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Sample records for nickel dithiolene complexes

  1. Negative Ion Photoelectron Spectroscopy Reveals Remarkable Noninnocence of Ligands in Nickel Bis(dithiolene) Complexes [Ni(dddt)2](-) and [Ni(edo)2](-).

    Science.gov (United States)

    Liu, Xing; Hou, Gao-Lei; Wang, Xuefeng; Wang, Xue-Bin

    2016-05-12

    [Ni(dddt)2](-) (dddt = 5,6-dihydro-1,4-dithiine-2,3-dithiolate) and [Ni(edo)2](-) (edo = 5,6-dihydro-1,4-dioxine-2,3-dithiolate) are two donor-type nickel bis(dithiolene) complexes, with the tendency of donating low binding energy electrons. These two structurally similar complexes differ only with respect to the outer atoms in the ligand framework where the former has four S atoms while the latter has four O atoms. Herein, we report a negative ion photoelectron spectroscopy (NIPES) study on these two complexes to probe the electronic structures of the anions and their corresponding neutrals. The NIPE spectra exhibit the adiabatic electron detachment energy (ADE) or, equivalently, the electron affinity (EA) of the neutral [Ni(L)2](0) to be relatively low for this type of complexes, 2.780 and 2.375 eV for L = dddt and edo, respectively. The 0.4 eV difference in ADEs shows a significant substitution effect for sulfur in dddt by oxygen in edo, i.e., noninnocence of the ligands, which has decreased the electronic stability of [Ni(edo)2](-) by lowering its electron binding energy by ∼0.4 eV. The observed substitution effect on gas-phase EA values correlates well with the measured redox potentials for [Ni(dddt)2](-/0) and [Ni(edo)2](-/0) in solutions. The singlet-triplet splitting (ΔEST) of [Ni(dddt)2](0) and [Ni(edo)2](0) is also determined from the spectra to be 0.57 and 0.53 eV, respectively. Accompanying DFT calculations and molecular orbital (MO) composition analyses show significant ligand contributions to the redox MOs and allow the components of the orbitals involved in each electronic transition and spectral assignments to be identified.

  2. Fine and Clean Photothermally Controlled NIR Drug Delivery from Biocompatible Nickel-bis(dithiolene)-Containing Liposomes.

    Science.gov (United States)

    Mebrouk, Kenny; Ciancone, Mathieu; Vives, Thomas; Cammas-Marion, Sandrine; Benvegnu, Thierry; Le Goff-Gaillard, Catherine; Arlot-Bonnemains, Yannick; Fourmigué, Marc; Camerel, Franck

    2017-11-08

    This work demonstrates that metal-bis(dithiolene) complexes can be efficiently incorporated inside organic nanocarriers and, that under near-infrared (NIR) irradiation, their high photothermal activity can be finely used to release encapsulated drugs on demand. In contrast to gold nanoparticles and other organic NIR dyes, nickel-bis(dithiolene) complexes do not produce singlet oxygen under irradiation, a highly desirable characteristic to preserve the chemical integrity and activity of the loaded drug during the NIR-triggered release from the nanocarriers. Finally, cytotoxicity experiments performed on various cell lines have shown that the incorporation of such metal complexes do not increase the toxicity of the final liposomal formulation. These results offer great promise for the development of innovative biocompatible drug nanocargos that are able to safely deliver their content on demand under NIR laser irradiation. Moreover, this work demonstrates that metal-bis(dithiolene) complexes, owing to their versatility of functionalization and metal complexation, are attractive photothermal agents for the development of original NIR-responsive materials for application not only in biotechnology but also in materials science. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Ethylene oligomerization using nickel dithiolene complexes Ni(S2C2R2)2 (R=Ph, CF3) and the crystal structure of Ni[S2C2(CF3)2]2.

    Science.gov (United States)

    Wang, Kun; Patil, Abhimanyu O; Zushma, Stephen; McConnachie, Jonathan M

    2007-11-01

    Nickel bis(dithiolene) complexes have been known for over four decades, yet little is known regarding the chemistry of this important subclass of inorganic coordination complexes in olefin oligomerization or polymerization. We report here that Ni(S(2)C(2)R(2))(2) (R=Ph, CF(3)) are converted to active catalysts for ethylene oligomerization when activated with methylaluminoxane (MAO). The catalyst activity is comparable to some nickel coordination complexes with N-donor ligands under similar conditions. The products are mainly butenes and hexenes, with small amounts of higher oligomers. The product distribution pattern is consistent with a nickel hydride species being the active center, where fast beta-hydride elimination limits the products to mostly butenes and hexenes. The exact nature of the active center and the reaction mechanism remain to be investigated. In addition, we determined the crystal structure for Ni[S(2)C(2)(CF(3))(2)](2). The molecule crystallizes in the P2(1)/n space group and adopts a planar geometry with expected bond lengths and angles. Comparing this structure with that for the donor-acceptor complex with perylene reveals elongation of both the Ni-S and the S-C bonds in the latter, suggesting reduction of Ni[S(2)C(2)(CF(3))(2)](2) may have occurred in the latter.

  4. Structural and spectroscopic characterization of five coordinate iron and cobalt bis(dithiolene)-trimethylphosphine complexes

    Science.gov (United States)

    Selby-Karney, Troy; Grossie, David A.; Arumugam, Kuppuswamy; Wright, Eyglo; Chandrasekaran, P.

    2017-08-01

    Heteroleptic bis(dithiolene)-phosphine iron and cobalt complexes [Fe(adt)2(PMe3)] (1) and [Co(adt)2(PMe3)] (2) (adt = para-anisyldithiolene) have been synthesized from corresponding bis(dithiolene) dimers [M2(adt)4]2 (M = Fe, Co) by reacting with excess PMe3 in dichloromethane. Solid-state structures of 1 and 2 have been determined by single crystal X-ray crystallography, and the dithiolene ligands Csbnd S (≈1.72 Å) and Csbnd C (≈1.37 Å) bond distances reveal the coordination of π-radical monoanionic dithiolene (adt•1-) ligands to metal centers. Intense low energy ligand-to-ligand-charge transfer (LLCT) absorption band (743 nm for 1; 905 nm for 2) in UV-vis spectra and characteristic ν(Cdbnd S•) (1168 cm-1 for 1; 1170 cm-1 for 2) in IR spectra affirms coordination of π-radical monoanionic dithiolenes to divalent metal ions. The cyclic voltammogram of 1 and 2 shows reversible oxidation and reduction waves attributed to MII → MIII + e- (+0.52 V for 1; +0.29 V for 2) and adt•1- + e- → adt2- (-0.63 V for 1; -0.46 V for 2) redox process respectively. Comprehensive structural and spectroscopic investigations conclude, [M2III(adt2-)2(adt•1-)2] → 2 [MII(adt•1-)2(PMe3)] intramolecular redox interplay during phosphine coordination induced cleavage of homoleptic bis(dithiolene) dimers to produce square pyramidal complexes.

  5. Synthesis and analysis of nickel dithiolene dyes in a nematic liquid crystal host. 1998 summer research program for high school juniors at the University of Rochester's Laboratory for Laser Energetics. Student research reports

    International Nuclear Information System (INIS)

    Lippa, I.

    1999-03-01

    The Liquid Crystal Point Diffraction Interferometer (LCPDI) can be employed to evaluate the Omega Laser system for optimum firing capabilities. This device utilizes a nickel dithiolene infrared absorbing liquid crystal dye dissolved in a liquid crystal host medium (Merck E7). Three nickel dithiolene dyes were characterized for both their solubility in the E7 host and their infrared spectral absorption

  6. Infrared Multiple Photon Dissociation Spectroscopy of a Gas-Phase Oxo-Molybdenum Complex with 1,2-Dithiolene Ligands

    Science.gov (United States)

    2015-01-01

    Electrospray ionization (ESI) in the negative ion mode was used to create anionic, gas-phase oxo-molybdenum complexes with dithiolene ligands. By varying ESI and ion transfer conditions, both doubly and singly charged forms of the complex, with identical formulas, could be observed. Collision-induced dissociation (CID) of the dianion generated exclusively the monoanion, while fragmentation of the monoanion involved decomposition of the dithiolene ligands. The intrinsic structure of the monoanion and the dianion were determined by using wavelength-selective infrared multiple-photon dissociation (IRMPD) spectroscopy and density functional theory calculations. The IRMPD spectrum for the dianion exhibits absorptions that can be assigned to (ligand) C=C, C–S, C—C≡N, and Mo=O stretches. Comparison of the IRMPD spectrum to spectra predicted for various possible conformations allows assignment of a pseudo square pyramidal structure with C2v symmetry, equatorial coordination of MoO2+ by the S atoms of the dithiolene ligands, and a singlet spin state. A single absorption was observed for the oxidized complex. When the same scaling factor employed for the dianion is used for the oxidized version, theoretical spectra suggest that the absorption is the Mo=O stretch for a distorted square pyramidal structure and doublet spin state. A predicted change in conformation upon oxidation of the dianion is consistent with a proposed bonding scheme for the bent-metallocene dithiolene compounds [Lauher, J. W.; Hoffmann, R. J. Am. Chem. Soc.1976, 98, 1729−1742], where a large folding of the dithiolene moiety along the S···S vector is dependent on the occupancy of the in-plane metal d-orbital. PMID:24988369

  7. Computer-aided design and modeling of nickel dithiolene near-infrared dyes. 1998 summer research program for high school juniors at the University of Rochester's Laboratory for Laser Energetics. Student research reports

    International Nuclear Information System (INIS)

    Corsello, S.

    1999-03-01

    Recent advances in computational chemistry have made it feasible to design many types of molecules and predict their properties theoretically. The author applied these techniques to the design of organometallic transition-metal dyes absorbing in the near-infrared region of the spectrum which possess the combination of a large molar extinction coefficient, good chemical and thermal stability, and a high solubility in liquid crystal (LC) hosts. These properties are required for the dye to function as a near-infrared (IR) attenuator in a liquid crystal point diffraction interferometer (LCPDI) device that will be used as a beam diagnostic on the 60-beam OMEGA solid-state Nd:glass laser system at the University of Rochester's Laboratory for Laser Energetics. Using commercially available software, both the absorption spectra and solubility characteristics of bis[1,2-di-(p-n alkoxyphenyl)ethane-1,2-dithione] nickel dye complexes were modeled in an isotropic host (cyclohexane) and, in most cases, excellent agreement was found with experimental data. Two additional compounds utilizing the same nickel dithiolene core but with alkylthio and phenylalkylthio terminal groups have been designed and show excellent potential to produce dramatic improvements in both solubility and optical density (absorbance) in liquid crystalline hosts. Based upon my work, a new dye not previously reported, 2(C 4 S)2(C 4 SPh)DTNi, has been proposed to satisfy the LCPDI device requirements. The nickel dithiolene dyes may also find important applications in other technology areas such as near-IR photography and laser-based near-IR communications

  8. MS characterization of some metallocene dithiolene chelate complexes of the early transition metals - first synthesis of vanadocene toluene-3,4-dithiolate

    International Nuclear Information System (INIS)

    Klapoetke, T.; Koepf, H.

    1988-01-01

    Fragmentation patterns (under the conditions in the mass spectrometer) of the metallocene dithiolene chelate complexes of some early transition metals (subgroup IV-VI) were investigated. In some cases ion geneses could be elucidated by purchasing metastable transitions, using the linked scan technique. After cleavage of one cyclopentadienyl ring the unsubstituted ethene dithiolates surprisingly show an intense peak corresponding to an elimination of acetylene as a neutral particle, which contrasts to the analogous maleonitrile derivatives. The first synthesis of Cp 2 V(1,2-S 2 C 6 H 3 CH 3 -4) (Cp = C 5 H 5 ) is described. (author)

  9. Conducting metal dithiolate complexes

    DEFF Research Database (Denmark)

    Underhill, A. E.; Ahmad, M. M.; Turner, D. J.

    1985-01-01

    Further work on the chemical composition of the one-dimensional metallic metal dithiolene complex Li-Pt(mnt) is reported. The electrical conduction and thermopower properties of the nickel and palladium complexes are reported and compared with those of the platinum compound......Further work on the chemical composition of the one-dimensional metallic metal dithiolene complex Li-Pt(mnt) is reported. The electrical conduction and thermopower properties of the nickel and palladium complexes are reported and compared with those of the platinum compound...

  10. A new class of sulfido/oxo(dithiolene)-molybdenum(IV) complexes derived from sulfido/oxo-bis(tetrasulfido)molybdenum(IV) anions.

    Science.gov (United States)

    Sugimoto, Hideki; Suyama, Koichiro; Sugimoto, Kunihisa; Miyake, Hiroyuki; Takahashi, Isao; Hirota, Shun; Itoh, Shinobu

    2008-11-03

    Mono(dithiolene)sulfidomolybdenum(IV) complexes, [MoS(S4)(bdt)](2-) (2) and [MoS(S4)(bdtCl2)](2-) (3) (1,2-benzenedithiolate = bdt, 3,6-dichloro-1,2-benzenedithiolate = bdtCl2), were prepared by the substitution reaction of a tetrasulfido ligand in known [MoS(S4)2](2-) (1) with the corresponding dithiol. Complexes 2 and 3 were irreversibly oxidized to give bis(mu-sulfido) dimolybdenum(V) species, {[MoS(bdt)]2(mu-S)2}(2-) (4) and {[MoS(bdtCl2)]2(mu-S)2}(2-) (5), in aerobic acetonitrile. Mono(dithiolene)oxomolybdenum(IV) complexes, [MoO(S4)(bdt)](2-) (7) and [MoO(S4)(bdtCl2)](2-) (8), that are oxo derivatives of 2 and 3 were also synthesized from a known [MoO(S4)2](2-) (6) of an oxo derivative of 1 and the corresponding dithiol. Further, the electrophilic addition of dimethyl acetylenedicarboxylate to 7 gave [MoO(bdt)(S2C2(COOMe)2)](2-) (9), and ligand substitution of the tetrasulfido group of 7 with bdt and bdtCl2 yielded [MoO(bdt)2](2-) ( 10) and [MoO(bdt)(bdtCl2)](2-) (11), respectively. New sulfido/oxo molybdenum complexes were characterized by (1)H NMR, IR, ESI-MS, Raman, and UV-vis spectroscopies; cyclic voltammetry; and elemental analysis, and crystal structures of 2, 3, 5, 7, and 8 were determined by X-ray analysis.

  11. Chain ordering of regioregular polythiophene films through blending with a nickel bisdithiolene complex

    Energy Technology Data Exchange (ETDEWEB)

    Hernandez-Maldonado, D. [CNRS, LCC (Laboratoire de Chimie de Coordination), 205 Route de Narbonne, F-31077 Toulouse Cedex 4 (France); Université de Toulouse, UPS, INPT, LCC, F-31077 Toulouse (France); Ramos, B.; Bedel-Pereira, E.; Séguy, I. [LAAS-CNRS, 7 Avenue du Colonel Roche, F-31077 Toulouse Cedex 4 (France); Université de Toulouse, UPS, INPT, LCC, F-31077 Toulouse (France); Villeneuve-Faure, C. [LAPLACE, Université Paul Sabatier, 118 Route de Narbonne, 31062 Toulouse (France); Sournia-Saquet, A.; Moineau-Chane Ching, K. I., E-mail: kathleen.chane@lcc-toulouse.fr [CNRS, LCC (Laboratoire de Chimie de Coordination), 205 Route de Narbonne, F-31077 Toulouse Cedex 4 (France); LAAS-CNRS, 7 Avenue du Colonel Roche, F-31077 Toulouse Cedex 4 (France); Alary, F.; Heully, J. L. [LCPQ-IRSAMC, 118 Route de Narbonne, F-31077 Toulouse Cedex 4 (France)

    2014-03-10

    An “annealing-free” strategy consisting of using a planar nickel bisdithiolene complex nickel bis[1,2-di(3′,4′-di-n-decyloxyphenyl)ethene-1,2-dithiolene] ([Ni(4dopedt){sub 2}]) is proposed for structuring poly(3-hexyl-thiophene) (P3HT). Photoluminescence (PL) and Raman spectroscopies, in conjunction with electronic absorption, have been used for evidencing P3HT changes due to blending. PL and absorption observations are consistent and show a correlation between polymer chain organization and increasing amounts of [Ni(4dopedt){sub 2}]. Blending with [Ni(4dopedt){sub 2}] do not modify the Raman ring-breathing modes energies indicating that blending does not induce strongly disorder in P3HT chains. Atomic force microscopic measurements show that blends nanoscale morphology presents a homogeneous matrix and small fibrils related to [Ni(4dopedt){sub 2}] concentration, especially for blends with a [Ni(4dopedt){sub 2}] weight ratio lower than 50%.

  12. Uptake of one and two molecules of 1,3-butadiene by platinum bis(dithiolene): a theoretical study.

    Science.gov (United States)

    Dang, Li; Ni, Shao Fei; Hall, Michael B; Brothers, Edward N

    2014-09-15

    Platinum bis(dithiolene) complexes have reactivity toward alkenes like nickel bis(dithiolene) complexes. We examined the uptake of 1,3-butadiene by platinum bis(dithiolene) [Pt(tfd)2] (tfd = S2C2(CF3)2) via a density functional theory study; both 1,2- and 1,4-additions of 1,3-butadiene to the ligands of Pt(tfd)2 to form both interligand and intraligand adducts were studied. For single 1,3-butadiene addition, direct 1,4-addition on interligand S-S, 1,2-addition on intraligand S-S, and 1,4-addition on intraligand S-C are all feasible at room temperature and are controlled by the symmetry of the highest occupied molecular orbital of 1,3-butadiene and the lowest unoccupied molecular orbital of Pt(tfd)2. However, the formation of the interligand S-S adduct through 1,4-addition of one molecule of cis-1,3-butadiene is the most favorable route, with a reaction barrier of 9.3 kcal/mol. The other two addition processes cannot compete with this one due to both higher reaction barriers and unstable adducts. Other possible pathways, such as formation of cis-interligand S-S adduct from 1,2-addition of one molecule of 1,3-butadiene via a twisted trans-interligand S-S adduct, have higher barriers. Our calculated results show that 1,4-addition of a single molecule of 1,3-butadiene on the interligand S-S gives the kinetically stable product by a one-step pathway. But of at least equal importance is the apofacial 1,4-addition of two molecules of 1,3-butadiene on the intraligand S-C of the same ligand on Pt(tfd)2, which yields the thermodynamically stable product, obtained via a short lifetime intermediate, the 1:1 intraligand S-C adduct, being formed through several pathways. The calculated results in this study well explain the experimental observation that 1:1 interligand S-S adduct was formed in a short time, and the intraligand S-C adduct from two molecules of cis-1,3-butadiene was accumulated in 20 h at 50° and characterized by X-ray crystallography.

  13. Polymer supported nickel complex: Synthesis, structure and catalytic ...

    Indian Academy of Sciences (India)

    MOBdMBn-Ni] and polystyrene-anchored [P-3-MOBdMBn-Ni] nickel complexes is presented. The free and polymer-anchored metal complexes were synthesized by the reaction of nickel (II) with one molar equivalent of unsupported N N′-bis ...

  14. Studies on Bis(Para Anisidine Acetylacetonato) Nickel (II) Complex ...

    African Journals Online (AJOL)

    Studies on Bis(Para Anisidine Acetylacetonato) Nickel (II) Complex. HN Aliyu, UL Bilyamin. Abstract. Schiff base was prepared from the reaction of para anisidine and acetylacetone. Bis(para anisidineacetylacetonato)nickel(II) complex was synthesized by the reaction of the prepared para anisidineacetylacetone ligand and ...

  15. Preparation of fine Ni powders from nickel hydrazine complex

    International Nuclear Information System (INIS)

    Park, Jung Woo; Chae, Eun H.; Kim, Sang H.; Lee, Jong Ho; Kim, Jeong Wook; Yoon, Seon Mi; Choi, Jae-Young

    2006-01-01

    Fine nickel powders with narrow size distribution have been prepared from the reduction of nickel hydrazine complexes in aqueous solution. The pure nickel hydrazine complexes, [Ni(N 2 H 4 ) 3 ]Cl 2 were prepared with the molar ratio of N 2 H 4 /Ni 2+ = 4.5, while a mixture of complexes, such as Ni(N 2 H 4 ) 2 Cl 2 , [Ni(N 2 H 4 ) 3 ]Cl 2 , and [Ni(NH 3 ) 6 ]Cl 2 were formed with N 2 H 4 /Ni 2+ 2+ to metallic Ni powder proceeded via the formation of nickel hydroxide which was reduced by hydrazine liberated from the ligand exchange reaction between the nickel hydrazine complex and NaOH. The standard deviation of the particle size decreased with the decreasing molar concentration of nickel hydrazine complex while the mean particle size increased. As the amount of hydrazine increased, the surface roughness of the particles was improved significantly due to the catalytic decomposition of the excess hydrazine at the surface of the nickel particle. It was found that average particle size could be controlled from 150 to 380 nm by adjusting the reaction molar ratio and temperature

  16. hydrazines and their nickel(II) complexes: Syntheses, structures and ...

    Indian Academy of Sciences (India)

    G Narendra Babu

    the two trinuclear complexes were characterized by elemental (CHN) analysis, mass spectrometric, various spectroscopic (IR, UV-Vis and ... donors and assemble a square-planar trans-N2O2 coordination environment around the nickel centre. The redox ...... 1999 Synthesis and properties of cobalt(III) complexes of tripodal ...

  17. Mixed-Ligand Complexes Of Nickel (II) With 2-Acetylpyridine ...

    African Journals Online (AJOL)

    The preparation and spectral properties of five nickel (II) mixed-ligands complexes (Ni [2-Actsc.Y]CI2), derived from 2-acetylpyridinethiosermicarbazones and some nitrogen/sulphur monodentate ligands such as thiophene, ammonia, picoline, pyridine and aniline are described. The complexes have been characterized on ...

  18. Polymer supported nickel complex: Synthesis, structure and catalytic ...

    Indian Academy of Sciences (India)

    Polystyrene support; catalysis; organometallic catalyst, nickel complex; phenol oxidation. 1. Introduction. Schiff base catalysts have a great impact on both the scholastic research and polymer industry. Schiff base complexes have shown adaptable applications in different organic transformation reactions such as oxidation,1 ...

  19. Synthesis and Reactivity of New Aminophenolate Complexes of Nickel

    Directory of Open Access Journals (Sweden)

    Siqi Yu

    2014-09-01

    Full Text Available New well-defined, paramagnetic nickel complexes have been prepared and characterized by X-ray crystallography. The complexes were found to be active for the cross-coupling of alkyl electrophiles (especially ethyl 2-bromobutyrate with alkyl Grignard reagents. The ligand architecture in these new complexes could potentially be rendered chiral, opening up future possibilities for performing asymmetric cross-coupling reactions.

  20. Polymer supported nickel complex: Synthesis, structure and catalytic ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 126; Issue 6 ... Regular Articles Volume 126 Issue 6 November 2014 pp 1695-1705 ... In the present investigation, a new synthetic route for a novel recyclable free [3-MOBdMBn-Ni] and polystyrene-anchored [P-3-MOBdMBn-Ni] nickel complexes is presented. The free ...

  1. Nickel (II) complexes having Imidazol-2-ylidene-N′-phenylurea ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 127; Issue 8. Nickel(II) complexes having Imidazol-2-ylidene-N′-phenylurea ligand in the coordination sphere – syntheses and solid state structures. Kishor Naktode Abhinanda Kundu Sudeshna Saha Hari Pada Nayek Tarun K Panda. Regular Articles Volume 127 ...

  2. Synthesis of copper and nickel complexes using compartmental ...

    Indian Academy of Sciences (India)

    Administrator

    Synthesis of copper and nickel complexes using compartmental ligands: X-ray, electrochemical and magnetic studies. J MANONMANI, V NARAYANAN and M KANDASWAMY. Department of Inorganic Chemistry, University of Madras, Guindy Campus,. Chennai 600 025, India. The search for several synthetic routes leading ...

  3. Photooxidation of nickel(II) macrocyclic complexes from the charge ...

    Indian Academy of Sciences (India)

    Administrator

    The primary photochemical reaction involves oxidation of the metal centre leaving the ligand unaffected in most cases. The role of the solvent and dissolved oxygen primarily determine the nature of the products. Flash photolysis investigations have shown details of the reactions of the oxidised nickel(III) complex with the ...

  4. Gold and Nickel Extended Thiophenic-TTF Bisdithiolene Complexes

    Directory of Open Access Journals (Sweden)

    Rafaela A. L. Silva

    2018-02-01

    Full Text Available Gold and nickel bisdithiolene complexes with methyl and tert-butyl substituted thiophenetetrathiafulavalenedithiolate ligands (α-mtdt and α-tbtdt were prepared and characterized. These complexes were obtained, under anaerobic conditions, as tetrabutylammonium salts. The diamagnetic gold monoanion (n-Bu4N[Au(α-mtdt2] (3 and nickel dianionic species (n-Bu4Nx[Ni(α-mtdt2] (x = 1,2 (4 were similar to the related non-substituted extended thiophenic-TTF (TTF = tetrathiafulvalene bisdithiolenes. However the introduction of the large, bulky substituent tert-butyl, led to the formation of a Au (I dinuclear complex, (n-Bu4N2[Au2(α-tbtdt2] (5. The neutral methyl substituted gold and nickel complexes were easily obtained through air or iodine exposure as polycrystalline or amorphous fine powder. [Au(α-mtdt2] (6 and [Ni(α-mtdt2] (7 polycrystalline samples display properties of a metallic system with a room temperature electrical conductivity of 0.32 S/cm and ≈4 S/cm and a thermoelectric power of ≈5 µV/K and ≈32 µV/K, respectively. While [Au(α-mtdt2] (6 presented a Pauli-like magnetic susceptibility typical of conducting systems, in [Ni(α-mtdt2] (7 large magnetic susceptibilities indicative of high spin states were observed. Both electric transport properties and magnetic properties for gold and nickel [M(α-mtdt2] are indicative that these compounds are single component molecular conductors.

  5. Antibacterial, antimalarial and leishmanicidal activities of Cu (II) and nickel (II) complexes of diclofenac sodium

    International Nuclear Information System (INIS)

    Rehman, F.U.; Khan, M.F.; Khan, G.M.; Khan, H.; Khan, I.U.

    2010-01-01

    Metal complexes are famous for a wide array of chemotherapeutic effects. The current study was designed to synthesize and evaluate unexplored chemotherapeutic effects of Cu (II) and Nickel (II) complexes of the non-steroidal anti-inflammatory drug diclofenac. Nickel complex exhibited significant leishmanicidal activity against Lieshmania major, while the copper complex was found to possess low activity against the same pathogen. Both of the complexes revealed low antibacterial activities and were interestingly failed to produce any considerable antimalarial activity against Plasmodium falciparum 3D7. Selective leishmanicidal activities of Nickel (II) complex of diclofenac needs further improvement to be developed as potential new metal-based leishmanicidal agent.(author)

  6. Homocoupling of benzyl halides catalyzed by POCOP-nickel pincer complexes

    KAUST Repository

    Chen, Tao

    2012-08-01

    Two types of POCOP-nickel(II) pincer complexes were prepared by mixing POCOP pincer ligands and NiX 2 in toluene at reflux. The resulting nickel complexes efficiently catalyze the homocoupling reactions of benzyl halides in the presence of zinc. The coupled products were obtained in excellent to quantitative yields. © 2012 Elsevier Ltd. All rights reserved.

  7. Microplasma synthesis on aluminum with additions of iron and nickel soluble complexes in electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Rogov, A.B., E-mail: alex-lab@bk.ru [Nikolaev Institute of Inorganic Chemistry. 3, Acad. Lavrentiev Ave, Novosibirsk, 630090 (Russian Federation); Mironov, I.V.; Terleeva, O.P.; Slonova, A.I. [Nikolaev Institute of Inorganic Chemistry. 3, Acad. Lavrentiev Ave, Novosibirsk, 630090 (Russian Federation)

    2012-10-01

    Highlights: Black-Right-Pointing-Pointer Alkaline homogeneous electrolyte with transition metals complexes. Black-Right-Pointing-Pointer Coatings contain metallic iron, nickel and their oxides in alumina-silica matrix. Black-Right-Pointing-Pointer Effect of Fe/Ni ratio on coatings properties and process characteristics. - Abstract: The microplasma synthesis of coatings containing iron and nickel from homogeneous electrolytes has been studied. For stabilization of transition metals in solution, it is proposed to use chelation. It was found that the synthesis of coatings using alternating current leads to the formation of metallic iron and nickel particles in addition to oxide phases. The iron and nickel complexes concentrations ratio in the electrolyte correlates with the coatings composition. Obtained coatings have been studied by scanning electron microscopy with X-ray microanalyser and by X-ray diffraction with Cu and Mo radiation. The metal content in the coating was determined spectrophotometrically from the absorption of iron thiocyanate complexes and nickel dimethylglyoxime complex.

  8. Site-selective electroless nickel plating on patterned thin films of macromolecular metal complexes.

    Science.gov (United States)

    Kimura, Mutsumi; Yamagiwa, Hiroki; Asakawa, Daisuke; Noguchi, Makoto; Kurashina, Tadashi; Fukawa, Tadashi; Shirai, Hirofusa

    2010-12-01

    We demonstrate a simple route to depositing nickel layer patterns using photocross-linked polymer thin films containing palladium catalysts, which can be used as adhesive interlayers for fabrication of nickel patterns on glass and plastic substrates. Electroless nickel patterns can be obtained in three steps: (i) the pattern formation of partially quaterized poly(vinyl pyridine) by UV irradiation, (ii) the formation of macromolecular metal complex with palladium, and (iii) the nickel metallization using electroless plating bath. Metallization is site-selective and allows for a high resolution. And the resulting nickel layered structure shows good adhesion with glass and plastic substrates. The direct patterning of metallic layers onto insulating substrates indicates a great potential for fabricating micro/nano devices.

  9. Synthesis of benzoxazolylpyridine nickel complexes and their efficient dimerization of ethylene to alpha-butene.

    Science.gov (United States)

    Gao, Rong; Xiao, Liwei; Hao, Xiang; Sun, Wen-Hua; Wang, Fosong

    2008-11-07

    A series of new nickel complexes bearing benzoxazolylpyridines was synthesized and characterized by FT-IR spectroscopic and elemental analysis. The molecular structures of two representative complexes were determined by single-crystal X-ray diffraction. The complex [NiCl2[2-(2-benzoxazolyl)-6-methylpyridine

  10. THE STABILITY CONSTANTS OF NICKEL (II) COMPLEXES OF ...

    African Journals Online (AJOL)

    DR. AMINU

    2010-06-01

    Jun 1, 2010 ... chelate rings with nickel ion bound to α – nitrogen. Thus, from structural characteristics, if these amino acids are to behave as didentate ligands, then they will form 5 – membered and 6- mememberd chelate rings respectively with polar .... Determination of some mineral. Elements and Heavy metals in soils, ...

  11. Catecholato complexes of cobalt and nickel with 1, 4-disubstituted-1 ...

    Indian Academy of Sciences (India)

    ... indicates square-planar environment of metals. Chemical one-electron oxidation of nickel complexes proceeds through catecholate ligand and leads to o-semiquinonato adducts. EPR spectral parameters indicate preservation of square-planar configuration after oxidation. Complexes (DAB)M(Cat) (M = Ni, Co) undergo ...

  12. Cobalt and Nickel Complexes Bearing 2-(2-pyridyl-Benzimidazole: Synthesis and Ethylene Oligomerization

    Directory of Open Access Journals (Sweden)

    Jian-Long Du

    2005-01-01

    Full Text Available A series of cobalt and nickel complexes MLX2 (M=Co or Ni, X=Cl bearing 2-(2-pyridylbenzimidazole ligands were synthesized. Treatment of the complexes with methylaluminoxane (MAO leads to active catalysts for ethylene oligomerization. The oligomers were olefins from C2 to C6.

  13. Cobalt and Nickel Complexes Bearing 2-(2-pyridyl)-Benzimidazole: Synthesis and Ethylene Oligomerization

    OpenAIRE

    Du, Jian-Long; Li-Jun-Li

    2005-01-01

    A series of cobalt and nickel complexes MLX2 (M=Co or Ni, X=Cl) bearing 2-(2-pyridyl)benzimidazole ligands were synthesized. Treatment of the complexes with methylaluminoxane (MAO) leads to active catalysts for ethylene oligomerization. The oligomers were olefins from C2 to C6.

  14. Anion-controlled nuclearity in nickel complexes with potentially dinucleating, poly(oxime) amine ligands.

    Science.gov (United States)

    Deters, Elizabeth A; Goldcamp, Michael J; Krause Bauer, Jeanette A; Baldwin, Michael J

    2005-07-25

    Two new ligands consisting of bis(oxime) amine units tethered by a bridge have been synthesized. Their nickel chloride and nickel nitrate complexes have also been synthesized and characterized by X-ray crystallography, FTIR, mass spectrometry, and elemental analysis. One of these ligands, L1 (N,N,N',N'-tetra(1-propan-2-onyl oxime)-diamino-m-xylene), is always dinucleating, while the other ligand, L2 (N,N,N',N'-tetra(1-propan-2-onyl-oxime)-1,3-diaminopropane), shows an unusual anion dependence on the nuclearity. When nickel chloride is used, the ligand acts in a dinucleating manner and coordinates two nickels; however, when nickel nitrate is used, the ligand acts in a monodentate fashion and coordinates only one nickel. Once the mononuclear complex is formed, it is not possible to add a second nickel if Ni(NO(3))(2) is used as the nickel source; it is possible, however, to add a second nickel if NiCl(2) is used as the nickel source. The dinuclear complex can be converted to the mononuclear one by either using silver nitrate to exchange the chloride anions for nitrates or by dissolving the complex in water. Ni(2)(L1)Cl(4)(DMF)(2).DMF: orthorhombic, P2(1)2(1)2(1), a = 12.2524(11) A, b = 16.6145(15) A, c = 20.1234(19) A, V = 4096.5(6) A(3), Z = 4. [Ni(2)(L2)Cl(4)(DMF)](2).2DMF: triclinic, P-1, a = 12.5347(5) A, b = 12.5403(5) A, c = 14.3504(6) A, alpha = 67.348(1) degrees , beta = 69.705(1) degrees , gamma = 81.549(1) degrees , V = 1952.25(14) A(3), Z = 1. Ni(L2).(NO(3))(2): monoclinic, P2(1)/n, a = 9.6738(3) A, b = 30.2229(9) A, c = 15.8238(5) A, beta = 97.995(1) degrees , V = 4581.4(2) A(3), Z = 8.

  15. Optical and thermal properties of nickel(II) hydrazone complex for recordable blu-ray storage

    Science.gov (United States)

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

    2009-08-01

    A nickel(II) hydrazone complex was synthesized in order to obtain a suitable optical recording medium for the new generation recordable blu-ray disk. Smooth thin films of the nickel(II) hydrazone complex were prepared by using the spin-coating method. Absorption and reflectance spectra of the thin films were evaluated in the wavelength 300-700 nm. Thermal properties of the nickel(II) complex were investigated by thermogravimetry (TG) and differential scanning calorimetry (DSC). Optical constants (complex refractive indices N=n+ik) and thickness of the thin film, prepared on single-crystal silicon substrate, were investigated on a rotating analyzer-polarizer scanning ellipsometer in the wavelength 285-705 nm. In addition, in order to examine its possible use as a blu-ray recording medium, the spin-coated film of the nickel(II) complex was prepared on K9 glass substrate with a silver reflective layer, and was studied by static optical recording testing system with a 406.7 nm laser. It is found that the absorption spectra of the thin film has an strong absorption band in the wavelength region 360-420 nm and a moderate absorbance at the 405 nm side, which indicates that the absorption of the film is well matched with the laser wavelength of the 405 nm. The reflectance spectra show that a high reflectivity of the thin film at 405 nm wavelength can be obtained by an optimum film thickness and an appropriate metal reflective layer. The thin film of the nickel(II) complex gives a high n value of 1.62 and a low k value of 0.33, corresponding to the wavelength of the blue laser of 405 nm. Measurements of the thermal properties show that the nickel(II) complex holds a high thermal stability (~ 300 °C) and a sharp weight loss which are helpful to fabricate a small and sharp recording mark edge. The results of the static optical recording test, using the nickel(II) complex thin film as the recording layer, demonstrate that high reflectivity contrast (>50 %) can be obtained at

  16. Polymers containing nickel(II) complexes of Goedken's macrocycle: optimized synthesis and electrochemical characterization.

    Science.gov (United States)

    Paquette, Joseph A; Sauvé, Ethan R; Gilroy, Joe B

    2015-04-01

    The synthesis and characterization of a new class of nickel-containing polymers is described. The optimized copolymerization of alkyne-bearing nickel(II) complexes of Goedken's macrocycle (4,11-dihydro-5,7,12,14-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine) and brominated 9,9-dihexylfluorene produced polymers with potential application as functional redox-active materials. The title polymers exhibit electrochemically reversible, ligand-centered oxidation events at 0.24 and 0.73 V versus the ferrocene/ferrocenium redox couple. They also display exceptional thermal stability and interesting absorption properties due to the presence of the macrocyclic nickel(II) complexes and π-conjugated units incorporated in their backbones. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Synthesis, Characterization, and Biological Activity of Nickel (II) and Palladium (II) Complex with Pyrrolidine Dithiocarbamate (PDTC)

    OpenAIRE

    Sk Imadul Islam; Suvendu Bikash Das; Sutapa Chakrabarty; Sudeshna Hazra; Akhil Pandey; Animesh Patra

    2016-01-01

    The synthesis of square planar Ni(II) and Pd(II) complexes with pyrrolidine dithiocarbamate (PDTC) was characterized by elemental, physiochemical, and spectroscopic methods. Two complexes were prepared by the reaction of nickel acetate and palladium acetate with pyrrolidine dithiocarbamate (PDTC) in 1 : 2 molar ratio. The bovine serum albumin (BSA) interaction with complexes was examined by absorption and fluorescence spectroscopic techniques at pH 7.4. All the spectral data suggest that coor...

  18. Organic photovoltaic cell using near-infrared absorbing nickel complex

    Science.gov (United States)

    Enokido, Fuka; Katayama, Mikimasa; Kaji, Toshihiko

    2018-03-01

    Bis(dithiobenzil)nickel (BDBN) is well known as a stable material that absorbs long-wavelength light. However, there are no reports, to the best of our knowledge, about photovoltaic cells fabricated with this material. The purpose of this paper is to examine the reason for this. Although the charge separation between C60 and BDBN was confirmed by the analysis of photoluminescence spectra, the short-circuit current density (J SC) of the C60/BDBN cells was very low. By investigating charge transport, we found that BDBN is an ambipolar material. In order to reduce the ambipolarity, a MoO3 layer was added to the BDBN layer. The resultant changes in J SC and photoluminescence spectra confirmed that the ambipolarity of BDBN caused low efficiency.

  19. Synthesis of copper and nickel complexes using compartmental ...

    Indian Academy of Sciences (India)

    Administrator

    been analysed by X-ray crystallography. Complexes 1 and 3 have square pyramidal geometry. The co-ordination geometry around the metal ion in complex 7 is square planar and that in complex 10 is octahedral. The electrochemical property of the complexes was studied using cyclic voltammetry. A single quasi-reversible ...

  20. Nickel(II) Complexes Bearing 4-Arylimino-1,2,3-trihydroacridines: Synthesis, Characterization, and Ethylene Oligomerization

    OpenAIRE

    Wang, Shengdong; Du, Shizhen; Zhang, Wenjuan; Asuha, Sin; Sun, Wen-Hua

    2015-01-01

    Nickel(II) complexes have attracted much attention as a new generation of olefin catalysts since the ?-diiminonickel complex was discovered as a highly efficient procatalyst for ethylene polymerization. A series of novel 4-arylimino-1,2,3-trihydroacridylnickel(II) dihalide complexes was synthesized in a one-pot reaction of 2,3-dihydroacridine-4-one and different anilines with nickel(II) chloride or nickel(II) bromide 1,2-dimethoxyethane complex. The complexes were characterized by infrared sp...

  1. Nickel(II) complexes of N2S2 donor set ligand and halide ...

    Indian Academy of Sciences (India)

    Nickel(II) complexes of N2S2 donor set ligand and halide/pseudohalides: Synthesis, crystal structure, DNA and bovine/human serum albumin interaction. ANIMESH PATRAa ..... sitive to the length changes of nucleic acids, and so a classical intercalation mode should be indicated by a lengthening of the DNA double chain, ...

  2. Cationic Nickel(II) Complexes with Azine Diphosphines - Structural and Electrochemical Study

    Czech Academy of Sciences Publication Activity Database

    Almeida, F. M. T.; Carvalho, M. F. N. N.; Galvao, A. M.; Čermák, Jan; Blechta, Vratislav; Pombeiro, A. J. L.; Shaw, B. L.

    2002-01-01

    Roč. 338, - (2002), s. 201-209 ISSN 0020-1693 R&D Projects: GA ČR GA203/01/0554 Keywords : diphosphines * nickel complexes * cyclic voltammetry Subject RIV: CA - Inorganic Chemistry Impact factor: 1.566, year: 2002

  3. Nickel (II) complexes of N 2 S 2 donor set ligand and halide ...

    Indian Academy of Sciences (India)

    The complexes were characterized by physicochemical and spectroscopic methods along with detailed structural characterization of 1,2 and 3 by single crystal X-ray diffraction analyses. The structural study showed that the nickel(II) ion has a distorted octahedral geometry being chelated by the tetradentate N2S2 ligand ...

  4. Steric Effect on the Nucleophilic Reactivity of Nickel(III) Peroxo Complexes.

    Science.gov (United States)

    Kim, Jalee; Shin, Bongki; Kim, Hyunjeong; Lee, Junhyung; Kang, Joongoo; Yanagisawa, Sachiko; Ogura, Takashi; Masuda, Hideki; Ozawa, Tomohiro; Cho, Jaeheung

    2015-07-06

    A set of nickel(III) peroxo complexes bearing tetraazamacrocyclic ligands, [Ni(III)(TBDAP)(O2)](+) (TBDAP = N,N'-di-tert-butyl-2,11-diaza[3.3](2,6)pyridinophane) and [Ni(III)(CHDAP)(O2)](+) (CHDAP = N,N'-dicyclohexyl-2,11-diaza[3.3](2,6)pyridinophane), were prepared by reacting [Ni(II)(TBDAP)(NO3)(H2O)](+) and [Ni(II)(CHDAP)(NO3)](+), respectively, with H2O2 in the presence of triethylamine. The mononuclear nickel(III) peroxo complexes were fully characterized by various physicochemical methods, such as UV-vis, electrospray ionization mass spectrometry, resonance Raman, electron paramagnetic resonance, and X-ray analysis. The spectroscopic and structural characterization clearly shows that the NiO2 cores are almost identical where the peroxo ligand is bound in a side-on fashion. However, the different steric properties of the supporting ligands were confirmed by X-ray crystallography, where the CHDAP ligand gives enough space around the Ni core compared to the TBDAP ligand. The nickel(III) peroxo complexes showed reactivity in the oxidation of aldehydes. In the aldehyde deformylation reaction, the nucleophilic reactivity of the nickel(III) peroxo complexes was highly dependent on the steric properties of the macrocyclic ligands, with a reactivity order of [Ni(III)(TBDAP)(O2)](+) < [Ni(III)(CHDAP)(O2)](+). This result provides fundamental insight into the mechanism of the structure (steric)-reactivity relationship of metal peroxo intermediates.

  5. Nickel (II) complexes containing ONS donor ligands: Synthesis ...

    Indian Academy of Sciences (India)

    The analysis revealed that the complexes possess a distorted octahedral geometry with the ligand coordinating in a uni-negative tridentate ONS fashion. The catalytic activity of complexes towards some C–C coupling reactions (viz., Kumada-Corriu, Suzuki-Miyaura and Sonogashira) has been examined. The complexes ...

  6. Investigation on biomolecular interactions of nickel(II) complexes with monoanionic bidentate ligands

    Science.gov (United States)

    Jayamani, Arumugam; Sethupathi, Murugan; Ojwach, Stephen O.; Sengottuvelan, Nallathambi

    2018-01-01

    Reactions of monoanionic bidentate ligands 5-methylsalicylaldehyde (5-msal), 5-bromosalicylaldehyde (5-brsal), 5-nitrosalicylaldehyde (5-nsal) and 2-hydroxy-1-naphthaldehyde (2-hnap) with nickel perchlorate hexahydrate produced nickel(II) complexes 1-4, respectively. Single crystal X-ray analyses of complexes 1 and 2 confirmed bidentate mode of the ligands with O˄O coordination to give square planar geometry around nickel atoms. Complexes 1-4 showed one quasi-reversible redox peak at cathodic region (-0.67 to -0.80 V) and one redox peak at anodic region (+1.08 to +1.44 V) assignable to the Ni(II)/Ni(I) and Ni(II)/Ni(III) redox couples, respectively. The complexes exhibited good bovine serum albumin (BSA) binding abilities with a maximum binding constant of 1.96 × 105 M-1. The binding of complexes with calf thymus DNA (ctDNA) showed that the binding affinity is consistent with an increase in steric bulk of the ligands. The nuclease activity of the complexes showed efficient oxidative cleavage in the presence of hydrogen peroxide as an oxidizing agent. The complexes showed higher zone of inhibition when screened for antimicrobial activity against bacteria and human pathogenic fungi.

  7. Synthesis and Characterization of Novel Thiourea Derivatives and Their Nickel and Copper Complexes

    Directory of Open Access Journals (Sweden)

    Gün Binzet

    2013-01-01

    Full Text Available New benzoyl thiourea derivatives and their nickel and copper complexes were synthesized. The structure of the synthesized compounds were confirmed by elemental analysis, FT-IR, and 1H NMR techniques. Four of the synthesized compounds are analyzed by X-ray single crystal diffraction technique. Whereas N,N-dimethyl-N′-(4-fluorobenzoylthiourea, N,N-diethyl-N′-(4-fluorobenzoylthiourea, and N,N-di-n-butyl-N′-(4-fluorobenzoyl thiourea crystallize in the monoclinic system, bis(N,N-di-n-propyl-N′-(4-fluorobenzoylthioureato nickel(II complex crystallizes in the triclinic system. These ligand molecules form dimers through strong intermolecular hydrogen bonds such as N–H⋯S, C–H⋯O, and N–H⋯O. Moreover, there are different types of intramolecular interactions in the crystal structures. Bis(N,N-dimethyl-N′-(4-fluorobenzoylthioureato nickel(II complex has a nearly square-planar coordination. The distance of nickel atom from the best plane through the coordination sphere is 0.029 Å.

  8. Theoretical study of the binding nature of glassy carbon with nickel(II) phthalocyanine complexes

    Energy Technology Data Exchange (ETDEWEB)

    Cortez, Luis [Laboratorio de Quimica Teorica, Facultad de Quimica y Biologia, Universidad de Santiago de Chile (USACH), Casilla 40, Correo 33, Santiago (Chile); Berrios, Cristhian [Laboratorio de Electrocatalisis, Facultad de Quimica y Biologia, Universidad de Santiago de Chile (USACH), Casilla 40, Correo 33, Santiago (Chile); Yanez, Mauricio [Laboratorio de Recursos Renovables, Centro de Biotecnologia, Universidad de Concepcion, Casilla-160 C, Concepcion (Chile); Cardenas-Jiron, Gloria I., E-mail: gloria.cardenas@usach.cl [Laboratorio de Quimica Teorica, Facultad de Quimica y Biologia, Universidad de Santiago de Chile (USACH), Casilla 40, Correo 33, Santiago (Chile)

    2009-11-26

    A theoretical study at the semiempirical RHF/PM3(tm) level (tm: transition metal) of the binding nature between a glassy carbon (GC) cluster and a nickel(II) complex (nickel(II) phthalocyanine NiPc, nickel(II) tetrasulphophthalocyanine NiTSPc) was performed. Three types of interactions for GC...NiPc (NiTSPc) were studied: (a) through an oxo (O) bridge, (b) through an hydroxo (OH) bridge, and (c) non-bridge. One layer (NiPc, NiTSPc) and two layers (NiPc...NiPc) of complex were considered. The binding energy calculated showed that in both cases NiPc and NiTSPc, the oxo structures are more stable than the hydroxo ones, and than the non-bridge systems. Charge analysis (NAO) predicted that GC gained more electrons in an oxo structure than in the analogues hydroxo. The theoretical results showed an agreement with the experimental data available, an oxo binding between GC and a nickel complex (NiPc, NiTSPc) in aqueous alkaline solutions is formed.

  9. Theoretical study of the binding nature of glassy carbon with nickel(II) phthalocyanine complexes

    International Nuclear Information System (INIS)

    Cortez, Luis; Berrios, Cristhian; Yanez, Mauricio; Cardenas-Jiron, Gloria I.

    2009-01-01

    A theoretical study at the semiempirical RHF/PM3(tm) level (tm: transition metal) of the binding nature between a glassy carbon (GC) cluster and a nickel(II) complex (nickel(II) phthalocyanine NiPc, nickel(II) tetrasulphophthalocyanine NiTSPc) was performed. Three types of interactions for GC...NiPc (NiTSPc) were studied: (a) through an oxo (O) bridge, (b) through an hydroxo (OH) bridge, and (c) non-bridge. One layer (NiPc, NiTSPc) and two layers (NiPc...NiPc) of complex were considered. The binding energy calculated showed that in both cases NiPc and NiTSPc, the oxo structures are more stable than the hydroxo ones, and than the non-bridge systems. Charge analysis (NAO) predicted that GC gained more electrons in an oxo structure than in the analogues hydroxo. The theoretical results showed an agreement with the experimental data available, an oxo binding between GC and a nickel complex (NiPc, NiTSPc) in aqueous alkaline solutions is formed.

  10. Ethylene oligomerization in metal-organic frameworks bearing nickel(ii) 2,2'-bipyridine complexes.

    Science.gov (United States)

    Gonzalez, Miguel I; Oktawiec, Julia; Long, Jeffrey R

    2017-09-08

    The metal-organic frameworks Zr 6 O 4 (OH) 4 (bpydc) 6 (1; bpydc 2- = 2,2'-bipyridine-5,5'-dicarboxylate) and Zr 6 O 4 (OH) 4 (bpydc) 0.84 (bpdc) 5.16 (2; bpdc 2- = biphenyl-4,4'-dicarboxylate) were readily metalated with Ni(DME)Br 2 (DME = dimethoxyethane) to produce the corresponding metalated frameworks 1(NiBr 2 ) 6 and 2(NiBr 2 ) 0.84 . Both nickel(ii)-containing frameworks catalyze the oligomerization of ethylene in the presence of Et 2 AlCl. In these systems, the pore environment around the active nickel sites significantly influences their selectivity for formation of oligomers over polymer. Specifically, the single-crystal structure of 1(NiBr 2 ) 5.64 reveals that surrounding metal-linker complexes enforce a steric environment on each nickel site that causes polymer formation to become favorable. Minimizing this steric congestion by isolating the nickel(ii) bipyridine complexes in the mixed-linker framework 2(NiBr 2 ) 0.84 markedly improves both the catalytic activity and selectivity for oligomers. Furthermore, both frameworks give product mixtures that are enriched in shorter olefins (C 4-10 ), leading to deviations from the expected Schulz-Flory distribution of oligomers. Although these deviations indicate possible pore confinement effects on selectivity, control experiments using the nickel-treated biphenyl framework Zr 6 O 4 (OH) 4 (bpdc) 6 (NiBr 2 ) 0.14 (3(NiBr 2 ) 0.14 ) reveal that they likely arise at least in part from the presence of nickel species that are not ligated by bipyridine within 1(NiBr 2 ) 5.64 and 2(NiBr 2 ) 0.84 .

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

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Michael Edward [Univ. of California, Berkeley, CA (United States)

    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.

  12. Distorted tetrahedral nickel-nitrosyl complexes: spectroscopic characterization and electronic structure.

    Science.gov (United States)

    Soma, Shoko; Van Stappen, Casey; Kiss, Mercedesz; Szilagyi, Robert K; Lehnert, Nicolai; Fujisawa, Kiyoshi

    2016-09-01

    The linear nickel-nitrosyl complex [Ni(NO)(L3)] supported by a highly hindered tridentate nitrogen-based ligand, hydrotris(3-tertiary butyl-5-isopropyl-1-pyrazolyl)borate (denoted as L3), was prepared by the reaction of the potassium salt of the ligand with the nickel-nitrosyl precursor [Ni(NO)(Br)(PPh 3 ) 2 ]. The obtained nitrosyl complexes as well as the corresponding chlorido complexes [Ni(NO)(Cl)(PPh 3 ) 2 ] and [Ni(Cl)(L3)] were characterized by X-ray crystallography and different spectroscopic methods including IR/far-IR, UV-Vis, NMR, and multi-edge X-ray absorption spectroscopy at the Ni K-, Ni L-, Cl K-, and P K-edges. For comparative electronic structure analysis we also performed DFT calculations to further elucidate the electronic structure of [Ni(NO)(L3)]. These results provide the nickel oxidation state and the character of the Ni-NO bond. The complex [Ni(NO)(L3)] is best described as [Ni (II) (NO (-) )(L3)], and the spectroscopic results indicate that the phosphane complexes have a similar [Ni (II) (NO (-) )(X)(PPh 3 ) 2 ] ground state.

  13. Effect of organic complexing compounds and surfactants on coprecipitation of cesium radionuclides with nickel ferrocyanide precipitate

    International Nuclear Information System (INIS)

    Milyutin, V.V.; Gelis, V.M.; Ershov, B.G.; Seliverstov, A.F.

    2008-01-01

    One studied the effect of the organic complexing compounds and of the surfactants on the coprecipitation of Cs trace amounts with the nickel ferrocyanide precipitate. The presence of the oxalate- and ethylenediamin-tetraacetate-ions in the solutions is shown to result in the abrupt reduction of Cs coprecipitation degree. The effect of the various surfactants manifested itself not so explicitly. To reduce the negative effect of the organic compounds on the intimacy of Cs coprecipitation one tried out the procedure of their chemical destruction by ozon. Pre-ozonization of the solutions enabled to prevent the negative effect of the organic complexing compounds and of the surfactants on Cs coprecipitation with nickel ferrocyanide precipitate [ru

  14. Nickel(III) oxidation of its glycylglycylhistamine complex.

    Science.gov (United States)

    Green, Brandon J; Tesfai, Teweldemedhin M; Margerum, Dale W

    2004-11-07

    The doubly-deprotonated Ni(III) complex of Gly(2)Ha (where Ha is histamine) undergoes base-assisted oxidative self-decomposition of the peptide. At formaldehyde. Two-electron oxidations of the second glycyl and histamine residues occur as minor pathways (12% of the total possible reaction). Above p[H(+)] 8.5, two Ni(III)-peptide complexes form an oxo bridge in the axial positions to give a reactive dimer species. This proximity allows the resulting Ni(II)-peptide radical intermediates to undergo peptide-peptide cross-linking at the N-terminal glycyl residues. The products found below p[H(+)] 7.0 are observed above p[H(+)] 8.5 as well, although in lower yields. In contrast to this work, Ni(III)(H(-2)Gly(2)HisGly) undergoes a four-electron oxidation at the N-terminal glycyl residue. Oxidation at the internal glycyl and histidyl residues are not observed. The reactivity of Ni(III)(H(-2)Gly(2)Ha)(+) is also different than Cu(III)(H(-2)Gly(2)Ha)(+), which undergoes a two-electron oxidation at the histamine group with no peptide-peptide cross-linking in basic solution.

  15. C-H nickellation of phenol-derived phosphinites: regioselectivity and structures of cyclonickellated complexes.

    Science.gov (United States)

    Mangin, Loïc P; Zargarian, Davit

    2017-11-28

    This report describes the results of a study on the ortho-C-H nickellation of the aryl phosphinites i-Pr 2 P(OAr) derived from the following four groups of substituted phenols: 3-R-C 6 H 4 OH (R = F (b), Me (c), MeO (d), Cl (e)); 3,5-R 2 -C 6 H 3 OH (R = F (f), Me (g), Cl (h), OMe (i)); 2-R-C 6 H 4 OH (R = Me (j), Ph(k)); and 2,6-R 2 -C 6 H 3 OH (R = Me (l), Ph (m)). No nickellation was observed with the phosphinites derived from the 3,5-disubstituted phenols g and h, and the 2,6-disubstituted phenols l and m; in all other cases nickellation occurred at an ortho-C-H to generate either the Br-bridged dimers [{κ P ,κ C -(i-Pr) 2 POAr}Ni(μ-Br)] 2 (1b-1f, 1j, and 1k) or the monomeric acetonitrile adduct {κ P ,κ C -ArOP(i-Pr) 2 }Ni(Br)(NCMe) (1i-NCMe). Analysis of C-H nickellation regioselectivity with 3-R-C 6 H 4 OH pointed to the importance of substituent sterics, not electronics: nickellation occurred at the least hindered position either exclusively (for R = Me (c), MeO(d), and Cl (e)) or predominantly (for R = F (b); 6 : 1). This conclusion is also consistent with the observation that C-H nickellation is possible with the 3,5-disubstituted aryl phosphinites bearing F and OMe, but not with the more bulky substituents Me or Cl. For the 2-substituted aryl phosphinites, C-H nickellation occurs at the unsubstituted ortho-C-H and not on the R substituent, regardless of whether the alternative C-H moiety of the substituent is sp 3 (R = Me (j)) or sp 2 (R = Ph (k)). The system thus reveals a strong preference for formation of 5-membered metallacycles. Consistent with this reactivity, no nickellation occurs with (2,6-R 2 -C 6 H 3 O)P(i-Pr) 2 . Tests with the parent dimer derived from i-Pr 2 P(OPh) showed that conversion to the monomeric acetonitrile adduct is highly favored, going to completion with only a small excess of MeCN. All new cyclonickellated complexes reported in this study were fully characterized, including by single crystal X-ray diffraction studies

  16. Complexation of 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-7,14-diene dithiocyanate with nickel (II) acetate

    Energy Technology Data Exchange (ETDEWEB)

    Ishak, Nur Iliyani Mohd; Yamin, Bohari M. [Department of Chemistry, Faculty of Science and Technology, UniversitiKebangsaan Malaysia, 43600 Bangi, Selangor (Malaysia)

    2013-11-27

    The complexation of nickel acetate with tetraaza involves deprotonation of protonated amine nitrogen to form neutral ligand coordinated to the nickel via the four nitrogen atom. The dication complex is paired with thiocyanate anions. The complex was characterized by elemental analysis, UV-VIS and FTIR spectroscopic method. The crystal structure of nickel complex characterized by X-Ray crystallography and adopts square planar geometry.

  17. Liquid Membranes as a Tool for Chemical Speciation of Metals in Natural Waters: Organic and Inorganic Complexes of Nickel.

    Science.gov (United States)

    Vergel, Cristina; Mendiguchía, Carolina; Moreno, Carlos

    2018-04-15

    The different species of nickel present in natural waters exhibit different transport behaviour through bulk liquid membranes (BLMs). This fact has been used to design and optimise a separation/pre-concentration system applicable to separate labile and non-labile nickel fractions. A hydrazone derivative-1,2-cyclohexanedione bis-benzoyl-hydrazone (1,2-CHBBH) dissolved in toluene/dimethyl formamide (2% DMF)-was used as a chemical carrier of nickel species, from an aqueous source solution (sample) to a receiving acidic solution. Both chemical and hydrodynamic conditions controlling the transport system were studied and optimised. Under optimum conditions, variations in the transport of nickel ions as a function of organic (humic acids) and inorganic (chloride ions) ligands were studied. Relationships between the permeability coefficient ( P ) or recovery efficiency (%R) and the concentrations of ligands and nickel species were analysed using Winhumic V software. A negative correlation between P and the concentration of organic nickel complexes was found, suggesting that only labile nickel species are transported through the liquid membrane, with non-labile complexes remaining in the water sample; allowing for their separation and subsequent quantification in natural waters.

  18. Nickel(II) Complexes Bearing 4-Arylimino-1,2,3-trihydroacridines: Synthesis, Characterization, and Ethylene Oligomerization.

    Science.gov (United States)

    Wang, Shengdong; Du, Shizhen; Zhang, Wenjuan; Asuha, Sin; Sun, Wen-Hua

    2015-06-01

    Nickel(II) complexes have attracted much attention as a new generation of olefin catalysts since the α-diiminonickel complex was discovered as a highly efficient procatalyst for ethylene polymerization. A series of novel 4-arylimino-1,2,3-trihydroacridylnickel(II) dihalide complexes was synthesized in a one-pot reaction of 2,3-dihydroacridine-4-one and different anilines with nickel(II) chloride or nickel(II) bromide 1,2-dimethoxyethane complex. The complexes were characterized by infrared spectroscopy and elemental analysis. The molecular structures of the representative complexes 4-(2,6-diisopropylphenylimino)-1,2,3-trihydroacridylnickel(II) dichloride (C3), 4-(2,4,6-trimethylphenylimino)-1,2,3-trihydroacridylnickel dichloride(II) (C4), and 4-(2,4,6-trimethylphenylimino)-1,2,3-trihydroacridylnickel(II) dibromide (C9) were confirmed by single-crystal X-ray crystallography, revealing a distorted tetrahedral geometry around the nickel(II) of C3 and distorted trigonal bipyramidal geometry for C4 and C9. With the activation of trimethylaluminium (TMA), all nickel(II) complexes exhibited good activity for ethylene oligomerization, and oligomer products ranged from butene (C4) to hexadecene (C16).

  19. Molecular Mechanics and Quantum Chemistry Based Study of Nickel-N-Allyl Urea and N-Allyl Thiourea Complexes

    Directory of Open Access Journals (Sweden)

    P. D. Sharma

    2009-01-01

    Full Text Available Eigenvalue, eigenvector and overlap matrix of nickel halide complex of N-allyl urea and N-allyl thiourea have been evaluated. Our results indicate that ligand field parameters (Dq, B’ and β evaluated earlier by electronic spectra are very close to values evaluated with the help of eigenvalues and eigenvectors. Eigenvector analysis and population analysis shows that in bonding 4s, 4p, and 3dx2-y2, 3dyz orbitals of nickel are involved but the coefficient values differ in different complexes. Out of 4px, 4py, 4pz the involvement of either 4pz or 4py, is noticeable. The theoretically evaluated positions of infrared bands indicate that N-allyl urea is coordinated to nickel through its oxygen and N-allyl thiourea is coordinated to nickel through its sulphur which is in conformity with the experimental results.

  20. Synthesis, Characterization, and Biological Activity of Nickel (II and Palladium (II Complex with Pyrrolidine Dithiocarbamate (PDTC

    Directory of Open Access Journals (Sweden)

    Sk Imadul Islam

    2016-01-01

    Full Text Available The synthesis of square planar Ni(II and Pd(II complexes with pyrrolidine dithiocarbamate (PDTC was characterized by elemental, physiochemical, and spectroscopic methods. Two complexes were prepared by the reaction of nickel acetate and palladium acetate with pyrrolidine dithiocarbamate (PDTC in 1 : 2 molar ratio. The bovine serum albumin (BSA interaction with complexes was examined by absorption and fluorescence spectroscopic techniques at pH 7.4. All the spectral data suggest that coordination of the pyrrolidine dithiocarbamate (PDTC takes place through the two sulphur atoms in a symmetrical bidentate fashion. All the synthesized compounds were screened for their antimicrobial activity against some species of pathogenic bacteria (Escherichia coli, Vibrio cholerae, Streptococcus pneumonia, and Bacillus cereus. It has been observed that complexes have higher activity than the free ligand.

  1. Synthesis and Characterization of Novel Thiourea Derivatives and Their Nickel and Copper Complexes

    OpenAIRE

    Gün Binzet; Gülten Kavak; Nevzat Külcü; Süheyla Özbey; Ulrich Flörke; Hakan Arslan

    2013-01-01

    New benzoyl thiourea derivatives and their nickel and copper complexes were synthesized. The structure of the synthesized compounds were confirmed by elemental analysis, FT-IR, and 1H NMR techniques. Four of the synthesized compounds are analyzed by X-ray single crystal diffraction technique. Whereas N,N-dimethyl-N′-(4-fluorobenzoyl)thiourea, N,N-diethyl-N′-(4-fluorobenzoyl)thiourea, and N,N-di-n-butyl-N′-(4-fluorobenzoyl) thiourea crystallize in the monoclinic system, bis(N,N-di-n-propyl-N′-...

  2. Variation in the biomolecular interactions of nickel(II) hydrazone complexes upon tuning the hydrazide fragment.

    Science.gov (United States)

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

    2012-06-14

    Three 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 o-hydroxynaphthaldehyde with furoic acid hydrazide (H(2)L(1)) (1)/thiophene-2-acid hydrazide (H(2)L(2)) (2)/isonicotinic acid hydrazide (H(2)L(3)) (3)} and formulated as [Ni(L(1))(PPh(3))] (4), [Ni(L(2))(PPh(3))] (5) and [Ni(L(3))(PPh(3))] (6). Structural characterization of these compounds 4-6 were accomplished by using various physico-chemical techniques. Single crystal X-ray diffraction data of complexes 4 and 5 proved their distorted square planar geometry. In order to ascertain the potential of the above synthesised compounds towards biomolecular interactions, additional experiments involving interaction with calf thymus DNA (CT DNA) and bovine serum albumin (BSA) were carried out. All the ligands and corresponding nickel(ii) chelates have been screened for their scavenging effect towards O(2)(-), OH and NO radicals. The efficiency of complexes 4-6 to arrest the growth of HeLa, HepG-2 and A431 tumour cell lines has been studied along with the cell viability test against the non-cancerous NIH 3T3 cells under in vitro conditions.

  3. Oligomerization of ethylene catalysed by nickel complexes associated with nitrogen ligands in ionic liquids; Oligomerisation de l'ethylene catalysee par des complexes du nickel associes a des ligands azotes dans les liquides ioniques

    Energy Technology Data Exchange (ETDEWEB)

    Lecocq, V.

    2003-09-01

    We report here the use of a new class of catalytic systems based on a nickel active center associated with nitrogen ligands, such as di-imines, or imino-pyridines, for the oligomerization of ethylene in a biphasic medium using ionic liquids as the catalyst solvent. The nickel catalyst is immobilized in the ionic liquid phase in which the olefinic reaction products are poorly miscible. This biphasic system makes possible an easy separation and recycle of the catalyst. Numerous di-imine and imino-pyridine ligands with different steric and electronic properties have been synthesized and their corresponding nickel complexes isolated and characterized. Different ionic liquids, based on chloro-aluminates or non-chloro-aluminates anions, have also been prepared and characterized. The effect of the nature of the ligand, the ionic liquid, the nickel precursor and its mode of activation have been studied and correlated with the selectivity and activity of the transformation of ethylene. (author)

  4. Nickel and iron pincer complexes as catalysts for the reduction of carbonyl compounds.

    Science.gov (United States)

    Chakraborty, Sumit; Bhattacharya, Papri; Dai, Huiguang; Guan, Hairong

    2015-07-21

    The reductions of aldehydes, ketones, and esters to alcohols are important processes for the synthesis of chemicals that are vital to our daily life, and the reduction of CO2 to methanol is expected to provide key technology for carbon management and energy storage in our future. Catalysts that affect the reduction of carbonyl compounds often contain ruthenium, osmium, or other precious metals. The high and fluctuating price, and the limited availability of these metals, calls for efforts to develop catalysts based on more abundant and less expensive first-row transition metals, such as nickel and iron. The challenge, however, is to identify ligand systems that can increase the thermal stability of the catalysts, enhance their reactivity, and bypass the one-electron pathways that are commonly observed for first-row transition metal complexes. Although many other strategies exist, this Account describes how we have utilized pincer ligands along with other ancillary ligands to accomplish these goals. The bis(phosphinite)-based pincer ligands (also known as POCOP-pincer ligands) create well-defined nickel hydride complexes as efficient catalysts for the hydrosilylation of aldehydes and ketones and the hydroboration of CO2 to methanol derivatives. The hydride ligands in these complexes are substantially nucleophilic, largely due to the enhancement by the strongly trans-influencing aryl groups. Under the same principle, the pincer-ligated nickel cyanomethyl complexes exhibit remarkably high activity (turnover numbers up to 82,000) for catalytically activating acetonitrile and the addition of H-CH2CN across the C═O bonds of aldehydes without requiring a base additive. Cyclometalation of bis(phosphinite)-based pincer ligands with low-valent iron species "Fe(PR3)4" results in diamagnetic Fe(II) hydride complexes, which are active catalysts for the hydrosilylation of aldehydes and ketones. Mechanistic investigation suggests that the hydride ligand is not delivered to the

  5. Cobalt and Nickel Complexes Bearing 2,6-Bis(imino)phenoxy Ligands:Synthesis and Ethylene Oligomerization Study

    OpenAIRE

    Du, Jian-Long; Li, Li-Jun

    2006-01-01

    A series of new cobalt and nickel complexes MLX2 (M = Co or Ni, X = Cl) bearing 2,6-bis(imino)phenoxy ligands have been synthesized. Treatment of the complexes with methylaluminoxane (MAO) leads to active catalysts for ethylene oligomerization. The oligomers are olefins from C4 to C6.

  6. Cobalt and Nickel Complexes Bearing 2,6-Bis(iminophenoxy Ligands:Synthesis and Ethylene Oligomerization Study

    Directory of Open Access Journals (Sweden)

    Jian-Long Du

    2006-01-01

    Full Text Available A series of new cobalt and nickel complexes MLX2 (M = Co or Ni, X = Cl bearing 2,6-bis(iminophenoxy ligands have been synthesized. Treatment of the complexes with methylaluminoxane (MAO leads to active catalysts for ethylene oligomerization. The oligomers are olefins from C4 to C6.

  7. Synthesis and characterization of nickel complexes derived from Schiff-Bases

    Directory of Open Access Journals (Sweden)

    Mirian Y. Matsumoto

    2012-06-01

    Full Text Available Aromatic Schiff-Bases constitute a large class of organic compounds containing the imine group (C=N [1-3]. 2-hydroxybenzaldehyde (salicylaldehyde which has been frequently used for the synthesis of aromatic Schiff-Bases, it has many biological applications, such as analgesics, anti-inflammatory, antibacterial, antiviral and bactericidal activities [4-6]. From above, this project proposed the synthesis of three Schiff bases derived from salicylaldehyde prepared by condensation between salicylaldehyde with different p-substituted anilines (H, NO2 and MeO. Schiff-Bases synthesized were used as starting compound for the synthesis of nickel complexes. The synthesis of nickel complexes were carried out by adding of alcoholic solution of ligands (2 eq. in aqueous solution of NiCl2.6 H2O (1 eq. contain KOH (1eq. 3 hours. After thisMatsumoto et al. time, the reaction was kept to r.t. to obtain a precipitates. The precipitates were filtered under vacuum and they were characterized by GC-MS, FT-IR and UV-Vis

  8. Synthesis and characterization of palladium(II) and nickel(II) alcoholate-functionalized NHC complexes and of mixed nickel(II)-lithium(I) complexes.

