12 and Ni16 complexes from the use of pyridine-2-amidoxime.

    PubMed

    Efthymiou, Constantinos G; Cunha-Silva, Luís; Perlepes, Spyros P; Brechin, Euan K; Inglis, Ross; Evangelisti, Marco; Papatriantafyllopoulou, Constantina

    2016-11-01

    The use of pyridine-2-amidoxime (pyaoxH2) in Ni chemistry has provided access to a dodecanuclear complex and a hexadecanuclear Ni cluster, namely [Ni12(pyaox)6(pyaoxH)6(MeOH)2Cl2]Cl4·5MeOH (1·5MeOH) and [Ni16(pyaox)8(pyaoxH)8(MeOH)4](SO4)4·10H2O·26MeOH (2·10H2O·26MeOH). Complex 1·5MeOH was isolated by the reaction of NiCl2·6H2O, pyaoxH2 and NaOMe in a 1 : 1 : 2 molar ratio in MeOH in 60% yield. Treatment of NiSO4·6H2O with pyaoxH2 and NEt3 in a 1 : 1 : 2 molar ratio in MeOH afforded 2·10H2O·26MeOH in good yield (65%). The two compounds display a multi-decker configuration based on stacked Ni4 layers, {Ni4(pyaox)2(pyaoxH)2}(2+)x (x = 3, 1·5MeOH; x = 4, 2·10H2O·26MeOH); each deck consists of two square planar and two octahedral Ni(II) centres. The number of decks observed in 1·5MeOH and 2·10H2O·26MeOH depends on the nature of the inorganic anion that is present in the reaction system, which provides elements of synthetic control towards new high nuclearity Ni(II) species. 2·10H2O·26MeOH is the first structurally characterized complex of any metal displaying a quadruple-decker configuration, being also the highest nuclearity metal cluster bearing pyaoxH2 and the highest nuclearity Ni(II) cluster with any type of 2-pyridyl oxime. Each cluster cation displays ferromagnetic exchange between the octahedral Ni(II) ions resulting in a spin ground state of S = 6 for 1 and S = 8 for 2. Magnetothermal studies have been performed and discussed for both clusters.

  1. Antioxidant, electrochemical, thermal, antimicrobial and alkane oxidation properties of tridentate Schiff base ligands and their metal complexes

    NASA Astrophysics Data System (ADS)

    Ceyhan, Gökhan; Çelik, Cumali; Uruş, Serhan; Demirtaş, İbrahim; Elmastaş, Mahfuz; Tümer, Mehmet

    2011-10-01

    In this study, two Schiff base ligands (HL 1 and HL 2) and their Cu(II), Co(II), Ni(II), Pd(II) and Ru(III) metal complexes were synthesized and characterized by the analytical and spectroscopic methods. Alkane oxidation activities of the metal complexes were studied on cyclohexane as substrate. The ligands and their metal complexes were evaluated for their antimicrobial activity against Corynebacterium xerosis, Bacillus brevis, Bacillus megaterium, Bacillus cereus, Mycobacterium smegmatis, Staphylococcus aureus, Micrococcus luteus and Enterococcus faecalis (as Gram-positive bacteria) and Pseudomonas aeruginosa, Klebsiella pneumoniae, Escherichia coli, Yersinia enterocolitica, Klebsiella fragilis, Saccharomyces cerevisiae, and Candida albicans (as Gram-negative bacteria). The antioxidant properties of the Schiff base ligands were evaluated in a series of in vitro tests: 1,1-diphenyl-2-picrylhydrazyl (DPPH rad ) free radical scavenging and reducing power activity of superoxide anion radical generated non-enzymatic systems. Electrochemical and thermal properties of the compounds were investigated.

  2. Copper (II) complexes of N4, N4-disubstituted thio- and selenosemicarbazones of 2-acetylpyridine: ESR studies

    NASA Astrophysics Data System (ADS)

    K. Bhoon, Yudhvir; Scovill, John P.; Klayman, Daniel L.

    Copper(II) complexes of 3-azabicyclo[3.2.2]nonane-3-thiocarboxylic acid 2-[1-(pyridinyl)ethylidene]hydrazide, and its selenium analog, 3-azabicyclo[3.2.2]nonane-3-selenocarboxylic acid 2-[1-(2-pyridinyl)ethylidene]hydrazide, were studied by ESR spectrometry in chloroform solution at room temperature and at liquid nitrogen temperature. ESR spectra were also observed for the complexes as magnetically doped samples in the corresponding Ni(II) lattices at room temperature. Nitrogen superhyperfine splitting is observed at room temperature in all the spectra. Splitting patterns indicate the non-equivalent nature of the two coordinating nitrogen atoms. The covalency parameter for the metal—ligand bond was determined for selected complexes. An order of ligand field strength has been proposed based on the magnitude of the g| component of g observed in the polycrystalline state.

  3. Synthesis and characterization of metal complexes of Schiff base ligand derived from imidazole-2-carboxaldehyde and 4-aminoantipyrine

    NASA Astrophysics Data System (ADS)

    Selwin Joseyphus, R.; Shiju, C.; Joseph, J.; Justin Dhanaraj, C.; Arish, D.

    2014-12-01

    The Co(II), Ni(II), Cu(II) and Zn(II) complexes of the Schiff base derived from imidazole-2-carboxaldehyde and 4-aminoantipyrine were synthesized. These compounds were characterized by elemental analysis, IR, mass, 1H NMR, electronic spectra, magnetic moment, molar conductance, thermal analysis, powder XRD and SEM. The analytical data show that the metal to ligand ratio is 1:1. The IR results show that the ligand acts as a bidentate donor coordinating through the azomethine nitrogen and imidazole nitrogen atoms. From the electronic spectra and magnetic moment value predicts the geometry of the complexes. The surface morphology of the compounds was studied by SEM. The compounds were screened for their antibacterial activity and antifungal activity using Kirby Bayer disc diffusion method. The DNA cleavage and superoxide dismutase activities of the compounds were investigated. The anticancer activities of the complexes have been carried out towards HeLa and HCT116 cancer cells.

  4. Spectroscopic studies on 2-[2-(4-methylquinolin-2-yl)hydrazono]-1,2-diphenylethanone molecule and its metal complexes

    NASA Astrophysics Data System (ADS)

    Seleem, H. S.; El-Inany, G. A.; Mousa, M.; Hanafy, F. I.

    2009-11-01

    The electronic absorption spectra of a hydrazone: 2-[2-(4-methylquinolin-2-yl)hydrazono]-1,2-diphenylethanone (BHQ) derived from 2-hydrazino-4-methylquinoline and 1,2-diphenylethan-1,2-dione (benzil) have been studied in various solvents of different polarities. The dependence of the band shift Δ ύ on the solvent parameters viz.D, Z, ET, DN, AN, α, β and π* was discussed. Also, the effect of pH on the free hydrazone and its Co(II), Ni(II) and Cu(II) complexes was studied spectrophotometrically in 75% (v/v) dioxane-water in order to determine the dissociation and stability constants. The stoichiometry of the formed complexes was determined by three different methods: Job's, mole ratio and slope ratio which indicate the formation of 1:2, M:L complexes for Co(II) and Cu(II) and 1:1, Ni(II):L. Beer's law is valid in the range 0.32-7.04 μg/mL depending on the type of the metal ion. The use of BHQ as an indicator via a spectrophotometric titration of Cu(II) and Ni(II) with EDTA was efficient.

  5. Synthesis, spectroscopic characterization, electrochemistry and biological evaluation of some metal (II) complexes with ONO donor ligand containing benzo[b]thiophene and coumarin moieties

    NASA Astrophysics Data System (ADS)

    Mahendra Raj, K.; Mruthyunjayaswamy, B. H. M.

    2014-09-01

    Schiff base ligand 3-chloro-N‧-((7-hydroxy-4-methyl-2-oxo-2H-chromen-8-yl)methylene)benzo[b]thiophene-2-carbohydrazide and its Cu(II), Co(II), Ni(II) and Zn(II) complexes were synthesized, characterized by elemental analysis and various physico-chemical techniques like, IR, 1H NMR, ESI-mass, UV-Visible, thermogravimetry - differential thermal analysis, magnetic measurements and molar conductance. Spectral analysis indicates octahedral geometry for all the complexes. Cu(II) complex have 1:1 stoichiometry of the type [M(L)(Cl)(H2O)2], whereas Co(II), Ni(II) and Zn(II) complexes have 1:2 stoichiometric ratio of the type [M(L)2]. The bonding sites are the oxygen atom of amide carbonyl, nitrogen of azomethine function and phenolic oxygen of the Schiff base ligand via deprotonation. The thermogravimetry - differential thermal analysis studies gave evidence for the presence of coordinated water molecules in the composition of Cu(II) complex which was further supported by IR measurements. All the complexes were investigated for their electrochemical activity, but only the Cu(II) complex showed the redox property. In order to evaluate the effect of antimicrobial potency of metal ions upon chelation, ligand and its metal complexes along with their respective metal chlorides were screened for their antibacterial and antifungal activities by minimum inhibitory concentration (MIC) method. The results showed that the metal complexes were found to be more active than free ligand. Ligand and its complexes were screened for free radical scavenging activity by DPPH method and DNA cleavage activity using Calf-thymus DNA (Cat. No-105850).

  6. Heteronuclear Ni(ii)-Ln(iii) (Ln = La, Pr, Tb, Dy) complexes: synthesis and single-molecule magnet behaviour.

    PubMed

    Upadhyay, Apoorva; Das, Chinmoy; Langley, Stuart K; Murray, Keith S; Srivastava, Anant K; Shanmugam, Maheswaran

    2016-02-28

    The reaction of hydrated nickel(II) salts (chloride or nitrate) and hydrated lanthanide nitrate salts with the Schiff base ligand 2-methoxy-6-[(E)-phenyliminomethyl] phenol (HL) in methanol resulted in the isolation of three isostructural linear heterometallic trinuclear complexes and a heterometallic tetranuclear complex. The molecular structures of these complexes were determined via single crystal X-ray diffraction revealing molecular structures of formulae [Ni2La(L-)6](NO3)0.55(OH)0.45 (1), [Ni2Pr(L-)6](NO3)0.48(OH)0.52 (2), [Ni2Tb(L-)6](NO3)0.5(Cl)0.5 (3) and [Ni2Dy2(L-2(o-vanillin)2(CO3)2(NO3)2(MeOH)2] (4). Structural analysis for 1-3 reveals that the lanthanide ion is sandwiched between two Ni(II) ions and the Ni⋯Ln⋯Ni metallic core displays a linear arrangement, with an average ∠Ni⋯Ln⋯Ni bond angle of 179.7°. Analysis of 4 reveals the metal ions are arranged such that two Ni-Dy subunits are bridged by two carbonate ligands via the Dy sites. Direct current magnetic susceptibility measurements for complexes 1-4 reveal that the Ni(II) ions are coupled ferromagnetically with the Tb(III) (3) and Dy(III) (4) ions, and antiferromagnetically with the Pr(III) ion (2). For complex 1 a long range intramolecular ferromagnetic interaction is witnessed between the Ni(II) ions (Ni⋯Ni = 6.873(9) Å) via a closed shell La(III) ion. The magnetic data of 1 were fitted using the HDVV Hamiltonian revealing the following parameters; J = +0.46 cm(-1), g = 2.245, D = +4.91 cm(-1). Alternating current magnetic susceptibility measurements performed on complexes 2-4 revealed that 3 and 4 displayed frequency dependent χ′′M signals (Hac = 3.5 Oe and Hdc = 0 Oe) which is a characteristic signature of a single-molecule magnet behaviour.

  7. Synthesis, Characterization, Antioxidant, and Antibacterial Studies of Some Metal(II) Complexes of Tetradentate Schiff Base Ligand: (4E)-4-[(2-{(E)-[1-(2,4-Dihydroxyphenyl)ethylidene]amino}ethyl)imino]pentan-2-one

    PubMed Central

    Ejidike, Ikechukwu P.; Ajibade, Peter A.

