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Sample records for copper ii sulfate

  1. Decomposition of Copper (II) Sulfate Pentahydrate: A Sequential Gravimetric Analysis.

    ERIC Educational Resources Information Center

    Harris, Arlo D.; Kalbus, Lee H.

    1979-01-01

    Describes an improved experiment of the thermal dehydration of copper (II) sulfate pentahydrate. The improvements described here are control of the temperature environment and a quantitative study of the decomposition reaction to a thermally stable oxide. Data will suffice to show sequential gravimetric analysis. (Author/SA)

  2. Twinned low-temperature structures of tris(ethylenediamine)zinc(II) sulfate and tris(ethylenediamine)copper(II) sulfate.

    PubMed

    Lutz, Martin

    2010-11-01

    Tris(ethylenediamine)zinc(II) sulfate, [Zn(C(2)H(8)N(2))(3)]SO(4), (I), undergoes a reversible solid-solid phase transition during cooling, accompanied by a lowering of the symmetry from high-trigonal P31c to low-trigonal P3 and by merohedral twinning. The molecular symmetries of the cation and anion change from 32 (D(3)) to 3 (C(3)). This lower symmetry allows an ordered sulfate anion and generates in the complex cation two independent N atoms with significantly different geometries. The twinning is the same as in the corresponding Ni complex [Jameson et al. (1982). Acta Cryst. B38, 3016-3020]. The low-temperature phase of tris(ethylenediamine)copper(II) sulfate, [Cu(C(2)H(8)N(2))(3)]SO(4), (II), has only triclinic symmetry and the unit-cell volume is doubled with respect to the room-temperature structure in P31c. (II) was refined as a nonmerohedral twin with five twin domains. The asymmetric unit contains two independent formula units, and all cations and anions are located on general positions with 1 (C(1)) symmetry. Both molecules of the Cu complex are in elongated octahedral geometries because of the Jahn-Teller effect. This is in contrast to an earlier publication, which describes the complex as a compressed octahedron [Bertini et al. (1979). J. Chem. Soc. Dalton Trans. pp. 1409-1414].

  3. Spectroscopic study of copper(II) complexes with carboxymethyl dextran and dextran sulfate

    NASA Astrophysics Data System (ADS)

    Glišić, S.; Nikolić, G.; Cakić, M.; Trutić, N.

    2015-07-01

    The copper(II) ion complexes with carboxymethyl dextran (CMD) and dextran sulfate (DS) were studied by different methods. Content of copper was determined by atomic absorption spectroscopy. It was found that copper : ligand mole ratio (Cu : CMD) is 1 : 2, and Cu : DS is 1 : 1 by mole ratio method. Spectrophotometric parameters of synthesized compounds are characteristic for Cu(II) ion in octahedral ( O h ) coordination. Analyzing of FTIR spectra in ν(C=O) vibration region has showed that -COOH group acts as bidentate ligand, while the compounds of Cu(II) with DS copper ions are in the region of four oxygen atoms of two adjacent sulfo groups. The presence of crystalline water was determined by isotopic substitution of H2O molecules with D2O molecules. Comparison of spectra recorded at room (RT) and liquid nitrogen temperature (LNT) has enabled detection bands of water molecules libration indicating that they are coordinated complementing coordination sphere of Cu(II) ions to six. The complexes are of Cu(II) · (CMD)2 · (H2O)2 or Cu(II) · DS · (H2O)2 type. The similarities of the γ(C-H) range in a part of FTIR spectra indicate that there is no difference in the conformation of the 4 C 1 glucopyranose (Glc) unit CMD and DS synthesized Cu(II) complexes.

  4. Sulfate-bridged dimeric trinuclear copper(II)-pyrazolate complex with three different terminal ligands.

    PubMed

    Mezei, Gellert

    2016-08-01

    The reaction of CuSO4·5H2O, 4-chloro-pyrazole (4-Cl-pzH) and tri-ethyl-amine (Et3N) in di-methyl-formamide (DMF) produced crystals of di-aqua-hexa-kis-(μ-4-chloro-pyrazolato-κ(2) N:N')bis-(N,N-di-methyl-formamide)di-μ3-hydroxido-bis-(μ4-sulfato-κ(4) O:O':O'':O'')hexa-copper(II) N,N-di-methyl-formamide tetra-solvate dihydrate, [Cu3(OH)(SO4)(C3H2ClN2)3(C3H7NO)(H2O)]2·4C3H7NO·2H2O. The centrosymmetric dimeric molecule consists of two trinuclear copper-pyrazolate units bridged by two sulfate ions. The title compound provides the first example of a trinuclear copper-pyrazolate complex with three different terminal ligands on the Cu atoms, and also the first example of such complex with a strongly binding basal sulfate ion. Within each trinuclear unit, the Cu(II) atoms are bridged by μ-pyrazolate groups and a central μ3-OH group, and are coordinated by terminal sulfate, H2O and DMF ligands, respectively. Moreover, the sulfate O atoms coordinate at the apical position to the Cu atoms of the symmetry-related unit, providing square-pyramidal coordination geometry around each copper cation. The metal complex and solvent mol-ecules are involved in O-H⋯O hydrogen bonds, leading to a two-dimensional network parallel to (10-1).

  5. Sulfate-bridged dimeric trinuclear copper(II)–pyrazolate complex with three different terminal ligands

    PubMed Central

    Mezei, Gellert

    2016-01-01

    The reaction of CuSO4·5H2O, 4-chloro­pyrazole (4-Cl-pzH) and tri­ethyl­amine (Et3N) in di­methyl­formamide (DMF) produced crystals of di­aqua­hexa­kis­(μ-4-chloro­pyrazolato-κ2 N:N′)bis­(N,N-di­methyl­formamide)di-μ3-hydroxido-bis­(μ4-sulfato-κ4 O:O′:O′′:O′′)hexa­copper(II) N,N-di­methyl­formamide tetra­solvate dihydrate, [Cu3(OH)(SO4)(C3H2ClN2)3(C3H7NO)(H2O)]2·4C3H7NO·2H2O. The centrosymmetric dimeric molecule consists of two trinuclear copper–pyrazolate units bridged by two sulfate ions. The title compound provides the first example of a trinuclear copper–pyrazolate complex with three different terminal ligands on the Cu atoms, and also the first example of such complex with a strongly binding basal sulfate ion. Within each trinuclear unit, the CuII atoms are bridged by μ-pyrazolate groups and a central μ3-OH group, and are coordinated by terminal sulfate, H2O and DMF ligands, respectively. Moreover, the sulfate O atoms coordinate at the apical position to the Cu atoms of the symmetry-related unit, providing square–pyramidal coordination geometry around each copper cation. The metal complex and solvent mol­ecules are involved in O—H⋯O hydrogen bonds, leading to a two-dimensional network parallel to (10-1). PMID:27536383

  6. In vitro Solubility of Copper(II) Sulfate and Dicopper Chloride Trihydroxide for Pigs

    PubMed Central

    Park, C. S.; Kim, B. G.

    2016-01-01

    This study was conducted to determine the solubility of copper (Cu) in two sources of copper(II) sulfate (CuSO4) including monohydrate and pentahydrate and three sources of dicopper chloride trihydroxide (dCCTH) including α-form (dCCTH-α), β-form (dCCTH-β), and a mixture of α- and β-form (dCCTH-αβ) at different pH and a 3-step in vitro digestion assay for pigs. In Exp. 1, Cu sources were incubated in water-based buffers at pH 2.0, 3.0, 4.8, and 6.8 for 4 h using a shaking incubator at 39°C. The CuSO4 sources were completely dissolved within 15 min except at pH 6.8. The solubility of Cu in dCCTH-α was greater (p<0.05) than dCCTH-β but was not different from dCCTH-αβ during 3-h incubation at pH 2.0 and during 2-h incubation at pH 3.0. At pH 4.8, there were no significant differences in solubility of Cu in dCCTH sources. Copper in dCCTH sources were non-soluble at pH 6.8. In Exp. 2, the solubility of Cu was determined during the 3-step in vitro digestion assay for pigs. All sources of Cu were completely dissolved in step 1 which simulated digestion in the stomach. In Exp. 3, the solubility of Cu in experimental diets including a control diet and diets containing 250 mg/kg of additional Cu from five Cu sources was determined during the in vitro digestion assay. The solubility of Cu in diets containing additional Cu sources were greater (p<0.05) than the control diet in step 1. In conclusion, the solubility of Cu was influenced by pH of digesta but was not different among sources based on the in vitro digestion assay. PMID:27456425

  7. Temperature-dependent analysis of thermal motion, disorder and structures of tris(ethylenediamine)zinc(II) sulfate and tris(ethylenediamine)copper(II) sulfate.

    PubMed

    Smeets, Stef; Parois, Pascal; Bürgi, Hans-Beat; Lutz, Martin

    2011-02-01

    The crystal structures of the title compounds have been determined in the temperature range 140-290 K for the zinc complex, and 190-270 K for the copper complex. The two structures are isostructural in the trigonal space group P31c with the sulfate anion severely disordered on a site with 32 (D(3)) symmetry. This sulfate disorder leads to a disordered three-dimensional hydrogen-bond network, with the N-H atoms acting as donors and the sulfate O atoms as acceptors. The displacement parameters of the N and C atoms in both compounds contain disorder contributions in the out-of-ligand plane direction owing to ring puckering and/or disorder in hydrogen bonding. In the Zn compound the vibrational amplitudes in the bond directions are closely similar. Their differences show no significant deviations from rigid-bond behaviour. In the Cu compound, a (presumably) dynamic Jahn-Teller effect is identified from a temperature-independent contribution to the displacement ellipsoids of the N atom along the N-Cu bond. These conclusions derive from analyses of the atomic displacement parameters with the Hirshfeld test, with rigid-body models at different temperatures, and with a normal coordinate analysis. This analysis considers the atomic displacement parameters (ADPs) from all different temperatures simultaneously and provides a detailed description of both the thermal motion and the disorder in the cation. The Jahn-Teller radii of the Cu compound derived on the basis of the ADP analysis and from the bond distances in the statically distorted low-temperature phase [Lutz (2010). Acta Cryst. C66, m330-m335] are found to be the same.

  8. 21 CFR 184.1261 - Copper sulfate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Copper sulfate. 184.1261 Section 184.1261 Food and... Substances Affirmed as GRAS § 184.1261 Copper sulfate. (a) Copper sulfate (cupric sulfate, CuSO4·5H2O, CAS... the reaction of sulfuric acid with cupric oxide or with copper metal. (b) The ingredient must be of...

  9. 21 CFR 184.1261 - Copper sulfate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Copper sulfate. 184.1261 Section 184.1261 Food and... Substances Affirmed as GRAS § 184.1261 Copper sulfate. (a) Copper sulfate (cupric sulfate, CuSO4·5 H2O, CAS... the reaction of sulfuric acid with cupric oxide or with copper metal. (b) The ingredient must be of...

  10. 21 CFR 184.1261 - Copper sulfate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Copper sulfate. 184.1261 Section 184.1261 Food and....1261 Copper sulfate. (a) Copper sulfate (cupric sulfate, CuSO4·5 H2O, CAS Reg. No. 7758-99-8) usually... sulfuric acid with cupric oxide or with copper metal. (b) The ingredient must be of a purity suitable...

  11. 21 CFR 184.1261 - Copper sulfate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Copper sulfate. 184.1261 Section 184.1261 Food and... Substances Affirmed as GRAS § 184.1261 Copper sulfate. (a) Copper sulfate (cupric sulfate, CuSO4·5H2O, CAS... the reaction of sulfuric acid with cupric oxide or with copper metal. (b) The ingredient must be of...

  12. 21 CFR 184.1261 - Copper sulfate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Copper sulfate. 184.1261 Section 184.1261 Food and... Substances Affirmed as GRAS § 184.1261 Copper sulfate. (a) Copper sulfate (cupric sulfate, CuSO4·5 H2O, CAS... the reaction of sulfuric acid with cupric oxide or with copper metal. (b) The ingredient must be of...

  13. A bis-salicylaldoximato-copper(II) receptor for selective sulfate uptake.

    PubMed

    Wenzel, Marco; Knapp, Quintin W; Plieger, Paul G

    2011-01-07

    The preferential uptake of sulfate over the industrially important anions, chloride and nitrate and structurally similar dihydrogen phosphate has been achieved in aqueous media with a dicopper salicylaldoxime complex.

  14. A new copper(II) chelate complex with tridentate ligand: Synthesis, crystal and molecular electronic structure of aqua-(diethylenetriamine-N, N‧, N‧‧)-copper(II) sulfate monohydrate and its fire retardant properties

    NASA Astrophysics Data System (ADS)

    Lavrenyuk, H.; Mykhalichko, O.; Zarychta, B.; Olijnyk, V.; Mykhalichko, B.

    2015-09-01

    The crystals of a new aqua-(diethylenetriamine-N, N‧, N‧‧)-copper(II) sulfate monohydrate have been synthesized by direct interaction of solid copper(II) sulfate pentahydrate with diethylenetriamine (deta). The crystal structure of [Cu(deta)H2O]SO4ṡH2O (1) has been determined by X-ray diffraction methods at 100 K and characterized using X-ray powder diffraction pattern: space group P 1 bar, a = 7.2819(4), b = 8.4669(4), c = 8.7020(3) Å, α = 83.590(3), β = 89.620(4), γ = 84.946(4)°, Z = 2. The environment of the Cu(II) atom is a distorted, elongated square pyramid which consists of three nitrogen atoms of the deta molecule and oxygen atom of the water molecule in the basal plane of the square pyramid (the average lengths of the in-plane Cu-N and Cu-O bonds are 2.00 Å). The apical position of the coordination polyhedron is occupied by complementary oxygen atom of the sulfate anion (the length of the axial Cu-O bond is 2.421(1) Å). The crystal packing is governed by strong hydrogen bonds of O-H⋯O and N-H⋯O types. The ab initio quantum-chemical calculations have been performed by the restricted Hartree-Fock method with a basis set 6-31∗G using the structural data of [Cu(deta)H2O]SO4ṡH2O. It has been ascertained that the degenerate d-orbitals of the Cu2+ ion split under the co-action of both the square-pyramidal coordination and the chelation. It is significant that visually observed crystals color (blue-violet) of the [Cu(deta)H2O]SO4ṡH2O complex is in good agreement with the calculated value of wavelength of visible light (λ = 5735 Å) which is closely related to the energy of the absorbed photon (Δ = 2.161 eV). Furthermore, the stereo-chemical aspect of influence of the CuSO4 upon combustibility of modified epoxy-amine polymers has been scrutinized.

  15. Minnows get columnaris too; copper sulfate works!

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A study was conducted to compare the therapeutic effects of copper sulfate (CuSO4), when delivered in either a flow-through or static system, on the survival of golden shiner (Notemigonus crysoleucas; Fig. 1A) and fathead minnow (Pimephales promelas; Fig. 1B) infected with Flavobacterium columnare (...

  16. Status of copper sulfate research at SNARC

    Technology Transfer Automated Retrieval System (TEKTRAN)

    An overview of the Technical Sections completed and being worked on for the New Animal Drug Application (NADA) for copper sulfate will be given. The change in Sponsorship will also be discussed. The Initial label claim will be “For the treatment of ichthyophthiriasis (Ichthyophthirius multifiliis)...

  17. Copper sulfate: Liquid or crystals?

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Two separate experiments were conducted to evaluate copper toxicity to channel catfish and free-swimming Ichthyophthirius multifiliis or Ich (the stage of Ich that can be treated); the compounds we used were CuSO4 crystals and a non-chelated liquid CuSO4 product. In 96 hr tests conducted in aquaria...

  18. Comparative studies of the effects of copper sulfate and zinc sulfate on serum albumins

    NASA Astrophysics Data System (ADS)

    Plotnikova, O. A.; Melnikov, G. V.; Melnikov, A. G.; Kovalenko, A. V.

    2016-04-01

    The work is devoted to the study of the interaction of heavy metals with bovine serum albumin (BSA) and human serum albumin (HSA), by quenching of the intrinsic fluorescence of proteins and fluorescent probe pyrene by heavy metal ions. Sulfates of copper and zinc (CuSO4, ZnSO4) were taken as the metal salts. The value of the Stern-Volmer constants of quenching of intrinsic fluorescence of proteins and fluorescence probe pyrene reduced from Cu (II) to the Zn (II). It was experimentally found that the copper ions have a greater ability to fluorescence quenching, which is probably associated with the greater availability of protein chromophore groups to copper ions and with adsorbed fluorescent probe pyrene in the protein globule.

  19. Simultaneous sulfate reduction and copper removal by a PVA-immobilized sulfate reducing bacterial culture.

    PubMed

    Hsu, Hsiu-Feng; Jhuo, Yu-Sheng; Kumar, Mathava; Ma, Ying-Shih; Lin, Jih-Gaw

    2010-06-01

    The effect of a sulfate reducing bacteria immobilized in polyvinyl alcohol (PVA) on simultaneous sulfate reduction and copper removal was investigated. Batch experiments were designed using central composite design (CCD) with two parameters, i.e. the copper concentration (10-100mg/L), and the quantity of immobilized SRB in culture solution (19-235 mg of VSS/L). Response surface methodology (RSM) was used to model the experimental data, and to identify optimal conditions for the maximum sulfate reduction and copper removal. Under optimum condition, i.e. approximately 138.5mg VSS/L of sulfate reducing bacteria immobilized in PVA, and approximately 51.5mg/L of copper, the maximum sulfate reduction rate was 1.57 d(-1) as based on the first-order kinetic equation. The data demonstrate that immobilizing sulfate reducing bacteria in PVA can enhance copper removal and the resistance of the bacteria towards copper toxicity.

  20. A Copper-Sulfate-Based Inorganic Chemistry Laboratory for First-Year University Students That Teaches Basic Operations and Concepts.

    ERIC Educational Resources Information Center

    Rodriguez, Emilio; Vicente, Miguel Angel

    2002-01-01

    Presents a 10-hour chemistry experiment using copper sulfate that has three steps: (1) purification of an ore containing copper sulfate and insoluble basic copper sulfates; (2) determination of the number of water molecules in hydrated copper sulfate; and (3) recovery of metallic copper from copper sulfate. (Author/YDS)

  1. Analysis of Saprolegnia parasitica Transcriptome following Treatment with Copper Sulfate

    PubMed Central

    Ye, Xin; Sun, Qi; Yuan, Hai-Lan; Liang, Nan; Fang, Wen-Hong; Li, Hao-Ran; Yang, Xian-Le

    2016-01-01

    Background Massive infection caused by oomycete fungus Saprolegnia parasitica is detrimental to freshwater fish. Recently, we showed that copper sulfate demonstrated good efficacy for controlling S. parasitica infection in grass carp. In this study, we investigated the mechanism of inhibition of S. parasitica growth by copper sulfate by analyzing the transcriptome of copper sulfate—treated S. parasitica. To examine the mechanism of copper sulfate inhibiting S. parasitica, we utilized RNA-seq technology to compare differential gene expression in S. parasitica treated with or without copper sulfate. Results The total mapped rates of the reads with the reference genome were 90.50% in the control group and 73.50% in the experimental group. In the control group, annotated splice junctions, partial novel splice junctions and complete novel splice junctions were about 83%, 3% and 14%, respectively. In the treatment group, the corresponding values were about 75%, 6% and 19%. Following copper sulfate treatment, a total 310 genes were markedly upregulated and 556 genes were markedly downregulated in S. parasitica. Material metabolism related GO terms including cofactor binding (33 genes), 1,3-beta-D-glucan synthase complex (4 genes), carboxylic acid metabolic process (40 genes) were the most significantly enriched. KEGG pathway analysis also determined that the metabolism-related biological pathways were significantly enriched, including the metabolic pathways (98 genes), biosynthesis of secondary metabolites pathways (42 genes), fatty acid metabolism (13 genes), phenylalanine metabolism (7 genes), starch and sucrose metabolism pathway (12 genes). The qRT-PCR results were largely consistent with the RNA-Seq results. Conclusion Our results indicate that copper sulfate inhibits S. parasitica growth by affecting multiple biological functions, including protein synthesis, energy biogenesis, and metabolism. PMID:26895329

  2. Synthesis and characterization of bis-(2-cyano-1-methyl-3-{2- {{(5-methylimidazol-4-yl)methyl}thio}ethyl)guanidine copper(II) sulfate tetrahydrate

    NASA Astrophysics Data System (ADS)

    Rahardjo, Sentot B.; Endah Saraswati, Teguh; Pramono, Edy; Fitriana, Nur

    2016-02-01

    Complex of copper(II) with 2-cyano-1-methyl-3-{2-{{(5-methylimidazol-4- yl)methyl}thio}ethyl)guanidin(xepamet) had been synthesized in 1 : 4 mole ratio of metal to the ligand in methanol. The complex was characterized by metal analysis, thermal gravimetry/differential thermal analyzer (TG/DTA), molar conductivity meter, (Fourier transform infrared spectroscopy) FT-IR, UV-Vis spectroscopy, and magnetic susceptibility balance. The molar conductivity measurement shows that the complex was 2: 1 for electrolyte and SO42- which was acting as a counter ion. The thermal analysis by Thermogravimetric (TG) indicates that the complex contained four molecules of H2O. The Infrared spectral data indicates that functional groups of (C=N) imidazole and (C-S) are coordinated to the center ion Cu2+. Magnetic moment measurement shows that the complex is paramagnetic with peff = 1.78 ± 0.01 BM. Electronic spectra of the complex show a broad band at 608 nm (16447.23 cm-1) are due to Eg→T2g transition. Based on those of characteristics, The complex formula was estimated as [Cu(xepamet)2]SO4.4H2O. The structure of [Cu(xepamet)2]SO4.4H2O complex is probably square planar.

  3. Origins of contrasting copper coordination geometries in crystalline copper sulfate pentahydrate.

    PubMed

    Ruggiero, Michael T; Erba, Alessandro; Orlando, Roberto; Korter, Timothy M

    2015-12-14

    Metal-aqua ion ([M(H2O)n](X+)) formation is a fundamental step in mechanisms that are central to enzymatic and industrial catalysis. Past investigations of such ions have yielded a wealth of information regarding their properties, however questions still exist involving the exact structures of these complexes. A prominent example of this is hexaaqua copper(II) ([Cu(H2O)6](2+)), with the solution versus gas-phase configurations under debate. The differences are often attributed to the intermolecular interactions between the bulk solvent and the aquated complex, resulting in structures stabilized by extended hydrogen-bonding networks. Yet solution phase systems are difficult to study due to the lack of atomic-level positional details. Crystalline solids are ideal models for comparative study, as they contain fixed structures that can be fully characterized using diffraction techniques. Here, crystalline copper sulfate pentahydrate (CuSO4·5H2O), which contains two unique copper-water geometries, was studied in order to elucidate the origin of these contrasting hydrated metal envrionments. A combination of solid-state density functional theory and low-temperature X-ray diffraction was used to probe the electronic origins of this phenomenon. This was accomplished through implementation of crystal orbital overlap population and crystal orbital Hamiltonian population analyses into a developmental version of the CRYSTAL14 software. These new computational methods help highlight the delicate interplay between electronic structure and metal-water geometries.

  4. Copper accumulation in channel catfish (Ictalurus punctatus) exposed to water borne copper sulfate

    SciTech Connect

    Hobbs, M.; Griffin, B.; Schlenk, D.; Kadlubar, F.; Brand, C.D.

    1995-12-31

    Liver and axial muscle of channel catfish (Ictalurus punctatus) was analyzed for residual copper after exposure to water borne copper sulfate. Copper sulfate was continuously introduced into well water in three fiber glass tanks to achieve 1.7 mg/L, 2.7 mg/L and 3.6 mg/L copper sulfate concentrations in exposure waters. Milli-Q quality water was metered into a fourth tank at the same rate for unexposed fish. Actual levels of copper in exposure waters were determined by daily sampling and analysis by graphite furnace atomic absorption spectrophotometry (GFAA). Tissue samples were taken from six fish from each of the exposed and unexposed tanks at two-week intervals, Samples were collected until tissue analysis indicated an equilibrium had been established between the uptake and elimination in both the muscle and liver tissue. Elimination was followed until a clear rate of deputation could be established. Samples were digested in nitric acid in a micro wave digestor and analyzed by GFAA. Results of tissue analysis will be presented to demonstrate bioaccumulation and the effect of copper concentration, length of copper exposure, and gender on copper uptake, establishment of tissue:environmental copper equilibrium, and rate of copper elimination following exposure.

  5. Copper status of ewes fed increasing amounts of copper from copper sulfate or copper proteinate.

    PubMed

    Eckert, G E; Greene, L W; Carstens, G E; Ramsey, W S

    1999-01-01

    The Cu status of mature, crossbred ewes fed two sources (CuSO4 vs. Cu proteinate) and three levels (10, 20, or 30 mg/kg) of dietary Cu was determined in a 73-d feeding trial. Ewes (n = 30) were fed a basal diet containing rice meal feed, cottonseed hulls, cottonseed meal, meat and bone meal, cracked corn, and vitamin-mineral supplements at 2.5% of BW to meet NRC requirements for protein, energy, macrominerals, and microminerals, excluding Cu. The basal diet contained 5 mg/kg Cu, 113 mg/kg Fe, .1 mg/kg Mo, and .17% S. Copper sulfate or Cu proteinate was added to the basal diet to supply 10, 20, or 30 mg/kg of dietary copper in a 2x3 factorial arrangement of treatments. Ewes were housed in 3.7- x 9.1-m pens in an open-sided barn. Blood samples were collected on d 28 and 73. Ewes were slaughtered on d 74, and liver and other tissues were collected to determine Cu concentrations. An interaction (P = .08) occurred between source and level for liver Cu. The interaction existed due to an increase in liver Cu concentrations when ewes were fed increasing dietary Cu from CuSO4 but not when fed Cu proteinate diets. There was no source x level interaction (P>.10) for the blood constituents measured. On d 73, plasma ceruloplasmin activity was greater (P<.05) in ewes fed Cu proteinate than in those fed CuSO4 (33.1 vs. 26.8 microM x min(-1) x L(-1)). Increasing the concentration of dietary Cu did not affect (P>.10) plasma ceruloplasmin. Packed cell volume (PCV), red blood cell count (RBC), white blood cell count, whole blood hemoglobin (wHb), plasma hemoglobin, and plasma Cu were similar between sources of Cu. Ewes fed 20 mg/kg Cu had lower (P<.05) PCV, RBC, and wHb than those fed 10 or 30 mg/kg Cu diets. Feeding up to 30 mg/kg Cu from these sources did not cause an observable Cu toxicity during the 73-d period.

  6. 21 CFR 864.9320 - Copper sulfate solution for specific gravity determinations.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Copper sulfate solution for specific gravity... Establishments That Manufacture Blood and Blood Products § 864.9320 Copper sulfate solution for specific gravity determinations. (a) Identification. A copper sulfate solution for specific gravity determinations is a...

  7. 21 CFR 864.9320 - Copper sulfate solution for specific gravity determinations.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Copper sulfate solution for specific gravity... Establishments That Manufacture Blood and Blood Products § 864.9320 Copper sulfate solution for specific gravity determinations. (a) Identification. A copper sulfate solution for specific gravity determinations is a...

  8. 21 CFR 864.9320 - Copper sulfate solution for specific gravity determinations.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Copper sulfate solution for specific gravity... Establishments That Manufacture Blood and Blood Products § 864.9320 Copper sulfate solution for specific gravity determinations. (a) Identification. A copper sulfate solution for specific gravity determinations is a...

  9. 21 CFR 864.9320 - Copper sulfate solution for specific gravity determinations.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Copper sulfate solution for specific gravity... Establishments That Manufacture Blood and Blood Products § 864.9320 Copper sulfate solution for specific gravity determinations. (a) Identification. A copper sulfate solution for specific gravity determinations is a...

  10. 21 CFR 864.9320 - Copper sulfate solution for specific gravity determinations.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Copper sulfate solution for specific gravity... Establishments That Manufacture Blood and Blood Products § 864.9320 Copper sulfate solution for specific gravity determinations. (a) Identification. A copper sulfate solution for specific gravity determinations is a...

  11. Copper sulfate is an effective, economical, multi-use compound for fish

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Copper sulfate has a long and storied history of use in aquaculture. Copper sulfate also has a wide range of uses including aquatic weed control, snail control, and treating fish diseases. A number of studies have been conducted to show copper sulfate efficacy against diseases including columnaris d...

  12. Using copper sulfate to control fungus on fish eggs

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Copper sulfate (CuSO4) is widely used by the catfish industry as an economical treatment to control fungus (Saprolegnia spp.) on catfish eggs. This is an overview of our effectiveness and safety studies. Channel catfish spawns were 24 - 48 hrs old. Comparable portions of a single spawn were place...

  13. Copper Sulfate Research at Stuttgart National Aquaculture Research Center

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This is brief overview of the Technical Sections completed and being worked on for the New Animal Drug Application (NADA) for copper sulfate. The Initial label claim will be 'For the treatment of ichthyophthiriasis (Ichthyophthirius multifiliis) on Ictalurid catfish cultured in earthen ponds.' The...

  14. Dietary copper sulfate for control of gastrointestinal nematodes in goats

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Prevalence of anthelmintic resistance in goats has necessitated studies for alternative means of gastrointestinal nematode (GIN) control. The objective was to determine the effectiveness of dietary copper sulfate for control of GIN in meat goats. Naturally infected buck kids received 0 (LC), 78 (M...

  15. Practical use of copper sulfate in catfish production

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Copper sulfate has been used in aquaculture for many years to control weeds, algae, snails (which carry catfish trematode), and ecto-parasitic organisms in catfish production. Our research has also shown it to be safe and effective to treat fungus on various fish eggs (catfish, hybrid striped bass,...

  16. Pretreating channel catfish with copper sulfate affects susceptibility to columnaris

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Columnaris disease is a costly bacterial disease of commercially grown channel catfish. Three experiments were conducted to evaluate the effects of pre-exposing channel catfish fingerlings to 0, 1/2, 1, or 2 times the recommended copper sulfate rate for 24 hours on their susceptibility to columnaris...

  17. Control of Saprolegniasis on sunshine bass eggs with copper sulfate

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A major obstacle to successful hatchery production is water-mould (Saprolegniasis) growth on eggs. Copper sulfate (CuSO4) is commonly used to control Saprolegnia species in channel catfish hatcheries that use troughs, but the effectiveness of it on fish eggs hatched using different systems was not ...

  18. Effects of dietary supplementation with copper sulfate or tribasic copper chloride on broiler performance, relative copper bioavailability, and oxidation stability of vitamin E in feed.

    PubMed

    Luo, X G; Ji, F; Lin, Y X; Steward, F A; Lu, L; Liu, B; Yu, S X

    2005-06-01

    An experiment was conducted using a total of 420, 1-d-old, Arbor Acres commercial male chicks to compare copper sulfate and tribasic copper chloride (TBCC) as sources of supplemental copper for broilers. Chicks were randomly allotted to 1 of 7 treatments for 6 replicates of 10 birds each and were fed a basal corn-soybean meal diet (11.45 mg/kg copper) supplemented with 0, 150, 300, or 450 mg/kg copper from copper sulfate or TBCC for 21 d. Chicks fed 450 mg/kg copper as copper sulfate had lower (P < 0.01) average daily feed intake and average daily gain than those consuming other diets. Feeding supplemental copper increased linearly (P < 0.0001) liver copper concentrations regardless of copper source. The slopes of regressions of log10 liver copper on different independent variables used in regressions differ (P < 0.05) between the 2 copper sources. Linear regression over nonzero dietary levels of log10 transformed liver copper concentration on added copper intake resulted in a slope ratio estimate of 109.0 +/- 3.4% (with a 95% confidence interval from 102.2 to 115.8) for bioavailability of copper from TBCC compared with 100 for that in copper sulfate. When the feeds were stored at room temperature for 10 or 21 d, the vitamin E content in the feed fortified with 300 mg/kg copper as TBCC was higher (P < 0.01) than that in the feed added with 300 mg/kg copper as CuSO4. The vitamin E contents in liver and plasma of broilers given TBCC were also higher (P < 0.01) than those of birds fed copper sulfate. The results from this study indicate that TBCC is a safer product and more available to broilers than copper sulfate, and it is chemically less active than copper sulfate in promoting the oxidation of vitamin E in feed.

  19. Observations on Diseased Pigs with High Sulfate Intake and Normal Tissue Copper Levels

    PubMed Central

    Jericho, K. W. F.; Strausz, K. I.; Martin, P. J.

    1973-01-01

    Disease in a large pig herd reared intensively and kept on sulfate-rich drinking water is described. It is the first report of diseased progeny of sows with high sulfate intake. Results of two surveys are presented, one for water with sulfate in excess of 2000 ppm and one for water with less than 1000 ppm. The management practices are described in detail. Disease of Survey I was manifested by high morbidity and mortality (50% of 600) in piglets, incoordination in piglets and some adult stock and osteopathy in piglets and weaners. In Survey II disease was less severe and restricted to piglets. Detailed histopathological studies revealed myelin deficiency in brain and spinal cord of sows and piglets, interferred endochondreal ossification of long bones of piglets and weaners, fatty changes of livers and interstitial nephritis in piglets and weaners. The changes in the nervous tissue were considered due to delayed fixation as tissue was only immersed in fixative and not perfused with it immediately after death. Similar changes have been described for pigs deficient in copper. Copper content of tissue and body fluids of pigs of this study were normal, as were the serum inorganic phosphate and total calcium levels. The bone changes observed have also been reported for rats given dextran sulfate injections, for pigs on experimental low-copper sulfate-enriched diet and for pigs reported low in copper and fed a diet supplemented with sulfide. The cause of the locomotor disturbance and mortality in piglets was not established. ImagesFig. 1.Fig. 2.Fig. 3.Fig. 4.Fig. 5.Fig. 6.Fig. 7. PMID:4270430

  20. Magnetic field effects on copper metal deposition from copper sulfate aqueous solution.

    PubMed

    Udagawa, Chikako; Maeda, Aya; Katsuki, Akio; Maki, Syou; Morimoto, Shotaro; Tanimoto, Yoshifumi

    2014-05-08

    Effects of a magnetic field (≤0.5 T) on electroless copper metal deposition from the reaction of a copper sulfate aqueous solution and a zinc thin plate were examined in this study. In a zero field, a smooth copper thin film grew steadily on the plate. In a 0.38 T field, a smooth copper thin film deposited on a zinc plate within about 1 min. Then, it peeled off repeatedly from the plate. The yield of consumed copper ions increased about 2.1 times compared with that in a zero field. Mechanism of this magnetic field effect was discussed in terms of Lorentz force- and magnetic force-induced convection and local volta cell formation.