    Science.gov (United States)

    Hameury, Sophie; de Frémont, Pierre; Breuil, Pierre-Alain R; Olivier-Bourbigou, Hélène; Braunstein, Pierre

    2014-05-19

    The synthesis of Pd(II) and Ni(II) alcohol-functionalized N-heterocyclic carbene (NHC) complexes was explored to examine the possible influence of the functional arm attached to the NHC backbone on their structure and reactivity and, in the case of a Ni(II) complex, on its catalytic properties in ethylene oligomerization. Starting from the alcohol-functionalized imidazolium salt [ImDiPP(C2OH)]Cl (2), the new functionalized NHC palladium(II) complex [PdCl(acac){ImDiPP(C2OH)-CNHC}] (3) was synthesized and fully characterized. Two byproducts, [PdCl{μ-ImDiPP(C2O)-CNHC,O}]2 (4) and trans-[PdCl2{ImDiPP(C2OH)-CNHC}2] (5), formed during the synthesis of 3, were also fully characterized. Acids promoted the transformation of 3 into the new CNHC-bound complex [PdCl(μ-Cl){ImDiPP(C2OH)-CNHC}]2 (6), unveiling the lability of the acac ligand and the resistance of the Pd-NHC bond to acids. Complex 6 reacted with a base to afford complex 4, in which alkoxide coordination to Pd(II) has occurred to generate a CNHC,O chelate. The stability of 3 was also assessed under basic conditions, and the new complex [Pd(acac){ImDiPP(C2O)-CNHC,O}] (7) was characterized. The new nickel(II) alcoholate-functionalized NHC complex [NiCl{μ-ImDiPP(C2O)-CNHC,O}]2 (8) was synthesized by the reaction of the imidazolium salt 2 with n-BuLi and [NiCl2(dme)]. The reaction of 8 with HCl regenerates the imidazolium and alcohol functions to give [ImDiPP(C2OH)]2[NiCl4] (9). The mixed-metal Ni(II)-Li(I) complexes [Ni2{μ-ImDiPP(C2O)-CNHC,μ-O}4Li]BF4 (10), [Ni2{μ-ImDiPP(C2O)-CNHC,μ-O}4Li]Cl (11), and [Ni{ImDiPP(C2O)-CNHC,μ-O}2LiBr] (12) were isolated and characterized. However, it was not possible to synthesize a Ni(II) alcohol-functionalized NHC complex in high yield. Small amounts of the square-planar complex [NiCl2{ImDiPP(C2OH)-CNHC}2] (13) could be isolated, and this complex was characterized by single-crystal X-ray diffraction. In 13, only the CNHC atom of the alcohol-functionalized NHC ligand is bound

  9. Synthesis and characterization of divalent manganese, cobalt, nickel, copper and zinc complexes with nicotinic acid

    Science.gov (United States)

    Singh, Raghuvir; Rao, R. S. Sreenivas

    1981-02-01

    Coordination compounds of the transition metal(II) acetylacetonates of the formula [M(NA) 2(acac) 2 ] n (M = Mn, Co, Ni, Cu and Zn; NA = nicotinic acid and acac = acetyl-acetonate anion) have been synthesized and characterized by chemical analysis, magnetic susceptibility, ligand-field spectra, IR and far-IR spectral measurements as well as photoacoustic spectroscopy in the solid state. Tentative stereochemistries for the complexes isolated in the solid state are suggested. The ligand-field parameters 10 Dq, B, β, λ and CFSE are calculated for cobalt and nickel complexes and are in good agreement with the proposed geometries. The metal ions attain six-coordination through the four oxygens of the anion and two donor atoms of the nicotinic acid ligands acting always as monodentate ligands. The formation of the compound results in a considerable shift of v(M-O) to lower frequencies in all the compounds related to parent acetylacetonates.

  10. Bimetallic octahedral ruthenium-nickel carbido cluster complexes. Synthesis and structural characterization.

    Science.gov (United States)

    Saha, Sumit; Zhu, Lei; Captain, Burjor

    2013-03-04

    The reaction of Ru5(CO)15(μ5-C) with Ni(COD)2 in acetonitrile at 80 °C affords the bimetallic octahedral ruthenium-nickel cluster complex Ru5Ni(NCMe)(CO)15(μ6-C), 3. The acetonitrile ligand in 3 can be replaced by CO and NH3 to yield Ru5Ni(CO)16(μ6-C), 4, and Ru5Ni(NH3)(CO)15(μ6-C), 5, respectively. Photolysis of compound 3 in benzene and toluene solvent yielded the η(6)-coordinated benzene and toluene Ru5Ni carbido cluster complexes Ru5Ni(CO)13(η(6)-C6H6)(μ6-C), 6, and Ru5Ni(CO)13(η(6)-C7H8)(μ6-C), 7, respectively. All five new compounds were structurally characterized by single-crystal X-ray diffraction analyses.

  11. Syntheses, characterization and antifungal activity of heteroleptic nickel(II) complexes with N-alkylsulfonyldithiocarbimates and phosphines

    Science.gov (United States)

    Vidigal, Antonio E. C.; Rubinger, Mayura M. M.; Oliveira, Marcelo R. L.; Guilardi, Silvana; Souza, Rafael A. C.; Ellena, Javier; Zambolim, Laércio

    2016-06-01

    Four nickel(II) complexes of general formula [Ni(RSO2Ndbnd CS2) (PPh3)2] where R = CH3 (2a), CH3CH2 (2b), CH3(CH2)3 (2c) and CH3(CH2)7 (2d) and PPh3 = triphenylphosphine; and two nickel(II) complexes of general formula [Ni(RSO2Ndbnd CS2)dppe] where R = CH3(CH2)3 (3c) and CH3(CH2)7 (3d) and dppe = 1,2-bis(diphenylphosphine)ethane) were prepared. These new complexes were obtained by the reaction of nickel(II) chloride hexahydrate with potassium N-alkylsulfonyldithiocarbimates and the appropriate phosphine using ethanol/water as solvent. The IR, UV-Vis and 1H, 13C and 31P NMR spectra, elemental analysis of Ni and the HR-ESI-MS were consistent with the formation of square planar nickel(II) complexes with mixed ligands. The structures of the compounds 2b and 2c were determined by single crystal X-ray diffraction. The compounds are isostructural and crystallize in the space group P 1 bar of the triclinic system. The activities of the complexes were investigated in vitro against Botrytis cinerea, Colletotrichum acutatum and Alternaria solani, fungi species that affect various commercially important plants. All the complexes were active.

  12. FIBROUS CHEMISORBENTS-AMPHOLYTE BASED ON THE COMPLEX COMPOUND OF NICKEL(II CHLORID AND MONOETHANOLAMINE

    Directory of Open Access Journals (Sweden)

    R. E. Khoma

    2016-04-01

    Full Text Available The water vapor adsorption by complex compounds of nickel(II chloride and monoethanolamine with different molar ratio metal : ligand, deposited on a fibrous carrier from nonwoven web on the basis of polyester fiber has been investigated under static conditions. Water vapor adsorption isotherms were analyzed in the framework of Brunauer-Emmett-Teller (BET adsorption theory, monolayer capacitance values and the heats of water molecules adsorption in the first layer were determined. Sulphur dioxide and ammonia chemisorptions under static and dynamic conditions with obtained chemisorbents has been investigated. It was found the process of chemisorption of sulfur dioxide can take place only in the presence of «free» water formed on the fiber surface after formation of the monolayer, when the value of water vapor relative pressure of reaches P/PS = 0,25÷0,30. Under these conditions the destruction of the donor-acceptor bond in the cation complex between the nickel ions and monoethanolamine molecules within the domestic sphere of aminocomplexes takes place followed by the formation of more stable «onium» sulphites, hydrosulphites and pyrosulphite.  It is found in the case of ammonia chemisorption by above mentioned material prewetting of the sample does not significantly increase ammonia absorption. In this case the displacement of the water molecules from inner-aquaaminocomplexes composition and replacing it with an equivalent amount of ammonia molecules take place to form a mixedligand complex of the composition: [Ni(HOCH2CH2NH2n(NH36‑2n]Cl2. It is shown that the designed fibrous chemisorbent carries out a combined air purification both on sulfur dioxide and ammonia and may be used for the equipment of personal respiratory protection – lightweight respirators for dust and gases.

  13. Synthesis, Electrochemical, Spectroscopic, Antimicrobial, and Superoxide Dismutase Activity of Nickel (II Complexes with Bidentate Schiff Bases

    Directory of Open Access Journals (Sweden)

    R. N. Patel

    2013-01-01

    Full Text Available Five new nickel (II complexes, namely, [Ni(L12](ClO42(1; [Ni(L22](ClO42(2; [Ni(L32](ClO42(3; [Ni(L42](ClO42(4; [Ni(L52](ClO42(5, where L1 = benzoylhydrazide; L2 = N-[(1-1-(2-methylphenylethylidene]benzohydrazide; L3=N-[(1-1-(4-methylphenylethylidene]benzohydrazide; L4=N-[(1-1-(2-methoxyphenylethylidene]benzohydrazide; L5 = N-[(1-1-(4-methoxy-phenylethylidene]benzohydrazide, have been synthesized and characterized by various physicochemical and spectroscopic techniques. The synthesized complexes are stable powders, insoluble in common organic solvents such as ethanol, benzene, carbon tetrachloride, chloroform, and diethyl ether, and are nonelectrolytes. The magnetic and spectroscopic data indicate a distorted square planar geometry for all complexes. The superoxide dismutase activity of these complexes has been measured and discussed. Antibacterial and antifungal properties of these complexes were also tested.

  14. Reversible DNA condensation induced by a tetranuclear nickel(II) complex.

    Science.gov (United States)

    Dong, Xindian; Wang, Xiaoyong; He, Yafeng; Yu, Zhen; Lin, Miaoxin; Zhang, Changli; Wang, Jing; Song, Yajie; Zhang, Yangmiao; Liu, Zhipeng; Li, Yizhi; Guo, Zijian

    2010-12-17

    DNA condensing agents play a critical role in gene therapy. A tetranuclear nickel(II) complex, [Ni(II)(4)(L-2H)(H(2)O)(6)(CH(3)CH(2)OH)(2)]·6NO(3) (L=3,3',5,5'-tetrakis{[(2-hydroxyethyl)(pyridin-2-ylmethyl)amino]methyl}biphenyl-4,4'-diol), has been synthesized as a nonviral vector to induce DNA condensation. X-ray crystallographic data indicate that the complex crystallizes in the monoclinic system with space group P2(1)/n, a=10.291(9), b=24.15(2), c=13.896(11) Å, and β=98.175(13)°. The DNA condensation induced by the complex has been investigated by means of UV/Vis spectroscopy, fluorescence spectroscopy, circular dichroism spectroscopy, dynamic light scattering, atomic force microscopy, gel electrophoresis assay, and zeta potential analysis. The complex interacts strongly with DNA through electrostatic attraction and induces its condensation into globular nanoparticles at low concentration. The release of DNA from its compact state has been achieved using the chelator ethylenediaminetetraacetic acid (EDTA) for the first time. Other essential properties, such as DNA cleavage inactivity and biocompatibility, have also been examined in vitro. In general, the complex satisfies the requirements of a gene vector in all of these respects.

  15. The Developmental Toxicity of Complex Silica-Embedded Nickel Nanoparticles Is Determined by Their Physicochemical Properties.

    Science.gov (United States)

    Mahoney, Sharlee; Najera, Michelle; Bai, Qing; Burton, Edward A; Veser, Götz

    2016-01-01

    Complex engineered nanomaterials (CENs) are a rapidly developing class of structurally and compositionally complex materials that are expected to dominate the next generation of functional nanomaterials. The development of methods enabling rapid assessment of the toxicity risk associated with this type of nanomaterial is therefore critically important. We evaluated the toxicity of three differently structured nickel-silica nanomaterials as prototypical CENs: simple, surface-deposited Ni-SiO2 and hollow and non-hollow core-shell Ni@SiO2 materials (i.e., ~1-2 nm Ni nanoparticles embedded into porous silica shells with and without a central cavity, respectively). Zebrafish embryos were exposed to these CENs, and morphological (survival and malformations) and physiological (larval motility) endpoints were coupled with thorough characterization of physiochemical characteristics (including agglomeration, settling and nickel ion dissolution) to determine how toxicity differed between these CENs and equivalent quantities of Ni2+ salt (based on total Ni). Exposure to Ni2+ ions strongly compromised zebrafish larva viability, and surviving larvae showed severe malformations. In contrast, exposure to the equivalent amount of Ni CEN did not result in these abnormalities. Interestingly, exposure to Ni-SiO2 and hollow Ni@SiO2 provoked abnormalities of zebrafish larval motor function, indicating developmental toxicity, while non-hollow Ni@SiO2 showed no toxicity. Correlating these observations with physicochemical characterization of the CENs suggests that the toxicity of the Ni-SiO2 and hollow Ni@SiO2 material may result partly from an increased effective exposure at the bottom of the well due to rapid settling. Overall, our data suggest that embedding nickel NPs in a porous silica matrix may be a straightforward way to mitigate their toxicity without compromising their functional properties. At the same time, our results also indicate that it is critical to consider modification

  16. Highly efficient photocatalytic hydrogen evolution from nickel quinolinethiolate complexes under visible light irradiation

    Science.gov (United States)

    Rao, Heng; Yu, Wen-Qian; Zheng, Hui-Qin; Bonin, Julien; Fan, Yao-Ting; Hou, Hong-Wei

    2016-08-01

    Earth-abundant metal complexes have emerged as promising surrogates of platinum for catalyzing the hydrogen evolution reaction (HER). In this study, we report the design and synthesis of two novel nickel quinolinethiolate complexes, namely [Ni(Hqt)2(4, 4‧-Z-2, 2‧-bpy)] (Hqt = 8-quinolinethiol, Z = sbnd H [1] or sbnd CH3 [2], bpy = bipyridine). An efficient three-component photocatalytic homogeneous system for hydrogen generation working under visible light irradiation was constructed by using the target complexes as catalysts, triethylamine (TEA) as sacrificial electron donor and xanthene dyes as photosensitizer. We obtain turnover numbers (TON, vs. catalyst) for H2 evolution of 5923/7634 under the optimal conditions with 5.0 × 10-6 M complex 1/2 respectively, 1.0 × 10-3 M fluorescein and 5% (v/v) TEA at pH 12.3 in EtOH/H2O (1:1, v/v) mixture after 8 h irradiation (λ > 420 nm). We discuss the mechanism of H2 evolution in the homogeneous photocatalytic system based on fluorescence spectrum and cyclic voltammetry data.

  17. Electronic Transitions as a Probe of Tetrahedral versus Octahedral Coordination in Nickel(II) Complexes: An Undergraduate Inorganic Chemistry Experiment.

    Science.gov (United States)

    Filgueiras, Carlos A. L.; Carazza, Fernando

    1980-01-01

    Discusses procedures, theoretical considerations, and results of an experiment involving the preparation of a tetrahedral nickel(II) complex and its transformation into an octahedral species. Suggests that fundamental aspects of coordination chemistry can be demonstrated by simple experiments performed in introductory level courses. (Author/JN)

  18. Geometric and Electronic Structure and Reactivity of a Mononuclear “Side-On” Nickel(III)-Peroxo Complex

    Science.gov (United States)

    Cho, Jaeheung; Sarangi, Ritimukta; Annaraj, Jamespandi; Kim, Sung Yeon; Kubo, Minoru; Ogura, Takashi; Solomon, Edward I.; Nam, Wonwoo

    2010-01-01

    Metal-O2 adducts, such as metal-superoxo and -peroxo species, are key intermediates often detected in the catalytic cycles of dioxygen activation by metalloenzymes and biomimetic compounds. The synthesis and spectroscopic characterization of an end-on nickel(II)-superoxo complex with a 14-membered macrocyclic ligand was reported previously. Here we report the isolation, spectroscopic characterization, and high-resolution crystal structure of a mononuclear side-on nickel(III)-peroxo complex with a 12-membered macrocyclic ligand, [Ni(12-TMC)(O2)]+ (1) (12-TMC = 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane). Different from the end-on Ni(II)-superoxo complex, the Ni(III)-peroxo complex is not reactive in electrophilic reactions, but is capable of conducting nucleophilic reactions. The Ni(III)-peroxo complex transfers the bound dioxygen to manganese(II) complexes, thus affording the corresponding nickel(II) and manganese(III)-peroxo complexes. The present results demonstrate the significance of supporting ligands in tuning the geometric and electronic structures and reactivities of metal-O2 intermediates that have been shown to have biological as well as synthetic usefulness in biomimetic reactions. PMID:20711413

  19. Homo- and Heteroligand Nickel(II Complexes with Benzoic and para-Methoxybenzoic Acid Hydrazides and L-Histidine

    Directory of Open Access Journals (Sweden)

    N.V. Troshanin

    2017-03-01

    Full Text Available Complex formation of nickel(II with benzoic, para-methoxybenzoic acid hydrazides, and L-histidine have been studied by the methods of pH-metric titrimetry, spectrophotometry, and mathematical modelling in aqueous solutions with 1.0 mol dm–3 KNO3 as background at 298 K. Dissociation constants of ligands, as well as composition, formation constants, and spectral parameters of homo- and heteroligand complexes have been determined. It has been shown that stability of the complexes formed with para-methoxybenzoic acid hydrazide is higher than with benzoic acid hydrazide, which is consistent with the electron-donor properties of the methoxy group. Extra stabilization of the nickel(II heteroligand complexes with benzoic (para-methoxybenzoic acid hydrazide and L-histidine has been discovered and interpreted.

  20. Nickel(II) and palladium(II) triphenylphosphine complexes incorporating tridentate Schiff base ligands: Synthesis, characterization and biocidal activities

    Science.gov (United States)

    Shabbir, Muhammad; Akhter, Zareen; Ashraf, Ahmad Raza; Ismail, Hammad; Habib, Anum; Mirza, Bushra

    2017-12-01

    Nickel(II) and palladium(II) triphenylphosphine complexes incorporating tridentate Schiff bases have been prepared and characterized by elemental analysis as well as by spectroscopic techniques (FTIR & NMR). The synthesized compounds were assessed to check their potential biocidal activity by using different biological assays (brine shrimp cytotoxicity, antimicrobial, antioxidant, antitumor and drug-DNA interaction). Results of brine shrimp cytotoxicity assay showed that ligand molecules are more bioactive than metal complexes with LD50 as low as 12.4 μg/mL. The prominent antitumor activity was shown by nickel complexes while the palladium complexes exhibited moderate activity. The synthesized compounds have shown high propensity for DNA binding either through intercalation or groove binding which represents the mechanism of antitumor effect of these compounds. Additionally, ligand molecules and nickel metal complexes showed significant antioxidant activity with IC50 values as low as 3.1 μg/mL and 18.9 μg/mL respectively while palladium complexes exhibited moderate activity. Moreover, in antimicrobial assays H2L1, Ni(L1)PPh3 and H2L3 showed dual inhibition against bacterial and fungal strains while for the rest of the compounds varying degree of activity was recorded against different strains. Overall comparison of results suggests that the synthesized compounds can be promising candidate for drug formulation and development.

  1. Synthesis of copper/nickel nanoparticles using newly synthesized Schiff-base metals complexes and their cytotoxicity/catalytic activities.

    Science.gov (United States)

    Aazam, Elham S; El-Said, Waleed Ahmed

    2014-12-01

    Transition metal complexes compounds with Schiff bases ligand representing an important class of compounds that could be used to develop new metal-based anticancer agents and as precursors of metal NPs. Herein, 2,3-bis-[(3-ethoxy-2-hydroxybenzylidene)amino]but-2-enedinitrile Schiff base ligand and its corresponding copper/nickel complexes were synthesized. Also, we reported a facile and rapid method for synthesis nickel/copper nanoparticles based on thermal reduction of their complexes. Free ligand, its metal complexes and metals nanoparticles have been characterized based on elemental analysis, transmission electron microscopy, powder X-ray diffraction, magnetic measurements and by various spectroscopic (UV-vis, FT-IR, (1)H NMR, GC-MS) techniques. Additionally, the in vitro cytotoxic activity of free ligand and its complexes compounds were assessed against two cancer cell lines (HeLa and MCF-7 cells)and one healthy cell line (HEK293 cell). The copper complex was found to be active against these cancer cell lines at very low LD50 than the free ligand, while nickel complex did not show any anticancer activity against these cell lines. Also, the antibacterial activity of as-prepared copper nanoparticles were screened against Escherichia coli, which demonstrated minimum inhibitory concentration and minimum bactericidal concentration values lower than those values of the commercial Cu NPs as well as the previous reported values. Moreover, the synthesized nickel nanoparticles demonstrated remarkable catalytic performance toward hydrogenation of nitrobenzene that producing clean aniline with high selectivity (98%). This reactivity could be attributed to the high degree of dispersion of Ni nanoparticles. Copyright © 2014 Elsevier Inc. All rights reserved.

  2. Electrocatalytic Oxidation of Formate with Nickel Diphosphane Dipeptide Complexes. Effect of Ligands Modified with Amino Acids

    Energy Technology Data Exchange (ETDEWEB)

    Galan, Brandon R. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Reback, Matthew L. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Jain, Avijita [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Appel, Aaron M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Shaw, Wendy J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2013-09-03

    A series of nickel bis-diphosphine complexes with dipeptides appended to the ligands were investigated for the catalytic oxidation of formate. Typical rates of ~7 s-1 were found, similar to the parent complex (~8 s-1), with amino acid size and positioning contributing very little to rate or operating potential. Hydroxyl functionalities did result in lower rates, which were recovered by protecting the hydroxyl group. The results suggest that the overall dielectric introduced by the dipeptides does not play an important role in catalysis, but free hydroxyl groups do influence activity suggesting contributions from intra- or intermolecular interactions. These observations are important in developing a fundamental understanding of the affect that an enzyme-like outer coordination sphere can have upon molecular catalysts. This work was funded by the US DOE Basic Energy Sciences, Chemical Sciences, Geoscience and Biosciences Division (BRG, AJ, AMA, WJS), the US DOE Basic Energy Sciences, Physical Bioscience program (MLR). Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  3. Mechanically-induced solvent-less synthesis of cobalt and nickel complexes of cimetidine

    Directory of Open Access Journals (Sweden)

    Adedibu Clement Tella

    2011-09-01

    Full Text Available Solvent-less synthesis of [Co(CIM2](SO4 and [Ni(CIM2](OAC2 by grinding of CoSO4 and Ni(CH3COO2.4H2O with cimetidine without any solvent is described. The complexes have been characterized by elemental analysis, melting point, AAS, conductivity measurements, TLC, infrared and UV-Vis spectroscopies as well as X-ray powder diffraction. Cimetidine was found to be bidentate or tridentate ligand. Cobalt ion coordinate with cimetidine through the sulphur atom in the thiol group, nitrogen atom of imidazole ring and the nitrogen atom of the secondary amine to give an octahedral geometry with ligand acting as tridentate whereas nickel ion coordinates through the sulphur atom in the thiol group, nitrogen atom of imidazole ring to give tetrahedral structure with ligand acting as bidentate. X-Ray diffraction patterns of the complex were different from that of the ligand suggesting formation of coordination compounds. The method is quick and gives a quantatively yield, without the need for solvents or external heating. Clearly, it can present higher efficiency in terms of materials, energy and time compared to classical solution phase synthesis.

  4. A Biomimetic Nickel Complex with a Reduced CO2 Ligand Generated by Formate Deprotonation and its Behaviour towards CO2.

    Science.gov (United States)

    Limberg, Christian; Zimmermann, Philipp; Hoof, Santina; Braun-Cula, Beatrice; Herwig, Christian

    2018-04-10

    Reduced CO2 species are key intermediates in a variety of natural and synthetic processes. In the majority of systems, however, they elude isolation or characterisation due to high reactivity or limited accessibility (heterogeneous systems) and thus formulations often remain uncertain or based on calculations only. We herein report on a Ni-CO22- complex that is unique in many ways. While its structural and electronic features help understanding the CO2 bound state in Ni,Fe carbon monoxide dehydrogenases, its reactivity sheds light on how CO2 can be converted into CO/CO32- by nickel complexes. In addition, the complex has been generated via a rare example of formate β deprotonation, a mechanistical step relevant to nickel catalysed conversion of HxCOyz- at electrodes and formate oxidation in formate dehydrogenases. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Iminobisphosphines to (non-)symmetrical diphosphinoamine ligands : Metal-induced synthesis of diphosphorus nickel complexes and application in ethylene oligomerisation reactions

    NARCIS (Netherlands)

    Boulens, Pierre; Lutz, Martin|info:eu-repo/dai/nl/304828971; Jeanneau, Erwann; Olivier-Bourbigou, Hélène; Reek, Joost N H; Breuil, Pierre Alain R

    2014-01-01

    We describe the synthesis of a range of novel iminobisphosphine ligands based on a sulfonamido moiety [R1SO2N=P(R 2)2-P(R3)2]. These molecules rearrange in the presence of nickel by metal-induced breakage of the P-P bond to yield symmetrical and nonsymmetrical diphosphinoamine nickel complexes of

  6. Nickel(II) complexes having Imidazol-2-ylidene-N′-phenylurea ...

    Indian Academy of Sciences (India)

    Nickel(II); imidazol-2-ylidene-N′-phenylurea; hexa-coordination; chelating ligands; hydrogen bonding .... ized by combustion analysis as well as FT-IR technique. .... arrangement of the aniline coordination with respect to the acetylacetonate ligand towards nickel ion. Hydrogen bonding (2.625 Å) was observed between the ...

  7. Nickel(II-oxaloyldihydrazone complexes: Characterization, indirect band gap energy and antimicrobial evaluation

    Directory of Open Access Journals (Sweden)

    Ayman H. Ahmed

    2016-12-01

    Full Text Available A series of oxaloyldihydrazone ligands was prepared essentially by the usual condensation reaction between oxaloyldihydrazide and different aldehydes e.g. salicylaldehyde, 2-hydroxy-1-naphthaldehyde, 2-hydroxyacetophenone and 2-methoxy-benzaldehyde in 1:2 M ratio. The formed compounds were purified to give bis(salicylaldehydeoxaloyldihydrazone (L1, bis(2-hydroxy-1-naphthaldehydeoxaloyldihydrazone (L2, bis(2-hydroxyacetophenoneoxaloyldihydrazone(L3 and bis(2-methoxy-benzaldehydeoxaloyldihydrazone (L4. All the oxaloyldihydrazones (L1–L4 and their relevant solid nickel(II complexes have been prepared and structurally characterized on the basis of the elemental analyses, spectral (UV–vis, IR, mass and 1H NMR, magnetism and thermal (TG measurements. The dihydrazones coordinate to the metal center forming mononuclear complexes with L1, L3 and L4 in addition to binuclear complex with L2. The metal center prefers tetrahedral stereochemistry upon chelation. The optical indirect band gap energy for all compounds underlies the range of semiconductor materials. The prepared ligands and their metal complexes have been assayed for their antimicrobial activity against fungi as well as Gram-positive and Gram-negative bacteria. The resulting data indicate the ability of the investigated compounds to inhibit the growth of some micro-organisms, where L2 showed the highest activity among all the compounds. Minimum inhibitory concentration (MIC of L2 against the growth of five micro-organisms was determined which gives better response against Aspergillus fumigatus and Bacillis subtilis compared with some selected standard drugs.

  8. Decarbonylative Cross-Couplings: Nickel Catalyzed Functional Group Interconversion Strategies for the Construction of Complex Organic Molecules

    KAUST Repository

    Guo, Lin

    2018-04-13

    -mediated decarbonylation process of esters and proposed a reaction mechanism involving a C(acyl)-O bond cleavage and a CO extrusion. Key nickel intermediates were isolated and characterized by Shi and co-workers, supporting the assumption of a nickel/ N-heterocyclic carbene-promoted C(acyl)-O bond activation and functionalization. Our combined experimental and computational study of a ligand-controlled chemoselective nickel-catalyzed cross-coupling of aromatic esters with alkylboron reagents provided further insight into the reaction mechanism. We demonstrated that nickel complexes with bidentate ligands favor the C(aryl)-C bond cleavage in the oxidative addition step, resulting in decarbonylative alkylations, while nickel complexes with monodentate phosphorus ligands promote the activation of the C(acyl)-O bond, leading to the production of ketone products. Although more detailed mechanistic investigations need to be undertaken, the successful development of decarbonylative cross-coupling reactions can serve as a solid foundation for future studies. We believe that this type of decarbonylative cross-coupling reactions will be of significant value, in particularly in combination with the retrosynthetic analysis and synthesis of natural products and biologically active molecules. Thus, the presented ester substitution methods will pave the way for successful applications in the construction of complex frameworks by late-stage modification and functionalization of carboxylic acid derivatives.

  9. Nickel Dermatitis - Nickel Excretion

    DEFF Research Database (Denmark)

    Menné, T.; Thorboe, A.

    1976-01-01

    Nickel excretion in urine in four females -sensitive to nickel with an intermittent dyshidrotic eruption was measured with flameless atomic absorption. Excretion of nickel was found to be increased in association with outbreaks of vesicles. The results support the idea that the chronic condition...... was maintained by ingestion of nickel in food....

  10. Surface complexation modelling: Experiments on the sorption of nickel on quartz

    International Nuclear Information System (INIS)

    Puukko, E.; Hakanen, M.

    1995-10-01

    Assessing the safety of a final repository for nuclear wastes requires knowledge concerning the way in which the radionuclides released are retarded in the geosphere. The aim of the work is to aquire knowledge of empirical methods repeating the experiments on the sorption of nickel on quartz described in the reports published by the British Geological Survey (BGS). The experimental results were modelled with computer models at the Technical Research Centre of Finland (VTT Chemical Technology). The results showed that the experimental knowledge of the sorption of Ni on quartz have been acheved by repeating the experiments of BGS. Experiments made with the two quartz types, Min-U-Sil 5 (MUS) and Nilsiae, showed the difference in sorption of Ni in the low ionic strength solution (0.001 M NaNO 3 ). The sorption of Ni on MUS was higher than predicted by the Surface Complexation Model (SCM). The phenomenon was also observed by the BGS, and may be due to the different amounts of inpurities in the MUS and in the NLS. In other respects, the results of the sorption experiments fitted quite well with those predicted by the SCM model. (8 refs., 8 figs., 11 tabs.)

  11. Hydrogen Atom Transfer by a High-Valent Nickel-Chloride Complex.

    Science.gov (United States)

    Mondal, Prasenjit; Pirovano, Paolo; Das, Ankita; Farquhar, Erik R; McDonald, Aidan R

    2018-02-07

    Oxo-metal-halide moieties have often been implicated as C-H bond activating oxidants with the terminal oxo-metal entity identified as the electrophilic oxidant. The electrophilic reactivity of metal-halide species has not been investigated. We have prepared a high-valent nickel-halide complex [Ni III (Cl)(L)] (2, L = N,N'-(2,6-dimethylphenyl)-2,6-pyridinedicarboxamide) by one-electron oxidation of a [Ni II (Cl)(L)] - precursor. 2 was characterized using electronic absorption, electron paramagnetic resonance, and X-ray absorption spectroscopies and mass spectrometry. 2 reacted readily with substrates containing either phenolic O-H or hydrocarbon C-H bonds. Analysis of the Hammett, Evans-Polanyi, and Marcus relationships between the determined rate constants and substrate pK a , X-H bond dissociation energy, and oxidation potential, respectively, was performed. Through this analysis, we found that 2 reacted by a hydrogen atom transfer (HAT) mechanism. Our findings shine light on enzymatic high-valent oxo-metal-halide oxidants and open new avenues for oxidative halogenation catalyst design.

  12. Nickel Allergy

    Science.gov (United States)

    ... nickel may, in part, be inherited. Sources of nickel exposure Common items that may expose you to nickel ... items. The following tips may help you avoid nickel exposure: Wear hypoallergenic jewelry Avoid jewelry that contains nickel. ...

  13. Coordination functionalization of graphene oxide with tetraazamacrocyclic complexes of nickel(II): Generation of paramagnetic centers

    International Nuclear Information System (INIS)

    Basiuk, Vladimir A.; Alzate-Carvajal, Natalia; Henao-Holguín, Laura V.; Rybak-Akimova, Elena V.; Basiuk, Elena V.

    2016-01-01

    Highlights: • [Ni(cyclam)] 2+ and [Ni(tet b)] 2+ cations coordinate to carboxylic groups of GO. • The coordination takes place under basic conditions in aqueous-based medium. • The coordination results in the conversion from low-spin to high-spin Ni(II). • Functionalized GO samples were characterized by various instrumental techniques. - Abstract: 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

  14. Synthesis, characterization, single crystal X-ray determination, fluorescence and electrochemical studies of new dinuclear nickel(II) and oxovanadium(IV) complexes containing double Schiff base ligands.

    Science.gov (United States)

    Shafaatian, Bita; Ozbakzaei, Zahra; Notash, Behrouz; Rezvani, S Ahmad

    2015-04-05

    A series of new bimetallic complexes of nickel(II) and vanadium(IV) have been synthesized by the reaction of the new double bidentate Schiff base ligands with nickel acetate and vanadyl acetylacetonate in 1:1 M ratio. In nickel and also vanadyl complexes the ligands were coordinated to the metals via the imine N and enolic O atoms. The complexes have been found to possess 1:1 metals to ligands stoichiometry and the molar conductance data revealed that the metal complexes were non-electrolytes. The nickel and vanadyl complexes exhibited distorted square planar and square pyramidal coordination geometries, respectively. The emission spectra of the ligands and their complexes were studied in methanol. Electrochemical properties of the ligands and their metal complexes were also investigated in DMSO solvent at 150 mV s(-1) scan rate. The ligands and metal complexes showed both quasi-reversible and irreversible processes at this scan rate. The Schiff bases and their complexes have been characterized by FT-IR, 1H NMR, UV/Vis spectroscopies, elemental analysis and conductometry. The crystal structure of the nickel complex has been determined by single crystal X-ray diffraction. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Synthesis and X-ray diffraction study of some nickel(II) complexes of urea and thiourea

    International Nuclear Information System (INIS)

    Sharma, Pradeep; Bhale, Jaishree; Mishra, Ashutosh; Malviya, Pramod

    2014-01-01

    XRD of four biologically important nickel(II) complexes having urea and thiourea as primary ligands and sulphate and nitrate as secondary ligands have been studied using Bruker D8 Advance diffractometer at IUC, Indore. The synthesized metal complexes were characterized by XRD measurements in order to elucidate their geometry. The data obtained has been preceded using XRD data analysis program Origin 6.0 Professional. From the experimental measurements, various parameters, e.g., particle size, lattice parameter have been estimated.Particle size for Ni-urea complexes is found in the range of 4.23-9.01 nm while for Ni-thiourea complexes its range is 0.26-9.76 nm.Lattice parameter for all these complexes is found in the range of 7.47-8.06 Å. The XRD analysis revealed the crystalline nature of all the complexes.

  16. Iron and nickel complexes with heterocyclic ligands: stability, synthesis, spectral characterization, antimicrobial activity, acute and subacute toxicity.

    Science.gov (United States)

    Bouchoucha, Afaf; Terbouche, Achour; Zaouani, Mohamed; Derridj, Fazia; Djebbar, Safia

    2013-07-01

    The synthesis and characterization by elemental analysis, emission atomic spectroscopy, TG measurements, magnetic measurements, FTIR, (1)H NMR, UV-visible spectra and conductivity of a series of iron (II) and nickel (II) complexes with two heterocyclic ligands (L(1)(SMX): sulfamethoxazole and L(2)(MIZ): metronidazole) used in pharmaceutical field and with a new ligand derived benzoxazole (L(3)(MPBO): 2-(5-methylpyridine-2-yl)benzoxazole), were reported. The formulae obtained for the complexes are: [M(L(1))2 Cl2]·nH2O, [M(L(2))2Cl2(H2O)2]·H2O and [M(L(3))2(OH)2]·nH2O. Stability constants of these complexes have been determined by potentiometric methods in water-ethanol (90:10, v/v) mixture at a 0.2 mol L(-1) ionic strength (NaCl) and at 25.0±0.1 °C. Sirko program was used to determine the protonation constants as well as the binding constants of three species [ML2H2](2+), [ML2] and [ML](2+). The antimicrobial activity of the ligands and complexes was evaluated in vitro against different human bacteria and fungi using agar diffusion method. Iron sulfamethoxazole complex showed a remarkable inhibition of bacteria growth especially on Staphylococcus aureus and P. aeruginosa. The iron metronidazole complex is active against yeasts especially on Candida tropicalis strain. Nickel complexes presented different antibacterial and antifungal behavior's against bacteria and fungal. The acute toxicity study revealed that the iron complexes are not toxic at 2000 mg/kg dose orally administrated. LD50 for nickel complexes was determined using graphical method. No significant differences in the body weights between the control and the treated groups of both rat sexes in subacute toxicity study using for iron complexes. Hematological and clinical blood chemistry analysis revealed no toxicity effects of the iron complexes. Pathologically, neither gross abnormalities nor histopathological changes were observed for these complexes. Copyright © 2013 Elsevier GmbH. All rights

  17. Synthesis, characterization, nano-sized binuclear nickel complexes, DFT calculations and antibacterial evaluation of new macrocyclic Schiff base compounds

    Science.gov (United States)

    Parsaee, Zohreh; Mohammadi, Khosro

    2017-06-01

    Some new macrocyclic bridged dianilines tetradentate with N4coordination sphere Schiff base ligands and their nickel(II)complexes with general formula [{Ni2LCl4} where L = (C20H14N2X)2, X = SO2, O, CH2] have been synthesized. The compounds have been characterized by FT-IR, 1H and 13C NMR, mass spectroscopy, TGA, elemental analysis, molar conductivity and magnetic moment techniques. Scanning electron microscopy (SEM) shows nano-sized structures under 100 nm for nickel (II) complexes. NiO nanoparticle was achieved via the thermal decomposition method and analyzed by FT-IR, SEM and X-ray powder diffraction which indicates closeaccordance to standard pattern of NiO nanoparticle. All the Schiff bases and their complexes have been detected in vitro both for antibacterial activity against two gram-negative and two gram-positive bacteria. The nickel(II) complexes were found to be more active than the free macrocycle Schiff bases. In addition, computational studies of three ligands have been carried out at the DFT-B3LYP/6-31G+(d,p) level of theory on the spectroscopic properties, including IR, 1HNMR and 13CNMR spectroscopy. The correlation between the theoretical and the experimental vibrational frequencies, 1H NMR and 13C NMR of the ligands were 0.999, 0.930-0.973 and 0.917-0.995, respectively. Also, the energy gap was determined and by using HOMO and LUMO energy values, chemical hardness-softness, electronegativity and electrophilic index were calculated.

  18. Copper(II), cobalt(II) and nickel(II) complexes of lapachol: synthesis, DNA interaction, and cytotoxicity.

    Science.gov (United States)

    Tabrizi, Leila; Talaie, Faranak; Chiniforoshan, Hossein

    2017-11-01

    Three novel copper(II), cobalt(II), and nickel(II) complexes of lapachol (Lap) containing 110-phenanthroline (phen) ligand, [M(Lap) 2 (phen)] (M=Cu(II), 1, Co(II), 2, and Ni(II), 3), have been synthesized and characterized using, elemental analysis and spectroscopic studies. Their interactions with calf thymus DNA (CT DNA) were investigated using viscosity, thermal denaturation, circular dichorism, fluorescence quenching, and electronic absorption spectroscopy. The DNA cleavage abilities of 1-3 have been studied, where cleavage activity of copper complex 1 is more than the complexes 2 and 3. The in vitro cytotoxic potential of the complexes 1-3 against human cervical carcinoma (HeLa), human liver hepatocellular carcinoma (HepG-2), and human colorectal adenocarcinoma (HT-29) cells indicated their promising antitumor activity with quite low IC 50 values in the range of .15-2.41 μM, which are lower than those of cisplatin.

  19. Nickel(II Complexes of Hydrazone of Isoniazid and Their Magneto-Spectral, Electrochemical, Thermal and Antimicrobial Investigations

    Directory of Open Access Journals (Sweden)

    Surendra Prasad

    2008-01-01

    Full Text Available The synthesis of novel nickel(II complexes with new ligand derived from hydrazone of isoniazid has been reported. The complexes have general compositions [Ni(L2X2] or [Ni(L3](ClO42, where L = N-isonicotinamido-furfuraldimine (INH-FFL and X=Cl− or NCS−. The ligand hydrazone behaves as neutral bidentate (N and O donor through the carbonyl oxygen and azomethine nitrogen. On the basis of elemental analysis, molecular weight determinations, magnetic susceptibility/moment, thermogravimetric, electrochemical, and spectroscopic studies, the new complexes have been characterized with octahedral geometry. The antibacterial and antifungal studies of the present complexes show that they are moderate antibacterial and antifungal agents.

  20. Correlated coordination and redox activity of a hemilabile noninnocent ligand in nickel complexes

    Czech Academy of Sciences Publication Activity Database

    Paretzki, A.; Bubrin, M.; Fiedler, Jan; Záliš, Stanislav; Kaim, W.

    2014-01-01

    Roč. 20, č. 18 (2014), s. 5414-5422 ISSN 0947-6539 R&D Projects: GA MŠk LD11086 Institutional support: RVO:61388955 Keywords : coordination change * hemilabile ligands * nickel Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.731, year: 2014

  1. Syntheses, structures and characterizations of three novel vanadium selenites with organically bonded copper/nickel complex

    International Nuclear Information System (INIS)

    Qian, Cheng; Kong, Fang; Mao, Jiang-Gao

    2016-01-01

    A series of vanadium selenites covalently bonded with metal-organic complex, namely, Ni(2,2-bipy) 2 V 2 O 4 (SeO 3 ) 2 (1), Cu(2,2-bipy)V 2 O 4 (SeO 3 ) 2 ·0.5H 2 O (2) and Cu 2 (2,2-bipy) 2 V 5 O 12 (SeO 3 ) 2 (3) (2,2-bipy=2,2-bipyridine) have been hydrothermally synthesized and structurally characterized. They exhibit three different structural dimensions, from 0D cluster, 1D chain to 2D layer. Compound 1 features a 0D {Ni(2,2-bipy) 2 V 2 O 4 (SeO 3 ) 2 } 2 dimeric cluster composed of two {Ni(2,2-bipy) 2 } 2+ moieties connected by the {V 4 O 8 (SeO 3 ) 4 } 4- cluster. Compound 2 shows a 1D {Cu(2,2-bipy)V 2 O 4 (SeO 3 ) 2 } n chain in which the {Cu 2 (2,2-bipy) 2 } 4+ moieties are bridged by the {V 4 O 8 (SeO 3 ) 4 } 4− clusters. Compound 3 displays a 2D structure consisted of mixed valence vanadium selenites layers {V IV V V 4 Se IV 2 O 18 } n 4− and {Cu(2,2-bipy)} 2+ complex moieties. The adjacent layers are further interconnected via π-π interactions between the 2,2-bipy ligands exhibiting an interesting 3D supramolecular architecture. Both compound 1 and 2 contain a new {V 4 O 8 (SeO 3 ) 4 } 4− cluster and compound 3 exhibits the first 2D vanadate polyhedral layer in vanadium selenites/tellurites with organic moieties. - Graphical abstract: We got three new vanadium selenites with organically linked copper/nickel complex, namely, Ni(2,2-bipy) 2 V 2 O 4 (SeO 3 ) 2 (1), Cu(2,2-bipy)V 2 O 4 (SeO 3 ) 2 ·0.5H 2 O (2) and Cu 2 (2,2-bipy) 2 V 5 O 12 (SeO 3 ) 2 (3) by hydrothermally syntheses. They display three different structural dimensions, from 0D cluster, to 1D chain and 2D layer. Display Omitted - Highlights: • Three new compounds display three different structural dimensions, from 0D cluster, to 1D chain and 2D layer. • The Tetranuclear {V 4 O 8 (SeO 3 ) 4 } 4− cluster and the vanadate {V 5 O 17 } n 2D layer are observed firstly. • Optical Properties and Magnetic Properties of three compounds are reported.

  2. Polynuclear and mixed-ligand complexes of copper(II) and nickel(II) with (1-hydroxyethylidene)bisphosphonic acid

    Energy Technology Data Exchange (ETDEWEB)

    Amirov, R.R.; Saprykova, Z.A.

    1987-12-20

    The compositions and stabilities of heteronuclear and mixed-ligand copper(II) and nickel(II) (1-hydroxyethylidene)bisphosphonates were determined. Parameters of the compatibility of the ligands and central ions in the complexes were calculated. It was shown that the monoprotonated anion of (1-hydroxyethylidene)bisphosphonic acid is capable of terdentate coordination with the participation of the alcoholic hydroxy group. The acidities of the solutions were determined on a pH-673 meter. The spin-lattice relaxation time was measured on a pulse NMR spectrometer.

  3. Outer-Sphere Reactivity Shift of Secondary Phosphine Oxide-Based Nickel Complexes: From Ethylene Hydrophosphinylation to Oligomerization.

    Science.gov (United States)

    Lhermet, Rudy; Moser, Emile; Jeanneau, Erwann; Olivier-Bourbigou, Hélène; Breuil, Pierre-Alain R

    2017-06-01

    A new dimension for secondary phosphine oxide (SPOs) ligands is described in this article. Demonstrated on original π-allylic nickel structures, these self-assembled complexes trigger catalytic hydrophosphinylation reactions. Addition of a Lewis acid B(C 6 F 5 ) 3 switches the reactivity towards migratory insertion and thus ethylene oligomerization through an unprecedented outer-sphere interaction with the coordinated SPO ligand. NMR experiments and X-ray analyses allowed for the observation of the formation of zwitterionic active species as well as their degradation pathway. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Well-defined mono(η3-allyl)nickel complex MONi(η3-C3H5) (M = Si or Al) grafted onto silica or alumina: A molecularly dispersed nickel precursor for syntheses of supported small size nickel nanoparticles

    KAUST Repository

    Li, Lidong

    2014-01-01

    Preparing evenly-dispersed small size nickel nanoparticles over inert oxides remains a challenge today. In this context, a versatile method to prepare supported small size nickel nanoparticles (ca. 1-3 nm) with narrow size distribution via a surface organometallic chemistry (SOMC) route is described. The grafted mono(η3-allyl)nickel complexes MONi(η 3-C3H5) (M = Si or Al) as precursors are synthesized and fully characterized by elemental analysis, FTIR spectroscopy and paramagnetic solid-state NMR. © 2014 the Partner Organisations.

  5. Structure dependent hydrophobic and hydrophilic interactions between nickel(II) Schiff base complexes and serum albumins: Spectroscopic and docking studies

    International Nuclear Information System (INIS)

    Koley Seth, Banabithi; Ray, Aurkie; Banerjee, Mousumi; Bhattacharyya, Teerna; Bhattacharyya, Dhananjay; Basu, Samita

    2016-01-01

    A systematic and comparative binding study between serum-albumins (SA) and a series of monomeric nickel(II)-Schiff-base-complexes (NSCs), which might be imperative to investigate the function of SA behind nickel allergy, has been carried out through docking and different spectroscopic techniques. The initial docking studies indicate structure-dependent selective hydrophobic and hydrophilic interactions. The pyridine and phenyl containing NSCs, which are more aromatic, show better π–π staking compared to pyrrole one. Again all the NSCs bind with BSA though amino acid residues of IB domain affecting local environment of the Trp-134 surrounded by both hydrophobic and hydrophilic residues instead of the hydrophobically buried Trp-212. In HSA the hydophobically buried Trp-214 is influenced by NSCs. The experimental results nicely support the docking outcomes. The changes in Gibbs free energy, binding affinity and the nature of hydrophilic/hydrophobic interactions of NSC–SA systems indicate greater accessibility of N_2O_2 donor set complex compared to N_4 one towards SA. Quantum chemical structure optimizations support the better planarity of NSC with N_2O_2 which provides better binding. Therefore the structural variation of N_2O_2 donor set complexes becomes much more useful compared to N_4 one to search out the most compatible NSC towards SAs.

  6. Structure dependent hydrophobic and hydrophilic interactions between nickel(II) Schiff base complexes and serum albumins: Spectroscopic and docking studies

    Energy Technology Data Exchange (ETDEWEB)

    Koley Seth, Banabithi; Ray, Aurkie; Banerjee, Mousumi; Bhattacharyya, Teerna [Chemical Sciences Division, Saha Institute of Nuclear Physics, 1/AF Bidhannagar, Kolkata 700064 (India); Bhattacharyya, Dhananjay [Computational Sciences Division, Saha Institute of Nuclear Physics, 1/AF Bidhannagar, Kolkata 700064 (India); Basu, Samita, E-mail: samita.basu@saha.ac.in [Chemical Sciences Division, Saha Institute of Nuclear Physics, 1/AF Bidhannagar, Kolkata 700064 (India)

    2016-03-15

    A systematic and comparative binding study between serum-albumins (SA) and a series of monomeric nickel(II)-Schiff-base-complexes (NSCs), which might be imperative to investigate the function of SA behind nickel allergy, has been carried out through docking and different spectroscopic techniques. The initial docking studies indicate structure-dependent selective hydrophobic and hydrophilic interactions. The pyridine and phenyl containing NSCs, which are more aromatic, show better π–π staking compared to pyrrole one. Again all the NSCs bind with BSA though amino acid residues of IB domain affecting local environment of the Trp-134 surrounded by both hydrophobic and hydrophilic residues instead of the hydrophobically buried Trp-212. In HSA the hydophobically buried Trp-214 is influenced by NSCs. The experimental results nicely support the docking outcomes. The changes in Gibbs free energy, binding affinity and the nature of hydrophilic/hydrophobic interactions of NSC–SA systems indicate greater accessibility of N{sub 2}O{sub 2} donor set complex compared to N{sub 4} one towards SA. Quantum chemical structure optimizations support the better planarity of NSC with N{sub 2}O{sub 2} which provides better binding. Therefore the structural variation of N{sub 2}O{sub 2} donor set complexes becomes much more useful compared to N{sub 4} one to search out the most compatible NSC towards SAs.

  7. Synthesis, characterization and crystal structures of new Zinc(II) and Nickel(II) complexes containing morpholine moiety and their antibacterial studies

    Czech Academy of Sciences Publication Activity Database

    Goudarziafshar, H.; Rezaeivala, M.; Khosravi, F.; Abbasityula, Y.; Yousefi, S.; Özbek, N.; Eigner, Václav; Dušek, Michal

    2015-01-01

    Roč. 12, č. 1 (2015), 113-119 ISSN 1735-207X Grant - others:AV ČR(CZ) Praemium Academiae Institutional support: RVO:68378271 Keywords : crystal structure * morpholine moiety * antibacterial effects * zinc (ii) complex * nickel(ii) complex Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.300, year: 2015

  8. Neutral coordination polymers based on a metal-mono(dithiolene) complex: synthesis, crystal structure and supramolecular chemistry of [Zn(dmit)(4,4'-bpy)]n, [Zn(dmit)(4,4'-bpe)]n and [Zn(dmit)(bix)]n (4,4'-bpy = 4,4'-bipyridine, 4,4'-bpe = trans-1,2-bis(4-pyridyl)ethene, bix = 1,4-bis(imidazole-1-ylmethyl)-benzene.

    Science.gov (United States)

    Madhu, Vedichi; Das, Samar K

    2011-12-28

    This article describes a unique synthetic route that enables a neutral mono(dithiolene)metal unit, {Zn(dmit)}, to link with three different organic molecules, resulting in the isolation of a new class of neutral coordination polymers. The species {Zn(dmit)} coordinates with 4,4'-bipyridine (4,4'-bpy), trans-1,2-bis(4-pyridyl)ethene (4,4'-bpe) and 1,4-bis(imidazole-1-ylmethyl)-benzene (bix) as linkers giving rise to the formation of coordination polymers [Zn(dmit)(4,4'-bpy)](n) (1), [Zn(dmit)(4,4'-bpe)](n) (2) and [Zn(dmit)(bix)](n) (3) respectively. Compounds 1-3 were characterized by elemental analyses, IR, diffuse reflectance and single crystal X-ray diffraction studies. Compounds 1 and 3 crystallize in the monoclinic space group P2(1)/n, whereby compound 2 crystallizes in triclinic space group P1[combining macron]. In the present study, we chose three linkers 4,4'-bpy, 4,4'-bpe and bix (see , respectively, for their structural drawings), that differ in terms of their molecular dimensions. The crystal structures of compounds 1-3 are described here in terms of their supramolecular diversities that include π-π interactions, not only among aromatic stacking (compounds 1 and 3), but also between an aromatic ring and an ethylenic double bond (compound 2). The electronic absorption spectroscopy of compounds 1-3 support these intermolecular π-π interactions. This journal is © The Royal Society of Chemistry 2011

  9. Ethylene oligomerization studies by nickel(ii) complexes chelated by (amino)pyridine ligands: experimental and density functional theory studies.

    Science.gov (United States)

    Nyamato, George S; Ojwach, Stephen O; Akerman, Matthew P

    2016-02-28

    Reductions of imine compounds 2-methoxy-N-(1-(pyridin-2-yl)ethylidene)ethanamine (L1), 2-methoxy-N-((pyridin-2-yl)methylene)ethanamine (L2), N,N-diethyl-N-((pyridin-2-yl)methylene)ethane-1,2-diamine (L3) and 2-((pyridin-2-yl)methyleneamino)ethanol (L4) using NABH4 produced their corresponding amine analogues N-(2-methoxyethyl)-1-(pyridin-2-yl)ethanamine (L1a), 2-methoxy-N-((pyridin-2-yl)methyl)-ethanamine (L2a), N,N-diethyl-N-((pyridin-2-yl)methyl)ethane-1,2-diamine (L3a) and 2-((pyridin-2-yl)methylamino)ethanol (L4a) in good yields. Reactions of the (amino)pyridine ligands L1a–L4a with [NiBr2(DME)] afforded nickel(II) complexes, [NiBr2(L1a)2] (1), [NiBr2(L2a)2] (2), [NiBr2(L3a)2] (3) and [NiBr2(L4a)2] (4), respectively in quantitative yields. Molecular structures of complexes 2 and 4 confirmed the formation of the bis(chelated)nickel(II) complexes. Activation of complexes 1–4 with either EtAlCl2 or methylaluminoxane (MAO), produced active ethylene oligomerization catalysts to afford mostly ethylene dimers (C4), in addition to trimmers (C6) and tetramers (C8). Density functional theory studies provided valuable insight into the reactivity trends and influence of complex structure on the ethylene oligomerization reactions.

  10. Synthesis, structure and catalytic activities of nickel(II) complexes bearing N4 tetradentate Schiff base ligand

    Science.gov (United States)

    Sarkar, Saikat; Nag, Sanat Kumar; Chattopadhyay, Asoke Prasun; Dey, Kamalendu; Islam, Sk. Manirul; Sarkar, Avijit; Sarkar, Sougata

    2018-05-01

    Two new nickel(II) complexes [Ni(L)Cl2] (1) and [Ni(L)(NCS)2] (2) of a neutral tetradentate mono-condensed Schiff base ligand, 3-(2-(2-aminoethylamino)ethylimino)butan-2-one oxime (L) have been synthesized and characterized using different physicochemical techniques e.g. elemental analyses, spectroscopic (IR, Electronic, NMR) methods, conductivity and molecular measurements. The crystal structure of complex (2) has been determined by using single crystal X-ray diffraction method and it suggests a distorted octahedral geometry around nickel(II) having a NiN6 coordinating atmosphere. The non-coordinated Osbnd H group on the ligand L remain engaged in H-bonding interactions with the S end of the coordinated thiocyanate moiety. These H-bonding interactions lead to Osbnd S separations of 3.132 Å and play prominent role in crystal packing. It is observed that the mononuclear units are glued together with such Osbnd H…S interactions and finally results in an 1D supramolecular sheet-like arrangement. DFT/TDDFT based theoretical calculations were also performed on the ligand and the complexes aiming at the accomplishment of idea regarding their optimized geometry, electronic transitions and the molecular energy levels. Finally the catalytic behavior of the complexes for oxidation of styrene has also been carried out. A variety of reaction conditions like the effect of solvent, effect of temperature and time as well as the effect of ratio of substrate to oxidant were thoroughly studied to judge the catalytic efficiency of the Ni(II) coordination entity.

  11. Etude multi-échelle des mécanismes d'élaboration de revêtements d'alliage zinc-nickel à base d'électrolytes alcalins : germination, complexation et structures cristallines

    OpenAIRE

    Fedi , Baptiste

    2016-01-01

    The present work aims to deepen the understanding of the mechanisms of zinc-nickelelectrodeposition in alkaline baths. Zinc-nickel deposits containing between 12% and 16%nickel known for their anti-corrosion performance. Complexing agents are required toobtain soluble and reactive nickel forms, and to stabilize the electrolytes. A study ofthe complexing mechanisms has improved the understanding of their respective role andbehavior, and their influence on the stability and the morphology and c...

  12. Wear of carbide inserts with complex surface treatment when milling nickel alloy

    Science.gov (United States)

    Fedorov, Sergey; Swe, Min Htet; Kapitanov, Alexey; Egorov, Sergey

    2018-03-01

    One of the effective ways of strengthening hard alloys is the creating structure layers on their surface with the gradient distribution of physical and mechanical properties between the wear-resistant coating and the base material. The article discusses the influence of the near-surface layer which is modified by low-energy high-current electron-beam alloying and the upper anti-friction layer in a multi-component coating on the wear mechanism of the replaceable multifaceted plates in the dry milling of the difficult to machine nickel alloys.

  13. Catalytic ethylene dimerization and oligomerization: recent developments with nickel complexes containing P,N-chelating ligands.

    Science.gov (United States)

    Speiser, Fredy; Braunstein, Pierre; Saussine, Lucien

    2005-10-01

    Catalytic ethylene oligomerization represents a topic of considerable current academic and industrial interest, in particular for the production of linear alpha-olefins in the C4-C10 range, whose demand is growing fast. Identifying and fine-tuning the parameters that influence the activity and selectivity of metal catalysts constitute major challenges at the interface between ligand design, coordination/organometallic chemistry, and homogeneous catalysis. In this Account, we show how comparative studies aiming at modulating the coordinating properties of functional ligands for a metal, such as nickel, which is used in industrial processes, lead to beneficial effects in catalytic ethylene oligomerization.

  14. Synthesis, characterization and thermal studies of nickel (II), copper (II), zinc (II) and cadmium (II) complexes with some mixed ligands

    International Nuclear Information System (INIS)

    Mitra, Samiran; Kundu, Parimal; Singh, Rajkumar Bhubon

    1998-01-01

    Dichloro-(DCA) and trichloroacetate(TCA) -cyclic ligand morpholine (Morph)/thiomorpholine (Tmorph)/methylmorpholine (Mmorph)/dimethyl-piperazine (DMP) complexes of nickel (II), copper (II), zinc (II) and cadmium (II) with the compositions [Ni(tmorph) 2 (DCA) 2 ], [Ni(tmorph) 2 (TCA) 2 ].2H 2 O, [Cu(DMP) 2 (TCA) 2 ],[ML 2 X 2 ].nH 2 O where M=Zn II or Cd II , L=Morph, DMP or tmorph and X=DCA or TCA and n=O except in case of [Cd (Morph) 2 (TCA) 2 ] where n=1 have been synthesised. Some intermediate complexes have been isolated by temperature arrest technique (pyrolysis) and characterised. Configurational and conformational changes have been studied by elemental analyses, IR and electronic spectra, magnetic moment data (in the case of Ni(II) and Cu(II) complexes) and thermal analysis. E a * , ΔH, and ΔS for the decomposition reaction of these complexes are evaluated and the stability of the complexes with respect to activation energy has also been compared. The linear correlation has been found between E a * and ΔS for the decomposition of the complexes. (author)

  15. Probing the Intrinsic Electronic Structure of the Bis(dithiolene) Anions [M(mnt)2]2- and [M(mnt)2]1- (M=Ni, Pd, Pt; mnt=1,2-S2C2(CN)2) in the Gas Phase By Photoelectron Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Waters, Tom; Woo, Hin-koon; Wang, Xue B.; Wang, Lai S.

    2006-03-11

    A detailed understanding of the electronic structure of transition metal bis(dithiolene) complexes is important because of their interesting redox, magnetic, optical, and conducting properties and their relevance to enzymes containing molybdenum and tungsten bis(dithiolene) centers. The electronic structures of the bis(dithiolene) anions [M(mnt)2] n- (M ) Ni, Pd, Pt; mnt ) 1,2-S2C2(CN)2; n) 0-2) were examined by a combination of photodetachment photoelectron spectroscopy (PES) and density functional theory calculations. The combined experimental and theoretical data provide insight into the molecular orbital energy levels of [M(mnt)2]2- and the ground and excited states of [M(mnt)2]1- and [M(mnt)2]. Detachment features from ligand-based orbitals of [M(mnt)2]2- occur at similar energies for each species, independent of the metal center, while those arising from metal-based orbitals occur at higher energies for the heavier congeners. Electronic excitation energies inferred for [M(mnt)2]1- from the PES experiments agree well with those obtained in optical absorption experiments in solution, with the PES experiments providing additional insight into the changes in energy of these transitions as a function of metal. The singly charged anions [M(mnt)2]1- were also prepared and studied independently. Electron detachment from the ground states of these doublet anions accessed the lowest singlet and triplet states of neutral [M(mnt)2], thereby providing a direct experimental measure of their singlet-triplet splitting.

  16. Nickel extraction from nickel matte

    Science.gov (United States)

    Subagja, R.

    2018-01-01

    In present work, the results of research activities to make nickel metal from nickel matte are presented. The research activities were covering a) nickel matte characterization using Inductively Couple plasma (ICP), Electron Probe Micro Analyzer (EPMA) and X-Ray Diffraction (XRD), b) nickel matte dissolution process to dissolve nickel from nickel matte into the spent electrolyte solutions that contains hydrochloric acid, c) purification of nickel chloride leach solution by copper cementation process to remove copper using nickel matte, selective precipitation process to remove iron, solvent extraction using Tri normal octyl amine to separate cobalt from nickel chloride solutions and d) Nickel electro winning process to precipitate nickel into the cathode surface from purified nickel chloride solution by using direct current. The research activities created 99, 72 % pure nickel metal as the final product of the process.

  17. Copper(II), cobalt(II) and nickel(II) complexes of juglone: synthesis, structure, DNA interaction and enhanced cytotoxicity.

    Science.gov (United States)

    Tabrizi, Leila; Fooladivanda, Mahrokh; Chiniforoshan, Hossein

    2016-12-01

    Three novel copper(II), cobalt(II), and nickel(II) complexes of juglone (Jug) containing 1,10-phenanthroline (phen) ligand, [M(Jug) 2 (phen)] (M = Cu(II), 1, Co(II), 2, and Ni(II), 3), have been synthesized and characterized using, elemental analysis and spectroscopic studies. Their interactions with calf thymus DNA were investigated using viscosity measurements, UV-visible and fluorescence spectrophotometric methods. The catalytic activities on DNA cleavage of the complexes 1-3 were studied, which copper complex 1 showed better catalyst activity in the DNA cleavage process than complexes 2 and 3. The in vitro cytotoxic potential of the complexes 1-3 against human cervical carcinoma (HeLa), human liver hepatocellular carcinoma (HepG-2), and human colorectal adenocarcinoma (HT-29) cells indicated their promising antitumor activity with quite low IC 50 values in the range of 0.09-1.89 μM, which are 75 times lower than those of cisplatin.

  18. Iminopyridine-Based Cobalt(II and Nickel(II Complexes: Synthesis, Characterization, and Their Catalytic Behaviors for 1,3-Butadiene Polymerization

    Directory of Open Access Journals (Sweden)

    Quanquan Dai

    2016-01-01

    Full Text Available A series of iminopyridine ligated Co(II (1a–7a and Ni(II (1b–7b complexes were synthesized. The structures of complexes 3a, 4a, 5a, 7a, 5b, and 6b were determined by X-ray crystallographic analyses. Complex 3a formed a chloro-bridged dimer, whereas 4a, 5a, and 7a, having a substituent (4a, 5a: CH3; 7a: Br at the 6-position of pyridine, producing the solid structures with a single ligand coordinated to the central metal. The nickel atom in complex 5b features distorted trigonal-bipyramidal geometry with one THF molecule ligating to the metal center. All the complexes activated by ethylaluminum sesquichloride (EASC were evaluated in 1,3-butadiene polymerization. The catalytic activity and selectivity were significantly influenced by the ligand structure and central metal. Comparing with the nickel complexes, the cobalt complexes exhibited higher catalytic activity and cis-1,4-selectivity. For both the cobalt and nickel complexes, the aldimine-based complexes showed higher catalyst activity than their ketimine counterparts.

  19. Synthesis, X-ray structure, spectroscopic properties and DFT studies of some dithiocarbazate complexes of nickel(II)

    Science.gov (United States)

    Takjoo, Reza; Centore, Roberto

    2013-01-01

    Two nickel(II) complexes with formulae NiL2 (1) and NiL'Im (2) (HL = allyl 2-benzylidene-hydrazinecarbodithioate, H2L' = allyl 2-(2-hydroxybenzylidene)hydrazinecarbodithioate, Im = Imidazole) have been synthesized and characterized by elemental analysis, molar conductivities, FT-IR, 1H NMR and UV/Vis spectroscopy. The crystal structure of the complexes has been determined by single crystal X-ray diffractometry. Both L and L' ligands are coordinated to the metal in the thiolate form. In 1, the square planar coordination of the metal is achieved by coordination of two bidentate ligand units acting through azomethine nitrogen and the thiolato sulfur donor atoms. The complex 2 has a square-planar geometry with the tridentate ligand coordinated to the metal through salicylate oxygen, azomethine nitrogen and the thiolato sulfur atoms, while the fourth coordination position is occupied by one N atom of imidazole. Also natural bond orbitals (NBOs), frontier molecular orbitals (FMOs) and Mulliken charge computational studies on complexes carried out in the ground state with the DFT and theory at B3LYP/6-31G(d,p) level of theory.

  20. Potentiometric determination of stability constants of cyanoacetato complexes of cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II) and lead(II).

    Science.gov (United States)

    Matusinović, T; Filipović, I

    1981-03-01

    Stability constants of cyanoacetato complexes of cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II) and lead(II) were determined potentiometrically at 25.0 +/- 0.1 degrees and ionic strength 2M (sodium perchlorate). The stability constants were evaluated by a weighted least-squares method.

  1. On the stability of a POCsp3OP-type pincer ligand in nickel(II) complexes.

    Science.gov (United States)

    Hao, Jingjun; Mougang-Soumé, Berline; Vabre, Boris; Zargarian, Davit

    2014-03-17

    We describe the results of a study on the stabilities of pincer-type nickel complexes relevant to catalytic hydroalkoxylation and hydroamination of olefins, C-C and C-X couplings, and fluorination of alkyl halides. Complexes [(POCsp3 OP)NiX] are stable for X=OSiMe3 , OMes (Mes=1,3,5-Me3 C6 H2), NPh2, and CC-H, whereas the O(tBu) and N(SiMe3)2 derivatives decompose readily. The phenylacetylide derivative transforms gradually into the zero-valent species cis-[{κ(P),κ(C),κ(C')-(iPr2 POCH2 CHCH2 )}Ni{η(2),κ(C),κ(C')-(iPr2 P(O)CCPh)}]. Likewise, attempts to prepare [(POCsp3 OP)NiF] gave instead the zwitterionic trinuclear species [{(η(3) -allyl)Ni}2-{μ,κ(P),κ(O)-(iPr2 PO)4 Ni}]. Characterization of these two complexes provides concrete examples of decomposition processes that can dismantle POCsp3 OP-type pincer ligands by facile C-O bond rupture. These results serve as a cautionary tale for the inherent structural fragility of pincer systems bearing phosphinite donor moieties, and provide guidelines on how to design more robust analogues. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Contaminated nickel scrap processing

    Energy Technology Data Exchange (ETDEWEB)

    Compere, A.L.; Griffith, W.L.; Hayden, H.W.; Johnson, J.S. Jr.; Wilson, D.F.

    1994-12-01

    The DOE will soon choose between treating contaminated nickel scrap as a legacy waste and developing high-volume nickel decontamination processes. In addition to reducing the volume of legacy wastes, a decontamination process could make 200,000 tons of this strategic metal available for domestic use. Contaminants in DOE nickel scrap include {sup 234}Th, {sup 234}Pa, {sup 137}Cs, {sup 239}Pu (trace), {sup 60}Co, U, {sup 99}Tc, and {sup 237}Np (trace). This report reviews several industrial-scale processes -- electrorefining, electrowinning, vapormetallurgy, and leaching -- used for the purification of nickel. Conventional nickel electrolysis processes are particularly attractive because they use side-stream purification of process solutions to improve the purity of nickel metal. Additionally, nickel purification by electrolysis is effective in a variety of electrolyte systems, including sulfate, chloride, and nitrate. Conventional electrorefining processes typically use a mixed electrolyte which includes sulfate, chloride, and borate. The use of an electrorefining or electrowinning system for scrap nickel recovery could be combined effectively with a variety of processes, including cementation, solvent extraction, ion exchange, complex-formation, and surface sorption, developed for uranium and transuranic purification. Selected processes were reviewed and evaluated for use in nickel side-stream purification. 80 refs.

  3. Contaminated nickel scrap processing

    International Nuclear Information System (INIS)

    Compere, A.L.; Griffith, W.L.; Hayden, H.W.; Johnson, J.S. Jr.; Wilson, D.F.

    1994-12-01

    The DOE will soon choose between treating contaminated nickel scrap as a legacy waste and developing high-volume nickel decontamination processes. In addition to reducing the volume of legacy wastes, a decontamination process could make 200,000 tons of this strategic metal available for domestic use. Contaminants in DOE nickel scrap include 234 Th, 234 Pa, 137 Cs, 239 Pu (trace), 60 Co, U, 99 Tc, and 237 Np (trace). This report reviews several industrial-scale processes -- electrorefining, electrowinning, vapormetallurgy, and leaching -- used for the purification of nickel. Conventional nickel electrolysis processes are particularly attractive because they use side-stream purification of process solutions to improve the purity of nickel metal. Additionally, nickel purification by electrolysis is effective in a variety of electrolyte systems, including sulfate, chloride, and nitrate. Conventional electrorefining processes typically use a mixed electrolyte which includes sulfate, chloride, and borate. The use of an electrorefining or electrowinning system for scrap nickel recovery could be combined effectively with a variety of processes, including cementation, solvent extraction, ion exchange, complex-formation, and surface sorption, developed for uranium and transuranic purification. Selected processes were reviewed and evaluated for use in nickel side-stream purification. 80 refs

  4. Determination of the stability constants for cobalt, nickel and palladium homogeneous catalyst complexes containing triphenylphosphine ligands

    NARCIS (Netherlands)

    Djekic, T.; Zivkovic, Z.; van der Ham, Aloysius G.J.; de Haan, A.B.

    2006-01-01

    Homogeneous catalysts are complex compounds that are always in equilibrium with their free metal, free ligand and other forms of complexes. The ratios between different species are defined by the stability constants, which are influenced by different parameters such as the type of metal, ligand,

  5. Nickel-catalyzed proton-deuterium exchange (HDX) procedures for glycosidic linkage analysis of complex carbohydrates

    Science.gov (United States)

    The structural analysis of complex carbohydrates typically requires the assignment of three parameters: monosaccharide composition, the position of glycosidic linkages between monosaccharides, and the position and nature of non-carbohydrate substituents. The glycosidic linkage positions are often de...

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

    Science.gov (United States)

    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.

  7. Structure, Spectra, and DFT Simulation of Nickel Benzazolate Complexes with Tris(2-aminoethyl)amine Ligand.

    Science.gov (United States)

    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)]ClO 4 (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.