    2015-01-01

    Co(II), Ni(II), Cu(II), and Zn(II) complexes of (4E)-4-[(2-{(E)-[1-(2,4-dihydroxyphenyl)ethylidene]amino}ethyl)imino]pentan-2-one have been synthesized and characterized by elemental analyses, molar conductance, electronic and IR spectral studies, and XRD. FTIR confirmed the ligand coordinates the metal ion to form mononuclear complex via the oxygen and nitrogen atoms of the phenolic group and azomethine group, respectively. Tetrahedral geometry is proposed for Co(II) complex and square-planar geometry for Ni(II) and Cu(II) complexes. The antibacterial studies of the compounds were determined and they show that the metal complexes are more active than the free ligands. The antioxidant activity by DPPH and ABTS method was examined and it shows Cu(II); IC50 = 2.31 ± 1.54 µM for DPPH and Co(II); IC50 = 1.83 ± 1.08 µM for ABTS were the most active. PMID:26074738

  8. Design, synthesis, structural elucidation, pharmacological evaluation of metal complexes with pyrazoline derivatives.

    PubMed

    Muneera, M Sirajul; Joseph, J

    2016-10-01

    A bioactive pyrazoline derivatives have been synthesized by the base-catalyzed Claisen-Schmidt condensation of imidazole-2-carboxaldehyde with 1-acetyl-2-hydroxynaphthalene followed by cyclization with phenylhydrazine (L(1))/2,3-dimethylphenylhydrazine (L(2)) and 3-nitrophenylhydrazine (L(3)). The metal(II) complexes [Ni(II), Co(II), Cu(II) and Zn(II)] were formed by reacting the corresponding metal acetates with the ligands. All complexes were characterized by elemental analyses, electronic, IR, NMR, mass and ESR spectroscopic techniques. The synthesized metal complexes of pyrazoline compounds showed significant antibacterial activity against the organisms Escherichia coli, Staphylococcus aureus, Klebsiella pneumoniae, Proteus mirabilis and Salmonella typhii when compared with the standard antibiotic (Streptomycin). The ligands and their metal complexes were screened for antioxidant activity using DPPH radical scavenging and superoxide radical scavenging assay methods. All the complexes showed good free radical scavenging activity which is comparable to that of the standards. Among the metal complexes, the copper complex has showed higher activity. The results were indicated that 2-pyrazoline (structural core) and copper ion could be responsible for the potential candidate eliciting antioxidant activity. All compounds were evaluated for their in vitro antimycobacterial activity against Mycobacterium tuberculosis. The ligands and metal complexes were subjected to fluorescence properties and exhibited that the variable fluorescence emission behavior of complexes. It can be attributed to the combined effect of the substituents and naphthyl structural core present in the ligands.

  9. Synthesis, characterization and properties of some divalent metal(II) complexes: Their electrochemical, catalytic, thermal and antimicrobial activity studies

    NASA Astrophysics Data System (ADS)

    Tümer, Mehmet; Ekinci, Duygu; Tümer, Ferhan; Bulut, Akif

    2007-07-01

    In this study, we synthesized the amine compound 2-(2-aminoethyliminomethyl)phenol (H 3A) as the starting material, and then we prepared the polydentate Schiff base ligands from the reactions of the amine compound (H 3A) with phtaldialdehyde (H 2L), 4-methyl-2,6-di-formlyphenol (H 3L 1) and 4- t-butyl-2,6-di-formylphenol (H 3L 2) in the ethanol solution. Moreover, the complexes Cd(II), Cu(II), Co(II), Ni(II), Zn(II) and Sn(II) of the ligands H 2L, H 3L 1 and H 3L 2 have been prepared. All compounds have been characterized by the analytical and spectroscopic methods. In addition, the magnetic susceptibility and molar conductance measurements have been made. The catalytic properties of the mono- and binuclear Co(II) and Cu(II) complexes have been studied on the 3,5-di- tert-butylcatechol (3,5-DTBC) and ascorbic acid (aa) as a substrate. The oxidative C-C coupling properties of the Co(II) and Cu(II) complexes have been investigated on the sterically hindered 2,6-di- tert-butylphenol (dtbp). The antimicrobial activity properties of the ligands and their mono- and binuclear complexes have been studied against the bacteria and fungi. The results have been compared to the antibacterial and fungi drugs. The TGA curves show that the decomposition takes place in three steps for all complexes. Electrochemical properties of the complexes Cu(II) and Ni(II) have been investigated for the first time in acetonitrile by cyclic voltammetry.

  10. Synthesis, characterization and properties of some divalent metal(II) complexes: their electrochemical, catalytic, thermal and antimicrobial activity studies.

    PubMed

    Tümer, Mehmet; Ekinci, Duygu; Tümer, Ferhan; Bulut, Akif

    2007-07-01

    In this study, we synthesized the amine compound 2-(2-aminoethyliminomethyl)phenol (H(3)A) as the starting material, and then we prepared the polydentate Schiff base ligands from the reactions of the amine compound (H(3)A) with phtaldialdehyde (H(2)L), 4-methyl-2,6-di-formlyphenol (H(3)L(1)) and 4-t-butyl-2,6-di-formylphenol (H(3)L(2)) in the ethanol solution. Moreover, the complexes Cd(II), Cu(II), Co(II), Ni(II), Zn(II) and Sn(II) of the ligands H(2)L, H(3)L(1) and H(3)L(2) have been prepared. All compounds have been characterized by the analytical and spectroscopic methods. In addition, the magnetic susceptibility and molar conductance measurements have been made. The catalytic properties of the mono- and binuclear Co(II) and Cu(II) complexes have been studied on the 3,5-di-tert-butylcatechol (3,5-DTBC) and ascorbic acid (aa) as a substrate. The oxidative C-C coupling properties of the Co(II) and Cu(II) complexes have been investigated on the sterically hindered 2,6-di-tert-butylphenol (dtbp). The antimicrobial activity properties of the ligands and their mono- and binuclear complexes have been studied against the bacteria and fungi. The results have been compared to the antibacterial and fungi drugs. The TGA curves show that the decomposition takes place in three steps for all complexes. Electrochemical properties of the complexes Cu(II) and Ni(II) have been investigated for the first time in acetonitrile by cyclic voltammetry.

  11. Synthesis, antioxidant activities of the nickel(II), iron(III) and oxovanadium(IV) complexes with N2O2 chelating thiosemicarbazones.

    PubMed

    Bal-Demirci, Tülay; Sahin, Musa; Ozyürek, Mustafa; Kondakçı, Esin; Ulküseven, Bahri

    2014-05-21

    The nickel(II), iron(III) and oxovanadium(IV) complexes of the N2O2 chelating thiosemicarbazones were synthesized using 4-hydroxysalicyladehyde-S-methylthiosemicarbazone and R1-substitute-salicylaldehyde (R1: 4-OH, H) in the presence of Ni(II), Fe(III), VO(IV) ions by the template reaction. The structures of the thiosemicarbazone complexes were characterized by FT-IR, (1)H NMR, elemental, ESI-MS and APCI-MS analysis. The synthesized compounds were screened for their antioxidant capacity by using the cupric reducing antioxidant capacity (CUPRAC) method. Trolox equivalent antioxidant capacity (TEAC) of iron(III) complex, 1c, was measured to be higher than that of the other complexes. Other parameters of antioxidant activity (scavenging effects on •OH, O2(•-) and H2O2) of these compounds were also determined. All the compounds have shown encouraging ROS scavenging activities.

  12. NMR investigation of dynamic processes in complexes of nickel(II) and zinc(II) with iminodiacetate, n-methyliminodiacetate and n-ethyliminodiacetate

    SciTech Connect

    Wagner, M.R.

    1985-11-01

    Analysis of oxygen-17 bulk water relaxation rates with an aqueous solution of 1:1 Ni(II):ida reveals that two rate-limiting processes are involved with solvent exchange. Analysis of carbon-13 longitudinal relaxation rates of the bis-ligand complexes with zinc(II) are used to determine molecular tumbling rates and methyl rotation rates. The carbon-13 transverse relaxation rates for the carbons in the bis-ligand complex with Ni(II) are adequately fitted to the Solomon-Bloembergen equation. Three carboxylate carbon peaks are seen with the /sup 13/C spectrum of the 1:2 Ni(II):ida complex, which coalesce into a single peak above about 360 K. The mechanism and rate of ligand exchange are determined for the complexes Zn(II)L/sub 2//sup -2/ (L = mida, eida) in aqueous solution by total lineshape analysis of the proton spectrum at 500 MHz.

  13. Physicochemical studies and biological evaluation on (E)-3-(2-(1-(2-hydroxyphenyl)hydrazinyl)-3-oxo-N-(thiazol-2yl)propanamide complexes

    NASA Astrophysics Data System (ADS)

    Ibrahim, K. M.; Zaky, R. R.; Gomaa, E. A.; Abd El-Hady, M. N.

    2013-04-01

    Hydrazone complexes of Co(II), Ni(II), Cu(II), Pd(II), Cd(II), Zn(II) and U(VI)O2 with (E)-3-(2-(1-(2-hydroxyphenyl)hydrazinyl)-3-oxo-N-(thiazol-2yl)propanamide (H2o-HAH) have been synthesized. The complex structure has been elucidated by analysis (elemental and thermal), spectroscopy (1H NMR, 13C NMR, IR, UV-visible, ESR, MS) and physical measurements (magnetic susceptibility and molar conductance). The kinetic and thermodynamic parameters for the different decomposition steps of some complexes have been calculated using the Coats-Redfern equation. Also, the association and formation constants of Co(II) ion in absolute ethanol solutions at 294.15 K have been calculated by using electrical conductance. Moreover, the ligand and its complexes have been screened for their antibacterial (Escherichia coli and Clostridium sp.) and antifungal activities (Aspergillus sp. and Stemphylium sp.) by MIC method.

  14. Syntheses, crystal structures, anticancer activities of three reduce Schiff base ligand based transition metal complexes

    NASA Astrophysics Data System (ADS)

    Chang, Hui-Qin; Jia, Lei; Xu, Jun; Zhu, Tao-Feng; Xu, Zhou-Qing; Chen, Ru-Hua; Ma, Tie-Liang; Wang, Yuan; Wu, Wei-Na

    2016-02-01

    Three nickel(II) complexes, [Ni2(L1)2(tren)2(H2O)](ClO4)3 (1), [NiL2(tren)2](ClO4)·2.5H2O (2), [NiL2(tren)2]I·1.5H2O·CH3OH (3) based on amino acid reduced Schiff ligands are synthesized and characterized by physico-chemical and spectroscopic methods. The results show that in all complexes, the amino acid ligand is deprotonated and acts as an anionic ligand. In the dinuclear complex 1, each Ni(II) atom has a distorted octahedron geometry while with different coordination environment. However, the complexes 2 and 3 are mononuclear, almost with the same coordination environment. Furthermore, in vitro experiments are carried out, including MTT assay, Annexin V/PI flow cytometry and western blotting, to assess whether the complexes have antitumor effect. And the results show that all the three complexes have moderate anticancer activity towards human hepatic cancer (HepG2), human cervical cancer (HeLa) and human prostate (PC3) cell lines, in a concentration dependent way. The complex 1 exhibit higher cytotoxicity than the other two complexes and can induce human hepatic cancer cell (HepG2) to cell apoptosis by activating caspase 3.

  15. Enthused research on DNA-binding and DNA-cleavage aptitude of mixed ligand metal complexes

    NASA Astrophysics Data System (ADS)

    Mahalakshmi, Rajkumar; Raman, Natarajan

    2013-08-01

    Five new Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) mixed ligand complexes have been synthesized using a Schiff base precursor (obtained by the condensation of N-(4-aminophenyl)acetamide and 4-chlorobenzaldehyde) as main ligand and 1,10-phenanthroline as co-ligand. They have been characterized by microanalytical data, IR, UV-Vis, magnetic moment values, conductivity and electrochemical measurements. The spectral data reveal that all the complexes exhibit octahedral geometry. The high electrical conductance of the complexes supports their electrolytic nature. The monomeric nature of the complexes has been assessed from their magnetic susceptibility values. These complexes are better antimicrobial active agents than the free ligands. DNA (CT) binding properties of these complexes have been explored by UV-Vis., viscosity measurements, cyclic voltammetry, and differential pulse voltammetry measurements. The oxidative cleavage activity of the complexes has been studied using supercoiled pUC19 DNA by gel electrophoresis. The experimental results show that the complexes are good intercalators.

  16. Synthesis and antioxidant activities of transition metal complexes based 3-hydroxysalicylaldehyde-S-methylthiosemicarbazone.

    PubMed

    Bal-Demirci, Tülay; Şahin, Musa; Kondakçı, Esin; Özyürek, Mustafa; Ülküseven, Bahri; Apak, Reşat

    2015-03-05

    The nickel(II), iron(III), oxovanadium(IV) complexes of the 3-hydroxysalicylidene-S-methyl-thiosemicarbazone (L) were obtained from the 3-hydroxysalicyldehyde-S-methylthiosemicarbazone with the R1-substituted-salicylaldehyde (R1: H, 3-OH) in the presence of Ni(II), Fe(III), VO(IV) as template ion. The ligand and its complexes were characterized by elemental analysis, electronic, UV/Vis., (1)HNMR, EPR and IR studies. The free ligand and its metal complexes have been tested for in vitro antioxidant capacity by reduction of copper(II) neocuproine (Cu(II)-Nc) using the CUPRAC method. The ligand exhibited more potent in vitro antioxidant capacity than its complexes. The obtained trolox equivalent antioxidant capacity (TEAC) value of the iron(III) complex (TEACCUPRAC=3.27) was higher than those of other complexes. Furthermore, the antioxidant activity of the free ligand and its complexes were determined by in vitro methods measuring the scavenging activity of reactive oxygen species (ROS) including hydroxyl radical (OH), superoxide anion radical (O2(-)), and hydrogen peroxide (H2O2), showing that especially the V(IV) and Fe(III) complexes had significant scavenging activity for ROS.