  1. Differential sexual survival of Drosophila melanogaster on copper sulfate.

    PubMed

    Balinski, Michael A; Woodruff, Ronny C

    2017-04-01

    Based on studies of the influence of X-chromosomes on the viability of Drosophila melanogaster exposed to cadmium, and on the role of X-linked genes on copper homeostasis, we examined the effect of copper sulfate (CuSO4) on offspring viability using three independent, inbred D. melanogaster crosses (ensuring identical autosomes for males and females within each cross). Each cross was performed with attached X-chromosome females and males with a single X-chromosome. As female D. melanogaster have less metallothionein RNA expression than males, we predicted fewer female offspring than male offspring in crosses exposed to CuSO4, even though females have two copies of X-chromosome genes, possibly resulting in overdominant heterozygosity. In two of three crosses, CuSO4 caused significantly higher numbers of male offspring compared to female offspring. We hypothesized that these gender-based viability differences to copper exposure are caused by X-chromosome ploidy and X-linked genetic variation affecting metallothionein expression. Observed differential offspring viability responses among crosses to copper exposure also showed that different genetic backgrounds (autosomal and/or X-chromosome) can result in significant differences in heavy metal and metallothionein regulation. These results suggest that the effect of copper on offspring viability depends on both genetic background and gender, as both factors can affect the regulation of metallothionein proteins as well as homeostasis of biologically necessary heavy metals.

  2. Short communication: Efficacy of copper sulfate hoof baths against digital dermatitis--Where is the evidence?

    PubMed

    Thomsen, Peter T

    2015-04-01

    Digital dermatitis is a major problem in modern dairy production because of decreased animal welfare and financial losses. Individual cow treatments are often seen as too time consuming by farmers, and walk-through hoof baths have therefore been used extensively to control digital dermatitis. For decades, copper sulfate hoof baths have been used to treat and prevent digital dermatitis. Copper sulfate has been referred to as the industry gold standard when it comes to hoof-bath chemicals. In several scientific studies testing the efficacy of other hoof-care products, copper sulfate has been used as a positive control, thereby indicating that copper sulfate has a known positive effect. However, this may not be the case. A dilemma may exist between (1) copper sulfate generally being perceived as being effective against digital dermatitis and (2) a possible lack of well-documented scientific evidence of this effect. The objective of this study was to evaluate the existing scientific literature to determine whether the efficacy of copper sulfate used in hoof baths against digital dermatitis has in fact been demonstrated scientifically. A systematic literature search identified 7 peer-reviewed journal articles describing the efficacy of copper sulfate in hoof baths as treatment or prevention of bovine digital dermatitis. Only 2 of the 7 studies compared copper sulfate to a negative control; most studies were relatively small, and often no clear positive effect of copper sulfate was demonstrated. In conclusion, the frequent claim that copper sulfate is widely reported to be effective is supported by little scientific evidence. Well-designed clinical trials evaluating the effect of copper sulfate against digital dermatitis compared with a negative control are needed. Until such studies have been made, the efficacy of copper sulfate in hoof baths against digital dermatitis remains largely unproven.

  3. Bone sialoprotein II synthesized by cultured osteoblasts contains tyrosine sulfate

    SciTech Connect

    Ecarot-Charrier, B.; Bouchard, F.; Delloye, C. )

    1989-11-25

    Isolated mouse osteoblasts that retain their osteogenic activity in culture were incubated with (35S) sulfate. Two radiolabeled proteins, in addition to proteoglycans, were extracted from the calcified matrix of osteoblast cultures. All the sulfate label in both proteins was in the form of tyrosine sulfate as assessed by amino acid analysis and thin layer chromatography following alkaline hydrolysis. The elution behavior on DEAE-Sephacel of the major sulfated protein and the apparent Mr on sodium dodecyl sulfate gels were characteristic of bone sialoprotein II extracted from rat. This protein was shown to cross-react with an antiserum raised against bovine bone sialoprotein II, indicating that bone sialoprotein II synthesized by cultured mouse osteoblasts is a tyrosine-sulfated protein. The minor sulfated protein was tentatively identified as bone sialoprotein I or osteopontin based on its elution properties on DEAE-Sephacel and anomalous behavior on sodium dodecyl sulfate gels similar to those reported for rat bone sialoprotein I.

  4. Bone sialoprotein II synthesized by cultured osteoblasts contains tyrosine sulfate.

    PubMed

    Ecarot-Charrier, B; Bouchard, F; Delloye, C

    1989-11-25

    Isolated mouse osteoblasts that retain their osteogenic activity in culture were incubated with [35S] sulfate. Two radiolabeled proteins, in addition to proteoglycans, were extracted from the calcified matrix of osteoblast cultures. All the sulfate label in both proteins was in the form of tyrosine sulfate as assessed by amino acid analysis and thin layer chromatography following alkaline hydrolysis. The elution behavior on DEAE-Sephacel of the major sulfated protein and the apparent Mr on sodium dodecyl sulfate gels were characteristic of bone sialoprotein II extracted from rat. This protein was shown to cross-react with an antiserum raised against bovine bone sialoprotein II, indicating that bone sialoprotein II synthesized by cultured mouse osteoblasts is a tyrosine-sulfated protein. The minor sulfated protein was tentatively identified as bone sialoprotein I or osteopontin based on its elution properties on DEAE-Sephacel and anomalous behavior on sodium dodecyl sulfate gels similar to those reported for rat bone sialoprotein I.

  5. [Newly leaching method of copper from waste print circuit board using hydrochloric acid/n-butylamine/copper sulfate].

    PubMed

    Wang, Hong-Yan; Cui, Zhao-Jie; Yao, Ya-Wei

    2010-12-01

    A newly leaching method of copper from waste print circuit board was established by using hydrochloric acid-n-butylamine-copper sulfate mixed solution. The conditions of leaching were optimized by changing the hydrochloric acid, n-butylamine, copper sulfate,temperature and other conditions using copper as target mimics. The results indicated that copper could be leached completely after 8 h at 50 degrees C, hydrochloric acid concentration of 1.75 mol/L, n-butylamine concentration of 0.25 mol/L, and copper sulfate mass of 0.96 g. Under the conditions, copper leaching rates in waste print circuit board samples was up to 95.31% after 9 h. It has many advantages such as better effects, low cost, mild reaction conditions, leaching solution recycling.

  6. A hybrid water-splitting cycle using copper sulfate and mixed copper oxides

    NASA Technical Reports Server (NTRS)

    Schreiber, J. D.; Remick, R. J.; Foh, S. E.; Mazumder, M. M.

    1980-01-01

    The Institute of Gas Technology has derived and developed a hybrid thermochemical water-splitting cycle based on mixed copper oxides and copper sulfate. Similar to other metal oxide-metal sulfate cycles that use a metal oxide to 'concentrate' electrolytically produced sulfuric acid, this cycle offers the advantage of producing oxygen (to be vented) and sulfur dioxide (to be recycled) in separate steps, thereby eliminating the need of another step to separate these gases. The conceptual process flow-sheet efficiency of the cycle promises to exceed 50%. It has been completely demonstrated in the laboratory with recycled materials. Research in the electrochemical oxidation of sulfur dioxide to produce sulfuric acid and hydrogen performed at IGT indicates that the cell performance goals of 200 mA/sq cm at 0.5 V will be attainable using relatively inexpensive electrode materials.

  7. Are you keeping all your eggs in one basket? Think copper sulfate

    Technology Transfer Automated Retrieval System (TEKTRAN)

    SNARC has been involved with research on copper sulfate for several proposed label claims; this presentation will be about one of the claims, fungus on catfish eggs. A major obstacle in fish hatcheries is the inevitable fungal growth on eggs. Copper sulfate is commonly used for fungus control in c...

  8. Di-sulfated Keratan Sulfate as a Novel Biomarker for Mucopolysaccharidosis II, IVA, and IVB.

    PubMed

    Shimada, Tsutomu; Tomatsu, Shunji; Mason, Robert W; Yasuda, Eriko; Mackenzie, William G; Hossain, Jobayer; Shibata, Yuniko; Montaño, Adriana M; Kubaski, Francyne; Giugliani, Roberto; Yamaguchi, Seiji; Suzuki, Yasuyuki; Orii, Kenji E; Fukao, Toshiyuki; Orii, Tadao

    2015-01-01

    Keratan sulfate (KS) is a storage material in mucopolysaccharidosis IV (MPS IV). However, no detailed analysis has been reported on subclasses of KS: mono-sulfated KS and di-sulfated KS. We established a novel method to distinguish and quantify mono- and di-sulfated KS using liquid chromatography-tandem mass spectrometry and measured both KS levels in various specimens.Di-sulfated KS was dominant in shark cartilage and rat serum, while mono-sulfated KS was dominant in bovine cornea and human serum. Levels of both mono- and di-sulfated KS varied with age in the blood and urine from control subjects and patients with MPS II and IVA. The mean levels of both forms of KS in the plasma/serum from patients with MPS II, IVA, and IVB were elevated compared with that in age-matched controls. Di-sulfated KS provided more significant difference between MPS IVA and the age-matched controls than mono-sulfated KS. The ratio of di-sulfated KS to total KS in plasma/serum increased with age in control subjects and patients with MPS II but was age independent in MPS IVA patients. Consequently, this ratio can discriminate younger MPS IVA patients from controls. Levels of mono- and di-sulfated KS in urine of MPS IVA and IVB patients were all higher than age-matched controls for all ages studied.In conclusion, the level of di-sulfated KS and its ratio to total KS can distinguish control subjects from patients with MPS II, IVA, and IVB, indicating that di-sulfated KS may be a novel biomarker for these disorders.

  9. Impact of Copper Sulfate on Plankton in Channel Catfish Nursery Ponds

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We conducted a series of studies examining the survival of plankton following copper sulfate treatment. Copper additions were made at 3 and 6 mg/L (Cu) had different impacts on the phytoplankton – lower levels stimulated algal growth relative to the higher dosages. Therapeutic use of copper may be...

  10. A Copper (II) Aspirinate Project for the General Chemistry Laboratory

    ERIC Educational Resources Information Center

    Dudek, Emily

    1977-01-01

    Describes an experiment that involves the synthesis of copper (II) aspirinate and the analysis of copper content in the product using electrogravimetric, spectrophotometric, and titrimetric methods. (MLH)

  11. Sulfate reduction, molecular diversity, and copper amendment effects in bacterial communities enriched from sediments exposed to copper mining residues.

    PubMed

    Pavissich, Juan P; Silva, Macarena; González, Bernardo

    2010-02-01

    Sulfate-reducing bacterial communities from coastal sediments with a long-term exposure to copper (Cu)-mining residues were studied in lactate enrichments. The toxicity of excess copper may affect sulfate-reducing bacterial communities. Sulfate reduction was monitored by sulfate and organic acid measurements. Molecular diversity was analyzed by 16S rRNA, dissimilatory sulfate reduction dsrAB, and Cu translocating phospho-type adenosine triphosphatases (P-ATPases) cop-like gene sequence profiling. The influence of Cu amendment was tested in these enrichments. Results showed fast sulfate reduction mostly coupled to incomplete organic carbon oxidation and partial sulfate reduction inhibition due to copper amendment. The 16S rRNA clonal libraries analysis indicated that delta- and gamma-Proteobacteria and Cytophaga-Flexibacter-Bacteroides dominated the enrichments. The dsrAB libraries revealed the presence of Desulfobacteraceae and Desulfovibrionaceae families-related sequences. Copper produced significant shifts (i.e., a decrease in the relative abundance of sulfate-reducing microorganisms) in the enriched bacterial community structure as determined by terminal-restriction fragment length polymorphism (T-RFLP) profiling and multivariate analyses. Clonal libraries of cop-like sequences showed low richness in the enriched microbial communities, and a strong effect of copper on its relative abundance. Novel Cu-P(IB)-ATPase sequences encoding Cu resistance were detected. The present study indicates that Cu does not significantly affect sulfate reduction and genetic diversity of taxonomic and dissimilatory sulfate-reduction molecular markers. However, the diversity of Cu resistance genetic determinants was strongly modified by this toxic metal.

  12. Application of saccharose as copper(II) ligand for electroless copper plating solutions.

    PubMed

    Norkus, Eugenijus; Prusinskas, Kestutis; Vaskelis, Algirdas; Jaciauskiene, Jane; Stalnioniene, Irena; Macalady, Donald L

    2007-01-15

    Saccharose, forming sufficiently stable complexes with copper(II) ions in alkaline solutions, was found to be a suitable ligand for copper(II) chelating in alkaline (pH>12) electroless copper deposition solutions. Reduction of copper(II)-saccharose complexes by hydrated formaldehyde was investigated and the copper deposits formed were characterized. The thickness of the compact copper coatings obtained under optimal operating conditions in 1h reaches ca. 2 microm at ambient temperature. The plating solutions were stable and no signs of Cu(II) reduction in the bulk solution were observed. Results were compared with those systems operating with other copper(II) ligands.

  13. Structural trends in a series of isostructural lanthanide-copper metallacrown sulfates (Ln(III) = Pr, Nd, Sm, Eu, Gd, Dy and Ho): hexaaquapentakis[μ3-glycinehydroxamato(2-)]sulfatopentacopper(II)lanthanide(III) heptaaquapentakis[μ3-glycinehydroxamato(2-)]sulfatopentacopper(II)lanthanide(III) sulfate hexahydrate.

    PubMed

    Pavlishchuk, Anna V; Kolotilov, Sergey V; Fritsky, Igor O; Zeller, Matthias; Addison, Anthony W; Hunter, Allen D

    2011-07-01

    The seven isostructural complexes, [Cu(5)Ln(C(2)H(4)N(2)O(2))(5)(SO(4))(H(2)O)(6.5)](2)(SO(4))·6H(2)O, where Ln(III) = Pr, Nd, Sm, Eu, Gd, Dy and Ho, are representatives of the 15-metallacrown-5 family. Each dianion of glycinehydroxamic acid (GlyHA) links two Cu(II) cations forming a cyclic [CuGlyHA](5) frame. The Ln(III) cations are located at the centre of the [CuGlyHA](5) rings and are bound by the five hydroxamate O atoms in the equatorial plane. Five water molecules are coordinated to Cu(II) cations, and one further water molecule, located close to an inversion centre between two adjacent [Cu(5)Ln(GlyHA)(5)](2+) cations, is disordered around this inversion centre and coordinated to a Cu(II) cation of either the first or second metallacrown ether. Another water molecule and one of the two crystallographically independent sulfate anions are coordinated, the latter in a bidentate fashion, to the Ln(III) cation in the axial positions. The second sulfate anion is not coordinated to the cation, but is located in an interstitial position on a crystallographic inversion centre, thus leading to disorder of the O atoms around the centre of inversion. The Ln-O bond distances follow the trend of the lanthanide contraction. The apical Ln-O bond distances are very close to the sums of the ionic radii. However, the Ln-O distances within the metallacrown units are slightly compressed and the Ln(III) cations protrude significantly from the plane of the otherwise flat metallacrown ligand, thus indicating that the cavity is somewhat too small to accommodate the Ln(III) ions comfortably. This effect decreases with the size of the lanthanide cation from complex (I) (Ln(III) = Pr; 0.459) to complex (VII) (Ln(III) = Ho; 0.422), which indicates that the smaller lanthanide cations fit the cavity of the pentacopper metallacrown ring better than the larger ones. The diminished contraction of Ln-O distances within the metallacrown planes leads to an aniostropic contraction of the unit

  14. Side effects of 58 years of copper sulfate treatment of the Fairmont Lakes, Minnesota

    SciTech Connect

    Hanson, M.J.; Stefan, H.G.

    1984-12-01

    The shallow Fairmont Lakes in Southern Minnesota have been treated with copper sulfate for 58 years to reduce excessive algal growth. Copper sulfate was applied to five lakes at cumulative rates up to 1647 kg/ha (1470 lb/acre), totaling 1.5 million kilograms. Data collected since treatment of the Fairmont Lakes began in 1921 provide alarming insights into lake responses to sustained chemical treatment with copper sulfate. Short-term and long-term effects have occurred. Short-term effects include: a) the intended temporary killing of algae, b) dissolved oxygen depletion by decomposition of dead algae, c) accelerated phosphorus recycling from the lake bed and recovery of the agal population within 7 to 21 days, and d) occasional fish kills due to oxygen depletion or copper toxicity or both. Long-term effects are shown to include: a) copper accumulation in the sediments, b) tolerance adjustments of certain species of algae to higher copper sulfate dosages, c) shift of species from green to blue-green algae and from game fish to rough fish, d) disappearance of macrophytes, and e) reductions in benthic macroinvertebrates. The conclusion is that while copper sulfate treatments enjoy great popularity because they kill and remove algae almost instantaneously, other immediate or cumulative side effects can be harmful to many other aquatic organisms.

  15. Optimization and validation of a method for the determination of the refractive index of milk serum based on the reaction between milk and copper(II) sulfate to detect milk dilutions.

    PubMed

    Rezende, Patrícia Sueli; do Carmo, Geraldo Paulo; Esteves, Eduardo Gonçalves

    2015-06-01

    We report the use of a method to determine the refractive index of copper(II) serum (RICS) in milk as a tool to detect the fraudulent addition of water. This practice is highly profitable, unlawful, and difficult to deter. The method was optimized and validated and is simple, fast and robust. The optimized method yielded statistically equivalent results compared to the reference method with an accuracy of 0.4% and quadrupled analytical throughput. Trueness, precision (repeatability and intermediate precision) and ruggedness are determined to be satisfactory at a 95.45% confidence level. The expanded uncertainty of the measurement was ±0.38°Zeiss at the 95.45% confidence level (k=3.30), corresponding to 1.03% of the minimum measurement expected in adequate samples (>37.00°Zeiss).

  16. Toxic effects of copper sulfate and copper nanoparticles on minerals, enzymes, thyroid hormones and protein fractions of plasma and histopathology in common carp Cyprinus carpio.

    PubMed

    Hoseini, Seyyed Morteza; Hedayati, Aliakbar; Taheri Mirghaed, Ali; Ghelichpour, Melika

    2016-10-01

    Differences in toxicological effects of dissolved copper and copper nanoparticles were studied in common carp, Cyprinus carpio. The fish were exposed to 0.25mgL(-1) copper as copper sulfate (0.25Cu), 0.25mgL(-1) copper as copper oxide nanoparticles (0.25NCu) and 25mgL(-1) copper as copper oxide nanoparticles (25NCu) over 14days. Plasma biochemical, enzymatic and hormonal characteristics, and liver and kidney histopathology were examined at the end of the experiment. The results showed that both forms of copper had no significant effects on plasma calcium levels, however, significantly increased plasma phosphorous levels, compared to control group (no added copper). Plasma alanine transaminase (ALT) activity increased in 0.25Cu and 25NCu treatments compared to the control and 0.25NCu treatments. Nanoparticle copper exposure significantly decreased plasma alkaline phosphatase (ALP) activity compared to the control and 0.25Cu treatments. Only copper sulfate exposure caused plasma aspartate transaminase (AST) elevation. Both copper forms increased plasma T4 and free T4 (FT4); however, copper sulfate effect was higher than nanoparticle copper. Copper sulfate exposure increased plasma albumin fraction, whereas, 25mgL(-1) copper nanoparticle exposure increased plasma α2-globulin fraction compared to the control. Both copper forms damaged the fish liver and kidney, however, copper sulfate caused more severe damages compared to nanoparticle copper. Overall, except for plasma ALP and α2-globulin fraction, dissolved copper seems to be more toxic than nanoparticle copper in common carp.

  17. The effect of dietary copper sulfate on infectious proventriculitis.

    PubMed

    Bayyari, G R; Huff, W E; Beasley, J N; Balog, J M; Rath, N C

    1995-12-01

    Oral inoculation of day-old broiler chicks with a crude homogenate of affected proventricular tissue, or the same homogenate filtered through a .2 micron filter caused proventricular lesions similar to those responsible for carcass contamination of broilers at processing. Dietary copper sulfate (CUS) has also been shown to produce similar lesions. In this study, we investigated the interaction between crude proventriculus homogenate or filtered proventriculus homogenate and 1 g/kg CUS added to a standard chicken diet. Cobb x Cobb female broiler chicks were distributed into six groups with four replicate battery pens per group. Birds were fed either a standard broiler starter diet or the same diet with 1 g/kg CUS. Each dietary treatment was inoculated per os with 1 mL of either sterile saline, unfiltered homogenate, or filtered homogenate. Both crude and filtered homogenates had a much stronger affect on proventriculus score than did Cu by itself, resulting in no interaction between either homogenate or filtrate and CUS. There was a significant and possibly antagonistic interaction on proventriculus relative weights in the CUS by filtrate group during Week 1 and a synergistic interaction in the CUS by homogenate group during Week 4. Body weights were decreased in birds fed homogenate or CUS, but not in birds fed filtrate. There was a protective effect shown by filtrate on body weight of birds fed both filtrate and CUS only during Week 1. There was a synergistic decrease in body weight of birds fed homogenate and CUS during Week 2. Overall feed conversion efficiency was significantly decreased in the homogenate treatment (P = .04) and decreased in the birds fed CUS (P = .1). There was a (4.2 vs 2.3) (P = .1) decrease in feed conversion efficiency in birds fed both homogenate and CUS. Natural exposure to low levels of the infectious agent present in the homogenates may interact with excess dietary CUS, resulting in increased proventriculus size and decrease in body

  18. Effects of copper(II) and copper oxides on THMs formation in copper pipe.

    PubMed

    Li, Bo; Qu, Jiuhui; Liu, Huijuan; Hu, Chengzhi

    2007-08-01

    Little is known about how the growth of trihalomethanes (THMs) in drinking water is affected in copper pipe. The formation of THMs and chlorine consumption in copper pipe under stagnant flow conditions were investigated. Experiments for the same water held in glass bottles were performed for comparison. Results showed that although THMs levels firstly increased in the presence of chlorine in copper pipe, faster decay of chlorine as compared to the glass bottle affected the rate of THMs formation. The analysis of water phase was supplemented by surface analysis of corrosion scales using X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and energy dispersive spectroscopy (EDX). The results showed the scales on the pipe surface mainly consisted of Cu(2)O, CuO and Cu(OH)(2) or CuCO(3). Designed experiments confirmed that the fast depletion of chlorine in copper pipe was mainly due to effect of Cu(2)O, CuO in corrosion scales on copper pipe. Although copper(II) and copper oxides showed effect on THMs formation, the rapid consumption of chlorine due to copper oxide made THM levels lower than that in glass bottles after 4h. The transformations of CF, DCBM and CDBM to BF were accelerated in the presence of copper(II), cupric oxide and cuprous oxide. The effect of pH on THMs formation was influenced by effect of pH on corrosion of copper pipe. When pH was below 7, THMs levels in copper pipe was higher as compared to glass bottle, but lower when pH was above 7.

  19. Serum enzyme status of Chios ewes fed increasing amounts of copper from copper sulfate.

    PubMed

    Bampidis, V A; Christodoulou, V; Chatzipanagiotou, A; Sossidou, E; Salangoudis, A

    2010-06-01

    This study aimed to evaluate effects of orally administered copper (Cu) to Chios sheep breed on serum levels of aspartate aminotransferase (AST), l-alanine aminotransferase (ALT), lactate deydrogenase (LDH) and alkaline phosphatase (ALP), in order to establish a practical and effective method in diagnosing the prehemolytic stage of chronic Cu poisoning. Eighteen ewes were allocated to three treatments of six ewes and fed a diet that contained 16.4 mg/day of Cu. Ewes in treatment Cu-0 received no additional Cu (control), while those in treatments Cu-60 and Cu-95 received 60 and 95 mg additional Cu/day, respectively, as an oral solution of copper sulfate. Therefore the ewes in treatment Cu-0, Cu-60 and Cu-95 consumed 16.4, 76.4 and 111.4 mg Cu/day, respectively. Serum enzyme levels were similar among treatments and all ewes remained clinically healthy until the end of the experiment. Results suggest that Chios ewes exhibit tolerance to Cu supplementation for up to 6 weeks.

  20. Toxicity of copper sulfate and rotenone to Chinese mystery snail (Bellamya chinensis)

    USGS Publications Warehouse

    Haak, Danielle M.; Stephen, Bruce J.; Kill, Robert A.; Smeenk, Nicholas A.; Allen, Craig R.; Pope, Kevin L.

    2014-01-01

    The Chinese mystery snail (Bellamya chinensis) is a freshwater snail native to Southeast Asia, Japan, and Russia and is currently classified as an invasive species in at least 27 states in the USA. The species tolerates a wide range of environmental conditions, making management of established populations difficult. We tested the efficacy of two traditional chemical treatments, rotenone and copper sulfate, on the elimination of adult Chinese mystery snails in laboratory experiments. All snails (N=50) survived 72-hour exposure to rotenone-treated lake water, and 96% (N=25) survived 72-hour exposure to pre-determined rotenone concentrations of 0.25, 2.5, and 25.0 mg/L. All snails (N=10) survived exposure to 1.25 mg/L copper sulfate solution, 90% (N=10) survived exposure to 2.50 mg/L copper sulfate solution, and 80% (N=5) survived exposure to 5.0 mg/L copper sulfate solution. Neither rotenone nor copper sulfate effectively killed adult Chinese mystery snails in laboratory experiments, most likely due to their relatively large size, thick shell, and operculum. Therefore, it appears that populations will be very difficult to control once established, and management should focus on preventing additional spread or introductions of this species.

  1. Reactivity of copper(II)-alkylperoxo complexes.

    PubMed

    Tano, Tetsuro; Ertem, Mehmed Z; Yamaguchi, Satoru; Kunishita, Atsushi; Sugimoto, Hideki; Fujieda, Nobutaka; Ogura, Takashi; Cramer, Christopher J; Itoh, Shinobu

    2011-10-28

    Copper(II) complexes 1a and 1b, supported by tridentate ligand bpa [bis(2-pyridylmethyl)amine] and tetradentate ligand tpa [tris(2-pyridylmethyl)amine], respectively, react with cumene hydroperoxide (CmOOH) in the presence of triethylamine in CH(3)CN to provide the corresponding copper(II) cumylperoxo complexes 2a and 2b, the formation of which has been confirmed by resonance Raman and ESI-MS analyses using (18)O-labeled CmOOH. UV-vis and ESR spectra as well as DFT calculations indicate that 2a has a 5-coordinate square-pyramidal structure involving CmOO(-) at an equatorial position and one solvent molecule at an axial position at low temperature (-90 °C), whereas a 4-coordinate square-planar structure that has lost the axial solvent ligand is predominant at higher temperatures (above 0 °C). Complex 2b, on the other hand, has a typical trigonal bipyramidal structure with the tripodal tetradentate tpa ligand, where the cumylperoxo ligand occupies an axial position. Both cumylperoxo copper(II) complexes 2a and 2b are fairly stable at ambient temperature, but decompose at a higher temperature (60 °C) in CH(3)CN. Detailed product analyses and DFT studies indicate that the self-decomposition involves O-O bond homolytic cleavage of the peroxo moiety; concomitant hydrogen-atom abstraction from the solvent is partially involved. In the presence of 1,4-cyclohexadiene (CHD), the cumylperoxo complexes react smoothly at 30 °C to give benzene as one product. Detailed product analyses and DFT studies indicate that reaction with CHD involves concerted O-O bond homolytic cleavage and hydrogen-atom abstraction from the substrate, with the oxygen atom directly bonded to the copper(II) ion (proximal oxygen) involved in the C-H bond activation step.

  2. Effects of copper sulfate and copper nitrate in aquatic medium on the restoration potential and accumulation of copper in stem cuttings of the terrestrial medicinal plant, Portulaca oleracea linn.

    PubMed

    Mohanapriya, S; Senthilkumar, P; Sivakumar, S; Dineshkumar, M; Subbhuraam, C V

    2006-10-01

    The stem cuttings of the terrestrial, ornamental plant, Portulaca oleracea, grew well in distilled water by producing adventitious roots and leaves. However, when exposed to various concentrations of sulfate and nitrate salts of copper resulted in a suppression of root growth, increase in initiation time of roots and sprouts and decay of stem cuttings from the cut open end, decrease in number of leaves with an increase in concentration of copper in the growth medium. Accumulation of copper increased with increasing concentrations of both copper sulfate and copper nitrate. However, copper accumulation was greater in copper nitrate than in copper sulfate treatment. Hence, copper in the presence of nitrate is more toxic than in the presence of sulfate. The accumulation factors in all treatment concentrations were greater than 1, hence P. oleracea is a copper accumulator.

  3. trans-Bis(hexafluoroantimonato)(phthalocyaninato)copper(II).

    PubMed

    Gardberg, A S; Ibers, J A

    2001-05-01

    The title compound, trans-bis(hexafluoroantimonato-F)(phthalocyaninato-kappa(4)N(29,30,31,32))copper(II), [Cu(SbF(6))(2)(C(32)H(16)N(8))] or Cu(pc)(SbF(6))(2) (pc is phthalocyaninate), comprises a six-coordinate Cu atom, lying on an inversion center, bonded to four N atoms of a phthalocyanine ring and to F atoms of two trans SbF(6)(-) groups. The compound is presumed to consist of a Cu(II) center and a doubly oxidized phthalocyanine ring, by analogy with Cu(pc)(ReO(4))(2).

  4. Synergistic effects between sodium tripolyphosphate and zinc sulfate in corrosion inhibition for copper in neutral tap water

    SciTech Connect

    Feng, Y.; Siow, K.S.; Teo, W.K.; Tan, K.L.; Hsieh, A.K.

    1997-07-01

    The corrosion inhibition behavior of sodium tripolyphosphate (Na{sub 5}P{sub 3}O{sub 10}, or TPP) and zinc sulfate and the synergistic effects between them were studied for copper in neutral simulated tap water using electrochemical methods, x-ray photoelectron spectroscopy, and scanning electron microscopy. Zn{sup 2+} alone showed few inhibiting effects on copper corrosion. The film formed in the presence of Zn{sup 2+} was porous and composed mainly of cuprous oxide, which was similar in morphology and composition to films formed in the absence of the inhibitor. In the presence of TPP, a smooth and compact film, believed to be of Cu(II)-TPP compounds, formed on the copper surface. More protective films were formed in solutions containing TPP and Zn{sup 2+} as a blend. High zinc content (15% to 19%) was detected by XPS. Synergistic effects of TPP and Zn{sup 2+} were believed to result from formation of Zn(II)-TPP compounds that incorporated in the films, with Cu(II)-TPP in the upper layer and Cu{sub 2}O in the inner layer. The zinc compounds increased the anodic diffusion resistance of copper ions in the films and enhanced polarization of the cathodic reduction of dissolved oxygen.

  5. Effect of Copper Sulfate and Lead Acetate on Infection of Pines with Bursaphelenchus xylophilus

    PubMed Central

    Huber, M. C.; Winter, R. E. K.; Bolla, R. I.

    1989-01-01

    Treatment of 3-year-old Scots, white, and Austrian pine seedlings with copper sulfate or lead acetate significantly affected energy homeostasis and oleoresin production in the seedlings but did not induce wilting of the seedlings. Inoculation of copper sulfate-treated or lead acetate-treated white, Scots, and Austrian pine seedlings with the white pine specific pathotype of Bursaphelenchus xylophilus, VPSt-1, caused a significant increase in oleoresin production, stressed energy homeostasis, and induced rapid wilting of the seedlings. Scots pine lost tolerance and Austrian pine lost resistance to VPSt-1 after the seedlings were treated with either copper sulfate or lead acetate. These results suggest that environmental pollution may significantly affect susceptibility of pines to B. xylophilus and may have a role in establishment of this nematode in uninfested areas. PMID:19287570

  6. Efficacy of formalin, copper sulfate, and a commercial footbath product in the control of digital dermatitis.

    PubMed

    Teixeira, A G V; Machado, V S; Caixeta, L S; Pereira, R V; Bicalho, R C

    2010-08-01

    The objective was to evaluate the relative efficacy of a novel, commercially available disinfectant agent (T-Hexx Dragonhyde HBC, Hydromer, Branchburg, NJ) compared with formalin and copper sulfate. The hypothesis was 2 sided; therefore, the hypothesis was that the new agent would be better or worse compared with the industry gold standard footbath agents, formalin and copper sulfate. The study was conducted in a large commercial dairy farm located near Ithaca, New York, from June 18, 2009 to October 26, 2009. Two identical studies were conducted, the first comparing Dragonhyde (5% solution, twice weekly) and formalin (5% solution, twice weekly) and the second comparing Dragonhyde (5% solution, twice weekly) and copper sulfate (10% solution, twice weekly). The study design was identical for both studies with 4 pens (physically identical), 2 treatments (Dragonhyde vs. formalin and Dragonhyde vs. copper sulfate), 2 periods (crossing over the treatment within pen), and 3 repeated measures (3 observations per cow: enrollment, wk 2, and wk 4). For study 1, 406 cows were enrolled (n=201 formalin and 205 Dragonhyde). For study 2, 356 cows were enrolled (n=189 copper sulfate and 167 Dragonhyde). The adjusted odds of digital dermatitis lesion (DDL) throughout the study period were analyzed by mixed logistic regression model. In study 1, the odds of DDL were 1.36 times higher for the formalin group compared with the Dragonhyde group. In study 2, the data were analyzed by a similar statistical model and the variable treatment did not significantly affect the overall prevalence of DDL. In conclusion, the performance of 3 hoof care products was evaluated and it was concluded that Dragonhyde performed better than formalin and that there was no difference between copper sulfate and Dragonhyde.

  7. Anodonta imbecillis copper sulfate reference toxicant test, Clinch River - Environmental Restoration Program (CR-ERP)

    SciTech Connect

    Simbeck, D.J.

    1997-06-01

    Reference toxicant testing using juvenile freshwater mussels was conducted as part of the CR-ERP biomonitoring study of Clinch River sediments to assess the sensitivity of test organisms and the overall performance of the test. Tests were conducted using moderately hard synthetic water spiked with known concentrations of copper as copper sulfate. Toxicity testing of copper sulfate reference toxicant was conducted from May 12-21, 1993. The organisms used for testing were juvenile fresh-water mussels (Anodonta imbecillis). Results from this test showed an LC{sub 50} value of 1.12 mg Cu/L which is lower than the value of 2.02 mg Cu/L obtained in a previous test. Too few tests have been conducted with copper as the toxicant to determine a normal range of values.

  8. Studies on the feeding of cupric sulfate pentahydrate, cupric citrate, and copper oxychloride to broiler chickens.

    PubMed

    Ewing, H P; Pesti, G M; Bakalli, R I; Menten, J F

    1998-03-01

    Male commercial broiler strain chickens were fed either a control diet (based on corn and soybean meal) or the control diet supplemented with cupric sulfate pentahydrate, copper oxychloride, or cupric citrate in two experiments conducted in floor pens. In Experiment 1, feeding copper at 125 mg/kg diet for 42 d significantly increased broiler growth; and the response from cupric citrate was significantly better than either cupric sulfate or copper oxychloride. In Experiment 2, the inclusion of copper from cupric citrate was reduced to 63 mg/kg and the length of the experiment was increased to 56 d. Cupric sulfate pentahydrate and copper oxychloride treatments increased weight gain by 4.9% and cupric citrate increased weight gain by 9.1%. The feed conversion ratios (grams of feed:grams of gain of live birds) in the birds fed copper were not significantly different from those fed the basal diet (P > 0.05) unless corrections were made for the weights of the dead birds; the adjusted feed conversion ratios (grams of feed:grams of gain of live birds + grams of gain of mortalities) for the copper-treated birds in Experiments 1 and 2 were 5.2 and 7.6% lower, respectively, than the ratios of birds fed the basal diets. Plasma copper levels increased in supplemented chicks by 35% in Experiment 1 and 24% in Experiment 2. Liver copper levels in both experiments were increased by 26% with copper supplementation. Mortality was not affected by dietary treatment in either experiment (P > 0.05).