  8. Antimicrobial Activity of Some Thiourea Derivatives and Their Nickel and Copper Complexes

    Directory of Open Access Journals (Sweden)

    Cevdet Akbay

    2009-01-01

    Full Text Available Five thiourea derivative ligands and their Ni2+ and Cu2+ complexes have been synthesized. The compounds were screened for their in vitro anti-bacterial activity using Gram-positive bacteria (two different standard strains of Staphylococcus aureus, Staphylococcus epidermidis, Enterococcus faecalis, Streptococcus pyogenes, Bacillus cereus and Gram-negative bacteria (Esherichia coli, Pseudomonas aeruginosa, Enterobacter cloacae, Proteus vulgaris, Enterobacter aerogenes and in vitro anti-yeast activity (Candida albicans, Candida krusei, Candida glabrata, Candida tropicalis, Candida parapsilosis. The minimum inhibitory concentration was determined for all ligands and their complexes. In vitro anti-yeast activity of both ligands and their metal complexes is greater than their in vitro anti-bacterial activity. The effect of the structure of the investigated compounds on the antimicrobial activity is discussed.

  9. Nickel complexes with "click"-derived pyridyl-triazole ligands: weak intermolecular interactions and catalytic ethylene oligomerisation.

    Science.gov (United States)

    Schweinfurth, David; Su, Cheng-Yong; Wei, Shi-Chao; Braunstein, Pierre; Sarkar, Biprajit

    2012-11-07

    The ligands 1-(cyclohexyl)-4-(2-pyridyl)-1,2,3-triazole (1), 1-(2,6-diisopropylphenyl)-4-(2-pyridyl)-1,2,3-triazole (2), 1-(4-butoxyphenyl)-4-(2-pyridyl)-1,2,3-triazole (3) and 1-(methyl)-4-(2-pyridyl)-1,2,3-triazole (4) were synthesized by the Cu(I) catalyzed "Click" reaction between 2-pyridylacetylene and the corresponding azides. The ligands were then reacted with NiBr(2)·3H(2)O to generate the complexes (1)(2)NiBr(2) (1a), (2)(2)NiBr(2) (2a), (3)(2)NiBr(2) (3a) and (4)(2)NiBr(2) (4a). Structural characterization of 1a confirmed the mononuclear and distorted octahedral environment around the Ni(II) center, with the pyridyl-triazole ligands coordinating in a bis-chelating fashion. Bond length analysis inside the 1,2,3-triazole ring shows a short N=N double bond that is flanked by two longer C-N and N-N bonds pointing to the existence of "azo" character in the ring. The highly polar five-membered 1,2,3-triazole ring makes its C-H bond acidic, and these bonds participate in an extended weak intermolecular C-H···Br interactions with the Br-groups of neighboring molecules, resulting in a 3-D network. The nickel complexes with these "Click" ligands were tested as pre-catalysts for ethylene oligomerization, and the complexes showed moderate activity in that reaction with good selectivity towards C4 oligomers.

  10. Synthesis and Crystal Structure of Binuclear and Pentanuclear Nickel(II Complexes Containing 4-(salicylaldiminatoantipyrine Schiff base

    Directory of Open Access Journals (Sweden)

    Mohamed N. EL-Kaheli

    2015-11-01

    Full Text Available The new title binuclear Ni (II compound  (1 and the novel pentanuclear Ni (II cluster {[   } (2 are formed from the reaction of an asymmetric Schiff base ligand L (L = 4-(salicylaldiminatoantipyrine with Ni .4  in the former or Ni(ClO42.6H2O in presence of malonate in the later.  Complex (1 consists of ( ]+ cation and one uncoordinated tetraphenylborate anion.  The cation adopts a distorted octahedral arrangement around each metal center.  In the binuclear unit both Ni(II ions are linked through two phenolate (µ2-O oxygen atoms of L, and two oxygen atoms of a  bridging carboxylate group. Each Ni (II coordinates to four oxygen atoms at the basal plane, two oxygen atoms from two bridging phenolate groups, one from pyrazolone ring and the last of an aqua molecule, and at the axial positions to a bridging carboxylate-O atom and an azomethine nitrogen atom.  In the pentanuclear cluster (2 consisting of [ ]+2 cation and two tetraphenylborate anions, the core of the cation is assembled by four [Ni( ] units, linked to the central Ni-ion by two bridging water molecules. The resulting coordination sphere for the external symmetry related nickel ions is a pseudo octahedron.  The central Ni-atom unusually adopts dodecahedron geometry through its coordination to eight bridging water molecules. In complex (1 each Ni-atom is coordinated to one tridentate L ligand and in complex (2 each [Ni ( ] unit is coordinated to two bidentate L ligands.  Inter-and intramolecular hydrogen bonds are present in both crystal structures.

  11. Cobalt(III), nickel(II) and ruthenium(II) complexes of 1,10 ...

    Indian Academy of Sciences (India)

    Abstract. DNA binding and photocleavage characteristics of a series of mixed- ligand complexes of the type [M(phen)2LL]n+ (where M = Co(III), Ni(II) or Ru(II),. LL = 1,10-phenanthroline (phen), phenanthroline-dione (phen-dione) or dipyridophenazine (dppz) and n = 3 or 2) have been investigated in detail. Various.

  12. Synthesis, crystal structures, antimicrobial activities, and DFT calculations of two new azido nickel(II) complexes

    Czech Academy of Sciences Publication Activity Database

    Shaabani, B.; Khandar, A.A.; Dušek, Michal; Pojarová, Michaela; Maestro, M.A.; Mukherjee, R.; Mahmoudi, F.

    2014-01-01

    Roč. 67, č. 12 (2014), s. 2096-2109 ISSN 0095-8972 Grant - others:AV ČR(CZ) Praemium Academiae Institutional support: RVO:68378271 Keywords : uranium complex * isothiosemicarbazone * crystallography * spectra * thermal stability Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.012, year: 2014

  13. Sterically Hindered Square-Planar Nickel(II) Organometallic Complexes: Preparation, Characterization, and Substitution Behavior

    Science.gov (United States)

    Martinez, Manuel; Muller, Guillermo; Rocamora, Merce; Rodriguez, Carlos

    2007-01-01

    The series of experiments proposed for advanced undergraduate students deal with both standard organometallic preparative methods in dry anaerobic conditions and with a kinetic study of the mechanisms operating in the substitution of square-planar complexes. The preparation of organometallic compounds is carried out by transmetallation or…

  14. Cobalt(III), nickel(II) and ruthenium(II) complexes of 1,10 ...

    Indian Academy of Sciences (India)

    (phen)2(phen-dione)]2+ was prepared following a procedure analogous to that adopted for the synthesis of [Ru(phen)2(phen-dione)]2+ 25. The hexafluorophosphate salts of the synthesized complexes have been recrystallized by dissolving ...

  15. Nickel-catalyzed proton-deuterium exchange (HDX) for linkage analysis of complex carbohydrates

    Science.gov (United States)

    The structural assignment of complex carbohydrates typically requires the analysis of at least three parameters: 1. composition; 2. linkage; and 3. substituents. These are often assigned on a small scale by gas chromatography/mass spectrometry (GC/MS). Linkage positions are determined by permethylat...

  16. Nickel(II) complexes of N2S2 donor set ligand and halide ...

    Indian Academy of Sciences (India)

    Synthesis, crystal structure, DNA and bovine/human serum albumin interaction. ANIMESH ... Burdwan 713 104, India. bDepartment of Chemical and Pharmaceutical Sciences, Via Licio Giorgieri 1, 34127 Trieste, Italy ... and isothiocyanate anion (4)) have been synthesized and isolated in pure form. The complexes were ...

  17. Nickel complexes with new bidentate P,N phosphinitooxazoline and -pyridine ligands: application for the catalytic oligomerization of ethylene.

    Science.gov (United States)

    Speiser, Fredy; Braunstein, Pierre; Saussine, Lucien; Welter, Richard

    2004-03-08

    The phosphinitooxazoline 4,4-dimethyl-2-[1-oxy(diphenylphosphine)-1-methylethyl]-4,5-dihydrooxazole (9), the corresponding phosphinitopyridine ligands 2-ethyl-[1'-methyl-1'-oxy(diphenylphosphino)]pyridine (11) and 2-ethyl-6-methyl-[1'-methyl-1'-oxy(diphenylphosphino)]pyridine (12), which have a one-carbon spacer between the phosphinite oxygen and the heterocycle, and the homologous ligand 2-propyl-[2'-methyl-2'-oxy(diphenylphosphino)]pyridine (13), with a two-carbon spacer, were prepared in good yields. The corresponding mononuclear [NiCl(2)(P,N)] complexes 14 (P,N = 9), 15 (P,N = 11), and 16 (P,N = 12) and the dinuclear [NiCl(micro-Cl)(P,N)](2) 17 (P,N = 13) Ni(II) complex were evaluated in the catalytic oligomerization of ethylene. These four complexes were characterized by single-crystal X-ray diffraction in the solid state and in solution with the help of the Evans method, which indicated differences between the coordination spheres in the solution and the solid state. In the presence of methylalumoxane (MAO) or AlEt(3), only the decomposition of the Ni complexes was observed. However, complexes 14-17 provided activities up to 50000 mol C(2)H(4)/(mol Ni).h (16 and 17) in the presence of only 6 equiv of AlEtCl(2). The observed selectivities for ethylene dimers were higher than 91% (for 14 or 15 in the presence of only 1.3 equiv of AlEtCl(2)). The activities for 14-17 were superior to that of [NiCl(2)(PCy(3))(2)], a typical dimerization catalyst taken as a reference. The selectivities of the complexes 14-17 for ethylene dimers and alpha-olefins were the same order of magnitude. From the study of the phosphinite 9/AlEtCl(2) system, we concluded that in our case ligand transfer from the nickel atom to the aluminum cocatalyst is unlikely to represent an activation mechanism.

  18. Photophysical properties of open-framework germanates templated by nickel complexes

    KAUST Repository

    Peskov, Maxim

    2014-01-01

    Open-framework germanates are a group of germanium oxides with a well-defined porous structure, suitable for ion-exchange and gas adsorption applications. Recently, Ni incorporation into the porous structure by establishing Ge-O-Ni bonds with the molecular complexes [Ni(H 2N(CH2)2NH2)2] was realized. We investigate the optical and electronic features of these systems (SUT-1 and SUT-2) from first principles. To describe the photophysical behavior, we analyze the bonding between the Ni and nearest-neighboring atoms and simulate the absorption spectra. Because of their optical characteristics, germania-based nanomaterials are expected to be essential components of future optical and electronic devices. We discuss to what extent molecular transition-metal complexes embedded into porous germanium oxide can modify the optical response to potentially expand the area of applications. This journal is © the Partner Organisations 2014.

  19. Characterization of divalent and trivalent species generated in the chemical and electrochemical oxidation of a dimeric pincer complex of nickel.

    Science.gov (United States)

    Spasyuk, Denis M; Gorelsky, Serge I; van der Est, Art; Zargarian, Davit

    2011-03-21

    The electrolytic and chemical oxidation of the dimeric pincer complex [κ(P),κ(C),κ(N),μ(N)-(2,6-(i-Pr(2)POC(6)H(3)CH(2)NBn)Ni](2) (1; Bn = CH(2)Ph) has been investigated by various analytic techniques. Cyclic voltammetry measurements have shown that 1 undergoes a quasi-reversible, one electron, Ni-based redox process (ΔE(0)(1/2) = -0.07 V vs Cp(2)Fe/[Cp(2)Fe](+)), and spectroelectrochemical measurements conducted on the product of the electrolytic oxidation, [1](+•), have shown multiple low-energy electronic transitions in the range of 10,000-15,000 cm(-1). Computational studies using Density Functional Theory (B3LYP) have corroborated the experimentally obtained structure of 1, provided the electronic structure description, and helped interpret the experimentally obtained absorption spectra for 1 and [1](+·). These calculations indicate that the radical cation [1](+·) is a dimeric, mixed-valent species (class III) wherein most of the spin density is delocalized over the two nickel centers (Ni(+2.5)(2)N(2)), but some spin density is also present over the two nitrogen atoms (Ni(2+)(2)N(2)·). Examination of alternative structures for open shell species generated from 1 has shown that the spin density distribution is highly sensitive toward changes in the ligand environment of the Ni ions. NMR, UV-vis, electron paramagnetic resonance (EPR), and single crystal X-ray diffraction analyses have shown that chemical oxidation of 1 with N-Bromosuccinimide (NBS) follows a complex process that gives multiple products, including the monomeric trivalent species κ(P),κ(C),κ(N)-{2,6-(i-Pr(2)PO)(C(6)H(3))(CH═NBn)}NiBr(2) (2). These studies also indicate that oxidation of 1 with 1 equiv of NBS gives an unstable, paramagnetic intermediate that decomposes to a number of divalent species, including succinimide and the monomeric divalent complexes κ(P),κ(C),κ(N)-{2,6-(i-Pr(2)PO)(C(6)H(3))(CH═NBn)}NiBr (3) and κ(P),κ(C),κ(N)-{2,6-(i-Pr(2)PO)(C(6)H(3))(CH(2)N

  20. Mononuclear Nickel(II Complexes with Schiff Base Ligands: Synthesis, Characterization, and Catalytic Activity in Norbornene Polymerization

    Directory of Open Access Journals (Sweden)

    Yi-Mei Xu

    2017-03-01

    Full Text Available The nickel(II catalyst has manifested higher catalytic activity compared to that of other late transition metal catalysts for norbornene polymerization. Therefore, several structurally similar trans-nickel(II compounds of N,O-chelate bidentate ligands were synthesized and characterized. Both the electronic effect and the steric hindrance influence polymerization. The molecular structures of 2, 4 and 5 were further confirmed by single-crystal X-ray diffraction.

  1. Dinuclear nickel complexes with bidentate N,O ligands: synthesis, structure, and catalytic oligomerization of ethylene.

    Science.gov (United States)

    Speiser, Fredy; Braunstein, Pierre; Saussine, Lucien

    2004-07-12

    The new dicationic dinuclear complexes [Ni(micro-Cl)(2)(N,OH)(2)]Cl(2) (11, N,OH = 2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)-propan-2-ol; 12, N,OH = 2-pyridin-2-yl-propan-2-ol) were prepared in good yields and evaluated as precatalyts in the oligomerization of ethylene, using MAO or AlEtCl(2) as cocatalyst. These paramagnetic complexes were characterized by single-crystal X-ray diffraction in the solid state and in solution with the help of the Evans method, which revealed agreement between the octahedral coordination spheres found in solution and in the solid state. The N donor atoms of each chelating ligand are in mutual cis position, and the OH donors are mutually trans situated. Selectivities for 1-butene within the C(4) fraction of 61% (11) and 58% (12) were observed in the presence of 200 equiv of MAO, but better turnover frequencies (28 300 (11) and 20 400 (12) mol of C(2)H(4)/(mol of Ni.h)) were obtained when 800 equiv of MAO was used. In the presence of 6 equiv of AlEtCl(2), the activities were considerably increased, up to 174 300 (11) and 97 100 (12) mol of C(2)H(4)/(mol of Ni.h), and the selectivity for C(4) olefins was 70% and 64%, respectively.

  2. Thio-Pybox and Thio-Phebox complexes of chromium, iron, cobalt and nickel and their application in ethylene and butadiene polymerisation catalysis.

    Science.gov (United States)

    Nobbs, James D; Tomov, Atanas K; Cariou, Renan; Gibson, Vernon C; White, Andrew J P; Britovsek, George J P

    2012-05-21

    A series of bis(thiazolinyl)- and bis(thiazolyl)pyridine Thio-Pybox ligands and their metal complexes of chromium(III), iron(II), cobalt(II) and nickel(II) has been prepared, as well as a nickel(II) complex containing a monoanionic bis(thiazolinyl)phenyl Thio-Phebox ligand. These new metal complexes have been characterised and used as catalysts, in combination with the co-catalyst MAO, for the polymerisation of ethylene and for the polymerisation of butadiene. In the case of ethylene polymerisation, the Thio-Pybox and Thio-Phebox metal complexes have shown relatively low polymerisation activities, much lower compared to the related bis(imino)pyridine complexes of the same metals. In the polymerisation of butadiene, several Thio-Pybox cobalt(II) complexes show very high activities, significantly higher than the other metal complexes with the same ligand. It is the metal, rather than the ligand, that appears to have the most profound effect on the catalytic activity in butadiene polymerisation, unlike in the polymerisation of ethylene, where bis(imino)pyridine ligands provide highly active catalysts for a range of 1st row transition metals.

  3. Nickel and iron complexes with N,P,N-type ligands: synthesis, structure and catalytic oligomerization of ethylene.

    Science.gov (United States)

    Kermagoret, Anthony; Tomicki, Falk; Braunstein, Pierre

    2008-06-14

    The N,P,N-type ligands bis(2-picolyl)phenylphosphine (), bis(4,5-dihydro-2-oxazolylmethyl)phenylphosphine (), bis(4,4-dimethyl-2-oxazolylmethyl)phenylphosphine () and bis(2-picolyloxy)phenylphosphine () were used to synthesize the corresponding pentacoordinated Ni(ii) complexes [Ni{bis(2-picolyl)phenylphosphine}Cl(2)] (), [Ni{bis(4,5-dihydro-2-oxazolylmethyl)phenylphosphine}Cl(2)] (), [Ni{bis(4,4-dimethyl-2-oxazolylmethyl)phenylphosphine}Cl(2)] () and [Ni{bis(2-picolyloxy)phenylphosphine}Cl(2)] (), respectively. The hexacoordinated iron complexes [Fe{bis(2-picolyl)phenylphosphine}(2)][Cl(3)FeOFeCl(3)] (), [Fe{bis(4,5-dihydro-2-oxazolylmethyl)phenylphosphine}(2)][Cl(3)FeOFeCl(3)] () and the tetracoordinated complex [Fe{bis(4,4-dimethyl-2-oxazolylmethyl)phenylphosphine}Cl(2)] (abbreviated [FeCl(2)(NPN(Me2)-N,N)]) were prepared by reaction of FeCl(2).4H(2)O with ligands , respectively. The crystal structures of the octahedral complexes and , determined by X-ray diffraction, showed that two tridentate ligands are facially coordinated to the metal centre with a cis-arrangement of the P atoms and the dianion (mu-oxo)bis[trichloroferrate(iii)] compensates the doubly positive charge of the complex. The cyclic voltammograms of and showed two reversible redox couples attributed to the reduction of the dianion (Fe(2)OCl(6))(2-) (-0.24 V for and -0.20 V for vs. SCE) and to the oxidation of the Fe(ii) ion of the complex (0.67 V for and 0.52 V for vs. SCE). The cyclic voltammogram of [FeCl(2)(NPN(Me2)-N,N)] showed a reversible redox couple at -0.17 V vs. SCE assigned to the oxidation of the Fe(ii) atom and an irreversible process at 0.65 V. The complexes , and [FeCl(2)(NPN(Me2)-N,N)] have been evaluated in the catalytic oligomerization of ethylene with AlEtCl(2) or MAO as cocatalyst. The nickel complex proved to be the most active precatalyst in the series, with a turnover frequency (TOF) of 61 800 mol(C(2)H(4)) mol(Ni)(-1) h(-1) with 10 equiv. of AlEtCl(2) and 12 200 mol(C(2)H

  4. SHOP-type nickel complexes with alkyl substituents on phosphorus, synthesis and catalytic ethylene oligomerization.

    Science.gov (United States)

    Kermagoret, Anthony; Braunstein, Pierre

    2008-02-14

    The beta-keto phosphorus ylides (n-Bu)3P=CHC(O)Ph 6, (t-Bu)2PhP=CHC(O)Ph 7, (t-Bu)Ph2P=CHC(O)Ph 8, (n-Bu)2PhP=CHC(O)Ph 9, (n-Bu)Ph2P=CHC(O)Ph 10, Me2PhP=CHC(O)Ph 11 and Ph3P=CHC(O)(o-OMe-C6H4) 12 have been synthesized in 80-96% yields. The Ni(II) complexes [NiPh{Ph2PCH...C(...O)(o-OMeC6H4)}(PPh3)] 13, [NiPh{Ph(t-Bu)PCHC(O)Ph}(PPh3)] 15, [NiPh{(n-Bu)2PCH...C(...O)Ph}(PPh3)] 16 and [NiPh{Ph(n-Bu)PCH...C(...O)Ph}(PPh3)] 17 have been prepared by reaction of equimolar amounts of [Ni(COD)2] and PPh3 with the beta-keto phosphorus ylides 12 or 8-10, respectively, and characterized by 1H and 31P{1H} NMR spectroscopy. NMR studies and the crystal structure determination of 13 indicated an interaction between the hydrogen atom of the C-H group alpha to phosphorus and the ether function. The complexes [NiPh{Ph2PCHC(O)Ph}(Py)] 18, [NiPh{Ph(t-Bu)PCHC(O)Ph}(Py)] 19, [NiPh{(n-Bu)2PCH...C(...O)Ph}(Py)] 20, [NiPh{Ph(n-Bu)PCH...C(...O)Ph}(Py)] 21 and [NiPh{Me2PCH...C(...O)Ph}(Py)] 22 have been isolated from the reactions of [Ni(COD)2] and an excess of pyridine with the -keto phosphorus ylides Ph3PCH=C(O)Ph 3 or 8-11, respectively, and characterized by 1H and 31P{1H} NMR spectroscopy. Ligands 3, 8, 10 and 12 have been used to prepare in situ oligomerization catalysts by reaction with one equiv. of [Ni(COD)2] and PPh3 under an ethylene pressure of 30 or 60 bar. The catalyst prepared in situ from 12, [Ni(COD)2] and PPh3 was the most active of the series with a TON of 12700 mol C2H4 (mol Ni)-1 under 30 bar ethylene. When the beta-keto phosphorus ylide 8 was reacted in situ with three equiv. of [Ni(COD)2] and one equiv. of PPh3 under 30 bar of ethylene, ethylene polymerization was observed with a TON of 5500 mol C2H4 (mol Ni)-1.

  5. Beta-Phosphinoethylboranes as Ambiphilic Ligands in Nickel-Methyl Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Fischbach, Andreas; Bazinet, Patrick R.; Waterman, Rory; Tilley, T. Don

    2007-10-28

    The ambiphilic {beta}-phosphinoethylboranes Ph{sub 2}PCH{sub 2}CH{sub 2}BR{sub 2} (BR{sub 2} = BCy{sub 2} (1a), BBN (1b)), which feature a ethano spacer CH{sub 2}CH{sub 2} between the Lewis acidic boryl and Lewis basic phosphino groups, were synthesized in nearly quantitative yields via the hydroboration of vinyldiphenylphosphine. Compounds 1a and 1b were fully characterized by elemental analysis, and by NMR and IR spectroscopy. X-ray crystallographic studies of compound 1b revealed infinite helical chains of the molecules connected through P{hor_ellipsis}B donor-acceptor interactions. The ability of these ambiphilic ligands to concurrently act as donors and acceptors was highlighted by their reactions with (dmpe)NiMe{sub 2}. Zwitterionic complexes (dmpe)NiMe(Ph{sub 2}PCH{sub 2}CH{sub 2}BCy{sub 2}Me) (2a) and (dmpe)NiMe(Ph{sub 2}PCH{sub 2}CH{sub 2}[BBN]Me) (2b) were generated via the abstraction of one of the methyl groups, forming a borate, and intramolecular coordination of the phosphine moiety to the resulting cationic metal center. Compound 2b was characterized by X-ray crystallography. Furthermore, B(C{sub 6}F{sub 5}){sub 3} abstracts the methyl group of a coordinated borate ligand to generate a free, 3-coordinate borane center in [(dmpe)NiMe(1a)]{sup +}[MeB(C{sub 6}F{sub 5}){sub 3}]{sup -} (3).

  6. Bis(acetyl­acetonato-κ2 O,O′)[copper(II)nickel(II)(0.31/0.69)]: a mixed-metal complex

    Science.gov (United States)

    Shahid, Muhammad; Hamid, Mazhar; Mazhar, Muhammad; Azad Malik, Mohammad; Raftery, James

    2010-01-01

    The title complex, [Cu0.31Ni0.69(C5H7O2)2], was isolated from the reaction of bis­(N,N-dimethyamino­ethanol)copper(II) with bis­(acetyl­acetonato)nickel(II), which yielded crystals with mixed sites at the central metal position; the refined copper–nickel occupancy ratio is 0.31 (4):0.69 (4). Two acetyl­acetonate ligands, related by a centre of symmetry, are coordinated to the central metal atom in a square-planar configuration while the methyne C atoms of the acetyl­acetonate ligands, ca 3.02 Å away, are orthogonal to this plane at the metal site. PMID:21588179

  7. Bis(acetyl-acetonato-κO,O')[copper(II)nickel(II)(0.31/0.69)]: a mixed-metal complex.

    Science.gov (United States)

    Shahid, Muhammad; Hamid, Mazhar; Mazhar, Muhammad; Azad Malik, Mohammad; Raftery, James

    2010-07-17

    The title complex, [Cu(0.31)Ni(0.69)(C(5)H(7)O(2))(2)], was isolated from the reaction of bis-(N,N-dimethyamino-ethanol)copper(II) with bis-(acetyl-acetonato)nickel(II), which yielded crystals with mixed sites at the central metal position; the refined copper-nickel occupancy ratio is 0.31 (4):0.69 (4). Two acetyl-acetonate ligands, related by a centre of symmetry, are coordinated to the central metal atom in a square-planar configuration while the methyne C atoms of the acetyl-acetonate ligands, ca 3.02 Å away, are orthogonal to this plane at the metal site.

  8. Synthesis and characterization of Ni(III)N3S2 complexes as active site models for the oxidized form of nickel superoxide dismutase.

    Science.gov (United States)

    Chiang, Chien-Wei; Chu, Yun-Li; Chen, Hong-Ling; Kuo, Ting-Shen; Lee, Way-Zen

    2014-05-19

    Nickel complexes, [Ni(H2BA(R)TPP)](ClO4)2 (R = Ph for 1 or iPr for 2), supported by a pentadentate ligand H2BA(R)TPP were synthesized and oxidized to form Ni(III) species having a N3S2 coordination environment to mimic the active site of the oxidized form of nickel superoxide dismutase (NiSODox). The Ni(III) species 2(+) exhibited a rhombic signal with g values at 2.15, 2.12 and 2.02 similar to that of NiSODox. DFT calculations revealed that 2(+) has an unpaired electron primarily located in the dz2 orbital of the Ni(III) center, which strongly overlaps with the pz orbital of the axial pyridine nitrogen of H2BA(Pr)TPP. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Photometric method to determining boron microamounts in the form of β-diketonate complex in steel and alloys bsed on nickel

    International Nuclear Information System (INIS)

    Ishchenko, A.V.; Stashkova, N.V.; Timoteus, Kh.R.; Fedorova, S.F.

    1988-01-01

    A sensitive technique of determining boron microamounts in steels and alloys based on nickel, doped with chromium, tungsten, molybdenum, titanium and vanadium is developed. After boron preextraction by β-diol chloroform solutions its determination is carried out directly in organic phase in acidic and sulfuric acids by β-diketone class reagent: 4,4'-dihydroxydibensoylmethane (I) or 4,4'-dimethoxydibenzoylmethane. Molar light-absorption coefficient for reagent I at formation of boroxalate complex is 8.48x10 4 , at of complexing in presence of sulfuric acid -10.63x10 4 , of acetic acid-17.27x10 4

  10. Synthesis, characterization and ethylene oligomerization of nickel complexes bearing N-(2-(1H-benzo[d]imidazol-2-yl)quinolin-8-yl)benzamide derivatives.

    Science.gov (United States)

    Wang, Kefeng; Shen, Miao; Sun, Wen-Hua

    2009-06-07

    A series of N-(2-(1-R-1H-benzo[d]imidazol-2-yl)quinolin-8-yl)-2-R(1)-4-R(2)-benzamide derivatives (5-12) was synthesized and characterized. These compounds 5-11 (5: R = H, R(1) = H, R(2) = H; : R = H, R(1) = Cl, R(2) = H; :R = H, R(1) = H, R(2) = Cl; : R = H, R(1) = H, R(2) = Br; : R = Me, R(1) = H, R(2) = H; 10: R = Et, R(1) = H, R(2) = H; : R = (i)Pr, R(1) = H, R(2) = H.) were treated with KOH, and then reacted with Ni(Ac)(2).4H(2)O to form their nickel complexes (-), however, the dimethylated compound reacted with NiCl(2).6H(2)O to give complex 14a. Further investigation confirmed that compound hydrolysized into a new compound N-methyl-2-(1-methyl-1H-benzo[d]imidazol-2-yl)quinolin-8-amine 14, and alternative synthesis confirmed the formation mechanism of 14a. All nickel complexes were characterized by elemental and spectroscopic analyses, and molecular structures of the representative compounds (12, 5a and 14a ) were determined by the single-crystal X-ray diffraction. These Ni(ii) complexes exhibited good to high activities up to 7.6 x 10(6)g mol(-1)(Ni) h(-1) in ethylene oligomerization upon activation with Et(2)AlCl. The reaction conditions and the nature of ligands affected on the catalytic performances of nickel complexes.

  11. Mathematical modelling of brittle phase precipitation in complex ruthenium containing nickel-based superalloys

    International Nuclear Information System (INIS)

    Rettig, Ralf

    2010-01-01

    A new model has been developed in this work which is capable of simulating the precipitation kinetics of brittle phases, especially TCP-phases (topologically close packed phases) in ruthenium containing superalloys. The model simultaneously simulates the nucleation and the growth stage of precipitation for any number of precipitating phases. The CALPHAD method (Calculation of Phase Diagrams) is employed to calculate thermodynamic properties, such as the driving force or phase compositions in equilibrium. For calculation of diffusion coefficients, kinetic mobility databases which are also based on the CALPHAD-method are used. The model is fully capable of handling multicomponent effects, which are common in complex superalloys. Metastable phases can be treated and will automatically be dissolved if they get unstable. As the model is based on the general CALPHAD method, it can be applied to a broad range of precipitation processes in different alloys as long as the relevant thermodynamic and kinetic databases are available. The developed model proves that the TCP-phases precipitate in a sequence of phases. The first phase that is often formed is the metastable σ-phase because it has the lowest interface energy due to low-energy planes at the interface between matrix and precipitate. After several hundred hours the stable μ- and P-phases start to precipitate by nucleating at the σ-phase which is energetically favourable. During the growth of these stable phases the sigma-phase is continuously dissolved. It can be shown by thermodynamic CALPHAD calculations that the sigma-phase has a lower Gibbs free enthalpy than the μ- and P-phase. All required parameters of the model, such as interface energy and nucleate densities, have been estimated. The mechanisms of suppression of TCP-phase precipitation in the presence of ruthenium in superalloys were investigated with the newly developed model. It is shown by the simulations that ruthenium mostly affects the nucleation

  12. cobalt (ii), nickel (ii)

    African Journals Online (AJOL)

    DR. AMINU

    ABSTRACT. The manganese (II), cobalt (II), nickel (II) and copper (II) complexes of N, N' – bis(benzoin)ethylenediiminato have been prepared and characterized by infrared, elemental analysis, conductivity measurements and solubility. The potentiometric, and elemental analyses studies of the complexes revealed 1:1 ...

  13. Reappraisal of the amide coordination mode: solution properties of nickel(II) and copper(II) complexes of ligands involving simultaneously enamine and amide groups

    Energy Technology Data Exchange (ETDEWEB)

    Costes, J.P.; Laurent, J.P.

    1988-09-07

    The behavior of the Cu/sup 2+//L/sub 1/ system in solution was reappraised through the isolation and characterization of the copper(II) complexes involving the ligand L/sub 1/ in different states of protonation. Also included in the study are the homologous nickel(II) complexes and the copper(II) and nickel(II) complexes of related ligands L/sub 2/ and L/sub 3/. L/sub 1/ is the ligand 3,8-dimethyl-4,7-diazadeca-2,8-diene-1,10-diamide synthesized from acetoacetamide and 1,2,diaminoethane. L/sub 2/ and L/sub 3/ were similarly synthesized using acetoacetanilide and ethylacetoacetate instead of acetoamide. The complexes were studied by ESR and visible spectroscopy, and the data demonstrate that in all cases not only the ligand L/sub 3/ but also L/sub 1/ and L/sub 2/ are in the enamine form, and the first step of the protonation process concerns the proton of the enamine functions and not those of the amide group. 8 references, 2 tables.

  14. Rhodium, iridium and nickel complexes with a 1,3,5-triphenylbenzene tris-MIC ligand. Study of the electronic properties and catalytic activities

    Directory of Open Access Journals (Sweden)

    Carmen Mejuto

    2015-12-01

    Full Text Available The coordination versatility of a 1,3,5-triphenylbenzene-tris-mesoionic carbene ligand is illustrated by the preparation of complexes with three different metals: rhodium, iridium and nickel. The rhodium and iridium complexes contained the [MCl(COD] fragments, while the nickel compound contained [NiCpCl]. The preparation of the tris-MIC (MIC = mesoionic carbene complex with three [IrCl(CO2] fragments, allowed the estimation of the Tolman electronic parameter (TEP for the ligand, which was compared with the TEP value for a related 1,3,5-triphenylbenzene-tris-NHC ligand. The electronic properties of the tris-MIC ligand were studied by cyclic voltammetry measurements. In all cases, the tris-MIC ligand showed a stronger electron-donating character than the corresponding NHC-based ligands. The catalytic activity of the tri-rhodium complex was tested in the addition reaction of arylboronic acids to α,β-unsaturated ketones.

  15. Synthesis and Ligand Non-Innocence of Thiolate-Ligated (N4S) Iron(II) and Nickel(II) Bis(imino)pyridine Complexes

    Science.gov (United States)

    Widger, Leland R.; Jiang, Yunbo; Siegler, Maxime; Kumar, Devesh; Latifi, Reza; de Visser, Sam P.; Jameson, Guy N.L.; Goldberg, David P.

    2013-01-01

    The known iron(II) complex [FeII(LN3S)(OTf)] (1) was used as starting material to prepare the new biomimetic (N4S(thiolate)) iron(II) complexes [FeII(LN3S)(py)](OTf) (2) and [FeII(LN3S)(DMAP)](OTf) (3), where LN3S is a tetradentate bis(imino)pyridine (BIP) derivative with a covalently tethered phenylthiolate donor. These complexes were characterized by X-ray crystallography, UV-vis, 1H NMR, and Mössbauer spectroscopy, as well as electrochemistry. A nickel(II) analogue, [NiII(LN3S)](BF4) (5), was also synthesized and characterized by structural and spectroscopic methods. Cyclic voltammetric studies showed 1 – 3 and 5 undergo a single reduction process with E1/2 between −0.9 to −1.2 V versus Fc+/Fc. Treatment of 3 with 0.5% Na/Hg amalgam gave the mono-reduced complex [Fe(LN3S)(DMAP)]0 (4), which was characterized by X-ray crystallography, UV-vis, EPR (g = [2.155, 2.057, 2.038]) and Mössbauer (δ = 0.33 mm s−1; ΔEQ = 2.04 mm s−1) spectroscopies. Computational methods (DFT) were employed to model complexes 3 – 5. The combined experimental and computational studies show that 1 – 3 are 5-coordinate, high-spin (S = 2) FeII complexes, whereas 4 is best described as a 5-coordinate, intermediate-spin (S = 1) FeII complex antiferromagnetically coupled to a ligand radical. This unique electronic configuration leads to an overall doublet spin (Stotal = ½) ground state. Complexes 2 and 3 are shown to react with O2 to give S-oxygenated products, as previously reported for 1. In contrast, the mono-reduced 4 appears to react with O2 to give a mixture of S- and Fe-oxygenates. The nickel(II) complex 5 does not react with O2, and even when the mono-reduced nickel complex is produced, it appears to undergo only outer-sphere oxidation with O2. PMID:23992096

  16. Antibacterial, DNA interaction and cytotoxic activities of pendant-armed polyamine macrocyclic dinuclear nickel(II) and copper(II) complexes

    Science.gov (United States)

    Arthi, P.; Haleel, A.; Srinivasan, P.; Prabhu, D.; Arulvasu, C.; Kalilur Rahiman, A.

    2014-08-01

    A series of dinuclear nickel(II) and copper(II) complexes (1-6) of hexaaza macrocycles of 2,6-diformyl-4-methylphenol with three different benzoyl pendant-arms, 2,2‧-benzoyliminodi(ethylamine) trihydrochloride (L), 2,2‧-4-nitrobenzoyliminodi(ethylamine) trihydrochloride (L‧) and 2,2‧-3,5-dinitrobenzoyliminodi(ethylamine) trihydrochloride (L″) have been synthesized and characterized by spectral methods. The electrochemical studies of these complexes depict two irreversible one electron reduction processes around E1pc = -0.62 to -0.76 V and E2pc = -1.21 to -1.31, and nickel(II) complexes (1-3) exhibit two irreversible one electron oxidation processes around E1pa = 1.08 to 1.14 V and E2pa = 1.71 to 1.74 V. The room temperature magnetic moment values (μeff, 1.52-1.54 BM) indicate the presence of an antiferromagnetic interaction in the binuclear copper(II) complexes (4-6) which is also observed from the broad ESR spectra with a g value of 2.14-2.15. The synthesized complexes (1-6) were screened for their antibacterial activity. The results of DNA interaction studies indicate that the dinuclear complexes can bind to calf thymus DNA by intercalative mode and display efficient cleavage of plasmid DNA. Further, the cytotoxic activity of complexes 2, 5 and 6 on human liver adenocarcinoma (HepG2) cell line has been examined. Nuclear-chromatin cleavage has also been observed with PI staining and comet assays.

  17. Synthesis, Characterization, and Catalytic Activities of A Nickel(II) Monoamido-Tetradentate Complex: Evidence For NiIII-Oxo and NiIV-Oxo Species.

    Science.gov (United States)

    Bok, Kwon Hee; Lee, Myoung Mi; You, Ga Rim; Ahn, Hye Mi; Ryu, Ka Young; Kim, Sung-Jin; Kim, Youngmee; Kim, Cheal

    2017-03-02

    A new mononuclear nickel(II) complex, [Ni II (dpaq)Cl] (1), containing a tetradentate monoamido ligand, dpaq (dpaq=2-[bis(pyridin-2-ylmethyl)amino]-N-(quinolin-8-yl)acetamide), has been synthesized and characterized by IR spectroscopy, elemental analysis, and UV/Vis spectroscopy. The structure of the nickel complex has been determined by X-ray crystallography. This nonheme Ni II complex 1 catalyzed the epoxidation reaction of a wide range of olefins with meta-chloroperoxybenzoic acid (m-CPBA) under mild conditions. Olefin epoxidation using this catalytic system has been proposed to involve a new reactive Ni IV -oxo (4) species, based on the evidence from a PPAA (peroxyphenylacetic acid) probe, Hammett studies, H 2 18 O exchange experiments, and ESI mass spectroscopic analysis. Moreover, the nature of solvent significantly influenced partitioning between heterolytic and homolytic O-O bond cleavage of the Ni-acylperoxo intermediate (2). The O-O bond of 2 proceeded predominantly through heterolytic cleavage in a protic solvent, such as CH 3 OH. These results suggest that possibly a Ni IV -oxo species is a common reactive intermediate in protic solvents. The two active oxidants, namely Ni IV -oxo (3) and Ni III -oxo (4), which are responsible for stereospecific olefin epoxidation and radical-type oxidations, respectively, operate in aprotic solvents. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. A new PC(sp(3))P ligand and its coordination chemistry with low-valent iron, cobalt and nickel complexes.

    Science.gov (United States)

    Zhu, Gengyu; Li, Xiaoyan; Xu, Guoqiang; Wang, Lin; Sun, Hongjian

    2014-06-21

    A new PC(sp(3))P ligand N,N'-bis(diphenylphosphino)dipyrromethane [PCH2P] (1) was prepared and its iron, cobalt and nickel chemistry was explored. Two pincer-type complexes [PCHP]Fe(H)(PMe3)2 (2) and [PCHP]Co(PMe3)2 (4) were synthesized in the reaction of with Fe(PMe3)4 and Co(Me)(PMe3)4. 1 reacted with Co(PMe3)4 and Ni(PMe3)4 to afford Co(0) and Ni(0) complexes [PCH2P]Co(PMe3)2 (3) and [PCH2P]Ni(PMe3)2 (5). The structures of complexes 2-5 were determined by X-ray diffraction.

  19. Steady-State Spectroscopic Analysis of Proton-Dependent Electron Transfer on Pyrazine-Appended Metal Dithiolenes [Ni(pdt)2], [Pd(pdt)2], and [Pt(pdt)2] (pdt = 2,3-Pyrazinedithiol).

    Science.gov (United States)

    Kennedy, Steven R; Kozar, Morgan N; Yennawar, Hemant P; Lear, Benjamin J

    2016-09-06

    We report the structural, electronic, and acid/base properties of a series of ML2 metal dithiolene complexes, where M = Ni, Pd, Pt and L = 2,3-pyrazinedithiol. These complexes are non-innocent and possess strong electronic coupling between ligands across the metal center. The electronic coupling can be readily quantified in the monoanionic mixed valence state using Marcus-Hush theory. Analysis of the intervalence charge transfer (IVCT) band reveals that that electronic coupling in the mixed valence state is 5800, 4500, and 5700 cm(-1) for the Ni, Pd, and Pt complexes, respectively. We then focus on their response to acid titration in the mixed valence state, which generates the asymmetrically protonated mixed valence mixed protonated state. For all three complexes, protonation results in severe attenuation of the electronic coupling, as measured by the IVCT band. We find nearly 5-fold decreases in electronic coupling for both Ni and Pt, while, for the Pd complex, the electronic coupling is reduced to the point that the IVCT band is no longer observable. We ascribe the reduction in electronic coupling to charge pinning induced by asymmetric protonation. The more severe reduction in coupling for the Pd complex is a result of greater energetic mismatch between ligand and metal orbitals, reflected in the smaller electronic coupling for the pure mixed valence state. This work demonstrates that the bridging metal center can be used to tune the electronic coupling in both the mixed valence and mixed valence mixed protonated states, as well as the magnitude of change of the electronic coupling that accompanies changes in protonation state.

  20. Electron spin-relaxation via vibronic level of nickel (I) and nickel (III) cyanide complexes in NaCl single crystals.

    Science.gov (United States)

    Vugman, N V; de Araújo, M B; Pinhal, N M; Magon, C J; da Costa Filho, A J

    2004-05-01

    Electron spin-lattice relaxation rates for the low spin [Ni(CN)(4)](1-) and [Ni(CN)(4)](3-) complexes in NaCl host lattice were measured by the inversion recovery technique in the temperature range 7-50K. The data for both paramagnetic species fit very well to a relaxation process involving localized anharmonic vibration modes, also responsible for the g-tensor temperature dependence.

  1. Application of surface complexation modelling: Nickel sorption on quartz, manganese oxide, kaolinite and goethite, and thorium on silica

    International Nuclear Information System (INIS)

    Olin, M.; Lehikoinen, J.

    1997-12-01

    The study is a follow-up to a previous modelling task on mechanistic sorption. The experimental work has been carried out at the Laboratory of Radiochemistry, University of Helsinki (HYRL), and the sorption modelling was performed using the HYDRAQL code. Parameters taken from the open literature were employed in the modelling phase. The thermodynamic data for aqueous solutions were extracted from the EQ3/6 database and subsequently modified for HYDRAQL where necessary. The experimental data were obtained from five different experiments, four of which concerned the adsorption of nickel. The first experimental system was a mixture of Nilsiae quartz and manganese dioxide. In the second experiment, quartz was equilibrated with a fresh and saline groundwater simulant instead of an electrolyte solution. The third and fourth experiments dealt with nickel adsorption from an electrolyte solution onto goethite and kaolinite surfaces respectively. In the fifth experiment, adsorption of thorium onto a quartz surface was investigated

  2. Biological Active Cobalt(II and Nickel(II Complexes of 12-Membered Hexaaza [N6] Macrocyclic Ligand Synthetic and Spectroscopic Aspects

    Directory of Open Access Journals (Sweden)

    Umendra Kumar

    2010-01-01

    Full Text Available New cobalt(II and nickel(II complexes of 12-membered macrocyclic Schiff - base ligand containing thiosemicarbazone moiety as a part of ring have been prepared having general composition [MLX2] where M = Co(II or Ni(II, L=3,4,9,10–tetra-2-furanyl-1,2,5,6,8,11- hexaazacyclododeca-7,12- dithione - 2,4,8,10 – tetraene, X = Cl-, NO3-, NCS-. The complexes have been characterized by elemental analysis, molar conductance, magnetic susceptibility measurements, spectral (IR, electronic, EPR techniques and thermal analysis. Spectroscopic studies suggested a six coordinated octahedral geometry for all the complexes. The IR spectra of complexes suggest that ligand is coordinated to the metal ion through its four imines nitrogen. Conductivity measurements supported the non electrolytic nature of the complexes. The antifungal activities of complexes have been studied against a number of pathogenic fungi under laboratory conditions. The complexes showed good antifungal results. Thermal analysis of reported complexes suggests the absence of water molecule either in or outside the coordination sphere.

  3. Synthesis of cis - and trans-diisothiocyanato-bis(NHC) complexes of nickel(II) and applications in the Kumada-Corriu reaction

    KAUST Repository

    Jothibasu, Ramasamy

    2010-09-13

    Metathetical reaction of AgSCN with a series of trans-dihalido-bis(carbene) nickel(II) complexes in CH3CN readily afforded the novel diisothiocyanato-bis(carbene) complexes [Ni(NCS)2(NHC)2] (trans-2a, NHC = 1,3-diisopropylbenzimidazolin-2-ylidene; trans-2b, NHC = 1,3-diisobutylbenzimidazolin-2-ylidene; trans-2c, NHC = 1,3- dibenzylbenzimidazolin-2-ylidene; cis-2d, NHC = 1,3-di(2-propenyl) benzimidazolin-2-ylidene; cis-2e, NHC = 1-propyl-3-methylbenzimidazolin-2- ylidene) as greenish-yellow powders in moderate to good yields. While dihalido-bis(carbene) Ni(II) complexes exclusively form trans-complexes, a trans-cis isomerization occurs upon halido-isothiocyanato exchange with complexes bearing less bulky carbene ligands, i.e., cis-2d/e. DFT calculations indicated that this isomerization can be attributed to a reduced energy difference between trans- and cis-isomers of diisothiocyanato complexes. All complexes have been characterized by multinuclear NMR spectroscopy, ESI mass spectrometry, and X-ray diffraction analysis. A catalytic study revealed that cis-complexes generally exhibit greater activities in the Kumada-Corriu coupling reaction. © 2010 American Chemical Society.

  4. Directed synthesis of a heterobimetallic complex based on a novel unsymmetric double-Schiff-base ligand: preparation, characterization, reactivity and structures of hetero- and homobimetallic nickel(II) and zinc(II) complexes.

    Science.gov (United States)

    Roth, Arne; Buchholz, Axel; Rudolph, Manfred; Schütze, Eileen; Kothe, Erika; Plass, Winfried

    2008-01-01

    A series of bimetallic zinc(II) and nickel(II) complexes based on the novel dinucleating unsymmetric double-Schiff-base ligand benzoic acid [1-(3-{[2-(bispyridin-2-ylmethylamino)ethylimino]methyl}-2-hydroxy-5-methylphenyl)methylidene]hydrazide (H(2)bpampbh) has been synthesized and structurally characterized. The metal centers reside in two entirely different binding pockets provided by the ligand H(2)bpampbh, a planar tridentate [ONO] and a pentadentate [ON(4)] compartment. The utilized ligand H(2)bpampbh has been synthesized by condensation of the single-Schiff-base proligand Hbpahmb with benzoic acid hydrazide. The reaction of H(2)bpampbh with two equivalents of either zinc(II) or nickel(II) acetate yields the homobimetallic complexes [Zn(2)(bpampbh)(mu,eta(1)-OAc)(eta(1)-OAc)] (ZnZn) and [Ni(2)(bpampbh)(mu-H(2)O)(eta(1)-OAc)(H(2)O)](OAc) (NiNi), respectively. Simultaneous presence of one equivalent zinc(II) and one equivalent nickel(II) acetate results in the directed formation of the heterobimetallic complex [NiZn(bpampbh)(mu,eta(1)-OAc)(eta(1)-OAc)] (NiZn) with a selective binding of the nickel ions in the pentadentate ligand compartment. In addition, two homobimetallic azide-bridged complexes [Ni(2)(bpampbh)(mu,eta(1)-N(3))]ClO(4) (NiNi(N(3))) and [Ni(2)(bpampbh)(mu,eta(1)-N(3))(MeOH)(2)](ClO(4))(0.5)(N(3))(0.5) (NiNi(N(3))(MeOH)(2)) were synthesized. In all complexes, the metal ions residing in the pentadentate compartment adopt a distorted octahedral coordination geometry, whereas the metal centers placed in the tridentate compartment vary in coordination number and geometry from square-planar (NiNi(N(3))) and square-pyramidal (ZnZn and NiZn), to octahedral (NiNi and NiNi(N(3))(MeOH)(2)). In the case of complex NiNi(N(3)) this leads to a mixed-spin homodinuclear nickel(II) complex. All compounds have been characterized by means of mass spectrometry as well as IR and UV/Vis spectroscopies. Magnetic susceptibility measurements show significant zero

  5. Nickel allergy

    DEFF Research Database (Denmark)

    Fischer, L A; Johansen, J D; Menné, T

    2007-01-01

    BACKGROUND: The frequency of nickel allergy varies between different population groups. Exposure regulation has proven effective in decreasing the frequency. Experimental studies with other allergens have shown a significant relation between patch test reactivity and repeated open application test...... (ROAT) reactivity. OBJECTIVES: This study was aimed at determining the elicitation threshold in nickel-allergic individuals in a patch test and a ROAT, and comparing the threshold from these two test methods. METHODS: Twenty nickel-allergic persons were tested with a dilution series of 19 concentrations...... in a patch test and a dilution series of three concentrations in a ROAT, with duration of up to 21 days. Eighteen persons with no nickel allergy were included as control group for the ROAT. RESULTS: The predicted dose which will elicit a reaction in 10% of allergic individuals was calculated to be 0...

  6. Nickel(II) Complex of Polyhydroxybenzaldehyde N4-Thiosemicarbazone Exhibits Anti-Inflammatory Activity by Inhibiting NF-κB Transactivation

    Science.gov (United States)

    Loh, Sheng Wei; Looi, Chung Yeng; Hassandarvish, Pouya; Phan, Alicia Yi Ling; Wong, Won Fen; Wang, Hao; Paterson, Ian C.; Ea, Chee Kwee; Mustafa, Mohd Rais; Maah, Mohd Jamil

    2014-01-01

    Background The biological properties of thiosemicarbazone have been widely reported. The incorporation of some transition metals such as Fe, Ni and Cu to thiosemicarbazone complexes is known to enhance its biological effects. In this study, we incorporated nickel(II) ions into thiosemicarbazone with N4-substitution groups H3L (H; H3L1, CH3; H3L2, C6H5; H3L3 and C2H5; H3L4) and examined its potential anti-inflammatory activity. Methodology/Principal Findings Four ligands (1–4) and their respective nickel-containing complexes (5–8) were synthesized and characterized. The compounds synthesized were tested for their effects on NF-κB nuclear translocation, pro-inflammatory cytokines secretion and NF-κB transactivation activity. The active compound was further evaluated on its ability to suppress carrageenan-induced acute inflammation in vivo. A potential binding target of the active compound was also predicted by molecular docking analysis. Conclusions/Significance Among all synthesized compounds tested, we found that complex [Ni(H2L1)(PPh3)]Cl (5) (complex 5), potently inhibited IκBα degradation and NF-κB p65 nuclear translocation in LPS-stimulated RAW264.7 cells as well as TNFα-stimulated HeLa S3 cells. In addition, complex 5 significantly down-regulated LPS- or TNFα-induced transcription of NF-κB target genes, including genes that encode the pro-inflammatory cytokines TNFα, IFNβ and IL6. Luciferase reporter assays confirmed that complex 5 inhibited the transactivation activity of NF-κB. Furthermore, the anti-inflammatory effect of complex 5 was also supported by its suppressive effect on carrageenan-induced paw edema formation in wild type C57BL/6 mice. Interestingly, molecular docking study showed that complex 5 potentially interact with the active site of IKKβ. Taken together, we suggest complex 5 as a novel NF-κB inhibitor with potent anti-inflammatory effects. PMID:24977407

  7. Electronic structure of the [tris(dithiolene)chromium](z) (z = 0, 1-, 2-, 3-) electron transfer series and their manganese(IV) analogues. An X-ray absorption spectroscopic and density functional theoretical study.

    Science.gov (United States)

    Banerjee, Priyabrata; Sproules, Stephen; Weyhermüller, Thomas; Debeer George, Serena; Wieghardt, Karl

    2009-07-06

    From the reaction mixture of 3,6-dichlorobenzene-1,2-dithiol, H(2)(Cl(2)-bdt), [CrCl(3)(thf)(3)], and NEt(3) in tetrahydrofuran (thf) in the presence of air, dark green crystals of [N(n-Bu)(4)](2)[Cr(Cl(2)-bdt)(3)] (S = 1) (1) were isolated upon addition of [N(n-Bu)(4)]Br. Oxidation of the AsPh(4)(+) salt of 1 with [Fc]PF(6) yielded microcrystals of [AsPh(4)][Cr(Cl(2)-bdt)(3)] (S = (1)/(2)) (2) whereas the reduction of 1 with sodium amalgam produced light green crystals of [N-(n-Bu)(4)](3)[Cr(Cl(2)-bdt)(3)].thf (S = (3)/(2)) (3). The corresponding maleonitriledithiolato complexes [PPh(4)](2)[Cr(mnt)(3)] (S = 1) (4) and [PPh(4)](3)[Cr(mnt)(3)] (S = (3)/(2)) (5) have been synthesized. Isoelectronic manganese complexes of 3 and 5, namely, [NEt(4)](2)[Mn(Cl(2)-bdt)(3)] (S = (3)/(2)) (6) and [PPh(4)](2)[Mn(mnt)(3)] (S = (3)/(2)) (7), have also been prepared. Complexes 1, 6, and 7 have been characterized by single crystal X-ray crystallography. Complexes 1-7 have been electrochemically studied and their UV-vis and electron paramagnetic resonance spectra (EPR) have been recorded; magnetic properties have been elucidated by temperature-dependent susceptibility measurements. It is shown by chromium K-edge and sulfur K-edge X-ray absorption spectroscopy (XAS) that the oxidation state of the central Cr ion in each compound is the same (+III, d(3)) and that all one-electron redox processes are ligand-based, involving one, two, or three ligand pi radical monoanions. Complexes 6 and 7 possess a Mn(IV) ion with three dianionic ligands. The results have been corroborated by broken symmetry (BS) density functional theoretical (DFT) calculations by using the B3LYP functional. Time-dependent DFT calculations have been performed to calculate the metal and sulfur K-pre-edges. It is suggested that the neutral complexes [Cr(dithiolene)(3)](0) S = 0 possess octahedral rather than trigonal prismatic CrS(6) polyhedra. Three ligand pi radicals (S(rad) = (1)/(2)) couple antiferromagnetically

  8. A glassy carbon electrode modified with a nickel(II) norcorrole complex and carbon nanotubes for simultaneous or individual determination of ascorbic acid, dopamine, and uric acid

    International Nuclear Information System (INIS)

    Deng, Keqin; Li, Xiaofang; Huang, Haowen

    2016-01-01

    The authors report on the synthesis of a hybrid material consisting of the porphyrinoid metal complex nickel(II) norcorrole that was noncovalently bound to carbon nanotubes (CNT-NiNC). The hybrid was characterized by UV–vis, FTIR spectroscopy, and thermogravimetric analysis. The CNT-NiNC hybrid possesses high catalytic activity and selectivity toward the oxidation of ascorbic acid, dopamine, and uric acid. It was used to modify a glassy carbon electrode which then is shown to enable simultaneous or individual determination of ascorbic acid (AA), dopamine (DA), and uric acid (UA) at pH 6.5 and typical working potentials of −70, 200 and 380 mV (vs. SCE). The detection limits (at an SNR of 3) are 2.0 μM for AA, 0.1 μM for DA, and 0.4 μM for UA. (author)

  9. Effect of substituents on prediction of TLC retention of tetra-dentate Schiff bases and their Copper(II) and Nickel(II) complexes.

    Science.gov (United States)

    Stevanović, Nikola R; Perušković, Danica S; Gašić, Uroš M; Antunović, Vesna R; Lolić, Aleksandar Đ; Baošić, Rada M

    2017-03-01

    The objectives of this study were to gain insights into structure-retention relationships and to propose the model to estimating their retention. Chromatographic investigation of series of 36 Schiff bases and their copper(II) and nickel(II) complexes was performed under both normal- and reverse-phase conditions. Chemical structures of the compounds were characterized by molecular descriptors which are calculated from the structure and related to the chromatographic retention parameters by multiple linear regression analysis. Effects of chelation on retention parameters of investigated compounds, under normal- and reverse-phase chromatographic conditions, were analyzed by principal component analysis, quantitative structure-retention relationship and quantitative structure-activity relationship models were developed on the basis of theoretical molecular descriptors, calculated exclusively from molecular structure, and parameters of retention and lipophilicity. Copyright © 2016 John Wiley & Sons, Ltd.

  10. Copper(II), cobalt(II), nickel(II) and zinc(II) complexes of Schiff base ...

    Indian Academy of Sciences (India)

    Unknown

    metal (II) complexes with Schiff bases, in the pre- sent paper we report the synthesis and characteriza- tion of Cu(II), Co(II), Ni(II) and Zn(II) complexes of Schiff base derived from the condensation of benzil-2,4-dinitrophenylhydrazone with aniline. The proposed structure of the complexes is shown in chart 1. 2. Experimental.

  11. Radiosensitization by nickel lapachol.

    Science.gov (United States)

    Skov, K A; Adomat, H; Farrell, N P

    1993-12-01

    The properties of interest in the radiosensitization of a metal complex, nickel lapachol, are compared with those of the 2-nitroimidazole, misonidazole. These very different compounds were found to be surprisingly similar in terms of their reduction potential (-370 mV), enhancement ratios for killing of hypoxic Chinese hamster ovary cells by X-irradiation, and enhancement of DNA breaks in hypoxia. For nitroimidazoles, the sensitization depends on 'electron affinity', reduction of the nitro group; for nickel lapachol it is the metal which is necessary for reduction, yet the sensitization efficiencies are remarkably close. However, the metal complex has additional activities (some sensitization in aerobic cells; increased sensitization with preincubation) which are as yet unexplained but are assumed to be related to the nature of the naphthoquinone ligand, rather than to the reduction of the metal.

  12. Radiosensitization by nickel lapachol

    Energy Technology Data Exchange (ETDEWEB)

    Skov, K.A.; Adomat, H. (B.C. Cancer Research Centre, Vancouver, BC (Canada)); Farrell, N.P. (Vermont Univ., Burlington, VT (United States). Dept. of Chemistry)

    1993-12-01

    The properties of interest in the radiosensitization of a metal complex, nickel lapachol, are compared with those of the 2-nitroimidazole, misonidazole. These very different compounds were found to be surprisingly similar in terms of their reduction potential (-370 mV), enhancement ratios for killing of hypoxic Chinese hamster ovary cells by X-irradiation, and enhancement of DNA breaks in hypoxia. For nitroimidazoles, the sensitization depends on 'electron affinity', reduction of the nitro group; for nickel lapachol it is the metal which is necessary for reduction, yet the sensitization efficiencies are remarkably close. However, the metal complex has additional activities (some sensitization in aerobic cells; increased sensitization with preincubation) which are as yet unexplained but are assumed to be related to the nature of the naphthoquinone ligand, rather than to the reduction of the metal. (Author).

  13. Biomonitoring of humans exposed to arsenic, chromium, nickel, vanadium, and complex mixtures of metals by using the micronucleus test in lymphocytes.

    Science.gov (United States)

    Annangi, Balasubramanyam; Bonassi, Stefano; Marcos, Ricard; Hernández, Alba

    Various metals have demonstrated genotoxic and carcinogenic potential via different mechanisms. Until now, biomonitoring and epidemiological studies have been carried out to assess the genotoxic risk to exposed human populations. In this sense, the use of the micronucleus assay in peripheral blood lymphocytes has proven to be a useful tool to determine increased levels of DNA damage, as a surrogate biomarker of cancer risk. Here we review those biomonitoring studies focused on people exposed to arsenic, chromium, nickel, vanadium and complex mixtures of metals. Only those studies that used the frequency of micronuclei in binucleated (BNMN) cells have been taken into consideration, although the inclusion of other biomarkers of exposure and genotoxicity are also reflected and discussed. Regarding arsenic, most of the occupational and environmental biomonitoring studies find an increase in BNMN among the exposed individuals. Thus, it seems conclusive that arsenic exposure increases the risk of exposed human populations. However, a lack of correlation between the level of exposure and the increase in BNMN is also common, and a limited number of studies evaluated the genotype as a risk modulator. As for chromium, a BNMN increase in occupationally exposed subjects and a correlation between level of exposure and effect is found consistently in the available literature. However, the quality score of the studies is only medium-low. On the other hand, the studies evaluating nickel and vanadium are scarce and lacks a correct characterization of the individual exposure, which difficult the building of clear conclusions. Finally, several studies with medium-high quality scores evaluated a more realistic scenario of exposure which takes into account a mixture of metals. Among them, those which correctly characterized and measured the exposure were able to find association with the level of BNMN. Also, several genes associated with DNA damage repair such as OGG1 and XRCC1 were

  14. Visible-light photoredox catalysis: selective reduction of carbon dioxide to carbon monoxide by a nickel N-heterocyclic carbene-isoquinoline complex.

    Science.gov (United States)

    Thoi, V Sara; Kornienko, Nikolay; Margarit, Charles G; Yang, Peidong; Chang, Christopher J

    2013-09-25

    The solar-driven reduction of carbon dioxide to value-added chemical fuels is a longstanding challenge in the fields of catalysis, energy science, and green chemistry. In order to develop effective CO2 fixation, several key considerations must be balanced, including (1) catalyst selectivity for promoting CO2 reduction over competing hydrogen generation from proton reduction, (2) visible-light harvesting that matches the solar spectrum, and (3) the use of cheap and earth-abundant catalytic components. In this report, we present the synthesis and characterization of a new family of earth-abundant nickel complexes supported by N-heterocyclic carbene-amine ligands that exhibit high selectivity and activity for the electrocatalytic and photocatalytic conversion of CO2 to CO. Systematic changes in the carbene and amine donors of the ligand have been surveyed, and [Ni((Pr)bimiq1)](2+) (1c, where (Pr)bimiq1 = bis(3-(imidazolyl)isoquinolinyl)propane) emerges as a catalyst for electrochemical reduction of CO2 with the lowest cathodic onset potential (E(cat) = -1.2 V vs SCE). Using this earth-abundant catalyst with Ir(ppy)3 (where ppy = 2-phenylpyridine) and an electron donor, we have developed a visible-light photoredox system for the catalytic conversion of CO2 to CO that proceeds with high selectivity and activity and achieves turnover numbers and turnover frequencies reaching 98,000 and 3.9 s(-1), respectively. Further studies reveal that the overall efficiency of this solar-to-fuel cycle may be limited by the formation of the active Ni catalyst and/or the chemical reduction of CO2 to CO at the reduced nickel center and provide a starting point for improved photoredox systems for sustainable carbon-neutral energy conversion.

  15. Visible-Light Photoredox Catalysis: Selective Reduction of Carbon Dioxide to Carbon Monoxide by a Nickel N-Heterocyclic Carbene-Isoquinoline Complex

    Energy Technology Data Exchange (ETDEWEB)

    Thoi, VanSara; Kornienko, Nick; Margarit, C; Yang, Peidong; Chang, Christopher

    2013-06-07

    The solar-driven reduction of carbon dioxide to value-added chemical fuels is a longstanding challenge in the fields of catalysis, energy science, and green chemistry. In order to develop effective CO2 fixation, several key considerations must be balanced, including (1) catalyst selectivity for promoting CO2 reduction over competing hydrogen generation from proton reduction, (2) visible-light harvesting that matches the solar spectrum, and (3) the use of cheap and earth-abundant catalytic components. In this report, we present the synthesis and characterization of a new family of earth-abundant nickel complexes supported by N-heterocyclic carbene amine ligands that exhibit high selectivity and activity for the electrocatalytic and photocatalytic conversion of CO2 to CO. Systematic changes in the carbene and amine donors of the ligand have been surveyed, and [Ni(Prbimiq1)]2+ (1c, where Prbimiq1 = bis(3-(imidazolyl)isoquinolinyl)propane) emerges as a catalyst for electrochemical reduction of CO2 with the lowest cathodic onset potential (Ecat = 1.2 V vs SCE). Using this earth-abundant catalyst with Ir(ppy)3 (where ppy = 2-phenylpyridine) and an electron donor, we have developed a visible-light photoredox system for the catalytic conversion of CO2 to CO that proceeds with high selectivity and activity and achieves turnover numbers and turnover frequencies reaching 98,000 and 3.9 s1, respectively. Further studies reveal that the overall efficiency of this solar-to-fuel cycle may be limited by the formation of the active Ni catalyst and/or the chemical reduction of CO2 to CO at the reduced nickel center and provide a starting point for improved photoredox systems for sustainable carbon-neutral energy conversion.

  16. Half-metallicity of a kagome spin lattice: the case of a manganese bis-dithiolene monolayer

    Science.gov (United States)

    Zhao, Mingwen; Wang, Aizhu; Zhang, Xiaoming

    2013-10-01

    The spin ordering in kagome lattices has long been studied in the search for real materials with a spin-liquid ground state. The synthesis of a nickel bis-dichiolene complex (Ni3C12S12) nanosheet (T. Kambe et al., J. Am. Chem. Soc., 2013, 135, 2462) paved a way for realizing real two-dimensional kagome lattices. Using first-principles calculations, we predicted that a ferromagnetic kagome spin lattice with S = 3/2 on lattice vertices can be achieved in an Mn3C12S12 monolayer formed by substituting Ni with Mn atoms in nonmagnetic Ni3C12S12. Monte Carlo simulations on the basis of the Ising model suggest that it has a Curie temperature of about 212 K. A ferromagnetic Mn3C12S12 monolayer is half metallic with high carrier mobility in one spin channel and a band gap of 1.54 eV in another spin channel, which is quite promising for spintronic device applications. Additionally, a small band gap opens up at the Dirac point of the kagome bands due to the spin-orbital coupling effects, which may be implementable for achieving a quantum anomalous Hall effect.

  17. Does airborne nickel exposure induce nickel sensitization?

    Science.gov (United States)

    Mann, Eugen; Ranft, Ulrich; Eberwein, Georg; Gladtke, Dieter; Sugiri, Dorothee; Behrendt, Heidrun; Ring, Johannes; Schäfer, Torsten; Begerow, Jutta; Wittsiepe, Jürgen; Krämer, Ursula; Wilhelm, Michael

    2010-06-01

    Nickel is one of the most prevalent causes of contact allergy in the general population. This study focuses on human exposure to airborne nickel and its potential to induce allergic sensitization. The study group consisted of 309 children at school-starter age living in the West of Germany in the vicinity of two industrial sources and in a rural town without nearby point sources of nickel. An exposure assessment of nickel in ambient air was available for children in the Ruhr district using routinely monitored ambient air quality data and dispersion modelling. Internal nickel exposure was assessed by nickel concentrations in morning urine samples of the children. The observed nickel sensitization prevalence rates varied between 12.6% and 30.7%. Statistically significant associations were showed between exposure to nickel in ambient air and urinary nickel concentration as well as between urinary nickel concentration and nickel sensitization. Furthermore, an elevated prevalence of nickel sensitization was associated with exposure to increased nickel concentrations in ambient air. The observed associations support the assumption that inhaled nickel in ambient air might be a risk factor for nickel sensitization; further studies in larger collectives are necessary.

  18. Nickel allergy and orthodontics.

    Science.gov (United States)

    Rahilly, G; Price, N

    2003-06-01

    Nickel is the most common metal to cause contact dermatitis in orthodontics. Nickel-containing metal alloys, such as nickel-titanium and stainless steel, are widely used in orthodontic appliances. Nickel-titanium alloys may have nickel content in excess of 50 per cent and can thus potentially release enough nickel in the oral environment to elicit manifestations of an allergic reaction. Stainless steel has a lower nickel content (8 per cent). However, because the nickel is bound in a crystal lattice it is not available to react. Stainless steel orthodontic components are therefore very unlikely to cause nickel hypersensitivity. This article discusses the diagnosis of nickel allergy in orthodontics and describes alternative products that are nickel free or have a very low nickel content, which would be appropriate to use in patients diagnosed with a nickel allergy.

  19. Mesoporous silica nanoparticles supported copper(II) and nickel(II) Schiff base complexes: Synthesis, characterization, antibacterial activity and enzyme immobilization

    Science.gov (United States)

    Tahmasbi, Leila; Sedaghat, Tahereh; Motamedi, Hossein; Kooti, Mohammad

    2018-02-01

    Mesoporous silica nanoparticles (MSNs) were prepared by sol-gel method and functionalized with 3-aminopropyltriethoxysilane. Schiff base grafted mesoporous silica nanoparticle was synthesized by the condensation of 2-hydroxy-3-methoxybenzaldehyde and amine-functionalized MSNs. The latter material was then treated with Cu(II) and Ni(II) salts separately to obtain copper and nickel complexes anchored mesoporous composites. The newly prepared hybrid organic-inorganic nanocomposites have been characterized by several techniques such as FT-IR, LA-XRD, FE-SEM, TEM, EDS, BET and TGA. The results showed all samples have MCM-41 type ordered mesoporous structure and functionalization occurs mainly inside the mesopore channel. The presence of all elements in synthesized nanocomposites and the coordination of Schiff base via imine nitrogen and phenolate oxygen were confirmed. MSNs and all functionalized MSNs have uniform spherical nanoparticles with a mean diameter less than 100 nm. The as-synthesized mesoporous nanocomposites were investigated for antibacterial activity against Gram-positive (B. subtilis and S. aureus) and Gram-negative (E. coli and P. aeruginosa) bacteria, as carrier for gentamicin and also for immobilization of DNase, coagulase and amylase enzymes. MSN-SB-Ni indicated bacteriocidal effect against S.aureus and all compounds were found to be good carrier for gentamicin. Results of enzyme immobilization for DNase and coagulase and α-amylase revealed that supported metal complexes efficiently immobilized enzymes.

  20. Zinc, copper and nickel complexes of a macrocycle synthesized from pyridinedicarboxylic acid: A spectroscopic, thermal and theoretical study

    Directory of Open Access Journals (Sweden)

    Soleimani Esmaiel

    2017-01-01

    Full Text Available The metal(II ion complexes of a pentadentate macrocycle 1, namely 3,12-dioxa-6,9,18-triazabicyclo[12.3.1]octadeca-1(18,14,16-triene-2,13-dione are synthesized. This macrocycle is prepared from the reaction of dipotassium salt of 2,6-pyridinedicarboxylic acid with ethylenediamine and 1,2-dibromoethane. The reaction of 1 (L in methanol with MCl2.xH2O gave complexes with the general formula [M(LCl2] (where M= Ni(II 2, Cu(II 3 and Zn(II 4, respectively. The analysis of IR, 1H- and 13C-NMR spectral data of all complexes propose that 1 is bonded to metal(II ions through a nitrogen atom of pyridine ring, two nitrogen atoms of amine groups and two oxygen atoms of ester moieties. The thermal analysis indicated that there are no water molecules of hydration or coordinated in the structure of the complexes. Among these complexes, the Cu(II 3 complex demonstrated good antibacterial and antifungal activities. The molecular geometry, AIM atomic charge and frontier molecular orbitals of the compounds are investigated theoretically using DFT method. Based on the theoretical data of these complexes represented, a bipyramidal pentagonal arrangement can be envisaged in such a way that the N3O2 pentadentate donor sites form the planar pentagonal base of the bipyramid and the two Cl atoms occupy the vertexes.