  17. Synthesis, spectroscopic characterization and electrochemical studies of Girard's T chromone complexes

    NASA Astrophysics Data System (ADS)

    Al-Saeedi, Sameerah I.; Alaghaz, Abdel-Nasser M. A.; Ammar, Reda A.

    2016-05-01

    Complexes of cobalt(II), nickel(II), copper(II) and zinc(II) of general composition [M(L)2] have been. The elemental analyses, molar conductance, spectral, magnetic moment and thermal measurements studies of the compounds led to the conclusion that the ligand acts as a tridentate manner (OON). The molar conductance of the metal complexes in fresh solution of DMSO lies in the range of 8.10-10.18 Ω-1 cm2 mol-1 indicating their non-electrolytic behavior. On the basis of analytical and spectroscopic techniques, octahedral geometry of the complexes was proposed. The ligand field parameters were calculated for Co(II), Ni(II) and Cu(II) complexes and their values were found in the range reported for a octahedral structure. The data show that the complexes have composition of ML2 type. The activation of thermodynamic parameters are calculated using different equations. The octahedral geometry of the complexes is confirmed using DFT method from DMOL3 calculations and ligand field parameters. The cyclic voltammograms of the Cu(II)/Co(II)/Ni(II) complexes investigated in DMSO solution exhibit metal centered electroactivity in the potential range -1.5 to +1.5 V. The electrochemical data obtained for Cu(II) complexes explains the change of structural arrangement of the ligand around Cu(II) ions.

  18. Synthesis, structural characterisation, bio-potential efficiency and DNA cleavage applications of nicotinamide metal complexes

    NASA Astrophysics Data System (ADS)

    Surendra Dilip, C.; Siva Kumar, V.; John Venison, S.; Vetha potheher, I.; Rajalaxmi (a) Subahashini, D.

    2013-05-01

    Mixed ligand complexes were synthesised using nicotinamide as the primary ligand and nitrite as the secondary ligand were characterised by FT-IR, UV-Vis, 1H NMR, TG-DTA-DTG, X-ray powder diffraction and physical analytical studies. From the molar conductance, magnetic moment and electronic spectral data of the synthesised complexes a general formula of [M(ONO)2(NA)2] where M = Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) and [Cr2(ONO)6(NA)2] with a distorted octahedral structure were proposed. Thermal analyses show that the complexes lose molecules of hydration initially and subsequently expel anionic and organic ligands in continuous steps. The kinetic parameter values, such as, E*, ΔH*, ΔS* and ΔG* illustrate the spontaneous association of the metal and ligands in the formation of the complexes. The antimicrobial efficacy of the ligand and its complexes were examined by in vitro method against various pathogenic bacterial and fungal strains. The metal complexes were found to posses efficient antimicrobial properties compared to nicotinamide and a few of these complexes could turn out to be excellent models for the design of effective antibiotic drug substances. The intercalating interaction of Cu(II) complex with CT-DNA was inspected by absorption spectral and viscosity studies, thermal denaturation and electro-analytical experiments.

  19. Enthused research on DNA-binding and DNA-cleavage aptitude of mixed ligand metal complexes.

    PubMed

    Mahalakshmi, Rajkumar; Raman, Natarajan

    2013-08-01

    Five new Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) mixed ligand complexes have been synthesized using a Schiff base precursor (obtained by the condensation of N-(4-aminophenyl)acetamide and 4-chlorobenzaldehyde) as main ligand and 1,10-phenanthroline as co-ligand. They have been characterized by microanalytical data, IR, UV-Vis, magnetic moment values, conductivity and electrochemical measurements. The spectral data reveal that all the complexes exhibit octahedral geometry. The high electrical conductance of the complexes supports their electrolytic nature. The monomeric nature of the complexes has been assessed from their magnetic susceptibility values. These complexes are better antimicrobial active agents than the free ligands. DNA (CT) binding properties of these complexes have been explored by UV-Vis., viscosity measurements, cyclic voltammetry, and differential pulse voltammetry measurements. The oxidative cleavage activity of the complexes has been studied using supercoiled pUC19 DNA by gel electrophoresis. The experimental results show that the complexes are good intercalators.

  20. Dinuclear metal(ii)-acetato complexes based on bicompartmental 4-chlorophenolate: syntheses, structures, magnetic properties, DNA interactions and phosphodiester hydrolysis.

    PubMed

    Massoud, Salah S; Ledet, Catherine C; Junk, Thomas; Bosch, Simone; Comba, Peter; Herchel, Radovan; Hošek, Jan; Trávníček, Zdeněk; Fischer, Roland C; Mautner, Franz A

    2016-08-09

    A series of dinuclear metal(ii)-acetato complexes: [Ni2(μ-L(Cl)O)(μ2-OAc)2](PF6)·3H2O (1), [Ni2(μ-L(Cl)O)(μ2-OAc)2](ClO4)·CH3COCH3 (2), [Cu2(μ-L(Cl)O)(μ2-OAc)(ClO4)](ClO4) (3), [Cu2(μ-L(Cl)O)(OAc)2](PF6)·H2O (4), [Zn2(μ-L(Cl)O)(μ2-OAc)2](PF6) (5) and [Mn2(L(Cl)-O)(μ2-OAc)2](ClO4)·H2O (6), where L(Cl)O(-) = 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-chlorophenolate, were synthesized. The complexes were structurally characterized by spectroscopic techniques and single crystal X-ray crystallography. Six-coordinate geometries with doubly bridged acetato ligands were found in Ni(ii), Zn(ii) and Mn(ii) complexes 1, 2, 5 and 6, whereas with Cu(ii) complexes a five-coordinate species was obtained with 4, and mixed five- and six-coordinate geometries with a doubly bridged dimetal core were observed in 3. The magnetic properties of complexes 1-4 and 6 were studied at variable temperatures and revealed weak to very weak antiferromagnetic interactions in 1, 2, 4 and 6 (J = -0.55 to -9.4 cm(-1)) and ferromagnetic coupling in 3 (J = 15.4 cm(-1)). These results are consistent with DFT calculations performed at the B3LYP/def2-TZVP(-f) level of theory. Under physiological conditions, the interaction of the dinculear complexes 1-5 with supercoiled plasmid ds-DNA did not show any pronounced nuclease activity, but Ni(ii) complexes 1 and 2 revealed a strong ability to unwind the supercoiled conformation of ds-DNA. The mechanistic studies performed on the interaction of the Ni(ii) complexes with DNA demonstrated the important impact of the nickel(ii) ion in the unwinding process. In combination with the DNA study, the phosphatase activity of complexes 1, 3, and 5 was examined by the phosphodiester hydrolysis of bis(2,4-dinitrophenol)phosphate (BDNPP) in the pH range of 5.5-10.5 at 25 °C. The Michaelis-Menten kinetics performed at pH 7 and 10.7 showed that catalytic efficiencies kcat/KM (kcat = catalytic rate constant, KM = substrate binding constant) decrease in the order

  1. In vitro DNA binding profile of enantiomeric dinuclear Cu(II)/Ni(II) complexes derived from l-/d-histidine-terepthaldehyde reduced Schiff base as potential chemotherapeutic agents.

    PubMed

    Yousuf, Imtiyaz; Arjmand, Farukh

    2016-11-01

    New chiral reduced Schiff base ligands, L1 and L2 derived from l-/d-histidine and terepthaldehyde, and their Cu(II) and Ni(II) dinuclear complexes 1 &2 (a and b) were synthesized and thoroughly characterized by various spectroscopic techniques. Comparative binding profile of both l-/d-enantiomeric Cu(II) and Ni(II) complexes with ct-DNA was studied by employing optical and spectroscopic techniques to evaluate their enantiopreferential selectivity towards molecular target DNA and thereby explore their relative chemotherapeutic potential. Quantitative assessment of DNA binding propensity was ascertained by calculating Kb, K and Ksv values of 1 &2 (a and b) which demonstrated higher binding affinity of l-enantiomeric Cu(II) complex, 1a and followed the order as 1a>1b>2a>2b. Scanning electron microscopy (SEM) was used to analyze the morphological changes of the DNA condensate in presence of complexes 1 (a and b). The SEM micrographs condensates revealed morphological transitions and formation of different structural features implicating the condensation process between the complexes and biomolecule occurred to form compact massive structures. The gel electrophoretic assay of complex 1a was carried out with pBR322 plasmid DNA which revealed an efficient cleaving ability of the complex via oxidative pathway with the involvement of singlet oxygen ((1)O2) and the superoxide anion (O2(•-)) radicals as the ROS responsible the cleavage reactions. Molecular docking studies of 1 (a and b) with DNA revealed selective recognition of G-C residues of the narrow minor groove of the DNA duplex and complex 1a demonstrated binding affinity towards DNA ascertained from its higher binding energy values. Furthermore, the cytotoxic assessment of 1a was examined on a panel of cancer cell lines of different histological origin employing SRB assay which revealed remarkably good cytotoxic activity towards HL60, HeLa and MCF7 cancer cell lines.

  2. Synthesis, structural investigation, DNA and protein binding study of some 3d-metal complexes with N'-(phenyl-pyridin-2-yl-methylene)-thiophene-2-carboxylic acid hydrazide.

    PubMed

    Mishra, Monika; Tiwari, Karishma; Shukla, Sachin; Mishra, R; Singh, Vinod P

    2014-11-11

    The ligand, N'-(phenyl-pyridin-2-yl-methylene)-thiophene-2-carboxylic acid hydrazide (Hpmtc) derived from thiophene-2-carboxylic acid hydrazide and 2-benzoyl pyridine, and its metal complexes with Co(II), Ni(II), Cu(II) and Zn(II) have been synthesized. These compounds are characterized by elemental analyses, magnetic susceptibility measurements, IR, NMR and UV-Vis spectral studies. The molecular structures of Hpmtc and its Co(II) (1), Ni(II) (2), Cu(II) (3) and Zn(II) (4) complexes are finally determined by X-ray crystallography. Various spectral and single-crystal X-ray diffraction studies suggest that Hpmtc coordinates with metal ions as a monobasic tridentate ligand forming mononuclear distorted octahedral complexes of the type [M(pmtc)2]. The molecular structures of the complexes are stabilized by CH⋯N, CH⋯O intermolecular H-bonding, and CH⋯π and π⋯π interactions. The DNA binding experiment of the complexes 1, 3 and 4 by UV-Vis absorption, and EB-DNA displacement by fluorescence spectroscopy, reveal an intercalative mode of binding between CT-DNA (calf-thymus DNA) and the metal complexes. These complexes exhibit a moderate ability to cleave pBR322 plasmid DNA. A comparative bovine serum albumin (BSA) protein binding activity of the complexes 1, 3 and 4 has also been determined by UV-Vis absorption and fluorescence spectroscopy. The DNA binding and protein binding studies suggest that the complex 3 exhibits more effective binding activity (Kb=5.54×10(5) and Kq=1.26×10(6) M(-1), respectively) than complexes 1 and 4. However, the complex 1 shows better hydrolytic DNA cleavage activity compared to 3 and 4 complexes.

  3. Synthesis, structural investigation, DNA and protein binding study of some 3d-metal complexes with N‧-(phenyl-pyridin-2-yl-methylene)-thiophene-2-carboxylic acid hydrazide

    NASA Astrophysics Data System (ADS)

    Mishra, Monika; Tiwari, Karishma; Shukla, Sachin; Mishra, R.; Singh, Vinod P.

    2014-11-01

    The ligand, N‧-(phenyl-pyridin-2-yl-methylene)-thiophene-2-carboxylic acid hydrazide (Hpmtc) derived from thiophene-2-carboxylic acid hydrazide and 2-benzoyl pyridine, and its metal complexes with Co(II), Ni(II), Cu(II) and Zn(II) have been synthesized. These compounds are characterized by elemental analyses, magnetic susceptibility measurements, IR, NMR and UV-Vis spectral studies. The molecular structures of Hpmtc and its Co(II) (1), Ni(II) (2), Cu(II) (3) and Zn(II) (4) complexes are finally determined by X-ray crystallography. Various spectral and single-crystal X-ray diffraction studies suggest that Hpmtc coordinates with metal ions as a monobasic tridentate ligand forming mononuclear distorted octahedral complexes of the type [M(pmtc)2]. The molecular structures of the complexes are stabilized by Csbnd H⋯N, Csbnd H⋯O intermolecular H-bonding, and Csbnd H⋯π and π⋯π interactions. The DNA binding experiment of the complexes 1, 3 and 4 by UV-Vis absorption, and EB-DNA displacement by fluorescence spectroscopy, reveal an intercalative mode of binding between CT-DNA (calf-thymus DNA) and the metal complexes. These complexes exhibit a moderate ability to cleave pBR322 plasmid DNA. A comparative bovine serum albumin (BSA) protein binding activity of the complexes 1, 3 and 4 has also been determined by UV-Vis absorption and fluorescence spectroscopy. The DNA binding and protein binding studies suggest that the complex 3 exhibits more effective binding activity (Kb = 5.54 × 105 and Kq = 1.26 × 106 M-1, respectively) than complexes 1 and 4. However, the complex 1 shows better hydrolytic DNA cleavage activity compared to 3 and 4 complexes.