  9. Effects of environmental factors on the molluscicidal activities of slow-release hexabutyldistannoxane and copper sulfate*

    PubMed Central

    Chu, K. Y.

    1976-01-01

    Laboratory experiments were conducted to study the molluscicidal activities of slow-release hexabutyldistannoxane (TBTO) and copper sulfate under various environmental conditions. Organic materials such as mud and weeds reduced the molluscicidal efficacy of both chemicals. TBTO can be considered a good long-lasting molluscicide but, because of uncertainty as to its general toxic effects, it should not be used in field trials. The molluscicidal activity of slow-release copper sulfate was short-lived in plain lake water and was nil in the presence of mud or weeds at the concentration used. PMID:1088355

  10. Cell culture and gene transcription effects of copper sulfate on Chinese hamster ovary cells.

    PubMed

    Qian, Yueming; Khattak, Sarwat F; Xing, Zizhuo; He, Aiqing; Kayne, Paul S; Qian, Nan-Xin; Pan, Shih-Hsie; Li, Zheng Jian

    2011-07-01

    This study reports the effects of varying concentrations of copper sulfate on the metabolic and gene transcriptional profile of a recombinant Chinese hamster ovary (CHO) cell line producing an immunoglobulin G (IgG)-fusion protein (B0). Addition of 50 μM copper sulfate significantly decreased lactate accumulation in the cultures while increasing viable cell density and protein titer. These changes could be seen from day 6 and became increasingly evident with culture duration. Reducing the copper sulfate concentration to 5 μM retained all the above beneficial effects, but with the added benefit of reduced levels of the aggregated form of the B0 protein. To profile the cellular changes due to copper sulfate addition at the transcriptional level, Affymetrix® CHO microarrays were used to identify differentially expressed genes related to reduced cellular stresses and facilitated cell cycling. Based on the microarray results, down-regulation of the transferrin receptor and lactate dehydrogenase, and up-regulation of a cytochrome P450 family-2 polypeptide were then confirmed by Western blotting. These results showed that copper played a critical role in cell metabolism and productivity on recombinant CHO cells and highlighted the usefulness of microarray data for better understanding biological responses on medium modification.

  11. A copper sulfate and hydroxylysine treatment regimen for enhancing collagen cross-linking and biomechanical properties in engineered neocartilage.

    PubMed

    Makris, Eleftherios A; MacBarb, Regina F; Responte, Donald J; Hu, Jerry C; Athanasiou, Kyriacos A

    2013-06-01

    The objective of this study was to improve the biomechanical properties of engineered neotissues through promoting the development of collagen cross-links. It was hypothesized that supplementing medium with copper sulfate and the amino acid hydroxylysine would enhance the activity of lysyl oxidase enzyme to form collagen cross-links, increasing the strength and integrity of the neotissue. Neocartilage constructs were generated using a scaffoldless, self-assembling process and treated with copper sulfate and hydroxylysine, either alone or in combination, following a 2-factor, full-factorial study design. Following a 6-wk culture period, the biomechanical and biochemical properties of the constructs were measured. Results found copper sulfate to significantly increase pyridinoline (PYR) cross-links in all copper sulfate-containing groups over controls. When copper sulfate and hydroxylysine were combined, the result was synergistic, with a 10-fold increase in PYR content over controls. This increase in PYR cross-links manifested in a 3.3-fold significant increase in the tensile properties of the copper sulfate + hydroxylysine group. In addition, an 123% increase over control values was detected in the copper sulfate group in terms of the aggregate modulus. These data elucidate the role of copper sulfate and hydroxylysine toward improving the biomechanical properties of neotissues through collagen cross-linking enhancement.

  12. Deposition of copper and sulfate on Au(1 1 1): New insights

    NASA Astrophysics Data System (ADS)

    Madry, B.; Wandelt, K.; Nowicki, M.

    2016-12-01

    The adsorption of sulfate anions (SO42-) and copper cations on Au(1 1 1) from CuSO4 containing H2SO4 solution was investigated by cyclic voltammetry (CV) and scanning tunneling microscopy (STM). The underpotential deposition from solution results first in the formation of 2/3 monolayer of copper with the well known (√{ 3} ×√{ 3}) structure of sulfate followed by the completion of the first copper monolayer at lower potentials. Just after formation of 1ML of Cu STM reveals a disordered surface. At more negative potential values, already in the overpotential deposition region, the STM images reflect a (√{ 3} ×√{ 7}) sulfate structure on terraces of the first pseudomorphic Cu layer, a (√{ 3} ×√{ 3}) -like structure on terraces of the second uncompleted Cu layer with sulfate anions residing in atomic vacancies, and the known Moiré structure on terraces of the multi-layer Cu deposit. The formation of the (√{ 3} ×√{ 7}) sulfate structure on pseudomorphic monolayer Cu terraces on Au(1 1 1) is discussed in the context of results obtained for sulfate on bare Au(1 1 1) and Cu(1 1 1) electrodes in H2SO4 solution.

  13. The effects of copper sulfate on liver histology and biochemical parameters of term Ross broiler chicks.

    PubMed

    Oguz, Emin Oguzhan; Yuksel, Hayati; Enli, Yasar; Tufan, A Cevik; Turgut, Gunfer

    2010-03-01

    Copper is an essential trace element that is extremely toxic to organisms and organs at high doses. We have investigated the histological and biochemical effects of a toxic dose of copper sulfate on the liver of term Ross broiler chicks. Fertilized eggs were divided into three groups: experimental, injected with 50 mcg/0.1 ml copper sulfate in the air chambers on day 1; sham, injected with 0.1 ml saline; and control, no injection. Term chicks were killed and their livers investigated histologically, with hematoxylin-eosin-stained sections examined under light microscopy, and biochemically, for malondialdehyde and glutathione levels. Histological examinations showed copper-treated samples with granular degeneration and necrosis of hepatocytes and impairment to the cell lining of the remark cords. The samples had a congestive appearance, with blood in the vena centralis and sinusoids, slight connective tissue increase, and lymphocyte infiltration. Control and sham group sections had normal appearances. As oxidative damage parameters, in the copper-treated group, malondialdehyde levels were increased and glutathione levels decreased. In the sham and control groups, there were no significant differences. At this toxic dose, copper sulfate shows oxidative damage according to the histology of term chick liver that are confirmed biochemically by the changes in malondialdehyde and glutathione levels.

  14. Relationship between oxidative stress and heme oxygenase induction by copper sulfate.

    PubMed

    Ossola, J O; Groppa, M D; Tomaro, M L

    1997-01-15

    The effect of copper sulfate (CuSO4) on both hepatic oxidative stress and heme oxygenase induction was studied. A strong increase in in vivo rat liver chemiluminescence was observed 1 h after Cu(II) administration. To evaluate liver antioxidant enzymatic defenses, superoxide dismutase, catalase, and glutathione peroxidase activities were determined. Catalase and glutathione peroxidase were found to be significantly decreased 5 h after CuSO4 injection. In contrast, superoxide dismutase activity was increased. Heme oxygenase activity appeared 5 h after treatment, reaching a maximum value 18 h after CuSO4 administration. This induction was preceded by a decrease in the intrahepatic GSH pool and an increase in the generation of thiobarbituric acid reactive substances, both effects taking place a number of hours before induction of heme oxygenase. Administration of bilirubin, the end product of heme catabolism in mammals, and alpha-tocopherol, a widely employed antioxidant, completely prevented heme oxygenase induction as well as the decrease in hepatic GSH and the increase in chemiluminescence when administered 2 h before CuSO4 treatment. Under the same experimental conditions, beta-carotene showed a moderate preventive effect on both heme oxygenase induction and oxidative stress parameters. These data obtained with Cu(II) treatment are in agreement with our previous reports suggesting a correlation between heme oxygenase induction and oxidative stress.

  15. Effects of copper sulfate supplement on growth, tissue concentration, and ruminal solubilities of molybdenum and copper in sheep fed low and high molybdenum diets

    SciTech Connect

    Ivan, M.; Veira, D.M.

    1985-01-01

    Each of four groups of six wethers were fed one of a low molybdenum, high molybdenum, high molybdenum plus copper sulfate, or high molybdenum plus copper sulfate corn silage-based diet for ad libitum intake for 221 days. Average daily gains and ratios of feed/gain were depressed for the high molybdenum diet as compared with the low molybdenum diet suggesting molybdenum toxicity in sheep fed the high molybdenum diet. This was alleviated partly by the copper sulfate supplement. The supplement also decreased solubility of both copper and molybdenum in the rumen but had no effect on copper concentration in blood plasma. Concentration of molybdenum was higher in both liver and kidney in sheep fed high-molybdenum diets as compared with low-molybdenum diets. Copper concentration was higher in kidneys of sheep fed high-molybdenum diets, but no difference was significant in liver copper between sheep fed diets high or low in molybdenum.

  16. Separation of copper from aqueous sulfate solutions by mixtures of Cyanex 301 and LIX 984N.

    PubMed

    Fouad, E A

    2009-07-30

    The extraction equilibria of copper(II) with Cyanex 301, LIX 984N, and their mixtures have been investigated. Extraction was studied as a function of organic phase composition, sulfuric acid concentration, pH, temperature, initial copper concentration, mixing speed, and aqueous/organic volume ratio. Considerable synergistic enhancement has been observed in the extraction of Cu(2+) with mixtures of Cyanex 301 and LIX 984N. The results demonstrate that copper ion is extracted as CuRL(2)H with synergistic mixture. The thermodynamic parameter, enthalpy change (Delta H) of Cyanex 301, LIX 984N, and their mixtures have been determined and the endothermic process has been found. The synergistic enhancement factor of copper(II) with mixtures is higher at more acidic solutions, which suggests that it is a promising synergistic extraction system for the separation of copper(II) from more acidic medium. HCl was found to be more efficient for copper stripping from loaded synergistic mixtures.

  17. Nickel, manganese and copper removal by a mixed consortium of sulfate reducing bacteria at a high COD/sulfate ratio.

    PubMed

    Barbosa, L P; Costa, P F; Bertolino, S M; Silva, J C C; Guerra-Sá, R; Leão, V A; Teixeira, M C

    2014-08-01

    The use of sulfate-reducing bacteria (SRB) in passive treatments of acidic effluents containing heavy metals has become an attractive alternative biotechnology. Treatment efficiency may be linked with the effluent conditions (pH and metal concentration) and also to the amount and nature of the organic substrate. Variations on organic substrate and sulfate ratios clearly interfere with the biological removal of this ion by mixed cultures of SRB. This study aimed to cultivate a mixed culture of SRB using different lactate concentrations at pH 7.0 in the presence of Ni, Mn and Cu. The highest sulfate removal efficiency obtained was 98 %, at a COD/sulfate ratio of 2.0. The organic acid analyses indicated an acetate accumulation as a consequence of lactate degradation. Different concentrations of metals were added to the system at neutral pH conditions. Cell proliferation and sulfate consumption in the presence of nickel (4, 20 and 50 mg l(-1)), manganese (1.5, 10 and 25 mg l(-1)) and copper (1.5, 10 and 25 mg l(-1)) were measured. The presence of metals interfered in the sulfate biological removal however the concentration of sulfide produced was high enough to remove over 90 % of the metals in the environment. The molecular characterization of the bacterial consortium based on dsrB gene sequencing indicated the presence of Desulfovibrio desulfuricans, Desulfomonas pigra and Desulfobulbus sp. The results here presented indicate that this SRB culture may be employed for mine effluent bioremediation due to its potential for removing sulfate and metals, simultaneously.

  18. Bioremediation of copper-containing wastewater by sulfate reducing bacteria coupled with iron.

    PubMed

    Bai, He; Kang, Yong; Quan, Hongen; Han, Yang; Sun, Jiao; Feng, Ying

    2013-11-15

    In order to treat copper-containing wastewater effectively using sulfate reducing bacteria (SRB), iron (Fe(0)) was added to enhance the activity of SRB. The SRB system and the SRB + Fe(0) system were operated under continuous operation. The sulfate reduction efficiency of the SRB + Fe(0) system was twice as much as that of the SRB system with the sulfate loading rate at 125  mg L(-1) h(-1). The effect of COD/SO4(2-) on sulfate reduction indicates an enhanced activity of SRB by adding Fe(0). 99% of total sulfate was deducted in both systems at pH 4.0-7.0, and temperature slightly influenced the removal of sulfate in the SRB + Fe(0) system. In the copper-containing wastewater treatment, the SRB + Fe(0) system shows a better performance since sulfate removal in this system was higher than the SRB system, and the removal ratio of Cu(2+) was held above 95% in SRB + Fe(0) system at all influent Cu(2+) concentrations.

  19. [Molluscacide activity of a mixture of 6-n-alkyl salicylic acids (anacardic acid) and 2 of its complexes with copper (II) and lead (II)].

    PubMed

    Mendes, N M; de Oliveira, A B; Guimarães, J E; Pereira, J P; Katz, N

    1990-01-01

    The molluscicide activity of hexanic extract from Anacardium occidentale L. (cashew) nut shell, of copper (II) complex, of lead (II) complex and anacardic acid has been compared in the laboratory in an attempt to obtain better stability than anacardic acid. This was obtained from the hexanic extract of the cashew nut shell by precipitation with lead (II) hydroxide or cupric sulfate plus sodium hydroxide or (II) cupric hydroxide followed by treatment of lead (II) complex with a diluted solution of sulfuric acid. Ten products of the mixture obtained were tested on adults snails of Biomphalaria glabrata at 1 to 10 ppm. The most active products were copper (II) complex, obtained by cupric sulfate plus sodium hydroxide, and anacardic acid (sodium hydroxide) which presented activity at 4 ppm. The anacardic acid's lead content was above the limits accepted by the United States standards.

  20. Influence of alkalinity and hardness on copper sulfate toxicity to various fish

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Copper sulfate treatments are currently used to control parasites (mainly Ich) on fish and fungus (Saprolegnia) on fish eggs. This compound has also been used in the past to control columnaris on fish, although antibiotics are the common treatment now. In our lab’s efforts to gain an FDA-approval ...

  1. Treating sunshine bass eggs with copper sulfate controls fungus and increases survival

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A major obstacle to sunshine bass production is fungal growth on eggs. Copper sulfate (CuSO4) is commonly used for fungus control in channel catfish hatcheries that use troughs, but the effectiveness of it on fish eggs hatched using different systems was not known. Female white bass Morone chrysop...

  2. Using copper sulfate on hybrid striped bass eggs to control fungus and increase survival

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A major obstacle in fish hatcheries is reduced hatch rates due to fungal growth on eggs. Copper sulfate (CuSO4) is commonly used for fungus control in catfish hatcheries that use troughs, but effectiveness on other species of fish eggs in different hatching systems has only recently been investigat...

  3. Copper sulfate controls fungus on sunshine bass eggs and increases survival

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A major obstacle to sunshine bass production is fungal growth on eggs. Copper sulfate (CuSO4) is commonly used for fungus control in channel catfish hatcheries that use troughs, but the effectiveness of it on fish eggs hatched using different systems was not known. Female white bass Morone chrysop...

  4. The effect of copper sulfate, potassium permanganate, and peracetic acid on Ichthyobodo necator in channel catfish

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Ichthyobodo necator is a single celled biflagellate that can cause significant mortalities in fish, particularly young, tank-reared fish. Copper sulfate (CuSO4), potassium permanganate (KMnO4) and peracetic acid (PAA) were evaluated for effectiveness against Ichthybodosis in juvenile channel catfis...

  5. DEVELOPMENTAL TOXICITY OF COPPER SULFATE AND METHYLENE CHLORIDE TO SHRIMP EMBRYOS

    EPA Science Inventory

    The embryos of the grass shrimp (Palaemonetes pugio) have shown sensitivity to the water-soluble fraction of Number 2 fuel oil which indicates they may be a useful test species in estuarine developmental toxicity tests. Detailed concentration-response curves for copper sulfate an...

  6. Using a computer model to calculate copper sulfate treatments for Ich

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Copper sulfate (CuSO4) is often used to control infestations of Ichthyophthirius multifiliis (Ich) in pond aquaculture in the United States. In this study, we determined the acute toxicity of CuSO4 to the free-swimming theronts of Ich in reconstituted waters. Water chemistry characteristics, inclu...

  7. Impact of Copper Sulfate on Plankton in Channel Catfish Nursery Ponds

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Many fish culturists are interested in applying copper sulfate pentahydrate (CSP) to channel catfish, Ictalurus punctatus, nursery ponds as a prophylactic treatment for trematode infection and proliferative gill disease by killing snails and Dero sp., respectively, before stocking fry. However, copp...

  8. Using copper sulfate to control egg fungus at Keo Fish Farm

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Keo Fish Farm is the biggest producer of hybrid striped bass fry in the world. The hatchery manager asked about treatments to control fungus on eggs which occurred fairly often. Our lab has been working on gaining FDA-approval to use copper sulfate to control fungus on catfish eggs, so we were con...

  9. The use of copper sulfate in catfish hatcheries: safety and effectiveness

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Copper sulfate (CuSO4) is cheap, safe to the applicator and effective for controlling fungus on catfish eggs. Several studies were designed to determine the effectiveness and safety of CuSO4 to channel catfish eggs in pursuit of an FDA approval. In an effectiveness study for the FDA, we found that ...

  10. Using copper sulfate on hybrid striped bass eggs to control fungus and increase survival

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A major obstacle in fish hatcheries is the inevitable fungal growth on eggs. Copper sulfate (CuSO4) is commonly used for fungus control in channel catfish hatcheries that use troughs, but effectiveness on fish eggs hatched using different systems has only recently been investigated. Fish were spawn...

  11. Use of copper sulfate and peracetic acid as therapeutants on fish: can these replace formalin?

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Copper sulfate (CuSO4) and peracetic acid (PAA) are compounds that have been found to be useful in several areas of aquaculture around the world. In the United States, CuSO4 is used for treatment of an ectoparasite (Ichthyophthirius multifiliis) on fish (Straus 1993; Tieman and Goodwin 2001), and s...

  12. Use of copper sulfate to control Saprolegniasis at a commercial sunshine bass hatchery

    Technology Transfer Automated Retrieval System (TEKTRAN)

    An obstacle to sunshine bass (female white bass Morone chrysops × male striped bass M. saxatilis) larval production is fungal growth on eggs caused by the water-mold Saprolegnia spp. Copper sulfate (CuSO4) is commonly used for fungus control in troughs of catfish hatcheries, but the effectiveness o...

  13. Egg saprolegniasis in a commercial sunshine bass hatchery: Control regime developed using copper sulfate

    Technology Transfer Automated Retrieval System (TEKTRAN)

    An obstacle to sunshine bass (female white bass Morone chrysops × male striped bass M. saxatilis) larval production is fungal growth on eggs caused by the water-mold Saprolegnia spp. Copper sulfate (CuSO4) is commonly used for fungus control in troughs of catfish hatcheries, but the effectiveness o...

  14. Copper sulfate controls fungus on mat-spawned largemouth bass eggs

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Copper sulfate (CuSO4) is widely used by the catfish and hybrid striped bass industries as an economical treatment to control fungus (Saprolegnia spp.) on eggs; these industries use hatching troughs and McDonald jars, respectively, in moderate alkalinity waters. This study determined the effectivene...

  15. Novel copper (II) alginate hydrogels and their potential for use as anti-bacterial wound dressings.

    PubMed

    Klinkajon, Wimonwan; Supaphol, Pitt

    2014-08-01

    The incorporation of a metal ion, with antimicrobial activity, into an alginate dressing is an attractive approach to minimize infection in a wound. In this work, copper (II) cross-linked alginate hydrogels were successfully prepared using a two-step cross-linking procedure. In the first step, solid alginate films were prepared using a solvent-casting method from soft gels of alginate solutions that had been lightly cross-linked using a copper (II) (Cu(2+)) sulfate solution. In the second step, the films were further cross-linked in a corresponding Cu(2+) sulfate solution using a dipping method to further improve their dimensional stability. Alginate solution (at 2%w/v) and Cu(2+) sulfate solution (at 2%w/v) in acetate buffer at a low pH provided soft films with excellent swelling behavior. An increase in either Cu(2+) ion concentration or cross-linking time led to hydrogels with more densely-cross-linked networks that limited water absorption. The hydrogels clearly showed antibacterial activity against Escherichia coli, Staphylococcus aureus, methicillin-resistant Staphylococcus aureus (MRSA), Staphylococcus epidermidis and Streptococcus pyogenes, which was proportional to the Cu(2+) ion concentration. Blood coagulation studies showed that the tested copper (II) cross-linked alginate hydrogels had a tendency to coagulate fibrin, and possibly had an effect on pro-thrombotic coagulation and platelet activation. Conclusively, the prepared films are likely candidates as antibacterial wound dressings.

  16. Copper Deposits with High Tensile Strength and Elongation Electroformed in an Ultra-Low-Concentration Sulfate Bath without Additives

    NASA Astrophysics Data System (ADS)

    Shen, Chunjian; Zhu, Zengwei; Zhu, Di; Ren, Jianhua

    2017-02-01

    Superior mechanical properties of copper are needed in industries to meet high application requirement. In this study, an electroformed copper with superior mechanical properties is achieved by using a simple ultra-low-concentration copper sulfate bath containing neither chloride nor organic additives. Copper deposits obtained in the copper sulfate concentrations ranging from 30 to 60 g/L exhibit high tensile strength and elongation simultaneously. A maximum tensile strength of 256 MPa is achieved, with an elongation ratio of 31%, at a copper sulfate concentration of 30 g/L, while a maximum elongation ratio of 43% is achieved, with a tensile strength of 216 MPa, at a concentration of 50 g/L. It has been found that the copper sulfate concentration affected the hydrogen content, grain arrangement and orientation index of copper deposits which determine their mechanical properties. When the copper sulfate concentration is less than 30 g/L, the excessive hydrogen content of the deposits thus produced leads to poor compactness and inferior mechanical properties. At concentrations over 50 g/L, a disordered arrangement of grains and a significant increase in the peak of (111) lead to an increase in the tensile strength but a decrease in the elongation ratio. This approach provides an effective and economical method for the copper deposits achieving superior mechanical properties.

  17. Effects of copper sulfate on seedlings of Prosopis pubescens (screwbean mesquite).

    PubMed

    Zappala, Marian N; Ellzey, Joanne T; Bader, Julia; Peralta-Videa, Jose R; Gardea-Torresdey, Jorge

    2014-01-01

    Phytoextraction is an established method of removal of heavy metals from contaminated soils worldwide. Phytoextraction is most efficient if local plants are used in the contaminated site. We propose that Prosopis pubescens (Screw bean mesquite) would be a successful phytoextractor of copper in our local soils. In order to determine the feasibility of using Screw bean mesquite, we utilized inductively-coupled plasma-optical emission spectroscopy (ICP-OES) and elemental analysis to observe the uptake of copper and the effects on macro and micro nutrients within laboratory-grown seedlings. We have previously shown that P. pubescens is a hyperaccumulator of copper in soil-grown seedlings. Light and transmission electron microscopy demonstrated death of root cells and ultrastructural changes due to the presence of copper from 50 mg/L - 600 mg/L. Ultrastructural changes included plasmolysis, starch accumulation, increased vacuolation and swollen chloroplasts with disarranged thylakoid membranes in cotyledons. Inductively coupled plasma-optical emission spectroscopy analyses of macro- and micro-nutrients revealed that the presence of copper sulfate in the growth medium of Petri-dish grown Prosopis pubescens seedlings resulted in dramatic decreases of magnesium, potassium and phosphorus. At 500-600 mg/L of copper sulfate, a substantial increase of sulfur was present in roots.

  18. Effects of copper sulfate on seedlings of Prosopis pubescens (Screwbean mesquite)

    PubMed Central

    Zappala, Marian N.; Ellzey, Joanne T.; Bader, Julia; Peralta-Videa, Jose R.; Gardea-Torresdey, Jorge

    2013-01-01

    Phytoextraction is an established method of removal of heavy metals from contaminated soils worldwide. Phytoextraction is most efficient if local plants are used in the contaminated site. We propose that Prosopis pubescens (Screw bean mesquite) would be a successful phytoextractor of copper in our local soils. In order to determine the feasibility of using Screw bean mesquite, we utilized inductively coupled plasma-optical emission spectroscopy (ICP-OES) and elemental analysis to observe the uptake of copper and the effects on macro and micro nutrients within laboratory-grown seedlings. We have previously shown that pubescens is a hyperaccumulator of copper in soil-grown seedlings. Light and transmission electron microscopy demonstrated death of root cells and ultrastructural changes due to the presence of copper from 50 mg L-1 – 600 mg L-1. Ultrastructural changes included plasmolysis, starch accumulation, increased vacuolation and swollen chloroplasts with disarranged thylakoid membranes in cotyledons. Inductively coupled plasma-optical emission spectroscopy analyses of macro-and micro-nutrients revealed that the presence of copper sulfate in the growth mediium of Petri-dish grown Prosopis pubescens seedlings resulted in dramatic decreases of magnesium, potassium and phosphorus. At 500-600 mg L-1 of copper sulfate a substantial increase of sulfur was present in roots. PMID:24933900

  19. Comparison of the toxicity of two chelated copper algaecides and copper sulfate to non-target fish.

    PubMed

    Closson, K R; Paul, E A

    2014-12-01

    New pesticide products are reviewed by the United States Environmental Protection Agency for possible effects to non-target aquatic organisms. The required toxicity data are for the active ingredient only, and fail to include toxicity of the mixture of other ingredients found in these pesticides. These ingredients may increase the toxicity of the active ingredient to non-target organisms. Our study compares the toxicity of two formulations of chelated copper algaecides with each other, and to a copper sulfate algaecide. We were particularly interested in the effects of a surfactant that is present in one of the formulations. We found that copper becomes less toxic to fish (e.g. fathead minnow 48-h LC50 = 0.90 mg/L) when it is chelated, providing an additional margin of safety to non-target fish compared to copper sulfate. However, inclusion of a surfactant to the formulation resulted in increased toxicity (e.g. fathead minnow 48-h LC50 = 0.30 mg/L).

  20. Copper-Sulfate Pentahydrate as a Product of the Waste Sulfuric Acid Solution Treatment

    NASA Astrophysics Data System (ADS)

    Marković, Radmila; Stevanović, Jasmina; Avramović, Ljiljana; Nedeljković, Dragutin; Jugović, Branimir; Stajić-Trošić, Jasna; Gvozdenović, Milica

    2012-12-01

    The aim of this study is synthesis of copper-sulfate pentahydrate from the waste sulfuric acid solution-mother liquor generated during the regeneration process of copper bleed solution. Copper is removed from the mother liquor solution in the process of the electrolytic treatment using the insoluble lead anodes alloyed with 6 mass pct of antimony on the industrial-scale equipment. As the result of the decopperization process, copper is removed in the form of the cathode sludge and is precipitated at the bottom of the electrolytic cell. By this procedure, the content of copper could be reduced to the 20 mass pct of the initial value. Chemical characterization of the sludge has shown that it contains about 90 mass pct of copper. During the decopperization process, the very strong poison, arsine, can be formed, and the process is in that case terminated. The copper leaching degree of 82 mass pct is obtained using H2SO4 aqueous solution with the oxygen addition during the cathode sludge chemical treatment at 80 °C ± 5 °C. Obtained copper salt satisfies the requirements of the Serbian Standard for Pesticide, SRPS H.P1. 058. Therefore, the treatment of waste sulfuric acid solutions is of great economic and environmental interest.

  1. Effects of copper sulfate on growth, development, and escape behavior in Epidalea calamita embryos and larvae.

    PubMed

    García-Muñoz, E; Guerrero, F; Parra, G

    2009-04-01

    Epidalea calamita embryos at Gosner stages 3 and 19, and larvae at Gosner stage 25, were exposed to different copper sulfate concentrations, ranging from 0.05 to 0.40 mg Cu L(-1), in 96-h acute toxicity tests. Embryonic and larval mortality, development, growth, and larval escape behavior were evaluated. LC(50) at 96 h obtained at Gosner stages 3, 19, and 25 were 0.22, 0.08, and 0.11 mg Cu L(-1), respectively. Embryonic and larval developments were delayed after 96 h of copper sulfate exposure. Growth was also affected and individuals in control treatments grew to twice the size of those exposed to copper concentrations over 0.2 mg Cu L(-1) during the experiments initiated at Gosner stage 19. Escape behavior was altered after 96 h of copper sulfate exposure; larvae showed shorter distances moved and abnormal displacement types. However, after 4 days of recovery process, most of the larvae showed normal escape behavior. For amphibians that develop in temporary wetlands, increased development time, lower size, and altered escape behavior might have repercussions on the number of individuals that can successfully complete metamorphosis and, consequently, on recruitment.

  2. Crystal structures of copper(II) nitrate, copper(II) chloride, and copper(II) perchlorate complexes with 2-formylpyridine semicarbazone

    SciTech Connect

    Chumakov, Yu. M.; Tsapkov, V. I.; Antosyak, B. Ya.; Bairac, N. N.; Simonov, Yu. A.; Bocelli, G.; Pahontu, E.; Gulea, A. P.

    2009-05-15

    Compounds dinitrato(2-formylpyridinesemicarbazone)copper (I), dichloro(2-formylpyridinesemicarbazone) copper hemihydrate (II), and bis(2-formylpyridinesemicarbazone)copper(2+) perchlorate hydrate (III) are synthesized and their crystal structures are determined. In compounds I-III, the neutral 2-formylpyridine semicarbazone molecule (L) is tridentately attached to the copper atom via the N,N,O set of donor atoms. In compounds I and II, the Cu: L ratio is equal to 1: 1, whereas, in III, it is 1: 2. In complex I, the coordination sphere of the copper atom includes two nitrate ions with different structural functions in addition to the L ligand. The structure is built as a one-dimensional polymer in which the NO{sub 3} bidentate group fulfills a bridging function. The coordination polyhedron of the copper(2+) atom can be considered a distorted tetragonal bipyramid (4 + 1 + 1). Compound II has an ionic structure in which the main element is the [CuLCl{sub 2} . Cu(H{sub 2}O)LCl]{sup +} dimer. In the dimer, the copper atoms are linked via one of the {mu}{sub 2}-bridging chlorine atoms. The coordination polyhedra of the central atoms of the Cu(H{sub 2})LCl and CuLCl{sub 2} complex fragments are tetragonal bipyramid and tetragonal pyramid, respectively. In compound III, the copper atom is octahedrally surrounded by two L ligands in the mer configuration.

  3. Relative bioavailability of copper in tribasic copper chloride to copper in copper sulfate for laying hens based on egg yolk and feather copper concentrations.

    PubMed

    Kim, J W; Kim, J H; Shin, J E; Kil, D Y

    2016-07-01

    This experiment was conducted to determine the relative bioavailability (RBV) of Cu in tribasic copper chloride (TBCC) to Cu in copper sulfate (monohydrate form; CuSO4·H2O) for layer diets based on egg yolk and feather Cu concentrations. A total of 252, 72-wk-old Hy-Line Brown laying hens were allotted to 1 of 7 treatments with 6 replicates consisting of 6 hens per replicate in a completely randomized design. Hens were fed corn-soybean meal-based basal diets supplemented with 0 (basal), 100, 200, or 300 mg/kg Cu from CuSO4 or TBCC for 4 wk. Results indicated that egg production, egg weight, and egg mass were not affected by dietary treatments. However, increasing inclusion levels of Cu in diets from CuSO4 decreased (P < 0.05) feed conversion ratio (FCR), whereas increasing inclusion levels of Cu in diets from TBCC did not affect FCR, indicating significant interaction (P < 0.05). Increasing inclusion levels of Cu from TBCC or CuSO4 increased (P < 0.05) Cu concentrations of egg yolk and feathers. Feather Cu concentrations were greater (P < 0.01) for hens fed diets containing CuSO4 than for hens fed diets containing TBCC. The values for the RBV of Cu in TBCC to Cu in CuSO4 based on log10 transformed egg yolk and feather Cu concentrations were 107.4% and 69.5%, respectively. These values for the RBV of Cu in TBCC did not differ from Cu in CuSO4 (100%). The RBV measured in egg yolk did not differ from the RBV measured in feather. In conclusion, the RBV of Cu in TBCC to Cu in CuSO4 can be determined using Cu concentrations of egg yolk and feathers although the values depend largely on target tissues of laying hens. For a practical application, however, the RBV value of Cu in TBCC to Cu in CuSO4 could be 88.5% when the RBV values determined using egg yolk and feather Cu concentrations were averaged.

  4. Toxicity of copper sulfate to Flavobacterium psychrophilum and Rainbow Trout eggs.

    PubMed

    Wagner, Eric J; Oplinger, Randall W

    2013-06-01

    Tests were conducted to determine the concentrations of copper sulfate needed to kill Flavobacterium psychrophilum, the cause of bacterial coldwater disease, either in vitro or on Rainbow Trout Oncorhynchus mykiss eggs. For the in vitro test, a plastic strip dipped in a solution of F. psychrophilum was exposed for 15 min to copper sulfate solutions of 0, 1, 5, 10, 20, 35, 50, 75, or 100 mg/L. Bacteria were "too numerous to count" at concentrations ≤10 mg/L CuSO4; significant reductions in prevalence relative to untreated controls were noted for concentrations ≥35 mg/L. However, CFUs were still observed at 50 and 75 mg/L (20% of plates with tryptone yeast extract salts media). No yellow-pigmented CFUs typical of F. psychrophilum were observed at 100 mg/L CuSO4. For the in vivo test, eggs were exposed for 15 min to 100, 300, 500, and 700 mg/L CuSO4 or 100 mg/L iodine (control). Survival to hatch was significantly lower at 500 (44.3 ± 15.2%, mean ± SD) or 700 mg/L CuSO4 (1.7 ± 0.8%) than for controls treated with 100 mg/L iodine (93.6 ± 0.9%) or at copper sulfate concentrations ≤300 mg/L. The 15-min LD50 and LD10 for copper sulfate were 461 mg/L (95% confidence interval: 457-466 mg/L) and 259 mg/L (251-266 mg/L). The prevalence of yellow CFUs at 100 mg/L CuSO4 (40.0%) was significantly higher than in untreated controls. Significant reductions in yellow CFUs were achieved using 300, 500, or 700 mg/L CuSO4 (7.5, 2.5, or 0.0% of plates with CFUs, respectively) or 100 mg/L iodine (2.5%), relative to untreated control eggs. Overall, since the concentrations of copper sulfate required to eliminate F. psychrophilum were toxic to the eggs, copper sulfate is not recommended for coldwater disease control in Rainbow Trout eggs based on conditions and parameters in this study.

  5. Mixed metal copper(II)-nickel(II) and copper(II)-zinc(II) complexes of multihistidine peptide fragments of human prion protein.