  1. The impact of industrial emissions of copper-nickel smelter complex on the status of populations and communities of small mammals in the Kola Peninsula

    Directory of Open Access Journals (Sweden)

    Gennadiy D. Kataev

    2017-08-01

    Full Text Available The population status of the small mammals, Micromammalia, was studied in the central mountain and taiga part of the Kola Peninsula in the Lapland Biosphere Reserve and its buffer zone. For this purpose, control groups of animals were selected at a different distance from the Severonikel' industrial complex which is considered as the largest metallurgical company in Europe. It produces nickel, copper and other non-ferrous metals. The study sites were located at 4–30 km from the local source of industrial pollution. The analysis of population dynamics, faunistic structure and biological parameters of mass species of Soricidae, Myomorpha has revealed the differences in habitats depending on the distance to the industrial complex. The results of the chemical analysis of organs and tissue samples of small rodents, their morpho-physiological and genetic characteristics within emission plume were analysed. The abundance of the studied Mammalia species was the lowest at 5 km north and 7 km south of the metallurgical industrial complex. According to our results, animals in a zone of increased industrial emission (sulfur dioxide, compounds of heavy metals concentrations had more deviations from the biological norms in comparison with the same species from less polluted areas. Long-term (1936–2014 abundance dynamics of Clethrionomys glareolus was presented due to the new ecological situation in the region and reduction of the volume of sulfur dioxide emission by the Severonikel' industrial complex. This biotesting method using mammals as study objects may be applied for the definition of ecologically safe level criteria of heavy metal production and it may be used in studies of similar ecological situations.

  2. Nickel(II) complexes of pentadentate N5 ligands as catalysts for alkane hydroxylation by using m-CPBA as oxidant: a combined experimental and computational study.

    Science.gov (United States)

    Sankaralingam, Muniyandi; Balamurugan, Mani; Palaniandavar, Mallayan; Vadivelu, Prabha; Suresh, Cherumuttathu H

    2014-09-01

    A new family of nickel(II) complexes of the type [Ni(L)(CH(3)CN)](BPh(4))(2), where L=N-methyl-N,N',N'-tris(pyrid-2-ylmethyl)-ethylenediamine (L1, 1), N-benzyl-N,N',N'-tris(pyrid-2-yl-methyl)-ethylenediamine (L2, 2), N-methyl-N,N'-bis(pyrid-2-ylmethyl)-N'-(6-methyl-pyrid-2-yl-methyl)-ethylenediamine (L3, 3), N-methyl-N,N'-bis(pyrid-2-ylmethyl)-N'-(quinolin-2-ylmethyl)-ethylenediamine (L4, 4), and N-methyl-N,N'-bis(pyrid-2-ylmethyl)-N'-imidazole-2-ylmethyl)-ethylenediamine (L5, 5), has been isolated and characterized by means of elemental analysis, mass spectrometry, UV/Vis spectroscopy, and electrochemistry. The single-crystal X-ray structure of [Ni(L(3))(CH(3)CN)](BPh(4))(2) reveals that the nickel(II) center is located in a distorted octahedral coordination geometry constituted by all the five nitrogen atoms of the pentadentate ligand and an acetonitrile molecule. In a dichloromethane/acetonitrile solvent mixture, all the complexes show ligand field bands in the visible region characteristic of an octahedral coordination geometry. They exhibit a one-electron oxidation corresponding to the Ni(II) /Ni(III) redox couple the potential of which depends upon the ligand donor functionalities. The new complexes catalyze the oxidation of cyclohexane in the presence of m-CPBA as oxidant up to a turnover number of 530 with good alcohol selectivity (A/K, 7.1-10.6, A=alcohol, K=ketone). Upon replacing the pyridylmethyl arm in [Ni(L1)(CH(3)CN)](BPh(4))(2) by the strongly σ-bonding but weakly π-bonding imidazolylmethyl arm as in [Ni(L5)(CH(3)CN)](BPh(4))(2) or the sterically demanding 6-methylpyridylmethyl ([Ni(L3)(CH(3)CN)](BPh(4))(2) and the quinolylmethyl arms ([Ni(L4)(CH(3)CN)](BPh(4))(2), both the catalytic activity and the selectivity decrease. DFT studies performed on cyclohexane oxidation by complexes 1 and 5 demonstrate the two spin-state reactivity for the high-spin [(N5)Ni(II)-O(.)] intermediate (ts1(hs), ts2(doublet)), which has a low-spin state located closely in

  3. A study of fundamental reaction pathways for transition metal alkyl complexes. I. The reaction of a nickel methyl complex with alkynes. Ii. The mechanism of aldehyde formation in the reaction of a molybdenum hydride with molybdenum alkyls

    Energy Technology Data Exchange (ETDEWEB)

    Huggins, John Mitchell [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)

    1980-06-12

    I. This study reports the rapid reaction under mild conditions of internal or terminal alkynes with methyl (acetyl-acetonato) (triphenylphosphine) nickel (1) in either aromatic or ether solvents. In all cases vinylnickel products 2 are formed by insertion of the alkyne into the nickel=methyl bond. These complexes may be converted into a variety of organic products (e.g. alkenes, esters, vinyl halides) by treatment with appropriate reagents. Unsymmetrical alkynes give selectively the one regioisomer with the sterically largest substituent next to the nickel atom. In order to investigate the stereochemistry of the initial insertion, a x-ray diffraction study of the reaction of 1 with diphenylacetylene was carried out. This showed that the vinylnickel complex formed by overall trans insertion was the product of the reaction. Furthermore, subsequent slow isomerization of this complex, to a mixture of it and the corresponding cis isomer, demonstrated that this trans addition product is the kinetic product of the reaction. In studies with other alkynes, the product of trans addition was not always exclusively (or even predominantly) formed, but the ratio of the stereoisomers formed kinetically was substantially different from the thermodynamic ratio. Isotope labeling, added phosphine, and other experiments have allowed us to conclude that the mechanism of this reaction does involve initial cis addition. However, a coordinatively unsaturated vinylnickel complex is initially formed which can undergo rapid, phosphine-catalyzed cis-trans isomerization in competition with its conversion to the isolable phosphine-substituted kinetic reaction products. II. The reaction of CpMo(CO)3H (1a) with CpMo(CO)3R (2, R= CH3, C2H5) at 50°C in THF gives the aldehyde RCHO and the dimers [CpMo(CO)3]2 (3a) and [CpMo(CO)2]2 (4a). Labeling one of the reactants with a methylcyclopentadienyl ligand

  4. Color tuning of a nickel complex with a novel N2S2 pyridine-containing macrocyclic ligand.

    Science.gov (United States)

    Tamayo, Abel; Casabó, Jaume; Escriche, Lluis; Lodeiro, Carlos; Covelo, Berta; Brondino, Carlos D; Kivekäs, Raikko; Sillampää, Reijo

    2006-02-06

    The novel pyridine-containing 14-membered macrocycle 3,11-dithia-7,17-diazabicyclo[11.3.1]heptadeca-1(17),13,15-triene (L), which contains an N2S2 donor set, was synthesized, and its protonation behavior was studied by absorption titration with CH3SO3H. The reaction of L with Pd(II) was studied spectroscopically, and the square-planar complex [Pd(L)](BF4) was isolated and characterized. The reactions between L and NiX2 x 6 H2O (X = BF4, ClO4) in ethanol or acetonitrile afforded the octahedral complexes [Ni(CH3CN)(H2O)(L)](X)2 and [Ni(H2O)2(L)](X)2, respectively. The square-planar complexes [Ni(L)](X)2 were obtained by heating these octahedral complexes. Spectrophotometric titrations of [Ni(L)](BF4)2 were performed with neutral and negatively charged ligands. The color of nitromethane solutions of this square-planar complex turns from red to cyan, purple, blue, yellow-green, and pink following addition of halides, acetonitrile, water, pyridine, and 2,2'-bipyridine, respectively. X-ray structural analyses were carried out on the {[Ni(ClO4)(H2O)(L)][Ni(H2O)2(L)]}(ClO4)3, [Ni(CH3CN)(H2O)(L)](ClO4)2, [{Ni(L)}2(mu-Cl)2](ClO4)2, and [{Ni(L)}2(mu-Br)2]Br2 x 2 CH3NO2 complexes.

  5. Ion-exchange voltammetry of tris(2,2'-bipyridine) nickel(II), cobalt(II), and Co(salen) at polyestersulfonated ionomer coated electrodes in acetonitrile: Reactivity of the electrogenerated low-valent complexes

    International Nuclear Information System (INIS)

    Buriez, Olivier; Moretto, Ligia M.; Ugo, Paolo

    2006-01-01

    The electrochemical behaviour of [Ni(bpy) 3 (BF 4 ) 2 ], [Co(bpy) 3 (BF 4 ) 2 ], and Co(salen) (where bpy = 2,2'-bipyridine, and salen N,N'-bis(salicylidene)ethylenediamine) is studied at a glassy carbon electrode modified with the poly(estersulfonate) ionomer Eastman AQ 55 in acetonitrile (MeCN). It is shown that the nickel complex is strongly incorporated into the polymer. The reduction of the divalent nickel compound features a two-electron process leading to a nickel(0) species which is released from the coating because of the lack of electrostatic attraction with the ionomer. Yet, the neutral zerovalent nickel-bipyridine complex is reactive towards ethyl 4-iodobenzoate and di-bromocyclohexane despite the presence of the polymer. The activation of the aryl halide occurs through an oxidative addition, whereas, an electron transfer is involved in the presence of the alkyl halide making the catalyst regeneration much faster in the latter case. The electrochemical study of [Co(bpy) 3 (BF 4 ) 2 ] shows that incorporation of the cobalt complex into the polymer is efficient, provided excess bpy is used. This excess bpy does not interfere with the electrocatalytic activity of the cobalt complex incorporated in the AQ coating and efficient electrocatalysis is observed towards di-bromocyclohexane and benzyl-bromide as substrates. Finally, replacement of the bpy ligand with the macrocycle N,N'-bis(salicylidene)ethylenediamine, salen, leads to the incorporation of the non-charged Co II (salen) complex into the AQ 55 polymer showing the relevancy of hydrophobic interactions. The reaction between the electrogenerated [Co I (salen)] - with 1,2-dibromocyclohexane exhibits a fast inner sphere electron transfer

  6. Synthesis of nickel complexes with bidentate N,O-type ligands and application in the catalytic oligomerization of ethylene.

    Science.gov (United States)

    Kermagoret, Anthony; Braunstein, Pierre

    2008-03-28

    The dinuclear complexes [Ni(micro-Cl){(4,5-dihydro-4,4-dimethyloxazol-2-yl)methanol}](2)Cl(2) and [Ni(micro-Cl){(pyridin-2-yl)methanol}](2)Cl(2) 16 have been synthesized in high yields by reaction of NiCl(2) with 2 mol. equiv. of the ligands 4,5-dihydro-4,4-dimethyloxazol-2-yl)methanol 13 or (pyridin-2-yl)methanol 15, respectively. The reaction of NiCl(2) with 3 mol. equiv. of 15 afforded in high yield the mononuclear, octahedral mer-[Ni{(pyridin-2-yl)methanol}(3)Cl(2)] complex 18. The reaction of 16 with NaH led to the deprotonation of one of the pyridine alcohol ligands to form [Ni{(pyridin-2-yl)methanol}{(pyridin-2-yl)methanolate}Cl] 21 in which the metal is coordinated by one pyridine alcohol and one pyridine alcoholate ligand. The crystal structures of the dinuclear, chloride-bridged octahedral complexes in 14.C(6)H(12) and in 16.3CH(2)Cl(2) and of the mononuclear, octahedral complex 18 in 18.CH(2)Cl(2) have been determined by X-ray diffraction. In the latter case, intermolecular OH...Cl bonding interactions generate a centrosymmetric pseudo-dimer. Complexes 14, 16, and 21 have been tested in ethylene oligomerization with AlEtCl(2) (Al/Ni ratios of 2, 4 or 6) or MAO (50, 100 or 200 equiv.) as co-catalysts under 10 bar of ethylene and yielded mostly dimers and trimers. Complex 16 in the presence of 6 equiv. of AlEtCl(2) proved to be the most active system with a turnover frequency (TOF) up to 187 500 C(2)H(4) (mol Ni h)(-1). Complex 16 with 200 equiv. of MAO was also the most active, with TOF up to 104 300 C(2)H(4) (mol Ni h)(-1) under 30 bar of ethylene.

  7. Mixed-Ligand Nickel(II Complexes Containing Sulfathiazole and Cephalosporin Antibiotics: Synthesis, Characterization, and Antibacterial Activity

    Directory of Open Access Journals (Sweden)

    J. R. Anacona

    2012-01-01

    (L1,4, x=1; L2,3, x=0; L = monoanion of cefazolin HL1, cephalothin HL2, cefotaxime HL3, ceftriaxone HL4 and [Ni(L5(stz]Cl (cefepime L5, which were characterized by physicochemical and spectroscopic methods. Their spectra indicated that cephalosporins are acting as multidentate chelating agents, via the lactam carbonyl and carboxylate and N-azomoieties. The complexes are insoluble in water and common organic solvents but soluble in DMSO, where the [Ni(L5(stz]Cl complex is 1 : 1 electrolyte. They probably have polymeric structures. They have been screened for antibacterial activity, and the results are compared with the activity of commercial cephalosporins.

  8. A Facile Access to New Polymethylmethacrylate-Anchored Ferrocene Substituted Nickel(II) Unsymmetrical Schiff Base Complexes: Synthesis and Characterization.

    OpenAIRE

    Novoa , Néstor; Soto , Juan ,; Henríquez , Rodrigo; Manzur , Carolina; Carrillo , David; Hamon , Jean-René

    2013-01-01

    International audience; This paper discloses two new side-chain metallopolymers containing an unsymmetrical organometallic Schiff base complex of Ni(II) linked to a polymethylmethacrylate (PMMA) matrix. The neutral ferrocene substituted Schiff base complex 1, Ni{CpFe(η5-C5H4)-C(O)CH=C(CH3)N-o-C6H4N=CH-(2-O,5-OH-C6H3)} where (Cp = η5-C5H5), was synthesized via template reaction by condensation of the tridentate half-unit metalloligand Fc-C(O)CH=C(CH3)-N(H)-o-C6H4NH2 (Fc = ferrocenyl = CpFe(η5-...

  9. Synthesis and Characterization of Cu(II), Co(II) and Ni(II) Complexes of Trithiocyanuric Acid: The Structure of {N,N'-Bis(3-Aminopropyl)-1,3-Propanediamine}-(Trithiocyanurato)Nickel(II)

    Czech Academy of Sciences Publication Activity Database

    Kopel, P.; Trávníček, Zdeněk; Kvítek, L.; Černošek, Z.; Wrzeszcz, G.; Marek, J.

    2003-01-01

    Roč. 56, č. 1 (2003), s. 1-11 ISSN 0095-8972 R&D Projects: GA ČR GA203/00/0152; GA AV ČR IBS5038351 Institutional research plan: CEZ:AV0Z5038910 Keywords : Copper(II) * cobalt(II) and nickel(II) complexes * Trithiocyanuric acid Subject RIV: CE - Biochemistry Impact factor: 0.841, year: 2003

  10. Synthesis, crystallographic and spectral studies of homochiral cobalt(II) and nickel(II) complexes of a new terpyridylaminoacid ligand

    Science.gov (United States)

    Wang, Xing; Gao, Chang-Qing; Gao, Zhi-Yang; Wu, Ben-Lai; Niu, Yun-Yin

    2018-04-01

    Based on a chiral terpyridylaminoacid ligand, a series of homochiral Co(II) and Ni(II) complexes, namely, [Co(H2L)(HL)]·Cl·(PF6)2·2H2O (1), [Ni(H2L)(HL)]·Cl·(PF6)2 (2), [Co2(L)2(CH3OH)(H2O)]·(PF6)2·CH3OH (3), [Ni2(L)2(CH3OH)2]·(PF6)2·2CH3OH (4), [Co2(L)2(N3)2]·3H2O (5), and [Ni2(L)2(SCN)2]·4H2O (6) have been successfully synthesized and characterized by elemental analysis, TGA, spectroscopic methods (IR, CD and electronic absorption spectra) and single-crystal X-ray diffraction structural analysis (HL = (S)-2-((4-([2,2':6‧,2″-terpyridin]-4‧-yl)benzyl)amino)-4-methylpentanoic acid). In the acidic reaction conditions, one protonated (H2L)+ and one zwitterionic HL only used their terpyridyl groups to chelate one metal ion Co(II) or Ni(II), forming chiral mononuclear cationic complexes 1 or 2. But in the basic and hydro(solvo)thermal reaction conditions, deprotonated ligands (L)‒ acting as bridges used their terpyridyl and amino acid groups to link with two Co(II) or Ni(II) ions, fabricating chiral dinuclear metallocyclic complexes 3-6. Those chiral mononuclear and dinuclear complexes whose chirality originates in the homochiral ligand HL further self-assemble into higher-dimensional homochiral supramolecular frameworks through intermolecular hydrogen-bonding and π···π interactions. Notably, the coordination mode, hydrogen-bonding site, and existence form of HL ligand can be controlled by the protonation of its amino group, and the architectural diversity of those supramolecular frameworks is adjusted by pH and counter anions. Very interestingly, the 3D porous supramolecular frameworks built up from the huge chiral mononuclear cationic complexes 1 and 2 have novel helical layers only formed through every right-handed helical chain intertwining with two adjacent same helical chains, and the 2D supramolecular helicate 5 consists of two types of left-handed helical chains.

  11. Synthesis, characterization, crystal structure, superoxide dismutase and biological activities of nickel (II) complexes with bidentate ligands possessing N and O donor atoms

    Science.gov (United States)

    Sangeeta, S.; Ahmad, K.; Noorussabah, N.; Bharti, S.; Mishra, M. K.; Sharma, S. R.; Choudhary, M.

    2017-12-01

    Two new Schiff bases 2-((E)-(4-bromo-2-chlorophenylimino)methyl)-4-bromophenol(HL1) and1-((E)-(4-bromo-2-chlorophenylimino)methyl)naphthalene-2-ol (HL2) and their new nickel (II) complexes [Ni(L1)2]·DMF(1) and [Ni(L2)2] (2) have been synthesized and characterized by various physico- chemical and spectroscopic methods. The solid-state structures of synthesized compounds were determined by single crystal X-ray crystallography, which revealed square planar geometry around Ni (II) ion. Infrared spectra, UV-Vis, thermal analysis and magnetic susceptibility measurements agreed with the observed crystal structures. The ligand (HL1) crystallized in the Orthorhombic system of the space group Pbca,a = 7.5485(4)Å, b = 11.5514(5) Å, c = 30.1370(14)Å, α = 90°, β = 90°, γ = 90°and Z = 8. Complex[Ni(L1)2]·DMF(1) crystallized in the Triclinic system of the space group P-1, a = 8.9954(3) Å, b = 9.4593(4) Å, c = 13.2657(5) Å, α = 101.478°, β = 99.595°, γ = 117.651°and Z = 2, whereas complex [Ni(L2)2]·(2) crystallized in the Monoclinic system of the space group P21/c, a = 9.301(9)Å, b = 12.149(8)Å, c = 13.792(10)Å, α = 90°, β = 106.35(4).°, γ = 90°and Z = 2. The Schiff bases (HL1and HL2) behaved as monobasic bidentate ligands possessing N and O donor atoms. The SOD activities of HL1 and its Ni (II) complex[Ni(L1)2]·DMF(1) have been measured using xanthine-xanthine oxidase as a source of superoxide radical and NBT assay as O2- scavenger. In vitro antimicrobial activities of the Ni(II) complexes (1) and (2)against Bacillus cereus and Staphylococcus aureus as Gram + ve and Salmonella typhi, Klebsiella pneumonia and Escherichia coli as Gram-ve species have been investigated comparing with the Schiff base ligands (HL1and HL2).

  12. Human exposure to nickel.

    Science.gov (United States)

    Grandjean, P

    1984-01-01

    In order of abundance in the earth's crust, nickel ranks as the 24th element and has been detected in different media in all parts of the biosphere. Thus, humans are constantly exposed to this ubiquitous element, though in variable amounts. The average natural nickel exposure from food in the past has probably been somewhat, but not much, below current levels. Nickel is a useful metal, particularly in various alloys, in batteries and in nickel-plating. Nickel compounds are used especially as catalysts and pigments. In nickel-producing or nickel-using industries, about 0.2% of the work force may be exposed to considerable amounts of airborne nickel. In addition, nickel release, e.g., into cutting oils, and skin contact with nickel-containing or nickel-plated tools and other items may add to an occupational nickel hazard. Occupational exposures may lead to the retention of 100 micrograms of nickel per day. Environmental nickel levels depend particularly on natural sources, pollution from nickel-manufacturing industries and airborne particles from combustion of fossil fuels. Absorption from atmospheric nickel pollution is of minor concern. Vegetables usually contain more nickel than do other food items; high levels have been found in legumes, spinach, lettuce and nuts. Certain products, such as baking powder and cocoa powder, have been found to contain excessive amounts of nickel, perhaps related to nickel leaching during the manufacturing process. Soft drinking-water and acid beverages may dissolve nickel from pipes and containers. Leaching or corrosion processes may contribute significantly to the oral nickel intake, occasionally up to 1 mg/day. Scattered studies indicate a highly variable dietary intake of nickel, but most averages are about 200-300 micrograms/day. In addition, skin contact to a multitude of metal objects may be of significance to the large number of individuals suffering from contact dermatitis and nickel allergy. Finally, nickel alloys are often

  13. Enhancement of second hyperpolarizabilities in open-shell singlet slipped-stack dimers composed of square planar nickel complexes involving o-semiquinonato type ligands.

    Science.gov (United States)

    Fukui, Hitoshi; Shigeta, Yasuteru; Nakano, Masayoshi; Kubo, Takashi; Kamada, Kenji; Ohta, Koji; Champagne, Benoît; Botek, Edith

    2011-02-17

    Using the spin-unrestricted hybrid density functional theory method, we have investigated the intermolecular interaction effects on the longitudinal static second hyperpolarizability (γ) of open-shell singlet slipped-stack dimers composed of singlet diradical square planar nickel complexes involving o-semiquinonato type ligands, Ni(o-C(6)H(4)X(2))(2) (where X = O, NH, S, Se, PH). For comparison, we have also examined the γ values of a closed-shell singlet slipped-stack dimer composed of closed-shell monomers Ni[o-C(6)H(4)S(NH(2))](2). It is found that for interplanar distance ranging between 3.0 and 5.0 Å the slipped-stack dimers with intermediate monomer diradical characters exhibit larger γ values per monomer (γ(dimer)/2) than those with large monomer diradical characters or than the closed-shell dimer. These results extend the domain of validity of the relationship found between γ and the diradical character for individual molecules. It also turns out that the ratio R = (γ(dimer)/2)/γ(monomer) increases upon decreasing the interplanar distance and that this increase is larger for intermediate diradical character than for the other cases. These phenomena have been analyzed by considering the γ density distributions of the dimers, demonstrating a significant field-induced third-order charge transfer between the monomers in the case of intermediate diradical character. The present results indicate that open-shell singlet slipped-stack aggregates composed of monomers with intermediate diradical characters constitute another mean for achieving highly efficient and tunable third-order nonlinear optical materials.

  14. A Bimetallic Nickel–Gallium Complex Catalyzes CO 2 Hydrogenation via the Intermediacy of an Anionic d 10 Nickel Hydride

    Energy Technology Data Exchange (ETDEWEB)

    Cammarota, Ryan C. [Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States; Vollmer, Matthew V. [Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States; Xie, Jing [Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States; Supercomputing; Ye, Jingyun [Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States; Supercomputing; Linehan, John C. [Pacific Northwest National Laboratory, P.O. Box 999, MS K2-57, Richland, Washington 99352, United States; Burgess, Samantha A. [Pacific Northwest National Laboratory, P.O. Box 999, MS K2-57, Richland, Washington 99352, United States; Appel, Aaron M. [Pacific Northwest National Laboratory, P.O. Box 999, MS K2-57, Richland, Washington 99352, United States; Gagliardi, Laura [Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States; Supercomputing; Lu, Connie C. [Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States

    2017-09-28

    Large-scale CO2 hydrogenation could offer a renewable stream of industrially important C1 chemicals while reducing CO2 emissions. Critical to this opportunity is the requirement for inexpensive catalysts based on earth-abundant metals instead of precious metals. We report a nickel-gallium complex featuring a Ni(0)→Ga(III) bond that shows remarkable catalytic activity for hydrogenating CO2 to formate at ambient temperature (3150 turnovers, turnover frequency = 9700 h-1), compared with prior homogeneous Ni-centred catalysts. The Lewis acidic Ga(III) ion plays a pivotal role by stabilizing reactive catalytic intermediates, including a rare anionic d10 Ni hydride. The structure of this reactive intermediate shows a terminal Ni-H, for which the hydride donor strength rivals those of precious metal-hydrides. Collectively, our experimental and computational results demonstrate that modulating a transition metal center via a direct interaction with a Lewis acidic support can be a powerful strategy for promoting new reactivity paradigms in base-metal catalysis. The work was supported as part of the Inorganometallic Catalysis Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences under Award DE-SC0012702. R.C.C. and M.V.V. were supported by DOE Office of Science Graduate Student Research and National Science Foundation Graduate Research Fellowship programs, respectively. J.C.L., S.A.B., and A.M.A. were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  15. Robotized synthesis of [3-11C]-L-alanine using reaction of asymmetric alkylation of 11CH3I nickel complex of glycine Schiff base with S-2-N-(N'-benzylpropyl)aminobenzophenone

    International Nuclear Information System (INIS)

    Mosevich, I.K.; Kuznetsova, O.F.; Vasil'ev, D.A.; Anichkov, A.A.; Korsakov, M.V.

    1999-01-01

    Synthesis of [3- 11 C]-L-alanine based on 11 CH 3 I nickel complex (1) alkylation using different solvents (tetrahydrofuran, dimethylformamide, acetonitrile, acetone) and catalysts (potassium butylate, sodium hydride) was investigated. It was shown that synthesis of amino acids labelled with 11 C based on complex (1) use permits to obtain preparations with high degree of enantiomeric enrichment. The best results (enantiomeric excess of L-alanine up to 99 %) were obtained in reaction with acetonitrile as a solvent and potassium tret-butylate as a catalyst

  16. Synthesis, Characterization and Antimicrobial Studies of a New Mannich Base N-[Morpholino(phenylmethyl]acetamide and Its Cobalt(II, Nickel(II and Copper(II Metal Complexes

    Directory of Open Access Journals (Sweden)

    L. Muruganandam

    2012-01-01

    Full Text Available A new Mannich base N-[morpholino(phenylmethyl]acetamide (MBA, was synthesized and characterized by spectral studies. Chelates of MBA with cobalt(II, nickel(II and copper(II ions were prepared and characterized by elemental analyses, IR and UV spectral studies. MBA was found to act as a bidentate ligand, bonding through the carbonyl oxygen of acetamide group and CNC nitrogen of morpholine moiety in all the complexes. Based on the magnetic moment values and UV-Visible spectral data, tetracoordinate geometry for nitrato complexes and hexacoordinate geometry for sulphato complexes were assigned. The antimicrobial studies show that the Co(II nitrato complex is more active than the other complexes.

  17. 40 CFR 721.10045 - Diazotized substituted heteromonocycle coupled with naphthalene sulfonic acid derivative, nickel...

    Science.gov (United States)

    2010-07-01

    ... coupled with naphthalene sulfonic acid derivative, nickel complex, alkaline salt (generic). 721.10045... derivative, nickel complex, alkaline salt (generic). (a) Chemical substance and significant new uses subject... heteromonocycle coupled with naphthalene sulfonic acid derivative, nickel complex, alkaline salt (PMN P-02-737) is...

  18. Direct synthesis of cis-dihalido-bis(NHC) complex of nickel(II) and catalytic application in olefin addition polymerization: effect of halogen co-ligands and density functional theory study.

    Science.gov (United States)

    Zhang, Dao; Zhou, Sen; Li, Zhiming; Wang, Quanrui; Weng, Linhong

    2013-09-07

    Two novel amine-containing N-heterocyclic carbene ligand precursors [H(1a-b)]Br have been prepared in good yield and fully characterized. Direct syntheses of cis- and trans-dihalido-bis(NHC) nickel complexes [Ni(NHC)2X2] (X = Cl, Br) are reported. The solid structures of trans-[Ni(1a-b)2Br2] (2a-b) and cis-[Ni(1a)2Cl2] (3) were determined by single-crystal X-ray analysis and 3 was found to be the first example of cis-configuration coordination of monodentate NHC ligands to a metal center for dihalido-bis(NHC) nickel complexes. DFT calculations were conducted to determine the energy difference between cis- and trans-isomers of complexes 2a and 3 bearing bromide and chloride co-ligands. The cis-[Ni(1a)2Cl2] (cis-3) is 1.77-1.55 kcal mol(-1) lower in energy than its trans-isomer in polar solvents including CH2Cl2 and THF, while the trans-[Ni(1a)2Br2] (trans-2a) is more stable than the cis-isomer similarly in the gas phase. The cis nickel complex 3 with two coordinated monodentate NHCs was tested for olefin addition polymerization at standard conditions. It was found that cis-3 was inactive in ethylene polymerization but showed moderate catalytic activities (0.5-3.0 × 10(6) g of PNB (mol of Ni)(-1) h(-1)) in the addition polymerization of norbornene in the presence of methylaluminoxane (MAO) as cocatalyst.

  19. NICKEL PLATING PROCESS

    Science.gov (United States)

    Hoover, T.B.; Zava, T.E.

    1959-05-12

    A simplified process is presented for plating nickel by the vapor decomposition of nickel carbonyl. In a preferred form of the invention a solid surface is nickel plated by subjecting the surface to contact with a mixture containing by volume approximately 20% nickel carbonyl vapor, 2% hydrogen sulfide and .l% water vapor or 1% oxygen and the remainder carbon dioxide at room temperature until the desired thickness of nickel is obtained. The advantage of this composition over others is that the normally explosive nickel carbonyl is greatly stabilized.

  20. A novel nickel-thiourea-triethylamine complex adsorbed on graphitic C3N4 for low-cost solar hydrogen production.

    Science.gov (United States)

    Wang, Donghong; Zhang, Yuewei; Chen, Wei

    2014-02-18

    A low-cost photocatalytic system composed of earth-abundant elements has been synthesized, with the nickel-thiourea-triethylamine catalyst in situ formed on the C3N4 photocatalyst, which exhibits a comparable H2 production with a C3N4-Pt photocatalytic system and a long term photocatalytic activity.

  1. [Nickel allergy and orthodontics].

    Science.gov (United States)

    Leenen, R L J; Kuijpers-Jagtman, A M; Jagtman, B A; Katsaros, C

    2009-04-01

    Nickel hypersensitivity is a common problem, especially among young females, with a prevalence of 5 to 10%, increasing to 30%. In comparison with the oral mucosa, skin is more sensitive to an allergic reaction. The oral mucosa is less sensitive to nickel due to the difference in anatomical structure and the presence of pellicle. Nickel is used in many orthodontic appliances. Due to corrosion nickel ions can be released into the oral cavity. The extent of the corrosion of the appliance depends on the pH, the composition of saliva and plaque, temperature and mechanical loading. In spite of the relatively high amount of nickel processed in orthodontic appliances nickel allergies are rare. In cases of nickel-hypersensitivity, nickel-free appliances should be used.

  2. Synthesis, Characterization and Antimicrobial Studies of a New Mannich Base N-[Morpholino(phenyl)methyl]acetamide and Its Cobalt(II), Nickel(II) and Copper(II) Metal Complexes

    OpenAIRE

    L. Muruganandam; K. Krishnakumar

    2012-01-01

    A new Mannich base N-[morpholino(phenyl)methyl]acetamide (MBA), was synthesized and characterized by spectral studies. Chelates of MBA with cobalt(II), nickel(II) and copper(II) ions were prepared and characterized by elemental analyses, IR and UV spectral studies. MBA was found to act as a bidentate ligand, bonding through the carbonyl oxygen of acetamide group and CNC nitrogen of morpholine moiety in all the complexes. Based on the magnetic moment values and UV-Visible spectral data, tetrac...

  3. Urine nickel concentrations in nickel-exposed workers.

    Science.gov (United States)

    Bernacki, E J; Parsons, G E; Roy, B R; Mikac-Devic, M; Kennedy, C D; Sunderman, F W

    1978-01-01

    Electrothermal atomic absorption spectrometry was employed for analyses of nickel concentrations in urine samples from nickel-exposed workers in 10 occupational groups and from non-exposed workers in two control groups. Mean concentrations of nickel in urine were greatest in workers who were exposed to inhalation of aerosols of soluble nickel salts (e.g., workers in nickel plating operations and in an electrolytic nickel refinery). Less marked increases in urine nickel concentrations were found in groups of metal sprayers, nickel battery workers, bench mechanics and are welders. No significant increases in mean concentrations of nickel were found in urine samples from workers who performed grinding, buffing and polishing of nickel-containing alloys or workers in a coal gasification plant who employed Raney nickel as a hydrogenation catalyst. Measurements of nickel concentrations in urine are more sensitive and practical than measurements of serum nickel concentrations for evaluation of nickel exposures in industrial workers.

  4. Nitrogen atom transfer mediated by a new PN3P-pincer nickel core via a putative nitrido nickel intermediate.

    Science.gov (United States)

    Yao, Changguang; Wang, Xiufang; Huang, Kuo-Wei

    2018-02-20

    A 2nd generation PN 3 P-pincer azido nickel complex (PN 3 P)Ni(N 3 ) reacts with isocyanides to afford monosubstituted carbodiimides under irradiation, presumably via a transient nitrido intermediate. The resulting species can further generate unsymmetrical carboddimides and the PN 3 P nickel halide complex, accomplishing a synthetic cycle for a complete nitrogen atom transfer reaction.

  5. Nitrogen atom transfer mediated by a new PN3P-pincer nickel core via a putative nitrido nickel intermediate

    KAUST Repository

    Yao, Changguang

    2018-02-13

    A 2nd generation PN3P-pincer azido nickel complex (PN3P)Ni(N3) reacts with isocyanides to afford monosubstituted carbodiimides under irradiation, presumably via a transient nitrido intermediate. The resulting species can further generate unsymmetrical carboddimides and the PN3P nickel halide complex, accomplishing a synthetic cycle for a complete nitrogen atom transfer reaction.

  6. Analysis of thermoelectric properties of high-temperature complex alloys of nickel-base, iron-base and cobalt-base groups

    Science.gov (United States)

    Holanda, R.

    1984-01-01

    The thermoelectric properties alloys of the nickel-base, iron-base, and cobalt-base groups containing from 1% to 25% 106 chromium were compared and correlated with the following material characteristics: atomic percent of the principle alloy constituent; ratio of concentration of two constituents; alloy physical property (electrical resistivity); alloy phase structure (percent precipitate or percent hardener content); alloy electronic structure (electron concentration). For solid-solution-type alloys the most consistent correlation was obtained with electron concentration, for precipitation-hardenable alloys of the nickel-base superalloy group, the thermoelectric potential correlated with hardener content in the alloy structure. For solid-solution-type alloys, no problems were found with thermoelectric stability to 1000; for precipitation-hardenable alloys, thermoelectric stability was dependent on phase stability. The effects of the compositional range of alloy constituents on temperature measurement uncertainty are discussed.

  7. Cobalt(II), nickel(II), copper(II), zinc(II) and hafnium(IV) complexes of N'-(furan-3-ylmethylene)-2-(4-methoxyphenylamino)acetohydrazide.

    Science.gov (United States)

    Emam, Sanaa M; El-Saied, Fathy A; Abou El-Enein, Saeyda A; El-Shater, Heba A

    2009-03-01

    Cobalt(II), nickel(II), copper(II), zinc(II) and hafnium(IV) complexes of furan-2-carbaldehyde 4-methoxy-N-anilinoacetohydrazone were synthesized and characterized by elemental and thermal (TG and DTA) analyses, IR, UV-vis and (1)H NMR spectra as well as magnetic moment and molar conductivity. Mononuclear complexes are obtained with 1:1 molar ratio except complexes 3 and 9 which are obtained with 1:2 molar ratios. The IR spectra of ligand and metal complexes reveal various modes of chelation. The ligand behaves as a neutral bidentate one and coordination occurs via the carbonyl oxygen atom and azomethine nitrogen atom. The ligand behaves also as a monobasic tridentate one and coordination occurs through the enolic oxygen atom, azomethine nitrogen atom and the oxygen atom of furan ring. Moreover, the ligand behaves as a neutral tridentate and coordination occurs via the carbonyl oxygen, azomethine nitrogen and furan oxygen atoms as well as a monobasic bidentate and coordination occurs via the enolic oxygen atom and azomethine nitrogen atom. The electronic spectra and magnetic moment measurements reveal that all complexes possess octahedral geometry except the copper complex 10 possesses a square planar geometry. The thermal studies showed the type of water molecules involved in metal complexes as well as the thermal decomposition of some metal complexes.

  8. One-pot synthesis of a new 2-substituted 1,2,3-triazole 1-oxide derivative from dipyridyl ketone and isonitrosoacetophenone hydrazone: Nickel(II) complex, DNA binding and cleavage properties.

    Science.gov (United States)

    Gup, Ramazan; Erer, Oktay; Dilek, Nefise

    2017-04-01

    An efficient and simple one-pot synthesis of a new 1,2,3-triazole-1-oxide via reaction between isonitrosoacetophenone hydrazone and dipyridyl ketone in the EtOH/AcOH at room temperature has been developed smoothly in high yield. The reaction proceeds via metal salt free, in-situ formation of asymmetric azine followed by cyclization to provide 1,2,3-triazole 1-oxide compound. It has been structurally characterized. 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 ], hexa-coordinated within an octahedral geometry. Characterization of the 1,2,3-triazole compound and its Ni(II) complex with FTIR, 1 H and 13 C NMR, UV-vis and elemental analysis also confirms the proposed structures of the compounds. The interactions of the compounds with Calf thymus DNA (CT-DNA) have been investigated by 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, also with a slight partial intercalation in the case of ligand. DNA cleavage experiments have been also investigated by agarose gel electrophoresis in the presence and absence of an oxidative agent (H 2 O 2 ). Both 1,2,3-triazole 1-oxide ligand and its nickel(II) complex show nuclease activity in the presence of hydrogen peroxide. DNA binding and cleavage affinities of the 1,2,3-triazole 1-oxide ligand is stronger than that of the Ni(II) complex. Copyright © 2017 Elsevier Inc. All rights reserved.

  9. Synthesis of Two Potentially Heptadentate (N4O3 Schiff-base Ligands Derived from Condensation of Tris(3-aminopropyl-amine and Salicylaldehyde or 4-Hydroxysalicylaldehyde. Nickel(II and Copper(II Complexes of the Former Ligand

    Directory of Open Access Journals (Sweden)

    R. V. Parish

    2002-02-01

    Full Text Available Two potentially heptadentate (N4O3 tripodal Schiff-base ligands: tris(3-(salicylideneiminopropylamine (H3L1 and tris(3-(4’-hydroxysalicylideneimino-propylamine (H3L2 have been prepared and characterized by various spectroscopic methods (IR, FAB-MS, NMR. They are derived from the condensation reactions of tris(3-aminopropylamine (tpt, with 3 equivalents of either salicylaldehyde or the ringsubstituted salicylaldehyde, 4-hydroxysalicylaldehyde. The nickel(II and copper(II complexes of H3L1 were obtained from the its reactions Ni(II and Cu(II salts in absolute methanol. These complexes were studied by IR and FAB-Mass spectrometry.

  10. Kinetic and Structural Studies of Aldehyde Oxidoreductase from Desulfovibrio gigas Reveal a Dithiolene-Based Chemistry for Enzyme Activation and Inhibition by H2O2

    Science.gov (United States)

    Brondino, Carlos D.; Moura, José J. G.; Romão, Maria J.; González, Pablo J.; Santos-Silva, Teresa

    2013-01-01

    Mononuclear Mo-containing enzymes of the xanthine oxidase (XO) family catalyze the oxidative hydroxylation of aldehydes and heterocyclic compounds. The molybdenum active site shows a distorted square-pyramidal geometry in which two ligands, a hydroxyl/water molecule (the catalytic labile site) and a sulfido ligand, have been shown to be essential for catalysis. The XO family member aldehyde oxidoreductase from Desulfovibrio gigas (DgAOR) is an exception as presents in its catalytically competent form an equatorial oxo ligand instead of the sulfido ligand. Despite this structural difference, inactive samples of DgAOR can be activated upon incubation with dithionite plus sulfide, a procedure similar to that used for activation of desulfo-XO. The fact that DgAOR does not need a sulfido ligand for catalysis indicates that the process leading to the activation of inactive DgAOR samples is different to that of desulfo-XO. We now report a combined kinetic and X-ray crystallographic study to unveil the enzyme modification responsible for the inactivation and the chemistry that occurs at the Mo site when DgAOR is activated. In contrast to XO, which is activated by resulfuration of the Mo site, DgAOR activation/inactivation is governed by the oxidation state of the dithiolene moiety of the pyranopterin cofactor, which demonstrates the non-innocent behavior of the pyranopterin in enzyme activity. We also showed that DgAOR incubation with dithionite plus sulfide in the presence of dioxygen produces hydrogen peroxide not associated with the enzyme activation. The peroxide molecule coordinates to molybdenum in a η2 fashion inhibiting the enzyme activity. PMID:24391748

  11. Kinetic and structural studies of aldehyde oxidoreductase from Desulfovibrio gigas reveal a dithiolene-based chemistry for enzyme activation and inhibition by H(2O(2.

    Directory of Open Access Journals (Sweden)

    Jacopo Marangon

    Full Text Available Mononuclear Mo-containing enzymes of the xanthine oxidase (XO family catalyze the oxidative hydroxylation of aldehydes and heterocyclic compounds. The molybdenum active site shows a distorted square-pyramidal geometry in which two ligands, a hydroxyl/water molecule (the catalytic labile site and a sulfido ligand, have been shown to be essential for catalysis. The XO family member aldehyde oxidoreductase from Desulfovibrio gigas (DgAOR is an exception as presents in its catalytically competent form an equatorial oxo ligand instead of the sulfido ligand. Despite this structural difference, inactive samples of DgAOR can be activated upon incubation with dithionite plus sulfide, a procedure similar to that used for activation of desulfo-XO. The fact that DgAOR does not need a sulfido ligand for catalysis indicates that the process leading to the activation of inactive DgAOR samples is different to that of desulfo-XO. We now report a combined kinetic and X-ray crystallographic study to unveil the enzyme modification responsible for the inactivation and the chemistry that occurs at the Mo site when DgAOR is activated. In contrast to XO, which is activated by resulfuration of the Mo site, DgAOR activation/inactivation is governed by the oxidation state of the dithiolene moiety of the pyranopterin cofactor, which demonstrates the non-innocent behavior of the pyranopterin in enzyme activity. We also showed that DgAOR incubation with dithionite plus sulfide in the presence of dioxygen produces hydrogen peroxide not associated with the enzyme activation. The peroxide molecule coordinates to molybdenum in a η(2 fashion inhibiting the enzyme activity.

  12. Kinetic and structural studies of aldehyde oxidoreductase from Desulfovibrio gigas reveal a dithiolene-based chemistry for enzyme activation and inhibition by H(2)O(2).

    Science.gov (United States)

    Marangon, Jacopo; Correia, Hugo D; Brondino, Carlos D; Moura, José J G; Romão, Maria J; González, Pablo J; Santos-Silva, Teresa

    2013-01-01

    Mononuclear Mo-containing enzymes of the xanthine oxidase (XO) family catalyze the oxidative hydroxylation of aldehydes and heterocyclic compounds. The molybdenum active site shows a distorted square-pyramidal geometry in which two ligands, a hydroxyl/water molecule (the catalytic labile site) and a sulfido ligand, have been shown to be essential for catalysis. The XO family member aldehyde oxidoreductase from Desulfovibrio gigas (DgAOR) is an exception as presents in its catalytically competent form an equatorial oxo ligand instead of the sulfido ligand. Despite this structural difference, inactive samples of DgAOR can be activated upon incubation with dithionite plus sulfide, a procedure similar to that used for activation of desulfo-XO. The fact that DgAOR does not need a sulfido ligand for catalysis indicates that the process leading to the activation of inactive DgAOR samples is different to that of desulfo-XO. We now report a combined kinetic and X-ray crystallographic study to unveil the enzyme modification responsible for the inactivation and the chemistry that occurs at the Mo site when DgAOR is activated. In contrast to XO, which is activated by resulfuration of the Mo site, DgAOR activation/inactivation is governed by the oxidation state of the dithiolene moiety of the pyranopterin cofactor, which demonstrates the non-innocent behavior of the pyranopterin in enzyme activity. We also showed that DgAOR incubation with dithionite plus sulfide in the presence of dioxygen produces hydrogen peroxide not associated with the enzyme activation. The peroxide molecule coordinates to molybdenum in a η(2) fashion inhibiting the enzyme activity.

  13. Two new twisted helical nickel (II) and cobalt (III) octahedral ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 126; Issue 6. Two new twisted helical nickel(II) and cobalt(III) octahedral monomer complexes: Synthesis and structural characterization. Malay Dolai ... Keywords. Coordination chemistry; nickel(II); cobalt(III); Schiff base; twisted helicity; supramolecular interactions.

  14. Bisamidate and mixed amine/amidate NiN2S2 complexes as models for nickel-containing acetyl coenzyme A synthase and superoxide dismutase: an experimental and computational study.

    Science.gov (United States)

    Mathrubootham, Vaidyanathan; Thomas, Jason; Staples, Richard; McCraken, John; Shearer, Jason; Hegg, Eric L

    2010-06-21

    The distal nickel site of acetyl-CoA synthase (Ni(d)-ACS) and reduced nickel superoxide dismutase (Ni-SOD) display similar square-planar Ni(II)N(2)S(2) coordination environments. One difference between these two sites, however, is that the nickel ion in Ni-SOD contains a mixed amine/amidate coordination motif while the Ni(d) site in Ni-ACS contains a bisamidate coordination motif. To provide insight into the consequences of the different coordination environments on the properties of the Ni ions, we systematically examined two square-planar Ni(II)N(2)S(2) complexes, one with bisthiolate-bisamidate ligation (Et(4)N)(2)(Ni(L1)).2H(2)O (2) [H(4)L1 = N-(2-mercaptoacetyl)-N'-(2-mercaptoethyl)glycinamide] and another with bisthiolate-amine/amidate ligation K(Ni(HL2)) (3) [H(4)L2 = N-(2''-mercaptoethyl)-2-((2'-mercaptoethyl)amino)acetamide]. Although these two complexes differ only by a single amine versus amidate ligand, their chemical properties are quite different. The stronger in-plane ligand field in the bisamidate complex (Ni(II)(L1))(2-) (2) results in an increase in the energies of the d --> d transitions and a considerably more negative oxidation potential. Furthermore, while the bisamidate complex (Ni(II)(L1))(2-) (2) readily forms a trinuclear species (Et(4)N)(2)({Ni(L1)}(2)Ni).H(2)O (1) and reacts rapidly with O(2), presumably via sulfoxidation, the mixed amine/amidate complex (Ni(II)(HL2))(-) (3) remains monomeric and is stable for days in air. Interestingly, the Ni(III) species of the bisamidate complex formed by chemical oxidation with I(2) can be detected by electron paramagnetic resonance (EPR) spectroscopy while the mixed amine/amidate complex immediately decomposes upon oxidation. To explain these experimentally observed properties, we performed S K-edge X-ray absorption spectroscopy and low-temperature (77 K) electronic absorption measurements as well as both hybrid density functional theory (hybrid-DFT) and spectroscopy oriented configuration

  15. Surfactant-free synthesis of nickel nanoparticles in near-critical water

    International Nuclear Information System (INIS)

    Hald, Peter; Bremholm, Martin; Iversen, Steen Brummerstedt; Iversen, Bo Brummerstedt

    2008-01-01

    Nickel nanoparticles have been produced by combining two well-tested methods: (i) the continuous flow supercritical reactor and (ii) the reduction of a nickel salt with hydrazine. The normal precipitation of a nickel-hydrazine complex, which would complicate pumping and mixing of the precursor, was controlled by the addition of ammonia to the precursor solution, and production of nickel nanoparticles with average sizes from 40 to 60 nm were demonstrated. The method therefore provides some size control and enables the production of nickel nanoparticles without the use of surfactants. The pure nickel nanoparticles can be easily isolated using a magnet. - Graphical abstract: A surfactant-free synthesis route to nickel nanoparticles has been successfully transferred to near-critical water conditions reducing synthesis times from hours to seconds. Nickel nanoparticles in the 40-60 nm range have been synthesised from an ammonia stabilised hydrazine complex with the average size controlled by reaction temperature

  16. [Mechanisms of nickel allergy].

    Science.gov (United States)

    Czarnobilska, Ewa; Obtułowicz, Krystyna; Wsołek, Katarzyna; Pietowska, Justyna; Spiewak, Radosław

    2007-01-01

    Nickel allergy constitutes a serious health problem of modern societies. Hypersensitivity to this metal is found in 13% adults and 8% children. Risk factors for nickel allergy are: female gender and early exposure to nickel, e.g. piercing. Various mechanisms of inducing nickel allergy are possible, which is also reflected in the different clinical pictures. Nickel can induce allergic reaction in 3 different ways: 1) it binds to carrier protein in the extracellular space and subsequently is processed and presented by antigen presenting cell (APC) in the context of MHC class II molecule, which activates CD4+ lymphocytes, 2) Ni penetrates into the cell where it binds to intracellular proteins, and subsequently it is presented in the context of MHC class I molecule, which activates CD8+ lymphocytes, 3) Ni can "bridge" MHC molecule together with the TCR receptor on lymphocyte without actually filling the antigen-binding site, which is in analogy to superantigens. Both Th2/Tc2 (IL-4, IL-5, IL-13) and Th1/ Tc1 (IFNgamma) take their part in the development of contact allergy to nickel. The trafficking of the effector cells to target organs (where the inflammatory reaction actually takes place) is controlled by homing antigens and chemokine receptors that are expressed on their surface. The accumulation of effector cells in a target organ can determine the symptoms of nickel allergy (the skin, mucosa etc.). The acquisition of nickel tolerance is possibly dependent on the IL-10 secretion by specific lymphocytes.

  17. [Nickel allergy and orthodontics

    NARCIS (Netherlands)

    Leenen, R.L.; Kuijpers-Jagtman, A.M.; Jagtman, B.A.; Katsaros, C.

    2009-01-01

    Nickel hypersensitivity is a common problem, especially among young females, with a prevalence of 5 to 10%, increasing to 30%. In comparison with the oral mucosa, skin is more sensitive to an allergic reaction. The oral mucosa is less sensitive to nickel due to the difference in anatomical structure

  18. Electroless nickel plating on abs plastics from nickel chloride and nickel sulfate baths

    International Nuclear Information System (INIS)

    Inam-ul-haque; Ahmad, S.; Khan, A.

    2005-01-01

    Aqueous acid nickel chloride and alkaline nickel sulphate bath were studied for electroless nickel planting on acrylonitrile-butadiene-styrene (ABS) plastic. Before electroless nickel plating, specimens were etched, sensitized and activated. Effects of sodium hypophosphite and sodium citrate concentration on the electroless nickel plating thickness were discussed. Aqueous acid nickel chloride bath comprising, nickel chloride 10 g/L, sodium hypophosphite 40 g/L, sodium citrate 40g/L at pH 5.5, temperature 85 deg. C and density of 1 Be/ for thirty minutes gave best coating thickness in micrometer. It was found that acid nickel chloride bath had a greater stability, wide operating range and better coating thickness results than alkaline nickel sulphate bath. Acid nickel chloride bath gave better coating thickness than alkaline nickel sulfate bath

  19. Preparation and characterization of nanoplatelets of nickel hydroxide and nickel oxide

    Energy Technology Data Exchange (ETDEWEB)

    Zhou Gentao [CAS Key Laboratory of Crust-Mantle Materials and Environments, School of Earth and Space of Sciences, University of Science and Technology of China, Hefei 230026, Anhui (China)]. E-mail: gtzhou@ustc.edu.cn; Yao Qizhi [School of Chemistry and Materials, University of Science and Technology of China, Hefei 230026, Anhui (China); Wang Xinchen [Department of Chemistry, Chinese University of Hong Kong, Shatin, New Territories, Hong Kong (China); Yu, Jimmy C. [Department of Chemistry, Chinese University of Hong Kong, Shatin, New Territories, Hong Kong (China)

    2006-08-01

    A novel room-temperature coordination-precipitation technique was successfully developed for the synthesis of nickel hydroxide (theophrastite) nanoplatelets. This method has great potential for large-scale industrial production owing to facile size-controlled and low-cost. This platelet-like nickel hydroxide precursor can readily be converted to nickel oxide (bunsenite) nanoplatelets after 400 deg. C calcining. The synthesized products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetry-differential thermal analysis (TG-DTA) and X-ray photoelectron spectroscopy (XPS) techniques. The thickness of {beta}-Ni(OH){sub 2} nanoplatelets can be controlled by changing concentration of precipitant NaOH in the presence of ethylenediamine. The formation of Ni(en){sub 3} {sup 2+} complex ions in solution prior to precipitating nickel hydroxide may play a crucial role in controlling phase composition of resulting precipitate.

  20. Low Nickel Diet in Dermatology

    OpenAIRE

    Sharma, Ashimav D

    2013-01-01

    Nickel is a ubiquitous trace element and the commonest cause of metal allergy among the people. Nickel allergy is a chronic, recurring problem; females are affected more commonly than males. Nickel allergy may develop at any age. Once developed, it tends to persist life-long. Nickel is present in most of the dietary items and food is considered to be a major source of nickel exposure for the general population. Nickel in the diet of a nickel-sensitive person can provoke dermatitis. Careful se...

  1. trans-cis photoisomerization of azobenzene-conjugated dithiolato-bipyridine platinum(II) complexes: extension of photoresponse to longer wavelengths and photocontrollable tristability.

    Science.gov (United States)

    Sakamoto, Ryota; Kume, Shoko; Sugimoto, Manabu; Nishihara, Hiroshi

    2009-01-01

    Azobenzene derivatives modified with dithiolato-bipyridine platinum(II) complexes were synthesized, revealing their highly extended photoresponses to the long wavelength region as well as unique photocontrollable tristability. The absorptions of trans-1 and trans-2 with one azobenzene group on the dithiolene and bipyridine ligands, respectively, cover the range from 300 to 700 nm. These absorptions are ascribed, by means of time-dependent (TD)DFT calculations, to transitions from dithiolene(pi) to bipyridine(pi*), namely, interligand charge transfer (CT), pi-pi*, and n-pi* transitions of the azobenzene unit, and pi-pi* transitions of the bipyridine ligand. In addition, only trans-1 shows distinctive electronic bands, assignable to transitions from the dithiolene(pi) to azobenzene(pi*), defined as intraligand CT. Complex 1 shows photoisomerization behavior opposite to that of azobenzene: trans-to-cis and cis-to-trans conversions proceed with 405 and 312 nm irradiation, which correspond to excitation with the intraligand CT, and pi-pi* bands of the azobenzene and bipyridine units, respectively. In contrast, complex 2 shows photoisomerization similar to that of azobenzene: trans-to-cis and cis-to-trans transformations occur with 365 and 405 nm irradiation, respectively. Irradiation at 578 nm, corresponding to excitation of the interligand CT transitions, results in cis-to-trans conversion of both 1 and 2, which is the longest wavelength ever reported to effect the photoisomerization of the azobenzene group. The absorption and photochromism of 4, which has azobenzene groups on both the dithiolato and bipyridine ligands, have characteristics quite similar to those of 1 and 2, which furnishes 4 with photocontrollable tristability in a single molecule using light at 365, 405, and 578 nm. We also clarified that 1 and 2 have high photoisomerization efficiencies, and good thermal stability of the cis forms. Complexes 3 and 5 have almost the identical photoresponse to those

  2. Low nickel diet in dermatology

    Directory of Open Access Journals (Sweden)

    Ashimav D Sharma

    2013-01-01

    Full Text Available Nickel is a ubiquitous trace element and the commonest cause of metal allergy among the people. Nickel allergy is a chronic, recurring problem; females are affected more commonly than males. Nickel allergy may develop at any age. Once developed, it tends to persist life-long. Nickel is present in most of the dietary items and food is considered to be a major source of nickel exposure for the general population. Nickel in the diet of a nickel-sensitive person can provoke dermatitis. Careful selection of food with relatively low nickel concentration can bring a reduction in the total dietary intake of nickel per day. This can influence the outcome of the disease and can benefit the nickel sensitive patient.

  3. Low nickel diet in dermatology.

    Science.gov (United States)

    Sharma, Ashimav D

    2013-05-01

    Nickel is a ubiquitous trace element and the commonest cause of metal allergy among the people. Nickel allergy is a chronic, recurring problem; females are affected more commonly than males. Nickel allergy may develop at any age. Once developed, it tends to persist life-long. Nickel is present in most of the dietary items and food is considered to be a major source of nickel exposure for the general population. Nickel in the diet of a nickel-sensitive person can provoke dermatitis. Careful selection of food with relatively low nickel concentration can bring a reduction in the total dietary intake of nickel per day. This can influence the outcome of the disease and can benefit the nickel sensitive patient.

  4. Lead-nickel electrochemical batteries

    CERN Document Server

    Glaize, Christian

    2012-01-01

    The lead-acid accumulator was introduced in the middle of the 19th Century, the diverse variants of nickel accumulators between the beginning and the end of the 20th Century. Although old, these technologies are always very present on numerous markets. Unfortunately they are still not used in optimal conditions, often because of the misunderstanding of the internal electrochemical phenomena.This book will show that batteries are complex systems, made commercially available thanks to considerable amounts of scientific research, empiricism and practical knowledge. However, the design of

  5. NICKEL – ENVIRONMENTAL ALLERGEN

    Directory of Open Access Journals (Sweden)

    Henryka Langauer-Lewowicka

    2010-06-01

    Full Text Available Nickel (Ni is ubiquitus in our biosphere because of its emission from natural and anthropogenic sources. Its toxic and carcinogenic properties are well recognised only in workers exposed to high Ni concentrations. Nickel allergy is the most common form of cutaneus hypersensitivity in general population and also in occupationally exposed groups. As sensitizing agent Ni has a high prevalence of allergic contact dermatitis. The most important known risk factor associated with nickel allergy is ear piercing and use of other jewelry in females. In general population 17 % adults and 8 % children have Ni allergy symptoms. Permanently growing Ni allergy is regarded as serious risk for public health.

  6. Pulse plating of nickel deposits

    Energy Technology Data Exchange (ETDEWEB)

    Stimetz, C.J.; Stevenson, M.F.

    1980-02-01

    Pulse plated and conventional nickel deposits have been compared for differences in morphology, mechanical properties, and microstructure. The deposits were obtained from nickel sulfamate, nickel chloride, and Watts nickel plating solutions. No significant differences were found in the direct and pulse current deposits from the sulfamate and chloride solutions; however, significant differences in microstructure, yield strength, and microhardness were observed in deposits from the Watts nickel solution.

  7. Synthesis, characterization, and reactivity of nickel hydride complexes containing 2,6-C6H3(CH2PR2)2 (R = tBu, cHex, and iPr) pincer ligands.

    Science.gov (United States)

    Boro, Brian J; Duesler, Eileen N; Goldberg, Karen I; Kemp, Richard A

    2009-06-15

    The syntheses and full characterization of nickel hydrides containing the PCP "pincer"-type ligand, where PCP = 2,6-C(6)H(3)(CH(2)PR(2))(2) (R = tBu, cHex, and iPr), are reported. These Ni-H complexes are prepared by the conversion of ((R)PCP)NiCl precursors into the corresponding nickel hydrides by use of appropriate hydride donors. Surprisingly, although the ((R)PCP)NiCl precursors are quite similar chemically, the conversions to the hydrides were not straightforward and required different hydride reagents to provide analytically pure products. While NaBH(4) was effective in the preparation of pure ((tBu)PCP)NiH, Super-Hydride solution (LiEt(3)BH in THF) was required to prepare either ((cHex)PCP)NiH or ((iPr)PCP)NiH. Attempts to prepare a Ni-H from ((Ph)PCP)NiCl with a variety of hydride reagents yielded only the free ligand as an identifiable product. Two of the derivatives, tBu and cHex, have also been subjected to single crystal X-ray analysis. The solid-state structures each showed a classic, near-square planar arrangement for Ni in which the PCP ligand occupied three meridional ligand points with the Ni-H trans to the Ni-C bond. The resulting Ni-H bond lengths were 1.42(3) and 1.55(2) A for the tBu and cHex derivatives, respectively.

  8. DFT/TD-DFT study on spectroscopic properties of zinc(II, nickel(II, and palladium(II metal complexes with a thiourea derivative

    Directory of Open Access Journals (Sweden)

    Wang Xin

    2016-01-01

    Full Text Available The geometries, electronic structures, and spectral properties of three metal complexes Zn(C10H12N3OS2 (1, Ni(C10H12N3OS2 (2, and Pd(C10H12N3OS2 (3 with N-(2-pyridinylmorpholine-4-carbothioamide as a ligand are investigated by means of DFT (density functional theory and TD-DFT (time-dependent density functional theory methods. Complex 1 is a distorted tetrahedral geometry, while complexes 2 and 3 present a distorted square-planar coordination environment. In the simulated range, the spectrum of complex 1 has five obvious absorption peaks and one of them has the strongest intensity. The latter two complexes have one more absorption peak and shoulder peak with the similar intensity. Moreover, the strongest peaks of complexes 2.

  9. Solubilization of the carcinogen nickel subsulfide and its interaction with deoxyribonucleic acid and protein

    Energy Technology Data Exchange (ETDEWEB)

    Lee, J.E.; Ciccarelli, R.B.; Jennette, K.W.

    1982-02-16

    Significant concentrations (1-10 mM) of nickel(II) were found in solution after incubation of the potent carcinogen nickel subsulfide in 0.05 M Tris-HCl, pH 7.4, solutions containing DNA, rat liver microsomes, and NADPH. The presence of NADPH decreased the rate of solubilization of nickel subsulfide. The solubilized nickel exhibited electronic absorption spectra and magnetic moments characteristic of octahedral nickel(II). The solubilized nickel(II) bound to DNA with an apparent equilibrium constant of 730 M/sup -1/ and with a saturation binding value of one nickel per 2.4 nucleotides. Microsomes lowered the saturation binding of nickel to DNA but dramatically increased the amount of nickel-DNA complex stable to precipitation with salt and poly-(ethylene glycol). The amount of protein associated with DNA precipitated from protein-extracted solutions correlated with the amount of nickel bound to DNA. These results suggest that microsomes mediate the binding of nickel to DNA by forming a stable ternary protein-nickel(II)-DNA complex.

  10. Design, synthesis, spectral characterization, DNA interaction and biological activity studies of copper(II), cobalt(II) and nickel(II) complexes of 6-amino benzothiazole derivatives

    Science.gov (United States)

    Daravath, Sreenu; Kumar, Marri Pradeep; Rambabu, Aveli; Vamsikrishna, Narendrula; Ganji, Nirmala; Shivaraj

    2017-09-01

    Two novel Schiff bases, L1 = (2-benzo[d]thiazol-6-ylimino)methyl)-4,6-dichlorophenol), L2 = (1-benzo[d]thiazol-6-ylimino)methyl)-6-bromo-4-chlorophenol) and their bivalent transition metal complexes [M(L1)2] and [M(L2)2], where M = Cu(II), Co(II) and Ni(II) were synthesized and characterized by elemental analysis, NMR, IR, UV-visible, mass, magnetic moments, ESR, TGA, SEM, EDX and powder XRD. Based on the experimental data a square planar geometry around the metal ion is assigned to all the complexes (1a-2c). The interaction of synthesized metal complexes with calf thymus DNA was explored using UV-visible absorption spectra, fluorescence and viscosity measurements. The experimental evidence indicated that all the metal complexes strongly bound to CT-DNA through an intercalation mode. DNA cleavage experiments of metal(II) complexes with supercoiled pBR322 DNA have also been explored by gel electrophoresis in the presence of H2O2 as well as UV light, and it is found that the Cu(II) complexes cleaved DNA more effectively compared to Co(II), Ni(II) complexes. In addition, the ligands and their metal complexes were screened for antimicrobial activity and it is found that all the metal complexes were more potent than free ligands.

  11. Synthesis, characterization, thermal behavior, and DNA-cleaving studies of cyano-bridged nickel(II)-copper(II) complexes of 4-(pyridin-2-ylazenyl)resorcinol.

    Science.gov (United States)

    Karipcin, Fatma; Ozmen, Ismail; Cülü, Burcin; Celikoğlu, Umut

    2011-10-01

    We present here the syntheses of a mononuclear Cu(II) complex and two polynuclear Cu(II)-Ni(II) complexes of the azenyl ligand, 4-(pyridin-2-ylazenyl)resorcinol (HL; 1). The reaction of HL (1) and copper(II) perchlorate with KCN gave a mononuclear complex [CuL(CN)] (4). Using 4, one pentanuclear complex, [{CuL(NC)}(4) Ni](ClO(4))(2) (5) and one trinuclear complex, [{CuL(CN)}(2) NiL]ClO(4) (6), were prepared and characterized by elemental analyses, magnetic susceptibility, molar conductance, IR, and thermal analysis. Stoichiometric and spectral results of the mononuclear Cu(II) complex indicated that the metal/ligand/CN ratio was 1 : 1 : 1, and the ligand behaved as a tridentate ligand forming neutral metal chelates through the pyridinyl and azenyl N-, and resorcinol O-atom. The interaction between the compounds (the ligand 1, its Ni(II) and Cu(II) complexes without CN, i.e., 2 and 3, and its complexes with CN, 4-6) and DNA has also been investigated by agarose gel electrophoresis. The pentanuclear Cu(4) Ni complex (5) with H(2) O(2) as a co-oxidant exhibited the strongest DNA-cleaving activity. Copyright © 2011 Verlag Helvetica Chimica Acta AG, Zürich.

  12. Syntheses and spectroscopic properties of mercury(II) and nickel(II ...

    African Journals Online (AJOL)

    Mercury(II) complex, [Hg2(BPTU-2H)Cl2] and nickel(II) complex, [Ni(BPTU-H)2] were prepared by reacting Bis(N-phenylthiourea), BPTU, with mercury(II) chloride and nickel(II) acetate respectively. The complexes were characterized by IR, diffuse reflectance, 1H NMR spectra and elemental analysis. BPTU acts as ...

  13. Crystal structures of a copper(II and the isotypic nickel(II and palladium(II complexes of the ligand (E-1-[(2,4,6-tribromophenyldiazenyl]naphthalen-2-ol

    Directory of Open Access Journals (Sweden)

    Souheyla Chetioui

    2016-08-01

    Full Text Available In the copper(II complex, bis{(E-1-[(2,4,6-tribromophenyldiazenyl]naphthalen-2-olato}copper(II, [Cu(C16H8Br3N2O2], (I, the metal cation is coordinated by two N atoms and two O atoms from two bidentate (E-1-[(2,4,6-tribromophenyldiazenyl]naphthalen-2-olate ligands, forming a slightly distorted square-planar environment. In one of the ligands, the tribromobenzene ring is inclined to the naphthalene ring system by 37.4 (5°, creating a weak intramolecular Cu...Br interaction [3.134 (2 Å], while in the other ligand, the tribromobenzene ring is inclined to the naphthalene ring system by 72.1 (6°. In the isotypic nickel(II and palladium(II complexes, namely bis{(E-1-[(2,4,6-tribromophenyldiazenyl]naphthalen-2-olato}nickel(II, [Ni(C16H8Br3N2O2], (II, and bis{(E-1-[(2,4,6-tribromophenyldiazenyl]naphthalen-2-olato}palladium(II, [Pd(C16H8Br3N2O2], (III, respectively, the metal atoms are located on centres of inversion, hence the metal coordination spheres have perfect square-planar geometries. The tribromobenzene rings are inclined to the naphthalene ring systems by 80.79 (18° in (II and by 80.8 (3° in (III. In the crystal of (I, molecules are linked by C—H...Br hydrogen bonds, forming chains along [010]. The chains are linked by C—H...π interactions, forming sheets parallel to (011. In the crystals of (II and (III, molecules are linked by C—H...π interactions, forming slabs parallel to (10-1. For the copper(II complex (I, a region of disordered electron density was corrected for using the SQUEEZE routine in PLATON [Spek (2015. Acta Cryst. C71, 9–18]. The formula mass and unit-cell characteristics of the disordered solvent molecules were not taken into account during refinement.

  14. Magmatic sulfide-rich nickel-copper deposits related to picrite and (or) tholeiitic basalt dike-sill complexes-A preliminary deposit model

    Science.gov (United States)

    Schulz, Klaus J.; Chandler, Val W.; Nicholson, Suzanne W.; Piatak, Nadine M.; Seal, Robert R.; Woodruff, Laurel G.; Zientek, Michael L.

    2010-01-01

    Magmatic sulfide deposits containing nickel (Ni) and copper (Cu), with or without (?) platinum-group elements (PGEs), account for approximately 60 percent of the world's Ni production and are active exploration targets in the United States and elsewhere. On the basis of their principal metal production, magmatic sulfide deposits in mafic rocks can be divided into two major types: those that are sulfide-rich, typically with 10 to 90 percent sulfide minerals, and have economic value primarily because of their Ni and Cu contents; and those that are sulfide-poor, typically with 0.5 to 5 percent sulfide minerals, and are exploited principally for PGE. Because the purpose of this deposit model is to facilitate the assessment for undiscovered, potentially economic magmatic Ni-Cu?PGE sulfide deposits in the United States, it addresses only those deposits of economic significance that are likely to occur in the United States on the basis of known geology. Thus, this model focuses on deposits hosted by small- to medium-sized mafic and (or) ultramafic dikes and sills that are related to picrite and tholeiitic basalt magmatic systems generally emplaced in continental settings as a component of large igneous provinces (LIPs). World-class examples (those containing greater than 1 million tons Ni) of this deposit type include deposits at Noril'sk-Talnakh (Russia), Jinchuan (China), Pechenga (Russia), Voisey's Bay (Canada), and Kabanga (Tanzania). In the United States, this deposit type is represented by the Eagle deposit in northern Michigan, currently under development by Kennecott Minerals.