  4. Synthesis, Characterization and Antimicrobial Activity of d8-10 Metal Complexes of some 2-Substituted-1H-Benzimidazoles

    PubMed Central

    Tavman, Aydin; Ötük, Gülten

    1999-01-01

    The metal complexes of nine 2-substituted-1H-benzimidazoles (I-IX) with Ni(II), Pd(II), Cu(II), Ag(I), Zn(II) salts were synthesized. The compounds were characterized by melting point, analytical data, IR spectroscopy and magnetic susceptibility. The antimicrobial activity of the compounds was determined by the disk diffusion method in Mueller-Hinton Agar on Staphylococcus aureus ATCC 6538, Staphylococcus epidermidis ATCC 12228, Escherichia coli ATCC 8739, Klebsiella pneumoniae ATCC 4352, Pseudomonas aeruginosa ATCC 1539, Salmonella typhi, Shigella flexneri, Proteus mirabilis, Candida albicans ATCC 10231. Cu(II)and Ag(I)complexes of II, III and IV showed considerable activity against S. aureus, S. epidermidis, Ps. aeruginosa, S. typhi, Sh. flexneri and C. albicans microorganisms, the ligands themselves having no effect. PMID:18472907

  5. Novel heterometallic metal-azido complex synthesized by "one-step" reaction: synthetic strategy and magnetic properties

    NASA Astrophysics Data System (ADS)

    Jiao, Yong-Kun; Li, Xiu-Ping; Zhao, Cui; Wang, Hai-Chao; Xue, Min; Zhao, Jiong-Peng; Liu, Fu-Chen

    2013-06-01

    A novel heterometallic complex, [Ni2Mn(N3)2(nic)4·(H2O)2]n (1) (nic=nicotinate), was obtained by assembling MnCl2·4H2O, Ni(NO3)2·6H2O, NaN3 and nicotinic acid with a "one step" synthetic strategy—hydrothermal reaction. The 3D structure of the complex can be described as end-on (EO) azido and syn,syn carboxylates mixed bridged by alternate Ni-Mn-Ni trimers linked by the nicotinate. Dominant ferromagnetic interactions were observed between the NiII and MnII ions in the trimer.

  6. Spectroscopic and magnetic investigations of some transition metal complexes with N-4-methoxyphenyl- N-4-chlorobenzoyl hydrazide as ligand

    NASA Astrophysics Data System (ADS)

    David, L.; Rusu, M.; Cozar, O.; Rusu, D.; Todica, M.; Balan, C.

    1999-05-01

    The preparation, spectroscopic and magnetic properties of ML 2Cl 2 (M=Cu(II), Mn(II), Ni(II)) and [ML 3]Cl 3 (M=Fe(III), Cr(III)), L= N-4-methoxyphenyl- N-4-chlorobenzoyl hydrazide are reported. In all the studied complexes the N-4-methoxyphenyl- N-4-chlorobenzoyl hydrazide acts as a neutral bidentate chelating ligand with coordination involving the carbonyl oxygen and nitrogen atom of the secondary hydrazide group. The complexes appear to have an pseudo-octahedral stereochemistry. ESR parameters ( g1=4.432, g2=1.991, D=0.096 cm -1) and μeff=3.55 μB obtained for [CrL 3]Cl 3 also suggest the possibilities of magnetic dipole-dipole coupling interactions between Cr(III) ions.

  7. Organometallic nickel(III) complexes relevant to cross-coupling and carbon-heteroatom bond formation reactions.

    PubMed

    Zheng, Bo; Tang, Fengzhi; Luo, Jia; Schultz, Jason W; Rath, Nigam P; Mirica, Liviu M

    2014-04-30

    Nickel complexes have been widely employed as catalysts in C-C and C-heteroatom bond formation reactions. In addition to Ni(0) and Ni(II) intermediates, several Ni-catalyzed reactions are proposed to also involve odd-electron Ni(I) and Ni(III) oxidation states. We report herein the isolation, structural and spectroscopic characterization, and organometallic reactivity of Ni(III) complexes containing aryl and alkyl ligands. These Ni(III) species undergo transmetalation and/or reductive elimination reactions to form new C-C or C-heteroatom bonds and are also competent catalysts for Kumada and Negishi cross-coupling reactions. Overall, these results provide strong evidence for the direct involvement of organometallic Ni(III) species in cross-coupling reactions and oxidatively induced C-heteroatom bond formation reactions.

  8. Synthesis, characterization and biocidal activities of heterobimetallic complexes having tin(IV) as a padlock

    NASA Astrophysics Data System (ADS)

    Husain, Ahmad; Nami, Shahab A. A.; Siddiqi, K. S.

    2010-04-01

    A mononuclear precursor complex, [(CH 3) 2Sn(tpdtc)] and several of its heterobimetallic derivatives of the type, [(CH 3) 2Sn(tpdtc)]MCl 2 have been synthesized by the simple addition reaction of transition metal chlorides, MCl 2· nH 2O where tpdtc = tetraethylenepentamine bis(dithiocarbamate) anion, M = Fe(II), Co(II), Ni(II), Cu(II) and Zn(II). The synthesized complexes have been systematically characterized by the physicochemical and spectroscopic techniques. A square-pyramidal geometry has been proposed for all the transition metal atoms with chloride ions occupying the axial while the three nitrogen atoms occupying the equatorial positions. A symmetrical bidentate coordination has been observed for the dithiocarbamato moiety leading to the formation of 18 member cavity. The thermal studies reveal that the mononuclear complex decomposes in three stages while its heterobimetallic analog exhibits a simple two-stage profile. The conductivity measurement data (1 mmol solution) implies a non-electrolytic behavior for all the complexes as evident by their low conductivity values obtained at room temperature. The heterobimetallic complexes have also been tested against the bacterial ( Escherichia coli and Pseudomonas aeruginosa) and antifungal strains ( Aspergillus niger and Fusarium oxysporum). All the complexes were found to be active against the test organisms and maximum activity was found for [(CH 3) 2Sn(tpdtc)]CuCl 2 complex.

  9. Correlation between ionic radii of metal azodye complexes and electrical conductivity.

    PubMed

    El-Ghamaz, N A; El-Sonbati, A Z; Diab, M A; El-Bindary, A A; Mohamed, G G; Morgan, Sh M

    2015-08-05

    5-(2,3-Dimethyl-1-phenylpyrazol-5-one azo)-2-thioxo-4-thiazolidinone (HL) and its metal complexes with copper(II) (1), cobalt(II) (2) and nickel(II) (3) are synthesized and characterized by physico-chemical techniques. The thermal properties of the ligand (HL) and its metal complexes (1-3) are discussed. The thermal activation energies of decomposition (Ea) of HL and its metal complexes with Cu(II), Co(II) and Ni(II) are found to be 48.76, 36.83, 30.59 and 40.45 kJ/mol, respectively. The frequency and temperature dependence of ac conductivity, dielectric constants for HL and its complexes (1-3) are investigated in the temperature range 300-356 K and frequency range 0.1-100 kHz. Both of the ac conductivity and the values of the thermal activation energy for conduction, as well as the dielectric properties of the complexes of HL are found to depend on the nature of the metallic ions. The values of the thermal activation energies of electrical conductivity decrease with increasing the value of test frequency. The small polarons tunneling (SPT) is the dominant conduction mechanism for the ligand (HL), while for complex (2) the overlapping large tunneling model (OLPT) is the dominant conduction mechanism. The correlated barrier hopping (CBH) is the dominant conduction mechanism for both of the complexes (1) and (3).

  10. Spectral, XRD, SEM and biological activities of transition metal complexes of polydentate ligands containing thiazole moiety

    NASA Astrophysics Data System (ADS)

    Neelakantan, M. A.; Marriappan, S. S.; Dharmaraja, J.; Jeyakumar, T.; Muthukumaran, K.

    2008-11-01

    Metal complexes of o-vanillidene-2-aminobenzothiazole have been prepared and characterized by elemental and spectral (vibrational, electronic, 1H NMR and EPR) data as well as magnetic susceptibility measurements and thermo gravimetric analysis (TG/DTA). The low molar conductance values reveal the non-electrolytic nature of these complexes. The elemental analysis suggests that the stoichiometry to be 1:2 (metal:ligand). Magnetic susceptibility data coupled with electronic spectra suggest that two ligands coordinate to each metal atom by phenolic oxygen and imino nitrogen to form high spin octahedral complex with Co(II), Mn(II) and Ni(II). The fifth and sixth position of metal ion is satisfied with water molecules. The thermal behaviour (TG/DTA) of the synthesised complexes shows that the complexes loss water molecules in the first step followed by decomposition of the ligand. Spin Hamiltonian parameters predict a distorted tetrahedral geometry for the copper complex. XRD and SEM analysis provide the crystalline nature and the morphology of the metal complexes. The in vitro biological activity of the metal chelates is tested against the Gram positive bacteria ( Bacillus amyloliquifacians) and gram negative bacteria ( Pseudomonas species), fungus ( Aspergillus niger) and yeast ( Sacchromyces cereviaceae). Most of the metal chelates exhibited higher biological activities.

  11. Cytotoxic behavior and spectroscopic characterization of metal complexes of ethylacetoacetate bis(thiosemicarbazone) ligand

    NASA Astrophysics Data System (ADS)

    El-Tabl, Abdou Saad; El-wahed, Moshira Mohamed Abd; Rezk, Ahmed Mahmoud Salah Mahmoud

    2014-01-01

    Reaction of Cr(III), Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) ion with 2,4-dihydrazino-thioamido-1-ethoxybutane led to the formation of mono and binuclear complexes. These complexes have been characterized by elemental analyses, IR, UV-Vis spectra, magnetic moments, molar conductances, 1H NMR and mass spectra (ligand and its Zn(II) complex), thermal analyses (DTA and TGA) and ESR measurements. The IR data suggest the involvement of sulfur and azomethane nitrogen atoms in coordination to the central metal ion .The Molar conductances of the complexes in DMF are commensurate with their non-ionic character. The ESR spectra of Cu(II) complexes show axial type symmetry (d(x2-y2)) ground state with covalent bond character. On the basis of spectral studies, octahedral or tetrahedral geometry has been assigned to the metal complexes. Complexes have been tested invitro against tumor cells and number of microorganisms in order to assess their antitumor and antimicrobial properties.

  12. Coordination functionalization of graphene oxide with tetraazamacrocyclic complexes of nickel(II): Generation of paramagnetic centers

    NASA Astrophysics Data System (ADS)

    Basiuk, Vladimir A.; Alzate-Carvajal, Natalia; Henao-Holguín, Laura V.; Rybak-Akimova, Elena V.; Basiuk, Elena V.

    2016-05-01

    We describe a novel approach to functionalization of graphene oxide (GO) which allows for a facile generation of paramagnetic centers from two diamagnetic components. Coordination attachment of [Ni(cyclam)]2+ or [Ni(tet b)]2+ tetraazamacrocyclic cations to carboxylic groups of GO takes place under basic conditions in aqueous-based reaction medium. The procedure is very straightforward and does not require high temperatures or other harsh conditions. Changing the coordination geometry of Ni(II) from square-planar tetracoordinated to pseudooctahedral hexacoordinated brings about the conversion from low-spin to high-spin state of the metal centers. Even though the content of tetraazamacrocyclic complexes in functionalized GO samples was found to be relatively low (nickel content of ca. 1 wt%, as determined by thermogravimetric analysis, elemental analysis and energy dispersive X-ray spectroscopy), room temperature magnetic susceptibility measurements easily detected the appearance of paramagnetic properties in GO + [Ni(cyclam)] and GO + [Ni(tet b)] nanohybrids, with effective magnetic moments of 1.95 BM and 2.2 BM for, respectively. According to density functional theory calculations, the main spin density is localized at the macrocyclic complexes, without considerable extension to graphene sheet, which suggests insignificant ferromagnetic coupling in the nanohybrids, in agreement with the results of magnetic susceptibility measurements. The coordination attachment of Ni(II) tetraazamacrocycles to GO results in considerable changes in Fourier-transform infrared and X-ray photoelectron spectra, as well as in GO morphology, as observed by scanning and transmission electron microscopy, atomic force and scanning tunneling microscopy.