    PubMed

    Jószai, Viktória; Turi, Ildikó; Kállay, Csilla; Pappalardo, Giuseppe; Di Natale, Giuseppe; Rizzarelli, Enrico; Sóvágó, Imre

    2012-07-01

    Mixed metal copper(II)-nickel(II) and copper(II)-zinc(II) complexes of four peptide fragments of human prion protein have been studied by potentiometric, UV-vis and circular dichroism spectroscopic techniques. One peptide contained three histidyl residues: HuPrP(84-114) with H85 inside and H96, H111 outside the octarepeat domain. The other three peptides contained two histidyl residues; H96 and H111 for HuPrP(91-115) and HuPrP(84-114)H85A while HuPrP(84-114)H96A contained the histidyl residues at positions 85 and 111. It was found that both histidines of the latter peptides can simultaneously bind copper(II) and nickel(II) ions and dinuclear mixed metal complexes can exist in slightly alkaline solution. One molecule of the peptide with three histidyl residues can bind two copper(II) and one nickel(II) ions. H85 and H111 were identified as the major copper(II) and H96 as the preferred nickel(II) binding sites in mixed metal species. The studies on the zinc(II)-PrP peptide binary systems revealed that zinc(II) ions can coordinate to the 31-mer PrP peptide fragments in the form of macrochelates with two or three coordinated imidazol-nitrogens but the low stability of these complexes cannot prevent the hydrolysis of the metal ion in slightly alkaline solution. These data provide further support for the outstanding affinity of copper(II) ions towards the peptide fragments of prion protein but the binding of nickel(II) can significantly modify the distribution of copper(II) among the available metal binding sites.

  6. Effects of copper on sulfate reduction in bacterial consortia enriched from metal-contaminated and uncontaminated sediments.

    PubMed

    Jin, Song; Drever, James I; Colberg, Patricia J S

    2007-02-01

    The effects of copper amendments on bacterial sulfate reduction in enrichment cultures obtained from two types of freshwater sediment were examined. Sulfate-reducing bacterial (SRB) consortia were enriched from pond sediment with no known history of metal contamination (uncontaminated) and from reservoir sediment with a well-documented history of metal contamination (metal-contaminated). The rates and extent of sulfate reduction in each sediment type in the absence of added copper were indistinguishable. With amendments of 0.8 mg/L copper, no inhibitory effects on sulfate reduction were observed in either consortium type. At 8.0 mg/L copper, activity in uncontaminated SRB consortia was significantly inhibited, as evidenced by a delay in and decreased rate of sulfate reduction; sulfidogenesis in metal-contaminated consortia was apparently unaffected. When the dissolved copper concentration was 30.0 mg/L, sulfidogenic activity in pond sediment consortia was completely inhibited. The rate of sulfate reduction temporarily decreased in the metal-contaminated enrichments but recovered after a short time. In active microcosms, copper was precipitated as CuS. The results of this study suggest that SRB from metal-contaminated environments have a markedly higher metal tolerance than those enriched from uncontaminated environments. The most significant inference from this work is that metal sulfide formation alone does not explain observed differences in metal tolerance between SRB consortia enriched from uncontaminated sediments and those that are derived from metal-contaminated sediments.

  7. Sulfate reduction and copper precipitation by a Citrobacter sp. isolated from a mining area.

    PubMed

    Qiu, Rongliang; Zhao, Benliang; Liu, Jinling; Huang, Xiongfei; Li, Qingfei; Brewer, Eric; Wang, Shizhong; Shi, Ning

    2009-05-30

    A strain of sulfate-reducing bacteria, designated strain 'DBM', was isolated from sediments of a mining area. Phylogenetic analysis of the 16S rRNA gene sequence of the isolate revealed that it was related to members of the genus Citrobacter, with C. AzoR-4, C. freundii, C. braakii and C. werkmanii being the most closely related species (sequence similarity up to 98%). Few studies have been done on sulfate reduction ability in Citrobacter. Electron microscopy studies showed that the morphology of the strain DBM was rod-shaped. Strain DBM reduced 10mM of sulfate completely to sulfide within 7d, and it recovered its sulfate reduction ability after 7d of aerobic growth. Furthermore, strain DBM effectively precipitated 0.40 mM copper during its growth. Elemental composition of the resulting microbial precipitate was studied using electro-dispersive X-ray spectroscopy, and it was found that the ratio of S:Cu was 1.07. The result was consistent with the formation of copper sulfide. Heavy metal precipitation by Citrobacter sp. strain DBM was a phenomenon that may be useful in the bioremediation of acid mine drainage.

  8. Removal of copper in an integrated sulfate reducing bioreactor-crystallization reactor system.

    PubMed

    Sierra-Alvarez, Reyes; Hollingsworth, Jeremy; Zhou, Michael S

    2007-02-15

    Removal of copper was investigated using an innovative water treatment system integrating a sulfidogenic bioreactor with a fluidized-bed crystallization reactor containing fine sand to facilitate the recovery of copper as a purified copper-sulfide mineral. The performance of the system was tested using a simulated semiconductor manufacturing wastewater containing high levels of Cu2+ (4-66 mg/L), sulfate, and a mixture of citrate, isopropanol, and polyethylene glycol (Mn 300). Soluble copper removal efficiencies exceeding 99% and effluent copper concentrations averaging 89 micog/L were demonstrated in the two-stage system, with near complete metal removal occurring in the crystallizer. Copper crystals deposited on sand grains were identified as covellite (CuS). The removal of organic constituents did not exceed 70% of the initial chemical oxygen demand due to incomplete degradation of isopropanol and its breakdown product (acetone). Taken as a whole, these results indicate the potential of this novel reactor configuration for the simultaneous removal of heavy metals and organic constituents. The ability of this process to recover heavy metals in a purified form makes it particularly attractive for the treatment of contaminated aqueous streams, including industrial wastewaters and acid mine drainage.

  9. Heteroleptic bis(dipyrrinato)copper(II) and nickel(II) complexes.

    PubMed

    Toyoda, Ryojun; Tsuchiya, Mizuho; Sakamoto, Ryota; Matsuoka, Ryota; Wu, Kuo-Hui; Hattori, Yohei; Nishihara, Hiroshi

    2015-09-14

    Heteroleptic bis(dipyrrinato)copper(II) and nickel(II) complexes are synthesized. Their structures are determined by X-ray diffraction analysis, and their properties are investigated by using cyclic voltammetry, chronocoulometry, and UV/vis absorption spectroscopy.

  10. Quantification of toxic and inhibitory impact of copper and zinc on mixed cultures of sulfate-reducing bacteria.

    PubMed

    Utgikar, Vivek P; Tabak, Henry H; Haines, John R; Govind, Rakesh

    2003-05-05

    The adverse effects of copper and zinc on an acetate-utilizing mixed cultures of sulfate-reducing bacteria (SRB) at concentrations below the toxic concentration (minimum metal concentration at which no sulfate reduction is observed) are reported in this paper. Mathematical models were developed to incorporate the toxic and inhibitory effects (defined as the reduction in bacterial population upon exposure to the metal and the decrease in the metabolic rate of sulfate reduction by the SRB, respectively) into the sulfate-reduction biokinetics. The characteristic toxicity and inhibition constants were obtained from the measurements of bacterial populations and dissolved metal concentrations in serum bottle studies conducted at 35 degrees C and pH 6.6. Both copper and zinc had toxic and inhibitory effects on SRB. The toxicity constants for copper and zinc were 10.6 and 2.9 mM(-1), respectively, indicating that exposure to copper resulted in a higher mortality of SRB than did exposure to zinc. The values of the inhibition constants were found to be 17.9 +/- 2.5 and 25.2 +/- 1.0 mM(-1) for copper and zinc, respectively. This implies that dissolved zinc was slightly more inhibitory to SRB than copper. The models presented in the paper can be used to predict the response of a sulfate-reduction bioreactor to heavy metals during acid mine drainage treatment.

  11. PAPST1 regulates sulfation of heparan sulfate proteoglycans in epithelial MDCK II cells.

    PubMed

    Dick, Gunnar; Akslen-Hoel, Linn Kristin; Grøndahl, Frøy; Kjos, Ingrid; Maccarana, Marco; Prydz, Kristian

    2015-01-01

    Proteoglycan (PG) sulfation depends on activated nucleotide sulfate, 3'-phosphoadenosine-5'-phosphosulfate (PAPS). Transporters in the Golgi membrane translocate PAPS from the cytoplasm into the organelle lumen where PG sulfation occurs. Silencing of PAPS transporter (PAPST) 1 in epithelial MDCK cells reduced PAPS uptake into Golgi vesicles. Surprisingly, at the same time sulfation of heparan sulfate (HS) was stimulated. The effect was pathway specific in polarized epithelial cells. Basolaterally secreted proteoglycans (PGs) displayed an altered HS sulfation pattern and increased growth factor binding capacity. In contrast, the sulfation pattern of apically secreted PGs was unchanged while the secretion was reduced. Regulation of PAPST1 allows epithelial cells to prioritize between PG sulfation in the apical and basolateral secretory routes at the level of the Golgi apparatus. This provides sulfation patterns that ensure PG functions at the extracellular level, such as growth factor binding.

  12. Toxic effects of copper sulfate on the brains of term Hubbard broiler chicks: a stereological and biochemical study.

    PubMed

    Oğuz, E O; Enli, Y; Tufan, A C; Turgut, G

    2014-01-01

    Copper sulfate can cause different pathologies in different organ systems during development. We determined the effects of toxic levels of copper sulfate on brain development in term Hubbard broiler chicks using stereological and biochemical analyses. Hubbard broiler chicken eggs were divided into three groups: controls with no treatment, sham-treated animals and an experimental group. On day 1, 0.1 ml saline was injected into the air chambers of the sham and experimental groups. The experimental group received also 50 μg copper sulfate. At term (day 21), all chick brains were removed and their volumes were determined using the Cavalieri volume estimation. Parallel biochemical analyses were carried out for glutathione and malondialdehyde levels in the brain tissues as indicators of oxidative damage. With copper treatment, the mean brain volume (8079 μm(3)) was significantly decreased compared to both the control (10075 μm(3)) and sham (9547 μm(3)) groups. Copper treatment (143.8 nmol/g tissue) showed significantly decreased malondialdehyde levels compared to the control (293.6 nmol/g tissue) and sham groups (268.8 nmol/g tissue). Copper treatment (404.5 nmol/g tissue) showed significantly increased malondialdehyde levels compared to the control (158.6 nmol/g tissue) and sham (142.8 nmol/g tissue) groups. The morphological and biochemical parameters we measured demonstrated that in term Hubbard broiler chicks, toxic levels of copper sulfate cause developmental and oxidative brain damage.

  13. Copper sulfate pentahydrate reduced epithelial cytotoxicity induced by lipopolysaccharide from enterogenic bacteria.

    PubMed

    Feyzi, Adel; Delkhosh, Aref; Nasrabadi, Hamid Tayefi; Cheraghi, Omid; Khakpour, Mansour; Barekati-Mowahed, Mazyar; Soltani, Sina; Mohammadi, Seyede Momeneh; Kazemi, Masoumeh; Hassanpour, Mehdi; Rezabakhsh, Aysa; Maleki-Dizaji, Nasrin; Rahbarghazi, Reza; Namdarian, Reza

    2017-02-26

    The over usage of multiple antibiotics contributes to the emergence of a whole range of antibiotic-resistant strains of bacteria causing enterogenic infections in poultry science. Therefore, finding an appropriate alternative natural substance carrying an antibacterial capacity would be immensely beneficial. It has been previously discovered that the different types of cupric salts, especially copper sulfate pentahydrate (CuSO4·5H2O), to carry a potent bactericidal capacity. We investigated the neutralizing effect of CuSO4·5H2O (6.25μg/ml) on the reactive oxygen species generation, and expression of MyD88, an essential adaptor protein of Toll-like receptor, and NF-κB in three intestinal epithelial cell lines exposed to 50ng/ml lipopolysaccharide. In order to find the optimal cupric sulfate concentration without enteritis-inducing toxicity, broiler chickens were initially fed with water containing 0.4, 0.5, and 1mg/l during a period of 4days. After determination of appropriate dosage, two broiler chickens and turkey flocks with enteritis were fed with cupric compound for 4days. We found that cupric sulfate can lessen the cytotoxic effect of lipopolysaccharide by reducing the reactive oxygen species content (p<0.05). Additionally, the expression of MyD88 and NF-κB was remarkably down-regulated in the presence of lipopolysaccharide and cupric sulfate. The copper sulfate in doses lower than 0.4mg/ml expressed no cytotoxic effect on the liver, kidney, and the intestinal tract while a concentration of 0.5 and 1mg/ml contributed to a moderate to severe tissue injuries. Pearson Chi-Square analysis revealed the copper cation significantly diminished the rate of mortality during 4-day feeding of broiler chicken and turkey with enteritis (p=0.000). Thus, the results briefed above all confirm the potent anti-bactericidal feature of cupric sulfate during the course of enteritis.

  14. Electrochemical treatment of acidic aqueous ferrous sulfate and copper sulfate as models for acid mine drainage.

    PubMed

    Bunce, N J; Chartrand, M; Keech, P

    2001-12-01

    Acid mine drainage (AMD) is a serious environmental problem in the mining industry. The present work describes electrolytic reduction of solutions of synthetic AMD, comprising FeSO4/H2SO4 and CuSO4/H2SO4, in flow-through cells whose anode and cathode compartments were separated using ion exchange membranes. In the case of FeSO4/H2SO4 at constant flow rate, the pH of the effluent from the catholyte increased progressively with current at a variety of cathodes, due to electrolytic reduction of H+ ions to elemental hydrogen. Near-quantitative removal of iron was achieved by sparging air into the catholyte effluent, thereby precipitating iron outside the electrochemical cell, and avoiding fouling of the electrodes. The anode reaction was the oxidation of water to O2, a proton-releasing process. Using cation exchange membranes and sodium sulfate as the supporting electrolyte in the anode compartment, the efficiency of the process was compromised at high currents by transport of H+ competitively with Na+ from the anode to the cathode compartments. Higher efficiencies were obtained when anion exchange membranes were used, and in this case no additional supporting electrolyte other than dilute H2SO4 was needed, the net reaction being the electrochemically driven transfer of the elements of H2SO4 from the cathode to the anode compartments. Current efficiencies approximately 50% were achieved, the loss of efficiency being accounted for by ohmic heating of the solutions. In the case of CuSO4/H2SO4 and anion exchange membranes at high currents, reduction of Cu2+ and H+ ions and transport of SO4(2-) ions out of the catholyte caused unacceptably high potentials to be generated.

  15. Crystal structures of copper(II) chloride, copper(II) bromide, and copper(II) nitrate complexes with pyridine-2-carbaldehyde thiosemicarbazone

    SciTech Connect

    Chumakov, Yu. M.; Tsapkov, V. I.; Jeanneau, E.; Bairac, N. N.; Bocelli, G.; Poirier, D.; Roy, J.; Gulea, A. P.

    2008-09-15

    The crystal structures of chloro-(2-formylpyridinethiosemicarbazono)copper dimethyl sulfoxide solvate (I), bromo-(2-formylpyridinethiosemicarbazono)copper (II), and (2-formylpyridinethiosemicarbazono)copper(II) nitrate dimethyl sulfoxide solvate (III) are determined using X-ray diffraction. In the crystals, complexes I and II form centrosymmetric dimers in which the thiosemicarbazone sulfur atom serves as a bridge and occupies the fifth coordination site of the copper atom of the neighboring complex related to the initial complex through the center of symmetry. In both cases, the coordination polyhedron of the complexing ion is a distorted tetragonal bipyramid. Complex III in the crystal structure forms polymer chains in which the copper atom of one complex forms the coordination bond with the thicarbamide nitrogen atom of the neighboring complex. In this structure, the coordination polyhedron of the central atom is an elongated tetragonal bipyramid. It is established that complexes I-III at a concentration of 10{sup -5} mol/l selectively inhibit the growth of 60 to 90 percent of the cancer tumor cells of the human myeloid leukemia (HL-60).

  16. Effects of low molecular weight chondroitin sulfate on type II collagen-induced arthritis in DBA/1J mice.

    PubMed

    Cho, So Yean; Sim, Joon-Soo; Jeong, Choon Sik; Chang, Seung Yeup; Choi, Don Woong; Toida, Toshihiko; Kim, Yeong Shik

    2004-01-01

    In order to evaluate the improvement in the treatment of chronic arthritis, we investigated chondroitin sulfate depolymerization product (low molecular weight chondroitin sulfate, LMWCS) and intact chondroitin sulfate (CS) in vitro and in vivo. LMWCS was prepared by a chemical depolymerization process induced by hydrogen peroxide in the presence of copper salts. LMWCS (300 mg/kg) and CS (1200 mg/kg) were orally administered to DBA/1J mice once daily for 14 d prior to initial immunization with type II collagen. Their elastase activities and the production of cytokines in sera were examined on type II collagen-induced arthritis in DBA/1J mice. We also compared the paracellular transport of LMWCS and CS across Caco-2 cell monolayers and examined the inhibitory effects on elastase activities. LMWCS inhibited elastase activity slightly, but CS did not show inhibition. Hind paw edema was significantly decreased by LMWCS treatment. Levels of anti-type II collagen antibody and tumor necrosis factor-alpha (TNF-alpha) in sera were also reduced by LMWCS treatment but not in case of CS, although no significant difference was observed between LMWCS and CS on interleukin-6 (IL-6) induction. The LMWCS preparation showed preventive effects on the type II collagen-induced arthritis in DBA/1J mice and better permeability through Caco-2 cells.

  17. The Amyloid Precursor Protein of Alzheimer's Disease in the Reduction of Copper(II) to Copper(I)

    NASA Astrophysics Data System (ADS)

    Multhaup, Gerd; Schlicksupp, Andrea; Hesse, Lars; Beher, Dirk; Ruppert, Thomas; Masters, Colin L.; Beyreuther, Konrad

    1996-03-01

    The transition metal ion copper(II) has a critical role in chronic neurologic diseases. The amyloid precursor protein (APP) of Alzheimer's disease or a synthetic peptide representing its copper-binding site reduced bound copper(II) to copper(I). This copper ion-mediated redox reaction led to disulfide bond formation in APP, which indicated that free sulfhydryl groups of APP were involved. Neither superoxide nor hydrogen peroxide had an effect on the kinetics of copper(II) reduction. The reduction of copper(II) to copper(I) by APP involves an electron-transfer reaction and could enhance the production of hydroxyl radicals, which could then attack nearby sites. Thus, copper-mediated toxicity may contribute to neurodegeneration in Alzheimer's disease.

  18. Water soluble sodium sulfate nanorods as a versatile template for the designing of copper sulfide nanotubes.

    PubMed

    Das, Gautam; Kakati, Nitul; Lee, Seok Hee; Karak, Niranjan; Yoon, Young Soo

    2014-06-01

    The present study reports the use of water soluble sodium sulfate (Na2SO4) nanorods as a versatile template for generation of tubular copper sulfide (CuS) nanostructures. The Na2SO4 nanorods were synthesized from ammonium sulfate (NH4)2SO4 and sodium hydroxide (NaOH), under refluxing condition. The shape and morphology control of the Na2SO4 nanorods were studied with respect to nature of surfactant used and reactant mole ratio. While, PVP mole ratio was important to obtain homogeneous nanorods. Uniform and stable nanotubes of CuS were than obtained by the dissolution of the nanorods in water. The use of simple chemicals for synthesis of such nanotube templates opens the prospect for wide scale downstream applications.

  19. Effect of dietary copper sulfate, Aureo SP250, or clinoptilolite on ureolytic bacteria found in the pig large intestine.

    PubMed

    Varel, V H; Robinson, I M; Pond, W G

    1987-09-01

    The predominant ureolytic bacteria in the pig large intestine were determined while growing pigs were fed a basal diet or basal diet plus copper sulfate, Aureo SP250, or clinoptilolite. Fecal samples were collected from four pigs fed each diet at 3, 9, and 14 weeks and analyzed for total colony counts and percent ureolytic bacteria. Fecal urease activity, ammonia nitrogen, and identity of the ureolytic bacteria were determined at 14 weeks. Copper sulfate and Aureo SP250 reduced the number of ureolytic organisms, with a marked decrease occurring in the Streptococcus spp., which made up 74% of the ureolytic isolates from the pigs on the basal diet. Other ureolytic species detected at lower concentrations were Staphylococcus spp., Selenomonas ruminantium, Bacteroides multiacidus, and Eubacterium limosum. Copper sulfate also reduced fecal urease activity (P less than 0.10). Fecal ammonia concentrations were not different between pigs fed the various diets. These data suggest that the streptococci are the most numerous ureolytic species in the pig intestinal tract and are significantly reduced by copper sulfate and Aureo SP250; however, only copper sulfate reduced intestinal urease activity.

  20. Practical method to make a discrete memristor based on the aqueous solution of copper sulfate

    NASA Astrophysics Data System (ADS)

    Merrikh-Bayat, Farshad; Parvizi, Meysam

    2016-06-01

    A new method to realize a discrete memristor is proposed. The device under study consists of a tube filled of aqueous saturated solution of copper sulfate which can be electrolyzed by using two asymmetric copper electrodes, one of which has a considerably smaller cross-sectional area than to the other one. It is shown both theoretically and experimentally that this device has exactly the properties of a memristor if it is designed such that the electrical field and the current density on the thinner electrode when it acts as anode are sufficiently large. Different aspects of the proposed discrete memristor, including pinched hysteresis loop, on-off resistance ratio and memory volatilization, are studied and experimental results are presented.

  1. Stick-slip behaviour on Au(111) with adsorption of copper and sulfate.

    PubMed

    Podgaynyy, Nikolay; Wezisla, Sabine; Molls, Christoph; Iqbal, Shahid; Baltruschat, Helmut

    2015-01-01

    Several transitions in the friction coefficient with increasing load are found on Au(111) in sulfuric acid electrolyte containing Cu ions when a monolayer (or submonolayer) of Cu is adsorbed. At the corresponding normal loads, a transition to double or multiple slips in stick-slip friction is observed. The stick length in this case corresponds to multiples of the lattice distance of the adsorbed sulfate, which is adsorbed in a √3 × √7 superstructure on the copper monolayer. Stick-slip behaviour for the copper monolayer as well as for 2/3 coverage can be observed at F N ≥ 15 nN. At this normal load, a change from a small to a large friction coefficient occurs. This leads to the interpretation that the tip penetrates the electrochemical double layer at this point. At the potential (or point) of zero charge (pzc), stick-slip resolution persists at all normal forces investigated.

  2. Stick–slip behaviour on Au(111) with adsorption of copper and sulfate

    PubMed Central

    Podgaynyy, Nikolay; Wezisla, Sabine; Molls, Christoph; Iqbal, Shahid

    2015-01-01

    Summary Several transitions in the friction coefficient with increasing load are found on Au(111) in sulfuric acid electrolyte containing Cu ions when a monolayer (or submonolayer) of Cu is adsorbed. At the corresponding normal loads, a transition to double or multiple slips in stick–slip friction is observed. The stick length in this case corresponds to multiples of the lattice distance of the adsorbed sulfate, which is adsorbed in a √3 × √7 superstructure on the copper monolayer. Stick–slip behaviour for the copper monolayer as well as for 2/3 coverage can be observed at F N ≥ 15 nN. At this normal load, a change from a small to a large friction coefficient occurs. This leads to the interpretation that the tip penetrates the electrochemical double layer at this point. At the potential (or point) of zero charge (pzc), stick–slip resolution persists at all normal forces investigated. PMID:25977853

  3. A comparison of zooplankton sampling methods in evaluating copper sulfate toxicity in outdoor microcosms

    SciTech Connect

    Hellenbrandt, S.; La Point, T.W.; Shaw, J.L.; Marshall, S.J.; Ratte, H.T.

    1994-12-31

    Six outdoor microcosms (2m{sup 3}) were used to determine copper sulfate effects on epibenthic and planktonic zooplankton community structure. Microcosms were treated three times with CuSO{sub 4} at 0, 50, 100, 200, 350, 550 {mu}g Cu/L, respectively. Zooplankton was sampled biweekly from July through October 1993. Epibenthic zooplankton was collected with an inverted funnel trap, whereas planktonic zooplankton was sampled with an integrated water column sampler. Samples were sieved through a 35 {mu}m mesh and organisms preserved with 1% Lugol`s solution and later identified to genus or species level. Both communities initially decreased in total abundance at high copper rates. However, recovery started shortly after the final Cu application. Species richness was lowest at high copper concentrations, particularly in the epi-benthic community. Epibenthic zooplankton diversity decreased at high copper rates, whereas planktonic zooplankton diversity did not. Epi-benthic zooplankton may be a sensitive indicator of chemical stress and therefore be used to assess the bioavailability of sediment-bound xenobiotics.

  4. Copper(I) electrode function of two types of copper(II) ion-selective electrodes.

    PubMed

    Neshkova, M; Sheytanov, H

    1985-08-01

    The response of two types of solid-state copper ion-selective electrodes with homogeneous membranes of CuAgSe and Cu(2-x)Se has been investigated in copper(I) solutions, prepared electrochemically by insitu generation from a copper anode in chloride medium. The selectivity coefficient K(pot)(Cu+, Cu(2+)) both types of electrodes has been determined. It is 10(-5.7) for the copper selenide sensor, and 10(-6.2) for the copper silver selenide one. These values are very close to that calculated for an exchange reaction proceeding on the electrode surface. The similarity in K(pot)(Cu+ ,Cu(2+)) values for different chalcogenidebased sensors suggests a common potential-generating mechanism. High chloride concentration does not interfere with the electrode response towards Cu(I), but distorts the electrode response to Cu(II).

  5. Copper(I) and copper(II) uranyl heterometallic hybrid materials.

    PubMed

    Weng, Zhehui; Zhang, Zhi-hui; Olds, Travis; Sterniczuk, Marcin; Burns, Peter C

    2014-08-04

    Two copper-uranium heterometallic compounds, [(UO2)3Cu(II)O2(C6NO2)5] (1) and [(UO2)Cu(I)(C6NO2)3] (2), have been synthesized by the reaction of uranyl acetate with copper salts in the presence of isonicotinic acid. Both compounds have been characterized by single-crystal X-ray diffraction, IR, Raman, and UV-vis spectroscopy. In compound 1, interactions between copper and uranium centers occur and result in a three-dimensional pillar layered structure. Compound 1 is also the first example of a heterometallic uranyl organic framework with a trinuclear U3O18 building block. Compound 2 is the first uranyl organic framework that contains monovalent copper, which arises from the reaction of Cu(II) chloride and is assumed to be due to the oxidation of chloride at low pH.

  6. Histopathological and bacterial study of Persian sturgeon fry, Acipenser persicus (Borodin, 1897) exposed to copper sulfate and potassium permanganate.

    PubMed

    Moshtaghi, Batol; Khara, Hossein; Pazhan, Zabiyollah; Shenavar, Alireza

    2016-09-01

    Persian sturgeon frys were exposed to different concentrations of copper sulfate and potassium permanganate in order to the evaluation of their impacts on bacterial load of skin, gill and surrounding water and also the histopathological alternations of gill tissue. For this purpose, the sublethal doses were determined after a pre-test and then the experiment was done in 4 (for copper sulfate: 0.07, 0.14, 026 and 0.5 mg/l) and 5 (for potassium permanganate: 0.07, 0.14, 026, 0.5 and 1 mg/l) treatments with three replicates inside the glass aquaria. Also, one group without disinfecting drug was considered as control for each experiment. The microbial and histopathological investigations were done after 96 h exposure. According to our results, a range of histopathological alternations were observed in gills tissue including mucus coagulation and secretion, hyperplasia, lamellar necrosis, hyperplasia, lamellar adhesion, haemorrhage, thickening of secondary lamellae, hypertrophy of supporter cartilage, clubbing of gill lamellae and sliming of primary lamellae. The severity of these alternations increased with increasing of the doses of the copper sulfate and potassium permanganate. The bacterial load (CFU/g) of gill, skin and surrounding water was lower in 0.07 mg/l copper sulfate treatment and 1 mg/l potassium permanganate treatment (P < 0.05) than in other treatments. In conclusion, our results showed that the certain doses of the copper sulfate and potassium permanganate have disinfecting effects on bacterial load of gill, skin and surrounding water, although this is along with some histopathological alternations. Also, it seems that the copper sulfate has higher disinfecting power than potassium permanganate.

  7. Determination of kjeldahl nitrogen in fertilizers by AOAC official methods 978.02: effect of copper sulfate as a catalyst.

    PubMed

    Abrams, Dean; Metcalf, David; Hojjatie, Michael

    2014-01-01

    In AOAC Official Method 955.04, Nitrogen (Total) in Fertilizers, Kjeldahl Method, fertilizer materials are analyzed using mercuric oxide or metallic mercury HgO or Hg) as a catalyst. AOAC Official Methods 970.02, Nitrogen (Total) in Fertilizers is a comprehensive total nitrogen (including nitrate nitrogen) method adding chromium metal. AOAC Official Method 978.02, Nitrogen (Total) in Fertilizers is a modified comprehensive nitrogen method used to measure total nitrogen in fertilizers with two types of catalysts. In this method, either copper sulfate or chromium metal is added to analyze for total Kjeldahl nitrogen. In this study, the part of AOAC Official Method 978.02 that is for nitrate-free fertilizer products was modified. The objective was to examine the necessity of copper sulfate as a catalyst for the nitrate-free fertilizer products. Copper salts are not environmentally friendly and are considered pollutants. Products such as ammonium sulfate, diammonium phosphate, monoammonium phosphate, urea-containing fertilizers such as isobutylene diurea (IBDU), and urea-triazone fertilizer solutions were examined. The first part of the study was to measure Kjeldahl nitrogen as recommended by AOAC Official Method 978.02. The second part of the study was to exclude the addition of copper sulfate from AOAC Official Method 978.02 to examine the necessity of copper sulfate as a catalyst in nitrate-free fertilizers, which was the primary objective. Our findings indicate that copper sulfate can be eliminated from the method with no significant difference in the results for the nitrogen content of the fertilizer products.

  8. Development of a standardized sediment reference toxicant test using formulated sediment and copper sulfate

    SciTech Connect

    Suedel, B.C.; Hartzell, R.S.; Williams, C.W.; Connelly, R.A.

    1994-12-31

    The lack of suitable reference toxicant tests to assess the condition or health of populations of benthic test organisms is problematic because the precision and accuracy of definitive whole sediment tests cannot be assessed without this reference. To address this need, formulated sediment was prepared to provide a consistent substrate with respect to percent solids, particle size distribution, cation exchange capacity, organic carbon, organic matter, redox potential, and pH. Hyalella azteca and Chironomus tentans were exposed for 96-h to formulated sediment amended with serial dilutions of copper sulfate. Results indicate that (1) formulated sediments can be prepared consistently between batches with minimal variability with respect to sediment characteristics, providing a consistent test substrate; (2) when combined with formulated sediment, copper sulfate is a suitable sediment reference toxicant for assessing the condition and health of H. azteca and C tentans populations; and (3) formulated sediment provides a suitable substrate for H. azteca and C tentans (control survival > 80%). This method provides a means by which the health and sensitivity of benthic test organisms can be assessed and provides a measure of precision within and among laboratories through time.

  9. The Thermal Decomposition of Basic Copper(II) Sulfate.

    ERIC Educational Resources Information Center

    Tanaka, Haruhiko; Koga, Nobuyoshi

    1990-01-01

    Discussed is the preparation of synthetic brochantite from solution and a thermogravimetric-differential thermal analysis study of the thermal decomposition of this compound. Other analyses included are chemical analysis and IR spectroscopy. Experimental procedures and results are presented. (CW)

  10. Chronic copper toxicosis in sheep following the use of copper sulfate as a fungicide on fruit trees.

    PubMed

    Oruc, Hasan H; Cengiz, Murat; Beskaya, Atilla

    2009-07-01

    Between January and October 2006, 15 Chios sheep died in a field located near a factory in Orhangazi, Bursa, Turkey. In addition, in May 2007, 2 ewes died after aborting in the same field. Clinical signs in affected animals prior to death were anorexia, hematuria, icterus, incoordination, and ptyalism. Postmortem findings included generalized icterus; yellow, friable livers; distended gallbladders with dense, dark bile; and dark, hypertrophic kidneys with hemorrhage. Copper (Cu) concentrations were measured in multiple specimens of the following: 9 sera, 3 livers, 3 kidneys, 4 plants (including 2 artichoke leaf specimens), 3 soil samples, and 1 drinking water sample. High Cu concentrations were present in the livers, kidneys, and sera of dead sheep, as well as in the vegetation and soil samples from the field. Chronic Cu toxicosis was confirmed as the cause of death attributed primarily to the use of copper sulfate as a fungicide for fruit trees within the field. In addition, factory dust containing Cu might have been an additional factor in the toxicosis.

  11. Rofecoxib prevents ctdsDNA against damage induced by copper sulfate and ultraviolet B radiation in vitro study.

    PubMed

    Al-Nimer, Marwan S M; Al-Deen, Suad M; Abdul Lateef, Zainab W

    2010-12-01

    Rofecoxib is a selective cyclooxygenase COX-2 enzyme inhibitor with chemoprotective effect against cancer in experimental models. This study aimed to investigate the effect of rofecoxib against ctds DNA damage induced by copper ions or ultraviolet (UV)B radiation. Aliquot ctdsDNA samples were incubated with copper sulfate solution (50 nmol) and rofecoxib (0.8 mol) was added either before or after the admixing the ctdsDNA with copper sulfate. In another experimental series, aliquot of ctdsDNA were exposed to UVB radiation for 30 min in absence or presence of rofecoxib. Rofecoxib significantly attenuated the separation of double strands of DNA (detected by increase the absorbance of DNA at 260 nm) induced by Cu ions. Rofecoxib significantly offered protection against UVB-induced DNA damage. It is concluded that rofecoxib offered protection against copper ions or UVB induced-DNA damage via different mechanisms not related to the inhibition COX-2.

  12. Spectrophotometric determination of copper(II) with o-bromophenylfluorone.

    PubMed

    Yamaguchi, Takako; Samma, Megumi; Kamino, Shinichiro; Matsushita, Momoka; Hashimoto, Tomoyuki; Fujita, Yoshikazu

    2009-12-01

    A simple, reliable and sensitive spectrophotometric method for the determination of copper(II) was established with o-bromophenylfluorone (OBPF), a novel chemical probe, in the presence of poly(N-vinylpyrrolidone). Beer's law was obeyed in the range of 8-160 ng ml(-1), with an apparent molar absorptivity at 570 nm, the relative standard deviation being 3.64 x 10(5) dm3 mol(-1) cm(-1) and 0.72% (n = 5). This method was applied to the recovery tests of copper(II) in human urine, bovine serum and tap water; the results were satisfactory.

  13. The Effect of Ferrous Sulfate on Sulfide-Induced Corrosion of Copper-Base Condenser Alloys in Aerated Seawater.

    DTIC Science & Technology

    1982-01-01

    been further 8-16 enhanced by the addition of iron to the seawater. This iron has been introduced either through addition of ferrous sulfate or by...direct oxidation of an iron "waster piece" using an externally applied current. 6 North and Pryor conducted experiments on copper in sodium chloride... iron -containing surface films on copper alloys. 15 Gasparini, et al, built upon the work of North and Pryor by investigating the colloidal chemistry

  14. Sorption of copper(II) and silver(I) by four bacterial exopolysaccharides.

    PubMed

    Deschatre, M; Ghillebaert, F; Guezennec, J; Colin, C Simon

    2013-11-01

    Metal remediation was studied by the sorption of analytical grade copper Cu(II) and silver Ag(I) by four exopolysaccharides (EPS) produced by marine bacteria. Colorimetric analysis showed that these EPS were composed of neutral sugars, uronic acids (>20 %), acetate, and sulfate (29 %). Metal sorption experiments were conducted in batch process. Results showed that the maximum sorption capacities calculated according to Langmuir model were 400 mg g(-1) EPS (6.29 mmol g(-1)) and 333 mg g(-1) EPS (3.09 mmol g(-1)) for Cu(II) and Ag(I), respectively. Optimum pH values of Ag(I) sorption were determined as 5.7. Experiment results also demonstrated the influence of initial silver concentration and EPS concentrations. Microanalyzing coupled with scanning electron microscopy demonstrated the presence of metal and morphological changes of the EPS by the sorption of metallic cations. The Fourier transform infrared spectroscopy analysis indicated possible functional groups (e.g., carboxyl, hydroxyl, and sulfate) of EPS involved in the metal sorption processes. These results showed that EPS from marine bacteria are very promising for copper and silver remediation. Further development in dynamic and continuous process at the industrial scale will be established next.