  15. Complexation-Based Detection of Nickel(II at a Graphene-Chelate Probe in the Presence of Cobalt and Zinc by Adsorptive Stripping Voltammetry

    Directory of Open Access Journals (Sweden)

    Keagan Pokpas

    2017-07-01

    Full Text Available The adsorptive stripping voltammetric detection of nickel and cobalt in water samples at metal film electrodes has been extensively studied. In this work, a novel, environmentally friendly, metal-free electrochemical probe was constructed for the ultra-trace determination of Ni2+ in water samples by Adsorptive Cathodic Stripping Voltammetry (AdCSV. The electrochemical platform is based on the adsorptive accumulation of Ni2+ ions directly onto a glassy carbon electrode (GCE modified with dimethylglyoxime (DMG as chelating agent and a Nafion-graphene (NGr nanocomposite to enhance electrode sensitivity. The nafion-graphene dimethylglyoxime modified glassy carbon electrode (NGr-DMG-GCE shows superior detection capabilities as a result of the improved surface-area-to-volume ratio and enhanced electron transfer kinetics following the incorporation of single layer graphene, while limiting the toxic effects of the sensor by removal of the more common mercury, bismuth and lead films. Furthermore, for the first time the NGr-DMG-GCE, in the presence of common interfering metal ions of Co2+ and Zn2+ demonstrates good selectivity and preferential binding towards the detection of Ni2+ in water samples. Structural and morphological characterisation of the synthesised single layer graphene sheets was conducted by Raman spectrometry, HRTEM and HRSEM analysis. The instrumental parameters associated with the electrochemical response, including accumulation potential and accumulation time were investigated and optimised in addition to the influence of DMG and graphene concentrations. The NGr-DMG-GCE demonstrated well resolved, reproducible peaks, with RSD (% below 5% and a detection limit of 1.5 µg L−1 for Ni2+ reduction at an accumulation time of 120 s., the prepared electrochemical sensor exhibited good detection and quantitation towards Ni2+ detection in tap water samples, well below 0.1 mg L−1 set by the WHO and EPA standards. This comparable to the South

  16. Complexes of cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II) and dioxouranium(II) with thiophene-2-aldehydethiosemicarbazone

    International Nuclear Information System (INIS)

    Singh, Balwan; Misra, Harihar

    1986-01-01

    Metal complexes of thiosemicarbazides have been known for their pharmacological applications. Significant antitubercular, fungicidal and antiviral activities have been reported for thiosemicarbazides and their derivatives. The present study describes the systhesis and characterisation of complexes of Co II , Cu II , Zn II ,Cd II and UO II with thiosemicarbazone obtained by condensing thiophene-2-aldehyde with thiosemicarbazide. 17 refs., 2 tables. (author)

  17. Synthesis, structural, optical band gap and biological studies on iron (III), nickel (II), zinc (II) and mercury (II) complexes of benzyl α-monoxime pyridyl thiosemicarbazone

    Science.gov (United States)

    Bedier, R. A.; Yousef, T. A.; Abu El-Reash, G. M.; El-Gammal, O. A.

    2017-07-01

    New ligand, (E)-2-((E)-2-(hydroxyimino)-1,2-diphenylethylidene)-N-(pyridin-2 yl) hydrazinecarbothioamide (H2DPPT) and its complexes [Fe(DPPT)Cl(H2O)], [Ni(H2DPPT)2Cl2], [Zn(HDPPT)(OAc)] and [Hg(HDPPT)Cl](H2O)4 were isolated and characterized by various of physico-chemical techniques. IR spectra show that H2DPPT coordinates to the metal ions as neutral NN bidentate, mononegative NNS tridentate and binegative NNSN tetradentate, respectively. From the modeling studies, the bond length, bond angle, HOMO, LUMO and dipole moment had been calculated to confirm the geometry of the ligands and their investigated complexes. The thermal studies showed the type of water molecules involved in metal complexes Furthermore, the kinetic and thermodynamic parameters for the different decomposition steps were calculated using the Coats-Redfern and Horowitz-Metzger methods. Also, the optical band gap (Eg) has been calculated to elucidate the conductivity of the isolated complexes. The optical transition energy (Eg) is direct and equals 3.34 and 3.44 ev for Ni and Fe complexes, respectively. The ligand and their metal complexes were screened for antibacterial activity against the following bacterial species, Bacillus thuringiensis, Staphylococcus aureus, Pseudomonas aeuroginosa and Escherichia coli. The results revealed that the metal complexes have more potent antibacterial compared with the ligand. Also, the degradation effect of the investigated compounds was tested showing that, Ni complex exhibited powerful and complete degradation effect on DNA.

  18. Spectroscopic characterization of chromium(III), manganese(II) and nickel(II) complexes with a nitrogen donor tetradentate, 12-membered azamacrocyclic ligand

    Science.gov (United States)

    Chandra, Sulekh; Pundir, Meenakshi

    2008-01-01

    The complexes of Cr(III), Mn(II) and Ni(II) were synthesized with macrocyclic ligand i.e. 5,11-dimethyl-6,12-diethyl-dione-1,2,4,7,9,10-hexazacyclododeca -1,4,6,10-tetraene. The ligand (L) was prepared by [2 + 2] condensation reaction of 2,3-pentanedione and semicarbazide hydrochloride. These complexes were found to have the general composition [Cr(L)X 2]X and [M(L)X 2] (where M = Mn(II) and Ni(II); X = Cl -, NO 3-, (1/2)SO 42-, NCS - and L = ligand [N 6]). The ligand and its transition metal complexes were characterized by the elemental analysis, molar conductance, magnetic susceptibility, mass, IR, electronic and EPR spectral studies. On the basis of IR, electronic and EPR spectral studies, an octahedral geometry has been assigned for these complexes except sulphato complexes which are of five coordinated geometry.

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

    Science.gov (United States)

    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.

  20. Synthesis and Characterization of the Adducts of Morpholinedithioccarbamate Complexes of Oxovanadium (IV, Nickel(II, and Copper(II with Piperidine and Morpholine

    Directory of Open Access Journals (Sweden)

    Mousami Sharma

    2012-01-01

    Full Text Available A series of 1:1 adducts of bis(morpholinedithiocarbamato complex of VO(IV, 1:1 and 1:2 adducts of bis(morpholinedithiocarbamato complexes of Ni(II and Cu(II with piperidine and morpholine have been synthesized and characterized by elemental analysis, molar conductance, magnetic susceptibility, IR, UV-Vis, and TGA/DTA techniques. Analytical data reveals that VO(IV complex forms only 1:1 adducts with the formula [VO(morphdtc2L].H2O while Ni(II and Cu(II complexes form both 1:1 and 1:2 adducts with 1:1 adducts having general formula Ni(morphdtc2.L and Cu(morphdtc2.L and 1:2 adducts having general formula Ni(morphdtc2.L2 and Cu(morphdtc2.L2 (morphdtc = morpholinedithiocarbamate, L = morpholine and piperidine. Antifungal activity of some complexes has been carried out against the fungal strain Fusarium oxysporium. Thermal studies indicate a continuous weight loss. A square pyramidal geometry has been proposed for the 1:1 adducts of Ni(II and Cu(II complexes while an octahedral geometry has been proposed for the 1:1 adducts of VO(IV and for the 1:2 adducts of Ni(II and Cu(II complexes.

  1. Multi-Nuclear NMR Investigation of Nickel(II), Palladium(II), Platinum(II) and Ruthenium(II) Complexes of an Asymmetrical Ditertiary Phosphine

    Energy Technology Data Exchange (ETDEWEB)

    Raj, Joe Gerald Jesu [Institut National de la Recherche Scientifique, Quebec (China); Pathak, Devendra Deo [Indian School of Mines, Dhanbad (India); Kapoor, Pramesh N. [Univ. of Delhi, Delhi (India)

    2013-12-15

    Complexes synthesized by reacting alkyl and aryl phosphines with different transition metals are of great interest due to their catalytic properties. Many of the phosphine complexes are soluble in polar solvents as a result they find applications in homogeneous catalysis. In our present work we report, four transition metal complexes of Ni(II), Pd(II), Pt(II) and Ru(II) with an asymmetrical ditertiaryphosphine ligand. The synthesized ligand bears a less electronegative substituent such as methyl group on the aromatic nucleus hence makes it a strong σ-donor to form stable complexes and thus could effectively used in catalytic reactions. The complexes have been completely characterized by elemental analyses, FTIR, {sup 1}HNMR, {sup 31}PNMR and FAB Mass Spectrometry methods. Based on the spectroscopic evidences it has been confirmed that Ni(II), Pd(II) and Pt(II) complexes with the ditertiaryphosphine ligand showed cis whereas the Ru(II) complex showed trans geometry in their molecular structure.

  2. Solidification phenomena in nickel base brazes containing boron and silicon

    International Nuclear Information System (INIS)

    Tung, S.K.; Lim, L.C.; Lai, M.O.

    1996-01-01

    Nickel base brazes containing boron and/or silicon as melting point depressants are used extensively in the repair and joining of aero-engine hot-section components. These melting point depressants form hard and brittle intermetallic compounds with nickel which are detrimental to the mechanical properties of brazed joints. The present investigation studied the microstructural evolution in nickel base brazes containing boron and/or silicon as melting point depressant(s) in simple systems using nickel as the base metal. The basic metallurgical reactions and formation of intermetallic compounds uncovered in these systems will be useful as a guide in predicting the evolution of microstructures in similar brazes in more complex systems involving base metals of nickel base superalloys. The four filler metal systems investigated in this study are: Ni-Cr-Si; Ni-Cr-B; Ni-Si-B and Ni-Cr-Fe-Si-B

  3. Syntheses, characterization, superoxide dismutase, antimicrobial, crystal structure and molecular studies of copper (II) and nickel (II) complexes with 2-((E)-(2, 4-dibromophenylimino) methyl)-4-bromophenol as Schiff base ligand

    Science.gov (United States)

    Bharti, Sulakshna; Choudhary, Mukesh; Mohan, Bharti; Rawat, S. P.; Sharma, S. R.; Ahmad, Khursheed

    2017-12-01

    Three new copper (II) and nickel (II) complexes viz. [Cu(L)2](1a), [Cu(L)2](1b) and [Ni(L)2].DMF(2), where HL = 2-((E)-(2, 4-dibromophenylimino) methyl)-4-bromophenol, have been synthesized and characterized by using various physico-chemical and spectroscopic techniques. The crystal structures of Schiff base (HL) and their metal complexes (1a), (1b) and (2) were determined by single crystal X-ray diffraction. IR and UV-Vis spectra and magnetic susceptibility measurements agree with the observed crystal structures. The crystallographic and spectroscopic studies confirmed four coordinate environments around the metal (II) ions. The synthesized Schiff base ligand (HL) crystallizes in the orthorhombic system of the space group Pbca. Complex (1a) of HL was crystallized in the monoclinic system of the space group P21/c, a = 10.1712(9) Å, b = 10.9299(10) Å,c = 12.7684(11) Å,α = 90̊,β = 104.649(2)̊, γ = 90̊ and Z = 2 whereas complex (1b) and (2) crystallized in the triclinic system of the space group P-1, a = 11.499(5)Å, b = 11.598(5)Å, c = 12.211(5)Å, α = 98.860(5), β = 115.653(5),γ = 100.906(5) and Z = 2 for (1b), a = 9.080(6) Å, b = 9.545(8)Å, c = 9.545(8)Å, α = 101.43(4)º,β = 99.63(3)̊, γ = 117.71(2)º and Z = 1 for (2). The synthesized ligand (HL) was behaved as monobasic bidentate Schiff base ligand having N and O donor sites. The electron paramagnetic resonance spectra indicate a dx2-y2ground state (g|| > g⊥> 2.0023) for (1a) and (1b). Copper (II) complexes display X-band EPR spectra in 100% DMSO and 77 K, giving indicating dx2-y2ground state. Superoxide dismutase-like activities of HL and its complexes were investigated by nitrobluetetrazolium chloride-DMSO assay and IC50 values were evaluated. These complexes were also tested for their in vitro antimicrobial activities against two bacteria (E. coli and Salmonella typhi) and two fungi (Pencillium, Aspergillus sp.) comparing with the Schiff base. The antimicrobial results showed that the

  4. NMR investigation of dynamic processes in complexes of nickel(II) and zinc(II) with iminodiacetate, n-methyliminodiacetate and n-ethyliminodiacetate

    International Nuclear Information System (INIS)

    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 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 2 -2 (L = mida, eida) in aqueous solution by total lineshape analysis of the proton spectrum at 500 MHz

  5. Soil, nickel and low nickel food

    Science.gov (United States)

    Chami, Ziad Al; Cavoski, Ivana; Mondelli, Donato; Mimiola, Giancarlo; Miano, Teodoro

    2013-04-01

    Nickel is an ubiquitous trace element and occurs in soil, water, air and in the biosphere. Ni is an essential element for several plants, microorganisms and vertebrates. Human requirement for Ni has not been conclusively demonstrated. Nickel is normally present in human tissues at low concentration and, under conditions of high exposure, these levels may increase significantly. Food is the major source of Ni exposure. Nickel is present in many food products, especially vegetables. The amount of Ni present in vegetables is increasing because of environmental contamination and cultural practices. It has been demonstrated that the consumption of a Ni-rich diet can cause an increase of immunological disorders including Systemic Ni Allergy Syndrome (SNAS). The SNAS patients are currently treated with a diet that is closely Ni-free. Therefore, there is a need to produce certified and guaranteed vegetables with a low Ni concentration in the market. The proposed research aims to develop new methods for vegetable production and innovative cultural practices through a suitable choice of agricultural soil, cultivar, amendments and fertilizers as well as good agricultural practices in order to reduce Ni plant uptake and its translocation to the edible plant parts and therefore to produce Ni-free food products for SNAS patients.

  6. Complexation of manganese(II), cobalt(II), nickel(II), zink(II), and cadmium(II) cations with amoxicillin

    International Nuclear Information System (INIS)

    Alekseev, V.G.; Lyamtseva, O.I.; Samujlova, I.S.

    2007-01-01

    The interaction of amoxicillin anions (Axn - ) with Mn 2+ , Co 2+ , Ni 2+ , Zn 2+ , and Cd 2+ in aqueous solution at 20 deg C and an ionic strength of 0.1 (KNO 3 ) has been studied pH-metrically. In a neutral and weak alkaline solution, MAxn + and M(OH)Axn complexes are formed. The formation constants and the pH ranges of existence of these complexes have been determined [ru

  7. A phosphino-oxazoline ligand as a P,N-bridge in palladium/cobalt or P,N-chelate in nickel complexes: catalytic ethylene oligomerization.

    Science.gov (United States)

    Zhang, Shuanming; Pattacini, Roberto; Jie, Suyun; Braunstein, Pierre

    2012-01-14

    The Pd(II) complex [PdCl(2)(1)] [1 = ({oxazolin-2-yl}methyl)diphenylphosphine] was obtained by the 1:1 reaction of 1 with [PdCl(2)(NCPh)(2)]. Although this neutral complex is stable in the solid-state and in solution, it reacts with the dinuclear complex [CoCl(2)(μ-1)](2) to afford the heterometallic zwitterionic complex [{PdCl(1)}(+)(μ-1)(CoCl(3))(-)] (2). Under inert atmosphere, two equivalents of 1 reacted with [NiCl(2)(dme)] to give trans-[NiCl(2)(1)(2)] (3) in CH(2)Cl(2) but cis-[NiCl(2)(1)(2)] (4) in CHCl(3). When the latter reaction was performed in air, trans-[NiCl(2)(5)(2)] (6) [5 = ({oxazolin-2-yl}methyl)diphenylphosphine oxide] was obtained. All metal complexes, 2, 3, 4 and 6, have been structurally characterized by X-ray diffraction. Complexes 3, 4 and 6 have been evaluated as precatalysts for ethylene oligomerisation in the presence of AlEtCl(2) as cocatalyst. Complexes 3 and 6 yielded a turnover frequency (TOF) of 60,700 and 62,600 mol of C(2)H(4)/((mol of Ni)·h), respectively, in the presence of 10 equiv. of AlEtCl(2). In the presence of only 6 equiv. of cocatalyst, these Ni complexes yielded TOF values of 41,500 and 58,000 mol of C(2)H(4)/((mol of Ni)·h), respectively.

  8. Production method of nickel electrode

    Science.gov (United States)

    Ikeda, H.; Ohira, T.

    1982-01-01

    A nickel electrode having improved charging efficiency, an increased coefficient of discharging utilization, and large capacity is disclosed. Nickel hydroxide or nickel oxide is retained in a porous nickel substrate which is immersed in an aqueous solution of cobalt acetate with a pH 4.0 to 6.8. The electrode thus obtained is then immersed in an alkaline solution or heated to change cobalt acetate into cobalt hydroxide or cobalt oxide whereby the surface of nickel active material is covered with cobalt crystals and alloying of cobalt and nickel is promoted at the same time.

  9. Dissolution studies on Nickel ferrite in dilute chemical decontamination formulations

    Energy Technology Data Exchange (ETDEWEB)

    Ranganathan, S. [New Brunswick Univ., Fredericton, NB (Canada). Dept. of Chemical Engineering; Srinivasan, M.P. [Bhabha Atomic Research Centre (BARC) (India). Water and Steam Chemistry Laboratory; Raghavan, P.S. [Madras Christian College, Chennai (India); Narasimhan, S.V. [Bhabha Atomic Research Centre, Bombay (India); Gopalan, R. [Madras Christian College, Chennai (India). Department of Chemistry

    2004-09-01

    Nickel ferrite is one of the important corrosion products in the pipeline surfaces of water-cooled nuclear reactors. The dissolution of the nickel ferrite by chelating agents is very sensitive to the nature of the chelant, the nature of the reductant used in the formulation and the temperature at which the dissolution studies are performed. The dissolution is mainly controlled by the reductive dissolution of the ferrite particles, but complexing agents also play a significant role in the dissolution process. This study deals with the leaching of iron and nickel from nickel ferrite prepared by the solid-state method. The dissolution studies are performed in pyridine-2,6-dicarboxylic acid (PDCA), nitrilotriacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA) formulations containing organic reductants like ascorbic acid and low oxidation state transition metal ion reductants like Fe(II)-L (where L = PDCA, NTA, EDTA) at 85 C. The dissolution of nickel ferrite in PDCA, NTA and EDTA formulations is influenced by the presence of reductants in the formulations. The addition of Fe(II)-L in the formulation greatly enhances the dissolution of nickel ferrite. The preferential leaching of nickel over iron during the dissolution of nickel ferrite was observed in all the formulations. (orig.)

  10. Structural and spectroscopic characterization of iron(II), cobalt(II), and nickel(II) ortho-dihalophenolate complexes: insights into metal-halogen secondary bonding.

    Science.gov (United States)

    Machonkin, Timothy E; Boshart, Monica D; Schofield, Jeremy A; Rodriguez, Meghan M; Grubel, Katarzyna; Rokhsana, Dalia; Brennessel, William W; Holland, Patrick L

    2014-09-15

    Metal complexes incorporating the tris(3,5-diphenylpyrazolyl)borate ligand (Tp(Ph2)) and ortho-dihalophenolates were synthesized and characterized in order to explore metal-halogen secondary bonding in biorelevant model complexes. The complexes Tp(Ph2)ML were synthesized and structurally characterized, where M was Fe(II), Co(II), or Ni(II) and L was either 2,6-dichloro- or 2,6-dibromophenolate. All six complexes exhibited metal-halogen secondary bonds in the solid state, with distances ranging from 2.56 Å for the Tp(Ph2)Ni(2,6-dichlorophenolate) complex to 2.88 Å for the Tp(Ph2)Fe(2,6-dibromophenolate) complex. Variable temperature NMR spectra of the Tp(Ph2)Co(2,6-dichlorophenolate) and Tp(Ph2)Ni(2,6-dichlorophenolate) complexes showed that rotation of the phenolate, which requires loss of the secondary bond, has an activation barrier of ~30 and ~37 kJ/mol, respectively. Density functional theory calculations support the presence of a barrier for disruption of the metal-halogen interaction during rotation of the phenolate. On the other hand, calculations using the spectroscopically calibrated angular overlap method suggest essentially no contribution of the halogen to the ligand-field splitting. Overall, these results provide the first quantitative measure of the strength of a metal-halogen secondary bond and demonstrate that it is a weak noncovalent interaction comparable in strength to a hydrogen bond. These results provide insight into the origin of the specificity of the enzyme 2,6-dichlorohydroquinone 1,2-dioxygenase (PcpA), which is specific for ortho-dihalohydroquinone substrates and phenol inhibitors.

  11. Synthesis and characterization of a tetraaza macrocyclic ligand and its cobalt(II, nickel(II and copper(II complexes

    Directory of Open Access Journals (Sweden)

    SULEKH CHANDR

    2010-07-01

    Full Text Available Co(II, Ni(II, and Cu(II complexes with a tetradentate nitrogen donor [N4] macrocyclic ligand, viz. 6,15-dimethyl-8,17diphenyl-7,16-dihydrodibenzo[b,i][1.4.8.11]tetraazacyclotetradecine, were synthesized. Their structures were determined based on elemental analyses, molar conductance and magnetic susceptibility measurements, and IR, 1H-NMR (ligand and electronic spectral studies. Based on analytical and molar conductance data, the complexes may be formulated as [M(LCl2] and [M’(L]Cl2 (where M = Co(II and Cu(II, and M’ = Ni(II due to their non-electrolytic and 1:2 electrolytic nature. Based on spectral studies, an octahedral geometry was assigned for the Co(II complex, whereas square-planar and tetragonal geometry were proposed for the Ni(II and Cu(II complexes, respectively. The synthesized ligand and its complexes were screened for fungicidal activity against two pathogenic fungi (i.e., Fusarium moniliformae and Rhizoctonia solani to assess their growth inhibiting potential.

  12. Synthesis, characterization and structural studies of binuclear nickel(II complexes derived from dihydroxybenzaldehyde thiosemicarbazones, bridged by 1,2-bis(diphenylphosphinoethane

    Directory of Open Access Journals (Sweden)

    Hana B. Shawish

    2016-11-01

    Full Text Available The work described in this paper involves the synthesis and structural characterization of Ni(II complexes derived from dihydroxybenzaldehyde thiosemicarbazones (H3L1, H3L2, H3L3, H3L4 and 1,2-bis(diphenylphosphinoethane (dppe. Ligands and their Ni(II complexes were characterized by elemental analysis, IR, UV–Vis, (1H, 13C, 31P NMR, as well as magnetic moment and X-ray structure analysis. The results so obtained suggest that the thiosemicarbazone ligands behave as a tridentate ligand which were coordinated with Ni(II ion through O, N and S atoms. Furthermore, the dppe ligand was coordinated with Ni(II ion through the P atom. It is concluded that all Ni(II complexes have a Square-planar geometry.

  13. Efficient Synthesis and Characterization of Some Novel Nitro-Schiff Bases and Their Complexes of Nickel(II and Copper(II

    Directory of Open Access Journals (Sweden)

    Hossein Naeimi

    2013-01-01

    Full Text Available Synthesis and characterization of some new Schiff base ligands derived from various diamines and nitrosalicylaldehyde and their complexes of Ni(II and Cu(II are reported. Several spectral techniques such as UV-Vis, FT-IR, and NMR spectra were used to identify the chemical structures of the reported ligands and their complexes. The ligands are found to be bound to the metal atom through the oxygen atoms of the hydroxyl groups and nitrogen atoms of imine groups, which is also supported by spectroscopic techniques. The results obtained by FT-IR and NMR showed that the Schiff base complexes of transition metal (II have square-planar geometry.

  14. Synthesis, spectroscopic and thermal characterization of sulpiride complexes of iron, manganese, copper, cobalt, nickel, and zinc salts. Antibacterial and antifungal activity

    Science.gov (United States)

    Mohamed, Gehad G.; Soliman, Madiha H.

    2010-08-01

    Sulpiride (SPR; L) is a substituted benzamide antipsychotic which is reported to be a selective antagonist of central dopamine receptors and claimed to have mood-elevating properties. The ligation behaviour of SPR drug is studied in order to give an idea about its potentiality towards some transition metals in vitro systems. Metal complexes of SPR have been synthesized by reaction with different metal chlorides. The metal complexes of SPR with the formula [MCl 2(L) 2(H 2O) 2]· nH 2O [M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II); n = 0-2] and [FeCl 2(HL)(H 2O) 3]Cl·H 2O have been synthesized and characterized using elemental analysis (CHN), electronic (infrared, solid reflectance and 1H NMR spectra) and thermal analyses (TG and DTA). The molar conductance data reveal that the bivalent metal chelates are non-electrolytes while Fe(III) complex is 1:1 electrolyte. IR spectra show that SPR is coordinated to the metal ions in a neutral monodentate manner with the amide O. From the magnetic and solid reflectance spectra, octahedral geometry is suggested. The thermal decomposition processes of these complexes were discussed. The correlation coefficient, the activation energies, E*, the pre-exponential factor, A, and the entropies, Δ S*, enthalpies, Δ H*, Gibbs free energies, Δ G*, of the thermal decomposition reactions have been derived from thermogravimetric (TG) and differential thermogravimetric (DTG) curves. The synthesized ligand and its metal complexes were also screened for their antibacterial and antifungal activity against bacterial species ( Escherichia coli and Staphylococcus aureus) and fungi ( Aspergillus flavus and Candida albicans). The activity data show that the metal complexes are found to have antibacterial and antifungal activity than the parent drug and less than the standard.

  15. Influence of substituents of nickel(II) complexes of Schiff bases of substituted (S)-2-N-(benzylpropyl)aminobenzophenones and amino-acids on their asymmetric induction

    International Nuclear Information System (INIS)

    Nadvornik, M.; Lycka, A.; Gee, A.; Popkov, A.

    1999-01-01

    The aim of this work was to study of influence of substituents on benzophenone substituent on thermodynamic controlled induction of complexes as well as influence of substituents on benzyl group and on benzophenone on kinetically controlled asymmetric induction of complexes. [ 13 C]methyl iodide was used in the synthesis. Replace of benzyl group by 2,4,6-trimethylbenzyl group increase kinetically controlled asymmetric induction of synthesis of (S)-α-[ 13 C]methylalanine from 43% d.e. to 66% d.e

  16. Synthesis of α-Amino Acids via Asymmetric Phase Transfer-Catalyzed Alkylation of Achiral Nickel(II) Complexes of Glycine-Derived Schiff Bases

    NARCIS (Netherlands)

    Belokon, Yuri N.; Bespalova, Natalia B.; Churkina, Tatiana D.; Císařová, Ivana; Ezernitskaya, Marina G.; Harutyunyan, Syuzanna R.; Hrdina, Radim; Kagan, Henri B.; Kočovský, Pavel; Kochetkov, Konstantin A.; Larionov, Oleg V.; Lyssenko, Konstantin A.; North, Michael; Polášek, Miroslav; Peregudov, Alexander S.; Prisyazhnyuk, Vladimir V.; Vyskočil, Štěpán

    2003-01-01

    Achiral, diamagnetic Ni(II) complexes 1 and 3 have been synthesized from Ni(II) salts and the Schiff bases, generated from glycine and PBP and PBA, respectively, in MeONa/MeOH solutions. The requisite carbonyl-derivatizing agents pyridine-2-carboxylic acid(2-benzoyl-phenyl)-amide (PBP) and

  17. Cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II) and dioxouranium(II) complexes of thiophene-2-aldehyde-4-phenyl-thiosemicarbazone

    International Nuclear Information System (INIS)

    Singh, Balwan; Misra, Harihar

    1986-01-01

    The present paper describes the synthesis and characterisation of thiophene-2-aldehyde-4-phenylthiosemicarbazone (TAPTSC) and its metal complexes with Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and UO(II). (author). 30 refs., 1 table

  18. A novel homobimetallic nickel complex for the asymmetric direct Mannich reaction of imines: a practical method on a multi-gram scale.

    Science.gov (United States)

    Zhang, Shixiong; Deng, Ping; Zhou, Jing; Liu, Mouxiong; Liang, Guojuan; Xiong, Yan; Zhou, Hui

    2017-11-30

    A novel dinuclear Ni complex has been developed for the direct Mannich reaction of malonates with N-tosyl aryl imines with a low catalyst loading (0.1-0.05 mol%) on a preparative scale (5-50 mmol). The structure of the active species was verified via control experiments, ESI-HRMS, and DFT calculations.

  19. Structure-antiproliferative activity studies on l-proline- and homoproline-4-N-pyrrolidine-3-thiosemicarbazone hybrids and their nickel(ii), palladium(ii) and copper(ii) complexes.

    Science.gov (United States)

    Dobrova, Aliona; Platzer, Sonja; Bacher, Felix; Milunovic, Miljan N M; Dobrov, Anatolie; Spengler, Gabriella; Enyedy, Éva A; Novitchi, Ghenadie; Arion, Vladimir B

    2016-09-14

    Two water-soluble thiosemicarbazone-proline (H2L(1)) and thiosemicarbazone-homoproline hybrids (H2L(2)) were synthesised. By reaction of H2L(1) with NiCl2·6H2O, PdCl2 and CuCl2·2H2O in ethanol, the series of square-planar complexes [Ni(H2L(1))Cl]Cl·1.3H2O (1·1.3H2O), [Pd(H2L(1))Cl]Cl·H2O (2·H2O) and [Cu(H2L(1))Cl]Cl·0.7H2O (3·0.7H2O) was prepared, and starting from H2L(2) and CuCl2·2H2O in methanol, the complex [Cu(H2L(2))Cl2]·H2O (4·H2O) was obtained. The compounds have been characterised by elemental analysis, spectroscopic methods (IR, UV-vis and NMR spectroscopy), ESI mass spectrometry and single crystal X-ray crystallography (H2L(1), 1, 2 and 4). As a solid, 1 is diamagnetic, while it is paramagnetic in methanolic solution. The effective magnetic moment of 3.26 B.M. at room temperature indicates the change in coordination geometry from square-planar to octahedral upon dissolution. The in vitro anticancer potency of ligand precursors H2L(1) and H2L(2) and metal complexes 1-4 was studied in three human cancer cell lines (A549, CH1 and SW480) and in noncancerous murine embryonal fibroblasts (NIH/3T3), and the mechanism of cell death was also assayed by flow cytometry. Clear-cut structure-activity relationships have been established. The metal ions exert marked effects in a divergent manner: copper(ii) increases, whereas nickel(ii) and palladium(ii) decrease the cytotoxicity of the hybrids. The antiproliferative activity of H2L(1) and metal complexes 1-3 decreases in all three tumour cell lines in the following rank order: 3 > H2L(1) > 1 > 2. The role of square-planar geometry in the underlying mechanism of cytotoxicity of the metal complexes studied seems to be negligible, while structural modifications at the terminal amino group of thiosemicarbazide and proline moieties are significant for enhancing the antiproliferative activity of both hybrids and copper(ii) complexes.

  20. Sorption of nickel on chitosan

    International Nuclear Information System (INIS)

    Pivarciova, O.; Rosskopfova, O.; Galambos, M.

    2012-01-01

    This work was focused on the study of sorption properties of nickel on chitosan. Sorption of nickel on the selected sorbents was studied by batch method. Radionuclide 63 Ni was used as a tracer. Langmuir isotherm was used for interpretation of the sorption of nickel on chitosan by varying the concentration of Ni 2 + cations in aqueous phase.

  1. Dinuclear nickel and palladium complexes with bridging 2,5-diamino-1,4-benzoquinonediimines: synthesis, structures, and catalytic oligomerization of ethylene.

    Science.gov (United States)

    Taquet, Jean-Philippe; Siri, Olivier; Braunstein, Pierre; Welter, Richard

    2006-06-12

    Dinuclear, divalent acetylacetonato (acac) complexes of the type [M(acac){mu-C6H2(--NR)4}M(acac)] (M = Ni, Pd) have been prepared by the reaction of the corresponding bis(acac) metal precursor with 2,5-diamino-1,4-benzoquinonediimines C6H2(NHR)2(=NR)2 (4a, R = CH2-t-Bu; 4b, R = CH2Ph; 4c, R = Ph), which are metalated and become bridging ligands, also like in the complex [(C8H11)Pt{mu-C6H2(--NCH2-t-Bu)4}Pt(C8H11)] (6) obtained by the reaction of 4a with [PtCl2(COD)]. The complexes were fully characterized, including by X-ray diffraction for [Ni(acac){mu-C6H2(--NCH2Ph)4}Ni(acac)] (9b) and [Pd(acac){mu-C6H2(--NCH2-t-Bu)4}Pd(acac)] (10a). The coordination geometry around the metal ions is square-planar, and a complete electronic delocalization of the quinonoid pi system occurs between the metal centers over the two N--C--C--C--N halves of the ligand. The nature of the N substituent explains the differences between the supramolecular stacking arrangements found for [Ni(acac){mu-C6H2(--NR)4}Ni(acac)] (9a; R = CH2-t-Bu; 9b, R = CH2Ph). The Ni complexes were evaluated as catalyst precursors for ethylene oligomerization in the presence of AlEtCl(2) or MAO as the cocatalyst, in particular in order to study possible cooperative effects resulting from electronic communication between the metal centers and to examine the influence of the N substituent on the activity and selectivity. These catalysts afforded mostly ethylene dimers and trimers.

  2. Simultaneous determination of thermodynamic and kinetic parameters of aminopolycarbonate complexes of cobalt(II) and nickel(II) based on isothermal titration calorimetry data.

    Science.gov (United States)

    Tesmar, Aleksandra; Wyrzykowski, Dariusz; Muñoz, Eva; Pilarski, Bogusław; Pranczk, Joanna; Jacewicz, Dagmara; Chmurzyński, Lech

    2017-04-01

    The influence of the different side chain residues on the thermodynamic and kinetic parameters for complexation reactions of the Co 2 + and Ni 2 + ions has been investigated by using the isothermal titration calorimetry (ITC) technique supported by potentiometric titration data. The study was concerned with the 2 common tripodal aminocarboxylate ligands, namely, nitrilotriacetic acid and N-(2-hydroxyethyl) iminodiacetic acid. Calorimetric measurements (ITC) were run in the 2-(N-morpholino)ethanesulfonic acid hydrate (2-(N-morpholino) ethanesulfonic acid), piperazine-N,N'-bis(2-ethanesulfonic acid), and dimethylarsenic acid buffers (0.1 mol L -1 , pH 6) at 298.15 K. The quantification of the metal-buffer interactions and their incorporation into the ITC data analysis enabled to obtain the pH-independent and buffer-independent thermodynamic parameters (K, ΔG, ΔH, and ΔS) for the reactions under study. Furthermore, the kinITC method was applied to obtain kinetic information on complexation reactions from the ITC data. Correlations, based on kinetic and thermodynamic data, between the kinetics of formation of Co 2 + and Ni 2 + complexes and their thermodynamic stabilities are discussed. Copyright © 2016 John Wiley & Sons, Ltd.

  3. Electroplated tin-nickel coatings as a replacement for nickel to eliminate nickel dermatitis

    DEFF Research Database (Denmark)

    Møller, Per; Boyce, Jan M.; Nielsen, Lars Pleth

    2013-01-01

    Nickel dermatitis (skin allergy) is a growing problem in numerous countries. The alarming frequency of sensitization to nickel especially in the US caused nickel to be selected as the "Allergen of the Year" in 2008 by the American Contact Dermatitis Society. Nickel as coating in contact with skin...... has already been regulated by the nickel EU directive [94/27/EC] since 1994. In the present contribution tin/nickel alloy coatings (66.9 wt. % Sn), electrodeposited from a chloride/fluoride containing alloy electrolyte, will be presented as an alternative for both nickel and bright chromium coatings....... The main focus will be on the corrosion properties where the following corrosion investigations will be covered; corrosion potential measurements for the different coatings, estimation of corrosion rates for materials in galvanic coupling with tin/nickel coatings, salt spray test, medical tests...

  4. The cost of nickel allergy

    DEFF Research Database (Denmark)

    Hamann, Carsten R; Hamann, Dathan; Hamann, Curtis

    2013-01-01

    %), followed by aluminium-bronze (62, 17%). In total, 239 denominations released nickel (28%). Coins from Bolivia, Brazil and Costa Rica did not release nickel. Fewer than one-third of the denominations or issues from China, India, the euro area and Indonesia released nickel. In the United States, the Russian...... Federation, Japan, and Mexico, one-third or more of the denominations released nickel. Conclusions. This worldwide selection of circulating coins covered countries with 75% of the world population, and shows that the majority of the world population lives in countries where coins release nickel. Pertinently...

  5. Nickel in tap water

    DEFF Research Database (Denmark)

    Andersen, Klaus Ejner; Nielsen, G D; Flyvholm, Morten

    1983-01-01

    Nickel analyses of tap water from several sources in Copenhagen gave up to 490 X 10(-6) g X 1(-1) in the first 250 ml portions. Hot water gave higher values than cold water. After flushing for 5 min, low values were found. Considerable variation from time to time and from tap to tap was found...

  6. EPIDEMIOLOGICAL AND PATHOGENETIC ASPECTS OF NICKEL POISONING

    OpenAIRE

    Vladmila Bojanic; Vladimir Ilic; Biljana Jovic

    2007-01-01

    Nickel is widely distributed in the environment. High consumption of nickel containing products inevitably leads to environmental pollution by nickel and its derivatives at all stages of production, utilization, and disposal.Human exposure to nickel occurs primarily via inhalation and ingestion and is particularly high among nickel metallurgy workers. In addition, implantation of nickel-containing endoprostheses and iatrogenic administration of nickel-contaminated medica-tions leads to signif...

  7. SYNTHESIS AND STUDY OF COMPLEXES OF COPPER(II, ZINC, COBALT(II AND NICKEL(II WITH NITROFLUORENYLIDENE-9-AMINO(IMINO DERIVATIVES

    Directory of Open Access Journals (Sweden)

    S.B. Strashnova

    2009-12-01

    Full Text Available The complexes of general formula MCl2∙L1-4∙nH2O (where L1 - N-(2,4,7-trinitrofluorenilidene-9-p-dimethyl-aminoanilin, L2 - N-(2,4,5,7-tetranitrofluorenilidene-9-p-dimethylaminoaniline, L3 - N-(2,4,7-trinitrofluorenilidene-N-(p-dimethylaminophenylhydroxylamine, L4 - N-(2,4,5,7-tetranitrofluorenilidene-9-N-(p-dimethylaminophenyl-hydroxylamine; M=Cu, Co, Ni, Zn; n= 1-3 have been synthesized and investigated by different methods. Spectral criteria of co-ordination of the molecules L1 –L4 in electronic adsorption spectra were detected.

  8. Superposition model analysis of nickel(II) ions in trigonal bipyramidal complexes exhibiting huge zero field splitting (aka ‘giant magnetic anisotropy’)

    Energy Technology Data Exchange (ETDEWEB)

    Rudowicz, Czesław, E-mail: crudowicz@zut.edu.pl [Faculty of Chemistry, A. Mickiewicz University, 61-614 Poznań (Poland); Institute of Physics, West Pomeranian University of Technology, Szczecin (Poland); Açıkgöz, Muhammed [Department of Chemistry, Rutgers University, Newark, New Jersey 07102 (United States); Gnutek, Paweł [Institute of Physics, West Pomeranian University of Technology, Szczecin (Poland)

    2017-07-15

    Graphical abstract: Using crystal structure data for [Ni(Me{sub 6}tren)Cl](ClO{sub 4}) and [Ni(Me{sub 6}tren)Br](Br) as well as taking into account the Jahn-Teller distortions of five-fold coordinated Ni-complexes revealed by DFT geometry optimization, the ZFSPs are predicted for several structural models and wide ranges of model parameters. - Highlights: • Semiempirical study of potential SMM [Ni(Me{sub 6}tren)Cl](ClO{sub 4}) and [Ni(Me{sub 6}tren)Br](Br). • Superposition model analysis of zero field splitting (ZFS) parameters carried out. • Jahn-Teller distortions revealed by DFT geometry optimization considered. • SPM predicts D(ZFS) of observed magnitudes with positive or negative signs. • Results corroborate giant ZFS, which shall not be equated with magnetic anisotropy. - Abstract: Potential single-ion magnet Ni{sup 2+} systems: [Ni(Me{sub 6}tren)Cl](ClO{sub 4}) and [Ni(Me{sub 6}tren)Br](Br) reveal unusually high zero field splitting (ZFS). The ZFS parameter (ZFSP) D{sub expt} = −120 to −180 cm{sup −1} was determined indirectly by high-magnetic field, high-frequency electron magnetic resonance (HMF-EMR). Modeling ZFSPs using the density functional theory (DFT) codes predicts D values: −100 to −200 cm{sup −1}. Such ZFSP values may seem controversial in view of the D values usually not exceeding several tens of cm{sup −1} for Ni{sup 2+} ions. To corroborate or otherwise these results and elucidate the origin of the huge ZFS (named inappropriately as ‘giant uniaxial magnetic anisotropy’) and respective wavefunctions, we have undertaken semiempirical modeling based on the crystal field (CF) and spin Hamiltonians (SH) theory. In this paper, a feasibility study is carried out to ascertain if superposition model (SPM) calculations may yield such huge D values for these Ni{sup 2+} systems. Using crystal structure data for [Ni(Me{sub 6}tren)Cl](ClO{sub 4}) and [Ni(Me{sub 6}tren)Br](Br) as well as taking into account the Jahn

  9. The Effects of Electroless Nickel Plating Bath Conditions on Stability of Solution and Properties of Deposit

    International Nuclear Information System (INIS)

    Huh, Jin; Lee, Jae Ho

    2000-01-01

    Electroless depositions of nickel were conducted in different bath conditions to find optimum conditions of electroless nickel plating at low operating temperature and pH. The effect of complexing reagent on stability of plating solution was investigated. Sodium citrate complexed plating solution is more stable than sodium pyrophosphate complexed solution. The effects of nickel salt concentration, reducing agent, complexing agent and inhibitor on deposition rate was investigated. The effects of pH on deposition rate and content of phosphorous in deposited nickel were also analyzed. Electroless deposited nickel become crystallized with increasing pH due to lower phosphorous content. In optimum operating bath condition, deposition rate was 7 μm/hr at 60 .deg. C and pH 10.0 without stabilizer. The rate was decreased with stabilizer concentration

  10. Carbon deposition on nickel ferrites and nickel-magnetite surfaces

    International Nuclear Information System (INIS)

    Allen, G.C.; Jutson, J.A.

    1988-06-01

    Carbon deposition on Commercial Advanced Gas-Cooled Reactor (CAGR) fuel cladding and heat exchanger surfaces lowers heat transfer efficiency and increases fuel pin temperatures. Several types of deposit have been identified including both thin dense layers and also low density columnar deposits with filamentary or convoluted laminar structure. The low-density types are often associated with particles containing iron, nickel or manganese. To identify the role of nickel in the deposition process surfaces composed of nickel-iron spinels or metallic nickel/magnetite mixtures have been exposed to γ radiation in a gas environment simulating that in the reactor. Examination of these surfaces by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) have shown that while metallic nickel (Ni(O)) catalyses the formation of filamentary low density carbon deposits, the presence of divalent nickel (Ni(II)) sites in spinel type oxides is associated only with dense deposits. (author)

  11. Distribution of nickel between copper-nickel and alumina saturated iron silicate slags

    Energy Technology Data Exchange (ETDEWEB)

    Reddy, R.G.; Acholonu, C.C.

    1984-03-01

    The solubility of nickel in slag is determined in this article by equilibrating copper-nickel alloys with alumina-saturated iron silicate slags in an alumina crucible at 1573 K. The results showed that nickel dissolves in slag both as nickel oxide and as nickel metal. The presence of alumina is shown to increase the solubility of nickel in slags.

  12. Nickel ferrule applicators: a source of nickel exposure in children.

    Science.gov (United States)

    Jacob, Sharon E; Silverberg, Jonathan I; Rizk, Christopher; Silverberg, Nanette

    2015-01-01

    Eye makeup has been investigated for nickel content and found to have no direct association with nickel allergy and cosmetic dermatitis. However, the tools used (e.g., eyelash curlers, hairdressing scissors, hair curlers, and eye shadow and makeup applicators) may be sources. Nickel is ubiquitous and a wide range of sources have been reported, and makeup applicators (ferrules) now join the list. © 2015 Wiley Periodicals, Inc.

  13. SYNTHESIS AND CHARACTERIZATION OF IRON (II) AND NICKEL ...

    African Journals Online (AJOL)

    DR. AMINU

    SYNTHESIS AND CHARACTERIZATION OF IRON (II) AND NICKEL (II). SCHIFF BASE COMPLEXES. * Aliyu, H. N. and A. S. ... synthesis and magnetic studies on schiff base complexes of copper (II). Recently, Xishi et al. (2003) .... pyridylmethanimines as Tuneable Alternatives to Bipyridine Ligan in Copper Medicated Atom.

  14. Potentiometric studies of Nickel (II) and copper (II) acetyl acetonato ...

    African Journals Online (AJOL)

    Potentiometric studies of Nickel (II) and copper (II) acetyl acetonato complexes. HN Aliyu, A Mustapha. Abstract. The dissociation constant pKa of acetylacetone has been determined potentiometrically. The pKa value obtained is 9.40, indicating a weak acid. The stability constants of the complex compounds formed from the ...

  15. Pulse Reversal Plating of Nickel and Nickel Alloys for MEMS

    DEFF Research Database (Denmark)

    Tang, Peter Torben

    2001-01-01

    Pulse plating has previously been reported to improve the properties of nickel and nickel alloy deposits. Typically, focus has been on properties such as grain size, hardness and smoothness. When pulse plating is to be utilized for micro electromechanical systems (MEMS), internal stress and mater......Pulse plating has previously been reported to improve the properties of nickel and nickel alloy deposits. Typically, focus has been on properties such as grain size, hardness and smoothness. When pulse plating is to be utilized for micro electromechanical systems (MEMS), internal stress...

  16. NICKEL ALLERGY: Surgeons Beware.

    Science.gov (United States)

    Axe, Jeremie M; Sinz, Nathan J; Axe, Michael J

    2015-06-01

    When performing an orthopaedic device implantation, it should be routine practice for the surgeon to ask the patient if he or she has a metal allergy, and more specifically a nickel allergy. Ask the patient about costume jewelry or button reactions. If it is an elective surgery, obtain a confirmatory test with the aid of a dermatologist or allergist. It is recommended to use a non-nickel implant if the surgery is urgent, the patient has a confirmed allergy, or the patient does not want to undergo testing, as these implants are readily available in 2015. Finally, if the patient has a painful joint arthroplasty and all other causes have been ruled out, order a metal allergy test to aid in diagnosis.

  17. The role of nickel content and the magnetic remanence in iron-nickel alloys of lunar composition

    Science.gov (United States)

    Wasilewski, P.

    1974-01-01

    Lunar samples are magnetic primarily due to the body centered cubic (BCC) iron and iron-nickel alloys they contain. Presented for the first time are results which demonstrate that the magnitude of the martensitic thermal remanence (MTRM) induced on quenching iron-nickel alloy in the geomagnetic field depends on the nickel content of the alloy. High magnetic stability is due to the increasing dislocation density and increasingly complex microstructures associated with increasing nickel content in the alloys. The results agree with the mechanical and structural properties of the alloys. The characteristic quench martensite microstructure observed on metallographic examination provides a recognition criterion for the MTRM mechanism. These results are important for lunar and meteoritic research intending to ascertain the paleofield responsible for the observed remanent magnetization.-

  18. Occurrence model for magmatic sulfide-rich nickel-copper-(platinum-group element) deposits related to mafic and ultramafic dike-sill complexes: Chapter I in Mineral deposit models for resource assessment

    Science.gov (United States)

    Schulz, Klaus J.; Woodruff, Laurel G.; Nicholson, Suzanne W.; Seal, Robert R.; Piatak, Nadine M.; Chandler, Val W.; Mars, John L.

    2014-01-01

    Magmatic sulfide deposits containing nickel (Ni) and copper (Cu), with or without (±) platinum-group elements (PGE), account for approximately 60 percent of the world’s nickel production. Most of the remainder of the Ni production is derived from lateritic deposits, which form by weathering of ultramafic rocks in humid tropical conditions. Magmatic Ni-Cu±PGE sulfide deposits are spatially and genetically related to bodies of mafic and/or ultramafic rocks. The sulfide deposits form when the mantle-derived mafic and/or ultramafic magmas become sulfide-saturated and segregate immiscible sulfide liquid, commonly following interaction with continental crustal rocks.

  19. The accumulation of nickel in human lungs.

    OpenAIRE

    Edelman, D A; Roggli, V L

    1989-01-01

    Using data from published studies, lung concentrations of nickel were compare for persons with and without occupational exposure to nickel. As expected, the concentrations were much higher for persons with occupational exposure. To estimate the effects of nickel-containing tobacco smoke and nickel in the ambient air on the amount of nickel accumulated in lungs over time, a model was derived that took into account various variables related to the deposition of nickel in lungs. The model predic...

  20. Electronic, Magnetic, and Redox Properties and O2Reactivity of Iron(II) and Nickel(II) o-Semiquinonate Complexes of a Tris(thioether) Ligand: Uncovering the Intradiol Cleaving Reactivity of an Iron(II) o-Semiquinonate Complex.

    Science.gov (United States)

    Wang, Peng; Killian, Michelle M; Saber, Mohamed R; Qiu, Tian; Yap, Glenn P A; Popescu, Codrina V; Rosenthal, Joel; Dunbar, Kim R; Brunold, Thomas C; Riordan, Charles G

    2017-09-05

    The iron(II) semiquinonate character within the iron(III) catecholate species has been proposed by numerous studies to account for the O 2 reactivity of intradiol catechol dioxygenases, but a well-characterized iron(II) semiquinonate species that exhibits intradiol cleaving reactivity has not yet been reported. In this study, a detailed electronic structure description of the first iron(II) o-semiquinonate complex, [PhTt tBu ]Fe(phenSQ) [PhTt tBu = phenyltris(tert-butylthiomethyl)borate; phenSQ = 9,10-phenanthrenesemiquinonate; Wang et al. Chem. Commun. 2014, 50, 5871-5873], was generated through a combination of electronic and Mössbauer spectroscopies, SQUID magnetometry, and density functional theory (DFT) calculations. [PhTt tBu ]Fe(phenSQ) reacts with O 2 to generate an intradiol cleavage product, diphenic anhydride, in 16% yield. To assess the dependence of the intradiol reactivity on the identity of the metal ion, the nickel analogue, [PhTt tBu ]Ni(phenSQ), and its derivative, [PhTt tBu ]Ni(3,5-DBSQ) (3,5-DBSQ = 3,5-di-tert-butyl-1,2-semiquinonate), were prepared and characterized by X-ray crystallography, mass spectrometry, 1 H NMR and electronic spectroscopies, and SQUID magnetometry. DFT calculations, evaluated on the basis of the experimental data, support the electronic structure descriptions of [PhTt tBu ]Ni(phenSQ) and [PhTt tBu ]Ni(3,5-DBSQ) as high-spin nickel(II) complexes with antiferromagnetically coupled semiquinonate ligands. Unlike its iron counterpart, [PhTt tBu ]Ni(phenSQ) decomposes slowly in an O 2 atmosphere to generate 14% phenanthrenequinone with a negligible amount of diphenic anhydride. [PhTt tBu ]Ni(3,5-DBSQ) does not react with O 2 . This dramatic effect of the metal-ion identity supports the hypothesis that a metal(III) alkylperoxo species serves as an intermediate in the intradiol cleaving reactions. The redox properties of all three complexes were probed using cyclic voltammetry and differential pulse voltammetry, which indicate

  1. New nickel(II) and copper(II) complexes with unsymmetrical Schiff bases derived from (1R,2R)(-)cyclohexanediamine and the application of Cu(II) complexes for hybrid thin layers deposition.

    Science.gov (United States)

    Barwiolek, M; Szlyk, E; Surdykowski, A; Wojtczak, A

    2013-08-28

    New unsymmetrical Schiff bases obtained by condensation of (1R,2R)(-)cyclohexanediamine with 2-hydroxy-3,5-di-tert-butylbenzaldehyde (3,5-(t)bba) and 2-hydroxy-3-methoxybenzaldehyde (3-metoxba) or 2-hydroxy-5-nitrobenzaldehyde (5-nba) and 2-hydroxyacetophenone (hacphen) were used for the synthesis of Cu(ii) and Ni(ii) complexes. The ligands and complexes were characterized by circular dichroism (CD), UV-vis, IR, (1)H (NOE diff) (ligand) and (13)C NMR (ligand) spectra. The X-ray crystal structures solved for Ni(II)(1R,2R)(-)chxn(3,5-(t)bba)(hacphen) exhibit distortion of the coordination sphere towards tetrahedral in the solid phase. The complex crystallized in the orthorhombic non-centrosymmetric P2(1)2(1)2(1) space group. Thin layers of copper(II) complexes were deposited on Si(111) by a spin coating technique and characterized by scanning electron microscopy (SEM/EDS), atomic force microscopy (AFM) and fluorescence spectroscopy. Layer deposition conditions were studied and optimal parameters were found (1500 rpm, time 30 s). For copper(ii) layers the most intensive fluorescence band from intraligand transition at 514 nm was observed. CD spectra of complexes in MeCN suggest the tetrahedral distortion from the square planar geometry of the central ion of the coordination sphere in solution. The (1)H NMR NOE diff. spectra of ligands were measured and the positions of the nearest hydrogen atoms in the cyclohexane and aromatic rings were discussed.

  2. Synthesis and characterization of nickel(II), cobalt(II), copper(II), manganese(II), zinc(II), zirconium(IV), dioxouranium(VI) and dioxomolybdenum(VI) complexes of a new Schiff base derived from salicylaldehyde and 5-methylpyrazole-3-carbohydrazide

    International Nuclear Information System (INIS)

    Syamal, A.; Maurya, M.R.

    1986-01-01

    Synthesis of a new Schiff base derived from salicylaldehyde and 5-methylpyrazole-3-carbohydrazide, and its coordination compounds with nickel(II), cobalt(II), copper(II), manganese(II), zinc(II), zirconium(IV), dioxouranium(VI) and dioxomolybdenum(VI) are described. The ligand and the complexes have been characterized on the basis of analytical, conductance, molecular weight, i.r., electronic and n.m.r. spectra and magnetic susceptibility measurements. The stoichiometries of the complexes are represented as NiL . 3H 2 O, CoL . 2H 2 O, CuL, MnL . 2H 2 O, ZnL . H 2 O, Zr(OH) 2 (LH) 2 , Zr(OH) 2 L . 2MeOH, UO 2 L . MeOH and MoO 2 L . MeOH (where LH 2 =Schiff base). The copper(II) complex shows a subnormal magnetic moment due to antiferromagnetic exchange interaction while the nickel(II), cobalt(II) and manganese(II) complexes show normal magnetic moments at room temperature. The i.r. and n.m.r. spectral studies show that the Schiff base behaves as a dibasic and tridentate ligand coordinating through the deprotonated phenolic oxygen, enolic oxygen and azomethine nitrogen. (orig.)

  3. Nickel Excretion in Urine after Oral Administration

    DEFF Research Database (Denmark)

    Menne, T.; Mikkelsen, H. I.; Solgaard, Per Bent

    1978-01-01

    In recent years the importance of internal exposure to nickel in patients with recurrent hand eczema and nickel allergy has become evident. The present study was performed in order to investigate the value of urinary nickel determinations as an index of oral nickel intake. After oral administration...... of 5.6 mg nickel (as the sulfate), increased nickel excretion was found over the following 2-3 days. We conclude that consecutive urinary nickel determinations are able to disclose variations in oral intake of nickel....

  4. Nickel release from nickel-plated metals and stainless steels.

    Science.gov (United States)

    Haudrechy, P; Foussereau, J; Mantout, B; Baroux, B

    1994-10-01

    Nickel release from nickel-plated metals often induces allergic contact dermatitis, but, for nickel-containing stainless steels, the effect is not well-known. In this paper, AISI 304, 316L, 303 and 430 type stainless steels, nickel and nickel-plated materials were investigated. 4 tests were performed: patch tests, leaching experiments, dimethylglyoxime (DMG) spot tests and electrochemical tests. Patch tests showed that 96% of the patients were intolerant to Ni-plated samples, and 14% to a high-sulfur stainless steel (303), while nickel-containing stainless steels with a low sulfur content elicited no reactions. Leaching experiments confirmed the patch tests: in acidic artificial sweat, Ni-plated samples released about 100 micrograms/cm2/week of nickel, while low-sulfur stainless steels released less than 0.03 microgram/cm2/week of nickel, and AISI 303 about 1.5 micrograms/cm2/week. Attention is drawn to the irrelevance of the DMG spot test, which reveals Ni present in the metal bulk but not its dissolution rate. Electrochemical experiments showed that 304 and 316 grades remain passive in the environments tested, while Ni-plated steels and AISI 303 can suffer significant cation dissolution. Thus, Ni-containing 304 and 316 steels should not induce contact dermatitis, while 303 should be avoided. A reliable nitric acid spot test is proposed to distinguish this grade from other stainless steels.

  5. Electrolytic Recovery of Nickel from Spent Electroless Nickel Bath Solution

    Directory of Open Access Journals (Sweden)

    R. Idhayachander

    2010-01-01

    Full Text Available Plating industry is one of the largest polluting small scale industries and nickel plating is among the important surface finishing process in this industry. The waste generated during this operation contains toxic nickel. Nickel removal and recovery is of great interest from spent bath for environmental and economic reasons. Spent electroless nickel solution from a reed relay switch manufacturing industry situated in Chennai was taken for electrolytic recovery of nickel. Electrolytic experiment was carried out with mild steel and gold coated mild steel as cathode and the different parameters such as current density, time, mixing and pH of the solution were varied and recovery and current efficiency was studied. It was noticed that there was an increase in current efficiency up to 5 A/dm2 and after that it declines. There is no significant improvement with mixing but with modified cathode there was some improvement. Removal of nickel from the spent electroless nickel bath was 81.81% at 5 A/dm2 and pH 4.23. Under this condition, the content of nickel was reduced to 0.94 g/L from 5.16 g/L. with 62.97% current efficiency.

  6. Electrochemical and AFM study of nickel nucleation mechanisms on vitreous carbon from ammonium sulfate solutions

    International Nuclear Information System (INIS)

    Grujicic, Darko; Pesic, Batric

    2006-01-01

    Reaction and nucleation mechanisms of nickel in ammoniacal solutions have been investigated as a function of nickel concentration, solution pH, deposition potential, temperature and conditioning potential. Electrochemical mechanisms of nickel reduction were found to be pH dependent, while their kinetics was concentration dependent. A surface film formed by anodic oxidation passivates nickel clusters preventing their further oxidation. Nickel nucleation on vitreous carbon, which proceeds according to the progressive nucleation model, shows a large degree of inhibition at both pH 6 and pH 9. Cluster sizes were larger when electrodeposition was carried out from solutions with higher nickel concentrations. The clusters were also larger at more negative deposition potentials and at higher solution pH. Cluster population density increased with the increasing solution temperature. Different activation energies for the nickel-aquo and nickel-ammino complexes calculated from Arrhenius diagram indicate that electroreduction of nickel-ammino complex is energetically more demanding. All electrochemical results were further verified by the atomic force microscopy investigations

  7. Syntheses, X-ray, MSn, NMR and CD structure determination of nickel(II) complexes of Schiff bases of (S)-N-(2-benzoylphenyl)-1-benzylpyrrolidine-2-carboxamide and aromatic alpha-amino acids

    NARCIS (Netherlands)

    Nadvornik, Milan; Langer, Vratislav; Jirasko, Robert; Holcapek, Michal; Weidlich, Tomas; Lycka, Antonin; Popkov, Alexander

    2008-01-01

    A preparative procedure for the synthesis of an important chiral synthon of side-chain protected tyrosine was developed and optimised for the minimisation of nickel salts waste. While preparing a similar side-chain protected tryptophan synthon, an unexpected low stability was found of the

  8. Point defects in nickel

    International Nuclear Information System (INIS)

    Peretto, P.

    1969-01-01

    The defects in electron irradiated nickel (20 deg. K) or neutron irradiated nickel (28 deg. K) are studied by simultaneous analysis using the magnetic after-effect, electron microscopy and electrical resistivity recovery. We use zone refined nickel (99.999 per cent) which, for some experiments, is alloyed with a small amount of iron (for example 0.1 per cent Fe). The temperature dependant electrical recovery may be divided in four stages. The sub-stages I B (31 deg. K), I C (42 deg. K), I D (from to 57 deg. K) and I E (62 deg. K) of stage I are due to the disappearance of single interstitials into vacancies. The interstitial defect has a split configuration with a migration energy of about 0.15 eV. In the close pair which disappears in stage I B the interstitial is found to be in a 3. neighbour position whilst in stage I D it is near the direction from the vacancy. In stage I E there is no longer any interaction between the interstitial and the vacancy. The stage II is due to more complicated interstitial defects: di-interstitials for stage II B (84 deg. K) and larger and larger interstitial loops for the following sub-stages. The loops may be seen by electron microscopy. Impurities can play the role of nucleation centers for the loops. Stages III A (370 deg. K) and III B (376 deg. K) are due to two types of di-vacancies. During stage IV (410 deg. K) the single vacancies migrate. Vacancy type loops and interstitial type loops grow concurrently and disappear at about 800 deg. K as observed by electron microscopy. (author) [fr

  9. Nickel, cobalt, and their alloys

    CERN Document Server

    2000-01-01

    This book is a comprehensive guide to the compositions, properties, processing, performance, and applications of nickel, cobalt, and their alloys. It includes all of the essential information contained in the ASM Handbook series, as well as new or updated coverage in many areas in the nickel, cobalt, and related industries.

  10. Syntheses and study on nickel(II) complexes with thiodiglycolic acid and nitrogen-donor ligands. X-ray structures of [Ni(bpy)(tdga)(H2O)] . 4H2O and [(en)Ni(µ-tdga)2Ni(en)] . 4H2O (tdgaH2=thiodiglycolic acid)

    Czech Academy of Sciences Publication Activity Database

    Kopel, P.; Trávníček, Zdeněk; Marek, J.; Mrozinski, J.

    2004-01-01

    Roč. 23, č. 9 (2004), s. 1573-1578 ISSN 0277-5387 R&D Projects: GA ČR(CZ) GA203/02/0436 Grant - others:GA MŠk1(CZ) MSM 153100007; GA MŠK1(CZ) MSM 143100008; Polish State Committee for Scientific Research(PL) 4T09A 11523 Institutional research plan: CEZ:AV0Z5038910 Keywords : nickel(II) * thiodiglycolic acid complexes * X-ray structures Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.586, year: 2004

  11. Characterization and assessment of dermal and inhalable nickel exposures in nickel production and primary user industries.

    Science.gov (United States)

    Hughson, G W; Galea, K S; Heim, K E

    2010-01-01

    The aim of this study was to measure the levels of nickel in the skin contaminant layer of workers involved in specific processes and tasks within the primary nickel production and primary nickel user industries. Dermal exposure samples were collected using moist wipes to recover surface contamination from defined areas of skin. These were analysed for soluble and insoluble nickel species. Personal samples of inhalable dust were also collected to determine the corresponding inhalable nickel exposures. The air samples were analysed for total inhalable dust and then for soluble, sulfidic, metallic, and oxidic nickel species. The workplace surveys were carried out in five different workplaces, including three nickel refineries, a stainless steel plant, and a powder metallurgy plant, all of which were located in Europe. Nickel refinery workers involved with electrolytic nickel recovery processes had soluble dermal nickel exposure of 0.34 microg cm(-2) [geometric mean (GM)] to the hands and forearms. The GM of soluble dermal nickel exposure for workers involved in packing nickel salts (nickel chloride hexahydrate, nickel sulphate hexahydrate, and nickel hydroxycarbonate) was 0.61 microg cm(-2). Refinery workers involved in packing nickel metal powders and end-user powder operatives in magnet production had the highest dermal exposure (GM = 2.59 microg cm(-2) soluble nickel). The hands, forearms, face, and neck of these workers all received greater dermal nickel exposure compared with the other jobs included in this study. The soluble nickel dermal exposures for stainless steel production workers were at or slightly above the limit of detection (0.02 microg cm(-2) soluble nickel). The highest inhalable nickel concentrations were observed for the workers involved in nickel powder packing (GM = 0.77 mg m(-3)), although the soluble component comprised only 2% of the total nickel content. The highest airborne soluble nickel exposures were associated with refineries using

  12. Mechanisms of nickel toxicity in microorganisms

    OpenAIRE

    Macomber, Lee; Hausinger, Robert P.

    2011-01-01

    Nickel has long been known to be an important human toxicant, including having the ability to form carcinomas, but until recently nickel was believed to be an issue only to microorganisms living in nickel-rich serpentine soils or areas contaminated by industrial pollution. This assumption was overturned by the discovery of a nickel defense system (RcnR/RcnA) found in microorganisms that live in a wide range of environmental niches, suggesting that nickel homeostasis is a general biological co...

  13. Synthesis, characterization and crystal structure of new nickel ...

    Indian Academy of Sciences (India)

    Abstract. A novel nickel molybdenum complex with the 2,6-pyridine dicarboxylic acid ligand was successfully synthesized and characterized by thermogravimetric analysis and single crystal X-ray crystallography. The single-crystal X-ray data revealed that the structure is a hydrated 1-D polymer with two different Ni sites.

  14. Tris(catecholato)silicates of nickel: Synthesis, characterization and ...

    Indian Academy of Sciences (India)

    Administrator

    Catecholato complexes of transition metals have evoked interest for long and have also been the subject of recent studies due to their importance as useful model compounds for the study of microbial uptake and transport of iron. With regard to the constitutional and structural issues of nickel catecholates, many ...

  15. Comparative Studies of the Speciation Patterns of Nickel and ...

    African Journals Online (AJOL)

    NJD

    2005-01-31

    Jan 31, 2005 ... ABSTRACT. Results of speciation studies of nickel and chromium in wastewater, surface and groundwater systems using flame atomic absorption ... instance, chromium with oxidation state of +VI is relatively more toxic, shows ... former forms a complex with DTPA that is rendered electro- chemically inactive ...

  16. Cobalt(II), nickel(II), copper(II), and zinc(II) complexes with [3(5)]adamanzane, 1,5,9,13-tetraazabicyclo[7.7.3]nonadecane and [(2.3)(2).2(1)]adamanzane, 1,5,9,12-tetraazabicyclo[7.5.2]hexadecane

    DEFF Research Database (Denmark)

    Broge, Louise; Pretzmann, Ulla; Jensen, Nicolai

    2001-01-01

    ) and of three cobalt(II), four nickel(II), one copper(II), and two zinc(II) complexes with [3(5)]adamanzane. For nine of these compounds (2-8, 10b, and 12) the single-crystal X-ray structures were determined. The coordination geometry around the metal ion is square pyramidal in [Cu([(2.3)(2).2(1)]adz)Br]ClO4 (2......) and trigonal bipyramidal in the isostructural structures [Cu([3(5)]adz)Br]Br (3), [Ni-([3(5)]adz)Cl]Cl (5), [Ni([3(5)]adz)Br]Br (6), and [Co([3(5)]adz)Cl]Cl (8). In [Ni([3(5)]adz)(NO3)]NO3 (4) and [Ni([3(5)]-adz)(ClO4)]ClO4 (7) the coordination geometry around nickel(II) is a distorted octahedron...... with the inorganic ligands at cis positions. The coordination polyhedron around the metal ion in [Co([3(5)]adz)][ZnCl4] (10b) and [Zn([3(5)]adz)][ZnCl4] (12) is a slightly distorted tetrahedron. Anation equilibrium constants were determined spectrophotometrically for complexes 2-6 at 25 and 40 degreesC and fall...

  17. Cobalt(II), nickel(II), copper(II), and zinc(II) complexes with [3(5)]adamanzane, 1,5,9,13-tetraazabicyclo[7.7.3]nonadecane and [(2.3)(2).2(1)]adamanzane, 1,5,9,12-tetraazabicyclo[7.5.2]hexadecane

    DEFF Research Database (Denmark)

    Broge, Louise; Pretzmann, Ulla; Jensen, Nicolai

    2001-01-01

    Isolation of the free bicyclic tetraamine, [3(5)]adamanzane .H2O (1,5,9,13-tetraazabicyclo[7.7.3]nonadecane .H2O), is reported along with the synthesis and characterization of a copper(II) complex of the smaller macrocycle [(2.3)(2).2(1)]-adamanzane (1,5,9,12-tetraazabicyclo[7.5.2]hexadecane......) and of three cobalt(II), four nickel(II), one copper(II), and two zinc(II) complexes with [3(5)]adamanzane. For nine of these compounds (2-8, 10b, and 12) the single-crystal X-ray structures were determined. The coordination geometry around the metal ion is square pyramidal in [Cu([(2.3)(2).2(1)]adz)Br]ClO4 (2......) and trigonal bipyramidal in the isostructural structures [Cu([3(5)]adz)Br]Br (3), [Ni-([3(5)]adz)Cl]Cl (5), [Ni([3(5)]adz)Br]Br (6), and [Co([3(5)]adz)Cl]Cl (8). In [Ni([3(5)]adz)(NO3)]NO3 (4) and [Ni([3(5)]-adz)(ClO4)]ClO4 (7) the coordination geometry around nickel(II) is a distorted octahedron...

  18. Removing nickel from nickel-coated carbon fibers

    Science.gov (United States)

    Hardianto, A.; Hertleer, C.; De Mey, G.; Van Langenhove, L.

    2017-10-01

    Conductive fibers/yarns are one of the most important materials for smart textiles because of their electrically conductive functionality combined with flexibility and light weight. They can be applied in many fields such as the medical sector, electronics, sensors and even as thermoelectric generators. Temperature sensors, for example, can be made using the thermocouple or thermopile principle which usually uses two different metal wires that can produce a temperature-dependent voltage. However, if metal wires are inserted into a textile structure, they will decrease the flexibility properties of the textile product. Nickel-coated Carbon Fiber (NiCF), a conductive textile yarn, has a potential use as a textile-based thermopile if we can create an alternating region of carbon and nickel along the fiber which in turn it can be used for substituting the metallic thermopile. The idea was to remove nickel from NiCF in order to obtain a yarn that contains alternating zones of carbon and nickel. Due to no literature reporting on how to remove nickel from NiCF, in this paper we investigated some chemicals to remove nickel from NiCF.

  19. Initial study of Nickel Electrolyte for EnFACE Process

    Directory of Open Access Journals (Sweden)

    Tri Widayatno

    2015-03-01

    Full Text Available Nickel electrolyte for a micro-pattern transfer process without photolithography, EnFACE, has been developed. Previous work on copper deposition indicated that a conductivity of ~2.7 Sm-1 is required. Electrochemical parameters of electrolyte i.e. current density and overpotential are also crucial to govern a successful pattern replication. Therefore, the investigation focused on the measurement of physicochemical properties and electrochemical behaviour of the electrolyte at different nickel concentrations and complexing agents of chloride and sulfamate. Nickel electrolytes containing sulfamate, chloride and combined sulfamate-chloride with concentrations between 0.14 M and 0.3 M were investigated. Physicochemical properties i.e. pH and conductivity were measured to ensure if they were in the desired value. The electrochemical behaviour of the electrolytes was measured by polarisation experiments in a standard three-electrode cell. The working electrode was a copper disc (surface area of 0.196 cm2 and the counter electrode was platinum mesh. The potential was measured againts a saturated calomel reference electrode (SCE. The experiments were carried out at various scan rate and Rotating Disc Electrode (RDE rotation speed to see the effect of scan rate and agitation. Based on the measured physicochemical properties, the electrolyte of 0.19 M nickel sulfamate was chosen for experimentation. Polarisation curve of agitated solution suggested that overall nickel electrodeposition reaction is controlled by a combination of kinetics and mass transfer.  Reduction potential of nickel was in the range of -0.7 to -1.0 V. The corresponding current densities for nickel deposition were in the range of -0.1 to -1.5 mA cm-2.