  13. Exploring DNA binding and nucleolytic activity of few 4-aminoantipyrine based amino acid Schiff base complexes: A comparative approach

    NASA Astrophysics Data System (ADS)

    Raman, N.; Sakthivel, A.; Pravin, N.

    A series of novel Co(II), Cu(II), Ni(II) and Zn(II) complexes were synthesized from Schiff base(s), obtained by the condensation of 4-aminoantipyrine with furfural and amino acid (glycine(L1)/alanine(L2)/valine(L3)) and respective metal(II) chloride. Their structural features and other properties were explored from the analytical and spectral methods. The binding behaviors of the complexes to calf thymus DNA were investigated by absorption spectra, viscosity measurements and cyclic voltammetry. The intrinsic binding constants for the above synthesized complexes are found to be in the order of 102 to 105 indicating that most of the synthesized complexes are good intercalators. The binding constant values (Kb) clearly indicate that valine Schiff-base complexes have more intercalating ability than alanine and glycine Schiff-base complexes. The results indicate that the complexes bind to DNA through intercalation and act as efficient cleaving agents. The in vitro antibacterial and antifungal assay indicates that these complexes are good antimicrobial agents against various pathogens. The IC50 values of [Ni(L1)2] and [Zn(L1)2] complexes imply that these complexes have preferable ability to scavenge hydroxyl radical.

  14. Exploring DNA binding and nucleolytic activity of few 4-aminoantipyrine based amino acid Schiff base complexes: a comparative approach.

    PubMed

    Raman, N; Sakthivel, A; Pravin, N

    2014-05-05

    A series of novel Co(II), Cu(II), Ni(II) and Zn(II) complexes were synthesized from Schiff base(s), obtained by the condensation of 4-aminoantipyrine with furfural and amino acid (glycine(L1)/alanine(L2)/valine(L3)) and respective metal(II) chloride. Their structural features and other properties were explored from the analytical and spectral methods. The binding behaviors of the complexes to calf thymus DNA were investigated by absorption spectra, viscosity measurements and cyclic voltammetry. The intrinsic binding constants for the above synthesized complexes are found to be in the order of 10(2) to 10(5) indicating that most of the synthesized complexes are good intercalators. The binding constant values (Kb) clearly indicate that valine Schiff-base complexes have more intercalating ability than alanine and glycine Schiff-base complexes. The results indicate that the complexes bind to DNA through intercalation and act as efficient cleaving agents. The in vitro antibacterial and antifungal assay indicates that these complexes are good antimicrobial agents against various pathogens. The IC50 values of [Ni(L1)2] and [Zn(L1)2] complexes imply that these complexes have preferable ability to scavenge hydroxyl radical.

  15. DNA binding propensity and nuclease efficacy of biosensitive Schiff base complexes containing pyrazolone moiety: Synthesis and characterization

    NASA Astrophysics Data System (ADS)

    Paulpandiyan, Rajakkani; Raman, Natarajan

    2016-12-01

    A series of novel Co(II), Cu(II), Ni(II) and Zn(II) complexes (1-8) were synthesized from pyrazolone precursor Schiff base(s), obtained by the condensation of 4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one (4-aminoantipyrine) with cinnamaldehyde/benzaldehyde and respective metal(II) chloride. They have been characterized by elemental analysis, magnetic susceptibility, molar conductance measurements, UV-Vis., IR, NMR, ESI mass spectra and EPR studies. These complexes show lower conductance values, supporting their non-electrolytic nature. Spectroscopic and other analytical data of the complexes suggest octahedral geometry. The binding properties of these complexes with DNA have been explored by electronic absorption spectra, cyclic voltammetry and viscosity measurements which reveal that the complexes have the ability to interact with calf thymus DNA (CT DNA) by intercalative mode. The binding constant (Kb) values clearly signify that the complex 1 has more intercalating ability than other complexes. DNA cleavage efficacy of these complexes with pUC18 DNA has been investigated by gel electrophoresis technique. All the complexes have been found to promote cleavage of pUC18 DNA from the super coiled form I to the open circular form II in presence of hydrogen peroxide. The in vitro antibacterial and antifungal assay, investigated by Minimum Inhibitory Concentration (MIC) method indicates that these complexes are good antimicrobial agents against various pathogens.

  16. Novel metal-based pharmacologically dynamic agents of transition metal(II) complexes: Designing, synthesis, structural elucidation, DNA binding and photo-induced DNA cleavage activity

    NASA Astrophysics Data System (ADS)

    Raman, N.; Jeyamurugan, R.; Sakthivel, A.; Mitu, L.

    2010-01-01

    Novel Schiff base Cu(II), Ni(II), Co(II) and Zn(II) complexes have been designed and synthesized using the macrocyclic ligand derived from the condensation of diethylphthalate with Schiff base, obtained from benzene-1,2-diamine and 3-benzylidene-pentane-2,4-dione. The ligand and its complexes have been characterized by analytical and spectral techniques. DNA binding properties of these complexes have been investigated by UV-vis, viscosity measurements, cyclic voltammetric and differential pulse voltammogram studies. The intrinsic binding constants for Co(II), Ni(II), Cu(II) and Zn(II) complexes are 1.6 × 10 6, 1.8 × 10 6, 2.0 × 10 6 and 1.5 × 10 6 M -1 respectively which are obtained from electronic absorption experiment. Control DNA cleavage experiments using pUC19 supercoiled (SC) DNA and minor groove binder (distamycin) suggest the major groove binding tendency for the synthesized complexes. In the presence of a reducing agent like 3-mercaptopropionic acid (MPA), the synthesized complexes show chemical nuclease activity under dark reaction condition. The complexes also show efficient photo-induced DNA cleavage activity on irradiation with a monochromatic UV light of 360 nm in the presence of inhibitors. Control experiments show inhibition of cleavage in the presence of singlet oxygen quencher like sodium azide and enhancement of cleavage in D 2O, suggesting the formation of singlet oxygen as a reactive species in a type-II process.

  17. Selective separation of copper(II) and nickel(II) from aqueous media using the complexation-ultrafiltration process.

    PubMed

    Molinari, Raffaele; Poerio, Teresa; Argurio, Pietro

    2008-01-01

    The polyethylenimine (PEI) as complexing agent was used to study the complexation-ultrafiltration (CP-UF) process in the selective removal of Cu(II) from Ni(II) contained in aqueous media. Preliminary tests showed that optimal chemical conditions for Cu(II) and Ni(II) complexation by the PEI polymer were pH>6.0 and 8.0, respectively, and polymer/metal weight ratio of 3.0 and 6.0, respectively. The effect of some important operating parameters on process selectivity was studied by performing UF tests at different parameters: pH, polymer/metal weight ratio, transmembrane pressure (TMP), and membrane cut-off in a batch experimental set-up. It was observed that process selectivity was achieved by choosing the pH value for obtaining a preferential copper complexation (pH 6.0), and the polymer/metal ratio needed to bound only the copper ion (3.0). The selective separation by UF tests was performed by using both a laboratory aqueous solution and a real aqueous effluent (water from Emoli torrent, Rende (CS)). The Iris 30 membrane at TMP of 200 kPa (2 bar) for both aqueous media gave the best results. A complete nickel recovery was reached, and copper recovery was the highest for this membrane (94% and 92%). Besides at this pressure, a lower water amount was needed to obtain total nickel recovery by diafiltration. A little higher membrane fouling was obtained by using the river effluent due to the presence of dissolved organic and inorganic matter.

  18. Complexity Survey.

    ERIC Educational Resources Information Center

    Gordon, Sandra L.; Anderson, Beth C.

    To determine whether consensus existed among teachers about the complexity of common classroom materials, a survey was administered to 66 pre-service and in-service kindergarten and prekindergarten teachers. Participants were asked to rate 14 common classroom materials as simple, complex, or super-complex. Simple materials have one obvious part,…

  19. Polynuclear transition metal complexes with thiocarbohydrazide and dithiocarbamates

    NASA Astrophysics Data System (ADS)

    Siddiqi, K. S.; Khan, Sadaf; Nami, Shahab A. A.; El-ajaily, M. M.

    2007-07-01

    Sn(tch) 2{MCl 2} 2 was prepared from the precursor Sn(tch) 2 and MCl 2. It was subsequently allowed to react with diethyldithiocarbamate which yielded the trinuclear complexes of the type Sn(tch) 2{M 2(dtc) 4}, where tch = thiocarbohydrazide, M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and dtc = diethyldithiocarbamate. They were characterized on the basis of microanalytical, thermal (TGA/DSC), spectral (IR, UV-vis, EPR, 1H NMR) studies, conductivity measurement and magnetic moment data. On the basis of spectral data a tetrahedral geometry has been proposed for the halide complexes, Sn(tch) 2{MCl 2} 2 except for Cu(II) which exhibits a square planar coordination although the transition metal ion in Sn(tch) 2{M 2(dtc) 4} achieves an octahedral geometry where the dithiocarbamato moiety acts as a symmetrical bidentate ligand. The bidentate nature has been established by the appearance of a sharp single ν(C-S) around 1000 cm -1. A downfield shift observed in NH a and NH b protons on moving from Sn(tch) 2 to Sn(tch) 2{MCl 2} 2 is due to the drift of electrons toward metal atoms. A two-step pyrolysis has been observed in the Sn(tch) 2{MCl 2} 2 complexes while their dithiocarbamato derivatives exhibit a three-stage degradation pattern. Finally, the in vitro antibacterial activity of Sn(tch) 2{M 2(dtc) 4} and the mononuclear Sn(tch) 2 has been carried out on bacterial strains Escherichia coli and Salmonella typhi. The compounds were found to be active against the test organisms. The activity of the complexes is enhanced with increasing concentration. The maximum activity in both the strains was achieved by cobalt(II) dithiocarbamate complex. Minimum activity was found for Sn(tch) 2 which generally increases with the introduction of transition metal ion in the complex.

  20. Cobalt, nickel, copper and zinc complexes with 1,3-diphenyl-1H-pyrazole-4-carboxaldehyde Schiff bases: antimicrobial, spectroscopic, thermal and fluorescence studies.

    PubMed

    Singh, Kiran; Kumar, Yogender; Puri, Parvesh; Kumar, Mahender; Sharma, Chetan

    2012-06-01

    Two new Schiff bases of 1,3-diphenyl-1H-pyrazole-4-carboxaldehyde and 4-amino-5-mercapto-3-methyl/H-1,2,4-triazole [HL(1-2)] and their Cobalt, Nickel, Copper and Zinc complexes have been synthesized and characterized by elemental analyses, spectral (UV-vis, IR, (1)H NMR, Fluorescence) studies, thermal techniques and magnetic measurements. A square planar geometry for Cu(II) and octahedral geometry for Co(II), Ni(II) and Zn(II) complexes have been proposed. In order to evaluate the biological activity of Schiff bases and to assess the role of metal ion on biological activity, the pyrazole Schiff bases and their metal complexes have been studied in vitro antibacterial against Staphylococcus aureus, Bacillus subtilis, Escherichia coli, Pseudomonas aeruginosa and antifungal against Aspergillus niger, and Aspergillus flavus. In most of the cases higher activity was exhibited upon coordination with metal ions.

  1. Enantiomeric in vitro DNA binding, pBR322 DNA cleavage and molecular docking studies of chiral L- and D-ternary copper(II) complexes of histidine and picolinic acid.

    PubMed

    Parveen, Shazia; Arjmand, Farukh; Ahmad, Iqbal

    2014-01-05

    Novel chiral ternary Cu(II) and Ni(II) complexes of l/d-histidine and picolinic acid, 1 and 2(a and b) were synthesized and characterized by elemental analysis, molar conductance and spectroscopic data (IR, NMR, EPR, UV-vis). In vitro DNA binding profile of both Cu(II) and Ni(II) complexes have been investigated by UV-vis titrations, while fluorescence spectroscopy, circular dichroism and viscosity measurements were carried out for Cu(II) complexes 1(a and b). Both the enantiomers of 1 and 2(a and b) bind to CT DNA via electrostatic interactions and the intrinsic binding constant, Kb values for complexes 1 and 2(a and b) were found to be 5.6×10(4), 9.8×10(3), 8.2×10(3) and 6.7×10(3)M(-1), respectively suggesting greater binding propensity of l-form of Cu(II) complex 1a. The DNA cleavage activity of complexes 1(a and b), investigated by agarose gel electrophoresis suggested an oxidative pathway for DNA cleavage. Further, the molecular docking studies of complexes 1(a and b) were carried out with B-DNA revealing that the complexes bind to the adenine-thymine residues in the minor groove of the DNA. The resulting binding energies of docked metal complexes 1(a and b) were found to be -265.1 and -218.9KJmol(-1), respectively. Furthermore, enantiomeric complexes 1 and 2(a and b) were screened for in vitro antimicrobial activity.