  15. Modeling and experimental validation of electroplating deposit distributions in copper sulfate solutions

    NASA Astrophysics Data System (ADS)

    Robison, Mark Robert

    Uniform deposits are typically desired in electrodeposition; however, the geometry of the deposited surface often makes a uniform deposit difficult to achieve. The objectives of this thesis are to provide experimental and modeling data for deposit uniformity of several geometries in a copper sulfate solution and to create a model capable of predicting deposit uniformity on any geometry. Bench scale electroplating cells were set up to test deposit distributions of multiple geometries as well as to test deposit uniformity with varying copper concentrations and temperatures ranging from 30 g/L to 50 g/L Cu2+ and 30 °C to 60 °C. The deposit uniformity was determined by cross-sectioning the samples. Models were generated using a finite element analysis-based software package named COMSOL Multiphysics. The model results were compared to experimental results to verify model accuracy. Model results were determined to be accurate as long as the cathode size was not too small. In addition, a numerical model was developed based on cell geometry, current density, and limiting current density. This numerical model was compared with the COMSOL model, and the results show very good agreement between the two models. Results from the electrodeposition experiments, COMSOL model, and numerical model can be used to predict copper electrodeposition profiles and uniformity in a wide range of conditions and geometries.

  16. Electrochemical synthesis and structural characterization of a novel mixed-valence copper(I)-copper(II) complex: {[bis(ethylenediamine)copper(II)] bis[diiodocuprate(I)]}.

    PubMed

    Fotouhi, Lida; Dehghanpour, Saeed; Heravi, Majid M; Ardakani, Mahboobeh Dashti

    2007-07-12

    A novel, mixed-valent copper(I)-copper(II) complex, {[bis(ethylene-diamine)copper(II)] bis[diiodocuprate(I)]} (1), has been prepared by electrochemical dissolution of a sacrificial copper anode in a solution of ethylenediamine (en), I2 and tetraethylammoniumperchlorate (TEAP) as supporting electrolyte in acetonitrile (AcN)and characterized by single-crystal X-ray structure determination. The crystal structure of the complex 1 shows that it consists of a CuI2 polymer formed from I- ligands bridging Cu(I) ions, with a nearly square planar geometry of bivalent Cu(II) atoms chelated by two ethylenediamine ligands. The results also show that direct electrosynthesis of the complex had high current efficiency, purity and electrolysis yield.

  17. Copper avoidance and mortality of juvenile brown trout (Salmo trutta) in tests with copper-sulfate-treated water from West Branch Reservoir, Putnam County, New York

    USGS Publications Warehouse

    Baldigo, Barry P.; Baudanza, T.P.

    2001-01-01

    Copper-avoidance tests and acute-toxicity (mortality) tests on hatchery-reared, young-of- the-year brown trout (salmo trutta) were conducted with water from West Branch Reservoir to assess the avoidance response to copper sulfate treatment, which is used occasionally by New York City Department of Environmental Protection to decrease phytoplankton populations in the reservoir. Avoidance-test results indicate that juvenile brown trout tend to avoid dissolved copper concentrations greater than about 55 ?g/L (micrograms per liter), which is the approximate avoidance-response threshold. The mean net avoidance response of brown trout to dissolved copper concentrations of 70 and 100 ?g/L, and possibly 80 ?g/L, was significantly different (at a = 0.1) from the mean net avoidance response of fish to control (untreated) water and to treated water at most other tested concentrations. Mortality-test results indicate that the 96-hr median lethal concentration (LC50) of dissolved copper was 61.5 ?g/L. All (100 percent) of the brown trout died at a dissolved copper concentration of 85 ?g/L, many died at concentrations of 62 ?g/L and 70 ?g/L, and none died in the control waters (7 ?g/L) or at concentrations of 10, 20, or 45 ?g/L. The estimated concentration of dissolved copper that caused fish mortality (threshold) was 53.5 ?g/L, virtually equivalent to the avoidance-response threshold. Additional factors that could affect the copper-avoidance and mortality response of individual brown trout and their populations in West Branch Reservoir include seasonal variations in certain water-quality parameters, copper-treatment regimes, natural fish distributions during treatment, and increased tolerance due to acclimation. These warrant additional study before the findings from this study can be used to predict the effects that copper sulfate treatments have on resident fish populations in New York City reservoirs.

  18. Copper(II) complexes of rat amylin fragments.

    PubMed

    Kállay, Csilla; Dávid, Agnes; Timári, Sarolta; Nagy, Eszter Márta; Sanna, Daniele; Garribba, Eugenio; Micera, Giovanni; De Bona, Paolo; Pappalardo, Giuseppe; Rizzarelli, Enrico; Sóvágó, Imre

    2011-10-14

    The fragments of rat amylin rIAPP(17-29) (Ac-VRSSNNLGPVLPP-NH(2)), rIAPP(17-22) (Ac-VRSSNN-NH(2)), rIAPP(19-22) (Ac-SSNN-NH(2)) and rIAPP(17-20) (Ac-VRSS-NH(2)) together with the related mutant peptides (Ac-VASS-NH(2) and Ac-VRAA-NH(2)) have been synthesized and their copper(II) complexes studied by potentiometric, UV-Vis, CD and EPR spectroscopic methods. Despite the lack of any common strongly coordinating donor functions some of these fragments are able to bind copper(II) ions in the physiological pH range. The longest fragment rat amylin(17-29) keeps one equivalent copper(II) ion in solution in the whole pH range, while two other peptides Ac-VRSSNN-NH(2) and Ac-SSNN-NH(2) are also able to interact with copper(II) ions in the slightly alkaline pH range. According to the spectral parameters of the complexes, the peptides can be classified into two different categories: (i) the tetrapeptides Ac-VRSS-NH(2), Ac-VASS-NH(2) and Ac-VRAA-NH(2) can interact with copper(II) only under strongly alkaline conditions (pH > 10.0) and the formation of only one species with four amide nitrogen coordination can be detected; (ii) the peptides Ac-VRSSNNLGPVLPP-NH(2), Ac-VRSSNN-NH(2) and Ac-SSNN-NH(2) can form complexes above pH 6.0 with the major stoichiometries [CuH(-2)L], [CuH(-3)L](-) and [CuH(-4)L](2-). These data support that rIAPP(17-29) can interact with copper(II) ions under physiological conditions and the SSNN tetrapeptide fragment can be considered as the shortest sequence responsible for metal binding. Density functional theory (DFT) calculations provide some information on the possible coordination modes of Ac-SSNN-NH(2) towards the copper(II) ion and suggest that for [CuH(-2)L], [CuH(-3)L](-) and [CuH(-4)L](2-), the binding of two, three and four deprotonated amide nitrogens, with NH(-) of the side chain of asparagine as anchoring group, is probable. Moreover, these data reveal that peptides can be effective metal binding ligands even in the absence of anchoring

  19. The Synthesis of Copper(II) Carboxylates Revisited

    ERIC Educational Resources Information Center

    Kushner, Kevin; Spangler, Robert E.; Salazar, Ralph A., Jr.; Lagowski, J. J.

    2006-01-01

    An electrochemical synthesis of copper(II) carboxylates has been developed and used in the general chemistry laboratory course for chemistry majors. This synthesis, using nonaqueous solutions, supplements the strategy of providing experiences in synthetic chemistry described by Yoder et al. ("J. Chem. Educ." 1995, 72, 267). (Contains 1 table.)

  20. Thermal Decomposition of Copper (II) Calcium (II) Formate

    NASA Astrophysics Data System (ADS)

    Leyva, A. G.; Polla, G.; de Perazzo, P. K.; Lanza, H.; de Benyacar, M. A. R.

    1996-05-01

    The presence of different stages in the thermal decomposition process of CuCa(HCOO) 4has been established by means of TGA at different heating rates, X-ray powder diffraction of quenched samples, and DSC methods. During the first stage, decomposition of one of the two copper formate structural units contained in the unit cell takes place. The presence of CuCa 2(HCOO) 6has been detected. Calcium formate structural units break down at higher temperatures; the last decomposition peak corresponds to the appearance of different calcium-copper oxides.

  1. Comparative effects of copper sulfate or potassium permanganate on channel catfish concurrently infected with Flavobacterium columnare and Ichthyobodo necator

    Technology Transfer Automated Retrieval System (TEKTRAN)

    An opportunistic study was conducted to determine the effects of two chemical therapeutants on channel catfish (CCF) Ictalurus punctatus concurrently infected Flavobacterium columnare and Ichthyobodo necator. Copper sulfate (CuSO4) and potassium permanganate (KMnO4) were investigated for their abil...

  2. Genome sequence of Desulfosporosinus sp. OT, an acidophilic sulfate-reducing bacterium from copper mining waste in Norilsk, Northern Siberia.

    PubMed

    Abicht, Helge K; Mancini, Stefano; Karnachuk, Olga V; Solioz, Marc

    2011-11-01

    We have sequenced the genome of Desulfosporosinus sp. OT, a Gram-positive, acidophilic sulfate-reducing Firmicute isolated from copper tailing sediment in the Norilsk mining-smelting area in Northern Siberia, Russia. This represents the first sequenced genome of a Desulfosporosinus species. The genome has a size of 5.7 Mb and encodes 6,222 putative proteins.

  3. Assignment of the terahertz spectra of crystalline copper sulfate and its hydrates via solid-state density functional theory.

    PubMed

    Ruggiero, Michael T; Bardon, Tiphaine; Strlič, Matija; Taday, Philip F; Korter, Timothy M

    2014-10-30

    Terahertz (THz) vibrational spectroscopy is a promising tool for the nondestructive and potentially noninvasive characterization of historical objects, which can provide information on the materials used for their production as well as identify and monitor their chemical degradation. Copper sulfate (CuSO4) has drawn interest due to its inclusion in the preparation of iron gall inks found in historical artwork and documents. Copper sulfate rapidly forms hydrates which contribute to the formulation of these ink species and may influence their corrosive nature. In this study, copper sulfate has been studied using a combination of THz time-domain spectroscopy, powder X-ray diffraction (PXRD), and solid-state density functional theory (DFT) in order to better understand the spectral absorbances in the THz region. The results have revealed that the THz spectrum of commercially available "anhydrous" copper sulfate results from the presence of not only the anhydrous form but also the monohydrate (CuSO4·H2O) and trihydrate (CuSO4·3H2O) forms. Complete assignment of the experimental spectrum was achieved through a comparison of density functionals and extensive investigation of the influence of basis set polarization functions on the bonding interactions, lattice parameters, and low-frequency motions in these crystalline solids.

  4. Copper(II) and nickel(II) binding sites of peptide containing adjacent histidyl residues.

    PubMed

    Grenács, Ágnes; Sanna, Daniele; Sóvágó, Imre

    2015-10-01

    Copper(II) and nickel(II) complexes of the terminally protected nonapeptide Ac-SGAEGHHQK-NH2 modeling the metal binding sites of the (8-16) domain of amyloid-β have been studied by potentiometric, UV-vis, CD and ESR spectroscopic methods. The studies on the mutants containing only one of the histidyl residues (Ac-SGAEGAHQK-NH2, Ac-SGAEGHAQK-NH2) have also been performed. The formation of imidazole and amide coordinated mononuclear complexes is characteristic of all systems with a preference of nickel(II) binding to the His14 site, while the involvement of both histidines in metal binding is suggested in the corresponding copper(II) complexes. The formation of bis(ligand) and dinuclear complexes has also been observed in the copper(II)-Ac-SGAEGHHQK-NH2 system. The results provide further support for the copper(II) binding ability of the (8-16) domain of amyloid-β and support the previous assumptions that via the bis(ligand) complex formation copper(II) ions may promote the formation of the oligomers of amyloid-β.

  5. Phosphate effects on copper(II) and lead(II) sorption to ferrihydrite

    NASA Astrophysics Data System (ADS)

    Tiberg, Charlotta; Sjöstedt, Carin; Persson, Ingmar; Gustafsson, Jon Petter

    2013-11-01

    Transport of lead(II) and copper(II) ions in soil is affected by the soil phosphorus status. Part of the explanation may be that phosphate increases the adsorption of copper(II) and lead(II) to iron (hydr)oxides in soil, but the details of these interactions are poorly known. Knowledge about such mechanisms is important, for example, in risk assessments of contaminated sites and development of remediation methods. We used a combination of batch experiments, extended X-ray absorption fine structure (EXAFS) spectroscopy and surface complexation modeling with the three-plane CD-MUSIC model to study the effect of phosphate on sorption of copper(II) and lead(II) to ferrihydrite. The aim was to identify the surface complexes formed and to derive constants for the surface complexation reactions. In the batch experiments phosphate greatly enhanced the adsorption of copper(II) and lead(II) to ferrihydrite at pH < 6. The largest effects were seen for lead(II).

  6. Effects of copper sulfate, tri-basic copper chloride, and zinc oxide on weanling pig performance.

    PubMed

    Shelton, N W; Tokach, M D; Nelssen, J L; Goodband, R D; Dritz, S S; DeRouchey, J M; Hill, G M

    2011-08-01

    Three experiments were conducted to evaluate the effects of increasing dietary Cu and Zn on weanling pig performance. Diets were fed in 2 phases: phase 1 from d 0 to 14 postweaning and phase 2 from d 14 to 28 in Exp. 1 and 2 and d 14 to 42 in Exp. 3. The trace mineral premix, included in all diets, provided 165 mg/kg of Zn from ZnSO(4) and 16.5 mg/kg of Cu from CuSO(4). In Exp. 1, treatments were arranged in a 2 × 3 factorial with main effects of added Cu from tri-basic copper chloride (TBCC; 0 or 150 mg/kg) and added Zn from ZnO (0, 1,500, or 3,000 mg/kg from d 0 to 14 and 0, 1,000, or 2,000 mg/kg from d 14 to 28). No Cu × Zn interactions were observed (P > 0.10). Adding TBCC or Zn increased (P < 0.05) ADG and ADFI during each phase. In Exp. 2, treatments were arranged in a 2 × 3 factorial with main effects of added Zn from ZnO (0 or 3,000 mg/kg from d 0 to 14 and 0 or 2,000 mg/kg from d 14 to 28) and Cu (control, 125 mg/kg of Cu from TBCC, or 125 mg/kg of Cu from CuSO(4)). No Cu × Zn interactions (P > 0.10) were observed for any performance data. Adding ZnO improved (P < 0.02) ADG and ADFI from d 0 to 14 and overall. From d 0 to 28, supplementing CuSO(4) increased (P < 0.02) ADG, ADFI, and G:F, and TBCC improved (P = 0.006) ADG. In Exp. 3, the 6 dietary treatments were arranged in a 2 × 2 factorial with main effects of added Cu from CuSO(4) (0 or 125 mg/kg) and added Zn from ZnO (0 or 3,000 mg/kg from d 0 to 14 and 0 or 2,000 mg/kg from d 14 to 42). The final 2 treatments were feeding added ZnO alone or in combination with CuSO(4) from d 0 to 14 and adding CuSO(4) from d 14 to 42. Adding ZnO increased (P < 0.04) ADG, ADFI, and G:F from d 0 to 14 and ADG from d 0 to 42. Dietary CuSO(4) increased (P < 0.004) ADG and ADFI from d 14 to 42 and d 0 to 42. From d 28 to 42, a trend for a Cu × Zn interaction was observed (P = 0.06) for ADG. This interaction was reflective of the numeric decrease in ADG for pigs when Cu and Zn were used in combination compared with

  7. [Washing copper (II)-contaminated soil using surfactant solutions].

    PubMed

    Zhao, Bao-wei; Wu, Yong-qi; Ma, Chan-Yuan; Zhu, Rui-jia

    2009-10-15

    The batch equilibrium washing of copper (II) in the soil matrix by anionic surfactant, sodium dodecylbenzyl sulfonate (SDBS), nonionic surfactant, octylphenoxypolyethoxyethanol (TX100), and their mixture (SDBS-TX100), was studied and compared. The influences of surfactant concentrations, washing time, pH values of solutions, ratios of soil to water and inorganic salts on washing efficiency were investigated. It was shown that the washing efficiency differed with the kinds of surfactants. Given the initial surfactant concentrations, the washing of copper (II) by single SDBS was greater than those by single TX100 and the mixed SDBS-TX100. The washing efficiency by 6 000 mg x L(-1) of SDBS was up to 46.3%, which was 5.8, 10.8, 10.8 and 19.3 times as those by SDBS-TX100 (3:1), SDBS-TX100 (1:1), SDBS-TX100 (1:3) and single TX100 respectively. When the ratio of soil to water was 1 to 10 and washing time reached 24 h, the washing efficiency achieved the maximum. pH values of solutions had obvious effect on the washing of copper (II). The washing efficiency of copper decreased sharply with the increase of pH. At the high acidity (pH = 1.50), the washing efficiency of copper (II) was up to 95%. The smaller the ratios of soil to water were, the higher the washing efficiencies would be. The existence of inorganic salts with the certain concentrations, such as Na+, Ca2+ and Mg2+, could not influence the washing capacity of surfactants, but the excessive Mg2+ (more than 500 mg x L(-1)) could resulted in the precipitation of SDBS. The results will make an implication for surfactant-enhanced remediation of soils contaminated with heavy metals.

  8. Suppression of human fibroblast proliferation by D-penicillamine and copper sulfate in vitro.

    PubMed

    Matsubara, T; Hirohata, K

    1988-08-01

    We examined the effect of D-penicillamine (DP) and copper sulfate (CuSO4) on human fibroblast proliferation in vitro. DP plus CuSO4 inhibited both basal and interleukin-1 (IL-1)-induced tritiated thymidine incorporation into fibroblasts in a dose- and time-dependent manner. Significant inhibition was observed at the level of 60 microM in the presence of 4 microM CuSO4. At this range of concentrations, which is attained in serum and in tissues of treated patients, DP alone or CuSO4 alone did not affect fibroblast proliferation. Similar inhibition was observed with various thiols in the presence of copper, but not with disulfides such as DP disulfide or oxidized glutathione. Inhibition of fibroblast DNA synthesis induced by DP and CuSO4 was reversed by the simultaneous addition of catalase or horseradish peroxidase, but not by boiled catalase or superoxide dismutase. The inhibition by DP and CuSO4, therefore, may be attributable to hydrogen peroxide produced by these 2 agents. DP, in the presence of CuSO4, did not affect IL-1 secretion from human peripheral mononuclear phagocytes. These observations indicate that hydrogen peroxide produced by DP plus CuSO4 inhibits IL-1-induced fibroblast proliferation by directly affecting fibroblasts, without alteration of IL-1 secretion from mononuclear phagocytes. Thus, DP may play a role in inhibiting the growth of rheumatoid pannus and excessive collagenation in scleroderma by direct inhibition of fibroblast proliferation.

  9. Time-Lapse Observation of Electrolysis of Copper Sulfate with a Full-Field X-ray Fluorescence Imaging Microscope

    NASA Astrophysics Data System (ADS)

    Ohigashi, Takuji; Aota, Tatsuya; Watanabe, Norio; Takano, Hidekazu; Yokosuka, Hiroki; Aoki, Sadao

    2008-06-01

    The time-lapse observation of the electrodeposition of copper in copper sulfate solution was performed by imaging X-ray fluorescence from the copper deposition. The X-ray fluorescence was directly imaged with a full-field Wolter mirror microscope, which was constructed at the Photon Factory. Controlling the electric current in the solution from 0 to 71.7 µA, the deposition of copper on a Pt cathode was directly observed by imaging its X-ray fluorescence. One exposure time for obtaining an X-ray fluorescence image was 80 s. Then, it was 17 min later from the beginning of the electrolysis when the X-ray fluorescence image of the electrodeposition is observed for the first time. At this exposure time, the detection limit of the mass of copper was estimated to be 0.60 pg/image, which was calculated using test samples of 1.00×10-3-1.00 mol/l copper sulfate solutions.

  10. Two unprecedented 1D coordination polymer chains based on tetranuclear copper(II) building blocks

    SciTech Connect

    Li Gaijuan; Xing Yan Song Shuyan; Xu Ning; Liu Xianchun; Su Zhongmin

    2008-09-15

    The reaction of copper(II) sulfate with pyridine in DMF or methanol yield two unprecedented Cu(II) coordination polymers {l_brace}[Cu{sub 4}({mu}{sub 4}-O)(py){sub 4}(SO{sub 4}){sub 4}][{mu}-Cu(py)(DMF){sub 2}]{r_brace}{sub n}(1) and {l_brace}[Cu{sub 4}({mu}{sub 4}-O)(py){sub 4}(SO{sub 4}){sub 4}][{mu}-Cu(py){sub 4}]{r_brace}{sub n}(2), respectively. Single-crystal X-ray diffraction indicated that compound 1 crystallizes in the monoclinic system, space group p2(1)/n, a=14.542(5) A, b=16.359(5) A, c=18.951(5) A, {beta}=92.047(5){sup o}, V=4505(2) A{sup 3}, Z=4 while 2 is monoclinic C2/c, a=23.078(5) A, b=10.214(5) A, c=23.142(5) A, {beta}=115.471(5){sup o}, V=4925(3) A{sup 3}, Z=4. Both of the two compounds consist of tetrahedral tetranuclear [Cu{sub 4}({mu}{sub 4}-O)(py){sub 4}(SO{sub 4}){sub 4}] clusters that are bridged by pentacoordinated Cu atom for 1 or hexacoordinated Cu atoms for 2 through the sulfate oxygen to form the infinite one-dimensional polymer chains. - Graphical abstract: Two unprecedented Cu(II) coordination polymers have been prepared by using solvothermal method; they consist of tetrahedral tetranuclear clusters that are bridged by unique Cu(II) atom through the sulfate oxygen to form the infinite one-dimensional polymer chains (a) for complex 1 and (b) for complex 2.

  11. Determining the Amount of Copper(II) Ions in a Solution Using a Smartphone

    ERIC Educational Resources Information Center

    Montangero, Marc

    2015-01-01

    When dissolving copper in nitric acid, copper(II) ions produce a blue-colored solution. It is possible to determine the concentration of copper(II) ions, focusing on the hue of the color, using a smartphone camera. A free app can be used to measure the hue of the solution, and with the help of standard copper(II) solutions, one can graph a…

  12. Polyguluronate sulfate, polymannuronate sulfate, and their oligosaccharides have antithrombin III- and heparin cofactor II-independent anticoagulant activity

    NASA Astrophysics Data System (ADS)

    Zeng, Xuan; Lan, Ying; Zeng, Pengjiao; Guo, Zhihua; Hao, Cui; Zhang, Lijuan

    2017-04-01

    Cardiovascular disease is the leading causes of death. However, the complications can be treated with heparin and heparinoids, such as heparin pentasaccharide Fondaparinux, dermatan sulfate, and PSS made from alginate extracted from brown seaweeds by chemical sulfation. Alginate is composed of a linear backbone of polymannuronate (PM), polyguluronate (PG), and alternate residues of mannuronic acid and guluronic acid. It is unknown if heparin and sulfated PG (PGS)/PM (PMS) have the same or different anticoagulant molecular targets. In the current study, the anticoagulant activities of PGS, PMS, and their oligosaccharides were directly compared to that of heparin, Fondaparinux, and dermatan sulfate by the activated partial thrombinplastin time (aPTT) assay using normal, antithrombin III (ATIII)-deficient, heparin co-factor II (HCII)-deficient, and ATIII- and HCII-double deficient human plasmas. Our results showed that PGS, PMS, and their oligosaccharides had better anticoagulant activity than that of Fondaparinux in all four human plasmas tested. As expected, heparin was the best anticoagulant in normal plasma. Moreover, PGS, PGS6, PGS12, PGS25, PMS6, PMS12, and PMS25 were better anticoagulants than dermatan sulfate in HCII-deficient plasma. Most strikingly, PGS, PGS12, PGS25, PMS6, PMS12, and PMS25 were better anticoagulants than that of heparin in ATIII- and HCII-double deficient human plasma. The results revealed for the first time that sulfated alginate had ATIII- and HCII-independent anticoagulant activities. Therefore, developing PGS and PMS-based anticoagulants might require to discover their major molecular targets and to develop target-specific anticoagulant assays.

  13. The joint inhibitory effects of phenol, copper (II), oxytetracycline (OTC) and sulfide on Anammox activity.

    PubMed

    Yang, Guang-Feng; Jin, Ren-Cun

    2012-12-01

    A batch test was employed to analyze the joint toxicity of copper (II) and oxytetracycline (OTC), OTC and sulfide, phenol and sulfide (S(2-)), phenol and copper (II), and OTC, copper (II) and substrate on an Anammox mixed culture. The joint toxicity of OTC and copper (II) on the Anammox mixed culture was antagonistic, whereas the interaction between OTC and S(2-) and between phenol and S(2-) was generally synergistic. The joint toxicity of phenol and copper (II) was dependent on the level of phenol: the joint toxicity was antagonistic at a high phenol level of 300 mg L(-1), whereas the joint toxicity was synergistic at a low phenol level of 75 mg L(-1). The joint toxic effect of OTC, copper (II) and NO(2)(-)-N on the Anammox activity can be ranked in the following order: NO(2)(-)-N>copper (II)>OTC.

  14. Thermal Decomposition of Copper (II) Dicalcium (II) Formate

    NASA Astrophysics Data System (ADS)

    de Perazzo, P. K.; Leyva, A. G.; Polla, G.; Parisi, F.; de Benyacar, M. A. R.; Smichowski, P.; Lanza, H.

    1997-09-01

    The unit cell obtained through X-ray single crystal analysis of the synthetized CuCa 2(HCOO) 6crystals corresponds to a supercell of the basic structure described by M. Sanchis et al.( Inorg. Chem.31, 2915 (1992)). Thermal decomposition of this sample shows two stages up to 300°C; the first can be related to the superstructure, and the second corresponds to the breaking down of the remaining copper formate structural units and the simultaneous decomposition of the sample.

  15. Characterization of the Copper(II) Binding Sites in Human Carbonic Anhydrase II

    PubMed Central

    Nettles, Whitnee L.; Song, He; Farquhar, Erik R.; Fitzkee, Nicholas C.; Emerson, Joseph P.

    2015-01-01

    Human carbonic anhydrase (CA) is a well-studied, robust, mononuclear Zn-containing metalloprotein that serves as an excellent biological ligand system to study the thermodynamics associated with metal ion coordination chemistry in aqueous solution. The apo-form of human carbonic anhydrase II (CA) binds two equivalents of copper(II) with high affinity. The Cu2+ ions bind independently forming two non-coupled type-II copper centers in CA (CuA and CuB). However, the location and coordination mode of the CuA site in solution is unclear, compared to the CuB site that has been well characterized. Using paramagnetic NMR techniques and X-ray absorption spectroscopy we have identified an N-terminal Cu2+ binding location and collected information on the coordination mode of the CuA site in CA, which is consistent with a four to five coordinate N-terminal Cu2+ binding site reminiscent to a number of N-terminal copper(II) binding sites including the copper(II)-ATCUN and copper(II)-beta-amyloid complexes. Additionally, we report a more detailed analysis of the thermodynamics associated with copper(II) binding to CA. Although we are still unable to fully deconvolute Cu2+ binding data to the high-affinity CuA site, we have derived pH- and buffer-independent values for the thermodynamics parameters K and ΔH associated with Cu2+ binding to the CuB site of CA to be 2 × 109 and −17.4 kcal/mol, respectively. PMID:26010488

  16. Copper(II) enhances membrane-bound α-synuclein helix formation.

    PubMed

    Lucas, Heather R; Lee, Jennifer C

    2011-03-01

    Interactions of copper and membranes with α-synuclein have been implicated in pathogenic mechanisms of Parkinson's disease, yet work examining both concurrently is scarce. We have examined the effect of copper(ii) on protein/vesicle binding and found that both the copper(ii) affinity and α-helical content are enhanced for the membrane-bound protein.

  17. Structure of catabolite activator protein with cobalt(II) and sulfate

    SciTech Connect

    Rao, Ramya R.; Lawson, Catherine L.

    2014-04-15

    The crystal structure of E. coli catabolite activator protein with bound cobalt(II) and sulfate ions at 1.97 Å resolution is reported. The crystal structure of cyclic AMP–catabolite activator protein (CAP) from Escherichia coli containing cobalt(II) chloride and ammonium sulfate is reported at 1.97 Å resolution. Each of the two CAP subunits in the asymmetric unit binds one cobalt(II) ion, in each case coordinated by N-terminal domain residues His19, His21 and Glu96 plus an additional acidic residue contributed via a crystal contact. The three identified N-terminal domain cobalt-binding residues are part of a region of CAP that is important for transcription activation at class II CAP-dependent promoters. Sulfate anions mediate additional crystal lattice contacts and occupy sites corresponding to DNA backbone phosphate positions in CAP–DNA complex structures.

  18. Equilibrium and Redox Kinetics of Copper(II)-Thiourea Complexes.

    PubMed

    Doona, Christopher J.; Stanbury, David M.

    1996-05-22

    Stopped-flow spectrophotometric measurements identify and determine equilibrium data for thiourea (tu) complexes of copper(II) formed in aqueous solution. In excess Cu(II), the complex ion [Cu(tu)](2+) has a stability constant beta(1) = 2.3 +/- 0.1 M(-)(1) and molar absorptivity at 340 nm of epsilon(1) = (4.0 +/- 0.2) x 10(3) M(-)(1) cm(-)(1) at 25.0 degrees C, 2.48 mM HClO(4), and &mgr; = 464 mM (NaClO(4)). The fast reduction of Cu(II) by excess tu obeys the rate law -d[Cu(II)]/dt = k'[Cu(II)](2)[tu](7) with a value for the ninth-order rate constant k' = (1.60 +/- 0.18) x 10(14) M(-)(8) s(-)(1), which derives from a rate-determining step involving the bimolecular decomposition of two complexed Cu(II) species. Copper(II) catalyzes the reduction of hexachloroiridate(IV) by tu according to the rate law -d[IrCl(6)(2)(-)]/dt = (k(2,unc)[tu](2) + k(1,cat) [tu](5)[Cu(II)])[IrCl(6)(2)(-)]. Least-squares analysis yields values of k(2,unc) and k(1,cat) equaling 385 +/- 4 M(-)(2) s(-)(1) and (3.7 +/- 0.1) x 10(13) M(-)(6) s(-)(1), respectively, at &mgr; = 115 mM (NaClO(4)). The corresponding mechanism has a rate-determining step that involves the oxidation of [Cu(II)(tu)(5)](2+) by [IrCl(6)](2)(-) rather than the bimolecular reaction of two cupric-tu complexes.

  19. Species-dependent variation in sensitivity of Microcystis species to copper sulfate: implication in algal toxicity of copper and controls of blooms

    NASA Astrophysics Data System (ADS)

    Wu, Haiming; Wei, Gaojie; Tan, Xiao; Li, Lin; Li, Ming

    2017-01-01

    Copper sulfate is a frequently used reagent for Microcystis blooms control but almost all the previous works have used Microcystis aeruginosa as the target organism to determine dosages. The aim of this study was to evaluate interspecific differences in the responses of various Microcystis species to varying Cu2+ concentrations (0, 0.05, 0.10, 0.25, and 0.50 mg L‑1). The half maximal effective concentration values for M. aeruginosa, M. wesenbergii, M. flos-aquae, and M. viridis were 0.16, 0.09, 0.49, and 0.45 mg L‑1 Cu2+, respectively. This showed a species-dependent variation in the sensitivity of Microcystis species to copper sulfate. Malonaldehyde content did not decrease with increasing superoxide dismutase content induced by increasing Cu2+, suggesting that superoxide dismutase failed to reduce Cu2+ damage in Microcystis. Considering the risk of microcystin release when Microcystis membranes are destroyed as a result of Cu2+ treatment and the stimulation effects of a low level of Cu2+ on growth in various species, our results suggest that copper sulfate treatment for Microcystis control could be applied before midsummer when M. aeruginosa and M. viridis are not the dominant species and actual amount of Cu2+ used to control M. wesenbergii should be much greater than 0.10 mg L‑1.

  20. Species-dependent variation in sensitivity of Microcystis species to copper sulfate: implication in algal toxicity of copper and controls of blooms

    PubMed Central

    Wu, Haiming; Wei, Gaojie; Tan, Xiao; Li, Lin; Li, Ming

    2017-01-01

    Copper sulfate is a frequently used reagent for Microcystis blooms control but almost all the previous works have used Microcystis aeruginosa as the target organism to determine dosages. The aim of this study was to evaluate interspecific differences in the responses of various Microcystis species to varying Cu2+ concentrations (0, 0.05, 0.10, 0.25, and 0.50 mg L−1). The half maximal effective concentration values for M. aeruginosa, M. wesenbergii, M. flos-aquae, and M. viridis were 0.16, 0.09, 0.49, and 0.45 mg L−1 Cu2+, respectively. This showed a species-dependent variation in the sensitivity of Microcystis species to copper sulfate. Malonaldehyde content did not decrease with increasing superoxide dismutase content induced by increasing Cu2+, suggesting that superoxide dismutase failed to reduce Cu2+ damage in Microcystis. Considering the risk of microcystin release when Microcystis membranes are destroyed as a result of Cu2+ treatment and the stimulation effects of a low level of Cu2+ on growth in various species, our results suggest that copper sulfate treatment for Microcystis control could be applied before midsummer when M. aeruginosa and M. viridis are not the dominant species and actual amount of Cu2+ used to control M. wesenbergii should be much greater than 0.10 mg L−1. PMID:28079177

  1. 78 FR 78727 - Copper Sulfate Pentahydrate; Exemption From the Requirement of a Tolerance

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-12-27

    ... establishes recommended daily allowances (RDAs) of vitamins and minerals for the diet. The RDA for copper... with the deficiency rather than the excess of copper. Oral ingestion of excessive amounts of the copper... deficiency of copper intake than from excess intake. Copper also occurs naturally in a number of food...