  20. Contact hypersensitivity to nickel in patients with atopic dermatitis

    Directory of Open Access Journals (Sweden)

    Michał Rożalski

    2017-04-01

    Full Text Available Atopic dermatitis is a chronic, recurrent inflammatory dermatosis with a complex and not fully explained pathogenesis. Recent years’ research points to a significant percentage of patients with atopic eczema in whom hapten patch test results are positive, especially with respect to nickel. These observations undermine suggestions that contact allergy (type IV hypersensitivity is rare in this group due to the dominance of the Th2-type cellular response characteristic for type I allergic reactions. In this review we aimed to systematize current knowledge regarding the pathomechanisms of contact hypersensitivity to nickel in patients with atopic dermatitis and the potential influence of this hapten on the clinical course of the disease.

  1. The optimization of the analysis of nickel-63 in urine

    International Nuclear Information System (INIS)

    Kramer, G.H.

    1981-05-01

    A method has been developed that separates nickel-63 from urine. The subsequent estimation of activity is by liquid scintillation counting. The urine is wet ashed by a new procedure which is much faster than conventional ashing methods. Interfering phosphates are removed prior to a precipitation of Ni as the dimethylglyoxime complex. The effects of the carrier weight, the pH of the phosphate removal step and the pH of the dimethylglyoxime precipiation have been investigated and optimized to give a mean recovery of 97 +- 8% for nickel-63. The detection limit is estimated to be 1.5 pCi (55 mBq) per sample. (author)

  2. A Mechanistic Insight into the Nickel-Catalyzed Homocoupling Reaction of Terminal Alkynes

    OpenAIRE

    Ghosh, Subrata

    2018-01-01

    1,3-Diynes are frequently found as an important structural motif in natural products, pharmaceuticals and bioactive compounds, electronic and optical materials and supramolecular molecules. Copper and palladium complexes are widely used to prepare 1,3-diynes by homocoupling of terminal alkynes; albeit the potential of nickel complexes towards the same is essentially unexplored. Although a detailed study on the reported nickel-acetylene chemistry has not been carried out, a generalized mechani...

  3. Influence of dietary factors, age and nickel contact dermatitis on nickel excretion.

    Science.gov (United States)

    Darsow, Ulf; Fedorov, Michael; Schwegler, Ursula; Twardella, Dorothee; Schaller, Karl-Heinz; Habernegg, Renate; Fromme, Hermann; Ring, Johannes; Behrendt, Heidrun

    2012-12-01

    Nickel is a frequently detected cause of allergic contact dermatitis. Ingestion of nickel may lead to flares of nickel contact dermatitis. We examined nickel excretion in the urine of 164 female patients with and without nickel contact dermatitis. The associations between age, atopic dermatitis, nickel contact dermatitis and nickel exposure through nutrition (e.g. dietary supplements) and by patch tests were investigated prospectively. Nickel was measured with atomic absorption spectrometry with two different standardized methods. A nickel detection limit of 0.2 µg/l was exceeded by all samples. The 95th percentiles of urine nickel concentration were 3.77 µg/l (age 18-30 years) and 3.98 µg/l (age 31-46 years). Bivariate analyses pointed to significantly increased nickel excretion with increasing age, ingestion of dietary supplements, drinking of stagnant tap water, and consumption of nickel-rich food. In the multivariate analysis, age and dietary supplements remained significant predictors of high nickel excretion. A non-significant increase in the median concentration of nickel was observed after the administration of conventional nickel patch tests. Patients with atopic eczema showed urine nickel concentrations similar to those in non-atopic controls. The 95th percentile of nickel excretion in our study population markedly exceeded the actual reference value of 3 µg/l. Age and consumption of dietary supplements are the most important predictors. The use of stagnant tap water and consumption of nickel-rich food contribute to the total load. These factors should be explicitly mentioned when allergic patients on a low-nickel diet are counselled. In contrast, existing nickel contact sensitization was not more frequent in subjects with higher nickel excretion. Nickel patch testing may cause transient minor systemic nickel exposure. The findings of this study extend our understanding and management of factors associated with nickel allergy. © 2012 John Wiley

  4. Excessive nickel release from mobile phones--a persistent cause of nickel allergy and dermatitis

    DEFF Research Database (Denmark)

    Jensen, Peter; Johansen, Jeanne D; Zachariae, Claus

    2011-01-01

    phones, we showed that eight (19.5%) of 41 mobile phones marketed in Denmark between 2003 and 2007 released nickel in concentrations that may result in nickel allergy and dermatitis. In 2009, the EU Nickel Directive was revised to include nickel-releasing mobile phones.......Despite the political intention to limit nickel allergy and dermatitis in Europeans, nickel allergy remains frequent. There are several explanations for the persistence of nickel allergy and dermatitis, including the increasing use of mobile phones. Before regulation of nickel release from mobile...

  5. Biosorption of nickel with barley straw.

    Science.gov (United States)

    Thevannan, Ayyasamy; Mungroo, Rubeena; Niu, Catherine Hui

    2010-03-01

    Wastewater containing nickel sulphate generated from a nickel plating industry is of great concern. In the present work, biosorption of nickel by barley straw from nickel sulphate solution was investigated. Nickel uptake at room temperature (23+/-0.5 degrees C) was very sensitive to solution pH, showing a better uptake value at a pH of 4.85+/-0.10 among the tested values. The nickel biosorption isotherm fitted well the Langmuir equation. When the ionic strength (IS) of the solution was increased from less than 0.02-0.6M, nickel uptake was reduced to 12% of that obtained at IS of less than 0.02 M. Barley straw showed a higher nickel uptake (0.61 mmol/g) than acid washed crab shells (0.04 mmol/g), demonstrating its potential as an adsorbent for removal of nickel. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

  6. EPIDEMIOLOGICAL AND PATHOGENETIC ASPECTS OF NICKEL POISONING

    Directory of Open Access Journals (Sweden)

    Vladmila Bojanic

    2007-04-01

    Full Text Available Nickel is widely distributed in the environment. High consumption of nickel containing products inevitably leads to environmental pollution by nickel and its derivatives at all stages of production, utilization, and disposal.Human exposure to nickel occurs primarily via inhalation and ingestion and is particularly high among nickel metallurgy workers. In addition, implantation of nickel-containing endoprostheses and iatrogenic administration of nickel-contaminated medica-tions leads to significant parenteral exposures. Exposure to nickel compounds can produce a variety of adverse effects on human health. Nickel allergy in the form of contact dermatitis is the most common reaction.A frontal headache, vertigo, nausea, vomiting, insomnia, and irritability are the most common signs of acute poisoning with nickel compounds. The respiratory tract, kidneys and liver suffer the most significant changes like nickel pneumoconiosis, chronic rhinitis and sinonasal tumors and transitory nephropathy. Although the accumulation of nickel in the body through chronic exposure can lead to lung fibrosis, cardiovascular and kidney diseases, the most serious concerns relate to nickel’s carcinogenic activity. Nickel compounds are carcinogenic to humans and metallic nickel is possibly carcinogenic to humans.

  7. Relationship between nickel allergy and diet

    Directory of Open Access Journals (Sweden)

    Sharma Ashimav

    2007-01-01

    Full Text Available Nickel is a ubiquitous trace element and it occurs in soil, water, air and of the biosphere. It is mostly used to manufacture stainless steel. Nickel is the commonest cause of metal allergy. Nickel allergy is a chronic and recurring skin problem; females are affected more commonly than males. Nickel allergy may develop at any age. Once developed, it tends to persist life-long. Nickel is present in most of the dietary items and food is considered to be a major source of nickel exposure for the general population. Nickel content in food may vary considerably from place to place due to the difference in nickel content of the soil. However, certain foods are routinely high in nickel content. Nickel in the diet of a nickel-sensitive person can provoke dermatitis. Careful selection of food with relatively low nickel concentration can bring a reduction in the total dietary intake of nickel per day. This can influence the outcome of the disease and can benefit the nickel sensitive patient.

  8. Relationship between nickel allergy and diet.

    Science.gov (United States)

    Sharma, Ashimav Deb

    2007-01-01

    Nickel is a ubiquitous trace element and it occurs in soil, water, air and of the biosphere. It is mostly used to manufacture stainless steel. Nickel is the commonest cause of metal allergy. Nickel allergy is a chronic and recurring skin problem; females are affected more commonly than males. Nickel allergy may develop at any age. Once developed, it tends to persist life-long. Nickel is present in most of the dietary items and food is considered to be a major source of nickel exposure for the general population. Nickel content in food may vary considerably from place to place due to the difference in nickel content of the soil. However, certain foods are routinely high in nickel content. Nickel in the diet of a nickel-sensitive person can provoke dermatitis. Careful selection of food with relatively low nickel concentration can bring a reduction in the total dietary intake of nickel per day. This can influence the outcome of the disease and can benefit the nickel sensitive patient.

  9. Effect of degassing addition on the solidification segregation of nickel aluminum bronze

    Science.gov (United States)

    Syazwan, F.; Kavinjr, M.; Maghribi, S.; Ashraf, N.; Hadi, A.; Shayfull, Z.; Rashidi, M. M.

    2017-09-01

    The effect of degassing agent addition on the solidification segregation of Nickel Aluminum Bronze was investigated. The complex relationship between the development of the solidification microstructures and buildup of microsegregation in Nickel Aluminum Bronze was obtained by using microstructure analysis and EDS analysis. This experiment describes the characterization of microsegregation in Nickel Aluminum Bronze which was made using point to count microanalysis along the microstructure. With this method, the differences of elements distribution in alloys solidified in the microstructure were clearly evidenced. The results show a microstructure directly affected by segregation of elements in Nickel Aluminum Bronze matrix. There is segregation of elements in the Late To Freeze (LTF) region after solidification from melting. As for degassing treatment, higher degassing addition on the Nickel Aluminum Bronze increased the elements segregation.

  10. Nickel-resistant bacteria from anthropogenically nickel-polluted and naturally nickel-percolated ecosystems.

    Science.gov (United States)

    Stoppel, R; Schlegel, H G

    1995-06-01

    DNA fragments harboring the nickel resistance determinants from bacteria isolated from anthropogenically polluted ecosystems in Europe and Zaire were compared with those harboring the nickel resistance determinants from bacteria isolated from naturally nickel-percolated soils from New Caledonia by DNA-DNA hybridization. The biotinylated DNA probes were derived from the previously described Alcaligenes eutrophus CH34, Alcaligenes xylosoxidans 31A, Alcaligenes denitrificans 4a-2, and Klebsiella oxytoca CCUG 15788 and four new nickel resistance-determining fragments cloned from strains isolated from soils under nickel-hyperaccumulating trees. Nine probes were hybridized with endonuclease-cleaved plasmid and total DNA samples from 56 nickel-resistant strains. Some of the New Caledonian strains were tentatively identified as Acinetobacter, Pseudomonas mendocina, Comamonas, Hafnia alvei, Burkholderia, Arthrobacter aurescens, and Arthrobacter ramosus strains. The DNA of most strains showed homologies to one or several of the following nickel resistance determinants: the cnr and ncc operons of the strains A. eutrophus CH34 and A. xylosoxidans 31A, respectively, the nre operon of strain 31A, and the nickel resistance determinants of K. oxytoca. On the basis of their hybridization reactions the nickel resistance determinants of the strains could be assigned to four groups: (i) cnr/ncc type, (ii) cnr/ncc/nre type, (iii) K. oxytoca type, and (iv) others. The majority of the strains were assigned to the known groups. Among the strains from Belgium and Zaire, exclusively the cnr/ncc and the cnr/ncc/nre types were found. Among the New Caledonian strains all four types were represented. Homologies to the nre operon were found only in combination with the cnr/ncc operon. The homologies to the cnr/ncc operon were the most abundant and were detected alone or together with homologies to the nre operon. Only the DNA of the strains isolated from soil in Scotland and the United States

  11. The EU Nickel Directive revisited--future steps towards better protection against nickel allergy

    DEFF Research Database (Denmark)

    Thyssen, Jacob P; Uter, Wolfgang; McFadden, John

    2011-01-01

    In July 2001, the EU Nickel Directive came into full force to protect European citizens against nickel allergy and dermatitis. Prior to this intervention, Northern European governments had already begun to regulate consumer nickel exposure. According to part 2 of the EU Nickel Directive and the D......In July 2001, the EU Nickel Directive came into full force to protect European citizens against nickel allergy and dermatitis. Prior to this intervention, Northern European governments had already begun to regulate consumer nickel exposure. According to part 2 of the EU Nickel Directive...... and the Danish nickel regulation, consumer items intended to be in direct and prolonged contact with the skin were not allowed to release more than 0.5 µg nickel/cm2/week. It was considered unlikely that nickel allergy would disappear altogether as a proportion of individuals reacted below the level defined...

  12. Relationship between nickel allergy and diet

    OpenAIRE

    Sharma Ashimav

    2007-01-01

    Nickel is a ubiquitous trace element and it occurs in soil, water, air and of the biosphere. It is mostly used to manufacture stainless steel. Nickel is the commonest cause of metal allergy. Nickel allergy is a chronic and recurring skin problem; females are affected more commonly than males. Nickel allergy may develop at any age. Once developed, it tends to persist life-long. Nickel is present in most of the dietary items and food is considered to be a major source of nickel exposure for the...

  13. Pulse reversal plating of nickel alloys

    DEFF Research Database (Denmark)

    Tang, Peter Torben

    2007-01-01

    Pulse plating has previously been reported to improve the properties of nickel and nickel alloy deposits. Typically, focus has been on properties such as grain size, hardness and smoothness. When pulse plating is to be utilised for microtechnologies such as microelectromechanical systems (MEMS......), internal stress and material distribution are even more important. With baths based upon nickel chloride, and nickel and cobalt chlorides, pulse reversal plating of both pure nickel and nickel-cobalt alloys has been used to fabricate tools for microinjection moulding. Pulse reversal plating of ternary soft...... magnetic alloys, comprising 45-65%Co, 15-35%Fe and 15-35%Ni, is also reported....

  14. Mechanisms of nickel toxicity in microorganisms

    Science.gov (United States)

    Macomber, Lee

    2014-01-01

    Summary Nickel has long been known to be an important human toxicant, including having the ability to form carcinomas, but until recently nickel was believed to be an issue only to microorganisms living in nickel-rich serpentine soils or areas contaminated by industrial pollution. This assumption was overturned by the discovery of a nickel defense system (RcnR/RcnA) found in microorganisms that live in a wide range of environmental niches, suggesting that nickel homeostasis is a general biological concern. To date, the mechanisms of nickel toxicity in microorganisms and higher eukaryotes are poorly understood. In this review, we summarize nickel homeostasis processes used by microorganisms and highlight in vivo and in vitro effects of exposure to elevated concentrations of nickel. On the basis of this evidence we propose four mechanisms of nickel toxicity: 1) nickel replaces the essential metal of metalloproteins, 2) nickel binds to catalytic residues of non-metalloenzymes; 3) nickel binds outside the catalytic site of an enzyme to inhibit allosterically, and 4) nickel indirectly causes oxidative stress. PMID:21799955

  15. Surface wear of TiN coated nickel tool during the injection moulding of polymer micro Fresnel lenses

    DEFF Research Database (Denmark)

    Tosello, Guido; Hansen, Hans Nørgaard; Gasparin, Stefania

    2012-01-01

    Limited tool life of nickel mould inserts represents an issue for the mass-production of polymer optics with complex micro three-dimensional geometries by injection moulding. TiN coating was applied to a nickel insert for the injection moulding of polycarbonate micro Fresnel lenses. Surface wear ...

  16. AN ELECTROPLATING METHOD OF FORMING PLATINGS OF NICKEL, COBALT, NICKEL ALLOYS OR COBALT ALLOYS

    DEFF Research Database (Denmark)

    1997-01-01

    An electroplating method of forming platings of nickel, cobalt, nickel alloys or cobalt alloys with reduced stresses in an electrodepositing bath of the type: Watt's bath, chloride bath or a combination thereof, by employing pulse plating with periodic reverse pulse and a sulfonated naphthalene...... additive. This method makes it possible to deposit nickel, cobalt, nickel or cobalt platings without internal stresses....

  17. Excessive nickel release from mobile phones--a persistent cause of nickel allergy and dermatitis

    DEFF Research Database (Denmark)

    Jensen, Peter; Johansen, Jeanne D; Zachariae, Claus

    2011-01-01

    Despite the political intention to limit nickel allergy and dermatitis in Europeans, nickel allergy remains frequent. There are several explanations for the persistence of nickel allergy and dermatitis, including the increasing use of mobile phones. Before regulation of nickel release from mobile...

  18. Nickel exposure and plasma levels of biomarkers for assessing oxidative stress in nickel electroplating workers.

    Science.gov (United States)

    Tsao, Yu-Chung; Gu, Po-Wen; Liu, Su-Hsun; Tzeng, I-Shiang; Chen, Jau-Yuan; Luo, Jiin-Chyuan John

    2017-07-01

    The mechanism of nickel-induced pathogenesis remains elusive. To examine effects of nickel exposure on plasma oxidative and anti-oxidative biomarkers. Biomarker data were collected from 154 workers with various levels of nickel exposure and from 73 controls. Correlations between nickel exposure and oxidative and anti-oxidative biomarkers were determined using linear regression models. Workers with a exposure to high nickel levels had significantly lower levels of anti-oxidants (glutathione and catalase) than those with a lower exposure to nickel; however, only glutathione showed an independent association after multivariable adjustment. Exposure to high levels of nickel may reduce serum anti-oxidative capacity.

  19. Oral nickel exposure may induce Type I hypersensitivity reaction in nickel-sensitized subjects.

    Science.gov (United States)

    Büyüköztürk, Suna; Gelincik, Aslı; Ünal, Derya; Demirtürk, Mustafa; Çelik, Dolay Damla; Erden, Sacide; Çolakoğlu, Bahattin; Erdem Kuruca, Serap

    2015-05-01

    Little is known about the clinical and immunological changes in the nickel allergic patients with systemic symptoms. We aimed to evaluate T helper cell responses of patients with different clinical presentations due to nickel. Patients having various allergic symptoms and positive patch test results to nickel and 20 controls underwent skin prick tests with nickel. IL-10, IL-4, IL-5 and IFN-gamma were measured in the culture supernatants of PBMC stimulated by nickel during lymphocyte proliferation test (LTT). 69 patients (56 female, mean age: 49.2 ± 13.1), 97% having nickel containing dental devices and 20 controls (8 female, mean age 34.9 ± 12.06) were evaluated. Skin prick tests with nickel were positive in 70% of the patients (pnickel. Nickel containing dental alloys and oral nickel intake seem to trigger systemic symptoms in previously nickel sensitized patients. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. The EU Nickel Directive revisited--future steps towards better protection against nickel allergy

    DEFF Research Database (Denmark)

    Thyssen, Jacob P; Uter, Wolfgang; McFadden, John

    2011-01-01

    In July 2001, the EU Nickel Directive came into full force to protect European citizens against nickel allergy and dermatitis. Prior to this intervention, Northern European governments had already begun to regulate consumer nickel exposure. According to part 2 of the EU Nickel Directive...... and the Danish nickel regulation, consumer items intended to be in direct and prolonged contact with the skin were not allowed to release more than 0.5 µg nickel/cm2/week. It was considered unlikely that nickel allergy would disappear altogether as a proportion of individuals reacted below the level defined...... by the EU Nickel Directive. Despite this, the EU Nickel Directive part 2 was expected to work as an operational limit that would sufficiently protect European consumers against nickel allergy and dermatitis. This review presents the accumulation of epidemiological studies that evaluated the possible effect...

  1. Nickel may be released from laptop computers

    DEFF Research Database (Denmark)

    Jensen, Peter; Jellesen, Morten Stendahl; Møller, Per

    2012-01-01

    Consumer nickel sensitization and dermatitis is caused by prolonged or repeated skin exposure to items that release nickel, for example jewellery, belts, buttons, watches, and mobile phones (1–3). We recently described a patient in whom primary nickel contact sensitization and dermatitis developed...... following the use of an Apple laptop computer (4). To estimate nickel release from Apple laptop computers, we investigated a random sample of 20 devices....

  2. Distribution ratios on Dowex 50W resins of metal leached in the caron nickel recovery process

    Energy Technology Data Exchange (ETDEWEB)

    Reynolds, B.A.; Metsa, J.C.; Mullins, M.E.

    1980-05-01

    Pressurized ion exchange on Dowex 50W-X8 and 50W-X12 resins was investigated using elution techniques to determine distribution ratios for copper, nickel, and cobalt complexes contained in ammonium carbonate solution, a mixture which approximates the waste liquor from the Caron nickel recovery process. Results were determined for different feed concentrations, as well as for different concentrations and pH values of the ammonium carbonate eluant. Distribution ratios were compared with those previously obtained from a continuous annular chromatographic system. Separation of copper and nickel was not conclusively observed at any of the conditions examined.

  3. Distribution ratios on Dowex 50W resins of metal leached in the caron nickel recovery process

    International Nuclear Information System (INIS)

    Reynolds, B.A.; Metsa, J.C.; Mullins, M.E.

    1980-05-01

    Pressurized ion exchange on Dowex 50W-X8 and 50W-X12 resins was investigated using elution techniques to determine distribution ratios for copper, nickel, and cobalt complexes contained in ammonium carbonate solution, a mixture which approximates the waste liquor from the Caron nickel recovery process. Results were determined for different feed concentrations, as well as for different concentrations and pH values of the ammonium carbonate eluant. Distribution ratios were compared with those previously obtained from a continuous annular chromatographic system. Separation of copper and nickel was not conclusively observed at any of the conditions examined

  4. Photoelectron Spectroscopy of the Bis(dithiolene) Anions [M(mnt)2]n- (M = Fe - Zn; n = 1, 2): Changes in Electronic Structure with Variation of Metal Center and with Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Waters, Tom; Wang, Xue B; Woo, Hin-koon; Wang, Lai S

    2006-07-24

    A detailed understanding of the electronic structures of transition metal bis(dithiolene) centers is important in the context of their interesting redox, magnetic and optical properties. The electronic structures of the series [M(mnt)2]n- (M = Fe - Zn; mnt = 1,2-S2C2(CN)2; n = 1, 2) were examined by a combination of photodetachment photoelectron spectroscopy and density functional theory calculations, providing insights into changes in electronic structure with variation of the metal center and with oxidation. Significant changes were observed for the dianions [M(mnt)2]2- due to stabilization of the metal 3d levels from Fe to Zn and the transition from square-planar to tetrahedral coordination about the metal center (Fe-Ni, D2h →Cu D2 →Zn, D2d). Changes with oxidation from [M(mnt)2]2- to [M(mnt)2]1- were largely dependent on the nature of the redox-active orbital in the couple [M(mnt)2]2-/1-. In particular, the first detachment feature for [Fe(mnt)2]2- originated from a metal-based orbital (FeII →FeIII) while that for [Fe(mnt)2]1- originated from a ligand-based orbital, a consequence of stabilization of Fe 3d levels in the latter. In contrast, the first detachment feature for both of [Ni(mnt)2]2- and [Ni(mnt)2]1- originated from the same ligand-based orbital in both cases, a result of occupied Ni 3d levels being stabilized relative those of Fe 3d and occurring below the highest energy occupied ligand-based orbital for both of [Ni(mnt)2]2- and [Ni(mnt)2]1-. The combined data illustrate the subtle interplay between metal- and ligand-based redox chemistry in these species, and demonstrate changes in their electronic structures with variation of metal center, with oxidation, and with coordination geometry.

  5. Discovery of doubly magic nickel

    CERN Document Server

    CERN. Geneva

    2000-01-01

    An experiment at the French GANIL laboratory has recently discovered a new "doubly magic" nucleus-only the tenth such isotope known to science. A collaboration of French, Polish and Romanian physicists began an experiment at GANIL in Caen, France, to search for nickel-48, the last doubly magic nucleus accessible with present methods. A primary beam of nickel-58 with an average intensity of 10 /sup 12/ ions per second and an energy of 95 MeV per nucleon hit a natural nickel target in the superconducting solenoids of the SISSI device. The proton-rich projectile fragments were selected by the USE3 separator and finally identified by their time of flight, their energy loss and their total energy in a detection set-up consisting of a microchannel plate detector and a stack of five silicon detectors. This allowed the measurement of 10 independent parameters to identify each fragment arriving at the focal plane. (0 refs).

  6. The nickel resistance determinant cloned from the enterobacterium Klebsiella oxytoca: conjugational transfer, expression, regulation and DNA homologies to various nickel-resistant bacteria.

    Science.gov (United States)

    Stoppel, R D; Meyer, M; Schlegel, H G

    1995-01-01

    Klebsiella oxytoca strain CCUG 15788, isolated from a mineral oil emulsion tank in Göteborg, Sweden, was found to be nickel-resistant (tolerating 10 mM NiCl2 in non-complexing mineral-gluconate media; inducible resistance). The nickel resistance determinants were transferred by helper-assisted conjugation to various strains of Escherichia coli and Citrobacter freundii and expressed to between 5 and 10 mM NiCl2. A 4.3 kb HindIII fragment was cloned from the genomic DNA of K. oxytoca. Ligated into the vector pSUP202, the fragment caused constitutive nickel resistance (of up to 3 or 10 mM Ni2+) in various E. coli strains. After cloning into the broad host range vector pVDZ'2 the fragment even expressed low nickel resistance in the transconjugant of Alcaligenes eutrophus AE104. With the 4.3 kb HindIII fragment as a biotinylated DNA probe it was shown by DNA-DNA hybridization that the nickel resistance determinant resides on the chromosome of K. oxytoca and not on its circular plasmid pKO1 (160 kb) or linear plasmid pKO2 (50 kb). Nickel resistance strongly correlated with the presence of the 4.3 kb HindIII fragment in the transconjugants. No homologies were detected when the nickel resistance determinants of other well-known nickel-resistant bacteria, such as A. eutrophus CH34 or A. denitrificans 4a-2, were used as target DNA. Among the 60 strains examined, positive signals only appeared with the 3.1 kb DNA fragment from A. xylosoxydans 31A and the genomic DNA of two enterobacterial strains (5-1 and 5-5) isolated from nickel-rich soil in New Caledonia.

  7. Electrodeposition of zinc--nickel alloys coatings

    Energy Technology Data Exchange (ETDEWEB)

    Dini, J W; Johnson, H R

    1977-10-01

    One possible substitute for cadmium in some applications is a zinc--nickel alloy deposit. Previous work by others showed that electrodeposited zinc--nickel coatings containing about 85 percent zinc and 15 percent nickel provided noticeably better corrosion resistance than pure zinc. Present work which supports this finding also shows that the corrosion resistance of the alloy deposit compares favorably with cadmium.

  8. Investigation of hydrogen evolution activity for the nickel, nickel-molybdenum nickel-graphite composite and nickel-reduced graphene oxide composite coatings

    International Nuclear Information System (INIS)

    Jinlong, Lv; Tongxiang, Liang; Chen, Wang

    2016-01-01

    Graphical abstract: - Highlights: • Improved HER efficiency of Ni-Mo coatings was attributed to ‘cauliflower’ like microstructure. • RGO in nickel-RGO composite coating promoted refined grain and facilitated HER. • Synergistic effect between nickel and RGO facilitated HER due to large specific surface of RGO. - Abstract: The nickel, nickel-molybdenum alloy, nickel-graphite and nickel-reduced graphene oxide composite coatings were obtained by the electrodeposition technique from a nickel sulfate bath. Nanocrystalline molybdenum, graphite and reduced graphene oxide in nickel coatings promoted hydrogen evolution reaction in 0.5 M H 2 SO 4 solution at room temperature. However, the nickel-reduced graphene oxide composite coating exhibited the highest electrocatalytic activity for the hydrogen evolution reaction in 0.5 M H 2 SO 4 solution at room temperature. A large number of gaps between ‘cauliflower’ like grains could decrease effective area for hydrogen evolution reaction in slight amorphous nickel-molybdenum alloy. The synergistic effect between nickel and reduced graphene oxide promoted hydrogen evolution, moreover, refined grain in nickel-reduced graphene oxide composite coating and large specific surface of reduced graphene oxide also facilitated hydrogen evolution reaction.

  9. Investigation of hydrogen evolution activity for the nickel, nickel-molybdenum nickel-graphite composite and nickel-reduced graphene oxide composite coatings

    Energy Technology Data Exchange (ETDEWEB)

    Jinlong, Lv, E-mail: ljlbuaa@126.com [Beijing Key Laboratory of Fine Ceramics, Institute of Nuclear and New Energy Technology, Tsinghua University, Zhongguancun Street, Haidian District, Beijing 100084 (China); State Key Lab of New Ceramic and Fine Processing, Tsinghua University, Beijing 100084 (China); Tongxiang, Liang; Chen, Wang [Beijing Key Laboratory of Fine Ceramics, Institute of Nuclear and New Energy Technology, Tsinghua University, Zhongguancun Street, Haidian District, Beijing 100084 (China); State Key Lab of New Ceramic and Fine Processing, Tsinghua University, Beijing 100084 (China)

    2016-03-15

    Graphical abstract: - Highlights: • Improved HER efficiency of Ni-Mo coatings was attributed to ‘cauliflower’ like microstructure. • RGO in nickel-RGO composite coating promoted refined grain and facilitated HER. • Synergistic effect between nickel and RGO facilitated HER due to large specific surface of RGO. - Abstract: The nickel, nickel-molybdenum alloy, nickel-graphite and nickel-reduced graphene oxide composite coatings were obtained by the electrodeposition technique from a nickel sulfate bath. Nanocrystalline molybdenum, graphite and reduced graphene oxide in nickel coatings promoted hydrogen evolution reaction in 0.5 M H{sub 2}SO{sub 4} solution at room temperature. However, the nickel-reduced graphene oxide composite coating exhibited the highest electrocatalytic activity for the hydrogen evolution reaction in 0.5 M H{sub 2}SO{sub 4} solution at room temperature. A large number of gaps between ‘cauliflower’ like grains could decrease effective area for hydrogen evolution reaction in slight amorphous nickel-molybdenum alloy. The synergistic effect between nickel and reduced graphene oxide promoted hydrogen evolution, moreover, refined grain in nickel-reduced graphene oxide composite coating and large specific surface of reduced graphene oxide also facilitated hydrogen evolution reaction.

  10. Void formation in irradiated binary nickel alloys

    International Nuclear Information System (INIS)

    Shaikh, M.A.; Ahmed, M.; Akhter, J.I.

    1994-01-01

    In this work a computer program has been used to compute void radius, void density and swelling parameter for nickel and binary nickel-carbon alloys irradiated with nickel ions of 100 keV. The aim is to compare the computed results with experimental results already reported

  11. Improved nickel plating of Inconel X-750

    Science.gov (United States)

    Farmer, M. E.; Feeney, J. E.; Kuster, C. A.

    1969-01-01

    Electroplating technique with acid pickling provides a method of applying nickel plating on Inconel X-750 tubing to serve as a wetting agent during brazing. Low-stress nickel-plating bath contains no organic wetting agents that cause the nickel to blister at high temperatures.

  12. Synthesis, Structure, Characterization, and Decomposition of Nickel Dithiocarbamates: Effect of Precursor Structure and Processing Conditions on Solid-State Products

    Science.gov (United States)

    Hepp, Aloysius F.; Kulis, Michael J.; McNatt, Jeremiah S.; Duffy, Norman V.; Hoops, Michael D.; Gorse, Elizabeth; Fanwick, Philip E.; Masnovi, John; Cowen, Jonathan E.; Dominey, Raymond N.

    2016-01-01

    Single-crystal X-ray structures of four nickel dithiocarbamate complexes, the homoleptic mixed-organic bis-dithiocarbamates Ni[S2CN(isopropyl)(benzyl)]2, Ni[S2CN(ethyl)(n-butyl)]2, and Ni[S2CN(phenyl)(benzyl)]2, as well as the heteroleptic mixed-ligand complex NiCl[P(phenyl)3][(S2CN(phenyl)(benzyl)], were determined. Synthetic, spectroscopic, structural, thermal, and sulfide materials studies are discussed in light of prior literature. The spectroscopic results are routine. A slightly distorted square-planar nickel coordination environment was observed for all four complexes. The organic residues adopt conformations to minimize steric interactions. Steric effects also may determine puckering, if any, about the nickel and nitrogen atoms, both of which are planar or nearly so. A trans-influence affects the Ni-S bond distances. Nitrogen atoms interact with the CS2 carbons with a bond order of about 1.5, and the other substituents on nitrogen display transoid conformations. There are no strong intermolecular interactions, consistent with prior observations of the volatility of nickel dithiocarbamate complexes. Thermogravimetric analysis of the homoleptic species under inert atmosphere is consistent with production of 1:1 nickel sulfide phases. Thermolysis of nickel dithiocarbamates under flowing nitrogen produced hexagonal or -NiS as the major phase; thermolysis under flowing forming gas produced millerite (-NiS) at 300 C, godlevskite (Ni9S8) at 325 and 350 C, and heazlewoodite (Ni3S2) at 400 and 450 C. Failure to exclude oxygen results in production of nickel oxide. Nickel sulfide phases produced seem to be primarily influenced by processing conditions, in agreement with prior literature. Nickel dithiocarbamate complexes demonstrate significant promise to serve as single-source precursors to nickel sulfides, a quite interesting family of materials with numerous potential applications.

  13. Molecular Mechanisms of Nickel Allergy.

    Science.gov (United States)

    Saito, Masako; Arakaki, Rieko; Yamada, Akiko; Tsunematsu, Takaaki; Kudo, Yasusei; Ishimaru, Naozumi

    2016-02-02

    Allergic contact hypersensitivity to metals is a delayed-type allergy. Although various metals are known to produce an allergic reaction, nickel is the most frequent cause of metal allergy. Researchers have attempted to elucidate the mechanisms of metal allergy using animal models and human patients. Here, the immunological and molecular mechanisms of metal allergy are described based on the findings of previous studies, including those that were recently published. In addition, the adsorption and excretion of various metals, in particular nickel, is discussed to further understand the pathogenesis of metal allergy.

  14. Molecular Mechanisms of Nickel Allergy

    Directory of Open Access Journals (Sweden)

    Masako Saito

    2016-02-01

    Full Text Available Allergic contact hypersensitivity to metals is a delayed-type allergy. Although various metals are known to produce an allergic reaction, nickel is the most frequent cause of metal allergy. Researchers have attempted to elucidate the mechanisms of metal allergy using animal models and human patients. Here, the immunological and molecular mechanisms of metal allergy are described based on the findings of previous studies, including those that were recently published. In addition, the adsorption and excretion of various metals, in particular nickel, is discussed to further understand the pathogenesis of metal allergy.

  15. Ecological Considerations on Nickel Dermatitis

    Science.gov (United States)

    Marcussen, Poul V.

    1960-01-01

    The incidence of nickel dermatoses has shifted from the plating industry to other occupations and particularly to non-occupational causes. A Danish survey of 621 cases shows that 4% are due to nickel plating, 9·5% to other occupations, and 86·5% were not due to occupation. A primary eruption not due to occupation had occurred in 14% of the occupational cases. The importance of preventive measures for the community more than for the adequately controlled industry is underlined. PMID:14420983

  16. Nickel-based anodic electrocatalysts for fuel cells and water splitting

    Science.gov (United States)

    Chen, Dayi

    Our world is facing an energy crisis, so people are trying to harvest and utilize energy more efficiently. One of the promising ways to harvest energy is via solar water splitting to convert solar energy to chemical energy stored in hydrogen. Another of the options to utilize energy more efficiently is to use fuel cells as power sources instead of combustion engines. Catalysts are needed to reduce the energy barriers of the reactions happening at the electrode surfaces of the water-splitting cells and fuel cells. Nickel-based catalysts happen to be important nonprecious electrocatalysts for both of the anodic reactions in alkaline media. In alcohol fuel cells, nickel-based catalysts catalyze alcohol oxidation. In water splitting cells, they catalyze water oxidation, i.e., oxygen evolution. The two reactions occur in a similar potential range when catalyzed by nickel-based catalysts. Higher output current density, lower oxidation potential, and complete substrate oxidation are preferred for the anode in the applications. In this dissertation, the catalytic properties of nickel-based electrocatalysts in alkaline medium for fuel oxidation and oxygen evolution are explored. By changing the nickel precursor solubility, nickel complex nanoparticles with tunable sizes on electrode surfaces were synthesized. Higher methanol oxidation current density is achieved with smaller nickel complex nanoparticles. DNA aggregates were used as a polymer scaffold to load nickel ion centers and thus can oxidize methanol completely at a potential about 0.1 V lower than simple nickel electrodes, and the methanol oxidation pathway is changed. Nickel-based catalysts also have electrocatalytic activity towards a wide range of substrates. Experiments show that methanol, ethanol, glycerol and glucose can be deeply oxidized and carbon-carbon bonds can be broken during the oxidation. However, when comparing methanol oxidation reaction to oxygen evolution reaction catalyzed by current nickel

  17. Nickel exposure from keys: a Brazilian issue.

    Science.gov (United States)

    Suzuki, Nathalie Mie; Duarte, Ida Alzira Gomes; Hafner, Mariana de Figueiredo Silva; Lazzarini, Rosana

    2017-01-01

    Keys are a significant source of exposure to metal allergens and can be a relevant problem for nickel-allergic individuals. This study aimed to perform nickel and cobalt spot testing among the 5 most common Brazilian brands of keys. Among the tested keys, 100% showed positive result to nickel spot test, 83,3% presented strong positive reaction. 50% exhibited cobalt release as well. Nickel release from keys is very common in our country and may cause a negative impact on sensitized individual's quality of life. Study's results highlight the importance of establishing directives to regulate nickel release in Brazil.

  18. Heterospin systems constructed from [Cu2Ln]3+ and [Ni(mnt)2]1-,2- Tectons: First 3p-3d-4f complexes (mnt = maleonitriledithiolato).

    Science.gov (United States)

    Madalan, Augustin M; Avarvari, Narcis; Fourmigué, Marc; Clérac, Rodolphe; Chibotaru, Liviu F; Clima, Sergiu; Andruh, Marius

    2008-02-04

    New heterospin complexes have been obtained by combining the binuclear complexes [{Cu(H(2)O)L(1)}Ln(O(2)NO)(3)] or [{CuL(2)}Ln(O(2)NO)(3)] (L(1) = N,N'-propylene-di(3-methoxysalicylideneiminato); L(2) = N,N'-ethylene-di(3-methoxysalicylideneiminato); Ln = Gd(3+), Sm(3+), Tb(3+)), with the mononuclear [CuL(1)(2)] and the nickel dithiolene complexes [Ni(mnt)(2)](q)- (q = 1, 2; mnt = maleonitriledithiolate), as follows: (1)infinity[{CuL(1)}(2)Ln(O(2)NO){Ni(mnt)(2)}].Solv.CH(3)CN (Ln = Gd(3+), Solv = CH(3)OH (1), Ln = Sm(3+), Solv = CH(3)CN (2)) and [{(CH(3)OH)CuL(2)}(2)Sm(O(2)NO)][Ni(mnt)(2)] (3) with [Ni(mnt)2]2-, [{(CH(3)CN)CuL(1)}(2)Ln(H(2)O)][Ni(mnt)(2)]3.2CH(3)CN (Ln = Gd(3+) (4), Sm(3+) (5), Tb(3+) (6)), and [{(CH(3)OH)CuL(2)}{CuL(2)}Gd(O(2)NO){Ni(mnt)(2)}][Ni(mnt)(2)].CH(2)Cl(2) (7) with [Ni(mnt))(2]*-. Trinuclear, almost linear, [CuLnCu] motifs are found in all the compounds. In the isostructural 1 and 2, two trans cyano groups from a [Ni(mnt)2]2- unit bridge two trimetallic nodes through axial coordination to the Cu centers, thus leading to the establishment of infinite chains. 3 is an ionic compound, containing discrete [{(CH(3)OH)CuL(2)}(2)Sm(O(2)NO)](2+) cations and [Ni(mnt)(2)](2-) anions. Within the series 4-6, layers of discrete [CuLnCu](3+) motifs alternate with stacks of interacting [Ni(mnt)(2)](*-) radical anions, for which two overlap modes, providing two different types of stacks, can be disclosed. The strength of the intermolecular interactions between the open-shell species is estimated through extended Hückel calculations. In compound 7, [Ni(mnt)(2)](*-) radical anions coordinate group one of the Cu centers of a trinuclear [Cu(2)Gd] motif through a CN, while discrete [Ni(mnt)(2)](*-) units are also present, overlapping in between, but also with the coordinated ones. Furthermore, the [Cu(2)Gd] moieties dimerize each other upon linkage by two nitrato groups, both acting as chelate toward the gadolinium ion from one unit and monodentate toward a

  19. Assaying environmental nickel toxicity using model nematodes

    Science.gov (United States)

    Rudel, David; Douglas, Chandler; Huffnagle, Ian; Besser, John M.; Ingersoll, Christopher G.

    2013-01-01

    Although nickel exposure results in allergic reactions, respiratory conditions, and cancer in humans and rodents, the ramifications of excess nickel in the environment for animal and human health remain largely undescribed. Nickel and other cationic metals travel through waterways and bind to soils and sediments. To evaluate the potential toxic effects of nickel at environmental contaminant levels (8.9-7,600 µg Ni/g dry weight of sediment and 50-800 µg NiCl2/L of water), we conducted assays using two cosmopolitan nematodes, Caenorhabditis elegans and Pristionchus pacificus. We assayed the effects of both sediment-bound and aqueous nickel upon animal growth, developmental survival, lifespan, and fecundity. Uncontaminated sediments were collected from sites in the Midwestern United States and spiked with a range of nickel concentrations. We found that nickel-spiked sediment substantially impairs both survival from larval to adult stages and adult longevity in a concentration-dependent manner. Further, while aqueous nickel showed no adverse effects on either survivorship or longevity, we observed a significant decrease in fecundity, indicating that aqueous nickel could have a negative impact on nematode physiology. Intriguingly, C. elegansand P. pacificus exhibit similar, but not identical, responses to nickel exposure. Moreover, P. pacificus could be tested successfully in sediments inhospitable to C. elegans. Our results add to a growing body of literature documenting the impact of nickel on animal physiology, and suggest that environmental toxicological studies could gain an advantage by widening their repertoire of nematode species.

  20. Assaying environmental nickel toxicity using model nematodes.

    Directory of Open Access Journals (Sweden)

    David Rudel

    Full Text Available Although nickel exposure results in allergic reactions, respiratory conditions, and cancer in humans and rodents, the ramifications of excess nickel in the environment for animal and human health remain largely undescribed. Nickel and other cationic metals travel through waterways and bind to soils and sediments. To evaluate the potential toxic effects of nickel at environmental contaminant levels (8.9-7,600 µg Ni/g dry weight of sediment and 50-800 µg NiCl2/L of water, we conducted assays using two cosmopolitan nematodes, Caenorhabditis elegans and Pristionchus pacificus. We assayed the effects of both sediment-bound and aqueous nickel upon animal growth, developmental survival, lifespan, and fecundity. Uncontaminated sediments were collected from sites in the Midwestern United States and spiked with a range of nickel concentrations. We found that nickel-spiked sediment substantially impairs both survival from larval to adult stages and adult longevity in a concentration-dependent manner. Further, while aqueous nickel showed no adverse effects on either survivorship or longevity, we observed a significant decrease in fecundity, indicating that aqueous nickel could have a negative impact on nematode physiology. Intriguingly, C. elegans and P. pacificus exhibit similar, but not identical, responses to nickel exposure. Moreover, P. pacificus could be tested successfully in sediments inhospitable to C. elegans. Our results add to a growing body of literature documenting the impact of nickel on animal physiology, and suggest that environmental toxicological studies could gain an advantage by widening their repertoire of nematode species.

  1. Assaying environmental nickel toxicity using model nematodes.

    Science.gov (United States)

    Rudel, David; Douglas, Chandler D; Huffnagle, Ian M; Besser, John M; Ingersoll, Christopher G

    2013-01-01

    Although nickel exposure results in allergic reactions, respiratory conditions, and cancer in humans and rodents, the ramifications of excess nickel in the environment for animal and human health remain largely undescribed. Nickel and other cationic metals travel through waterways and bind to soils and sediments. To evaluate the potential toxic effects of nickel at environmental contaminant levels (8.9-7,600 µg Ni/g dry weight of sediment and 50-800 µg NiCl2/L of water), we conducted assays using two cosmopolitan nematodes, Caenorhabditis elegans and Pristionchus pacificus. We assayed the effects of both sediment-bound and aqueous nickel upon animal growth, developmental survival, lifespan, and fecundity. Uncontaminated sediments were collected from sites in the Midwestern United States and spiked with a range of nickel concentrations. We found that nickel-spiked sediment substantially impairs both survival from larval to adult stages and adult longevity in a concentration-dependent manner. Further, while aqueous nickel showed no adverse effects on either survivorship or longevity, we observed a significant decrease in fecundity, indicating that aqueous nickel could have a negative impact on nematode physiology. Intriguingly, C. elegans and P. pacificus exhibit similar, but not identical, responses to nickel exposure. Moreover, P. pacificus could be tested successfully in sediments inhospitable to C. elegans. Our results add to a growing body of literature documenting the impact of nickel on animal physiology, and suggest that environmental toxicological studies could gain an advantage by widening their repertoire of nematode species.

  2. Iron-nickel-chromium alloys

    International Nuclear Information System (INIS)

    Karenko, M.K.

    1981-01-01

    A specification is given for iron-nickel-chromium age-hardenable alloys suitable for use in fast breeder reactor ducts and cladding, which utilize the gamma-double prime strengthening phase and are characterized in having a delta or eta phase distributed at or near grain boundaries. A range of compositions is given. (author)

  3. Electrolytic nickel deposits upon uranium

    International Nuclear Information System (INIS)

    Baudin, G.; Chauvin, G.; Coriou, H.; Hure, J.

    1958-01-01

    The authors present a new possibility to protect uranium by very adherent nickel deposits got by aqueous medium electrolysis. Surface treatment of uranium is based upon the chemical etching method from Lietazke. After thermal treatments at 600, 700 and 800 deg. C, under vacuum, a good intermetallic U-Ni diffusion is observed for each case. (author) [fr

  4. Heat treatment of nickel alloys

    International Nuclear Information System (INIS)

    Smith, D.F. Jr.; Clatworthy, E.F.

    1975-01-01

    A heat treating process is described that can be used to produce desired combinations of strength, ductility, and fabricability characteristics in heat resistant age-hardenable alloys having precipitation-hardening amounts of niobium, titanium, and/or tantalum in a nickel-containing matrix. (U.S.)

  5. ELECTRODEPOSITION OF NICKEL ON URANIUM

    Science.gov (United States)

    Gray, A.G.

    1958-08-26

    A method is described for preparing uranium objects prior to nickel electroplating. The process consiats in treating the surface of the uranium with molten ferric chloride hexahydrate, at a slightiy elevated temperature. This treatment etches the metal surface providing a structure suitable for the application of adherent electrodeposits and at the same time plates the surface with a thin protective film of iron.

  6. Coin exposure may cause allergic nickel dermatitis

    DEFF Research Database (Denmark)

    Thyssen, Jacob P; Gawkrodger, David J; White, Ian R

    2012-01-01

    Nickel is used in coins because the metal has beneficial properties, including price, colour, weight, and corrosion resistance, and also because it is easy to stamp. It has often been claimed that the duration of skin contact with coins is too short to cause nickel release and dermatitis. However......, it is well known by dermatologists specialized in occupational skin diseases, and by their nickel-allergic patients, that hand eczema in cashiers and other professionals who handle coins may be caused or aggravated by nickel release from coins. In this review, we present evidence from past studies showing...... that nickel-containing coins can indeed pose a risk for those who handle them. For protection of the health of consumers, cashiers, and other workers who handle coins, it is suggested that coins without nickel release should be used as a substitute for the high nickel-releasing coins currently in widespread...

  7. The EU Nickel Directive revisited--future steps towards better protection against nickel allergy

    DEFF Research Database (Denmark)

    Thyssen, Jacob P; Uter, Wolfgang; McFadden, John

    2011-01-01

    In July 2001, the EU Nickel Directive came into full force to protect European citizens against nickel allergy and dermatitis. Prior to this intervention, Northern European governments had already begun to regulate consumer nickel exposure. According to part 2 of the EU Nickel Directive...... of this major public health intervention. Also, it evaluates recent exposure assessment studies that have been performed using the dimethyl glyoxime test. It is concluded that the EU Nickel Directive has started to change the epidemiology of nickel allergy in Europe but it should be revisited to better protect...... and the Danish nickel regulation, consumer items intended to be in direct and prolonged contact with the skin were not allowed to release more than 0.5 µg nickel/cm2/week. It was considered unlikely that nickel allergy would disappear altogether as a proportion of individuals reacted below the level defined...

  8. Prevalence of nickel allergy in Europe following the EU Nickel Directive - a review

    DEFF Research Database (Denmark)

    Ahlström, Malin G; Thyssen, Jacob P; Menné, Torkil

    2017-01-01

    Nickel contact allergy remains a problem in EU countries, despite the EU Nickel Directive. To study the prevalence of nickel allergy in EU countries following the implementation of the EU Nickel Directive, we performed a systematic search in PubMed for studies that examined the prevalence of nickel...... allergy in EU countries published during 2005-2016. We identified 46 studies: 10 in the general population and 36 in patch tested dermatitis patients. A significantly lower prevalence of nickel allergy after than before the implementation of the EU Nickel Directive was found in women aged 18-35 years (11......, and generally remained high, affecting 8-18% of the general population. A consistent pattern of decreasing prevalence of nickel allergy in some EU countries was observed, although the prevalence among young women remains high. Steps should be taken for better prevention of nickel allergy in EU countries....

  9. Nickel in nails, hair and plasma from nickel-hypersensitive women

    DEFF Research Database (Denmark)

    Gammelgaard, Bente; Veien, Niels

    1990-01-01

    The concentrations of nickel in finger-nails, toe-nails, hair and plasma from 71 nickel-hypersensitive women and 20 non-hypersensitive women were determined. Nickel concentrations in finger-nails were significantly higher than in toe-nails in both the nickel-hypersensitive group and the control...... group. Nickel-sensitive women had significantly higher levels of nickel in toe-nails, hair and plasma than had control subjects, whereas there was no significant difference in nickel concentration in finger-nails between the two groups. No correlation could be demonstrated between nickel levels in any...... combination of nails, hair and plasma in the nickel-hypersensitive or in the control group....

  10. Excessive nickel release from mobile phones--a persistent cause of nickel allergy and dermatitis.

    Science.gov (United States)

    Jensen, Peter; Johansen, Jeanne D; Zachariae, Claus; Menné, Torkil; Thyssen, Jacob P

    2011-12-01

    Despite the political intention to limit nickel allergy and dermatitis in Europeans, nickel allergy remains frequent. There are several explanations for the persistence of nickel allergy and dermatitis, including the increasing use of mobile phones. Before regulation of nickel release from mobile phones, we showed that eight (19.5%) of 41 mobile phones marketed in Denmark between 2003 and 2007 released nickel in concentrations that may result in nickel allergy and dermatitis. In 2009, the EU Nickel Directive was revised to include nickel-releasing mobile phones. To investigate the proportion of mobile phones sold in Denmark that release nickel after regulation. Metallic parts from 50 randomly selected mobile phones currently for sale in Denmark were tested for nickel release by use of the dimethylglyoxime (DMG)-nickel spot test. Nine (18%) phones showed at least one positive DMG test reaction and two phones had more than one DMG test-positive spot. Apparently, the proportion of mobile phones with significant nickel release remains unchanged, despite the 2009 revision of the EU Nickel Directive. We encourage manufacturers to measure nickel release from metallic components used in the assembly of mobile phones to ensure safe products. © 2011 John Wiley & Sons A/S.

  11. Synthesis and growth mechanism of sponge-like nickel using a hydrothermal method

    Science.gov (United States)

    Shao, Bin; Yin, Xueguo; Hua, Weidong; Ma, Yilong; Sun, Jianchun; Li, Chunhong; Chen, Dengming; Guo, Donglin; Li, Kejian

    2018-05-01

    Sponge-like nickel composed of micro-chains with a diameter of 1-5 μm was selectively synthesized by the hydrothermal method, using sodium hydroxide (NaOH) as the alkaline reagent, aqueous hydrazine as reducing agent and citric acid as a coordination agent. The time-dependent samples prepared at different NaOH concentrations were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Fourier transform infrared spectrometer (FTIR). The results showed that the agglomerates of nickel citrate hydrazine complex nanoplates were first precipitated and then reduced to prickly nickel micro-chains at a lower NaOH concentration, which played a role in the further formation of sponge-like nickel. Also, the probable growth mechanism of the sponge-like nickel was proposed. The magnetic properties of sponge-like nickel were studied using a vibrating sample magnetometer. The sponge-like nickel exhibited a ferromagnetic behavior with a saturation magnetization value of 43.8 emu g-1 and a coercivity value of 120.7 Oe.

  12. Nickel Inhibits Mitochondrial Fatty Acid Oxidation

    Science.gov (United States)

    Uppala, Radha; McKinney, Richard W.; Brant, Kelly A.; Fabisiak, James P.; Goetzman, Eric S.

    2015-01-01

    Nickel exposure is associated with changes in cellular energy metabolism which may contribute to its carcinogenic properties. Here, we demonstrate that nickel strongly represses mitochondrial fatty acid oxidation—the pathway by which fatty acids are catabolized for energy—in both primary human lung fibroblasts and mouse embryonic fibroblasts. At the concentrations used, nickel suppresses fatty acid oxidation without globally suppressing mitochondrial function as evidenced by increased glucose oxidation to CO2. Pre-treatment with L-carnitine, previously shown to prevent nickel-induced mitochondrial dysfunction in neuroblastoma cells, did not prevent the inhibition of fatty acid oxidation. The effect of nickel on fatty acid oxidation occurred only with prolonged exposure (>5 hr), suggesting that direct inhibition of the active sites of metabolic enzymes is not the mechanism of action. Nickel is a known hypoxia-mimetic that activates hypoxia inducible factor-1α (HIF1α). Nickel-induced inhibition of fatty acid oxidation was blunted in HIF1α knockout fibroblasts, implicating HIF1α as one contributor to the mechanism. Additionally, nickel down-regulated the protein levels of the key fatty acid oxidation enzyme very long-chain acyl-CoA dehydrogenase (VLCAD) in a dose-dependent fashion. In conclusion, inhibition of fatty acid oxidation by nickel, concurrent with increased glucose metabolism, represents a form of metabolic reprogramming that may contribute to nickel-induced carcinogenesis. PMID:26051273

  13. Gold, nickel and copper mining and processing.

    Science.gov (United States)

    Lightfoot, Nancy E; Pacey, Michael A; Darling, Shelley

    2010-01-01

    Ore mining occurs in all Canadian provinces and territories except Prince Edward Island. Ores include bauxite, copper, gold, iron, lead and zinc. Workers in metal mining and processing are exposed, not only to the metal of interest, but also to various other substances prevalent in the industry, such as diesel emissions, oil mists, blasting agents, silica, radon, and arsenic. This chapter examines cancer risk related to the mining of gold, nickel and copper. The human carcinogenicity of nickel depends upon the species of nickel, its concentration and the route of exposure. Exposure to nickel or nickel compounds via routes other than inhalation has not been shown to increase cancer risk in humans. As such, cancer sites of concern include the lung, and the nasal sinus. Evidence comes from studies of nickel refinery and leaching, calcining, and sintering workers in the early half of the 20th century. There appears to be little or no detectable risk in most sectors of the nickel industry at current exposure levels. The general population risk from the extremely small concentrations detectable in ambient air are negligible. Nevertheless, animal carcinogenesis studies, studies of nickel carcinogenesis mechanisms, and epidemiological studies with quantitative exposure assessment of various nickel species would enhance our understanding of human health risks associated with nickel. Definitive conclusions linking cancer to exposures in gold and copper mining and processing are not possible at this time. The available results appear to demand additional study of a variety of potential occupational and non-occupational risk factors.

  14. Photolysis of nickel hydroxy azide. | IROM | Global Journal of Pure ...

    African Journals Online (AJOL)

    Photolysis of nickel hydroxy azide at 380 ºK is compared with that of nickel azide under similar considerations. Nickel azide sample was prepared by adapting the method of Brauer while nickel hydroxy azide was obtained by dehydrating the dihydrate of nickel azide crystals (Ni(N3)2.2H2O) and exposing to atmospheric ...

  15. Spectroscopic studies on chromium(III), manganese(II), cobalt(II), nickel(II) and copper(II) complexes with hexadentate nitrogen-sulfur donor [N(2)S(4)] macrocyclic ligand.

    Science.gov (United States)

    Shukla, Deepak; Gupta, Lokesh Kumar; Chandra, Sulekh

    2008-12-01

    Complexes of transition metals have been synthesized with hexadentate ligand (2,6-bis(((2-mercaptophenyl)thio)methyl)pyridinato)metal(II). These complexes have been synthesized via the two step template reaction by using the benzene dithiol, 2,6-bis(chloro)methyl pyridine and corresponding metal salt as key raw materials. The structures of the complexes have been elucidated on the basis of elemental analysis, molar conductance measurements, magnetic susceptibility measurements, IR, electronic and EPR spectral studies. All of the complexes were found to possess six-coordinated geometry and are of high spin type.

  16. Spectroscopic studies on chromium(III), manganese(II), cobalt(II), nickel(II) and copper(II) complexes with hexadentate nitrogen-sulfur donor [N 2S 4] macrocyclic ligand

    Science.gov (United States)

    Shukla, Deepak; Gupta, Lokesh Kumar; Chandra, Sulekh

    2008-12-01

    Complexes of transition metals have been synthesized with hexadentate ligand (2,6-bis(((2-mercaptophenyl)thio)methyl)pyridinato)metal(II). These complexes have been synthesized via the two step template reaction by using the benzene dithiol, 2,6-bis(chloro)methyl pyridine and corresponding metal salt as key raw materials. The structures of the complexes have been elucidated on the basis of elemental analysis, molar conductance measurements, magnetic susceptibility measurements, IR, electronic and EPR spectral studies. All of the complexes were found to possess six-coordinated geometry and are of high spin type.

  17. A comparison of three-dimensional stress distribution and displacement of naso-maxillary complex on application of forces using quad-helix and nickel titanium palatal expander 2 (NPE2: a FEM study

    Directory of Open Access Journals (Sweden)

    Avinash Kumar

    2016-06-01

    Full Text Available Abstract Background Our objectives are to analyse and to compare the stress distribution and displacement of the craniofacial structures, following the application of forces from quad-helix and Nickel Titanium Palatal Expander-2 (NPE2 using finite element analysis. Methods Three-dimensional finite element models of young dried human skull, quad-helix appliance and NPE2 were constructed, and the initial activation of the expanders was stimulated to carry out the analysis and to evaluate the Von Misses stresses and displacement. Results Both the models demonstrated the highest stresses at the mid-palatal suture, with maximum posterior dislocation. The second highest stress was recorded at the fronto-zygomatic suture. The pattern of stress distribution was almost similar in both the groups, but NPE2 revealed lower magnitude stresses than quad-helix. The only exception being quad-helix model showed high stress levels around pterygo-maxillary suture whereas minimal stress around pterygo-maxillary suture was noticed after NPE2 activation. The cusp of the erupting canine and the erupting mesiobuccal cusp of the second molar showed outward, backward and downward displacement signifying increase in their eruption pattern following maxillary expansion. Conclusions Maxillary expansion using quad-helix and NPE2 can be used in posterior crossbite correction in cases where maximum skeletal changes are desirable at a younger age; it is furthermore effective in treating young patients with impacted or displaced teeth. Quad-helix and NPE2 produced acceptable forces for orthopaedic treatment even after being orthodontic appliances; their clinical application should be correctly planned as the effects of these appliances are largely age dependent.

  18. Characterization and Growth Mechanism of Nickel Nanowires Resulting from Reduction of Nickel Formate in Polyol Medium

    Directory of Open Access Journals (Sweden)

    Olga A. Logutenko

    2016-01-01

    Full Text Available Nickel linear nanostructures were synthesized by reduction of nickel formate with hydrazine hydrate in ethylene glycol medium in the absence of any surfactants or capping agents for direction of the particles growth. The effect of the synthesis conditions such as temperature, reduction time, type of polyol, and nickel formate concentration on the reduction products was studied. The size and morphology of the nickel nanowires were characterized by X-ray diffraction, scanning, and transmission electron microscopy. It was shown that the nickel nanocrystallites were wire-shaped with a face-center-cubic phase. Ethylene glycol was found to play a crucial role in the formation of the nickel nanowires. The possible growth processes of the wire-shaped particles taking place at 110 and 130°C are discussed. It was shown that, under certain synthesis conditions, nickel nanowires grow on the surface of the crystals of the solid intermediate of nickel with hydrazine hydrate.

  19. Low patch test reactivity to nickel in unselected adolescents tested repeatedly with nickel in infancy

    DEFF Research Database (Denmark)

    Christiansen, Elisabeth Soegaard; Andersen, Klaus Ejner; Bindslev-Jensen, Carsten

    2016-01-01

    BACKGROUND: It is questionable how repeated patch tests with nickel sulphate in infancy affect nickel patch test reactivity at a later age. METHODS: The DARC cohort encompasses 562 infants invited to a clinical examination including patch tests with nickel sulphate 6 times during the first 36...... months of life. At the follow-up investigation at 14 years of age (2013-14) participants were offered re-patch tests with nickel sulphate. The TOACS cohort encompasses 1501 schoolchildren evaluated for the first time at 14 years of age (1995-96) including clinical examination and nickel sulphate patch...... tests. The prevalence of nickel sensitization in the DARC cohort was compared to the prevalence in the TOACS cohort at 14 years of age. RESULTS: Nickel sulphate sensitization was found in 1.2% of the participants from the DARC cohort tested repeatedly with nickel sulphate in early childhood and retested...

  20. Geochemical prospecting for copper and nickel in the Wulgai and Tor Tangi areas southeast of Hindubagh, Quetta Division, Pakistan

    Science.gov (United States)

    Stanin, S. Anthony; Wahid, M.A.; Khan, Shamsher

    1975-01-01

    Showings of magnetite, copper, and possible nickel mineralization in the Hindubagh chromite mining district are near Wulgai and Tor Tangi. Several hundred samples of clastic material from dry streambeds in these areas were sieved for the minus-80-mesh fraction and analyzed for copper using 2, 2'-biquinoline and for nickel using alpha-furildioxime. The copper threshold is 75 ppm, and the nickel threshold is 400 ppm. A geochemical map has been prepared that shows nine areas of anomalously high copper and six areas of high nickel. The nickel anomalies may represent secondary dispersion patterns derived from the erosion of nickeliferous ultramafic rocks of the Hindubagh intrusive complex. Copper showings in and near four of the anomalous copper areas indicate that detailed geological investigation and detailed geochemical sampling of rocks, soil, and unconsolidated clastic material are required to determine the source of the anomalies.

  1. Molecular Mechanisms of Nickel Allergy

    OpenAIRE

    Saito, Masako; Arakaki, Rieko; Yamada, Akiko; Tsunematsu, Takaaki; Kudo, Yasusei; Ishimaru, Naozumi

    2016-01-01

    Allergic contact hypersensitivity to metals is a delayed-type allergy. Although various metals are known to produce an allergic reaction, nickel is the most frequent cause of metal allergy. Researchers have attempted to elucidate the mechanisms of metal allergy using animal models and human patients. Here, the immunological and molecular mechanisms of metal allergy are described based on the findings of previous studies, including those that were recently published. In addition, the adsorptio...

  2. Creep in an electrodeposited nickel

    Czech Academy of Sciences Publication Activity Database

    Sklenička, Václav; Kuchařová, Květa; Kvapilová, Marie; Svoboda, Milan; Král, Petr; Vidrich, G.

    2013-01-01

    Roč. 48, č. 13 (2013), s. 4780-4788 ISSN 0022-2461 R&D Projects: GA ČR(CZ) GAP108/11/2260; GA MŠk(CZ) ED1.1.00/02.0068 Institutional support: RVO:68081723 Keywords : nanocrystalline nickel * electrodeposited metals * nanocomposite * creep behavior * creep mechanisms Subject RIV: JG - Metallurgy Impact factor: 2.305, year: 2013

  3. Nickel allergy in relationship to previous oral and cutaneous nickel contact.

    OpenAIRE

    Todd, D. J.; Burrows, D.

    1989-01-01

    Potential relationships between the development of nickel allergy and previous ear piercing or orthodontic treatment with nickel-containing appliances were studied in 294 patients. We found 77 (31.2%) of 247 patients with pierced ears were allergic to nickel compared to only three (6.4%) patients without pierced ears (p = 0.001), which confirms earlier suggestions that nickel allergy (as assessed by patch testing) is promoted by ear piercing. If orthodontic treatment preceded the event of ear...

  4. Hydrogen vibrations in nickel hydride

    International Nuclear Information System (INIS)

    Eckert, J.; Daniels, W.B.; Kitchens, T.A.; Majkrzak, C.F.; Passell, L.

    1983-01-01

    This chapter examines nickel hydride which was prepared in a BeCu high pressure cell at room temperature by applying a hydrogen gas pressure of 7kbar to pellets pressed from fine nickel powder. It explains that the rate and degree of completion of the hydride formation was first checked by neutron diffraction using deuterium gas with the result that a deuterium to metal ratio of approximately 0.75 was reached. It points out that after desorption of the deuterium, the nickel sample was charged with hydrogen for the inelastic incoherent neutron scattering measurements. The chapter notes that measurements were performed with the Be filter technique at the Brookhaven High Flux Beam Reactor, and finds that the optic modes appear as a broad band in the phonon density of states from about 70 to 110 MeV with peaks at approximately 88 and 108 MeV. It finally discusses the effect of hydride formation on the acoustic phonon density of states

  5. Analysis of nickel refinery dusts.

    Science.gov (United States)

    Draper, M H; Duffus, J H; John, P; Metcalfe, L; Morgan, L; Park, M V; Weitzner, M I

    1994-06-06

    After characterization of bulk samples by inductively coupled plasma emission spectroscopic (ICP-ES) quantitative analysis and X-ray powder diffraction studies, single particle techniques using quantitative image analysis, scanning electron microscopy--energy dispersive analysis by X-ray, and finally laser beam ionization mass spectrometry analysis (LIMA) for surface analysis have been applied to historical nickel refinery dust samples from the nickel refining plant at Clydach in Wales. There were two historical samples of processed material from 1920 and 1929. These samples had a remarkably small particle size range, mean 3 microns and range, 0.75-24 microns. The most significant difference in elemental composition was the presence of 10% arsenic in the 1920 sample compared with 1% in the 1929 sample. The X-ray spectra revealed the presence of NiO in both. However, surprisingly, CuO was identified only in the 1929 sample. Of particular interest was the presence of a component, in the 1920 sample only, identified as the mineral orcelite, a copper-iron-nickel-arsenide-sulphide mineral, predominantly, Ni5-XAs2. Using the LIMA technique, it was found that in both samples, arsenic and arsenic derivative peaks are prominent, indicating the surface availability of arsenic compounds.

  6. Homogeneous Precipitation of Nickel Hydroxide Powders

    Energy Technology Data Exchange (ETDEWEB)

    Mavis, Bora [Iowa State Univ., Ames, IA (United States)

    2003-01-01

    Precipitation and characterization of nickel hydroxide powders were investigated. A comprehensive precipitation model incorporating the metal ion hydrolysis, complexation and precipitation reactions was developed for the production of the powders with urea precipitation method. Model predictions on Ni2+ precipitation rate were confirmed with precipitation experiments carried out at 90 C. Experimental data and model predictions were in remarkable agreement. Uncertainty in the solubility product data of nickel hydroxides was found to be the large contributor to the error. There were demonstrable compositional variations across the particle cross-sections and the growth mechanism was determined to be the aggregation of primary crystallites. This implied that there is a change in the intercalate chemistry of the primary crystallites with digestion time. Predicted changes in the concentrations of simple and complex ions in the solution support the proposed mechanism. The comprehensive set of hydrolysis reactions used in the model described above allows the investigation of other systems provided that accurate reaction constants are available. the fact that transition metal ions like Ni2+ form strong complexes with ammonia presents a challenge in the full recovery of the Ni2+. On the other hand, presence of Al3+ facilitates the complete precipitation of Ni2+ in about 3 hours of digestion. A challenge in their predictive modeling studies had been the fact that simultaneous incorporation of more than one metal ion necessitates a different approach than just using the equilibrium constants of hydrolysis, complexation and precipitation reactions. Another limitation of using equilibrium constants is that the nucleation stage of digestion, which is controlled mainly by kinetics, is not fully justified. A new program released by IBM Almaden Research Center (Chemical Kinetics Simulator™, Version 1.01) lets the user change

  7. Growth and characterization of semiconducting nickel sulfide nanocrystals from air-stable single-source metal organic precursors

    Directory of Open Access Journals (Sweden)

    Sohail Saeed

    2015-12-01

    Full Text Available Three symmetrical and unsymmetrical nickel(II complexes [cis-(C3H72NC(SNC(OC6H3(3,5-NO22]2Ni(II, [cis-(C4H92NC(SNC(OC6H3(3,5-NO22]2Ni(II, and [cis-(Hex(Me2NC(SNC(O C6H3(3,5-NO22]2Ni(II were synthesized and characterized by FTIR spectroscopy, elemental analysis, and mass spectrometry. These metal complexes have been used as single-source precursors for the preparation of semiconducting nickel sulfide nanocrystals. Rapid injection of metal complexes into oleylamine at 230°C, followed by immediate cooling, led to the formation of irregular-shaped 20–170-nm nickel sulfide nanocrystals. The deposited nickel sulfide nanocrystals were characterized by X-ray powder diffraction and transmission electron microscopy.

  8. Clinical bending of nickel titanium wires

    OpenAIRE

    Stephen Chain; Priyank Seth; Namrata Rastogi; Kenneth Tan; Mayank Gupta; Richa Singh

    2015-01-01

    Since the evolution and the involvement of Nickel Titanium wires in the field of Orthodontics. The treatment plan has evolved with the use of low force Nickel Titanium wires. Because of their high springback, low stiffness, they are the key initial wires in leveling and alignment but have poor formability. Since poor formability limits its ability to create variable arch forms thus; limits the form of treatment. We have devised a method to bend the Nickel Titanium wires to help in our invento...

  9. Recent advances in homogeneous nickel catalysis.

    Science.gov (United States)

    Tasker, Sarah Z; Standley, Eric A; Jamison, Timothy F

    2014-05-15

    Tremendous advances have been made in nickel catalysis over the past decade. Several key properties of nickel, such as facile oxidative addition and ready access to multiple oxidation states, have allowed the development of a broad range of innovative reactions. In recent years, these properties have been increasingly understood and used to perform transformations long considered exceptionally challenging. Here we discuss some of the most recent and significant developments in homogeneous nickel catalysis, with an emphasis on both synthetic outcome and mechanism.