  2. Synthesis, structure, magnetic properties and biological activity of supramolecular copper(II) and nickel(II) complexes with a Schiff base ligand derived from vitamin B6.

    PubMed

    Mukherjee, Tirtha; Costa Pessoa, João; Kumar, Amit; Sarkar, Asit R

    2013-02-21

    Three new complexes of Cu(II) and Ni(II), [Cu(II)(H(2)pydmedpt)](2+)·2Cl(-) (1), [Ni(II)(H(2)pydmedpt)](2+)·2Cl(-) (2) and [Ni(II)(pydmedpt)(OH)](-)·K(+) (3) of the Schiff base ligand [H(2)pydmedpt](2+)·2Cl(-) were synthesized by the in situ reaction of pyridoxal (pyd), a vitamer of vitamin B(6), N,N-bis[3-aminopropyl]methylamine (medpt) and copper(II) acetate or nickel(II) acetate, respectively. The molecular structures of 1 and 2 were determined by single crystal X-ray diffraction studies. The structure of 3 in the solid state was inferred by elemental analysis, diffuse reflectance spectrum, variable temperature magnetic moment studies and DFT calculations. The binding of the Schiff base ligand to the metal centers involves two phenolato oxygens, two imine nitrogens and one amine nitrogen. The coordination geometry around Cu in 1 is distorted square pyramidal and that around the Ni atom in 2 is intermediate between square-pyramidal and trigonal-bipyramidal. In the crystals the compounds form supramolecular one dimensional chain structures stabilized by hydrogen bonding and π-π stacking interactions. Variable temperature magnetic moment data of 2 indicate the presence of a momomeric high spin Ni(II) centre in the complex. The solid state diffuse reflectance spectrum, conductance and elemental analysis suggest that 3 is a Ni(II) complex with a tetragonally distorted octahedral field, the sixth position being occupied by the oxygen atom of a hydroxyl group. The variable temperature magnetic moment of 3 indicates the presence of a ferromagnetic dinuclear species (29.2%) along with the major monomeric species, the intra-dimer exchange term J value being 14.3 cm(-1). The competitive binding of 1 and 2 with DNA was studied in the concentration range 40 to 400 μM, the apparent binding constants being K = 2.9 × 10(3) and 6.7 × 10(3) M(-1), respectively. Human Serum Albumin (HSA) binding studies were carried out at concentrations of 800-1000 μM and 400-500

  3. Synthesis, electronic, photoacoustic and electron spin resonance investigations on some tetrathiocyanate binuclear mixed-metal complexes

    NASA Astrophysics Data System (ADS)

    Singh, Raghuvir

    Complexes of the type M 1M 2(SCN) 4xL[M 1 = Ni(II); M 2 = Cd(II) and Hg(II) and L = pyridine, morpholine, dioxan, benzo(f)quinoline, 2,2'-bipyridine, 2,2'-bipyridine N, N'-dioxide, isonicotinic acid hydrazide and 1,10-phenanthroline: x = 2 or 4] have been synthesized and characterized by chemical analysis, magnetic susceptibility, infrared, electronic and photoacoustic (PAS) spectra as well as electron spin resonance (ESR) spectral studies in the solid and solution state. The different coordination sites have been investigated in these ligands towards metal coordination and the behaviour of thiocyanate anions studied. Electron spin resonance spectral data for copper complexes show the distorted octahedral stereochemistry around copper(II) in these complexes. The parameters such as g∥, g⊥, A∥, A⊥, < g>, < A> and α 2 calculated for the copper complexes from their ESR spectra indicate the presence of unpaired electron in d x2- y2 or d z2 orbitals. The photoacoustic and electronic spectra of these complexes were studied in the solid state to see the nature of thiocyanate and overall symmetry of the complexes. The results on electronic and photoacoustic spectral studies are in good agreement with ESR data.

  4. Synthesis, Characterization and Biological Evaluation of Transition Metal Complexes Derived from N, S Bidentate Ligands

    PubMed Central

    Md Yusof, Enis Nadia; Ravoof, Thahira Begum S. A.; Tiekink, Edward R. T.; Veerakumarasivam, Abhimanyu; Crouse, Karen Anne; Mohamed Tahir, Mohamed Ibrahim; Ahmad, Haslina

    2015-01-01

    Two bidentate NS ligands were synthesized by the condensation reaction of S-2-methylbenzyldithiocarbazate (S2MBDTC) with 2-methoxybenzaldehyde (2MB) and 3-methoxybenzaldehyde (3MB). The ligands were reacted separately with acetates of Cu(II), Ni(II) and Zn(II) yielding 1:2 (metal:ligand) complexes. The metal complexes formed were expected to have a general formula of [M(NS)2] where M = Cu2+, Ni2+, and Zn2+. These compounds were characterized by elemental analysis, molar conductivity, magnetic susceptibility and various spectroscopic techniques. The magnetic susceptibility measurements and spectral results supported the predicted coordination geometry in which the Schiff bases behaved as bidentate NS donor ligands coordinating via the azomethine nitrogen and thiolate sulfur. The molecular structures of the isomeric S2M2MBH (1) and S2M3MBH (2) were established by X-ray crystallography to have very similar l-shaped structures. The Schiff bases and their metal complexes were evaluated for their biological activities against estrogen receptor-positive (MCF-7) and estrogen receptor-negative (MDA-MB-231) breast cancer cell lines. Only the Cu(II) complexes showed marked cytotoxicity against the cancer cell lines. Both Schiff bases and other metal complexes were found to be inactive. In concordance with the cytotoxicity studies, the DNA binding studies indicated that Cu(II) complexes have a strong DNA binding affinity. PMID:25988384

  5. Detecting Ni(II) in aqueous solution by 3-(2-pyridyl)-[1,2,3]triazolo[1,5-a]pyridine and dimethyl-β-cyclodextrin.

    PubMed

    Jullian, Carolina; Fernández-Sandoval, Samuel; Rojas-Aranguiz, Max; Gómez-Machuca, Horacio; Salgado-Figueroa, Paola; Celis-Barros, Cristián; Zapata-Torres, Gerald; Adam, Rosa; Abarca, Belén

    2014-07-17

    A new supramolecular sensitizer for nickel(II) ion in aqueous solution based on a pyridyltriazolopyridine-cyclodextrin inclusion complex is proposed. The inclusion complexation behavior, characterization and binding ability of pyridyltriazolopyridine (PTP) with dimethyl-β-cyclodextrin (DMβCD) has been investigated both in solution and solid state by means of absorption, fluorescence, (1)H NMR, DSC, and molecular modeling methods. The stoichiometry of the inclusion complex is 1:1, and the thermodynamic studies indicate that the inclusion of PTP is mainly an entropic driven process. The 2D NMR studies revealed that the pyridyl-triazolopyridine is included by both sides of cyclodextrin which are in good agreement with the docking results. The fluorescence changes upon addition of divalent cations to the inclusion complex indicate a high selectivity and sensitivity for Ni(2+) by fluorescence quenching in neutral aqueous solution.

  6. Spectral and structural properties of 2D network complex [Ni(4,4'-bipyridine) 2(NCS) 2] n

    NASA Astrophysics Data System (ADS)

    Zhang, Y.; Jianmin, L.; Nishiura, M.; Imamoto, T.

    2000-02-01

    The complex [Ni(4,4'-bipyridine) 2(NCS) 2] n, in which nickel atoms are linked by two different Ni-4,4'-bpy-Ni assemblies to form two-dimensional distorted square net structure and the most effective packing of layers, has been isolated and structurally characterized. It represents the first example of Ni(II)-4,4'-bpy complex possesses 2D network. Crystal data for I: Fw=487.23, a=12.156(3), b=11.38(2), c=16.646(8) Å, β=100.43(3), V=2265(1) Å3, Z=4, space group=C2/c, T=298 K, λ((Mo-K α)=0.71070 Å, ρ calc=1.429 g cm -3, μ=10.62 cm-1, F(000)=1000, R=0.054, Rw=0.086, GOF=3.98. The UV-VIS absorption spectrum of the title complex is also reported and explained perfectly by the scaling radial theory which proposed by us. The strong and broad absorption bands occurred at 10433, 16830, 26556 cm -1, and they are assigned as d-d transitions of Ni(II) ion in octahedral field: 3A2g→ 3T2ga,b+ 3T2gc; 3A2g→ 3T1gz+ 3T1gy,x; 3A2g→ 3T1gz+ 3T1gy,x. The calculated results of the d-d transition energy levels agree well with the experimental values.

  7. Synthesis, spectral characterization, molecular modeling and antimicrobial studies of tridentate azo-dye Schiff base metal complexes

    NASA Astrophysics Data System (ADS)

    Alaghaz, Abdel-Nasser M. A.; Zayed, Mohamed E.; Alharbi, Suliman A.

    2015-03-01

    Nine mononuclear Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pt(IV) complexes of azo-dye Schiff's base ligand were synthesized and determined by different physical techniques. All the nine metal complexes are reported using elemental analysis, molar conductance, magnetic susceptibility, IR, UV-Vis, thermal analysis and 1H NMR, 13C NMR, mass, SEM, TEM, EDX, XRD spectral studies. The molar conductance measurements of all the complexes in DMF solution correspond to non-electrolytic nature. All complexes were of the high-spin type and found to have six-coordinate octahedral geometry except the Cu(II) complex which was four coordinate, square planar. Quantum chemical calculations were performed with semi-empirical method to find the optimum geometry of the ligand and its complexes. In molecular modeling the geometries of azo-dye Schiff base ligand HL and its metal (II/III/IV) complexes were fully optimized with respect to the energy using the 6-31G basis set. These ligand and its metal complexes have also been screened for their in vitro antimicrobial activities.

  8. Synthesis, characterization and experimental, theoretical, electrochemical, antioxidant and antibacterial study of a new Schiff base and its complexes

    NASA Astrophysics Data System (ADS)

    Baykara, Haci; Ilhan, Salih; Levent, Abdulkadir; Salih Seyitoglu, M.; Özdemir, Sadin; Okumuş, Veysi; Öztomsuk, Abdussamet; Cornejo, Mauricio

    2014-09-01

    A new Schiff base ligand was synthesized by reaction of salicylaldehyde with 1,6-bis(4-chloro-2-aminophenoxy)hexane. Then the Schiff base complexes were synthesized by metal salts and the Schiff base. The metal to ligand ratio of metal complexes was found to be 1:1. The Cu(II) complex is proposed to be square planar and the Co(II), Ni(II), Mn(II) and Zn(II) complexes are proposed to be tetrahedral geometry. The Ti(III) and V(III) complexes are proposed to be a capped octahedron in which a seventh ligand has been added to triangular face. The complexes are non-electrolytes as shown by their molar conductivities (ΛM). The structure of metal complexes is proposed from elemental analysis, FT-IR, UV-vis, magnetic susceptibility measurements, molar conductivity measurements, Mass Spectra and thermal gravimetric analysis. In addition antimicrobial and antioxidant studies, cyclic voltammetry of the complexes, theoretical 1H NMR and HOMO-LUMO energy calculations of the new di-functional ligand were done.

  9. Synthesis, characterization and experimental, theoretical, electrochemical, antioxidant and antibacterial study of a new Schiff base and its complexes.

    PubMed

    Baykara, Haci; Ilhan, Salih; Levent, Abdulkadir; Salih Seyitoglu, M; Özdemir, Sadin; Okumuş, Veysi; Öztomsuk, Abdussamet; Cornejo, Mauricio

    2014-09-15

    A new Schiff base ligand was synthesized by reaction of salicylaldehyde with 1,6-bis(4-chloro-2-aminophenoxy)hexane. Then the Schiff base complexes were synthesized by metal salts and the Schiff base. The metal to ligand ratio of metal complexes was found to be 1:1. The Cu(II) complex is proposed to be square planar and the Co(II), Ni(II), Mn(II) and Zn(II) complexes are proposed to be tetrahedral geometry. The Ti(III) and V(III) complexes are proposed to be a capped octahedron in which a seventh ligand has been added to triangular face. The complexes are non-electrolytes as shown by their molar conductivities (ΛM). The structure of metal complexes is proposed from elemental analysis, FT-IR, UV-vis, magnetic susceptibility measurements, molar conductivity measurements, Mass Spectra and thermal gravimetric analysis. In addition antimicrobial and antioxidant studies, cyclic voltammetry of the complexes, theoretical 1H NMR and HOMO-LUMO energy calculations of the new di-functional ligand were done.