  2. Reactions of copper(II)-phenol systems with O2: models for TPQ biosynthesis in copper amine oxidases.

    PubMed

    Tabuchi, Kae; Ertem, Mehmed Z; Sugimoto, Hideki; Kunishita, Atsushi; Tano, Tetsuro; Fujieda, Nobutaka; Cramer, Christopher J; Itoh, Shinobu

    2011-03-07

    Copper(II) complexes supported by a series of phenol-containing bis(pyridin-2-ylmethyl)amine N(3) ligands (denoted as L(o)H, L(m)H, and L(p)H) have been synthesized, and their O(2) reactivity has been examined in detail to gain mechanistic insights into the biosynthesis of the TPQ cofactor (2,4,5-trihydroxyphenylalaninequinone, TOPA quinone) in copper-containing amine oxidases. The copper(II) complex of L(o)H (ortho-phenol derivative) involves a direct phenolate to copper(II) coordination and exhibits almost no reactivity toward O(2) at 60 °C in CH(3)OH. On the other hand, the copper(II) complex of L(m)H (meta-phenol derivative), which does not involve direct coordinative interaction between the phenol moiety and the copper(II) ion, reacts with O(2) in the presence of triethylamine as a base to give a methoxy-substituted para-quinone derivative under the same conditions. The product structure has been established by detailed nuclear magnetic resonance (NMR), infrared (IR) spectroscopy, and electrospray ionization-mass spectroscopy (ESI-MS) (including (18)O-labeling experiment) analyses. Density functional theory predicts that the reaction involves (i) intramolecular electron transfer from the deprotonated phenol (phenolate) to copper(II) to generate a copper(I)-phenoxyl radical; (ii) the addition of O(2) to this intermediate, resulting in an end-on copper(II) superoxide; (iii) electrophilic substitution of the phenolic radical to give a copper(II)-alkylperoxo intermediate; (iv) O-O bond cleavage concomitant with a proton migration, giving a para-quinone derivative; and (v) Michael addition of methoxide from copper(II) to the para-quinone ring and subsequent O(2) oxidation. This reaction sequence is similar to that proposed for the biosynthetic pathway leading to the TPQ cofactor in the enzymatic system. The generated para-quinone derivative can act as a turnover catalyst for aerobic oxidation of benzylamine to N-benzylidene benzylamine. Another type of copper(II

  3. Responses of phtyoplankton photosynthesis and phosphorus kinetics to resuspended sediments in copper sulfate-treated ponds

    SciTech Connect

    Nalewajko, C.; Prepas, E.E.

    1996-01-01

    Six farm ponds (dugouts) and one lake that differ in the history of copper sulfate (CuSO{sub 4}) treatment were selected for studies of effects of sediments resuspension on phytoplankton. All sites are located within 50 km of Peace River, Alberta, and are shallow, hardwater, and eutrophic. Effects of sediment resuspension on phytoplankton photosynthesis were assessed by changes in the photosynthesis-irradiance P-D curve parameters, Pmax and {alpha}, after addition of sediment at 2% v/v to lakewater samples; the effects on phytoplankton P-state were assessed by changes in {sup 32}PO{sub 4} turnover time. Copper concentrations in sediments of Gour No. 4, the dugout that had received the largest dosage of CuSO{sub 4}, were 60-times greater than untreated sites but were only 1.5 to 3-times greater at the other treated sites. Changes of Pmax and {alpha} were not correlated with Cu concentrations in the sediments. Instead, the prevailing P-state in lakewater could better explain the observed trends in Pmax after sediment addition. Pmax values decreased at sites where phytoplankton were P-limited ({sup 32} P-PO{sub 4} turnover time <63 min) and increased at more P-sufficient sites ({sup 32}P-PO{sub 4} turnover time >63 min). Stimulation of Pmax and increase in {sup 32}P-PO{sub 4} turnover time were positively correlated. With the exception of Gour No. 4, values of a increased in all treatments. Similar changes in Pmax and a in response to sediment addition occurred in laboratory experiments with P-sufficient cultures of Anabaena flos-aquae. We suggest that, with the exception of grossly Cu-polluted sediments, resuspension of sediments in waters previously treated with CuSO{sub 4} will enhance phytoplankton photosynthesis by increasing P availability, and possibly by supplying Cu at trace metal levels. 25 refs., 4 figs., 6 tabs.

  4. Suppressive Effects of Copper Sulfate Accumulation on the Spermatogenesis of Rats.

    PubMed

    Liu, J Y; Yang, X; Sun, X D; Zhuang, C C; Xu, F B; Li, Y F

    2016-12-01

    This study investigated the effect of copper sulfate (CuSO4) in the rat spermatogenesis. Forty male rats, weighing 70-80 g, were randomly divided into four groups: control group (CG, 0 mg/kg BW), low-dose group (LG, 100 mg/kg BW), mid-dose group (MG, 200 mg/kg BW), and high-dose group (HG, 400 mg/kg BW). Rats were administered CuSO4 by gavage for 30 days. A variety of measurements were taken including the testis coefficients, the sperm count, the abnormal malformation rate, testosterone (T), luteinizing hormone (LH), and follicle-stimulating hormone (FSH) concentrations in the serum. In addition, glutathione peroxidase (GSH-Px) and superoxide dismutase (SOD) activities, and malondialdehyde (MDA) concentration in the testis were determined. The results showed that in the CuSO4-treated groups, the testis coefficients, sperm count, T, LH, and FSH concentrations, and GSH-Px and SOD activities decreased, while the abnormal malformation rate and MDA concentration increased, compared with the CG. It indicates that CuSO4 exposure impairs the sperm quality and inhibits secretion of sex hormone and gonadotropin, and testis anti-oxidative function, suppressing the rat spermatogenesis.

  5. Effects of various polyoxyethylene sorbitan monooils (Tweens) and sodium dodecyl sulfate on reflux synthesis of copper nanoparticles

    SciTech Connect

    Zhang Xifeng; Yin Hengbo . E-mail: yin@ujs.edu.cn; Cheng Xiaonong; Hu Huifeng; Yu Qi; Wang Aili

    2006-11-09

    Size-controlled synthesis of phase pure Cu nanoparticles was carried out by using copper sulfate pentahydrate as a precursor, ascorbic acid as a reductant, Tweens and sodium dodecyl sulfate (SDS) as modifiers in an aqueous solution at 80 deg. C. The as-prepared Cu nanoparticles were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and Fourier transform infrared (FT-IR). The stabilizing effects of SDS and Tweens on the Cu nanoparticles should be through the coordination between Cu nanoparticles and the respective sulfate group and oxygen-containing bond. The synergic effect of the composite SDS and Tweens on Cu nanoparticles was different from those arising from the individuals.

  6. Desorption measurements of copper and copper alloys for PEP-II

    SciTech Connect

    Foerster, C.L.; Halama, H.; Korn, G.; Calderon, M.; Barletta, W.

    1992-12-31

    PEP-II will be a meson factory circulating asymmetric beams of 9 GeV and 3.1 GeV having maximum currents of 3.0A. Copper beam chambers and absorbers will intercept resulting synchrotron radiation and it is critical that the dynamic gas load from photo stimulated desorption (PSD) and thermal outgassing is below 2 {times} 10{sup {minus}1} molecules per photon. An experiment was set up to measure PSD from 1m long bar samples and a chamber sample, fabricated from selected copper and copper alloys then exposed to white light with a critical energy of 500 eV, on beamline U10B at the VUV ring of the National Synchrotron Light Source (NSLS). Based on U10B results a prototype chamber was built and will be exposed to white light with higher critical energies of up to 5 KeV, on beamline X-28A at the X-ray Ring of the NSLS. This paper presents the measurements of H{sub 2}, CO, CO{sub 2} and CH{sub 4} desorption yields as function of accumulated photon flux, angle of incidence, sample material, and surface condition. The results are compared with that of previous work on similar materials and with that of others for copper.

  7. Anodonta imbecillis copper sulfate reference toxicant/food test, Clinch River - Environmental Restoration Program (CR-ERP)

    SciTech Connect

    Simbeck, D.J.

    1997-06-01

    Reference toxicant testing using juvenile freshwater mussels was conducted as part of the CR-ERP biomonitoring study of Clinch River sediments to assess the sensitivity of test organisms and the overall performance of the test. Tests were conducted using moderately hard synthetic water spiked with known concentrations of copper as copper sulfate. Two different foods, phytoplankton and YCT-Selenastrum (YCT-S), were tested in side by side tests to compare food quality. Toxicity testing of copper sulfate reference toxicant was conducted from July 6-15, 1993. The organisms used for testing were juvenile fresh-water mussels (Anodonta imbecillis). Results from this test showed LC{sub 50} values of 0.97 and 0.84 mg Cu/L for phytoplankton and YCT-S, respectively. Previously obtained values for phytoplankton tests are 2.02 and 1.12 mg Cu/L. Too few tests have been conducted with copper as the toxicant to determine a normal range of values. Although significant reduction in growth, compared to the phytoplankton control, was seen in all treatments, including the YCT-S Control, the consequence of this observation has not been established. Ninety-day testing of juvenile mussels exhibited large variations in growth within treatment and replicate groups.

  8. Characterisation of freeze-dried type II collagen and chondroitin sulfate scaffolds.

    PubMed

    Tamaddon, M; Walton, R S; Brand, D D; Czernuszka, J T

    2013-05-01

    Collagen type-II is the dominant type of collagen in articular cartilage and chondroitin sulfate is one of the main components of cartilage extracellular matrix. Afibrillar and fibrillar type-II atelocollagen scaffolds with and without chondroitin sulfate were prepared using casting and freeze-drying methods. The scaffolds were characterised to highlight the effects of fibrillogenesis and chondroitin sulfate addition on viscosity, pore structure, porosity and mechanical properties. Microstructure analysis showed that fibrillogenesis increased the circularity of pores significantly in collagen-only scaffolds, whereas with it, no significant change was observed in chondroitin sulfate-containing scaffolds. Addition of chondroitin sulfate to afibrillar scaffolds increased the circularity of the pores and the proportion of pores between 50 and 300 μm suitable for chondrocytes growth. Fourier transform infrared spectroscopy explained the bonding between chondroitin sulfate and afibrillar collagen- confirmed with rheology results- which increased the compressive modulus 10-fold to 0.28 kPa. No bonding was observed in other scaffolds and consequently no significant changes in compressive modulus were detected.

  9. Genome sequence of Desulfovibrio sp. A2, a highly copper resistant, sulfate-reducing bacterium isolated from effluents of a zinc smelter at the Urals.

    PubMed

    Mancini, Stefano; Abicht, Helge K; Karnachuk, Olga V; Solioz, Marc

    2011-12-01

    Desulfovibrio sp. A2 is an anaerobic gram-negative sulfate-reducing bacterium with remarkable tolerance to copper. It was isolated from wastewater effluents of a zinc smelter at the Urals. Here, we report the 4.2-Mb draft genome sequence of Desulfovibrio sp. A2 and identify potential copper resistance mechanisms.

  10. Dermatan sulfate in tunicate phylogeny: Order-specific sulfation pattern and the effect of [→4IdoA(2-Sulfate)β-1→3GalNAc(4-Sulfate)β-1→] motifs in dermatan sulfate on heparin cofactor II activity

    PubMed Central

    2011-01-01

    Background Previously, we have reported the presence of highly sulfated dermatans in solitary ascidians from the orders Phlebobranchia (Phallusia nigra) and Stolidobranchia (Halocynthia pyriformis and Styela plicata). Despite the identical disaccharide backbone, consisting of [→4IdoA(2S)β-1→3GalNAcβ-1→], those polymers differ in the position of sulfation on the N-Acetyl galactosamine, which can occur at carbon 4 or 6. We have shown that position rather than degree of sulfation is important for heparin cofactor II activity. As a consequence, 2,4- and 2,6-sulfated dermatans have high and low heparin cofactor II activities, respectively. In the present study we extended the disaccharide analysis of ascidian dermatan sulfates to additional species of the orders Stolidobranchia (Herdmania pallida, Halocynthia roretzi) and Phlebobranchia (Ciona intestinalis), aiming to investigate how sulfation evolved within Tunicata. In addition, we analysed how heparin cofactor II activity responds to dermatan sulfates containing different proportions of 2,6- or 2,4-disulfated units. Results Disaccharide analyses indicated a high content of disulfated disaccharide units in the dermatan sulfates from both orders. However, the degree of sulfation decreased from Stolidobranchia to Phlebobranchia. While 76% of the disaccharide units in dermatan sulfates from stolidobranch ascidians are disulfated, 53% of disulfated disaccharides are found in dermatan sulfates from phlebobranch ascidians. Besides this notable difference in the sulfation degree, dermatan sulfates from phlebobranch ascidians contain mainly 2,6-sulfated disaccharides whereas dermatan sulfate from the stolidobranch ascidians contain mostly 2,4-sulfated disaccharides, suggesting that the biosynthesis of dermatan sulfates might be differently regulated during tunicates evolution. Changes in the position of sulfation on N-acetylgalactosamine in the disaccharide [→4IdoA(2-Sulfate)β-1→3GalNAcβ-1→] modulate heparin

  11. EXAFS study of mercury(II) sorption to Fe- and Al-(hydr)oxides - II. Effects of chloride and sulfate

    USGS Publications Warehouse

    Kim, C.S.; Rytuba, J.J.; Brown, Gordon E.

    2004-01-01

    Common complexing ligands such as chloride and sulfate can significantly impact the sorption of Hg(II) to particle surfaces in aqueous environmental systems. To examine the effects of these ligands on Hg(II) sorption to mineral sorbents, macroscopic Hg(II) uptake measurements were conducted at pH 6 and [Hg]i=0.5 mM on goethite (??-FeOOH), ??-alumina (??-Al2O3), and bayerite (??-Al(OH)3) in the presence of chloride or sulfate, and the sorption products were characterized by extended X-ray absorption fine structure (EXAFS) spectroscopy. The presence of chloride resulted in reduced uptake of Hg(II) on all three substrates over the Cl- concentration ([Cl-]) range 10-5 to 10-2 M, lowering Hg surface coverages on goethite, ??-alumina, and bayerite from 0.42 to 0.07 ??mol/m2, 0.06 to 0.006 ??mol/m2, and 0.55 to 0.39 ??mol/m2 ([Cl -]=10-5 to 10-3 M only), respectively. This reduction in Hg(II) uptake is primarily a result of the formation of stable, nonsorbing aqueous HgCl2 complexes in solution, limiting the amount of free Hg(II) available to sorb. At higher [Cl-] beam reduction of Hg(II) to Hg(I) was observed, resulting in the possible formation of aqueous Hg2Cl2 species and the precipitation of calomel, Hg 2Cl2(s). The presence of sulfate caused enhanced Hg(II) uptake over the sulfate concentration ([SO42-]) range 10-5 to 0.9 M, increasing Hg surface coverages on goethite, ??-alumina, and bayerite from 0.39 to 0.45 ??mol/m2, 0.11 to 0.38 ??mol/m2, and 0.36 to 3.33 ??mol/m2, respectively. This effect is likely due to the direct sorption or accumulation of sulfate ions at the substrate interface, effectively reducing the positive surface charge that electrostatically inhibits Hg(II) sorption. Spectroscopic evidence for ternary surface complexation was observed in isolated cases, specifically in the Hg-goethite-sulfate system at high [SO42-] and in the Hg-goethite-chloride system. ?? 2003 Elsevier Inc. All rights reserved.

  12. Understanding Dermatan Sulfate-Heparin Cofactor II Interaction through Virtual Library Screening.

    PubMed

    Raghuraman, Arjun; Mosier, Philip D; Desai, Umesh R

    2010-09-09

    Dermatan sulfate, an important member of the glycosaminoglycan family, interacts with heparin cofactor II, a member of the serpin family of proteins, to modulate antithrombotic response. Yet, the nature of this interaction remains poorly understood at a molecular level. We report the genetic algorithm-based combinatorial virtual library screening study of a natural, high-affinity dermatan sulfate hexasaccharide with heparin cofactor II. Of the 192 topologies possible for the hexasaccharide, only 16 satisfied the "high-specificity" criteria used in computational study. Of these, 13 topologies were predicted to bind in the heparin-binding site of heparin cofactor II at a ∼60° angle to helix D, a novel binding mode. This new binding geometry satisfies all known solution and mutagenesis data and supports thrombin ternary complexation through a template mechanism. The study is expected to facilitate the design of allosteric agonists of heparin cofactor II as antithrombotic agents.

  13. In situ single-crystal to single-crystal (SCSC) transformation of the one-dimensional polymer catena-poly[[diaqua(sulfato)copper(II)]-μ₂-glycine] into the two-dimensional polymer poly[μ₂-glycine-μ₄-sulfato-copper(II)].

    PubMed

    Stoeckli-Evans, Helen; Sereda, Olha; Neels, Antonia; Oguey, Sebastien; Ionescu, Catherine; Jacquier, Yvan

    2014-11-01

    The one-dimensional coordination polymer catena-poly[diaqua(sulfato-κO)copper(II)]-μ2-glycine-κ(2)O:O'], [Cu(SO4)(C2H5NO2)(H2O)2]n, (I), was synthesized by slow evaporation under vacuum of a saturated aqueous equimolar mixture of copper(II) sulfate and glycine. On heating the same blue crystal of this complex to 435 K in an oven, its aspect changed to a very pale blue and crystal structure analysis indicated that it had transformed into the two-dimensional coordination polymer poly[(μ2-glycine-κ(2)O:O')(μ4-sulfato-κ(4)O:O':O'':O'')copper(II)], [Cu(SO4)(C2H5NO2)]n, (II). In (I), the Cu(II) cation has a pentacoordinate square-pyramidal coordination environment. It is coordinated by two water molecules and two O atoms of bridging glycine carboxylate groups in the basal plane, and by a sulfate O atom in the apical position. In complex (II), the Cu(II) cation has an octahedral coordination environment. It is coordinated by four sulfate O atoms, one of which bridges two Cu(II) cations, and two O atoms of bridging glycine carboxylate groups. In the crystal structure of (I), the one-dimensional polymers, extending along [001], are linked via N-H···O, O-H···O and bifurcated N-H···O,O hydrogen bonds, forming a three-dimensional framework. In the crystal structure of (II), the two-dimensional networks are linked via bifurcated N-H···O,O hydrogen bonds involving the sulfate O atoms, forming a three-dimensional framework. In the crystal structures of both compounds, there are C-H···O hydrogen bonds present, which reinforce the three-dimensional frameworks.

  14. Effect of zirconia on the physicochemical properties of copper (II) imidazolate frameworks

    NASA Astrophysics Data System (ADS)

    Shaharun, Maizatul S.; Shaharun, Salina; Al-Shaibani, Asem

    2016-11-01

    Copper(II) bis(imidazolate) and copper(II)-zirconia(IV) bimetallic imidazolate were synthesized by metal oxides in aqueous solutions using acid catalyst procedure. The metal imidazolate frameworks were characterized by fourier transform infrared spectra (FTIR), transmission electron microscopy (TEM), ultraviolet-visible spectroscopy (UV-Vis) and N2 adsorption-desorption. The addition of ZrO2 increased the surface area and porosity of the metal organic frameworks. The modification of the copper(II) bis(imidazolate) with addition of ZrO2 enhances the visible light absorbance. The band gap of copper(II)-zirconia(II) bimetallic imidazolate is increased to 2.40 eV with more absorbance in the visible region compared to copper(II) bis(imidazolate).

  15. An Investigation of Microbiologically Mediated Corrosion of Copper-Nickel Piping Systems Selectively Treated with Ferrous Sulfate

    DTIC Science & Technology

    1987-01-01

    the Pipes treated with ferrouIs sulfate were exposed to American Petroleum Institute technique [28] which a ;0 ppb solution of Fe for 48 hours. The...review. Br. Corros. J., Vol. 7, pp. 61-68. (28) American Petroleum Institute Recommended % Procedure 38: Section II, Paragraph 28, and Section (14) FeSO 4

  16. Efficient electron-induced removal of oxalate ions and formation of copper nanoparticles from copper(II) oxalate precursor layers

    PubMed Central

    Rückriem, Kai; Grotheer, Sarah; Vieker, Henning; Penner, Paul; Beyer, André; Gölzhäuser, Armin

    2016-01-01

    Summary Copper(II) oxalate grown on carboxy-terminated self-assembled monolayers (SAM) using a step-by-step approach was used as precursor for the electron-induced synthesis of surface-supported copper nanoparticles. The precursor material was deposited by dipping the surfaces alternately in ethanolic solutions of copper(II) acetate and oxalic acid with intermediate thorough rinsing steps. The deposition of copper(II) oxalate and the efficient electron-induced removal of the oxalate ions was monitored by reflection absorption infrared spectroscopy (RAIRS). Helium ion microscopy (HIM) reveals the formation of spherical nanoparticles with well-defined size and X-ray photoelectron spectroscopy (XPS) confirms their metallic nature. Continued irradiation after depletion of oxalate does not lead to further particle growth giving evidence that nanoparticle formation is primarily controlled by the available amount of precursor. PMID:27547602

  17. Persistent endosulfan sulfate is found with highest abundance among endosulfan I, II, and sulfate in German forest soils.

    PubMed

    Bussian, Bernd M; Pandelova, Marchela; Lehnik-Habrink, Petra; Aichner, Bernhard; Henkelmann, Bernhard; Schramm, Karl-Werner

    2015-11-01

    Endosulfan - an agricultural insecticide and banned by Stockholm Convention - is produced as a 2:1 to 7:3 mixture of isomers endosulfan I (ESI) and endosulfan II (ESII). Endosulfan is transformed under aerobic conditions into endosulfan sulfate (ESS). The study shows for 76 sampling locations in German forests that endosulfan is abundant in all samples with an opposite ratio between the ESI and ESII than the technical product, where the main metabolite ESS is found with even higher abundance. The ratio between ESI/ESII and ESS show clear dependence on the type of stands (coniferous vs. deciduous) and humus type and increases from deciduous via mixed to coniferous forest stands. The study argues for a systematic monitoring of ESI, ESII, and ESS and underlines the need for further research, specifically on the fate of endosulfan including biomagnifications and bioaccumulation in soil.

  18. Static renewal tests using Anodonta imbecillus (freshwater mussels). Anodonta imbecillis copper sulfate reference toxicant test, Clinch River-Environmental Restoration Program (CR-ERP)

    SciTech Connect

    Simbeck, D.J.

    1993-12-31

    Reference toxicant testing using juvenile freshwater mussels was conducted as part of the CR-ERP biomonitoring study of Clinch River sediments to assess the sensitivity of test organisms and the overall performance of the test. Tests were conducted using moderately hard synthetic water spiked with known concentrations of copper as copper sulfate. Toxicity testing of copper sulfate reference toxicant was conducted from May 12--21, 1993. The organisms used for testing were juvenile fresh-water mussels (Anodonta imbecillis). Results from this test showed an LC{sub 50} value of 1.12 mg Cu/L which is lower than the value of 2.02 mg Cu/L obtained in a previous test. Too few tests have been conducted with copper as the toxicant to determine a normal range of values. Attachments to this report include: Toxicity test bench sheets and statistical analyses; Copper analysis request and results; and Personnel training documentation.

  19. Copper(II) complexes with heterocyclic hydroxyimino-containing ligands

    SciTech Connect

    Kogan, V.A.; Burlov, A.S.; Popov, L.D.; Lukov, V.V.; Koshchienko, Yu.V.; Tsupak, E.B.; Barchan, G.P.; Chigarenko, G.G.; Bolotnikov, V.S.

    1988-05-01

    The reaction of oximes (R = Ph (L'), C=N (L'')) with the copper(II) salts CuA/sub 2/ in methanol has given the complexes CuL/sub 2/ ' x H/sub 2/O and CuL/sub 2//sup ''/ x 2H/sub 2/O (I) (A = Acet/sup -/), CuHLCl/sub 2/ x H/sub 2/O (II) (A = Cl/sup -/), CuLOH(ClO/sub 4/)/sub 2/ x 2H/sub 2/O (III) (A = ClO/sub 4//sup -/) and the complexes Cu/sub 3/L/sub 3//sup '/OH(NO/sub 3/)/sub 2/ and Cu/sub 3/L/sub 3//sup ''/(OH)/sub 2/NO/sub 3/ (IV) (A = NO/sub 3//sup -/). Their physicochemical properties have been studied by the methods of IR spectroscopy and magnetochemistry. It has been shown that complexes I have a chelate structure and that their magnetic moments are not dependent on the temperature. An anti-ferromagnetic exchange interaction takes place in complexes II-IV. On the basis of magnetochemical measurements over a broad temperature range and data calculated in the framework of the Heisenberg-Dirac-Van Vleck model of isotropic exchange interactions, a dimeric structure has been proposed for the complexes of type II, and a trinuclear cluster structure has been proposed for complexes III and IV.

  20. Biosorption of copper(II) and cobalt(II) from aqueous solutions by crab shell particles.

    PubMed

    Vijayaraghavan, K; Palanivelu, K; Velan, M

    2006-08-01

    Biosorption of each of the heavy metals, copper(II) and cobalt(II) by crab shell was investigated in this study. The biosorption capacities of crab shell for copper and cobalt were studied at different particle sizes (0.456-1.117 mm), biosorbent dosages (1-10 g/l), initial metal concentrations (500-2000 mg/l) and solution pH values (3.5-6) in batch mode. At optimum particle size (0.767 mm), biosorbent dosage (5 g/l) and initial solution pH (pH 6); crab shell recorded maximum copper and cobalt uptakes of 243.9 and 322.6 mg/g, respectively, according to Langmuir model. The kinetic data obtained at different initial metal concentrations indicated that biosorption rate was fast and most of the process was completed within 2h, followed by slow attainment of equilibrium. Pseudo-second order model fitted the data well with very high correlation coefficients (>0.998). The presence of light and heavy metal ions influenced the copper and cobalt uptake potential of crab shell. Among several eluting agents, EDTA (pH 3.5, in HCl) performed well and also caused low biosorbent damage. The biosorbent was successfully regenerated and reused for five cycles.

  1. Evolution of copper(II) as a new alkene amination promoter and catalyst

    PubMed Central

    Chemler, Sherry R.

    2010-01-01

    Copper(II) carboxylates and chiral copper(II) triflate·bis(oxazoline) complexes promote and catalyze intramolecular alkene carboamination, diamination and aminooxygenation reactions, creating an array of nitrogen heterocycles. High diastereoselectivity and enantioselectivity can be achieved in these transformations. This account reviews the discovery and development of these useful and interesting reactions. PMID:21379363

  2. Histopathological and bacterial study of skin and gill of grass carp, Ceteopharyngodon idella, (Valenciennes 1844) exposed to copper sulfate and potassium permanganate.

    PubMed

    Jooyandeh, Fatemeh; Sadeghpour, Ali; Khara, Hossein; Pajand, Zabihollah

    2016-09-01

    The gill histology and bacterial load of skin of the grass carp juveniles were investigated in relation to various concentrations of copper sulfate and potassium permanganate. For this purpose, the sublethal doses were determined after a pre-test and then the experiment was done in five treatments (for copper sulfate: 1, 1.94, 3.71, 7.07 and 15 mg/l and for potassium permanganate: 0.25, 0.52, 1.91, 2.27 and 5 mg/l) with three replicates inside the glass aquaria. Also, one group without disinfecting product was considered as control for each experiment. The microbial and histopathological investigations were done after 96 h exposure. According to results, the lowest bacterial load (CFU/g) of skin was observed in 15 mg/l copper sulfate treatment and 0.25 mg/l potassium permanganate treatment (P < 0.05). Also, the histological investigation showed a range of histopathological alternations in gills tissue including lamellar necrosis, hyperplasia, lamellar adhesion, haemorrhage, clubbing of gill lamellae. The severity of these alternations increased with increasing of the doses of the copper sulfate and potassium permanganate. In this regard, the highest histological damages were observed in 15 mg/l copper sulfate and 5 mg/l potassium permanganate respectively. Our results showed that low dosage of potassium permanganate has best effect on reducing of bacterial load of skin with lowest adverse effects on gill tissue.

  3. Proteomic analysis of acute responses to copper sulfate stress in larvae of the brine shrimp, Artemia sinica

    NASA Astrophysics Data System (ADS)

    Zhou, Qian; Wu, Changgong; Dong, Bo; Li, Fuhua; Liu, Fengqi; Xiang, Jianhai

    2010-03-01

    Proteomics was used to reveal the differential protein expression profiles of acute responses to copper sulfate exposure in larvae of Artemia sinica. Fourteen differentially displayed protein spots were detected and seven of them were identified. Three spots were up-expressed and identified: actin, heat shock protein 70, and chaperone subunit 1; three down-regulated proteins were identified: arginine kinase, elongation factor-2, and glycine-rich protein; and a newly expressed protein was identified as peroxiredoxin. The study indicates the involvement of all the differentially expressed proteins in the early responses of protein expression, and in the survival of A. sinica in the presence of copper and other heavy metals; the findings improve understanding of the organism’s adaptive responses and resistance.

  4. Adiabatic polymerization of acrylamide in water under the effect of the potassium persulfate-sodium metabisulfite-copper sulfate system

    SciTech Connect

    Kurenkov, V.F.; Baiburdov, T.A.; Stupen'kova, L.L.

    1988-04-10

    Since adiabatic polymerization of acrylamide (AA) has been studied very little and the information on the effect of copper ions on polymerization of AA prepared in dilute aqueous solutions is very limited, the features of adiabatic polymerization of AA in concentrated aqueous solutions in the presence of the potassium persulfate-sodium metabisulfite-copper sulfate redox initiating system were investigated in this study. The empirical equation for the overall rate of adiabatic polymerization of acrylamide in concentrated aqueous solutions was found, and the effective total activation energy, which decreases with an increase in the concentration of CuSO/sub 4/, was determined. An increase in the molecular weight of the polymer with an increase in the concentration of the monomer and a decrease in the concentration of the components of the initiating system was demonstrated.

  5. Sequestration of chelated copper by structural Fe(II): Reductive decomplexation and transformation of Cu(II)-EDTA.

    PubMed

    He, Hongping; Wu, Deli; Zhao, Linghui; Luo, Cong; Dai, Chaomeng; Zhang, Yalei

    2016-05-15

    Chelated coppers, such as Cu(II)-EDTA, are characteristically refractory and difficult to break down because of their high stability and solubility. Cu(II)-EDTA sequestration by structural Fe(II) (Fe(II)) was investigated intensively in this study. Up to 101.21mgCu(II)/gFe(II) was obtained by Fe(II) in chelated copper sequestration under near neutral pH condition (pH 7.70). The mechanism of Cu(II)-EDTA sequestration by Fe(II) was concluded as follows: 3Cu(II)-EDTA+7Fe(II)+9H2O → Cu(0)↓+ Cu2O↓(the major product)+2Fe2O3·H2O↓+3Fe(II)-EDTA +14H(+) Novel results strongly indicate that Cu(II) reductive transformation induced by surface Fe(II) was mainly responsible for chelated copper sequestration. Cu(0) generation was initially facilitated, and subsequent reduction of Cu(II) into Cu(I) was closely combined with the gradual increase of ORP (Oxidation-Reduction Potential). Cu-containing products were inherently stable, but Cu2O would be reoxidized to Cu(II) with extra-aeration, resulting in the release of copper, which was beneficial to Cu reclamation. Concentration diminution of Cu(II)-EDTA within the electric double layer and competitive adsorption were responsible for the negative effects of Ca(2+), Mg(2+). By generating vivianite, PO4(3-) was found to decrease surface Fe(II) content. This study is among the first ones to identify the indispensible role of reductive decomplexation in chelated copper sequestration. Given the high feasibility and reactivity, Fe(II) may provide a potential alternative in chelated metals pollution controlling.

  6. Design, syntheses, characterization, and cytotoxicity studies of novel heterobinuclear oxindolimine copper(II)-platinum(II) complexes.

    PubMed

    Aranda, Esther Escribano; Matias, Tiago Araújo; Araki, Koiti; Vieira, Adriana Pires; de Mattos, Elaine Andrade; Colepicolo, Pio; Luz, Carolina Portela; Marques, Fábio Luiz Navarro; da Costa Ferreira, Ana Maria

    2016-12-01

    Herein, the design and syntheses of two new mononuclear oxindolimine-copper(II) (1 and 2) and corresponding heterobinuclear oxindolimine Cu(II)Pt(II) complexes (3 and 4), are described. All the isolated complexes were characterized by spectroscopic techniques (UV/Vis, IR, EPR), in addition to elemental analysis and mass spectrometry. Cyclic voltammetry (CV) measurements showed that in all cases, one-electron quasi-reversible waves were observed, and ascribed to the formation of corresponding copper(I) complexes. Additionally, waves related to oxindolimine ligand reduction was verified, and confirmed using analogous oxindolimine-Zn(II) complexes. The Pt(IV/II) reduction, and corresponding oxidation, for complexes 3 and 4 occurred at very close values to those observed for cisplatin. By complementary fluorescence studies, it was shown that glutathione (GSH) cannot reduce any of these complexes, under the experimental conditions (room temperature, phosphate buffer 50mM, pH7.4), using an excess of 20-fold [GSH]. All these complexes showed characteristic EPR spectral profile, with parameters values gǁ>g⊥ suggesting an axially distorted environment around the copper(II) center. Interactions with calf thymus-DNA, monitored by circular dichroism (CD), indicated different effects modulated by the ligands. Finally, the cytotoxicity of each complex was tested toward different tumor cells, in comparison to cisplatin, and low values of IC50 in the range 0.6 to 4.0μM were obtained, after 24 or 48h incubation at 37°C. The obtained results indicate that such complexes can be promising alternative antitumor agents.

  7. Cationic imprinting of Pb(II) within composite networks based on bovine or fish chondroitin sulfate.

    PubMed

    Ferreira, Vanessa R A; Azenha, Manuel A; Mêna, M Teresa; Moura, Cosme; Pereira, Carlos M; Pérez-Martín, Ricardo I; Vázquez, José A; Silva, A Fernando

    2017-02-03

    Imprinting chondroitin sulfate (CS)/silica composites with Pb(II) and Cu(II) cations was explored with CS of bovine and different fish species origin. The process was based on the assumption that particular arrangements of the linear CS chains in aqueous solution, induced so as to accommodate cross complexation with the cations, would be embodied into a tridimensional matrix created through an organoalkoxysilane sol-gel scheme. The presence of Cu(II) in the synthesis of the composites did not result in the production of significantly stronger Cu(II)-oriented binding arrangements, and therefore, the imprinting was not successful. Inversely, for Pb(II), the materials obtained exhibited a "memory" effect for the Pb(II) ions, expressed in the observation of stronger (13%-44%) binding as compared to the nonimprinted counterparts, and increased selectivity (1.5-2 folds) against Cd(II). The imprinting features observed were dependent on the CS source. However, it was not possible to identify, among a set of their properties (carboxylate and sulfate abundance, percent of disulfated units, 4S/6S ratio, and molecular weight), any that correlated directly with the observed imprinting features. The augmented selectivity provided by the cation-imprinting process may be advantageous in areas such as analytical separation, remediation, purification, sensing, and others, particularly in those cases where a certain cation is of special interest within a mixture of them.

  8. Binuclear copper(II) oxidation products from copper(I) complexes with tridentate ligands. Magnetostructural characterization.