  10. Topical and systemic therapies for nickel allergy.

    Science.gov (United States)

    Tammaro, Antonella; Narcisi, Alessandra; Persechino, Severino; Caperchi, Cristiano; Gaspari, Anthony

    2011-01-01

    Nickel allergy can result in both cutaneous and systemic manifestations, and can range from mild to severe symptoms. A severe form of this allergy is the Systemic nickel allergy syndrome, clinically characterized by cutaneous manifestions (contact dermatitis, pompholyx, hand dermatitis dyshydrosis, urticaria) with chronic course and systemic symptoms (headache, asthenia, itching, and gastrointestinal disorders related to histopathological alterations of gastrointestinal mucosa, borderline with celiac disease). This review aims to briefly update the reader on past and current therapies for nickel contact allergy.

  11. THERMAL STABILITY OF NICKEL AZIDES | Irom | Global Journal of ...

    African Journals Online (AJOL)

    . The samples, prepared using different methods, are fresh nickel azide, fresh nickel hydroxy axide and the third sample was obtained by ageing fresh nickel hydroxy azide for almost one year. Thermal decomposition of the samples at different ...

  12. PROCESS OF COATING WITH NICKEL BY THE DECOMPOSITION OF NICKEL CARBONYL

    Science.gov (United States)

    Hoover, T.B.

    1959-04-01

    An improved process is presented for the deposition of nickel coatings by the thermal decomposition of nickel carbonyl vapor. The improvement consists in incorporating a small amount of hydrogen sulfide gas in the nickel carbonyl plating gas. It is postulated that the hydrogen sulfide functions as a catalyst. i

  13. Cobalt (II, nickel (II, copper (II and zinc (II complexes of 1-(phenyl(phenylamino methylpyrrolidine-2,5-dione and 2-((phenylaminomethyl isoindoline-1,3-dione and their biological activity

    Directory of Open Access Journals (Sweden)

    D. Tamil Vendan

    2010-12-01

    Full Text Available The new Mannich bases 1-(phenyl(phenylaminomethylpyrrolidine-2,5-dione (SBA was synthesized from the condensation of succinimide, benzaldehyde and aniline. 2-((phenylaminomethylisoindoline-1,3-dione (PFA was derived from pthalimide, formaldehyde and aniline. The general formula of the Co (II, Ni (II, Cu (II and Zn (II chloro complexes, ML2X2 are reported. The ligands and the complexes have been characterized by various physical-chemical techniques such as elemental analysis, molar conductance, magnetic susceptibility measurements, infrared and electronic spectra. The spectral analysis to ascertain mode of bonding and overall geometry of the complexes revealed octahedral geometries.

  14. METHOD OF APPLYING NICKEL COATINGS ON URANIUM

    Science.gov (United States)

    Gray, A.G.

    1959-07-14

    A method is presented for protectively coating uranium which comprises etching the uranium in an aqueous etching solution containing chloride ions, electroplating a coating of nickel on the etched uranium and heating the nickel plated uranium by immersion thereof in a molten bath composed of a material selected from the group consisting of sodium chloride, potassium chloride, lithium chloride, and mixtures thereof, maintained at a temperature of between 700 and 800 deg C, for a time sufficient to alloy the nickel and uranium and form an integral protective coating of corrosion-resistant uranium-nickel alloy.

  15. Aluminium and nickel in human albumin solutions

    DEFF Research Database (Denmark)

    Gammelgaard, Bente; Sandberg, E

    1989-01-01

    Five different brands of commercially available human albumin solutions for infusion were analysed for their aluminium and nickel contents by atomic absorption spectrometry. The aluminium concentrations ranged from 12 micrograms/l to 1109 micrograms/l and the nickel concentrations ranged from 17...... micrograms/l to 77 micrograms/l. Examination of the aluminium and nickel contents of the constituents for the production of one brand showed too low levels to explain the final contamination of the product. By following the aluminium and nickel concentrations of the same brand during the production...

  16. Mineral resource of the month: nickel

    Science.gov (United States)

    Kuck, Peter H.

    2006-01-01

    Together with chromium, nickel makes steel more resistant to corrosion. Stainless steel thus accounts for more than 65 percent of primary nickel consumption in the world. One of the more common grades of stainless steel is Type 304, which contains 18 to 20 percent chromium and 10.5 to 12 percent nickel. Owing to their high corrosion resistance, nickel-bearing stainless steels are widely used in the transportation sector, the energy sector, the food preparation and processing industry, the beverage industry, the pharmaceutical industry and the medical community.

  17. The many faces of nickel allergy.

    Science.gov (United States)

    Darlenski, Razvigor; Kazandjieva, Jana; Pramatarov, Kyrill

    2012-05-01

    Hypersensitivity reactions to nickel are one of the most common in the modern world. Nickel allergy prevalence is constantly growing in many countries and represents a major health and socioeconomic issue. Herein the current understanding on nickel allergy is summarized with a practical approach to the dermatologist, allergist, and general practitioner. The personal experience with some practical clinical cases of nickel dermatitis is shared. A special emphasis is put on the possible strategies for treatment and prevention of the disease. © 2012 The International Society of Dermatology.

  18. Effects of nickel on eosinophil survival.

    Science.gov (United States)

    Ishihara, Kenji; Goi, Yoshiaki; Hong, Jang Ja; Seyama, Toshio; Ohtsu, Hiroshi; Wada, Hiroshi; Ohuchi, Kazuo; Hirasawa, Noriyasu

    2009-01-01

    Accessories, watches, coins and other items containing metal sometimes cause contact dermatitis and metal allergy. Among metals, nickel in alloys is ionized by sweat on the surface of the skin and exhibits particularly marked irritancy and allergenicity. Although eosinophils play important roles in allergy, the effects of nickel on eosinophils have not been elucidated. Eosinophils were prepared from the peritoneal cavity in rats immunized with Ascaris suum extract. Purified rat eosinophils were incubated in the presence of various kinds of metals including nickel. The viability of eosinophils was analyzed using a flow cytometer. When rat eosinophils were incubated for 3 days in the presence of nickel chloride at 30-1,000 microM, the viability of eosinophils was decreased in a concentration-dependent manner. Nickel chloride at 300 muM significantly increased the percentage of annexin V+ PI- eosinophils. The population of annexin V+ PI- eosinophils was also increased by nickel sulfate, cobalt chloride and zinc sulfate. The binding of nickel ions to eosinophils was detected by flow cytometer. Nickel ions bind to eosinophils and decrease the viability of eosinophils through the induction of apoptosis. Nickel ions may exhibit activity which modifies the function of eosinophils in allergy. Copyright 2009 S. Karger AG, Basel.

  19. [Immediate type allergies due to metal - nickel].

    Science.gov (United States)

    van Kampen, V; Merget, R; Brüning, T

    2003-11-01

    Occupational allergies of the immediate type due to metals, which are predominantly caused by nickel, platinum, chromium and cobalt, are rather rare. The present paper reviews the results of the evaluation of literature data concerning the occupational airway sensitization due to nickel, which is used in many different industrial fields - especially in the electroplating industry. Cases of specific airway sensizitation caused by nickel are verified by a number of studies, predominantly case histories. In conclusion, there is sufficient evidence that nickel may cause IgE-mediated hypersensitivity with typical symptoms.

  20. Nickel-induced cytokine production from mononuclear cells in nickel-sensitive individuals and controls. Cytokine profiles in nickel-sensitive individuals with nickel allergy-related hand eczema before and after nickel challenge

    DEFF Research Database (Denmark)

    Borg, L; Christensen, J M; Kristiansen, J

    2000-01-01

    Exposure to nickel is a major cause of allergic contact dermatitis which is considered to be an inflammatory response induced by antigen-specific T cells. Here we describe the in vitro analysis of the nickel-specific T-cell-derived cytokine response of peripheral blood mononuclear cells from 35...... was somewhat of a surprise, since previous studies have suggested a Th1 response in nickel-mediated allergic contact dermatitis. Subsequently, the nickel-allergic individuals were randomized to experimental exposure to nickel or vehicle in a double-blind design. A daily 10-min exposure of one finger to 10 ppm...... nickel solution for 1 week followed by 100 ppm for an additional week evoked a clinical response of hand eczema in the nickel-exposed group. Blood samples were drawn on days 7 and 14 after the start of this exposure to occupationally relevant concentrations of nickel. No statistically significant...

  1. Templated synthesis of nickel nanoparticles: Toward heterostructured nanocomposites for efficient hydrogen storage

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, Nicholas Cole [Iowa State Univ., Ames, IA (United States)

    2013-01-01

    The world is currently facing an energy and environmental crisis for which new technologies are needed. Development of cost-competitive materials for catalysis and hydrogen storage on-board motor vehicles is crucial to lead subsequent generations into a more sustainable and energy independent future. This thesis presents work toward the scalable synthesis of bimetallic heterostructures that can enable hydrogen to compete with carbonaceous fuels by meeting the necessary gravimetric and volumetric energy densities and by enhancing hydrogen sorption/desorption kinetics near ambient temperatures and pressures. Utilizing the well-known phenomenon of hydrogen spillover, these bimetallic heterostructures could work by lowering the activation energy for hydrogenation and dehydrogenation of metals. Herein, we report a novel method for the scalable synthesis of silica templated zero-valent nickel particles (Ni$\\subset$ SiO2) that hold promise for the synthesis of nickel nanorods for use in bimetallic heterostructures for hydrogen storage. Our synthesis proceeds by chemical reduction of a nickel-hydrazine complex with sodium borohydride followed by calcination under hydrogen gas to yield silica encapsulated nickel particles. Transmission electron microscopy and powder X-ray diffraction were used to characterize the general morphology of the resultant nanocapsules as well as the crystalline phases of the incorporated Ni0 nanocrystals. The structures display strong magnetic behavior at room temperature and preliminary data suggests nickel particle size can be controlled by varying the amount of nickel precursor used in the synthesis. Calcination under different environments and TEM analysis provides evidence for an atomic migration mechanism of particle formation. Ni$\\subset$SiO2 nanocapsules were used as seeds to induce heterogeneous nucleation and subsequent growth within the nanocapsule via electroless nickel plating. Nickel nanoparticle

  2. Nickel release from stainless steels.

    Science.gov (United States)

    Haudrechy, P; Mantout, B; Frappaz, A; Rousseau, D; Chabeau, G; Faure, M; Claudy, A

    1997-09-01

    In 1994, a study of nickel release and allergic contact dermatitis from nickel-plated metals and stainless steels was published in this journal. It was shown that low-sulfur stainless steel grades like AISI 304, 316L or 430 (S AISI 303-S approximately 0.3%) releases about 1.5 micrograms/cm2/week in this acid artificial sweat. Applied on patients sensitized to nickel, these metals elicit positive reactions in 96% and 14%, respectively, of the patients. The main conclusion was that low-sulfur stainless steels like AISI 304, 316L or 430, even when containing Ni, should not elicit nickel contact dermatitis, while metals having a mean corrosion resistance like a high-sulfur stainless steel (AISI 303) or nickel-plated steel should be avoided. The determining characteristic was in fact the corrosion resistance in chloride media, which, for stainless steels, is connected, among other factors, to the sulfur content. Thus, a question remained concerning the grades with an intermediate sulfur content, around 0.03%, which were not studied. They are the object of the study presented in this paper. 3 tests were performed: leaching experiments, dimethylglyoxime and HNO3 spot tests, and clinical patch tests; however, only stainless steels were tested: a low-sulfur AISI 304 and AISI 303 as references and 3 grades with a sulfur content around 0.03%: AISI 304L, AISI 304L added with Ca, AISI 304L+Cu. Leaching experiments showed that the 4 non-resulfurised grades released less than 0.5 microgram/cm2/week in acid sweat while the reulfurized AISI 303 released around or more than 0.5 microgram/cm2/week. This is explained by the poorer corrosion resistance of the resulfurized grade. Yet all these grades had the same reaction to the DMG test (negative result), which shows again its lack of sensitivity. In contrast, the HNO3 spot test distinguished AISI 303 from the non-resulfurized grades. Clinical patch tests again showed that some patients (4%) were intolerant to AISI 303, while none were

  3. Risk assessment of nickel carcinogenicity and occupational lung cancer.

    OpenAIRE

    Shen, H M; Zhang, Q F

    1994-01-01

    Recent progress in risk assessment of nickel carcinogenicity and its correlation with occupational lung cancer in nickel-exposed workers is reviewed. Epidemiological investigations provide reliable data indicating the close relation between nickel exposure and high lung cancer risk, especially in nickel refineries. The nickel species-specific effects and the dose-response relationship between nickel exposure and lung cancer are among the main questions that are explored extensively. It is als...

  4. Behavioral interventions to reduce nickel exposure in a nickel processing plant.

    Science.gov (United States)

    Rumchev, Krassi; Brown, Helen; Wheeler, Amanda; Pereira, Gavin; Spickett, Jeff

    2017-10-01

    Nickel is a widely-used material in many industries. Although there is enough evidence that occupational exposure to nickel may cause respiratory illnesses, allergies, and even cancer, it is not possible to stop the use of nickel in occupational settings. Nickel exposure, however, can be controlled and reduced significantly in workplaces. The main objective of this study was to assess if educational intervention of hygiene behavior could reduce nickel exposure among Indonesian nickel smelter workers. Participants were randomly assigned to three intervention groups (n = 99). Group one (n = 35) received only an educational booklet about nickel, related potential health effects and preventive measures, group two (n = 35) attended a presentation in addition to the booklet, and group three (n = 29) received personal feedback on their biomarker results in addition to the booklet and presentations. Pre- and post-intervention air sampling was conducted to measure concentrations of dust and nickel in air along with worker's blood and urine nickel concentrations. The study did not measure significant differences in particles and nickel concentrations in the air between pre- and post-interventions. However, we achieved significant reductions in the post intervention urine and blood nickel concentrations which can be attributed to changes in personal hygiene behavior. The median urinary nickel concentration in the pre-intervention period for group one was 52.3 µg/L, for group two 57.4 µg/L, and group three 43.2 µg/L which were significantly higher (pnickel with significantly (p nickel levels of 0.1 µg/L for all groups. The study showed that educational interventions can significantly reduce personal exposure levels to nickel among Indonesian nickel smelter workers.

  5. Synthesis and chemistry of fluorinated alpha-Iminocarboxamide Nickel and Zirconium catalysts

    International Nuclear Information System (INIS)

    Alsaygh, A.A.

    2007-01-01

    Synthesis and investigations of Nickel-based olefin oligomerization and polymerization catalysts, fluorinated alpha-Iminocarboxamide u3-Penzyl (II) Ni Complexes is reported. The synthesis of the above mentioned catalysts by the direct reaction of the potassium salt of the ligand, Ni(COD)2 (bis(1, 5-cyclooctadiene)-nickel and Benzyl halide in THF and starting temperature of -35C led to the formation of the two isomers: The [N-O] and the [N-N]. Moreover, the complexes di alpha-fluorinated Iminocarboxamide Zr-dimmer has been synthesized, investigated and tested for ethylene polymerization. (author)

  6. MD-2 Determinants of Nickel and Cobalt-Mediated Activation of Human TLR4

    Science.gov (United States)

    Oblak, Alja; Pohar, Jelka; Jerala, Roman

    2015-01-01

    Recent findings unexpectedly revealed that human TLR4 can be directly activated by nickel ions. This activation is due to the coordination of nickel by a cluster of histidine residues on the ectodomain of human TLR4, which is absent in most other species. We aimed to elucidate the role of MD-2 in the molecular mechanism of TLR4/MD-2 activation by nickel, as nickel binding site on TLR4 is remote from MD-2, which directly binds the endotoxin as the main pathological activator of TLR4. We identified MD-2 and TLR4 mutants which abolished TLR4/MD-2 receptor activation by endotoxin but could nevertheless be significantly activated by nickel, which acts in synergy with LPS. Human TLR4/MD-2 was also activated by cobalt ions, while copper and cadmium were toxic in the tested concentration range. Activation of TLR4 by cobalt required MD-2 and was abolished by human TLR4 mutations of histidine residues at positions 456 and 458. We demonstrated that activation of TLR4 by nickel and cobalt ions can trigger both the MyD88-dependent and the –independent pathway. Based on our results we propose that predominantly hydrophobic interactions between MD-2 and TLR4 contribute to the stabilization of the TLR4/MD-2/metal ion complex in a conformation that enables activation. PMID:25803856

  7. MD-2 determinants of nickel and cobalt-mediated activation of human TLR4.

    Directory of Open Access Journals (Sweden)

    Alja Oblak

    Full Text Available Recent findings unexpectedly revealed that human TLR4 can be directly activated by nickel ions. This activation is due to the coordination of nickel by a cluster of histidine residues on the ectodomain of human TLR4, which is absent in most other species. We aimed to elucidate the role of MD-2 in the molecular mechanism of TLR4/MD-2 activation by nickel, as nickel binding site on TLR4 is remote from MD-2, which directly binds the endotoxin as the main pathological activator of TLR4. We identified MD-2 and TLR4 mutants which abolished TLR4/MD-2 receptor activation by endotoxin but could nevertheless be significantly activated by nickel, which acts in synergy with LPS. Human TLR4/MD-2 was also activated by cobalt ions, while copper and cadmium were toxic in the tested concentration range. Activation of TLR4 by cobalt required MD-2 and was abolished by human TLR4 mutations of histidine residues at positions 456 and 458. We demonstrated that activation of TLR4 by nickel and cobalt ions can trigger both the MyD88-dependent and the -independent pathway. Based on our results we propose that predominantly hydrophobic interactions between MD-2 and TLR4 contribute to the stabilization of the TLR4/MD-2/metal ion complex in a conformation that enables activation.

  8. The cost of nickel allergy: a global investigation of coin composition and nickel and cobalt release.

    Science.gov (United States)

    Hamann, Carsten R; Hamann, Dathan; Hamann, Curtis; Thyssen, Jacob P; Lidén, Carola

    2013-01-01

    Nickel is widely used in coins; nickel may cause contact allergy and allergic contact dermatitis in those who handle them. To investigate alloy use, coin composition and nickel and cobalt release for a worldwide selection of currently circulating coins. Eight hundred and fifty coins of 361 different denominations or issues from 52 countries were collected and analysed with X-ray fluorescence spectrometry and nickel and cobalt spot tests. Copper-nickel was the most frequently identified coin alloy, being observed in 100 denominations (28%), followed by aluminium-bronze (62, 17%). In total, 239 denominations released nickel (28%). Coins from Bolivia, Brazil and Costa Rica did not release nickel. Fewer than one-third of the denominations or issues from China, India, the euro area and Indonesia released nickel. In the United States, the Russian Federation, Japan, and Mexico, one-third or more of the denominations released nickel. This worldwide selection of circulating coins covered countries with 75% of the world population, and shows that the majority of the world population lives in countries where coins release nickel. Pertinently, ∼ 40% of circulating coin denominations do not release nickel. © 2012 John Wiley & Sons A/S.

  9. Weak interactions modulating the dimensionality in supramolecular architectures in three new nickel(II)-hydrazone complexes, magnetostructural correlation, and catalytic potential for epoxidation of alkenes under phase transfer conditions.

    Science.gov (United States)

    Sadhukhan, Dipali; Ray, Aurkie; Pilet, Guillaume; Rizzoli, Corrado; Rosair, Georgina M; Gómez-García, Carlos J; Signorella, Sandra; Bellú, Sebastián; Mitra, Samiran

    2011-09-05

    Three different ONO donor acetyl hydrazone Schiff bases have been synthesized from the condensation of acetic hydrazide with three different carbonyl compounds: salicylaldehyde (HL(1)), 2-hydroxyacetophenone (HL(2)), and 2, 3-dihydroxybenzaldehyde (HL(3)). These tridentate ligands are reacted with Ni(OOCCF(3))(2)·xH(2)O to yield three new Ni(II) complexes having distorted octahedral geometry at each Ni center: [Ni(L(1))(OOCCF(3))(CH(3)OH)](2) (1), [Ni(L(2))(OOCCF(3))(H(2)O)](2) (2), and [Ni(L(3))(L(3)H)](OOCCF(3))(H(2)O)(1.65)(CH(3)OH)(0.35) (3). The ligands and the complexes have been characterized by elemental analysis and IR and UV-vis spectroscopy, and the structures of the complexes have been established by single crystal X-ray diffraction (XRD) study. 1 and 2 are centrosymmetric dinuclear complexes and are structural isomers whereas 3 is a bis chelated cationic monomer coordinated by one neutral and one monoanionic ligand. O-H···O hydrogen bonds in 3 lead to the formation of a dimer. Slight steric and electronic modifications in the ligand backbone provoke differences in the supramolecular architectures of the complexes, leading to a variety of one, two, and three-dimensional hydrogen bonded networks in complexes 1-3 respectively. Variable temperature magnetic susceptibility measurements reveal that moderate antiferromagnetic interactions operate between phenoxo bridged Ni(II) dimers in 1 and 2 whereas very weak antiferromagnetic exchange occurs through hydrogen bonding and π-π stacking interactions in 3. All complexes are proved to be efficient catalysts for the epoxidation of alkenes by NaOCl under phase transfer condition. The efficiency of alkene epoxidation is dramatically enhanced by lowering the pH, and the reactions are supposed to involve high valent Ni(III)-OCl or Ni(III)-O· intermediates. 3 is the best epoxidation catalyst among the three complexes with 99% conversion and very high turnover number (TON, 396).

  10. Nickel allergy in a Danish population 25 years after the first nickel regulation

    DEFF Research Database (Denmark)

    Ahlström, Malin G; Menné, Torkil; Thyssen, Jacob P

    2017-01-01

    BACKGROUND: Nickel in metallic items has been regulated in Denmark since 1990; however, 10% of young Danish women are still sensitized to nickel. There is a need for continuous surveillance of the effect of regulation. OBJECTIVES: To identify current self-reported metallic exposures leading...... reactions within 30 min of contact were reported by 30.7% of patients. CONCLUSIONS: Nickel exposures that led to the implementation of a nickel regulation seem to persist. The durations of contact with metallic items to fall under the current REACH regulation of nickel correspond well with the results...... to dermatitis in nickel-allergic patients, and the minimum contact time needed for dermatitis to occur. METHODS: A questionnaire was sent to all patients who reacted positively to nickel sulfate 5% pet. within the last 5 years at the Department of Dermatology and Allergy, Gentofte Hospital. RESULTS...

  11. Nickel concentrations in fingernails as a measure of occupational exposure to nickel

    DEFF Research Database (Denmark)

    Peters, K; Gammelgaard, Bente; Menné, T

    1991-01-01

    in nails (p less than 0.001). The difference between the 2 levels was also significant (p less than 0.001). No correlation between the nickel concentration in fingernails and the duration of exposure could be demonstrated. It was concluded that the higher the nickel level in the fingernails, the greater...... is the possibility that the person is occupationally exposed to nickel. Nail analysis is suggested as a measure of occupational exposure to nickel.......The nickel concentration in fingernails from 2 groups of people occupationally exposed to nickel was determined. In one group, comprising 83 persons moderately exposed to nickel, the mean +/- standard deviation (SD) was 29.2 micrograms/g +/- 56.7 micrograms/g and the median 13.8 micrograms/g (range...

  12. [Nickel dermatitis, systemic nickel allergy syndrome, immuno-genesis, immune-tolerance: an Italian study].

    Science.gov (United States)

    Cirla, A M; Cirla, P E

    2012-01-01

    Subjects with Nickel sensitization proved by patch test may suffer of contact eczema, but also of a Sistemic Nickel Allergy Syndrome (SNAS) consisting of urticaria-like troubles, itch, erythema, cutaneous rush, headache, intestinal symptoms, recurrent vesicular palmar dermatitis. 160 subjects (130 F, 30 M) were classified into three groups and underwent dosage of Nickel in urines (U-Ni) and blood (B-Ni). The two groups with SNAS showed an higher indicators of Nickel absorption, while the only-eczema group did not. 95 subjects with SNAS were enrolled for a Nickel-scanty diet: most of them improved. 24 ones again symptomatic were admitted to an experimental treatment, by a schedule of oral increasing microdose (nanograms) of Nickel sulphate: all of them improved. In conclusion Nickel pathology is changing, allergy seems to be due to different mechanism, dietary intake is important, an immune-tolerance can be induced.

  13. Inhibition in fertilisation of coral gametes following exposure to nickel and copper.

    Science.gov (United States)

    Gissi, Francesca; Stauber, Jenny; Reichelt-Brushett, Amanda; Harrison, Peter L; Jolley, Dianne F

    2017-11-01

    The mining and production of nickel in tropical regions have the potential to impact on ecologically valuable tropical marine ecosystems. Currently, few data exist to assess the risks of nickel exposure to tropical ecosystems and to derive ecologically relevant water quality guidelines. In particular, data are lacking for keystone species such as scleractinian corals, which create the complex structural reef habitats that support many other marine species. As part of a larger study developing risk assessment tools for nickel in the tropical Asia-Pacific region, we investigated the toxicity of nickel on fertilisation success in three species of scleractinian corals: Acropora aspera, Acropora digitifera and Platygyra daedalea. In the literature, more data are available on the effects of copper on coral fertilisation, so to allow for comparisons with past studies, the toxicity of copper to A. aspera and P. daedalea was also determined. Overall, copper was more toxic than nickel to the fertilisation success of the species tested. Acropora aspera was the most sensitive species to nickel (NOEC 4610µg Ni/L). Acropora aspera was also the more sensitive species to copper with an EC10 of 5.8µg Cu/L. The EC10 for P. daedalea was 16µg Cu/L, similar to previous studies. This is the first time that the toxicity of nickel on fertilisation success in Acropora species has been reported, and thus provides valuable data that can contribute to the development of reliable water quality guidelines for nickel in tropical marine waters. Copyright © 2017. Published by Elsevier Inc.

  14. Crystallographic orientations and twinning of electrodeposited nickel

    DEFF Research Database (Denmark)

    Alimadadi, Hossein; da Silva Fanta, Alice Bastos; Somers, Marcel A. J.

    2014-01-01

    A series of nickel layers was electrodeposited at different current densities from a Watts type electrolyte containing the additive 2-butyne-1,4-diol in various concentrations. The internal structure of the nickel electrodeposits was systematically investigated applying complementary microscopic...

  15. Systemic contact dermatitis due to nickel

    Directory of Open Access Journals (Sweden)

    Taruli Olivia

    2015-08-01

    Full Text Available Introduction: Systemic contact dermatitis (SCD is a systemic reactivation of a previous allergic contact dermatitis. The initial exposure may usually be topical, followed by oral, intravenous or inhalation exposure leading to a systemic hypersensitivity reaction. A case of a 27 year-old male with SCD due to nickel is reported Case Report: A 27 year-old male presented with recurrent pruritic eruption consist of deep seated vesicles on both palmar and left plantar since 6 months before admission. This complaint began after patient consumed excessive amounts of chocolate, canned food, and beans. The patient worked as a technician in a food factory. History of allergy due to nickel was acknowledged since childhood. The clinical presentation was diffuse deep seated vesicles, and multiple erythematous macules to plaques, with collarette scale. Patch test using the European standard showed a +3 result to nickel. The patient was diagnosed as systemic contact dermatitis due to nickel. The treatments were topical corticosteroid and patient education of avoidance of both contact and systemic exposure to nickel. The patient showed clinical improvement after 2 weeks. Discussion: SCD was diagnosed due to the history of massive consumption of food containing nickel in a patient who had initial sensitization to nickel, with clinical features and the patch test result. Advice to be aware of nickel and its avoidance is important in SCD management.

  16. Method of nickel-plating large components

    International Nuclear Information System (INIS)

    Wilbuer, K.

    1997-01-01

    The invention concerns a method of nickel-plating components, according to which even large components can be provided with an adequate layer of nickel which is pore- and stress-free and such that water is not lost. According to the invention, the component is heated and, after heating, is pickled, rinsed, scoured, plated in an electrolysis process, and rinsed again. (author)

  17. Interaction between chiral ions: synthesis and characterization of tartratovanadates(V) with tris(2,2′-bipyridine) complexes of iron(II) and nickel(II) as cations

    Czech Academy of Sciences Publication Activity Database

    Antal, P.; Schwendt, P.; Tatiersky, J.; Gyepes, Robert; Drábik, M.

    2014-01-01

    Roč. 39, č. 8 (2014), s. 893-900 ISSN 0340-4285 Institutional support: RVO:61388955 Keywords : RACEMIC COMPOUND FORMATION * TRIS(DIIMINE)-METAL COMPLEXES * CONGLOMERATE FORMATION Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.306, year: 2014

  18. Microwave absorption enhancement and dual-nonlinear magnetic resonance of ultra small nickel with quasi-one-dimensional nanostructure

    Science.gov (United States)

    Xu, Wei; Pan, Ya-Fei; Wei, Wei; Wang, Guang-Sheng; Qu, Peng

    2018-01-01

    Quasi-one-dimensional (Q1D)nickel nanostructures were prepared by a facial wet chemical process, and then the nickel chains/polyvinylidene fluoride (PVDF) composites were fabricated using the hot-molding procedure. Both the complex permittivity and permeability of the Ni/PVDF composites could be artificially adjusted by changing the nickel proportions, which contribute to enhancing the microwave absorption. An excellent reflection loss (RL) of -42.08 dB at 7.4 GHz with a low filler loading(20 wt%)and effective bandwidth (RL microwave absorbers.

  19. Structure investigations of electrodeposited nickel

    Energy Technology Data Exchange (ETDEWEB)

    Vertes, A.; Czako-Nagy, I.; Lakatos-Varsani, M. (Eoetvoes Lorand Tudomanyegyetem, Budapest (Hungary). Dept. of Physical Chemistry); Kajcsos, Z. (Hungarian Academy of Sciences, Budapest. Central Research Inst. for Physics); Csordas, L. (Eoetvoes Lorand Tudomanyegyetem, Budapest (Hungary). Dept. of Solid State Physics); Brauer, G. (Zentralinstitut fuer Kernforschung, Rossendorf bei Dresden (German Democratic Republic)); Leidheiser, H. Jr. (Lehigh Univ., Bethlehem, PA (USA). Center for Surface and Coatings Research)

    1982-08-01

    Nickel, electrodeposited under different conditions and yielding different values of stress, was investigated by positron annihilation (lifetime and Doppler-broadening), Moessbauer effect and X-ray diffraction measurements. Two-component positron lifetime spectra were obtained. The first component is thought to result from bulk annihilation and trapping at single trapping centres (TC). Estimations of TC-concentrations are obtained by means of the trapping model. The second one possibly denotes annihilation at voids, the number of which is dependent on the stress in the deposit. Results of Doppler-broadening measurements support this interpretation. The Moessbauer results show differences in the magnetic orientation in the three samples examined.

  20. Hydrothermal synthesis and study of an inorganic-organic hybrid vanadate of a nickel(II) coordination complex with pyrazine, Ni{sub 3}(C{sub 4}H{sub 4}N{sub 2}){sub 3}(V{sub 8}O{sub 23})

    Energy Technology Data Exchange (ETDEWEB)

    Larrea, Edurne S. [Dpto. de Mineralogia y Petrologia, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco/Euskal Herriko Unibertsitatea, UPV/EHU, Apdo. 644, E-48080 Bilbao (Spain); Mesa, Jose L., E-mail: joseluis.mesa@ehu.es [Dpto. de Quimica Inorganica, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco/Euskal Herriko Unibertsitatea, UPV/EHU, Apdo. 644, E-48080 Bilbao (Spain); Arriortua, Maria I. [Dpto. de Mineralogia y Petrologia, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco/Euskal Herriko Unibertsitatea, UPV/EHU, Apdo. 644, E-48080 Bilbao (Spain)

    2011-06-15

    Highlights: {yields} A novel inorganic-organic hybrid vanadate of nickel(II) coordination complex with pyrazine has been synthesized hydrothermally. {yields} The thermal and spectroscopic behavior has been studied. {yields} The compound shows AFM interactions which has been fitted to a magnetic model of lineal chains. -- Abstract: The three-dimensional hybrid compound Ni{sub 3}(C{sub 4}H{sub 4}N{sub 2}){sub 3}(V{sub 8}O{sub 23}) has been synthesized by mild hydrothermal methods under autogenous pressure at 170 {sup o}C. The structure of the phase is stable until 380 {sup o}C. The removal of the pyrazine molecules from the structure induces its collapse. The IR spectrum shows the vibration modes of the pyrazine molecule and those of the [VO{sub 4}]{sup 3-} groups. A UV-visible spectrum shows the characteristic bands of the Ni(II) d{sup 8}-high-spin cation in a slightly distorted octahedral coordination. Magnetic measurements indicate the existence of antiferromagnetic interactions that can be fitted with a chain model to give g = 2.31, J/k = -5.3, and zJ'/k = -5.5.

  1. Preparation, Characterization and Catalytic Activity of Nickel Molybdate (NiMoO4 Nanoparticles

    Directory of Open Access Journals (Sweden)

    Hicham Oudghiri-Hassani

    2018-01-01

    Full Text Available Nickel molybdate (NiMoO4 nanoparticles were synthesized via calcination of an oxalate complex in static air at 500 °C. The oxalate complex was analyzed by thermal gravimetric analysis (TGA and Fourier transform infrared spectroscopy (FTIR. The as-synthesized nickel molybdate was characterized by Brunauer–Emmett–Teller technique (BET, X-ray diffraction (XRD, and transmission electron microscopy (TEM and its catalytic efficiency was tested in the reduction reaction of the three-nitrophenol isomers. The nickel molybdate displays a very high activity in the catalytic reduction of the nitro functional group to an amino. The reduction progress was controlled using Ultraviolet-Visible (UV-Vis absorption.

  2. Simulations on Nickel target preparation and separation of Ni(II)-Cu(II) matrix for production of radioisotope 64Cu

    International Nuclear Information System (INIS)

    Sunarhadijoso Soenarjo; Wira Y Rahman; Sriyono; Triyanto

    2011-01-01

    The simulations on Nickel target preparation and separation of Ni(II)-Cu(II) matrix has been carried out as a preliminary study for production of medical radioisotope Cu-64 based on nuclear reaction of 64 Ni (p,n) 64 Cu. The nickel target preparation was performed by means of electroplating method using acidic solution of nickel chloride - boric acid mixture and basic solution of nickel sulphate - nickel chloride mixture on a silver - surfaced-target holder. The simulated solution of Ni(II) - Cu(II) matrix was considered as the solution of post-proton-irradiated nickel target containing both irradiated nickel and radioactive copper, but in the presented work the proton irradiation of nickel target was omitted, while the radioactive copper was originally obtained from neutron irradiation of CuO target. The separation of radioactive copper from the nickel target matrix was based on anion exchange column chromatography in which the radiocopper was conditioned to form anion complex CuCl 4 2- and retained on the column while the nickel was kept in the form of Ni 2+ cation and eluted off from the column. The retained radioactive copper was then eluted out the column in the condition of dilute HCl changing back the copper anion complex into Cu 2+ cation. It was found that the electroplating result from the acidic solution was more satisfied than that from the basic solution. By conditioning the matrix solution at HCl 6 M, the radioactive copper was found in the forms of Cu 2+ and CuCl 4 2- while the nickel was totally in the form of Ni 2+ . In the condition of HCl 9 M, the radioactive copper was mostly in the form of CuCl 4 2- while the nickel was found as both Ni 2+ and NiCl 4 2- . The best condition of separation was in HCl 8 M in which the radioactive copper was mostly in the form of CuCl 4 2- while the nickel was mostly in the form of Ni 2+ . The retained CuCl 4 2- was then changed back into Cu 2+ cation form and eluted out the column by using HCl 0.05 M. The

  3. Synthesis and Characterization of Acyclic and Cyclic Azabridged Ligands Incorporating 2,2'-Bipyridine Subunits and Their Complexes With Copper(II, Cobalt(II, and Nickel(II

    Directory of Open Access Journals (Sweden)

    Andrea Pappalardo

    2003-07-01

    Full Text Available The synthesis of a series of N,N'-disubstituted acyclic (AL and cyclic (CL aza-bridged ligands incorporating 2,2-pipryidine subunits is described. 1H-NMR and IR spectral data support the proposed ligand structures. Dynamic 1H-NMR studies on diurea and diamide derivatives point to the presence of slowly interconverting conformers on the 1H-NMR time-scale, owing to N−H···N hydrogen bonding and/or a restricted rotation around the amide bonds. The ligands synthesized form 1:1 complexes with divalent transition metal ions. Upon complexation, bis-ester derivatives AL5 and CL5 undergo a metal-induced hydrolysis of the ester groups to carboxyl functions, which act as additional binding sites for the metal ion, as well as hydrogen-bonding donor-acceptor binding site to produce dimeric complexes.

  4. Recent progress in nickel carcinogenesis

    Energy Technology Data Exchange (ETDEWEB)

    Sunderman, F.W. Jr.

    1984-01-01

    Positive bacterial mutagenesis tests have been obtained with Ni(II) in Corynybacterium, but not in E. coli, S. typhimurium, or B. subtilis. Transformation assays of several soluble and crystalline Ni compounds have been positive in Syrian hamster embryo cells. Ni(II) binds to DNA, RNA, and nucleoproteins, and becomes localized in nucleoli. Genotoxic effects of Ni include: (a) chromosomal aberrations, including sister-chromatid exchanges, (b) DNA strandbreaks and DNA-protein crosslinks, (c) inhibition of DNA and RNA synthesis, (d) infidelity of DNA transcription, and (e) mutations at the HGPRTase locus in Chinese hamster cells and the TK locus in mouse lymphoma cells. These findings are consistent with somatic mutation as the mechanism for initiation of nickel carcinogenesis. Ni compounds cause reversible transition of double-stranded poly(dG-dC) DNA from the right-handed B-helix to the left-handed Z-helix, suggesting a mechanism whereby nickel might modulate oncogene expression. 99 references, 4 tables.

  5. Low patch test reactivity to nickel in unselected adolescents tested repeatedly with nickel in infancy.

    Science.gov (United States)

    Christiansen, Elisabeth Soegaard; Andersen, Klaus Ejner; Bindslev-Jensen, Carsten; Halken, Susanne; Kjaer, Henrik Formsgaard; Eller, Esben; Høst, Arne; Mortz, Charlotte Gotthard

    2016-09-01

    It is questionable how repeated patch tests with nickel sulfate in infancy affect nickel patch test reactivity at a later age. The Danish Allergy Research Center (DARC) cohort encompasses 562 infants invited to a clinical examination including patch tests with nickel sulfate six times during the first 36 months of life. At the follow-up investigation at 14 years of age (2013-2014), participants were offered re-patch tests with nickel sulfate. The Odense Adolescence Cohort Study TOACS cohort encompasses 1501 schoolchildren evaluated for the first time at 14 years of age (1995-1996) including clinical examination and nickel sulfate patch tests. The prevalence of nickel sensitization in the DARC cohort was compared to the prevalence in the TOACS cohort at 14 years of age. Nickel sulfate sensitization was found in 1.2% of the participants from the DARC cohort tested repeatedly with nickel sulfate in early childhood and retested at 14 years of age compared to 8.6% of the participants from the TOACS cohort patch-tested for the first time at 14 years of age using the same patch test system and test concentration. The significant difference in nickel patch test reactivity comparing the two cohorts may reflect an immunologic effect or the effect of nickel regulation. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  6. Rates of nickel(II) capture from complexes with NTA, EDDA, and related tetradentate chelating agents by the hexadentate chelating agents EDTA and CDTA: Evidence of a "semijunctive" ligand exchange pathway

    Science.gov (United States)

    Boland, Nathan E.; Stone, Alan T.

    2017-09-01

    Many siderophores and metallophores produced by soil organisms, as well as anthropogenic chelating agent soil amendments, rely upon amine and carboxylate Lewis base groups for metal ion binding. UV-visible spectra of metal ion-chelating agent complexes are often similar and, as a consequence, whole-sample absorbance measurements are an unreliable means of monitoring the progress of exchange reactions. In the present work, we employ capillary electrophoresis to physically separate Ni(II)-tetradentate chelating agent complexes (NiL) from Ni(II)-hexadentate chelating agent complexes (NiY) prior to UV detection, such that progress of the reaction NiL + Y → NiY + L can be conveniently monitored. Rates of ligand exchange for Ni(II) are lower than for other +II transition metal ions. Ni(II) speciation in environmental media is often under kinetic rather than equilibrium control. Nitrilotriacetic acid (NTA), with three carboxylate groups all tethered to a central amine Lewis base group, ethylenediamine-N,N‧-diacetic acid (EDDA), with carboxylate-amine-amine-carboxylate groups arranged linearly, plus four structurally related compounds, are used as tetradentate chelating agents. Ethylenediaminetetraacetic acid (EDTA) and the structurally more rigid analog trans-cyclohexaneethylenediaminetetraacetic acid (CDTA) are used as hexadentate chelating agents. Effects of pH and reactant concentration are explored. Ni(II) capture by EDTA was consistently more than an order of magnitude faster than capture by CDTA, and too fast to quantify using our capillary electrophoresis-based technique. Using NiNTA as a reactant, Ni(II) capture by CDTA is independent of CDTA concentration and greatly enhanced by a proton-catalyzed pathway at low pH. Using NiEDDA as reactant, Ni(II) capture by CDTA is first order with respect to CDTA concentration, and the contribution from the proton-catalyzed pathway diminished by CDTA protonation. While the convention is to assign either a disjunctive

  7. A tetranuclear cubane-like nickel(II complex with a tridentate salicylideneimine Schiff base ligand: tetrakis[μ3-4-methyl-N-(2-oxidophenylsalicylideneiminato]tetrakis[methanolnickel(II] methanol 0.8-solvate

    Directory of Open Access Journals (Sweden)

    Gordana Pavlović

    2016-12-01

    Full Text Available The tetranuclear title complex, [Ni4(C14H11NO24(CH3OH4]·0.8CH3OH, has a distorted cubane topology shaped by four Schiff base ligands. The cubane [Ni4(μ3-O4] core is formed via the O atoms from the Schiff base ligands. The octahedrally coordinated NiII ions occupy alternating vertices of the cube. Each NiII ion is coordinated by one O,N,O′-tridentate dianionic ligand, two O atoms of oxidophenyl groups from adjacent ligands and the O atom of a coordinating methanol molecule. The cubane core is stabilized via an intramolecular O—H...O hydrogen bond between the hydroxy group of the coordinating methanol molecules and the phenolate O atom of the aldehyde Schiff base fragment. Additional stabilization is obtained via intramolecular C—H...O hydrogen bonds involving aromatic C—H groups and the oxygen atoms of adjacent methanol molecules. In the crystal, complex molecules are linked into chains parallel to the c axis via weak C—H...O hydrogen bonds. The partial-occupancy disordered methanol solvent molecule has a site occupancy of 0.8 and is linked to the tetranuclear unit via an intermolecular C—H...O hydrogen bond involving a phenolate O atom.

  8. Nickel oral hyposensitization in patients with systemic nickel allergy syndrome.

    Science.gov (United States)

    Di Gioacchino, Mario; Ricciardi, Luisa; De Pità, Ornella; Minelli, Mauro; Patella, Vincenzo; Voltolini, Susanna; Di Rienzo, Valerio; Braga, Marina; Ballone, Enzo; Mangifesta, Rocco; Schiavino, Domenico

    2014-02-01

    This is the first randomized, double-blind, placebo-controlled trial (EUDRACT No. 2009-013923-43) evaluating nickel oral hyposensitizing treatment (NiOHT) in patients with "systemic nickel allergy syndrome" (SNAS), characterized by Ni-allergic contact dermatitis and systemic reactions after eating Ni-rich food. Adults with positive Ni-patch test, who reported symptoms suggesting SNAS, which improved after Ni-poor diet, and were positive to Ni-oral challenge were eligible. Patients were randomly assigned to three treatments (1.5 μg, 0.3 μg, or 30 ng Ni/week) or placebo for a year, with progressive reintroduction of Ni-rich foods form the 5(th) month. Out of 141 patients randomized, 113 completed the trial. Endpoints were efficacy and tolerability of treatment. During Ni-rich food re-introduction, the 1.5 μg Ni/week group had a mean VAS score significantly higher than placebo (p = 0.044), with significant improvement of gastrointestinal symptoms (p = 0.016;) and significantly fewer rescue medications. Cutaneous manifestations also improved but without reaching statistical significance. After the treatment, oral challenge with higher Ni doses than at baseline were needed to cause symptoms to flare-up in significantly more patients given 1.5 μg Ni/week than placebo (p = 0.05). Patients reported no side-effects. NiOHT is effective in SNAS, in particular on gastrointestinal manifestations, with trend toward improvement of cutaneous symptoms.

  9. Environmental and human toxicology of nickel - a review; Umwelt- und Humantoxikologie von Nickel - eine aktuelle Uebersicht

    Energy Technology Data Exchange (ETDEWEB)

    Beyersmann, D. [Fachbereich Biologie und Chemie, Univ. Bremen (Germany)

    2006-07-01

    Nickel is a relatively rare element, and its concentrations in ambient air, soils and waters are very low. Higher burdens of nickel are found in nickel industries and their proximity. The human uptake of nickel from the ambient air is neglectably low, except in industrial exposures. The main fraction of human nickel uptake is from food, nearly 50% stems from vegetables. Only about 2% of the oral uptake of nickel are resorbed and distributed over all organs investigated. The uptake of nickel compounds through the skin generally is very low. However, chronic skin contact with nickel and nickel compounds causes a specific contact allergy. This disease was observed after occupational exposure but also frequently in the general population. The number of new cases has dropped considerably due to reinforced prevention. Epidemiological studies with workers of nickel smelting and refining plants have demonstrated increased risks of nose and lung cancer. Human data are supported by results from animal experiments which have shown that inhalation of various nickel compounds caused lung cancer. Furthermore, animal experiments have yielded evidence that oral and inhalative exposure to nickel compounds impair reproduction. National and international agencies have classified various nickel compounds as carcinogenic to humans. The unit cancer risk attributed to life-long inhalation of 1 {mu}g Ni/m{sup 3} air is estimated to be between 2 x 10{sup -4} and 7 x 10{sup -4}. Occupational exposure limits in Germany have been the Technical Guidance Values of 0.5 mg/m{sup 3} for nickel and weakly soluble nickel compounds and of 0.05 mg/m{sup 3} for inhalable droplets of soluble nickel salts. The German limit value for ambient immission is 0.015 mg Ni/m{sup 2}. d, and for emission 0,5 mg Ni/m{sup 3}. Limit values for nickel in air are to be taken not as safe thresholds but as guidance values for the delimitation of the cancer risk. (orig.)

  10. Nickel impact on human health: An intrinsic disorder perspective.

    Science.gov (United States)

    Zambelli, Barbara; Uversky, Vladimir N; Ciurli, Stefano

    2016-12-01

    The interplay of the presence of nickel and protein disorder in processes affecting human health is the focus of the present review. Many systems involving nickel as either a cofactor or as a toxic contaminant are characterized by large disorder. The role of nickel in the biochemistry of bacterial enzymes is discussed here, covering both the beneficial effects of nickel in the human microbiota as well as the role of nickel-depending bacteria in human pathogenesis. In addition, the hazardous health effects caused by nickel exposure to humans, namely nickel-induced carcinogenesis and allergy, are triggered by non-specific interactions of nickel with macromolecules and formation of reactive compounds that mediate cellular damage. Cellular response to nickel is also related to signal transduction cascades. This review thus highlights the most promising systems for future studies aimed at decreasing the adverse effects of nickel on human health. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. Nickel on the Swedish market: follow-up 10 years after entry into force of the EU Nickel Directive.

    NARCIS (Netherlands)

    Biesterbos, J.W.H.; Yazar, K.; Liden, C.

    2010-01-01

    BACKGROUND: The EU Nickel Directive, aimed at primary and secondary prevention of nickel allergy by limitation of nickel release from certain items, came fully into force in July 2001. OBJECTIVES: To assess the prevalence on the market of items with nickel release and to compare the outcome with

  12. Nickel-induced cytokine production from mononuclear cells in nickel-sensitive individuals and controls. Cytokine profiles in nickel-sensitive individuals with nickel allergy-related hand eczema before and after nickel challenge.

    Science.gov (United States)

    Borg, L; Christensen, J M; Kristiansen, J; Nielsen, N H; Menné, T; Poulsen, L K

    2000-06-01

    Exposure to nickel is a major cause of allergic contact dermatitis which is considered to be an inflammatory response induced by antigen-specific T cells. Here we describe the in vitro analysis of the nickel-specific T-cell-derived cytokine response of peripheral blood mononuclear cells from 35 nickel-allergic and 30 non-nickel-allergic individuals. Peripheral blood mononuclear cells were stimulated with 10(-4) and 10(-5) mol/l NiSO4 for 6 days and then additionally with ionomycin and phorbol myristate acetate for 24 h. Culture supernatants were analysed for interleukin-4 (IL-4), IL-5, interferon-gamma (IFN-gamma) and tumour necrosis factor-alpha (TNF-alpha) by quantitative ELISA. The analysis showed that the synthesis of IL-4 and IL-5 but not of IFN-gamma or TNF-alpha was significantly higher in the nickel-allergic individuals. The finding of preferential synthesis of Th2 cytokines was somewhat of a surprise, since previous studies have suggested a Th1 response in nickel-mediated allergic contact dermatitis. Subsequently, the nickel-allergic individuals were randomized to experimental exposure to nickel or vehicle in a double-blind design. A daily 10-min exposure of one finger to 10 ppm nickel solution for 1 week followed by 100 ppm for an additional week evoked a clinical response of hand eczema in the nickel-exposed group. Blood samples were drawn on days 7 and 14 after the start of this exposure to occupationally relevant concentrations of nickel. No statistically significant differences were observed in the nickel-induced in vitro cytokine response during the exposure period. Our results indicate the possibility that IL-4 and IL-5 are involved in the pathogenesis of nickel-mediated contact dermatitis.

  13. Nickel vacancy behavior in the electrical conductance of nonstoichiometric nickel oxide film

    Science.gov (United States)

    Soo Kim, Dong; Chul Lee, Hee

    2012-08-01

    Nickel vacancy behavior in electrical conductance is systematically investigated using various analysis methods on nickel oxide films deposited at different oxygen partial pressures. The results of Rutherford backscattering, x-ray diffraction, and Auger electron spectroscopy analyses demonstrate that the sputtered nickel oxide films are nickel-deficient. Through the deconvolution of Ni2p and O1s spectra in the x-ray photoelectron spectroscopy data, the number of Ni3+ ions is found to increase with the O2 ratio during the deposition. According to the vacancy model, nickel vacancies created from the non-stoichiometry are concluded to produce Ni3+ ions which lead to an increment of the conductivity of the nickel oxide films due to the increase of the hole concentration.

  14. Assessment of nickel and cobalt release from jewelry from a non-nickel directive country.

    Science.gov (United States)

    Boonchai, Waranya; Maneeprasopchoke, Pitchaya; Suiwongsa, Bordeesuda; Kasemsarn, Pranee

    2015-01-01

    A directive restricting nickel release from jewelry and other skin-contact products has not been initiated in Thailand or in the United States. The prevalence of nickel and cobalt allergies is increasing, and the main cause of sensitization seems to be jewelry. We aimed to investigate nickel and cobalt release from jewelry available in Thai marketplaces and to study the factors associated with nickel and cobalt release. Used costume jewelry items were collected from volunteers. They were tested with the dimethylglyoxime and cobalt tests. Five hundred fifty-one items, including belt buckles, bracelets, earrings, necklaces, rings, and watches, were tested; 216 (39.2%) gave positive dimethylglyoxime tests, and 206 (37.4%) gave positive cobalt tests. The factors that determined nickel or cobalt release were shopping location and jewelry price. Cobalt-containing jewelry could be identified by its dark color. A large proportion of the jewelry sold in Thai markets release nickel or cobalt.

  15. Fermi surfaces of rare-earth nickel borocarbides

    Energy Technology Data Exchange (ETDEWEB)

    Dugdale, S B; Utfeld, C; Wilkinson, I; Laverock, J; Major, Zs; Alam, M A [H H Wills Physics Laboratory, University of Bristol, Tyndall Avenue, Bristol BS8 1TL (United Kingdom); Canfield, P C [Ames Laboratory and Department of Physics and Astronomy, Iowa State University, Ames, IA 50011 (United States)], E-mail: s.b.dugdale@bristol.ac.uk

    2009-01-15

    A full three-dimensional study of the Fermi surface of LuNi{sub 2}B{sub 2}C is presented, using positron annihilation. The previously identified nesting feature, part of a complex multiply connected Fermi surface sheet, is clearly revealed and observed to extend across approximately 20% of the Brillouin zone. A cuboidal Fermi surface sheet is also found, in agreement with de Haas-van Alphen observations. The Fermi surface topology of the rare-earth nickel borocarbides is shown to vary little for rare-earth elements such as Er, Tm and Yb, suggesting that this topology is broadly common.

  16. The mechanism of nickel ferrite formation by glow discharge effect

    Science.gov (United States)

    Frolova, L. A.

    2018-04-01

    The influence of various factors on the formation of nickel ferrite by the glow discharge effect has been studied. The ferritization process in the system FeSO4-NiSO4-NaOH-H2O has been studied by the methods of potentiometric titration, measurement of electrical conductivity, residual concentrations and apparent sediment volume. It has been established that the process proceeds in a multistage fashion at pH 11-12 with the formation of polyhydroxo complexes, an intermediate compound and the ferrite formation by its oxidation with active radicals.

  17. Aluminium and nickel in human albumin solutions

    DEFF Research Database (Denmark)

    Gammelgaard, Bente; Sandberg, E

    1989-01-01

    Five different brands of commercially available human albumin solutions for infusion were analysed for their aluminium and nickel contents by atomic absorption spectrometry. The aluminium concentrations ranged from 12 micrograms/l to 1109 micrograms/l and the nickel concentrations ranged from 17...... of a batch of albumin solution, filtration was shown to contribute to contamination, although the largest increase in aluminium as well as nickel concentrations appeared during the bulk concentrating process. To avoid health risks to certain patients, regulations should be established requiring aluminium...

  18. Clinical bending of nickel titanium wires

    Directory of Open Access Journals (Sweden)

    Stephen Chain

    2015-01-01

    Full Text Available Since the evolution and the involvement of Nickel Titanium wires in the field of Orthodontics. The treatment plan has evolved with the use of low force Nickel Titanium wires. Because of their high springback, low stiffness, they are the key initial wires in leveling and alignment but have poor formability. Since poor formability limits its ability to create variable arch forms thus; limits the form of treatment. We have devised a method to bend the Nickel Titanium wires to help in our inventory but also customized the wire according to the treatment.

  19. Nickel and titanium nanoboride composite coating

    International Nuclear Information System (INIS)

    Efimova, K A; Galevsky, G V; Rudneva, V V; Kozyrev, N A; Orshanskaya, E G

    2015-01-01

    Electrodeposition conditions, structural-physical and mechanical properties (microhardness, cohesion with a base, wear resistance, corrosion currents) of electroplated composite coatings on the base of nickel with nano and micro-powders of titanium boride are investigated. It has been found out that electro-crystallization of nickel with boride nanoparticles is the cause of coating formation with structural fragments of small sizes, low porosity and improved physical and mechanical properties. Titanium nano-boride is a component of composite coating, as well as an effective modifier of nickel matrix. Nano-boride of the electrolyte improves efficiency of the latter due to increased permissible upper limit of the cathodic current density. (paper)

  20. Determination of electroless deposition by chemical nickeling

    Directory of Open Access Journals (Sweden)

    M. Badida

    2013-07-01

    Full Text Available Increasing of technical level and reliability of machine products in compliance with the economical and ecological terms belongs to the main trends of the industrial development. During the utilisation of these products there arise their each other contacts and the interaction with the environment. That is the reason for their surface degradation by wear effect, corrosion and other influences. The chemical nickel-plating allows autocatalytic deposition of nickel from water solutions in the form of coherent, technically very profitable coating without usage of external source of electric current. The research was aimed at evaluating the surface changes after chemical nickel-plating at various changes of technological parameters.

  1. Synthesis and Spectral Investigations of Manganese(II, Cobalt(II, Nickel(II, Copper(II and Zinc(II Complexes of New Polydentate Ligands Containing a 1,8-Naphthyridine Moiety

    Directory of Open Access Journals (Sweden)

    Sunkari Jyothi

    2006-12-01

    Full Text Available 2-(o-Hydroxyphenyl-1,8-naphthyridine (HN, 2-(4-hydroxy-6-methylpyran-2-one-3-yl-1,8-naphthyridine (HMPN and 2-(benzimidazol-2-yl-1,8-naphthyridine(BN react with acetates of Mn(II, Co(II, Ni(II, Cu(II and Zn(II to yield metal ioncomplexes of definite composition. These compounds were characterized by elementalanalyses, molar conductivity, magnetic susceptibility measurements, thermal studies, IR,UV-visible, NMR and mass spectral investigations. The complexes are found to have theformulae [M(HN2(H2O2], [M(HMPN2(H2O2] and [M(BN2(OAc2], respectively.

  2. Two new twisted helical nickel(II) and cobalt(III) octahedral monomer ...

    Indian Academy of Sciences (India)

    two complexes are isostructural with octahedral coordination environment exhibiting helical twist topology. They also display strong H-bonding as well as CH-π interactions to generate 1D chain. Keywords. Coordination chemistry; nickel(II); cobalt(III); Schiff base; twisted helicity; supramolecular interactions. 1. Introduction.

  3. Absorption and retention of nickel from drinking water in relation to food intake and nickel sensitivity

    DEFF Research Database (Denmark)

    Nielsen, G D; Søderberg, U; Jørgensen, Poul Jørgen

    1999-01-01

    Two studies were performed to examine the influence of fasting and food intake on the absorption and retention of nickel added to drinking water and to determine if nickel sensitization played any role in this regard. First, eight nonallergic male volunteers fasted overnight before being given......-related difference in gastric emptying rates may play a role. Thus, food intake and gastric emptying are of substantial significance for the bioavailability of nickel from aqueous solutions....

  4. Absorption and retention of nickel from drinking water in relation to food intake and nickel sensitivity.

    Science.gov (United States)

    Nielsen, G D; Søderberg, U; Jørgensen, P J; Templeton, D M; Rasmussen, S N; Andersen, K E; Grandjean, P

    1999-01-01

    Two studies were performed to examine the influence of fasting and food intake on the absorption and retention of nickel added to drinking water and to determine if nickel sensitization played any role in this regard. First, eight nonallergic male volunteers fasted overnight before being given nickel in drinking water (12 micrograms Ni/kg) and, at different time intervals, standardized 1400-kJ portions of scrambled eggs. When nickel was ingested in water 30 min or 1 h prior to the meal, peak nickel concentrations in serum occurred 1 h after the water intake, and the peak was 13-fold higher than the one seen 1 h after simultaneous intake of nickel-containing water and scrambled eggs. In the latter case, a smaller, delayed peak occurred 3 h after the meal. Median urinary nickel excretion half-times varied between 19.9 and 26.7 h. Within 3 days, the amount of nickel excreted corresponded to 2.5% of the nickel ingested when it was mixed into the scrambled eggs. Increasing amounts were excreted as the interval between the water and the meal increased, with 25.8% of the administered dose being excreted when the eggs were served 4 h prior to the nickel-containing drinking water. In the second experiment, a stable nickel isotope, 61Ni, was given in drinking water to 20 nickel-sensitized women and 20 age-matched controls, both groups having vesicular hand eczema of the pompholyx type. Nine of 20 nickel allergic eczema patients experienced aggravation of hand eczema after nickel administration, and three also developed a maculopapular exanthema. No exacerbation was seen in the control group. The course of nickel absorption and excretion in the allergic groups did not differ and was similar to the pattern seen in the first study, although the absorption in the women was less. A sex-related difference in gastric emptying rates may play a role. Thus, food intake and gastric emptying are of substantial significance for the bioavailability of nickel from aqueous solutions

  5. Coordination chemistry of bis(delta-camphorquinone dioximato)nickel(II) and -palladium(II). Reactions and structural studies of some M/sub 3/Ag/sub 3/ cluster complexes of camphorquinone dioxime

    Energy Technology Data Exchange (ETDEWEB)

    Ma, M.S.; Angelici, R.J.; Powell, D.; Jacobson, R.A.

    1980-01-01

    Reactions of AgNO/sub 3/ with Ni(delta-HCQD)/sub 2/ or Pd(delta-HCQD)/sub 2/, where delta-HCQD/sup -/ is delta-camphorquinone dioximato, yielded the hexanuclear metal cluster complexes (Ni(delta-HCQD)/sub 2/Ag)/sub 3/ x 2.5CHCl/sub 3/, Ni-Ag, and (Pd(delta-HCQD)/sub 2/Ag)/sub 3/ x 2CHCl/sub 3/, Pd-Ag, respectively. X-ray crystallographic studies performed on both complexes showed them to belong to space group P2/sub 1/2/sub 1/2/sub 1/. The unit cell dimensions of Ni-Ag are a = 15.990 (5) A, b = 38.44 (1) A, c = 13.437 (5) A, V = 8260.97 A/sup 3/, and Z = 4 while those of Pd-Ag are a = 16.110 (6), b = 38.92 (1), c = 13.393 (3) A, V = 8395.55 A/sup 3/, and Z = 4. Block-diagonal least-squares refinement of 3021 observed reflections for Ni-Ag and 6112 for Pd-Ag converged to R/sub F/ = 10.7 and 11.4 (R/sub w/ = 12.7 and 15.0) for the Ni-Ag and Pd-Ag structures, respectively. Their structures indicate that each hexanuclear molecule consists of three individual M(delta-HCQD)/sub 2//sup -/ units which act as multidentate ligands coordinating to a linear chain of three silver atoms. The coordination geometry around each M ion in the M(delta-HCQD)/sub 2//sup -/ units is square planar, and the delta-HCQD/sup -/ ligands are coordinated to M via N and O atoms. The Ag in the center of the molecule is coordinated to six O atoms with average Ag-O distances of 2.49 (3) and 2.45 (2) A for Ni-Ag and Pg-Ag, respectively. The two silver atoms at the ends of the chain are each coordinated to three nitrogen atoms from the M(delta-HCQD)/sub 2//sup -/ units with average Ag-N distances of 2.20 (4) and 2.27 (3) A, respectively. The Ag-Ag distances, 3.059 (5) and 3.052 (5) A in Ni-Ag and 3.173 (3) and 3.179 (3) A in Pd-Ag, are somewhat longer than those (2.89 A) in Ag metal and indicate that there are Ag-Ag interactions along the linear chains. The bis(pyridine) adduct of Ni(delta-HCQD)/sub 2/ was also prepared. A proposed structure for this complex is based on the similarity of its ir

  6. Coordination chemistry of bis(delta-camphorquinone dioximato)nickel(II) and -palladium(II). Reactions and structural studies of some M/sub 3/Ag/sub 3/ cluster complexes of camphorquinone dioxime

    Energy Technology Data Exchange (ETDEWEB)

    Ma, M.S.; Angelici, R.J.; Powell, D.; Jacobson, R.A.

    1980-10-01

    Reactions of AgNO/sub 3/ with Ni(delta-HCQD)/sub 2/ or Pd(delta-HCQD)/sub 2/, where delta-HCQD/sup -/ is delta-camphorquinone dioximato, yielded the hexanuclear metal cluster complexes (Ni(delta-HCQD)/sub 2/Ag)/sub 3/.2.5CHCl/sub 3/, Ni-Ag, and (Pd(delta-HCQD)/sub 2/Ag)/sub 3/.2CHCl/sub 3/, Pd-Ag, respectively. X-ray crystallographic studies performed on both complexes showed them to belong to space group P2/sub 1/2/sub 1/2/sub 1/. The unit cell dimensions of Ni-Ag are a = 15.990 (5) A, B = 38.44 (1) A, c = 13.437 (5) A, V = 8260.97 A/sup 3/, and Z = 4 while those of Pd-Ag are a = 16.110 (6), b = 38.92 (1), c = 13.393 (3) A, V = 8395.55 A/sup 3/, and Z = 4. Block-diagonal least-squares refinement of 3021 observed reflections for Ni-Ag and 6112 for Pd-Ag converged to R/sub F/ = 10.7 and 11.4 (R/sub w/ = 12.7 and 15.0) for the Ni-Ag and Pd-Ag structures, respectively. Their structures indicate that each hexanuclear molecule consists of three individual M(delta-HCQD)/sub 2//sup -/units which act as multidentate ligands coordinating to a linear chain of three silver atoms. The coordination geometry around each M ion in the M(delta-HCQD)/sub 2//sup -/units is square planar, and the delta-HCQD/sup -/ligands are coordinated to M via N and O atoms. The Ag in the center of the molecule is coordinated to six O atoms with average Ag-O distances of 2.49 (3) and 2.45 (2) A for Ni-Ag and Pd-Ag, respectively. The two silver atoms at the ends of the chain are each coordinated to three nitrogen atoms from the M(delta-HCQD)/sub 2//sup -/ units with average Ag-N distances of 2.20 (4) and 2.27 (3) A, respectively. The Ag-Ag distances, 3.059 (5) and 3.052 (5) A in Ni-Ag and 3.173 (3) and 3.179 (3) A in Pd-Ag, are somewhat longer than those (2.89 A) in Ag metal and indicate that there are Ag-Ag interactions along the linear chains.

  7. Two isomorphous transition metal complexes containing a protonated diaminopurine ligand: diaquabis(2,6-diamino-7H-purin-1-ium-κN9)bis(homophthalato-κO)nickel(II) tetrahydrate and the cobalt(II) analogue.

    Science.gov (United States)

    Atria, Ana María; Corsini, Gino; Herrera, Natalia; Garland, Maria Teresa; Baggio, Ricardo

    2011-05-01

    The two isomorphous title compounds, [M(C(5)H(7)N(6))(2)(C(9)H(6)O(4))(2)(H(2)O)(2)]·4H(2)O or M(2+)(Hdap(+))(2)(hpt(2-))(2)(H(2)O)(2)·4H(2)O {where dap is 2,6-diaminopurine, H(2)hpt is homophthalic acid [2-(2-carboxyphenyl)acetic acid] and M is Ni(II) or Co(II)}, consist of neutral M(2+)(Hdap(+))(2)(hpt(2-))(2)(H(2)O)(2) monomers, where the M(II) cation lies on an inversion centre and its MN(2)O(4) octahedral environment is defined by one N atom (from Hdap(+)), two O atoms (from one hpt(2-) dianion and one water molecule) and their inversion images. The structures are unusual in that the Hdap(+) cation occurs in an uncommon protonated state (as 2,6-diamino-7H-purin-1-ium) and both ligands bind in an unprecedented monodentate fashion. The existence of a large number of donors and acceptors for hydrogen bonding, together with π-π interactions, leads to a rather complex three-dimensional structure. © 2011 International Union of Crystallography

  8. Organic chemistry: Nickel steps towards selectivity

    Science.gov (United States)

    Gaunt, Matthew; Williamson, Patrick

    2017-05-01

    Hydrocarbons called alkenes are isolated from petroleum as mixtures of isomers, often making it hard to use them as reagents for synthesis. A reaction involving a migrating nickel atom offers a possible solution. See Letter p.84

  9. Sintering of nickel steam reforming catalysts

    DEFF Research Database (Denmark)

    Sehested, Jens; Larsen, Niels Wessel; Falsig, Hanne

    2014-01-01

    The lifetimes of heterogeneous catalysts in many widely used industrial processes are determined by the loss of active surface area. In this context, the underlying physical sintering mechanism and quantitative information about the rate of sintering at industrial conditions are relevant....... In this paper, particle migration and coalescence in nickel steam reforming catalysts is studied. Density functional theory calculations indicate that Ni-OH dominate nickel transport at nickel surfaces in the presence of steam and hydrogen as Ni-OH has the lowest combined energies of formation and diffusion...... compared to other potential nickel transport species. The relation between experimental catalyst sintering data and the effective mass diffusion constant for Ni-OH is established by numerical modelling of the particle migration and coalescence process. Using this relation, the effective mass diffusion...

  10. [Nickel allergy in contact and atopic dermatitis].

    Science.gov (United States)

    Antoszczyk, Grazyna; Obtułowicz, Krystyna; Wojas-Pelc, Anna; Szmigiel-Michalak, Katarzyna; Bogdaszewska-Czabanowska, Jadwiga; Obtułowicz, Aleksander

    2003-01-01

    The study is aimed to determine the importance of type I and type IV allergy in eczema caused by allergy to nickel. The study was performed at 55 patients (42 women, 13 men, aged 16-58 yrs) suffering from hand dermatitis (19 cases), disseminated eczema (22 cases) and atopic dermatitis (14 cases) with positive skin patch test to 2.5% nickel sulphate. In each patients history of illness was analyzed, total serum IgE level (tIgE) was estimated and specific IgE (sIgE) for nickel and also absolute blood eosinophils and basophils counts were estimated for the evaluation of the atopy features. In each patient patch skin test with different nickel sulphate dilutions were performed as well as skin prick tests with different dilutions of nickel sulphate. The following oral provocation tests were carried out with the nickel sulphate in doses 0.56 mg, 1.12 mg, 2.24 mg, 5.6 mg and 11.2 mg. The test was stopped at the dose provoking the symptoms of illness. Positive family history, the increased tIgE serum level as well as absolute counts of eosinophils and basophils were present in some patients with atopic and contact dermatitis and they were not useful in differential diagnosis of this forms of skin allergy. Skin patch test with different concentrations of nickel sulphate was helpful to establish the degree of contact sensitivity in all patients. The oral provocation test with different dose of nickel sulphate also provoked symptoms in some patients in each observed groups, but the reaction to the lowest dose was observed only in patients with atopic dermatitis. Specific IgE to nickel as well as skin prick testing also with different dilutions of nickel sulphate are not useful in the diagnosis of nickel allergy. In the all examined patients they were negative. It seems that both types of allergy (type I and IV) may take part in the patho-mechanism of atopic and contact skin allergy with alternate prevalence of one of its depending on patient condition.

  11. Nickel metal hydride LEO cycle testing

    Science.gov (United States)

    Lowery, Eric

    1995-01-01

    The George C. Marshall Space Flight Center is working to characterize aerospace AB5 Nickel Metal Hydride (NiMH) cells. The cells are being evaluated in terms of storage, low earth orbit (LEO) cycling, and response to parametric testing (high rate charge and discharge, charge retention, pulse current ability, etc.). Cells manufactured by Eagle Picher are the subjects of the evaluation. There is speculation that NiMH cells may become direct replacements for current Nickel Cadmium cells in the near future.

  12. Toxicity of nickel ores to marine organisms.

    Science.gov (United States)

    Florence, T M; Stauber, J L; Ahsanullah, M

    1994-06-06

    Queensland Nickel proposes to import New Caledonian (Ballande) and Indonesian (Gebe) nickel ores, one option being ship-to-barge transfer in Halifax Bay, North Queensland. Because small amounts of ore may be split during the unloading and transfer operations, it was important to investigate the potential impact of the spilt ore on the ecological health of the Bay. Long-term leaching of the ores with seawater showed that only nickel and chromium (VI) were released from the ores in sufficient concentrations to cause toxicity to a range of marine organisms. The soluble fractions of nickel and chromium (VI) were released from the ores within a few days. Nickel, chromium (VI) and the ore leachates showed similar toxicity to the juvenile banana prawn Penaeus merguiensis, the amphipod Allorchestes compressa and both temperature (22 degrees C) and tropical (27 degrees C) strains of the unicellular marine alga Nitzschia closterium. In a series of 30-day sub-chronic microcosm experiments, juvenile leader prawns Penaeus monodon, polychaete worms Galeolaria caespitosa and the tropical gastropod Nerita chamaeleon were all very resistant to the nickel ores, with mortality unaffected by 700 g ore per 50 l seawater. The growth rate of the leader prawns was, however, lower than that of the controls. From these data, a conservative maximum safe concentration of the nickel ores in seawater is 0.1 g l-1. The nickel ore was not highly toxic and if spilt in the quantities predicted, would not have a significant impact on the ecological health of the Bay.