  10. Three novel dipicolinate complexes with the pyridine-2,6-dimethanol - A combined structural, spectroscopic, antimicrobial and computational study

    NASA Astrophysics Data System (ADS)

    Uçar, İbrahim; Tamer, Ömer; Sarıboğa, Bahtiyar; Büyükgüngör, Orhan

    2013-01-01

    Three new dipicolinate complexes, [M(dmp)(dpc)]·H2O [M = Co(II) (1); Zn(II) (2); Ni(II) (3); dmp: pyridine-2,6-dimethanol; dpc: dipicolinate or pyridine-2,6-dicarboxylate], were synthesized and combined with experimental and theoretical study on molecular, vibrational and electronical properties. The central M(II) ion in all complexes is bonded to dpc and dmp ligands through pyridine nitrogen atom together with two oxygen atom, forming the distorted octahedral geometry. The complex molecules, connected via O-H⋯O hydrogen bonds, form a supramolecular structure. The complexes were also screened for antimicrobial activity against human pathogenic Gram-positive, Gram-negative bacteria and fungi. Among the tested microorganisms, Streptococcus pneumoniae was the most sensitive strain, especially to H2dpc and its complexes. The EPR spectra of Cu2+ doped polycrystalline complexes indicate that the paramagnetic center has a rhombic symmetry. Although the supramolecular interactions have some influences on the molecular geometry in solid state phase, calculated data show that the predicted geometries can reproduce the structural parameters. The electronic station in the frontier orbitals of the dipicolinate complexes calculated from the experimental data is compared to the results of time-depended DFT calculations with the polarizable continuum model and UV-Vis spectrum of the complexes has been discussed on this basis. Calculated vibrational frequencies using the DFT and HF method are consistent with the experimental IR data.

  11. Synthesis, characterization and biological studies of homo and hetero-binuclear 13-membered pentaaza bis (macrocyclic) complexes

    NASA Astrophysics Data System (ADS)

    Zafar, Hina; Kareem, Abdul; Sherwani, Asif; Mohammad, Owais; Khan, Tahir Ali

    2015-01-01

    A new series of homo and hetero binuclear 13-membered pentaaza bis (macrocyclic) complexes, [MM‧LX4], [M = Cu(II), M‧ = Cu(II), Co(II), Ni(II) and Sn(II); L = ligand and X = Cl or NO3] have been synthesized by the template reaction of dichloro/dinitrato diphenyl sulphone 1,3,6,9,12-tetra hydro pentaazacyclo pantane copper (II) complexes with formaldehyde, triethylenetetraamine, and respective metal salts in 1:2:1:1 molar ratio. The complexes have been characterized by elemental analyses, molar conductance measurements, ESI-mass, 1H, 13C and 119Sn NMR, IR, electronic and EPR spectral studies. The results of elemental analyses, ESI-mass and conductivity measurements confirmed the stoichiometry of the complexes while the characteristic absorption bands and resonance peaks in IR and NMR spectra confirmed the formation of macrocyclic frameworks of the complexes. These studies showed octahedral geometry around the metal ion. The thermal stability of copper complexes was also studied by TGA and DTA analyses. Some complexes of this series were also studied for their in vitro anticancer activity against cancer cells lines: Hep3B, MCF7, and HeLa. The recorded IC50 values for the tested complexes show moderate to good cytotoxicity against these cancer cell lines.

  12. Simultaneous preconcentration of Co(II), Ni(II), Cu(II), and Cd(II) from environmental samples on Amberlite XAD-2000 column and determination by FAAS.

    PubMed

    Duran, Celal; Senturk, Hasan Basri; Elci, Latif; Soylak, Mustafa; Tufekci, Mehmet

    2009-02-15

    A new method for the preconcentration of some trace metals (Co, Ni, Cu, and Cd) as complexed with ammonium pyrrolidynedithiocarbamate (APDC) was developed using a mini-column filled with Amberlite XAD-2000 resin. Metal contents were determined by flame atomic absorption spectrometry (FAAS) after the metal complexes accumulated on the resin were eluted with 1M HNO(3) in acetone. The effects of the analytical parameters such as sample pH, quantity of complexing agent, eluent type, resin quantity, sample volume, sample flow rate, and matrix ions were investigated on the recovery of the metals from aqueous solutions. The relative standard deviation (R.S.D.) of the method was <6%. The validation of the method was confirmed using two certified reference materials (CRM TMDW-500 Drinking Water and CRM SA-C Sandy Soil C). The method was successfully applied to some stream waters and mushroom samples from Eastern Black Sea Region (Trabzon city) of Turkey.

  13. Synthesis, characterization and biological relevance of some metal (II) complexes with oxygen, nitrogen and oxygen (ONO) donor Schiff base ligand derived from thiazole and 2-hydroxy-1-naphthaldehyde

    NASA Astrophysics Data System (ADS)

    Nagesh, G. Y.; Mruthyunjayaswamy, B. H. M.

    2015-04-01

    The novel Schiff base ligand 2-((2-hydroxynaphthalen-1-yl)methylene)-N-(4-phenylthiazol-2-yl)hydrazinecarboxamide (L) obtained by the condensation of N-(4-phenylthiazol-2-yl)hydrazinecarboxamide with 2-hydroxy-1-naphthaldehyde and its newly synthesized Cu(II), Co(II), Ni(II), Zn(II) and Cd(II) complexes have been characterized by microanalysis, molar conductance, IR, 1H NMR, ESI-mass, UV-Visible, TGA/DTA, ESR and powder X-ray diffraction data to explicate their structures. The IR results confirmed the tridentate binding of the ligand involving oxygen atom of amide carbonyl, azomethine nitrogen and naphthol oxygen. 1H NMR spectral data of the ligand (L) and its Zn(II) complex agreed well with the proposed structures. Thermogravimetric studies for Cu(II) and Ni(II) complexes indicated the presence of coordinated water molecules and the final product is the metal oxide. In order to appraise the effect of antimicrobial activity of metal ions upon chelation, the newly synthesized ligand and its metal complexes were screened for their antimicrobial activity by minimum inhibitory concentration (MIC) method. The DNA cleavage activities were studied using plasmid DNA pBR322 (Bangal re Genei, Bengaluru, Cat. No 105850) as a target molecule by agarose gel electrophoresis method. The brine shrimp bioassay was also carried out to study the in vitro cytotoxicity properties against Artemia salina. Furthermore, the antioxidant activity were determined in vitro by reduction of 1,1-diphenyl-2-picryl hydrazyl (DPPH). The ligand exhibited better in vitro-antioxidant activity than its metal complexes.

  14. Complex derivatives

    NASA Astrophysics Data System (ADS)

    Battiston, Stefano; Caldarelli, Guido; Georg, Co-Pierre; May, Robert; Stiglitz, Joseph

    2013-03-01

    The intrinsic complexity of the financial derivatives market has emerged as both an incentive to engage in it, and a key source of its inherent instability. Regulators now faced with the challenge of taming this beast may find inspiration in the budding science of complex systems.

  15. Designing Complexity

    ERIC Educational Resources Information Center

    Glanville, Ranulph

    2007-01-01

    This article considers the nature of complexity and design, as well as relationships between the two, and suggests that design may have much potential as an approach to improving human performance in situations seen as complex. It is developed against two backgrounds. The first is a world view that derives from second order cybernetics and radical…

  16. Complex odontoma.

    PubMed

    Preetha, A; Balikai, Bharati S; Sujatha, D; Pai, Anuradha; Ganapathy, K S

    2010-01-01

    Odontomas are hamartomatous lesions or malformations composed of mature enamel, dentin, and pulp. They may be compound or complex, depending on the extent of morphodifferentiation or their resemblance to normal teeth. The etiology of odontoma is unknown, although several theories have been proposed. This article describes a case of a large infected complex odontoma in the residual mandibular ridge, resulting in considerable mandibular expansion.

  17. Studies on DNA binding behaviour of biologically active transition metal complexes of new tetradentate N2O2 donor Schiff bases: Inhibitory activity against bacteria

    NASA Astrophysics Data System (ADS)

    Sobha, S.; Mahalakshmi, R.; Raman, N.

    A series of Cu(II), Ni(II) and Zn(II) complexes of the type ML have been synthesized with Schiff bases derived from o-acetoacetotoluidide, 2-hydroxybenzaldehyde and o-phenylenediamine/1,4-diaminobutane. The complexes are insoluble in common organic solvents but soluble in DMF and DMSO. The measured molar conductance values in DMSO indicate that the complexes are non-electrolytic in nature. All the six metal complexes have been fully characterized with the help of elemental analyses, molecular weights, molar conductance values, magnetic moments and spectroscopic data. The analytical data helped to elucidate the structure of the metal complexes. The Schiff bases are found to act as tetradentate ligands using N2O2 donor set of atoms leading to a square-planar geometry for the complexes around all the metal ions. The binding properties of metal complexes with DNA were investigated by absorption spectra, viscosity measurements and cyclic voltammetry. Detailed analysis reveals that the metal complexes intercalate into the DNA base stack as intercalators. All the metal complexes cleave the pUC19 DNA in presence of H2O2. The Schiff bases and their complexes have been screened for their antibacterial activity against five bacterial strains (Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli, Staphylococcus epidermidis, Klebsiella pneumoniae) by disk diffusion method. All the metal complexes have potent biocidal activity than the free ligands.

  18. Spectroscopic, cyclic voltammetric and biological studies of transition metal complexes with mixed nitrogen-sulphur (NS) donor macrocyclic ligand derived from thiosemicarbazide

    NASA Astrophysics Data System (ADS)

    Chandra, Sulekh; Gupta, Lokesh Kumar; Sangeetika

    2005-11-01

    The complexation of new mixed thia-aza-oxa macrocycle viz., 2,12-dithio-5,9,14,18-tetraoxo-7,16-dithia-1,3,4,10,11,13-hexaazacyclooctadecane containing thiosemicarba-zone unit with a series of transition metals Co(II), Ni(II) and Cu(II) has been investigated, by different spectroscopic techniques. The structural features of the ligand have been studied by EI-mass, 1H NMR and IR spectral techniques. Elemental analyses, magnetic moment susceptibility, molar conductance, IR, electronic, and EPR spectral studies characterized the complexes. Electronic absorption and IR spectra of the complexes indicate octahedral geometry for chloro, nitrato, thiocyanato or acetato complexes. The dimeric and neutral nature of the sulphato complexes are confirmed from magnetic susceptibility and low conductance values. Electronic spectra suggests square-planar geometry for all sulphato complexes. The redox behaviour was studied by cyclic voltammetry, show metal-centered reduction processes for all complexes. The complexes of copper show both oxidation and reduction process. The redox potentials depend on the conformation of central atom in the macrocyclic complexes. Newly synthesized macrocyclic ligand and its transition metal complexes show markedly growth inhibitory activity against pathogenic bacterias and plant pathogenic fungi under study. Most of the complexes have higher activity than that of the metal free ligand.

  19. Preparation, structures and antimicrobial activity of four different type metal complexes on the base of diethanolamine and o-nitrobenzoic acid

    NASA Astrophysics Data System (ADS)

    Ibragimov, A. B.; Ashurov, J. M.; Ibragimov, B. T.; Zakirov, B. S.

    2017-01-01

    Crystallization under identical conditions from aqueous ethanol solutions of diethanolamine (DEA), o-nitrobenzoic acid (ONBA) and definite metal salt yields 4 different type metal complexes and one organic salt - the monoligand complex of Zn(II) with DEA (1), monoligand complex of Cu(II) with ONBA (2), mixed-ligand complex of Ni(II) with DEA and ONBA (3), supramolecular complex between monoligand complex molecule of Zn(II) with DEA and ONBA (4) and DEA+·ONBA- salt (5). In 1 two meridionally distributed DEA molecules are coordinated by a tridentate mode, 2 is a binuclear copper complex with 4 ONBA molecules which are bidentately coordinated through carboxylate groups. In 3 two DEA and two ONBA molecules are coordinated by bidentate and monodentate fashions, respectively. The compound 4 consists of a complex molecule with two facial distributed tridentate DEA molecules and ONBA ones in an outer sphere. Hence, in coordination compounds 1 and 4 Zn-complex ions with two tridentately coordinated DEA molecules are found in different isomeric forms of which a mer-distribution is recorded for the first time. The maximal enhancement of the ligands antimicrobial activity is observed for the mixed-ligand metal complex. The Zn-complex with mer-distributed ligand molecules demonstrated more antimicrobial activity in contrast to fac-isomer.

  20. Studies on DNA binding behaviour of biologically active transition metal complexes of new tetradentate N2O2 donor Schiff bases: inhibitory activity against bacteria.