    PubMed

    Rojas, Darío; García, Ana M; Vega, Andrés; Moreno, Yanko; Venegas-Yazigi, Diego; Garland, María T; Manzur, Jorge

    2004-10-04

    The bis-pyridine tridentate ligands (6-R-2-pyridylmethyl)-(2-pyridylmethyl) benzylamine (RDPMA, where R = CH(3), CF(3)), (6-R-2-pyridylmethyl)-(2-pyridylethyl) benzylamine (RPMPEA, where R = CH(3), CF(3)), and the bidentate ligand di-benzyl-(6-methyl-2-pyridylmethyl)amine (BiBzMePMA) have been synthesized and their copper(I) complexes oxidized in a methanol solution to afford self-assembled bis-micro-methoxo-binuclear copper(II) complexes (1, 2, 4, 6) or hydroxo- binuclear copper(II) complexes (3). Oxidation of the nonsubstituted DPMA (R = H) in dichloromethane gives a chloride-bridged complex (5). The crystal structures for [Cu(MeDPMA)(MeO)](2)(ClO(4))(2) (1), [Cu(RPMPEA)(MeO)](2)(ClO(4))(2) (for 2, R= Me, and for 4, R = CF(3)), [Cu(BiBzMePMA)(MeO)](2)(ClO(4))(2) (6), [Cu(FDPMA)(OH)](2)(ClO(4))(2) (3), and [Cu(DPMA)(Cl)](2)(ClO(4))(2) (5) have been determined, and their variable-temperature magnetic susceptibility has been measured in the temperature range of 10-300 K. The copper coordination geometries are best described as square pyramidal, except for 6, which is square planar, because of the lack of one pyridine ring in the bidentate ligand. In 1-4 and 6, the basal plane is formed by two pyridine N atoms and two O atoms from the bridging methoxo or hydroxo groups, whereas in 5, the bridging Cl atoms occupy axial-equatorial sites. Magnetic susceptibility measurements show that the Cu atoms are strongly coupled antiferromagnetically in the bis-methoxo complexes 1, 2, 4, and 6, with -2J > 600 cm(-)(1), whereas for the hydroxo complex 3, -2J = 195 cm(-)(1) and the chloride-bridged complex 5 shows a weak ferromagnetic coupling, with 2J = 21 cm(-)(1) (2J is an indicator of the magnetic interaction between the Cu centers).

  9. Synthesis, superoxide dismutase, nuclease, and anticancer activities of copper(II) complexes incorporating bis(2-picolyl)amine with different counter anions

    NASA Astrophysics Data System (ADS)

    Ibrahim, Mohamed M.; Ramadan, Abdel-Motaleb M.; Mersal, Gaber A. M.; El-Shazly, Samir A.

    2011-07-01

    Interaction of the tridentate ligand bis(2-picolyl)amine L with copper(II) salts gave a series of copper(II) complexes with the formula types: [ LCu(X) 2] (X = Cl -1, = Br -2), [( LCu (H 2O)(μ-SO 4)( LCu(H 2O)]SO 43, [ LCu(OAc)](OAc )H 2O 4, [ LCu(H 2O) 2](Y) 2 (Y = NO3-5, = ClO4-6). Their structures and properties were characterized by elemental analysis, thermal analysis (TGA), IR, UV-vis and ESR spectroscopy, electrochemical measurements including cyclic voltammetry and electrical molar conductivity, and magnetic moment measurements. A square pyramidal geometry is proposed for the halogeno complexes 1 and 2 in monomeric structures. For sulfate complex, the sulfate group bridged two copper(II) ions of the two [N 3O] donor units to give the dimeric complex molecule 3 in square pyramidal environment around the copper(II) ions. In the case of complexes 4- 6, square planar stereochemistries in monomeric structures are suggested. The SOD biomimetic catalytic activity of the obtained complexes was assessed for their ability to inhibit the reduction of nitroblue tetrazolium (NBT). The catalytic efficiency of O2- scavenging by complexes depends on the nature of the particular acidic anion radical incorporated in the complex molecule and follows the order: NO3- > ClO4- > Br - ⩾ Cl - > SO4- > AcO -. A probable mechanistic implications for the catalytic dismutation of O2- by copper(II) complexes are proposed. Furthermore, complex 1 exhibits significant hydrolytic cleavage of the genomic DNA in the absence of any external additives. In addition, the in vitro study of cytotoxicity of complex 1 on colon cancer cell line (Caco-2) indicates that the complex has the potential to act as an effective anticancer drug with IC 50 value of 156 ± 0.35 μM.

  10. Redox transformation, solid phase speciation and solution dynamics of copper during soil reduction and reoxidation as affected by sulfate availability

    NASA Astrophysics Data System (ADS)

    Fulda, Beate; Voegelin, Andreas; Ehlert, Katrin; Kretzschmar, Ruben

    2013-12-01

    In periodically flooded soils, interactions of Cu with biogenic sulfide formed during soil reduction lead to the precipitation of sparingly soluble Cu-sulfides. In contaminated soils, however, the amounts of Cu can exceed the amount of sulfate available for microbial reduction to sulfide. In laboratory batch experiments, we incubated a paddy soil spiked to ∼4.4 mmol kg-1 (280 mg kg-1) Cu(II) to monitor temporal changes in the concentrations of dissolved Cu and the speciation of solid-phase Cu during 40 days of soil reduction and 28 days of reoxidation as a function of initially available reducible sulfate (0.06, 2.09 or 5.92 mmol kg-1). Using Cu K-edge EXAFS spectroscopy, we found that a large fraction of Cu(II) became rapidly reduced to Cu(I) (23-39%) and Cu(0) (7-17%) before the onset of sulfate reduction. Combination with results from sequential Cu extraction and chromium reducible sulfur (CRS) data suggested that complexation of Cu(I) by reduced organic S groups (Sorg) may be an important process during this early stage. In sulfate-depleted soil, Cu(0) and Cu(I)-Sorg remained the dominant species over the entire reduction period, whereas in soils with sufficient sulfate, initially formed Cu(0) and (remaining) Cu(II) became transformed into Cu-sulfide during continuing sulfate reduction. The formation of Cu(0), Cu(I)-Sorg, and Cu-sulfide led to an effective decrease in dissolved Cu concentrations. Differences in Cu speciation at the end of soil reduction however affected the dynamics of Cu during reoxidation. Whereas Cu(0) was rapidly oxidized to Cu(II), more than half of the S-coordinated Cu fraction persisted over 14 days of aeration. Our results show that precipitation of Cu(0) and complexation of Cu(I) by reduced organic S groups are important processes in periodically flooded soils if sulfide formation is limited by the amount of available sulfate or the duration of soil flooding. The speciation changes of Cu described in this study may also affect the

  11. Chemical residuals in the environment and on chicken carcasses associated with scalding chickens in an acidic, copper sulfate-based commercial sanitizer during poultry processing.

    PubMed

    Russell, Scott M

    2008-01-01

    A study was conducted to determine if an acidic, copper sulfate-based commercial sanitizer evolves into surrounding air when introduced in a commercial poultry scalder. Two identical slaughter lines in a large poultry processing plant were used. One scalder was dosed with the sanitizer, and the other one was not. Four air samples were collected per day over the treated and control lines by an impingement method for 4 days for each of the two lines. Results showed that dosing the scalder with an acidic, copper sulfate-based commercial sanitizer resulted in no significant increase (P < or = 0.05) in the levels of the chemical components (sulfuric acid, ammonium sulfate, and copper sulfate) in the air above the scalder. Another study was conducted to evaluate the effect of the addition of this sanitizer during scalding on chemical residuals on chicken skin, meat, and fat. Five chickens were tagged and scalded in commercial scald water (136 degrees F [57.8 degrees C]), and five chickens were tagged and scalded in scald water (136 degrees F) treated with an acidic, copper sulfate-based commercial sanitizer as above. The chickens for both the control and treated lines were allowed to continue down the processing line and be exposed to the various washes (inside and outside bird washer and on-line reprocessing system) and the chiller. Skin, breast meat, and fat were removed from each carcass and analyzed. Three repetitions were conducted. Results demonstrated that there was no significant difference (P < or = 0.05) in the amount of sulfuric acid, ammonium sulfate, or copper sulfate recovered from these carcass parts.

  12. Differences in Median Ultraviolet Light Transmissions of Serial Homeopathic Dilutions of Copper Sulfate, Hypericum perforatum, and Sulfur.

    PubMed

    Klein, Sabine D; Sandig, Annegret; Baumgartner, Stephan; Wolf, Ursula

    2013-01-01

    Homeopathic remedies are produced by potentising, that is, the serial logarithmic dilution and succussion of a mother tincture. Techniques like ultraviolet spectroscopy, nuclear magnetic resonance, calorimetry, or thermoluminescence have been used to investigate their physical properties. In this study, homeopathic centesimal (c) potencies (6c to 30c) of copper sulfate, Hypericum perforatum, and sulfur as well as succussed water controls were prepared. Samples of these preparations were exposed to external physical factors like heat, pressure, ultraviolet radiation, or electromagnetic fields to mimic possible everyday storage conditions. The median transmissions from 190 nm to 340 nm and 220 nm to 340 nm were determined by ultraviolet light spectroscopy on five measurement days distributed over several months. Transmissions of controls and potencies of sulfur differed significantly on two of five measurement days and after exposure to physical factors. Transmissions of potencies exposed to ultraviolet light and unexposed potencies of copper sulfate and Hypericum perforatum differed significantly. Potency levels 6c to 30c were also compared, and wavelike patterns of higher and lower transmissions were found. The Kruskal-Wallis test yielded significant differences for the potency levels of all three substances. Aiming at understanding the physical properties of homeopathic preparations, this study confirmed and expanded the findings of previous studies.

  13. Enhanced bioremediation of heavy metal from effluent by sulfate-reducing bacteria with copper-iron bimetallic particles support.

    PubMed

    Zhou, Qin; Chen, Yongzhe; Yang, Ming; Li, Wenkai; Deng, Le

    2013-05-01

    The purpose of this study was to investigate the potential of copper-iron bimetallic particles supported sulfate-reducing bacteria (SRB) in enhancing the reduction of Cu(2+) and Zn(2+) in effluent. The results showed that the copper-iron bimetallic particles can enhance Cu(2+) and Zn(2+) removal and the resistance of the sulfate-reducing bacteria towards metals toxicity, the inhibiting concentration of Cu(2+) and Zn(2+) for SRB was significantly increased (from 100 to 200 mg/L for Cu(2+) and 300 to 400 mg/L for Zn(2+)). The removal efficiencies of Cu(2+) and Zn(2+) (initial concentration 100 mg/L) were 98.17% and 99.67% in SRB-Cu/Fe system after 48 h, while only 29.83% Cu(2+), 90.88% Zn(2+) and 63.81% Cu(2+), 72.63% Zn(2+) were removed in the SRB and Cu/Fe system at the same condition.

  14. Characterization of a Marine Microbial Community Used for Enhanced Sulfate Reduction and Copper Precipitation in a Two-Step Process.

    PubMed

    García-Depraect, Octavio; Guerrero-Barajas, Claudia; Jan-Roblero, Janet; Ordaz, Alberto

    2016-11-23

    Marine microorganisms that are obtained from hydrothermal vent sediments present a great metabolic potential for applications in environmental biotechnology. However, the work done regarding their applications in engineered systems is still scarce. Hence, in this work, the sulfate reduction process carried out by a marine microbial community in an upflow anaerobic sludge blanket (UASB) reactor was investigated for 190 days under sequential batch mode. The effects of 1000 to 5500 mg L(-1) of SO4(-2) and the chemical oxygen demand (COD)/SO4(-2) ratio were studied along with a kinetic characterization with lactate as the electron donor. Also, the feasibility of using the sulfide produced in the UASB for copper precipitation in a second column was studied under continuous mode. The system presented here is an alternative to sulfidogenesis, particularly when it is necessary to avoid toxicity to sulfide and competition with methanogens. The bioreactor performed better with relatively low concentrations of sulfate (up to 1100 mg L(-1)) and COD/SO4(-2) ratios between 1.4 and 3.6. Under the continuous regime, the biogenic sulfide was sufficient to precipitate copper at a removal rate of 234 mg L(-1) day(-1). Finally, the identification of the microorganisms in the sludge was carried out; some genera of microorganisms identified were Desulfitobacterium and Clostridium.

  15. Crystal structure of catena-poly[[copper(II)-μ2-salicylato-[diaqua­copper(II)]-μ2-salicylato] dihydrate

    PubMed Central

    van der Horn, Jitschaq A.; Lutz, Martin

    2017-01-01

    The title compound, {[Cu2(C7H4O3)2(H2O)2]·2H2O}n, contains two copper(II) cations in special positions (one on a twofold rotation axis and one on an inversion centre) and the the salicylate ligand in its dianionic form. By four- and six-coordinate metal coordination, chains are formed parallel to [001], which are extended by O—H⋯O hydrogen bonding into sheets extending parallel to (100). These sheets are weakly connected by O—H⋯O hydrogen bonding via the non-coordinating lattice water mol­ecules into a three-dimensional network. PMID:28217350

  16. Solvent effects on the stability of nifuroxazide complexes with cobalt(II), nickel(II) and copper(II) in alcohols.

    PubMed

    Khan, Mustayeen A; Ali, S Kauser; Bouet, Gilles M

    2002-05-21

    A spectrophotometric study of the complexation of nifuroxazide with cobalt(II), nickel(II) and copper(II) was carried out in different alcohols. The formation of a complex in each case is reported and their stability constants have been calculated. For a given solvent, the stability of the complexes increases from cobalt to copper. In the case of copper(II), the stability varies as an inverse function of the dielectric constant of the solvent. A possible structure of the complex is proposed.

  17. Electrochemistry of Ferrous Sulfate-Sodium Thiosulphate and Copper Sulfate-Sodium Thiosulphate Systems for Template-Assisted Nanowire Synthesis

    NASA Astrophysics Data System (ADS)

    Brogan, Lee Jeffery

    Two related series of investigations are presented in this dissertation. First, two candidate systems for electrochemical deposition of metal sulfides for photovoltaic applications have been characterized. Secondly, a general electrochemical synthesis method allowing countable numbers of wires embedded in porous anodic alumina arrays to be measured using macroscopic contacts was developed. Electrochemical studies of the FeSO4-Na2S 2O3 system and the CuSO4-Na2S 2O3 system were undertaken to evaluate their suitability as electrodeposition baths for FeS2 and CuxS, respectively. Each solution system was studied extensively using cyclic voltammetry to characterize electrochemical processes at various concentrations. The iron sulfide / thiosulfate system was found to be unsuitable for the synthesis of FeS2 due to the preferential formation of FeS. The copper sulfide / thiosulfate system was found to be suitable for the synthesis of Cu2S, with thiosulfate concentration being the most important parameter due to the high complexation of Cu(I) by thiosulfate. Investigations into the electrochemical synthesis of metal wires in porous anodic alumina templates revealed an interesting synthesis mechanism wherein sparse, isolated wires are created in a very small fraction of the available pores. These wires are nucleated through the reduction of metal from the deposition bath by aluminum at the base of the alumina pores. This reduction causes a localized increase in acidity, accelerating the dissolution of the alumina barrier layer and allowing more typical wire deposition to occur. The sparse nucleation is exaggerated by the increasing rate of wire deposition as the wires lengthen and the swift rate of overgrowth formation at the surface of the template, resulting in domes of overgrowth attached to countable numbers of nanowires. This geometry has been exploited to obtain in situ measurements of known numbers of nanowires.

  18. Biosorption studies on copper (II) and cadmium (II) using pretreated rice straw and rice husk.

    PubMed

    Li, W C; Law, F Y; Chan, Y H M

    2015-07-25

    This study investigated the adsorption and removal behaviour of copper (Cu) (II) and cadmium (Cd) (II) ions using rice husk and rice straw in aqueous solutions. Different parameters were used to investigate their adsorption performance in saline conditions and the optimal level of biosorption at different pH levels. The main parameters were pH (3, 6 and 9), initial concentration level of heavy metals (Cu (II) 5, 10, 20, 40 and 60 mg/L and Cd (II) 0.5, 1, 2, 4 and 8 mg/L, respectively), salinity (0, 50 and 100 mM NaCl) and contact time (ranging from 3 to 60 min). Langmuir and Freundlich isotherm models were applied to analyse the removal efficiency and sorption capacity of the pretreated rice husk and rice straw. The removal efficiency and adsorption capacity generally increased with the pH and reached a plateau in alkaline conditions. The percentage removal of Cu (II) by rice husk reached 97 % at pH 9 and 95 % by rice straw at pH 6. Biosorption performance increased in the absence of NaCl. Kinetic studies for both metals revealed that the biosorption of Cu (II) and Cd (II) onto rice straw and husk was pseudo-second order.

  19. Toxicity of copper(II) ions to microorganisms in biological wastewater treatment systems.

    PubMed

    Ochoa-Herrera, Valeria; León, Glendy; Banihani, Qais; Field, Jim A; Sierra-Alvarez, Reyes

    2011-12-15

    Copper is an essential element, however, this heavy metal is an inhibitor of microbial activity at relatively low concentrations. The objective of this study was to evaluate the inhibitory effect of copper(II) towards various microbial trophic groups responsible for the removal of organic constituents and nutrients in wastewater treatment processes. The results of the batch bioassays indicated that copper(II) caused severe inhibition of key microbial populations in wastewater treatment systems. Denitrifying bacteria were found to be very sensitive to the presence of copper(II). The concentrations of copper(II) causing 50% inhibition (IC(50)) on the metabolic activity of denitrifiers was 0.95 mg L(-1). Copper was also inhibitory to fermentative bacteria, aerobic glucose-degrading heterotrophs, and nitrifying bacteria (IC(50) values=3.5, 4.6 and 26.5 mg L(-1), respectively). Nonetheless, denitrifying and nitrifying bacteria showed considerable recovery of their metabolic activity after only several days of exposure to high copper levels (up to 25 and 100mg Cu(II) L(-1) for denitrification and nitrification, respectively). The recovery could be due to attenuation of soluble copper or to microbial adaptation.

  20. Antioxidant promotion of tyrosine nitration in the presence of copper(II).

    PubMed

    Qiao, Liang; Liu, Baohong; Girault, Hubert H

    2013-06-01

    Copper(II) is known to catalyze the generation of reactive nitrogen species in the presence of hydrogen peroxide, nitrite or nitric oxide, leading to tyrosine nitration, a biomarker for free radical species associated diseases. Here, we find that biological antioxidants such as ascorbic acid can promote tyrosine nitration in the presence of copper(II) and nitrite under aerobic and weak acidic conditions. Tyrosine nitration is demonstrated on both the β-amyloid peptide and angiotensin I. These studies show that (i) ascorbic acid works as a pro-oxidant in the presence of copper(II) to induce oxidation and nitration on peptides, (ii) both free and coordinated copper(II) can catalyze peptide oxidation and nitration, (iii) nitration occurs under mild acidic conditions (pH = 6.0-6.5).

  1. Impact of copper on the abundance and diversity of sulfate-reducing prokaryotes in two chilean marine sediments.

    PubMed

    Besaury, Ludovic; Ouddane, Baghdad; Pavissich, Juan Pablo; Dubrulle-Brunaud, Carole; González, Bernardo; Quillet, Laurent

    2012-10-01

    We studied the abundance and diversity of the sulfate-reducing prokaryotes (SRPs) in two 30-cm marine chilean sediment cores, one with a long-term exposure to copper-mining residues, the other being a non-exposed reference sediment. The abundance of SRPs was quantified by qPCR of the dissimilatory sulfite reductase gene β-subunit (dsrB) and showed that SRPs are sensitive to high copper concentrations, as the mean number of SRPs all along the contaminated sediment was two orders of magnitude lower than in the reference sediment. SRP diversity was analyzed by using the dsrB-sequences-based PCR-DGGE method and constructing gene libraries for dsrB-sequences. Surprisingly, the diversity was comparable in both sediments, with dsrB sequences belonging to Desulfobacteraceae, Syntrophobacteraceae, and Desulfobulbaceae, SRP families previously described in marine sediments, and to a deep branching dsrAB lineage. The hypothesis of the presence of horizontal transfer of copper resistance genes in the microbial population of the polluted sediment is discussed.

  2. XPS and XAS studies of copper(II) sorbed onto a synthetic pyrite surface.

    PubMed

    Naveau, Aude; Monteil-Rivera, Fanny; Guillon, Emmanuel; Dumonceau, Jacques

    2006-11-01

    Compounds containing copper are likely candidates to delay iodide migration in environmental media through the formation of sparingly soluble phases. Preliminary experiments showed that iodide was neither sorbed onto chalcopyrite nor by a binary system pyrite/copper(II), although significant amounts of copper were present at the pyrite surface. In the present study, spectroscopic studies (XPS, XANES and EXAFS) were thus performed to determine the nature of sorbed copper species. Although introduced as Cu(II), copper was mainly present at the oxidation state (I) on the pyrite surface suggesting a heterogeneous reduction process. Moreover, copper appeared tetrahedrally coordinated to two sulfur and two oxygen atoms onto the pyrite surface, a chemical environment, which seemingly stabilized the metal and made it unreactive towards iodide.

  3. Effect of dietary supplementation with copper sulfate or tribasic copper chloride on the growth performance, liver copper concentrations of broilers fed in floor pens, and stabilities of vitamin E and phytase in feeds.

    PubMed

    Lu, Lin; Wang, Run L; Zhang, Zheng J; Steward, Fred A; Luo, Xugang; Liu, Bin

    2010-12-01

    An experiment was conducted using a total of 840, 1-day-old, Arbor Acres commercial male broilers to compare copper (Cu) sulfate and tribasic Cu chloride (TBCC, Cu(2)(OH)(3)Cl) as sources of supplemental Cu for broilers fed in floor pens. Chicks were randomly allotted to one of seven treatments for six replicate pens of 20 birds each, and were fed a basal corn-soybean meal diet (10.20 mg/kg Cu) supplemented with 0, 100, 150, or 200 mg/kg Cu from either Cu sulfate or TBCC for 21 days. Chicks fed 200 mg/kg Cu as TBCC had a higher (P < 0.05) average daily gain (ADG) than those consuming other diets. Liver Cu contents of broilers fed diets supplemented with TBCC were numerically lower (P > 0.05) than those of broilers fed diets supplemented with Cu sulfate. The vitamin E contents and the phytase activities in the feed fortified with TBCC were higher (P < 0.01) and numerically higher (P > 0.05) compared with those in the feeds fortified with Cu sulfate stored at room temperature, respectively. The vitamin E contents in liver and plasma of broilers fed diets supplemented with TBCC were higher (P < 0.05) than those of birds fed diets supplemented with Cu sulfate. This result indicates that TBCC is more effective than Cu sulfate in improving the growth of broilers fed in floor pens, and it is chemically less active than Cu sulfate in promoting the undesirable oxidation of vitamin E in feeds.

  4. Effects of tribasic copper chloride versus copper sulfate provided in corn-and molasses-based supplements on forage intake and copper status of beef heifers.

    PubMed

    Arthington, J D; Spears, J W

    2007-03-01

    The objective of this study was to investigate the effect of supplemental tribasic copper chloride (Cu(2)(OH(3))Cl; TBCC) vs. Cu sulfate (CuSO(4)) on Cu status and voluntary forage DMI in growing heifers. Two 90-d experiments were conducted using 48 non-pregnant, crossbred heifers (24 heifers/experiment; 355 +/- 10.7 and 309 +/- 9.9 kg for Exp. 1 and 2, respectively). In each experiment, 3 supplemental Cu treatments were randomly allocated to heifers in individual pens consisting of (1) 100 mg of Cu/d from CuSO(4), (2) 100 mg of Cu/d from TBCC, or (3) 0 mg of Cu/d. The 2 experiments differed by the form of supplement used to deliver the Cu treatments (corn- vs. molasses-based supplements for Exp. 1 and 2, respectively). Supplements were formulated and fed to provide equivalent amounts of CP and TDN daily but differed in their concentration of the Cu antagonists, Mo (0.70 vs. 1.44 mg/kg), Fe (113 vs. 189 mg/kg), and S (0.18 vs. 0.37%) for corn- and molasses-based supplements, respectively. All heifers were provided free-choice access to ground stargrass (Cynodon spp.) hay. Jugular blood and liver biopsy samples were collected on d 0, 30, 60, and 90 of each experiment. Heifer BW was collected on d 0 and 90. Heifer ADG was not affected by Cu treatment (average = 0.22 +/- 0.11 and 0.44 +/- 0.05 kg for Exp. 1 and 2, respectively; P > 0.20). In Exp. 1, heifers provided supplemental Cu, independent of source, had greater (P < 0.05) liver Cu concentrations on d 60 and 90 compared with heifers provided no supplemental Cu. In Exp. 2, average liver Cu concentrations were greater (P = 0.04) for heifers receiving supplemental Cu compared with heifers receiving no Cu; however, all treatments experienced a decrease in liver Cu concentration over the 90-d treatment period. Plasma ceruloplasmin concentrations did not differ in Exp. 1 (P = 0.83) but were greater (P = 0.04) in Exp. 2 for heifers receiving supplemental Cu compared with heifers receiving no Cu. In Exp. 1, voluntary

  5. Ion paired chromatography of iron (II,III), nickel (II) and copper (II) as their 4,7-Diphenyl-1,10-phenanthroline chelates.

    PubMed

    Mudasir; Yoshioka, N; Inoue, H

    1997-07-01

    A reversed phase ion-paired chromatographic method that can be used to determine trace amounts of iron (II,III), nickel (II) and copper (II) was developed and applied to the determination of iron (II) and iron (III) levels in natural water. The separation of these metal ions as their 4,7-diphenyl-1,10-phenanthroline (bathophenanthroline) chelates on an Inertsil ODS column was investigated by using acetonitrile-water (80/20, v/v) containing 0.06 M perchloric acid as mobile phase and diode array spectrophotometric detection at 250-650 nm. Chromatographic parameters such as composition of mobile phase and concentration of perchloric acid in mobile phase were optimized. The calibration graphs of iron (II), nickel (II) and copper (II) ions were linear (r > 0.991) in the concentration range 0-0.5, 0-2.0 and 0-4.0 mug ml(-1), respectively. The detection limit of iron (II), nickel (II) and copper (II) were 2.67, 5.42 and 18.2 ng ml(-1) with relative standard deviation (n = 5) of 3.11, 5.81 and 7.16% at a concentration level of 10 ng ml(-1) for iron (II) and nickel (II) and 25 ng ml(-1) for copper (II), respectively. The proposed method was applied to the determination of iron(II) and iron(III) in tap water and sea water samples without any interference from other common metal ions.

  6. Mono-nuclear copper complexes mimicking the intermediates for the binuclear copper center of the subunit II of cytochrome oxidase: a peptide based approach.

    PubMed

    Dutta Gupta, Dwaipayan; Usharani, Dandamudi; Mazumdar, Shyamalava

    2016-11-28

    Three stable copper complexes of peptides derived from the copper ion binding loop of the subunit II of cytochrome c oxidase have been prepared and characterized by various spectroscopic techniques. These stable copper complexes of peptides were found to exhibit cysteine, histidine and/or methionine ligation, which has predominant σ-contribution in the Cys-Cu charge transfer. The copper(ii) peptide complexes showed type-2 EPR spectra, which is uncommon in copper-cysteinate complexes. UV-visible spectra, Raman and EPR results support a tetragonal structure of the coordination geometry around the copper ion. The copper complex of the 9-amino acid peptide suggested the formation of a 'red' copper center while the copper complexes of the 12- and 11-amino acid peptides showed the formation of a 'green' copper center. The results provide insights on the first stable models of the copper complexes formed in the peptide scaffold that mimic the mono-nuclear copper bound protein intermediates proposed during the formation of the binuclear Cu2S2 core of the enzyme. These three copper complexes of peptides derived from the metal ion binding loop of the CuA center of the subunit II of cytochrome c oxidase showed novel spectroscopic properties which have not so far been reported in any stable small complex.

  7. Growth and characterization of Cu (II) doped negatively soluble lithium sulfate monohydrate crystals

    NASA Astrophysics Data System (ADS)

    Boopathi, K.; Ramasamy, P.; Bhagavannarayana, G.

    2014-01-01

    Single crystals of pure and Cu (II) doped negatively soluble lithium sulfate monohydrate have been grown by slow evaporation solution technique. In the present work, to improve the crystalline quality of lithium sulfate monohydrate crystal, metal dopant was incorporated into the pure crystals. The as grown crystals are clear, transparent and the sizes of the crystals were up to 18×12×3 mm3 and 50×15×5 mm3. The presence of metal dopant has been confirmed by energy dispersive spectroscopy, atomic absorption spectroscopy analysis. Single crystal and powder X-ray diffraction studies were carried out to ascertain lattice parameters and identify different phase nature. Optical transmission spectrum of the grown crystals was recorded. FT-IR and thermal analysis were carried out to investigate the functional group and thermal behavior of the grown crystals respectively. The grown crystal was subjected to Vickers micro hardness, HRXRD, piezoelectric, laser damage threshold measurements and second harmonic generation efficiency studies.

  8. Spectral studies of copper(II) complexes of 6-(3-thienyl) pyridine-2-thiosemicarbazone

    SciTech Connect

    Mahjoub, Omima Abdalla; Farina, Yang

    2014-09-03

    Two novel copper(II) complexes [Cu(HL)Cl]Cl.H{sub 2}O (1) and [Cu(L)NO{sub 3}]Ðœ‡H{sub 2}O (2) of the three NNS donor thiosemicarbazone ligand 6-(3-thienyl) pyridine-2-thiosemicarbazone have been synthesized. The ligand and its copper(II) complexes were characterized by elemental analysis (C, H, N, and S), FT-IR, UV-visible, magnetic susceptibility and molar conductance. The thiosemicarbazone is present either as the thione form in complex 1 or as thiol form in complex 2 and is coordinated to copper(II) atom via the pyridine nitrogen atom, the azomethine nitrogen atom and the sulfur atom. The physicochemical and spectral data suggest square planar geometry for copper(II) atoms.

  9. The effectiveness of flow-through and/or static copper sulfate treatments on the survival of Golden Shiners and Fathead Minnows infected with Flavobacterium columare

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Four studies were done comparing various treatments of copper sulfate (CuSO4) on the survival of golden shiner and fathead minnow (both economically important baitfish) that had columnaris disease. The treatments were observed for their ability to reduce mortality in well water. In experiment 1 and ...

  10. The effectiveness of flow-through and/or static copper sulfate treatments on the survival of Golden Shiners and Fathead Minnows infected with Flavobacterium columare

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Four studies were done comparing various treatments of copper sulfate (CuSO4) on the survival of golden shiner and fathead minnow (both economically important baitfish) that had columnaris disease. The treatments were observed for their ability to reduce mortality in well water. In experiment 1 an...

  11. Efficacy of bath treatments of formalin and copper sulfate on cultured white bass, Morone chrysops, concurrently infected by Onchocleidus mimus and Ichthyophthirius multifiliis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Treatment efficacy of repeated 1 h baths of formalin (100 mg/L) or copper sulfate (CuSO4) (2.1 mg/L) were evaluated against concurrent infections of Onchocleidus mimus (Mueller, 1936; Monogenoidea: Ancyrocephalidae) and Ichthyophthirius multifiliis (Fouquet, 1876; Hymenostomatida: Ichthyopththiriida...

  12. Effectiveness of copper sulfate, potassium permanganate, and peracetic acid to reduce mortality and infestation of Ichthyobodo nector in channel catfish Ictalurus punctatus (Rafinesque 1818)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Ichthyobodo necator is a single celled bi-flagellate parasite, and in high density can causes significant mortality in young fish. Copper sulfate (CuSO4), potassium permanganate (KMnO4) and peracetic acid (PAA) were evaluated for effectiveness against ichthyobodosis. Treatments were: untreated con...

  13. The effectiveness of repeated tank treatments of copper sulfate and formalin on gill flukes and Ich in naturally infested white bass

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Ectoparasites infesting the gills of juvenile fish reared in tanks can cause serious fish losses. Multiple treatments of formalin and copper sulfate (CuSO4) were evaluated for effectiveness against a natural infestation of gill flukes Onchocleidus mimus (Monogenoidea: Ancyrocephalidae) and Ichthyop...

  14. Treatment of Wilson's disease with zinc. II. Validation of oral /sup 64/copper with copper balance

    SciTech Connect

    Hill, G.M.; Brewer, G.J.; Juni, J.E.; Prasad, A.S.; Dick, R.D.

    1986-12-01

    The efficacy of zinc as a therapeutic agent to control copper balance in Wilson's disease patients has been previously documented with balance studies. In an attempt to develop a simpler and faster tool for evaluating the adequacy of zinc therapy, a technique that measures the uptake into blood of a small oral dose of /sup 64/copper was studied in conjunction with copper balance. The mean peak /sup 64/copper uptake into blood of nine Wilson's disease patients on D-penicillamine, trien, or no medication was 6.04 +/- 2.74%, comparable with normal controls. Seven patients on zinc therapy had a markedly and significantly reduced mean uptake of 0.79 +/- 1.05% after treatment. The data demonstrate that the prevention of copper uptake into blood in Wilson's disease patients by zinc therapy can be evaluated by /sup 64/copper uptake and that peak uptakes of less than 1% occur in patients with neutral or negative copper balance.

  15. Extended X-ray absorption studies of copper (II) dibenzoyal methane diquinoline complexes

    NASA Astrophysics Data System (ADS)

    Mishra, A.; Sharma, P.; Malviya, P. K.

    2013-06-01

    X-ray K-absorption spectroscopic studies have been carried out on copper (II) mixed-ligand complexes. Copper is a transition metal, which in the zero oxidation state has an electron configuration of [Ar] 4s24p63d9. Copper is found in three different oxidation states: Cu(I), Cu(II), and Cu(III). In the copper (II) oxidation state, the metal has 9 d electrons. Jahn-Teller distortion causes a splitting of eg and t2g orbitals. Most Cu(II) complexes are square planar for this reason. In a series of those compounds, we have prepared copper (II) complexes containing two nitrato ligands and a 2,2'-dipyridylamine(dpa) derivative ligand. The 2,2' - dipyridylamine and its derivatives have been widely used for metal complexes because of their good chelating property, structural flexibility. we have estimated the average metalligand bond distances from the fine structure data. We have determined the bond lengths for the copper (II) complexes with the help of Levy's, LSS, Fourier transform, Lytle's Methods.

  16. The effect of dietary supplementation with copper sulfate or tribasic copper chloride on broiler performance, relative copper bioavailability, and dietary prooxidant activity.

    PubMed

    Miles, R D; O'Keefe, S F; Henry, P R; Ammerman, C B; Luo, X G

    1998-03-01

    Three experiments were conducted to study Cu sulfate and tribasic Cu chloride (TBCC) as sources of supplemental Cu for poultry. In Experiment 1, 252 chicks were fed the basal corn-soybean meal diet (26 ppm Cu) supplemented with either 0, 150, 300, or 450 ppm Cu from Cu sulfate or TBCC for 21 d. Chicks fed 450 ppm Cu from sulfate had lower (P < 0.05) feed intake than those consuming other diets. Feeding supplemental Cu increased (P < 0.0001) liver Cu concentration linearly with increasing dietary Cu regardless of Cu source. The slopes of regression of log10 liver Cu on dietary Cu intake did not differ between sources (P > 0.10). Linear regression over nonzero dietary levels of log10 transformed liver Cu concentration (parts per million of DM) on analyzed total Cu intake (micrograms) resulted in a slope ratio estimate of 106+/-19 for bioavailability of Cu from TBCC compared to 100 for that in Cu sulfate. In Experiment 2, a 42-d floor pen study was conducted with 1,260 broiler chicks given the basal corn-soybean meal diet supplemented with 0, 200, 400, or 600 ppm Cu from either feed-grade Cu sulfate or TBCC. Body weight and feed conversion did not differ in birds fed up to 400 ppm Cu from either source. Birds given 600 ppm Cu from either source had lower feed intake, poorer growth, and feed conversion (P < 0.0001). Liver Cu increased (P < 0.0001) linearly with increasing dietary Cu. Based on log10 liver Cu concentration, Cu in TBCC was 112% available compared to 100% for the standard Cu sulfate. In Experiment 3, Cu sources were added to broiler starter diets at concentrations of 25, 100, and 300 ppm Cu and diets were stored at an elevated temperature to examine the effect of particle size on oxidation. Diets were stored at 37 C for up to 20 d and samples were removed at 4-d intervals. At 300 ppm added Cu, oxidation in TBCC diets was lower (P < 0.0001) than oxidation in diets fortified with coarse Cu sulfate, even though TBCC modal diameter for particle size was almost

  17. Synthesis, spectroscopic and thermal studies of the copper(II) aspartame chloride complex

    NASA Astrophysics Data System (ADS)

    Çakır, S.; Coşkun, E.; Naumov, P.; Biçer, E.; Bulut, İ.; İçbudak, H.; Çakır, O.