  13. Application of ultrasound in solvent extraction of nickel and gallium

    Energy Technology Data Exchange (ETDEWEB)

    Pesic, B.

    1996-07-01

    The effects of ultrasound on the rate of solvent extraction of nickel with Lix 65N and Lix 70, and gallium with Kelex 100 were investigated. These solvent extraction systems are noted by their sluggish nature. Low frequency (20 kHz) ultrasound increased the rates of extraction of nickel by factors of four to seven. The ultrasound had no effect on the final chemical equilibrium. Gallium extraction rates were enhanced with the use of ultrasound by as much as a factor of 15. Again, the ultrasound had no effect on extraction equilibrium. For both nickel and gallium, the enhanced rates were attributed to increased interfacial surface area associated with ultrasonically induced cavitation and microdroplet formation. The stability of the microdroplets permitted intermittent application of ultrasound with corresponding decreases in ultrasonic energy requirements. The lowest energy consumption was observed with short (0.25 to 5 s) bursts of high power (41 to 61 W) ultrasonic inputs. The study also provided insight into the factors that affect the complex extraction of gallium from sodium aluminate solutions. The rate controlling step was found to be the dehydration of the gallate ion, Ga(OH)4, and the first complex formation between gallium and Kelex 100. Sodium was found to enhance the extraction rate up to a point, beyond which increased concentration was detrimental. Increasing aluminum concentration was found to slow extraction rates. Modifiers and diluents were shown to markedly affect extraction rates even without ultrasound. Ketone modifiers, particularly 2-undecanone, when used with Kermac 470B or Escaid 200 diluents enhanced extraction rates of gallium to the point that the use of ultrasound provided no additional benefits. The positive effects of ketone modifiers for the solvent extraction of gallium had not been previously reported.

  14. fusion on metal ion complexation of porphycene

    Indian Academy of Sciences (India)

    Complexation of −′ fused -extended porphycene, namely dinaphthoporphycene was carried out successfully with copper(II) and its solid state structure shows a square-type planar N4-coordination core. The photophysical and electrochemical properties of this complex, along with the nickel(II) complex were also ...

  15. Synthesis of late transition nickel(II) coordination polymer and their catalysis for olefinic polymerization

    Science.gov (United States)

    Chenfei, Xu; Zhang, Danfeng

    2017-09-01

    It was illustrated in this paper the successful synthesization of one α-diimine ligand and one new polycondensate ligand. The structure of the ligand was characterized by 1H NMR spectrum, and the structure of the polycondensate ligand was characterized by Thermogravimetric Analysis (TGA) and Element Analysis. Then these two ligands reacted with (DME)NiBr2 for the purpose of preparing α-diimine nickel complex and nickel coordination polymer characterized by Element Analysis and X-ray Photoelectron Spectroscopy (XPS). Then these two catalysts were adopted to facilitate ethylene polymerization and to compare the difference between them. It was found that the activities from nickel coordination polymer/MAO reached 106(g/molNi·h) and the molecule weights were about 105.

  16. Synthesis of uniform-sized bimetallic iron-nickel phosphide nanorods

    International Nuclear Information System (INIS)

    Yoon, Ki Youl; Jang, Youngjin; Park, Jongnam; Hwang, Yosun; Koo, Bonil; Park, Je-Geun; Hyeon, Taeghwan

    2008-01-01

    We synthesized uniform-sized nanorods of iron-nickel phosphides from the thermal decomposition of metal-phosphine complexes. Uniform-sized (Fe x Ni 1-x ) 2 P nanorods (0≤x≤1) of various compositions were synthesized by thermal decomposition of Ni-trioctylphosphine (TOP) complex and Fe-TOP complex. By measuring magnetic properties, we found that blocking temperature and coercive field depend on Ni content in the nanorods. Both parameters were more sensitive to doping compared with bulk samples. - Graphical abstract: We synthesized uniform-sized nanorods of iron-nickel phosphides from thermal decomposition of metal-phosphine complexes. The magnetic studies showed that blocking temperature and coercive field depend on Ni content in the nanorods

  17. On magnetism of nickel clusters in nanoporous carbon

    Science.gov (United States)

    Danishevskii, A. M.; Shanina, B. D.; Rogachev, A. Yu.; Sokolov, V. V.; Kalmykov, A. E.; Kyutt, R. N.; Gordeev, S. K.

    2017-10-01

    The structural and magnetometric characteristics of a nanoporous carbon with nickel clusters in nanopores have been studied. The main attention is focused on the fact of substantial decrease in the nickel magnetization as nickel has a close contact to carbon as compared to similar parameter of free nickel microparticles with almost the same sizes. A theoretical model of a periodic cluster consisting of 16 carbon atoms and one nickel atom in a micropore surrounded by carbon atoms has been built. The electron density in such a cluster and its magnetism were found by computer calculations. It is shown that the magnetic moment of a nickel atom in the cluster is substantially smaller than that of a free nickel atom. Based on the results, it is concluded that the decrease in the magnetization of nickel clusters in the carbon environment observed experimentally is due to the adsorption interaction of the nickel and carbon electron subsystems.

  18. Nickel acts as an adjuvant during cobalt sensitization

    DEFF Research Database (Denmark)

    Bonefeld, Charlotte Menne; Nielsen, Morten Milek; Vennegaard, Marie T.

    2015-01-01

    Metal allergy is the most frequent form of contact allergy with nickel and cobalt being the main culprits. Typically, exposure comes from metal-alloys where nickel and cobalt co-exist. Importantly, very little is known about how co-exposure to nickel and cobalt affects the immune system. We...... investigated these effects by using a recently developed mouse model. Mice were epicutaneously sensitized with i) nickel alone, ii) nickel in the presence of cobalt, iii) cobalt alone, or iv) cobalt in the presence of nickel, and then followed by challenge with either nickel or cobalt alone. We found...... that sensitization with nickel alone induced more local inflammation than cobalt alone as measured by increased ear-swelling. Furthermore, the presence of nickel during sensitization to cobalt led to a stronger challenge response to cobalt as seen by increased ear-swelling and increased B and T cell responses...

  19. Effects of repeated skin exposure to low nickel concentrations

    DEFF Research Database (Denmark)

    Nielsen, N H; Menné, T; Kristiansen, J

    1999-01-01

    We studied the effects of repeated daily exposure to low nickel concentrations on the hands of patients with hand eczema and nickel allergy. The concentrations used were chosen to represent the range of trace to moderate occupational nickel exposure. The study was double-blinded and placebo...... and nickel allergy, either on normal or on SLS-treated forearm skin. The present study strongly suggests that the changes observed were specific to nickel exposure. Standardized methods to assess trace to moderate nickel exposure on the hands, and the associated effects in nickel-sensitized subjects...... controlled. Patients immersed a finger for 10 min daily into a 10-p.p.m. nickel concentration in water for the first week, and during the second week into a 100-p.p.m. nickel concentration. This regimen significantly increased (P = 0.05) local vesicle formation and blood flow (P = 0.03) as compared...

  20. Synthesis and analytical application of a novel tetradentate N(2)O(2) Schiff base as a chromogenic reagent for determination of nickel in some natural food samples.

    Science.gov (United States)

    Fakhari, Ali Reza; Khorrami, Afshin Rajabi; Naeimi, Hossein

    2005-05-15

    A novel sensitive chromogenic reagent, N,N'-bis(3-methylsalicylidene)-ortho-phenylene diamine (MSOPD), has been synthesized and used in the spectrophotometric determination of nickel. At pH 8, MSOPD can react with nickel ion at room temperature to form a 1:1 complex. The apparent molar absorptivity is 9.5x10(4)lmol(-1)cm(-1) at 430nm. Beer's low is obeyed over the range 0-1.0x10(-5)M of nickel with a detection limit of 1.36x10(-8)M. The relative standard deviation for measurement of 3.41x10(-6)M nickel is 1.3% (n=10). The method has successfully been applied to determination of trace amounts of nickel in some natural food samples.

  1. Nickel biopathways in tropical nickel hyperaccumulating trees from Sabah (Malaysia).

    Science.gov (United States)

    van der Ent, Antony; Callahan, Damien L; Noller, Barry N; Mesjasz-Przybylowicz, Jolanta; Przybylowicz, Wojciech J; Barnabas, Alban; Harris, Hugh H

    2017-02-16

    The extraordinary level of accumulation of nickel (Ni) in hyperaccumulator plants is a consequence of specific metal sequestering and transport mechanisms, and knowledge of these processes is critical for advancing an understanding of transition element metabolic regulation in these plants. The Ni biopathways were elucidated in three plant species, Phyllanthus balgooyi, Phyllanthus securinegioides (Phyllanthaceae) and Rinorea bengalensis (Violaceae), that occur in Sabah (Malaysia) on the Island of Borneo. This study showed that Ni is mainly concentrated in the phloem in roots and stems (up to 16.9% Ni in phloem sap in Phyllanthus balgooyi) in all three species. However, the species differ in their leaves - in P. balgooyi the highest Ni concentration is in the phloem, but in P. securinegioides and R. bengalensis in the epidermis and in the spongy mesophyll (R. bengalensis). The chemical speciation of Ni 2+ does not substantially differ between the species nor between the plant tissues and transport fluids, and is unambiguously associated with citrate. This study combines ion microbeam (PIXE and RBS) and metabolomics techniques (GC-MS, LC-MS) with synchrotron methods (XAS) to overcome the drawbacks of the individual techniques to quantitatively determine Ni distribution and Ni 2+ chemical speciation in hyperaccumulator plants.

  2. Nickel biopathways in tropical nickel hyperaccumulating trees from Sabah (Malaysia)

    Science.gov (United States)

    van der Ent, Antony; Callahan, Damien L.; Noller, Barry N.; Mesjasz-Przybylowicz, Jolanta; Przybylowicz, Wojciech J.; Barnabas, Alban; Harris, Hugh H.

    2017-02-01

    The extraordinary level of accumulation of nickel (Ni) in hyperaccumulator plants is a consequence of specific metal sequestering and transport mechanisms, and knowledge of these processes is critical for advancing an understanding of transition element metabolic regulation in these plants. The Ni biopathways were elucidated in three plant species, Phyllanthus balgooyi, Phyllanthus securinegioides (Phyllanthaceae) and Rinorea bengalensis (Violaceae), that occur in Sabah (Malaysia) on the Island of Borneo. This study showed that Ni is mainly concentrated in the phloem in roots and stems (up to 16.9% Ni in phloem sap in Phyllanthus balgooyi) in all three species. However, the species differ in their leaves - in P. balgooyi the highest Ni concentration is in the phloem, but in P. securinegioides and R. bengalensis in the epidermis and in the spongy mesophyll (R. bengalensis). The chemical speciation of Ni2+ does not substantially differ between the species nor between the plant tissues and transport fluids, and is unambiguously associated with citrate. This study combines ion microbeam (PIXE and RBS) and metabolomics techniques (GC-MS, LC-MS) with synchrotron methods (XAS) to overcome the drawbacks of the individual techniques to quantitatively determine Ni distribution and Ni2+ chemical speciation in hyperaccumulator plants.

  3. Performance improvement of pasted nickel electrodes with multi-wall carbon nanotubes for rechargeable nickel batteries

    International Nuclear Information System (INIS)

    Song, Q.S.; Aravindaraj, G.K.; Sultana, H.; Chan, S.L.I.

    2007-01-01

    Carbon nanotubes (CNTs) were employed as a functional additive to improve the electrochemical performance of pasted nickel-foam electrodes for rechargeable nickel-based batteries. The nickel electrodes were prepared with spherical β-Ni(OH) 2 powder as the active material and various amounts of CNTs as additives. Galvanostatic charge/discharge cycling tests showed that in comparison with the electrode without CNTs, the pasted nickel electrode with added CNTs exhibited better electrochemical properties in the chargeability, specific discharge capacity, active material utilization, discharge voltage, high-rate capability and cycling stability. Meanwhile, the CNT addition also lowered the packing density of Ni(OH) 2 particles in the three-dimensional porous nickel-foam substrate, which could lead to the decrease in the active material loading and discharge capacity of the electrode. Hence, the amount of CNTs added to Ni(OH) 2 should be optimized to obtain a high-performance nickel electrode, and an optimum amount of CNT addition was found to be 3 wt.%. The superior electrochemical performance of the nickel electrode with CNTs could be attributed to lower electrochemical impedance and less γ-NiOOH formed during charge/discharge cycling, as indicated by electrochemical impedance spectroscopy and X-ray diffraction analyses. Thus, it was an effective method to improve the electrochemical properties of pasted nickel electrodes by adding an appropriate amount of CNTs to spherical Ni(OH) 2 as the active material

  4. Corrosion properties of plasma deposited nickel and nickel-based alloys

    Czech Academy of Sciences Publication Activity Database

    Voleník, Karel; Pražák, M.; Kalabisová, E.; Kreislová, K.; Had, J.; Neufuss, Karel

    2003-01-01

    Roč. 48, č. 3 (2003), s. 215-226 ISSN 0001-7043 R&D Projects: GA ČR GA106/99/0298 Institutional research plan: CEZ:AV0Z2043910 Keywords : plasma deposits, nickel, nickel-based alloys Subject RIV: JK - Corrosion ; Surface Treatment of Materials

  5. Repeated patch testing to nickel during childhood do not induce nickel sensitization

    DEFF Research Database (Denmark)

    Søgaard Christiansen, Elisabeth

    2014-01-01

    Background: Previously, patch test reactivity to nickel sulphate in a cohort of unselected infants tested repeatedly at 3-72 months of age has been reported. A reproducible positive reaction at 12 and 18 months was selected as a sign of nickel sensitivity, provided a patch test with an empty Finn...

  6. Nickel allergy in a Danish population 25 years after the first nickel regulation.

    Science.gov (United States)

    Ahlström, Malin G; Menné, Torkil; Thyssen, Jacob P; Johansen, Jeanne D

    2017-06-01

    Nickel in metallic items has been regulated in Denmark since 1990; however, 10% of young Danish women are still sensitized to nickel. There is a need for continuous surveillance of the effect of regulation. To identify current self-reported metallic exposures leading to dermatitis in nickel-allergic patients, and the minimum contact time needed for dermatitis to occur. A questionnaire was sent to all patients who reacted positively to nickel sulfate 5% pet. within the last 5 years at the Department of Dermatology and Allergy, Gentofte Hospital. The response rate was 63.2%. Earrings were the foremost cause of dermatitis after the EU Nickel Directive had been implemented, followed by other jewellery, buttons on clothing, belt buckles, and wrist watches. Dermatitis reactions within 10 min of contact were reported by 21.4% of patients, and dermatitis reactions within 30 min of contact were reported by 30.7% of patients. Nickel exposures that led to the implementation of a nickel regulation seem to persist. The durations of contact with metallic items to fall under the current REACH regulation of nickel correspond well with the results of this study. © 2017 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  7. A review of nickel hydrogen battery technology

    Science.gov (United States)

    Smithrick, John J.; Odonnell, Patricia M.

    1995-01-01

    This paper on nickel hydrogen batteries is an overview of the various nickel hydrogen battery design options, technical accomplishments, validation test results and trends. There is more than one nickel hydrogen battery design, each having its advantage for specific applications. The major battery designs are individual pressure vessel (IPV), common pressure vessel (CPV), bipolar and low pressure metal hydride. State-of-the-art (SOA) nickel hydrogen batteries are replacing nickel cadmium batteries in almost all geosynchronous orbit (GEO) applications requiring power above 1 kW. However, for the more severe low earth orbit (LEO) applications (greater than 30,000 cycles), the current cycle life of 4000 to 10,000 cycles at 60 percent DOD should be improved. A NASA Lewis Research Center innovative advanced design IPV nickel hydrogen cell led to a breakthrough in cycle life enabling LEO applications at deep depths of discharge (DOD). A trend for some future satellites is to increase the power level to greater than 6 kW. Another trend is to decrease the power to less than 1 kW for small low cost satellites. Hence, the challenge is to reduce battery mass, volume and cost. A key is to develop a light weight nickel electrode and alternate battery designs. A common pressure vessel (CPV) nickel hydrogen battery is emerging as a viable alternative to the IPV design. It has the advantage of reduced mass, volume and manufacturing costs. A 10 Ah CPV battery has successfully provided power on the relatively short lived Clementine Spacecraft. A bipolar nickel hydrogen battery design has been demonstrated (15,000 LEO cycles, 40 percent DOD). The advantage is also a significant reduction in volume, a modest reduction in mass, and like most bipolar designs, features a high pulse power capability. A low pressure aerospace nickel metal hydride battery cell has been developed and is on the market. It is a prismatic design which has the advantage of a significant reduction in volume and a

  8. Bioassay of environmental nickel dusts in a particle feeding ciliate

    Energy Technology Data Exchange (ETDEWEB)

    Smith-Sonneborn, J.; Leibovitz, B.; Donathan, R.; Fisher, G.L.

    1986-01-01

    The ciliated protozoan Paramecium was used to quantitate cytotoxic and genotoxic effects of nickel particles. The biological response of these eukaryotic cells to pure nickel powder and iron-nickel powder was assayed and compared to the effect of the inorganic carcinogen nickel subsulfide. Cytotoxicity was determined by the percent survival of treated cells. Genotoxicity was indicated by significant increases in the fraction of nonviable offspring (presumed index of lethal mutations) found after self-fertilization (autogamy) in parents from the nickel-treated versus neutral control groups. The cells were exposed to the dusts and the biological effects determined. Only the nickel subsulfide consistently showed a significant increase in offspring lethality.

  9. Nickel allergy from adolescence to adulthood in the TOACS cohort

    DEFF Research Database (Denmark)

    Mortz, Charlotte G; Bindslev-Jensen, Carsten; Andersen, Klaus Ejner

    2013-01-01

    Background In 1995, we established a cohort of 1501 unselected eighth-grade schoolchildren to investigate the course of nickel allergy into adult life. Objectives To follow the course of nickel allergy and clinically relevant nickel dermatitis over 15 years from adolescence to adulthood, and the ......Background In 1995, we established a cohort of 1501 unselected eighth-grade schoolchildren to investigate the course of nickel allergy into adult life. Objectives To follow the course of nickel allergy and clinically relevant nickel dermatitis over 15 years from adolescence to adulthood...

  10. Filtration resistances of nickel carbonate

    Directory of Open Access Journals (Sweden)

    Jorge Rafael Gutiérrez-Olmos

    2017-12-01

    Full Text Available In the present work, the filtration of nickel carbonate was studied experimentally to laboratory scale, to evaluate the effects of suspension pH, chemical composition and fineness of the salt over of specific cake resistance and the medium resistance. The filtration was realized to a temperature of 80 ºC, 16 % in weight of solids and constant pressure drop of 3,758.104 N/m, applying as membrane the Kraft paper. It was obtained that by increasing the concentration of carbon dioxide on salt (1, 9 to 4, 4 %, it diminishes the content of sulphur (3, 09 to 1, 84 % and the specific cake resistance. It was showed the pH’s range for the minimum of specific resistance and cake humidity; when the pH increases from 7, 40 to 8, 76, increment the concentration of solids in the filtrate from 38 to 105 mg/l. To smallest pH than 7, 82, the inferior values of average particle diameter (dp was obtained; and the specific cake resistance incremented due to the combined effect between the variables: Concentration of carbon dioxide in salt, the pH of the suspension and dp. A model to estimate the specific cake resistance were proposed.

  11. Nickel exposure from keys: alternatives for protection and prevention.

    Science.gov (United States)

    Hamann, Dathan; Scheman, Andrew J; Jacob, Sharon E

    2013-01-01

    Keys are an important exposure source of metal allergens to consumers and confer a significant problem for nickel-allergic individuals because of repeated daily use. The aims of this study were to investigate the frequency of nickel and cobalt release in keys and to consider the effectiveness of coatings for preventing metallic allergen release from common metal allergen-releasing keys. Keys from a variety of common stores were nickel and cobalt spot tested. Nickel-releasing keys were coated with enamel sprays, subjected to a use test, and retested to assess for metal allergen release. Of 55 tested keys, 80% showed a strong positive result to the nickel spot test. None of the tested keys exhibited cobalt release. No keys initially released nickel after enamel coatings. Key coatings chipped at the portion inserted into a lock after 30 insertions, and keys were found to release nickel. The handle of the key was not found to release nickel after 60 insertions. Nickel release from keys is very common; nickel-allergic consumers should consider purchasing keys that do not release nickel (eg, brass, anodized). Enamel coating may be useful in protecting nickel-sensitive individuals from their keys but cannot consistently prevent nickel-release from portions used frequently.

  12. Nickel-induced cytokine production from mononuclear cells in nickel-sensitive individuals and controls. Cytokine profiles in nickel-sensitive individuals with nickel allergy-related hand eczema before and after nickel challenge

    DEFF Research Database (Denmark)

    Borg, L; Christensen, J M; Kristiansen, J

    2000-01-01

    Exposure to nickel is a major cause of allergic contact dermatitis which is considered to be an inflammatory response induced by antigen-specific T cells. Here we describe the in vitro analysis of the nickel-specific T-cell-derived cytokine response of peripheral blood mononuclear cells from 35 n...

  13. Cobalt release from inexpensive jewellery: has the use of cobalt replaced nickel following regulatory intervention?

    DEFF Research Database (Denmark)

    Thyssen, Jacob Pontoppidan; Jellesen, Morten S; Menné, Torkil

    2010-01-01

    Before the introduction of the EU Nickel Directive, concern was raised that manufacturers of jewellery might turn from the use of nickel to cobalt following the regulatory intervention on nickel exposure.......Before the introduction of the EU Nickel Directive, concern was raised that manufacturers of jewellery might turn from the use of nickel to cobalt following the regulatory intervention on nickel exposure....

  14. Synthesis and electrochemical characterization of stabilized nickel nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Dominguez-Crespo, M.A.; Ramirez-Meneses, E.; Torres Huerta, A.M. [Centro de Investigacion en Ciencia Aplicada y Tecnologia Avanzada, CICATA-IPN Unidad Altamira, Carretera Tampico-Puerto Industrial, C.P. 89600 Altamira, Tamaulipas (Mexico); Montiel-Palma, V. [Centro de Investigaciones Quimicas, Universidad Autonoma del Estado de Morelos, Av. Universidad 1001, Colonia Chamilpa, C.P.62201 Cuernavaca, Morelos (Mexico); Dorantes Rosales, H. [Departamento de Metalurgia, Escuela Superior de Ingenieria Quimica e Industrias Extractivas - IPN, C.P. 07300, D.F. (Mexico)

    2009-02-15

    Nickel stabilized nanoparticles produced by an organometallic approach (Chaudret's method) starting from the complex Ni(1,5-COD){sub 2} were used as electrode materials for hydrogen evolution in NaOH at two temperatures (298 and 323 K). The synthesis of the nickel nanoparticles was performed in the presence of two different stabilizers, 1,3-diaminopropane (DAP) and anthranilic acid (AA), by varying the molar ratios (1:1, 1:2 and 1:5 metal:ligand) in order to evaluate their influence on the shape, dispersion, size and electrocatalytic activity of the metallic particles. The presence of an appropriate amount of stabilizer is an effective alternative to the synthesis of small monodispersed metal nanoparticles with diameters around 5 and 8 nm for DAP and AA, respectively. The results are discussed in terms of morphology and the surface state of the nanoparticles. The importance of developing a well-controlled synthetic method which results in higher performances of the resulting nanoparticles is highlighted. Herein we found that the performance with respect to the HER of the Ni electrodes dispersed on a carbon black Vulcan substrate is active and comparable to that reported in the literature for the state-of-the-art electrocatalysts. Appreciable cathodic current densities of {proportional_to}240 mA cm{sup -2} were measured with highly dispersed nickel particles (Ni-5{sub DAP}). This work demonstrates that the aforementioned method can be extended to the preparation of highly active stabilized metal particles without inhibiting the electron transfer for the HER reaction, and it could also be applied to the synthesis of bimetallic nanoparticles. (author)

  15. Lactose intolerance in systemic nickel allergy syndrome.

    Science.gov (United States)

    Cazzato, I A; Vadrucci, E; Cammarota, G; Minelli, M; Gasbarrini, A

    2011-01-01

    Some patients affected by nickel-contact allergy present digestive symptoms in addition to systemic cutaneous manifestations, falling under the condition known as systemic nickel allergy syndrome (SNAS). A nickel-related pro-inflammatory status has been documented at intestinal mucosal level. The aim of the present study is to evaluate the prevalence of lactose intolerance in patients affected by SNAS compared to a healthy population. Consecutive patients affected by SNAS referring to our departments were enrolled. The control population consisted of healthy subjects without gastrointestinal symptoms. All subjects enrolled underwent lactose breath test under standard conditions. One hundred and seventy-eight SNAS patients and 60 healthy controls were enrolled. Positivity of lactose breath test occurred in 74.7% of the SNAS group compared to 6.6% of the control group. Lactose intolerance is highly prevalent in our series of patients affected by SNAS. Based on our preliminary results, we can hypothesize that in SNAS patients, the nickel-induced pro-inflammatory status could temporarily impair the brush border enzymatic functions, resulting in hypolactasia. Further trials evaluating the effect of a nickel-low diet regimen on lactase activity, histological features and immunological pattern are needed.

  16. Numerous dilemmas surrounding the 1917 nickel coins

    Directory of Open Access Journals (Sweden)

    Pantelić Svetlana

    2017-01-01

    Full Text Available The Law on Extraordinary Loans Amounting to 200 Million Dinars and the Minting of Silver and Nickel Coins in 1916 was the legal basis for minting the 5-, 10-, and 20-para nickel coins of the Kingdom of Serbia featuring the year 1917 as their minting year. Some authors believe that these coins were minted in the Minting House in Paris, whereas the others agree that they were certainly minted in France, but in a still unidentified minting house. There are authors who in recent reference literature underline the possibility of their minting in the USA Gorham Company, in Providence, Rhode Island. These coins had all the characteristics of the nickel coins of the Kingdom of Serbia from 1883, 1884, 1904 and 1912. Although, according to the Law, the Minister of Finance was authorized to mint 10 million dinars of these nickel coins, only 5 million pieces in each denomination were actually minted, in the total nominal value of just 1,750,000 dinars. The general opinion is that after the war only a small amount of these nickel coins reached Serbia, because the ships transporting the Serbian coins from the minting house sank on their way. The only varying aspect in this explanation is the location from which the ships were sailing towards Corfu, i.e. from the USA or from France. These coins stopped being legal tender as of 30 November 1931.

  17. Crystal Structure of [Bis(L-AlaninatoDiaqua]Nickel(II Dihydrate

    Directory of Open Access Journals (Sweden)

    Awni Khatib

    2009-01-01

    Full Text Available The title complex, [Ni(C3H6O2N2(H2O2]⋅2H2O, has been prepared from nickel(II chloride in aqueous solution by adding L-alanine and potassium hydroxide. It has been crystallized from aqueous solution, and its structure was determined by X-ray structure analysis. The nickel(II ion adopts distorted octahedral coordination geometry with two bidentate L-alanine molecules and two water molecules. The complex is neutral and dihydrated. The crystal structure shows the hydrogen bonding between water and amide hydrogens within the lattice, and each fragment of the complex contains two water molecules as hydrated water. The L-alaninato ligand skeleton of the compound adopts the most stable trans-III configuration in the solid state. The alternating two five-membered chelate rings are in the stable gauche conformation.

  18. Bioavailability of nickel in man: effects of foods and chemically-defined dietary constituents on the absorption of inorganic nickel.

    Science.gov (United States)

    Solomons, N W; Viteri, F; Shuler, T R; Nielsen, F H

    1982-01-01

    By serial determination of the change in plasma nickel concentration following a standard dose of 22.4 mg of nickel sulfate hexahydrate containing 5 mg of elemental nickel, the bioavailability of nickel was estimated in human subjects. Plasma nickel concentration was stable in the fasting state and after an unlabeled test meal, but after the standard dose of nickel in water was elevated 48.8, 73.0, 80.0, and 53.3 microgram/1, respectively, at hours 1, 2, 3, and 4. Plasma nickel did not rise above fasting levels when 5 mg of nickel was added to two standard meals: a typical Guatemalan meal and a North American breakfast. When 5 mg of nickel was added to five beverages-whole cow milk, coffee, tea, orange juice, and Coca Cola-the rise in plasma nickel was significantly suppressed with all but Coca Cola. Response to nickel also was suppressed in the presence of 1 g of ascorbic acid. Phytic acid in a 2:1 molar ratio with nickel, however, did not affect the rise in plasma nickel. The chelate of iron and ethylenediaminetetraacetate, NaFeEDTA, an iron-fortifying agent suggested for application in Central America, slightly but not significantly depressed plasma nickel rise at 2 hours, whereas disodium EDTA depressed plasma nickel levels significantly below the fasting nickel curve at 3 and 4 hours postdose. These studies suggest that the differential responses of inorganic nickel to distinct foods, beverages, and chemically-defined dietary constituents could be important to human nutrition.

  19. Systemic contact dermatitis after oral exposure to nickel

    DEFF Research Database (Denmark)

    Jensen, Christian Stab; Menné, Torkil; Johansen, Jeanne Duus

    2006-01-01

    Systemic contact dermatitis can be elicited experimentally in nickel-sensitive individuals by oral nickel exposure. A crucial point interpreting such experiments has been the relevance of nickel exposure from drinking water and diet. The aim of this meta-analysis study on former nickel-exposure...... of the doses that, theoretically, would cause systemic contact dermatitis in exposed nickel-sensitive patients. The results from the 2 most sensitive groups show that 1% of these individuals may react with systemic contact dermatitis at normal daily nickel exposure from drinking water and diet, i.e. 0...... investigations was to provide the best possible estimation of threshold values of nickel doses that may cause systemic contact dermatitis in nickel-sensitive patients. 17 relevant investigations were identified, and statistical analyses were performed in a stepwise procedure. 9 studies were included in the final...

  20. Mechanical Properties of Electrolyte Jet Electrodeposited Nickel Foam

    Directory of Open Access Journals (Sweden)

    Jinsong Chen

    2013-07-01

    Full Text Available Principles of the preparation of nickel foam by electrolyte jet electrodeposition were introduced, Nickel foam samples with different porosity were fabricated. Effect of different porosity on microhardness and uniaxial tensile properties of nickel foam was discussed. The results show that the microhardness of nickel foam is 320~400 HV, lower than entitative metal clearly. The lower the porosity of nickel foam, the higher the microhardness is. During the process of uniaxial tensile, nickel foam is characterized by three distinct regions, e.g. elastic deforming region, plastic plateau region and densification region. The higher the porosity of nickel foam, the lower the plastic plateau and the poorer the strength of nickel foam, accordingly

  1. Occupational exposure to nickel salts in electrolytic plating.

    Science.gov (United States)

    Kiilunen, M; Aitio, A; Tossavainen, A

    1997-04-01

    An occupational hygiene survey was made in 38 nickel plating shops in Finland and exposure to nickel was studied by means of biological measurements and, in three shops, by using air measurements. The average after-shift urinary nickel concentration of 163 workers was 0.16 mumol l.-1 (range 0.001-4.99 mumol l.-1). After the 1-5 week vacation the urinary nickel concentration was higher than the upper reference limit of non-exposed Finns indicating that a part of water-soluble nickel salts is accumulated in the body. Urinary nickel concentrations in the shops considered clean in the industrial hygiene walk-through were not different from those observed in the shops considered dirty. The correlation between the concentrations of nickel in the air and in the urine was low, and the amount of nickel excreted in the urine exceeded the calculated inhaled amounts, indicating exposure by other routes such as ingestion.

  2. Preliminary evaluation of electrowinning for nickel scrap processing

    Energy Technology Data Exchange (ETDEWEB)

    Brown, G.M.; Compere, A.L.; Griffith, W.L.; Hayden, H.W.; Wilson, D.F.

    1996-12-01

    Purification of the 70,000 to 245,000 tons of diffusion plant nickel scrap permit its use in a variety of DOE and, with establishment of de minimus standards, foreign and domestic industrial applications. Nickel recycle would also substantially decrease DOE legacy wastes. This report presents data on electrolytes and separations which could be used in electrolytic purification of radiologically contaminated nickel scrap from first generation diffusion plants. Potentiometric scans and plating tests indicate that both industrial electrolytes, buffered nickel sulfate-sodium chloride and nickel chloride, provide good current densities. Electrolytes which contain ammonium thiocyanate or ammonium chloride also perform well. Nickel does not plate appreciably from nitrate solutions because the nitrate was preferentially reduced to nitrite. Solvent extractions of cobalt, a common contaminant in commercial nickel, and pertechnate, a radiological contaminant expected in DOE nickel scrap, are also successful.

  3. Nickel(II) complexes containing ONS donor ligands: Synthesis ...

    Indian Academy of Sciences (India)

    Blanchard-Desce M 2002 Org. Lett. 4 719; (b) Wegner. G and Mullen K 1998 In Electronic Materials: The. Oligomer Approach (Weinheim: Wiley- VCH). 26. Beletskaya I P, Latyshev G V, Tsvetkov A V and. Lukashev N V 2003 Tetrahedron Lett. 44 5011. 27. Muthu Tamizh M and Karvembu R 2012 Inorg Chem. Commun 25 30.

  4. Photooxidation of nickel (II) macrocyclic complexes from the charge ...

    Indian Academy of Sciences (India)

    Author Affiliations. P Natarajan1 P Paul1 2 T Dhanasekaran1 H Prakash1. Department of Inorganic Chemistry and National Centre for Ultrafast Processes, University of Madras, Chennai 600 025, India; Catalysis Division, Central Salt and Marine Chemicals Research Institute, Bhavnagar 364 002, India ...

  5. Nickel(II) complexes containing ONS donor ligands: Synthesis ...

    Indian Academy of Sciences (India)

    Phenylmagnesium chloride (10 mmol) was then added dropwise and the reaction mixture was stirred for 4 h at room temperature. Then the reaction was ended by addition of water. The mixture was extracted with ethyl acetate and the obtained organic layer was dried over MgSO4. The crude mix- ture was analyzed by gas ...

  6. Copper (II), nickel (II) and cobalt (II) complexes of n ...

    African Journals Online (AJOL)

    aminoalkylaminomethanephosphonic acids, (n-ampa). LM Durosinmi, IAO Oje, Jide Ige. Abstract. No Abstract. Nigerian Journal of Chemical Research Vol. 1 1996: 53-60. Full Text: EMAIL FREE FULL TEXT EMAIL FREE FULL TEXT · DOWNLOAD FULL TEXT ...

  7. hydrazines and their nickel(II) complexes: Syntheses, structures and ...

    Indian Academy of Sciences (India)

    G Narendra Babu

    organic synthesis, biological and medicinal chemistry, agrochemicals and materials science.5–15 Consequently, there is a continuous endeavour to design and syn- thesize ferrocene containing new molecules, which will have potential utility as functional materials or catalysts in organic synthetic reactions. Recently, we.

  8. Nickel adsorption by wild type and nickel resistant isolate of chlorella sp

    International Nuclear Information System (INIS)

    Shakya, P.R.

    2007-01-01

    Use of unicellular green microalgae has several advantages over conventional methods for removing heavy metals from contaminated sites. Here, a comparative study was made to investigate nickel detoxification mechanisms between a wild type(WT) Chlorella sp. and a nickel resistant, EMS-5 cell line isolated from the same species by EMS (Ethyl Methane Sulphonate) mutagenesis. Results showed that the growth rate of the tested algal cells was inhibited with increasing nickel concentrations in the liquid growth medium. Higher ID/sub 50/ value of EMS-5 compared to the WT revealed some degree of resistance to nickel. Removal and adsorption of Ni/sub 2+/ were found rapid during the first few hours in both the algal cultures when exposed to 50 microM Ni/sub 2+/. However, kinetic experiments showed significantly higher removal and adsorption of Ni by EMS-5 compared to the WT throughout the treatment hours. Besides, the total nickel accumulation, surface bound and intracellular nickel in EMS-5 was significantly higher to that of the WT. Hence the EMS-5 appeared more resistant to nickel. (author)

  9. Non-thiolate ligation of nickel by nucleotide-free UreG of Klebsiella aerogenes

    Energy Technology Data Exchange (ETDEWEB)

    Martin-Diaconescu, Vlad; Joseph, Crisjoe A.; Boer, Jodi L.; Mulrooney, Scott B.; Hausinger, Robert P.; Maroney, Michael J.

    2016-12-21

    Nickel-dependent ureases are activated by a multiprotein complex that includes the GTPase UreG. Prior studies showed that nucleotide-free UreG from Klebsiella aerogenes is monomeric and binds one nickel or zinc ion with near-equivalent affinity using an undefined binding site, whereas nucleotide-free UreG from Helicobacter pylori selectively binds one zinc ion per dimer via a universally conserved Cys-Pro-His motif in each protomer. Iodoacetamide-treated K. aerogenes UreG was nearly unaffected in nickel binding compared to non-treated sample, suggesting the absence of thiolate ligands to the metal. X-ray absorption spectroscopy of nickel-bound UreG showed the metal possessed four-coordinate geometry with all O/N donor ligands including one imidazole, thus confirming the absence of thiolate ligation. The nickel site in Strep-tag II-modified protein possessed six-coordinate geometry, again with all O/N donor ligands, but now including two or three imidazoles. An identical site was noted for the Strep-tag II-modified H74A variant, substituted in the Cys-Pro-His motif, ruling out coordination by this His residue. These results are consistent with metal binding to both His6 and a His residue of the fusion peptide in Strep-tagged K. aerogenes UreG. We conclude that the nickel- and zinc-binding site in nucleotide-free K. aerogenes UreG is distinct from that of nucleotide-free H. pylori UreG and does not involve the Cys-Pro-His motif. Further, we show the Strep-tag II can perturb metal coordination of this protein.

  10. Nickel and manganese transfer from soil to plant in lateritic mining soils from New Caledonia

    Science.gov (United States)

    Pouschat, P.; Rose, J.; Alliot, I.; Dominici, C.; Keller, C.; Laffont-Schwob, I.; Olivi, L.; Ambrosi, J.-P.

    2009-04-01

    New Caledonian ferritic soils (more than 50 % of iron) are naturally rich in metals (chromium, nickel, cobalt, and manganese), deficient in major nutrients (nitrogen, phosphorous, and potassium), and unbalanced for the calcium/magnesium ratio. Under these particular ecological conditions, New Caledonia, recognized as a hot-spot of biodiversity, is a natural laboratory to study and understand the adaptation strategies of plants to metalliferous soils, and particularly the tolerance and (hyper)accumulation of metals by plants. Moreover, understanding such mechanisms is essential to develop rehabilitation or phytoremediation techniques for polluted soils, as well as phytomining techniques. Thus, in order to understand the soil - plant relationship and metal mobility along a toposequence in a future nickel mining massif, field experiments were conducted in an isolated ultramafic massif of New Caledonia. Several plant species of two endemic and frequent plant genera were chosen: Tristaniopsis guillainii and T. calobuxus (Myrtaceae), and Phyllanthus serpentinus and P. favieri (Euphorbiaceae), because of their nickel and/or manganese accumulating or hyperaccumulating nature. Leaves, twigs, and roots of all plants were collected along the soil sequence and their associated rhizospheric and bulk soils were sampled. Next, a series of characterization techniques were adapted and then coupled to cryogenics. The combined use of those multiple techniques (cryo-microtomy, cryo-SEM, µXRF, cryo-XAS, and soil characterization) allowed to study co-location and speciation of nickel and manganese in the different plant organs and soils (rhizospheric and bulk). Bioaccumulated nickel and manganese had different distribution patterns. In leaves, Ni accumulated in non photosynthetic tissues (e.g. epidermis) whereas Mn preferentially accumulated in mesophyll whatever the plant species. Nevertheless, in spite of a different speciation in soils, nickel and manganese were both found as

  11. Nickel acts as an adjuvant during cobalt sensitization.

    Science.gov (United States)

    Bonefeld, Charlotte Menné; Nielsen, Morten Milek; Vennegaard, Marie T; Johansen, Jeanne Duus; Geisler, Carsten; Thyssen, Jacob P

    2015-03-01

    Metal allergy is the most frequent form of contact allergy with nickel and cobalt being the main culprits. Typically, exposure comes from metal-alloys where nickel and cobalt co-exist. Importantly, very little is known about how co-exposure to nickel and cobalt affects the immune system. We investigated these effects by using a recently developed mouse model. Mice were epicutaneously sensitized with i) nickel alone, ii) nickel in the presence of cobalt, iii) cobalt alone, or iv) cobalt in the presence of nickel, and then followed by challenge with either nickel or cobalt alone. We found that sensitization with nickel alone induced more local inflammation than cobalt alone as measured by increased ear-swelling. Furthermore, the presence of nickel during sensitization to cobalt led to a stronger challenge response to cobalt as seen by increased ear-swelling and increased B and T cell responses in the draining lymph nodes compared to mice sensitized with cobalt alone. In contrast, the presence of cobalt during nickel sensitization only induced an increased CD8(+) T cell proliferation during challenge to nickel. Thus, the presence of nickel during cobalt sensitization potentiated the challenge response against cobalt more than the presence of cobalt during sensitization to nickel affected the challenge response against nickel. Taken together, our study demonstrates that sensitization with a mixture of nickel and cobalt leads to an increased immune response to both nickel and cobalt, especially to cobalt, and furthermore that the adjuvant effect appears to correlate with the inflammatory properties of the allergen. © 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  12. Nickel allergy induced systemic reaction to an intracardiac amplatzer device.

    Science.gov (United States)

    Prestipino, Filippo; Pragliola, Claudio; Lusini, Mario; Chello, Massimo

    2014-05-01

    Nickel hypersensitivity is reported in about 10-15% of the general population and manifests mainly with dermatological signs. Chest discomfort, palpitations, signs and symptoms of pericarditis, and migraine are symptoms reported in rare cases of nickel hypersensitivity after implantation of a cardiac device made of nickel. We present the case of a patient with a nickel allergy from an Amplatzer device in which the removal of the device produced resolution of the symptoms. © 2014 Wiley Periodicals, Inc.

  13. Air Force nickel-hydrogen experiment

    Science.gov (United States)

    Harsch, B.

    1977-01-01

    An experiment to obtain some flight experience with a nickel-hydrogen battery in low earth orbit is described. The battery was built to be as compatible with the satellite bus as possible because the satellite bus is used for recharge power. The battery is mounted on an experimental pallet on the satellite. It has its own charge control system, a modification of an existing system that is used for nickel-cadmium, which primarily uses temperature compensated voltage as its criteria. Also, on the pallet is a load bank, a resistive load band, which allows switch to various load regimes. There is some other equipment on the satellite such as the nickel-hydrogen battery to power it. Monitors attached to the 21-cell battery are described.

  14. Nickel release from inexpensive jewelry and hair clasps purchased in an EU country - Are consumers sufficiently protected from nickel exposure?

    DEFF Research Database (Denmark)

    Thyssen, Jacob Pontoppidan; Menné, Torkil; Johansen, Jeanne Duus

    2009-01-01

    BACKGROUND: Nickel allergic subjects are at risk factor of acquiring hand eczema. In 1990 and 1994, respectively, Denmark and member states in the EU regulated nickel release from selected consumer products. The intention was that the nickel epidemic could be controlled and prevented if the general...... population was protected from high cutaneous nickel concentrations. Despite a decrease, the prevalence of nickel allergy remains high as nearly 10% of young women are nickel allergic. OBJECTIVE: This study aimed to perform dimethylglyoxime (DMG) testing of inexpensive jewelry and hair clasps purchased from...... random stores in Copenhagen, Denmark to detect the proportion of items that may result in nickel allergy. METHODS: Inexpensive jewelry and hair clasps were purchased from 36 stores and street vendors in Copenhagen and were later tested for nickel release using the DMG test. RESULTS: The study showed...

  15. Electrospinning of nickel oxide nanofibers: Process parameters and morphology control

    International Nuclear Information System (INIS)

    Khalil, Abdullah; Hashaikeh, Raed

    2014-01-01

    In the present work, nickel oxide nanofibers with varying morphology (diameter and roughness) were fabricated via electrospinning technique using a precursor composed of nickel acetate and polyvinyl alcohol. It was found that the diameter and surface roughness of individual nickel oxide nanofibers are strongly dependent upon nickel acetate concentration in the precursor. With increasing nickel acetate concentration, the diameter of nanofibers increased and the roughness decreased. An optimum concentration of nickel acetate in the precursor resulted in the formation of smooth and continuous nickel oxide nanofibers whose diameter can be further controlled via electrospinning voltage. Beyond an optimum concentration of nickel acetate, the resulting nanofibers were found to be ‘flattened’ and ‘wavy’ with occasional cracking across their length. Transmission electron microscopy analysis revealed that the obtained nanofibers are polycrystalline in nature. These nickel oxide nanofibers with varying morphology have potential applications in various engineering domains. - Highlights: • Nickel oxide nanofibers were synthesized via electrospinning. • Fiber diameter and roughness depend on nickel acetate concentration used. • With increasing nickel acetate concentration the roughness of nanofibers decreased. • XRD and TEM revealed a polycrystalline structure of the nanofibers

  16. Chemistry of nickel and copper production from sulphide ores | Love ...

    African Journals Online (AJOL)

    Nickel is one of Zimbabwe's principle metallurgical exports. It is processed to a very high level of purity and hence has a high value. The economics of nickel production can be difficult, as the selling value of nickel varies tremendously with time, from a low of US$ 3 900 per ton in late 1998 to US$ 10 100 per ton in May 2000, ...

  17. Reduced frequency of nickel allergy upon oral nickel contact at an early age

    DEFF Research Database (Denmark)

    Van Hoogstraten, I M; Andersen, Klaus Ejner; Von Blomberg, B M

    1991-01-01

    the feasibility of oral prevention of undesired T cell-mediated immunity in man. Potentially tolerizing (oral nickel contacts via orthodontic braces) as well as sensitizing (ear piercing) events were studied retrospectively in 2176 patients attending nine European patch test clinics. Patients were interviewed...... by means of a confidential questionnaire. The results show that ear piercing strongly favoured development of nickel ACH. More importantly, patients having had oral contacts with nickel-releasing appliances (dental braces) at an early age, but only if prior to ear piercing, showed a reduced frequency...

  18. Risk assessment for nickel contact allergy.

    Science.gov (United States)

    Boonchai, Waranya; Chaiwanon, Onjuta; Kasemsarn, Pranee

    2014-12-01

    Nickel is one of the most common allergens causing allergic contact dermatitis worldwide. The aim of the study was to evaluate the contributing factors to nickel contact allergy (NiCA) in Asians who have a unique culture and lifestyle. We randomly selected 324 previously patch-tested patients, 162 nickel patch test (PT)-positive patients and 162 nickel PT-negative patients. The patients were telephone interviewed for their lifestyle information. Most of the nickel PT-positive patients (93.2%) were female with a mean age of 38.9 ± 13.3 years compared with the other group of nickel PT-negative patients who had a smaller proportion of females (76.5%) with an older mean age of 44.1 ± 14.9 years (P = 0.001). Multivariate analysis was able to establish that the significant risk factors for NiCA were female sex (odds ratio [OR], 6.38; 95% confidence interval [CI], 2.15-18.94), young age (OR, 0.98; 95% CI, 0.96-1.00), occupation with long periods of exposure to metal (OR, 3.08; 95% CI, 1.18-8.02), seafood (OR, 1.96; 95% CI, 1.17-3.27) and canned food consumption (OR, 3.12; 95% CI, 1.17-8.33) (P < 0.05). The adjusted factors found to associate with NiCA were female sex, young age, occupation with long periods of exposure to metal, seafood and canned food consumption. © 2014 Japanese Dermatological Association.

  19. Prototype nickel component demonstration. Final report

    International Nuclear Information System (INIS)

    Boss, D.E.

    1994-01-01

    We have been developing a process to produce high-purity nickel structures from nickel carbonyl using chemical vapor deposition (CVD). The prototype demonstration effort had been separated into a number of independent tasks to allow Los Alamos National Laboratory (LANL) the greatest flexibility in tailoring the project to their needs. LANL selected three of the proposed tasks to be performed--Task 1- system modification and demonstration, Task 2-stainless steel mandrel trials, and Task 4-manufacturing study. Task 1 focused on converting the CVD system from a hot-wall to a cold-wall configuration and demonstrating the improved efficiency of the reactor type by depositing a 0.01-inch-thick nickel coating on a cylindrical substrate. Since stainless steel substrates were preferred because of their low α-emitter levels, Task 2 evaluated mandrel configurations which would allow removal of the nickel tube from the substrate. The manufacturing study was performed to develop strategies and system designs for manufacturing large quantities of the components needed for the Sudbury Nuetrino Observatory (SNO) program. Each of these tasks was successfully completed. During these efforts, BIRL successfully produced short lengths of 2-inch-diameter tubing and 6-inch-wide foil with levels of α-radiation emitting contaminants lower than either conventional nickel alloys or electroplated materials. We have produced both the tubing and foil using hot-substrate, cold-wall reactors and clearly demonstrated the advantages of higher precursor efficiency and deposition rate associated with this configuration. We also demonstrated a novel mandrel design which allowed easy removal of the nickel tubing and should dramatically simplify the production of 1.5-meter-long tubes in the production phase of the program

  20. Adsorption properties of Silochrom chemically modified with nickel acetylacetonate

    Science.gov (United States)

    Pakhnutova, Evgeniya; Slizhov, Yuriy

    2017-11-01

    One of the areas of development of gas chromatography is the creation of new chromatographic materials that have improved sorption and analytical characteristics. In this work, for the first time, a new sorbent based on Silochrom C-120 modified with nickel acetylacetonate was studied using a complex of physico-chemical methods. It has been established that due to chemical modification of silica gel surface with nickel acetylacetonate the surface area of the specific surface decreases from 112 to 98 m2/g and surface acidity diminishes by 1.2 pH units. Using the thermogravimetric analysis it has been revealed that the obtained sorbent can be used in gas chromatography up to 290°C. Gas chromatography method was used to investigate the adsorption properties of the modified materials. According to the retention data of adsorbates: n-alkanes (C6-C9), benzene, ethanol, nitropropane and butanone-2 the differential molar adsorption energy q¯dif, 1, Henry adsorption constants K1,C, the differential molar entropy ΔS¯S1 and Δ q¯dif, 1 (special) of adsorbates in dispersion and specific interactions were calculated. The influence of the modifying additive on the changings in the thermodynamic retention characteristics of all sorbates because of the manifestation of specific sorbate-sorbent interactions has been shown. The highest values of the thermodynamic parameters were indicative for sorbates forming hydrogen bonds and capable of donor-acceptor interaction.

  1. PROTECTIVE LAYERS OF IRON AND NICKEL ALUMINIDES ON STEEL

    Directory of Open Access Journals (Sweden)

    Milena Voděrová

    2013-07-01

    Full Text Available Intermediary phases Ni-Al and Fe-Al are promising materials due to their superior properties such as hardness and good resistance against oxidation at high temperatures. Moreover, Fe-Al phases are resistant in sulphur - containing atmospheres. Because of these characteristics, the above mentioned intermetallic phases seem to be prospective for the use in many technical applications such as energetics, chemical or automotive industry in a form of a bulk material or coatings. Presently, the protective aluminide layer is usually prepared by thermal spraying. Nevertheless, this method is not suitable for complex-shaped components. Therefore, the aim of this work was to find an alternative way to prepare layers consisting of nickel or iron aluminides by other technique than thermal spraying. At first, carbon steel samples were coated using galvanic or electroless nickel plating. Coated samples were subsequently submerged into molten aluminium at various temperatures and process durations. The influence of the temperature and duration on the intermetallic phase growth was studied by scanning electron and light microscopy. Thickness and microhardness of the intermetallic layer was also measured.

  2. PROTECTIVE LAYERS OF IRON AND NICKEL ALUMINIDES ON STEEL

    Directory of Open Access Journals (Sweden)

    Milena Voderova

    2013-05-01

    Full Text Available Intermediary phases Ni-Al and Fe-Al are promising materials due to their superior properties such as hardness and good resistance against oxidation at high temperatures. Moreover, Fe-Al phases are resistant in sulphur - containing atmospheres. Because of these characteristics, the above mentioned intermetallic phases seem to be prospective for the use in many technical applications such as energetics, chemical or automotive industry in a form of a bulk material or coatings. Presently, the protective aluminide layer is usually prepared by thermal spraying. Nevertheless, this method is not suitable for complex-shaped components. Therefore, the aim of this work was to find an alternative way to prepare layers consisting of nickel or iron aluminides by other technique than thermal spraying. At first, carbon steel samples were coated using galvanic or electroless nickel plating. Coated samples were subsequently submerged into molten aluminium at various temperatures and process durations. The influence of the temperature and duration on the intermetallic phase growth was studied by scanning electron and light microscopy. Thickness and microhardness of the intermetallic layer was also measured.

  3. Metallic nickel nano- and fine particles induce JB6 cell apoptosis through a caspase-8/AIF mediated cytochrome c-independent pathway

    Directory of Open Access Journals (Sweden)

    Castranova Vincent

    2009-04-01

    Full Text Available Abstract Background Carcinogenicity of nickel compounds has been well documented. However, the carcinogenic effect of metallic nickel is still unclear. The present study investigates metallic nickel nano- and fine particle-induced apoptosis and the signal pathways involved in this process in JB6 cells. The data obtained from this study will be of benefit for elucidating the pathological and carcinogenic potential of metallic nickel particles. Results Using 3-(4,5-dimethylthiazol-2-yl-2,5-diphenyltetrazolium bromide (MTT assay, we found that metallic nickel nanoparticles exhibited higher cytotoxicity than fine particles. Both metallic nickel nano- and fine particles induced JB6 cell apoptosis. Metallic nickel nanoparticles produced higher apoptotic induction than fine particles. Western-blot analysis showed an activation of proapoptotic factors including Fas (CD95, Fas-associated protein with death domain (FADD, caspase-8, death receptor 3 (DR3 and BID in apoptotic cells induced by metallic nickel particles. Immunoprecipitation (IP western blot analysis demonstrated the formation of the Fas-related death-inducing signaling complex (DISC in the apoptotic process. Furthermore, lamin A and beta-actin were cleaved. Moreover, we found that apoptosis-inducing factor (AIF was up-regulated and released from mitochondria to cytoplasm. Interestingly, although an up-regulation of cytochrome c was detected in the mitochondria of metallic nickel particle-treated cells, no cytochrome c release from mitochondria to cytoplasm was found. In addition, activation of antiapoptotic factors including phospho-Akt (protein kinase B and Bcl-2 was detected. Further studies demonstrated that metallic nickel particles caused no significant changes in the mitochondrial membrane permeability after 24 h treatment. Conclusion In this study, metallic nickel nanoparticles caused higher cytotoxicity and apoptotic induction than fine particles in JB6 cells. Apoptotic cell death

  4. Important Parameters and Applications for Nickel Electroforming

    DEFF Research Database (Denmark)

    Tang, Peter Torben; Benzon, Michael Eis; Rasmussen, J.P.

    1996-01-01

    Electroforming is versatile process that is being used more and more, although the basic idea is almost a hundred years old. This paper will concentrate on the important mechanical properties and electrolyte parameters of nickel electroforming. Electrolyte parameters such as current density, p......H-value, temperature and the use of pulse plating and additives will be examined with respect to mechanical properties such as internal stress, material distribution and hardness. Pulse plating in a chloride and Watts nickel bath and DC plating in sulphamate bath will be discussed, as well as different methods...... for measuring internal stress and material distribution....

  5. Nitrogen solubility in nickel base multicomponent melts

    International Nuclear Information System (INIS)

    Bol'shov, L.A.; Stomakhin, A.Ya.; Sokolov, V.M.; Teterin, V.G.

    1984-01-01

    Applicability of various methods for calculation of nitrogen solubility in high-alloyed nickel base alloys, containing Cr, Fe, W, Mo, Ti, Nb, has been estimated. A possibility is shown to use the formUla, derived for the calculation of nitrogen solubility in iron on the basis of statistical theory for a grid model of solution which does not require limitations for the content of a solvent component. The calculation method has been used for nickel alloys, with the concentration of solvent, iron, being accepted equal to zero, and employing parameters of nitrogen interaction as determined for iron-base alloys

  6. Site-isolation effects in a dendritic nickel catalyst for the oligomerization of ethylene.

    Science.gov (United States)

    Müller, Christian; Ackerman, Lily J; Reek, Joost N H; Kamer, Paul C J; van Leeuwen, Piet W N M

    2004-11-17

    Dendrimers, specifically suited to construct site-isolated groups due to their well-defined hyperbranched structure, have been used as a ligand design element for the construction of nickel catalysts for ethylene oligomerization. The dendritic P,O ligand indeed suppresses the formation of inactive bis(P,O)Ni complexes in toluene, as is evident from NMR studies, and, as a consequence, outperforms the parent ligand in catalysis in this solvent. The dendritic effect observed in methanol is more subtle because both the dendritic ligand 1 and the parent 2 form bis(P,O)nickel complexes in solution according to NMR spectroscopy. Unlike the parent complex 8, the dendritic bis(P,O)Ni complex 7 derived from dendrimer ligand 1 is able to dissociate to a mono-ligated species under catalytic conditions, that is, 40 bar ethylene and 80 degrees C, which can enter the catalytic cycle. Indeed, dendritic ligand 1 gives much more active nickel catalysts for the oligomerization in methanol than does 2.

  7. Nickel allergy and relationship with Staphylococcus aureus in atopic dermatitis.

    Science.gov (United States)

    Bogdali, Anna M; Anna, Bogdali M; Grazyna, Antoszczyk; Wojciech, Dyga; Aleksander, Obtulowicz; Anna, Bialecka; Andrzej, Kasprowicz; Zofia, Magnowska; Krystyna, Obtulowicz

    2016-01-01

    The increase of nickel air pollution is supposed to frequent side effects of nickel action related to virulence potential of Staphylococcus aureus in patients with nickel allergy in atopic dermatitis. The goal was to investigate the relationship between nickel allergy and infection by S. aureus in atopic dermatitis. Nickel allergy was confirmed in atopic patients and excluded in healthy volunteers using patch testing. Infection by S. aureus was tested in atopic patients and healthy volunteers by use of API Staph system. The specific IgE for staphylococcal enterotoxin A and B were measured. Secretion of IFN-g, IL-2, IL-13 by PBMC under nickel sulfate and the enterotoxins A and B stimulations were studied with ELISpot. We found the increased number of infections by S. aureus in atopic patients with nickel allergy in comparison to atopic patients and healthy volunteers without nickel allergy. The elevated secretion of IL-2 under nickel sulfate stimulation in vitro was exclusively found in atopic patients with nickel allergy infected by S. aureus. Our data suggest that nickel allergy and infection by S. aureus are linked in atopic dermatitis. Copyright © 2015 Elsevier GmbH. All rights reserved.

  8. Microwave dielectric properties of nanostructured nickel ferrite

    Indian Academy of Sciences (India)

    Wintec

    Ferrites are also used in camouflaging military aircrafts and missiles against radar detection (Meshram et al 2002). Among the spinel type ferrites, nickel ... agglomeration of the particles. The precipitate formed was separated and washed several times in distilled water to free it from ions and other impurities. Finally it was.

  9. Exposure to nickel by hair mineral analysis.

    Science.gov (United States)

    Michalak, Izabela; Mikulewicz, Marcin; Chojnacka, Katarzyna; Wołowiec, Paulina; Saeid, Agnieszka; Górecki, Henryk

    2012-11-01

    The aim of the present work was to investigate the exposure to nickel from various sources by investigation of mineral composition of human scalp hair. The research was carried out on hair sampled from subjects, including 87 males and 178 females (22 ± 2 years). The samples of hair were analyzed by ICP-OES. The effect of several factors on nickel content in hair was examined: lifestyle habits (e.g. hair coloring, hair spray, hair straighteners, hair drier, drugs); dietary factors (e.g. yoghurts, blue cheese, lettuce, lemon, mushroom, egg, butter); other (e.g. solarium, cigarette smoking, tap water pipes, tinned food, PVC foil, photocopier, amalgam filling). These outcomes were reached by linking the results of nickel level in hair with the results of questionnaire survey. Basing on the results it can be concluded that exposure to nickel ions can occur from different sources: lifestyle, eating habits and environmental exposure. Copyright © 2012 Elsevier B.V. All rights reserved.

  10. Nickel hydroxide modified electrodes for urea determination

    Directory of Open Access Journals (Sweden)

    Luiz Henrique Dall´Antonia

    2007-03-01

    Full Text Available Nickel hydroxide films were prepared by electrodeposition from a solution Ni(NO32 0,05 mol L ?¹ on ITO electrodes (Tin oxide doped with Indium on PET-like plastic film, applying a current of - 0,1 A cm ?² during different time intervals between 1800 and 7200 s. The electrochemical behavior of the nickel hydroxide electrode was investigated through a cyclic voltammogram, in NaOH 1,0 mol L ?¹, where it was observed two peaks in the profile in 0,410 and 0,280 V, corresponding to redox couple Ni(II/Ni(III. A sensor for urea presenting a satisfactory answer can be obtained when, after the deposit of the film of Ni(OH2 on the electrode of nickel, it is immersed in a solution of NaOH 1,0 mol L ?¹ and applying a potential of + 0,435 V, where the maximum of the anodic current occurs in the cyclic voltammogram. Analyzing the results it can be observed that, for a range of analite concentration between 5 to 50 m mol L ?¹, the behavior is linear and the sensibility found was of 20,3 mA cm?² (mol L?¹?¹, presenting reproducibility confirming the nickel hydroxide electrodes utilization for the determination of urea.

  11. Hydrogen embrittlement in nickel-hydrogen cells

    Science.gov (United States)

    Gross, Sidney

    1989-01-01

    It was long known that many strong metals can become weakened and brittle as the result of the accumulation of hydrogen within the metal. When the metal is stretched, it does not show normal ductile properties, but fractures prematurely. This problem can occur as the result of a hydrogen evolution reaction such as corrosion or electroplating, or due to hydrogen in the environment at the metal surface. High strength alloys such as steels are especially susceptible to hydrogen embrittlement. Nickel-hydrogen cells commonly use Inconel 718 alloy for the pressure container, and this also is susceptible to hydrogen embrittlement. Metals differ in their susceptibility to embrittlement. Hydrogen embrittlement in nickel-hydrogen cells is analyzed and the reasons why it may or may not occur are discussed. Although Inconel 718 can display hydrogen embrittlement, experience has not identified any problem with nickel-hydrogen cells. No hydrogen embrittlement problem is expected with the 718 alloy pressure container used in nickel-hydrogen cells.

  12. Large Scale Evaluation fo Nickel Aluminide Rolls

    Energy Technology Data Exchange (ETDEWEB)

    None

    2005-09-01

    This completed project was a joint effort between Oak Ridge National Laboratory and Bethlehem Steel (now Mittal Steel) to demonstrate the effectiveness of using nickel aluminide intermetallic alloy rolls as part of an updated, energy-efficient, commercial annealing furnace system.

  13. SBA-15-Supported Nickel Phosphide Hydrotreating Catalysts.

    Czech Academy of Sciences Publication Activity Database

    Korányi, T.I.; Vít, Zdeněk; Poduval, D.G.; Ryoo, R.; Kim, H.S.; Hensen, E.J. M.

    2008-01-01

    Roč. 253, 1 (2008) , s. 119-131 ISSN 0021-9517 R&D Projects: GA ČR(CZ) GA104/06/0870 Institutional research plan: CEZ:AV0Z40720504 Keywords : nickel phosphide * sba-15 * hydrodesulfurization Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.167, year: 2008

  14. Nickel removal from nickel plating waste water using a biologically active moving-bed sand filter.

    Science.gov (United States)

    Pümpel, Thomas; Macaskie, Lynne E; Finlay, John A; Diels, Ludo; Tsezos, Marios

    2003-12-01

    Efficient removal of dissolved nickel was observed in a biologically active moving-bed 'MERESAFIN' sand filter treating rinsing water from an electroless nickel plating plant. Although nickel is fully soluble in this waste water, its passage through the sand filter promoted rapid removal of approximately 1 mg Ni/l. The speciation of Ni in the waste water was modelled; the most probable precipitates forming under the conditions in the filter were predicted using PHREEQC. Analyses of the Ni-containing biosludge using chemical, electron microscopical and X-ray spectroscopic techniques confirmed crystallisation of nickel phosphate as arupite (Ni3(PO4)2 x 8H2O), together with hydroxyapatite within the bacterial biofilm on the filter sand grains. Biosorption contributed less than 1% of the overall sequestered nickel. Metabolising bacteria are essential for the process; the definitive role of specific components of the mixed population is undefined but the increase in pH promoted by metabolic activity of some microbial components is likely to promote nickel desolubilisation by others.

  15. Nickel allergy and relationship with Staphylococcus aureus in atopic dermatitis

    DEFF Research Database (Denmark)

    Anna, Bogdali M.; Grazyna, Antoszczyk; Wojciech, Dyga

    2016-01-01

    Background: The increase of nickel air pollution is supposed to frequent side effects of nickel action related to virulence potential of Staphylococcus aureus in patients with nickel allergy in atopic dermatitis. The goal was to investigate the relationship between nickel allergy and infection by S....... aureus in atopic dermatitis. Methods: Nickel allergy was confirmed in atopic patients and excluded in healthy volunteers using patch testing. Infection by S. aureus was tested in atopic patients and healthy volunteers by use of API Staph system. The specific IgE for staphylococcal enterotoxin A and B...... were measured. Secretion of IFN-g, IL-2, IL-13 by PBMC under nickel sulfate and the enterotoxins A and B stimulations were studied with ELISpot. Results: We found the increased number of infections by S. aureus in atopic patients with nickel allergy in comparison to atopic patients and healthy...

  16. Nickel allergy from adolescence to adulthood in the TOACS cohort.

    Science.gov (United States)

    Mortz, Charlotte G; Bindslev-Jensen, Carsten; Andersen, Klaus E

    2013-06-01

    In 1995, we established a cohort of 1501 unselected eighth-grade schoolchildren to investigate the course of nickel allergy into adult life. To follow the course of nickel allergy and clinically relevant nickel dermatitis over 15 years from adolescence to adulthood, and the effect of ear piercing, atopic dermatitis and degree of nickel patch test reactivity. One thousand two hundred and six young adults from the cohort were asked to complete a questionnaire and participate in a clinical examination including patch testing with TRUE Test® including a nickel dilution series. The questionnaire was answered by 899 (74.6%), and 442 (36.7%) had patch tests performed. The point prevalence of nickel allergy was 11.8% (clinical relevance 80.8%). The 15-year incidence rate was 6.7%. Most new sensitizations were clinically relevant with strong reactions, and many participants reacted to low concentrations. Only a few positive reactions were lost. Nickel allergy was more common among women with childhood atopic dermatitis, whereas no association with ear piercing was found. However, there was a significantly higher prevalence of nickel allergy among women ear pierced before implementation of the nickel regulation in Denmark. This follow-up study in young adults 15 years after leaving primary school showed a high prevalence and a high incidence rate of nickel allergy, despite the nickel regulation. Most reactions from childhood could be reproduced and were clinically relevant. In women, childhood atopic dermatitis was associated with nickel allergy in adulthood, whereas only ear piercing before the Danish nickel regulation was associated with adult nickel allergy. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  17. Selected-area growth of nickel micropillars on aluminum thin films by electroless plating for applications in microbolometers

    Directory of Open Access Journals (Sweden)

    Do Ngoc Hieu

    2017-06-01

    Full Text Available An optimization process of electroless plating of nickel was carried out with NiCl2 as the nickel ion source, NaH2PO2 as the reduction agent, CH3COONa and Na3C6H5O7 as complexing agents. Electroless plated nickel layers on sputtered aluminum corning glass substrates with a resistivity of about 75.9 μΩ cm and a nickel concentration higher than 93% were obtained. This optimum process was successfully applied in growing nickel micropillars at selected areas with a well-controlled height. The microstructure of the masking layers was fabricated by means of optical photolithography for subsequent growth of nickel micropillars on selected areas. Micropillars size was defined by the opening size and the height was controlled by adjusting the plating time at a growth rate of 0.41 μm/min. This result shows that electroless nickel plating could be a good candidate for growing micropillars for applications in microbolometers.

  18. Aqueous Corrosion Characteristics of Nickel Aluminides

    International Nuclear Information System (INIS)

    Kim, Jung Gu

    1996-01-01

    The aqueous corrosion characteristics of three nickel aluminides were studied by using (a) immersion corrosion test and (b) cyclic anodic polarization measurements. The immersion tests were conducted in 15 different solutions at 25 .deg. C and 95 .deg. C. The nickel aluminides were found to have good corrosion resistance in inorganic acids, organic acids and basic solutions 25 .deg. C except at a higher concentration of hydrochloric acid in ferric chloride solution at the temperature. All three nickel aluminides were suitably resistant to corrosion in the organic acids (oxalic acid, acetic acid), sodium chloride solution, and bases (sodium hydoxide, ammonium hydroxide) at 95 .deg. C. The cyclic anodic polarization curves were developed in N 2 -deaerated solution at 25 .deg. C and 95 .deg. C. In addition, open-circuit corrosion potentials were determined for the solutions in the aerated condition at 25 .deg. C to compare with the anodic curves. At 25 .deg. C, although all materials exhibited active-passive behavior in all solutions except the hydrofluoric acid, at E corr (aerated), passive corrosion was only indicated for the acetic acid, sodium hydroxide, and sodium chloride solutions. Nevertheless, in all cases, the predicted dissolution rates were consistent with immersion test results. Hysteresis loops indicating susceptibility to localized corrosion were observed in 0.6M sodium chloride(pH=7) solution. At 95 .deg. C, active-passive behavior was demonstrated in the acetic acid, sodium chloride, and to a limited extent in the nitric acid: but only active behavior was shown in the sulfuric and hydrofluoric acids. From the above results, it was noted that anodic dissolution of nickel aluminides significantly increased with increasing temperature and that the Cr-containing compositions had better corrosion resistance in several solutions than the Cr-free composition. Prior manufacturing procedures, i.e., casting and powder metallurgy processes did not appear to

  19. Two-dimensional spatially ordered system of nickel nanowires probed by polarized SANS

    International Nuclear Information System (INIS)

    Napolskii, K.S.; Chumakov, A.P.; Grigoriev, S.V.; Grigoryeva, N.A.; Eckerlebe, H.; Eliseev, A.A.; Lukashin, A.V.; Tretyakov, Yu.D.

    2009-01-01

    Structural and magnetic properties of two-dimensional spatially ordered system of ferromagnetic nickel nanowires embedded into Al 2 O 3 matrix have been studied using polarized small-angle neutron scattering. The small-angle diffraction pattern exhibits many diffraction peaks, which corresponds to the scattering from highly correlated hexagonal structure of pores and magnetic nanowires. Magnetic contribution to the scattering has complex behavior and cannot be explained without taking into account stray fields located between magnetized nanowires.

  20. Reduction of CO2 by nickel (II) macrocycle catalyst at HMDE

    Indian Academy of Sciences (India)

    Unknown

    desired product formation and reduction in electricity consumption. The nickel (II) complex of 1,3,6,9,11,14-hexaazatricyclo [12⋅2⋅1⋅1]octadecane is a suitable choice due to its geometry, i.e. because square planar structure provides the axial site free for the approach and interaction of CO2 with the metal centre and also ...