    PubMed

    Sobha, S; Mahalakshmi, R; Raman, N

    2012-06-15

    A series of Cu(II), Ni(II) and Zn(II) complexes of the type ML have been synthesized with Schiff bases derived from o-acetoacetotoluidide, 2-hydroxybenzaldehyde and o-phenylenediamine/1,4-diaminobutane. The complexes are insoluble in common organic solvents but soluble in DMF and DMSO. The measured molar conductance values in DMSO indicate that the complexes are non-electrolytic in nature. All the six metal complexes have been fully characterized with the help of elemental analyses, molecular weights, molar conductance values, magnetic moments and spectroscopic data. The analytical data helped to elucidate the structure of the metal complexes. The Schiff bases are found to act as tetradentate ligands using N(2)O(2) donor set of atoms leading to a square-planar geometry for the complexes around all the metal ions. The binding properties of metal complexes with DNA were investigated by absorption spectra, viscosity measurements and cyclic voltammetry. Detailed analysis reveals that the metal complexes intercalate into the DNA base stack as intercalators. All the metal complexes cleave the pUC19 DNA in presence of H(2)O(2.) The Schiff bases and their complexes have been screened for their antibacterial activity against five bacterial strains (Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli, Staphylococcus epidermidis, Klebsiella pneumoniae) by disk diffusion method. All the metal complexes have potent biocidal activity than the free ligands.

  1. Determination of kinetic and equilibrium parameters of the batch adsorption of Mn(II), Co(II), Ni(II) and Cu(II) from aqueous solution by black carrot (Daucus carota L.) residues.

    PubMed

    Güzel, Fuat; Yakut, Hakan; Topal, Giray

    2008-05-30

    In this study, the effect of temperature on the adsorption of Mn(II), Ni(II), Co(II) and Cu(II) from aqueous solution by modified carrot residues (MCR) was investigated. The equilibrium contact times of adsorption process for each heavy metals-MCR systems were determined. Kinetic data obtained for each heavy metal by MCR at different temperatures were applied to the Lagergren equation, and adsorption rate constants (kads) at these temperatures were determined. These rate constants related to the adsorption of heavy metal by MCR were applied to the Arrhenius equation, and activation energies (Ea) were determined. In addition, the isotherms for adsorption of each heavy metal by MCR at different temperatures were also determined. These isothermal data were applied to linear forms of isotherm equations that they fit the Langmuir adsorption isotherm, and the Langmuir constants (qm and b) were calculated. b constants determined at different temperatures were applied to thermodynamic equations, and thermodynamic parameters such as enthalpy (Delta H), free energy (Delta G), and entropy (Delta S) were calculated and these values show that adsorption of heavy metal on MCR was an endothermic process and process of adsorption was favoured at high temperatures.

  2. Highly efficient simultaneous ultrasonic-assisted adsorption of Pb(II), Cd(II), Ni(II) and Cu (II) ions from aqueous solutions by graphene oxide modified with 2,2'-dipyridylamine: Central composite design optimization.

    PubMed

    Zare-Dorabei, Rouholah; Ferdowsi, Somayeh Moazen; Barzin, Ahmad; Tadjarodi, Azadeh

    2016-09-01

    In present work, a graphene oxide chemically modified with 2,2'-dipyridylamine (GO-DPA), was synthesized by simple, fast and low-cost process for the simultaneous adsorption of four toxic heavy metals, Pb(II), Cd(II), Ni(II) and Cu(II), from aqueous solutions. The synthesized adsorbent was characterized by FT-IR, XRD, XPS, SEM and AFM measurements. The effects of variables such as pH solution, initial ion concentrations, adsorbent dosage and sonicating time were investigated on adsorption efficiency by rotatable central composite design. The optimum conditions, specified as 8mg of adsorbent, 20mgL(-1) of each ion at pH 5 and short time of 4min led to the achievement of a high adsorption capacities. Ultrasonic power had important role in shortening the adsorption time of ions by enhancing the dispersion of adsorbent in solution. The adsorption kinetic studies and equilibrium isotherms for evaluating the mechanism of adsorption process showed a good fit to the pseudo-second order and Langmuir model, respectively. The maximum adsorption capacities (Qm) of this adsorbent were 369.749, 257.201, 180.893 and 358.824mgg(-1) for lead, cadmium, nickel and copper ions, respectively. The removal performance of adsorbent on the real wastewater samples also showed the feasibility of adsorbent for applying in industrial purposes.

  3. Chitosan film loaded with silver nanoparticles-sorbent for solid phase extraction of Al(III), Cd(II), Cu(II), Co(II), Fe(III), Ni(II), Pb(II) and Zn(II).

    PubMed

    Djerahov, Lubomir; Vasileva, Penka; Karadjova, Irina; Kurakalva, Rama Mohan; Aradhi, Keshav Krishna

    2016-08-20

    The present study describes the ecofriendly method for the preparation of chitosan film loaded with silver nanoparticles (CS-AgNPs) and application of this film as efficient sorbent for separation and enrichment of Al(III), Cd(II), Cu(II), Co(II), Fe(III), Ni(II), Pb(II) and Zn(II). The stable CS-AgNPs colloid was prepared by dispersing the AgNPs sol in chitosan solution at appropriate ratio and further used to obtain a cast film with very good stability under storage and good mechanical strength for easy handling in aqueous medium. The incorporation of AgNPs in the structure of CS film and interaction between the polymer matrix and nanoparticles were confirmed by UV-vis and FTIR spectroscopy. The homogeneously embedded AgNPs (average diameter 29nm, TEM analysis) were clearly observed throughout the film by SEM. The CS-AgNPs nanocomposite film shows high sorption activity toward trace metals under optimized chemical conditions. The results suggest that the CS-AgNPs nanocomposite film can be feasibly used as a novel sorbent material for solid-phase extraction of metal pollutants from surface waters.

  4. Role of Radical Species in Salicylaldiminato Ni(II) Mediated Polymer Chain Growth: A Case Study for the Migratory Insertion Polymerization of Ethylene in the Presence of Methyl Methacrylate.

    PubMed

    Ölscher, Franz; Göttker-Schnetmann, Inigo; Monteil, Vincent; Mecking, Stefan

    2015-11-25

    To date, an inconclusive and partially contradictive picture exists on the behavior of neutral Ni(II) insertion polymerization catalysts toward methyl methacrylate (MMA). We shed light on this issue by a combination of comprehensive mechanistic NMR and EPR studies, isolation of a key Ni(I) intermediate, and pressure reactor studies with ethylene and MMA, followed by detailed polymer analysis. An interlocking mechanistic picture of an insertion and a free radical polymerization is revealed. Both polymerizations run simultaneously (25 bar ethylene, neat MMA, 70 °C); however, the chain growth cycles are independent of each other, and therefore exclusively a physical mixture of homo-PE and homo-PMMA is obtained. A Ni-C bond cleavage was excluded as a free radical source. Rather a homolytic P-C bond cleavage in the labile aryl phosphine ligand and the reaction of low-valent Ni(0/I) species with specific iodo substituted N^O (Ar-I) ligands were shown to initiate radical MMA polymerizations. Several reductive elimination decomposition pathways of catalyst precursor or active intermediates were shown to form low-valent Ni species. One of those pathways is a bimolecular reductive coupling via intermediate (N^O)Ni(I) formation. These intermediate Ni(I) species can be prevented from ultimate decomposition by capturing with organic radical sources, forming insertion polymerization active [(N^O)Ni(II)-R] species and prolonging the ethylene polymerization activity.

  5. Methanol-Triggered Vapochromism Coupled with Solid-State Spin Switching in a Nickel(II)-Quinonoid Complex.

    PubMed

    Kar, Paramita; Yoshida, Masaki; Shigeta, Yasuhiro; Usui, Akane; Kobayashi, Atsushi; Minamidate, Takaaki; Matsunaga, Noriaki; Kato, Masako

    2017-02-20

    A highly methanol-selective vapochromic response has been realized in a Ni(II) -quinonoid complex, [Ni(HL(Me) )2 ] (H2 L(Me) =4-methylamino-6-methyliminio-3-oxocyclohexa-1,4-dien-1-olate) which exhibits a reversible structural transformation including a coordination geometrical change between the square-planar and octahedral structure by the selective uptake of methanol vapor. This was accompanied by a remarkable color change between purple and orange, as well as temperature-robust spin-state switching in the solid state under ambient conditions. It is remarkable that the properties are derived by the fine structural modification of the quinonoid ligand such as methyl or ethyl analogues. Such a system has high potential for applications in memory devices as well as chemical sensors and smart responsive materials.

  6. Design and synthesis of metal complexes of (2E)-2-[(2E)-3-phenylprop-2-en-1-ylidene]hydrazinecarbothioamide and their photocatalytic degradation of methylene blue.

    PubMed

    Krishna, P Murali; Reddy, N B Gopal; Kottam, Nagaraju; Yallur, B C; Katreddi, Hussain Reddy

    2013-01-01

    The photocatalytic degradation has been considered to be an efficient process for the degradation of organic pollutants, which are present in the effluents released by industries. The photocatalytic bleaching of cationic dye methylene blue was carried out spectrometrically on irradiation of UV light using Cu(II), Ni(II), and Co(II) complexes of (2E)-2-[(2E)-3-phenylprop-2-en-1-ylidene]hydrazinecarbothioamide (HL). The effects of pH and metal ion were studied on the efficiency of the reaction. Cu(II) complex shows better catalytic activity and the highest percentage degradation (~88.8%) of methylene blue was observed at pH 12. A tentative mechanism has also been proposed for the photocatalytic degradation of methylene blue.

  7. Alkylation of a bioinspired high spin Ni(II)N{sub 3}S{sub 2} complex with bifunctional reagents

    SciTech Connect

    Chohan, B. S.

    2013-12-15

    Crystal structures of two S-alkylated complexes generated from the reaction of iodoacetamide and iodoethanol with an air and moisture sensitive high spin Ni(II) pentacoordinate triaminodithiolate complex, 1 are determined by X-ray structure analysis. Crystals of complex 2, [NiC{sub 16}H{sub 31}N{sub 5}O{sub 2}S{sub 2}]I{sub 2}, are triclinic, sp. gr. P-bar1 , Z = 2. Crystals of complex 3, [NiC{sub 16}H{sub 28}N{sub 3}O{sub 2}S{sub 2}]I{sub 2}, are monoclinic, sp. gr. P2{sub 1}/c, Z = 4. Structures of complexes 2 and 3 are very similar: one of the S-acetamide (2) or S-ethanol (3) groups coordinates to the Ni center through the oxygen atom forming N{sub 3}S{sub 2}O hexacoordination; the other group remains unbound to the Ni and left dangling. Crystal packing shows that complexes 2 and 3 interact with the iodide counterions, and that only complex 2 interact with neighboring molecules; some of these close intermolecular contacts include H-bonding interactions.

  8. Alkylation of a bioinspired high spin Ni(II)N3S2 complex with bifunctional reagents

    NASA Astrophysics Data System (ADS)

    Chohan, B. S.

    2013-12-01

    Crystal structures of two S-alkylated complexes generated from the reaction of iodoacetamide and iodoethanol with an air and moisture sensitive high spin Ni(II) pentacoordinate triaminodithiolate complex, 1 are determined by X-ray structure analysis. Crystals of complex 2, [NiC16H31N5O2S2]I2, are triclinic, sp. gr. , Z = 2. Crystals of complex 3, [NiC16H28N3O2S2]I2, are monoclinic, sp. gr. P21/ c, Z = 4. Structures of complexes 2 and 3 are very similar: one of the S-acetamide ( 2) or S-ethanol ( 3) groups coordinates to the Ni center through the oxygen atom forming N3S2O hexacoordination; the other group remains unbound to the Ni and left dangling. Crystal packing shows that complexes 2 and 3 interact with the iodide counterions, and that only complex 2 interact with neighboring molecules; some of these close intermolecular contacts include H-bonding interactions.

  9. Synthesis, spectroscopic, coordination and biological activities of some transition metal complexes containing ONO tridentate Schiff base ligand.

    PubMed

    Belal, A A M; El-Deen, I M; Farid, N Y; Zakaria, Rosan; Refat, Moamen S

    2015-01-01

    The main target of this paper is to get an interesting data for the preparation and characterizations of metal oxide (MO) nanoparticles using H2L Schiff base complexes as precursors through the thermal decomposition procedure. Five Schiff base complexes of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) metal ions were synthesized from 2-[(2-hydroxy-naphthalen-1-ylmethylene)-amino]-benzoic acid new adduct (H2L). Theses complexes were characterized using infrared, electronic, mass and (1)H NMR spectroscopic techniques. The elemental analysis data was confirmed that the stoichiometry of (metal:H2L) is 1:1 molar ratio. The molar conductance indicates that all of complexes are non electrolytic. The general chemical formulas of these complexes is [M(L)(NH3)]·nH2O. All complexes are tetrahedral geometry. The thermal decomposition behavior of H2L hydrated and anhydrous complexes has been discussed using thermogravimetric analysis (TG/DTG) and differential thermal analyses (DTA) under nitrogen atmosphere. The crystalline phases of the reaction products were checked using X-ray diffractometer (XRD) and scanning electron microscopy (SEM).

  10. Synthesis, spectral, thermal and antimicrobial studies of transition metal complexes of 14-membered tetraaza[N₄] macrocyclic ligand.

    PubMed

    Shankarwar, Sunil G; Nagolkar, Bhagwat B; Shelke, Vinod A; Chondhe