    2002-08-01

    Aspartame adduct of copper(II) chloride Cu(Asp) 2Cl 2·2H 2O (Asp=aspartame) is synthesized and characterized by elemental analysis, FT IR, UV/vis, ESR spectroscopies, TG, DTG, DTA measurements and molecular mechanics calculations. Aqueous solution of the green solid absorbs strongly at 774 and 367 nm. According to the FT IR spectra, the aspartame moiety coordinates to the copper(II) ion via its carboxylate ends, whereas the ammonium terminal groups give rise to hydrogen bonding network with the water, the chloride ions or neighboring carboxylate groups. The results suggest tetragonally distorted octahedral environment of the copper ions.

  18. Reaction of beta-diketiminate copper(II) complexes and Na2S2.

    PubMed

    Inosako, Masayuki; Kunishita, Atsushi; Shimokawa, Chizu; Teraoka, Junji; Kubo, Minoru; Ogura, Takashi; Sugimoto, Hideki; Itoh, Shinobu

    2008-11-28

    Reaction of beta-diketiminate copper(II) complexes and Na2S2 resulted in formation of (mu-eta2:eta2-disulfido)dicopper(II) complexes (adduct formation) or beta-diketiminate copper(I) complexes (reduction of copper(II)) depending on the substituents of the supporting ligands. In the case of sterically less demanding ligands, adduct formation occurred to provide the (mu-eta2:eta2-disulfido)dicopper(II) complexes, whereas reduction of copper(II) took place to give the corresponding copper(I) complexes with sterically more demanding beta-diketiminate ligands. Spectroscopic examinations of the reactions at low temperature using UV-vis and ESR as well as kinetic analysis have suggested that a 1 : 1 adduct LCuII-S-SNa with an end-on binding mode is initially formed as a common intermediate, from which different reaction pathways exist depending on the steric environment of the metal-coordination sphere provided by the ligands. Thus, with the sterically less demanding ligands, rearrangement of the disulfide adduct from end-on to side-on followed by self-dimerisation occurs to give the (mu-eta2:eta2-disulfido)dicopper(II) complexes, whereas such an intramolecular rearrangement of the disulfide co-ligand does not take place with the sterically more demanding ligands. In this case, homolytic cleavage of the CuII-S bond occurs to give the reduced copper(I) product. The steric effects of the supporting ligands have been discussed on the basis of detailed analysis of the crystal structures of the copper(II) starting materials.

  19. Diffusion behavior of copper atoms under Cu(II) reduction in Cucurbit[8]uril cavity at elevated temperatures

    SciTech Connect

    Bakovets, Vladimir V.; Nadolinnii, Vladimir A.; Kovalenko, Ekaterina A.; Plyusnin, Pavel E.; Dolgovesova, Irina P.; Zaikovskii, Vladimir I.

    2015-01-15

    In this paper we describe copper clusters and nanoparticles formation by the reduction of copper (II) ions inside cavities of macrocycle molecules using supramolecular compound [Cu(Cyclen)(H{sub 2}O)@CB[8

  20. The use of continuous low-dosage copper sulfate as a molluscicide on an irrigation scheme in Kenya*

    PubMed Central

    Teesdale, C.; Hadman, D. F.; Nguriathi, J. N.

    1961-01-01

    On a developing irrigation scheme in Kenya where there was a potential danger of Schistosoma mansoni transmission, copper sulfate at a concentration of between 0.125 p.p.m. and 0.25 p.p.m. was introduced as soon as water started flowing into the canals; there was no pre-sulfation at a higher concentration and mechanical barriers were not used. It was hoped that if this method proved successful it could be adopted for the routine control of bilharziasis, but as it proved impossible to provide day-to-day supervision, no definite conclusions as to the efficacy of the method can be made. The available data, however, indicated that at an average of 0.25 p.p.m. a barrier was created which was lethal to snails which passed through it, but that at an average of 0.125 p.p.m. results were indeterminate. Further trials to obtain more precise data on the mechanism of chemical barriers are recommended. PMID:13920077

  1. Structural Diversity of Copper(II) Complexes with 9-Deazahypoxanthine and Their in Vitro SOD-Like Activity

    PubMed Central

    Gáliková, Jana; Trávníček, Zdeněk

    2015-01-01

    Two structurally different copper(II) complexes of the compositions [{Cu(9dhx)(H2O)3}2(µ-SO4)2] (1) and [Cu(9dhx)2(H2O)2(NO3)2]·H2O (2), involving 9-deazahypoxanthine (9dhx; 6-oxo-9-deazapurine; 9-deazahypoxanthine), have been prepared and characterized by elemental analysis, infrared and electronic spectroscopy, electrospray ionisation (ESI) mass spectrometry, thermogravimetric (TG) and differential thermal (DTA) analyses, and cyclic voltammetry. The X-ray structures of complexes 1 and [Cu(9dhx)2(H2O)2(NO3)2] (2a) revealed the distorted octahedral geometry in the vicinity of the copper(II) atoms, with the NO5 and N2O4 donor set, respectively. In the dimeric compound 1, the {Cu(9dhx)(H2O)3}2 units are bridged by sulfate groups with the Cu···Cu separation being 5.3446(2) Å. In both structures the 9dhx ligands are coordinated through the N3 atoms of the pyrimidine moieties. The SOD-like activity of complexes 1 and 2 was evaluated in vitro showing moderate effect, with the IC50 values equal to 18.20, and 53.33 μM, respectively. PMID:26184182

  2. Crystal growth, stability and photoluminescence studies of tetra aqua diglycine magnesium (II) hexa aqua magnesium (II) bis sulfate crystal

    NASA Astrophysics Data System (ADS)

    Senthil Murugan, G.; Ramasamy, P.

    2011-03-01

    Single crystals of tetra aqua diglycine magnesium (II) hexa aqua magnesium (II) bis sulfate have been grown from saturated aqueous solution by slow evaporation solution growth technique. The solubility of the title compound in water at various temperatures has been determined. Single-crystal X-ray diffraction analyses reveal that the title compound crystallizes in triclinic system with space group P1¯. Fourier transform infrared spectral analyses confirm the presence of functional groups in the grown crystal. The thermal stability of the grown crystal has been investigated by thermogravimetric and differential scanning calorimetric analysis. It indicates that the material is stable upto 100 °C. The crystalline perfection of the grown crystal has been evaluated by high-resolution X-ray diffraction technique. Vickers microhardness measurements indicate the mechanical strength of the grown crystal. Photoluminescence of the grown crystal has been investigated and it reveals that the crystal has blue-violet fluorescence emission.

  3. Iron versus Copper II. Principles and Applications in Bioinorganic Chemistry.

    ERIC Educational Resources Information Center

    Ochiai, Ei-Ichiro

    1986-01-01

    Discusses the differences between iron and copper. Describes various aspects of the behaviors of these two elements, including those of biological and environmental significance. Addresses the evolution of the atmosphere and sedimentary ore formation, the phylogeny of iron and copper, and some anthropological notes regarding the use of the metals.…

  4. Pyrrolidine dithiocarbamate-zinc(II) and -copper(II) complexes induce apoptosis in tumor cells by inhibiting the proteasomal activity

    SciTech Connect

    Milacic, Vesna; Chen Di; Giovagnini, Lorena; Diez, Alejandro; Fregona, Dolores; Dou, Q. Ping

    2008-08-15

    Zinc and copper are trace elements essential for proper folding, stabilization and catalytic activity of many metalloenzymes in living organisms. However, disturbed zinc and copper homeostasis is reported in many types of cancer. We have previously demonstrated that copper complexes induced proteasome inhibition and apoptosis in cultured human cancer cells. In the current study we hypothesized that zinc complexes could also inhibit the proteasomal chymotrypsin-like activity responsible for subsequent apoptosis induction. We first showed that zinc(II) chloride was able to inhibit the chymotrypsin-like activity of a purified 20S proteasome with an IC{sub 50} value of 13.8 {mu}M, which was less potent than copper(II) chloride (IC{sub 50} 5.3 {mu}M). We then compared the potencies of a pyrrolidine dithiocarbamate (PyDT)-zinc(II) complex and a PyDT-copper(II) complex to inhibit cellular proteasomal activity, suppress proliferation and induce apoptosis in various human breast and prostate cancer cell lines. Consistently, zinc complex was less potent than copper complex in inhibiting the proteasome and inducing apoptosis. Additionally, zinc and copper complexes appear to use somewhat different mechanisms to kill tumor cells. Zinc complexes were able to activate calpain-, but not caspase-3-dependent pathway, while copper complexes were able to induce activation of both proteases. Furthermore, the potencies of these PyDT-metal complexes depend on the nature of metals and also on the ratio of PyDT to the metal ion within the complex, which probably affects their stability and availability for interacting with and inhibiting the proteasome in tumor cells.

  5. Synthesis and crystal structure of thiosemicarbazide complexes of nickel(II) and copper(II)

    NASA Astrophysics Data System (ADS)

    Sadikov, G. G.; Antsyshkina, A. S.; Koksharova, T. V.; Sergienko, V. S.; Kurando, S. V.; Gritsenko, I. S.

    2012-07-01

    Thiosemicarbazide complexes of nickel(II) [Ni( TSC)2](H Sal)2 ( I) and copper(II) [Cu( TSC)2](H Sal)2 ( Ia) ( TSC is thiosemicarbazide and H Sal is a salycilate anion), as well as complexes [Ni( TSC)2](SO4) · 2H2O ( II) and [Ni( TSC)3]Cl2 · H2O ( III), are synthesized and characterized by IR spectroscopy and X-ray diffraction. Monoclinic crystals I and Ia are isostructural; space group P21/ n, Z = 2. Crystals II are monoclinic, space group P21/ m, Z = 2. Crystals III are orthorhombic, space group Pbca, Z = 8. In I and Ia, two planar salycilate anions sandwich a planar centrosymmetric [Ni( TSC)2]2+ cation to form a supermolecule. The cation and anions are additionally bound by hydrogen bonds. Other hydrogen bonds connect supermolecules into planar layers. In structure II, centrosymmetric [Ni( TSC)2]2+ cations are connected by π-stacking interactions into supramolecular ensembles of a specific type. The ensembles, water molecules, and (SO4)2- anions are bound in the crystal via hydrogen bonds. In the [Ni( TSC)3]2+ cation of structure III, ligands coordinate the Ni atom by the bidentate chelate pattern with the formation of five-membered metallocycles. These metallocycles have an envelope conformation unlike those in I and II, which are planar. In III (unlike in analogous complexes), a meridional isomer of the coordination octahedron of the Ni atom is formed. Together with Cl1- and Cl2- anions, cations form supermolecules, which are packed into planar layers with a square-cellular structure. The layers are linked by hydrogen bonds formed by crystallization water molecules that are located between the layers.

  6. Structural analysis and physico-chemical characterization of mononuclear manganese(II) and polynuclear copper(II) complexes with pyridine-based alcohol

    NASA Astrophysics Data System (ADS)

    Zienkiewicz-Machnik, Małgorzata; Masternak, Joanna; Kazimierczuk, Katarzyna; Barszcz, Barbara

    2016-12-01

    Two novel manganese(II) and copper(II) complexes, mononuclear [Mn(H2O)2(2-(CH2)2OHpy)2](NO3)2 (1) and polynuclear [Cu(SO4)(2-(CH2)2OHpy)2]n (2), based on 2-(hydroxyethyl)pyridine (2-(CH2)2OHpy) were synthesised and fully characterised using X-ray structure analysis as well as spectroscopic, magnetic and thermal methods. Both central metal ions Mn(1) and Cu(1) are coordinated by two N,O-donor 2-(CH2)2OHpy ligands and possess an almost perfect octahedral geometry (a chromophore of {MN2O4} type). The coordination sphere of Mn(II) is completed by two molecules of water, whereas, in polynuclear complex 2, Cu(II) atoms are linked along the a crystallographic direction by bridging sulfate ligands in a μ2-κ2 binding mode to form chains. The intermolecular interactions in 1 and 2 have been interpreted in view of the 3D Hirshfeld surface analysis and associated 2D fingerprint plots. Furthermore, the complexes have been tested with ABTSrad + assay in order to assess their antioxidant activity. In addition, the IC50 values calculated for 1 and 2 revealed that the complexes show a higher antioxidant activity than corresponding ligand.

  7. Copper(II), nickel(II) and zinc(II) complexes of the N-terminal nonapeptide fragment of amyloid-β and its derivatives.

    PubMed

    Grenács, Ágnes; Sóvágó, Imre

    2014-10-01

    Copper(II), nickel(II) and zinc(II) complexes of the nonapeptide fragment of amyloid-β Aβ(1-9) (NH2-DAEFRHDSG-NH2) and its two derivatives: NH2-DAAAAHAAA-NH2 and NH2-DAAAAAHAA-NH2 have been studied by potentiometric, UV-visible and CD spectroscopic methods. The results reveal the primary role of the amino terminus of peptides in copper(II) and nickel(II) binding. The formation of dinuclear complexes was also possible in the copper(II) containing systems but only the first six amino acids from the amino terminus were involved in metal binding in the physiologically relevant pH range. The coordination chemistry of the two alanine mutated peptides is almost the same as that of the native nonapeptide, but the thermodynamic stability of the copper(II) complexes of the mutants is significantly reduced. This difference probably comes from the secondary interactions of the polar side chains of Asp, Glu, Ser and Arg residues present in the native peptide. Moreover, this difference reveals that the amino acid sequence of the N-terminal domains of amyloid peptides is especially well suited for the complexation with copper(II) ions.

  8. Synthesis and DNA cleavage activities of mononuclear macrocyclic polyamine zinc(II), copper(II), cobalt(II) complexes which linked with uracil.

    PubMed

    Wang, Xiao-Yan; Zhang, Ji; Li, Kun; Jiang, Ning; Chen, Shan-Yong; Lin, Hong-Hui; Huang, Yu; Ma, Li-Jian; Yu, Xiao-Qi

    2006-10-01

    Mononuclear macrocyclic polyamine zinc(II), copper(II), cobalt(II) complexes, which could attach to peptide nucleic acid (PNA), were synthesized as DNA cleavage agents. The structures of these new mononuclear complexes were identified by MS and (1)H NMR spectroscopy. The catalytic activities on DNA cleavage of these mononuclear complexes with different central metals were subsequently studied, which showed that copper complex was better catalyst in the DNA cleavage process than zinc and cobalt complexes. The effects of reaction time, concentration of complexes were also investigated. The results indicated that the copper(II) complexes could catalyze the cleavage of supercoiled DNA (pUC 19 plasmid DNA) (Form I) under physiological conditions to produce selectively nicked DNA (Form II, no Form III produced) with high yields. The mechanism of the cleavage process was also studied.

  9. Effect of phosphate and sulfate on Ni repartitioning during Fe(II)-catalyzed Fe(III) oxide mineral recrystallization

    NASA Astrophysics Data System (ADS)

    Hinkle, Margaret A. G.; Catalano, Jeffrey G.

    2015-09-01

    Dissolved Fe(II) activates coupled oxidative growth and reductive dissolution of Fe(III) oxide minerals, causing recrystallization and the repartitioning of structurally-compatible trace metals. Phosphate and sulfate, two ligands common to natural aquatic systems, alter Fe(II) adsorption onto Fe(III) oxides and affect Fe(III) oxide dissolution and precipitation. However, the effect of these oxoanions on trace metal repartitioning during Fe(II)-catalyzed Fe(III) oxide recrystallization is unclear. The effects of phosphate and sulfate on Ni adsorption and Ni repartitioning during Fe(II)-catalyzed Fe(III) oxide recrystallization were investigated as such repartitioning may be affected by both Fe(II)-oxoanion and metal-oxoanion interactions. In most systems examined, phosphate alters Ni repartitioning during Fe(II)-catalyzed recrystallization to a larger extent than sulfate. Phosphate substantially enhances Ni adsorption onto hematite but decreases (nearly inhibiting) Fe(II)-catalyzed Ni incorporation into and release from this mineral. In the goethite system, however, phosphate suppresses Ni release but enhances Ni incorporation in the presence of aqueous Fe(II). In contrast, sulfate has little effect on macroscopic Ni adsorption and release of Ni from Fe(III) oxides, but substantially enhances Ni incorporation into goethite. This demonstrates that phosphate and sulfate have unique, mineral-specific interactions with Ni during Fe(II)-catalyzed Fe(III) oxide recrystallization. This research suggests that micronutrient bioavailability at redox interfaces in hematite-dominated systems may be especially suppressed by phosphate, while both oxoanions likely have limited effects in goethite-rich soils or sediments. Phosphate may also exert a large control on contaminant fate at redox interfaces, increasing Ni retention on iron oxide surfaces. These results further indicate that trace metal retention by iron oxides during lithification and later repartitioning during

  10. Effect of ammonium sulfate fertilization on bahiagrass quality and copper metabolism in grazing beef cattle.

    PubMed

    Arthington, J D; Rechcigl, J E; Yost, G P; McDowell, L R; Fanning, M D

    2002-10-01

    To assess the impact of S fertilization on bahiagrass (Paspalum notatum) quality and Cu metabolism in cattle, two studies were conducted during the summer grazing season (1999 and 2000). Pasture replicates (16.2 ha; n = 2/treatment) received the same fertilizer treatment in each growing season, consisting of 1) 67 kg N/ha from ammonium sulfate (AS), 2) 67 kg N/ha from ammonium nitrate (AN), and 3) control (no fertilizer; C). Forage sampling was conducted at 28-d intervals following fertilization by the collection of whole plants (four samples/pasture) in randomly distributed 1-m2 grazing exclusion cages and analyzed for CP, in vitro organic matter digestibility, S, P, Ca, K, Mg, Na, Fe, Al, Mn, Cu, and Zn. To determine the effect of fertilizer treatment on liver trace mineral concentrations in grazing cattle, random liver tissue samples were collected (n = 12; four/treatment) at the start and end of the study period in 2000. Ammonium sulfate fertilization increased (P < 0.001) forage S concentration in both years. Plant tissue N concentrations were increased by N fertilization, regardless of source, in 2000, but not in 1999. Cows grazing AS pastures had lower (P < 0.05) liver Cu concentrations at the end of the study period in 2000 compared to AN and C. In Exp. 2, 37 Cu-deficient heifers grazing AS fertilized pastures were obtained from the same location and allocated to one of two treatments, consisting of supplements providing 123 mg/d of either inorganic (Cu sulfate; n = 12) or organic (Availa-Cu; n = 15) Cu. Treatments were delivered for 83 d. Liver Cu increased over time in all heifers regardless of treatment; however, heifers supplemented with Availa-Cu tended (P = 0.09) to have higher mean liver Cu concentrations than those receiving Cu sulfate. The results of these studies indicate that AS fertilization of bahiagrass increases forage S concentrations. When provided free-choice access to a complete salt-based trace mineral supplement, cows grazing AS

  11. Utilizing reversible copper(II) peptide coordination in a sequence-selective luminescent receptor.

    PubMed

    Stadlbauer, Stefan; Riechers, Alexander; Späth, Andreas; König, Burkhard

    2008-01-01

    Although vast information about the coordination ability of amino acids and peptides to metal ions is available, little use of this has been made in the rational design of selective peptide receptors. We have combined a copper(II) nitrilotriacetato (NTA) complex with an ammonium-ion-sensitive and luminescent benzocrown ether. This compound revealed micromolar affinities and selectivities for glycine- and histidine-containing sequences, which closely resembles those of copper(II) ion peptide binding: the two free coordination sites of the copper(II) NTA complex bind to imidazole and amido nitrogen atoms, replicating the initial coordination steps of non-complexed copper(II) ions. The benzocrown ether recognizes the N-terminal amino moiety intramolecularly, and the significantly increased emission intensity signals the binding event, because only if prior coordination of the peptide has taken place is the intramolecular ammonium ion-benzocrown ether interaction of sufficient strength in water to trigger an emission signal. Intermolecular ammonium ion-benzocrown ether binding is not observed. Isothermal titration calorimetry confirmed the binding constants derived from emission titrations. Thus, as deduced from peptide coordination studies, the combination of a truncated copper(II) coordination sphere and a luminescent benzocrown ether allows for the more rational design of sequence-selective peptide receptors.

  12. Uncommon isonicotinamide supramolecular synthons in copper(II) complexes directed by nitrate and perchlorate anions.

    PubMed

    Daković, Marijana; Popović, Zora

    2009-09-01

    The title compounds, trans-diaquabis(nitrato-kappaO)bis(pyridine-4-carboxamide-kappaN(1))copper(II), [Cu(NO(3))(2)(C(6)H(6)N(2)O)(2)(H(2)O)(2)], (I), and trans-diaquatetrakis(pyridine-4-carboxamide-kappaN(1))copper(II) bis(perchlorate), [Cu(C(6)H(6)N(2)O)(4)(H(2)O)(2)](ClO(4))(2), (II), are composed of mononuclear coordination entities involving Cu(II) ions and isonicotinamide. In (I), the centrosymmetric tetragonally distorted octahedral copper(II) environment contains trans-related isonicotinamide and water molecules in the equatorial plane and two nitrate ions occupying the axial sites. In (II), the equatorial plane of the C(2)-symmetric distorted octahedron is built up of four isonicotinamide ligands, while water molecules occupy the axial positions. The complex molecules of (I) and (II) are linked into three-dimensional supramolecular frameworks by O-H...O and N-H...O hydrogen bonds. The nitrate and perchlorate ions are building blocks that disturb the robust R(2)(2)(8) amide supramolecular motif commonly found in crystal structures of copper-isonicotinamide complexes.

  13. Precipitation and Characterization of Arsenate Phases from Calcium-Copper-Iron-Arsenic Oxide-Sulfate Hydrothermal Systems

    NASA Astrophysics Data System (ADS)

    Gomez, Mario Alberto

    The scope of this thesis is the study of three Fe(III)-As(V) hydrothermal systems. The first one is the Fe(III)-AsO4-SO 4 system and crystalline phases that are produced under high temperature (150-225°C); this was studied to clear up previous contradicting information on this system in relation to industrial arsenic products that are formed during the autoclave processing of arsenical sulphide gold feedstocks and asses their arsenic stability. The second system studied was Cu(II)-Fe(III)-AsO 4-SO4 system at 150°C; this was investigated due to its relevance to industrial pressure leaching of copper concentrates. This system was studied in order to examine the possible effect of copper on the precipitation of scorodite. Finally, the structural and molecular examination of two members of the Ca(II)-Fe(III)-AsO4 system, namely yukonite (synthetic and natural and arseniosiderite was undertaken due to their relatively unknown nature and the potential role play in controlling arsenic release in tailings.

  14. Efficient degradation of atrazine by magnetic porous copper ferrite catalyzed peroxymonosulfate oxidation via the formation of hydroxyl and sulfate radicals.

    PubMed

    Guan, Ying-Hong; Ma, Jun; Ren, Yue-Ming; Liu, Yu-Lei; Xiao, Jia-Yue; Lin, Ling-qiang; Zhang, Chen

    2013-09-15

    Magnetic porous copper ferrite (CuFe2O4) showed a notable catalytic activity to peroxymonosulfate (PMS). More than 98% of atrazine was degraded within 15 min at 1 mM PMS and 0.1 g/L CuFe2O4. In contrast, CuFe2O4 exhibited no obvious catalytic activity to peroxodisulfate or H2O2. Several factors affecting the catalytic performance of PMS/CuFe2O4 were investigated. Results showed that the catalytic degradation efficiency of atrazine increased with PMS and CuFe2O4 doses, but decreased with the increase of natural organic matters concentration. The catalytic oxidation also showed a dependence on initial pH. The presence of bicarbonate stimulated atrazine degradation by PMS/CuFe2O4 at low concentrations but inhibited the degradation at high concentrations. Furthermore, the reactive species for atrazine degradation in PMS/CuFe2O4 system were identified as hydroxyl radical (HO) and sulfate radical (SO4(·-)) through competition reactions of atrazine and nitrobenzene, instead of commonly used alcohol scavenging, which was not a reliable method in metal oxide catalyzed oxidation. Surface hydroxyl groups of CuFe2O4 were a critical part in radical generation and the copper on CuFe2O4 surface was an active site to catalyze PMS. The catalytic degradation of atrazine by PMS/CuFe2O4 was also effective under the background of actual waters.

  15. 1D μ-glycine-briged copper (II) chain in complex [Cu(μ-Gly)Im(ClO4)]n and ferromagnetic interactions among copper (II)

    NASA Astrophysics Data System (ADS)

    Pan, Lu; Lv, Xue-Chuan; Luo, Guan-Hua; Gao, Xiao-Han; Tan, Zhi-Cheng

    2016-12-01

    Complex [Cu(μ-Gly)Im(ClO4)]n(Im = imidazole, and Gly = glycine) with μ-glycine-briged copper (II) chain, containing six-coordination distorted elongated octahedron, was synthesized and characterized. The complex belongs to space group P 21/c measured by X-ray single crystal diffraction. In the cluster, each Cu2+ ion are six-coordination by one nitrogen atom and two oxygen atoms of glycine, one nitrogen atoms of imidazole, and two of oxygen atoms of two perchlorate. Each Cu2+ ion has an N2O4 donor set, which forms the distorted elongated octahedron due to the Jahn-Teller (JT) effect. The magnetic and thermodynamic properties were researched. Magnetic susceptibilities of the complex showed that ferromagnetic interactions occurred between the Cu (II) atoms. The Curie-Weiss constant C = 0.565 cm3 K·mol-1 and the Weiss constant θ = 1.0585 K were given by the Curie-Weiss law The ferromagnetic nature of the interaction could be deduced as the exchange pathway of Cusbnd Osbnd Csbnd Osbnd Cu, which involved an equatorial position at one copper (II) ion and an axial position of the nearest copper (II). The complex decomposed from 511 to 538 K as two steps.

  16. Toxic effects of copper on photosystem II of spinach chloroplasts

    SciTech Connect

    Hsu, Bandar; Lee, Jeeyau )

    1988-05-01

    The room temperature fluorescence induction of chloroplasts was utilized as a probe to locate the site of inhibition on PSII by copper. It was found that, while the initial fluorescence yield was hardly affected, the variable fluorescence yield was lowered without significant change in its kinetics. Addition of DCMU, or abolishing oxygen evolution capability by Tris treatment, did not alter this basic inhibition pattern. Copper was also found to lower the fluorescence yield of chloroplasts treated with linolenic acid which inhibited the secondary electron transport on both oxidizing and reducing sides of PSII. The data indicate that copper adversely affects the primary change separation at the PSII reaction center. We suggest that the inhibition is due to creation of a lesion close to the reaction center, leading to increased dissipation of incoming excitation energy to heat.

  17. Vascular dermatan sulfate regulates the antithrombotic activity of heparin cofactor II

    PubMed Central

    He, Li; Giri, Tusar K.; Vicente, Cristina P.

    2008-01-01

    Heparin cofactor II (HCII)–deficient mice form occlusive thrombi more rapidly than do wild-type mice following injury to the carotid arterial endothelium. Dermatan sulfate (DS) and heparan sulfate (HS) increase the rate of inhibition of thrombin by HCII in vitro, but it is unknown whether vascular glycosaminoglycans play a role in the antithrombotic effect of HCII in vivo. In this study, we found that intravenous injection of either wild-type recombinant HCII or a variant with low affinity for HS (K173H) corrected the abnormally short thrombosis time of HCII-deficient mice, while a variant with low affinity for DS (R189H) had no effect. When HCII was incubated with frozen sections of the mouse carotid artery, it bound specifically to DS in the adventitia. HCII was undetectable in the wall of the uninjured carotid artery, but it became concentrated in the adventitia following endothelial injury. These results support the hypothesis that HCII interacts with DS in the vessel wall after disruption of the endothelium and that this interaction regulates thrombus formation in vivo. PMID:18281504

  18. Selenium isotope fractionation during reduction by Fe(II)-Fe(III) hydroxide-sulfate (green rust)

    USGS Publications Warehouse

    Johnson, T.M.; Bullen, T.D.

    2003-01-01

    We have determined the extent of Se isotope fractionation induced by reduction of selenate by sulfate interlayered green rust (GRSO4), a Fe(II)-Fe(III) hydroxide-sulfate. This compound is known to reduce selenate to Se(0), and it is the only naturally relevant abiotic selenate reduction pathway documented to date. Se reduction reactions, when they occur in nature, greatly reduce Se mobility and bioavailability. Se stable isotope analysis shows promise as an indicator of Se reduction, and Se isotope fractionation by various Se reactions must be known in order to refine this tool. We measured the increase in the 80Se/76Se ratio of dissolved selenate as lighter isotopes were preferentially consumed during reduction by GRSO4. Six different experiments that used GRSO4 made by two methods, with varying solution compositions and pH, yielded identical isotopic fractionations. Regression of all the data yielded an instantaneous isotope fractionation of 7.36 ?? 0.24???. Selenate reduction by GRSO4 induces much greater isotopic fractionation than does bacterial selenate reduction. If selenate reduction by GRSO4 occurs in nature, it may be identifiable on the basis of its relatively large isotopic fractionation. ?? 2003 Elsevier Science Ltd.

  19. Decomposition of reactive oxygen species by copper(II) bis(1-pyrazolyl)methane complexes.

    PubMed

    Schepetkin, Igor; Potapov, Andrei; Khlebnikov, Andrei; Korotkova, Elena; Lukina, Anna; Malovichko, Galina; Kirpotina, Lilia; Quinn, Mark T

    2006-06-01

    Two bis(1-pyrazolyl)alkane ligands, bis(3,5-dimethyl-1-pyrazolyl)methane and bis(4-iodo-3,5-dimethyl-1-pyrazolyl)methane, and their copper(II) complexes, bis(3,5-dimethyl-1-pyrazolyl)methanedinitratocopper(II) [CuL1(NO3)2] and bis(4-iodo-3,5-dimethyl-1-pyrazolyl)methanedinitratocopper(II) [CuL2(NO3)2] x 2H2O, were prepared. Physiochemical properties of the copper(II) complexes were studied by spectroscopic (UV-vis, IR, EPR) techniques and cyclic voltammetry. Spectroscopic analysis revealed a 1:1 stoichiometry of ligand:copper(II) ion and a bidentate coordination mode for the nitrate ions in both of the complexes. According to experimental and theoretical ab initio data, the copper(II) ion is located in an octahedral hexacoordinated environment. Both complexes were able to catalyze the dismutation of superoxide anion (O2*-) (pH 7.5) and decomposition of H2O2 (pH 7.5) and peroxynitrite (pH 10.9). In addition, both complexes exhibited superoxide dismutase (SOD) like activity toward extracellular and intracellular reactive oxygen species produced by activated human neutrophils in whole blood. Thus, these complexes represent useful SOD mimetics with a broad range of antioxidant activity toward a variety of reactive oxidants.

  20. Synthesis, spectral, photolysis and electrochemical studies of mononuclear copper(II) complex with a new asymmetric tetradentate ligand: Application as copper nanoparticle precursor

    NASA Astrophysics Data System (ADS)

    Habibi, Mohammad Hossein; Mikhak, Maryam

    2012-10-01

    A copper(II) complex with asymmetric tetradentate Schiff base ligand, obtained by the single condensation of 1,2-diaminopropane with 2-hydroxy-5-methoxy benzaldehyde was prepared. The ligand and complex were characterized by their IR, UV-Vis, FT-IR, NMR spectra and CV. Crystal structures of the mononuclear copper complex have been obtained by X-ray diffraction studies which revealed to be distorted square planner coordination geometry. The spectral data confirm coordination of ligand to copper ion center. The redox properties of complex at different scan rates exhibit grossly similar features consisting of an electrochemically pseudo-reversible Cu(II)/Cu(I) reduction at ca. -0.97 V and pseudo-reversible Cu(I)/Cu(II) oxidation at ca. -0.81 V. The copper nanoparticles with average size of 73 nm were formed by thermal reduction of copper complex in the presence of triphenylphosphine.

  1. Synthesis, spectral, photolysis and electrochemical studies of mononuclear copper(II) complex with a new asymmetric tetradentate ligand: application as copper nanoparticle precursor.

    PubMed

    Habibi, Mohammad Hossein; Mikhak, Maryam

    2012-10-01

    A copper(II) complex with asymmetric tetradentate Schiff base ligand, obtained by the single condensation of 1,2-diaminopropane with 2-hydroxy-5-methoxy benzaldehyde was prepared. The ligand and complex were characterized by their IR, UV-Vis, FT-IR, NMR spectra and CV. Crystal structures of the mononuclear copper complex have been obtained by X-ray diffraction studies which revealed to be distorted square planner coordination geometry. The spectral data confirm coordination of ligand to copper ion center. The redox properties of complex at different scan rates exhibit grossly similar features consisting of an electrochemically pseudo-reversible Cu(II)/Cu(I) reduction at ca. -0.97 V and pseudo-reversible Cu(I)/Cu(II) oxidation at ca. -0.81 V. The copper nanoparticles with average size of 73 nm were formed by thermal reduction of copper complex in the presence of triphenylphosphine.

  2. Effects of copper sulfate-oxidized or myeloperoxidase-modified LDL on lipid loading and programmed cell death in macrophages under hypoxia

    PubMed Central

    Vlaminck, Benoit; Calay, Damien; Genin, Marie; Sauvage, Aude; Ninane, Noelle; Zouaoui Boudjeltia, Karim; Raes, Martine; Michiels, Carine

    2014-01-01

    Atheromatous plaques contain heavily lipid-loaded macrophages that die, hence generating the necrotic core of these plaques. Since plaque instability and rupture is often correlated with a large necrotic core, it is important to understand the mechanisms underlying foam cell death. Furthermore, macrophages within the plaque are associated with hypoxic areas but little is known about the effect of low oxygen partial pressure on macrophage death. The aim of this work was to unravel macrophage death mechanisms induced by oxidized low-density lipoproteins (LDL) both under normoxia and hypoxia. Differentiated macrophages were incubated in the presence of native, copper sulfate-oxidized, or myeloperoxidase-modified LDL. The unfolded protein response, apoptosis, and autophagy were then investigated. The unfolded protein response and autophagy were triggered by myeloperoxidase-modified LDL and, to a larger extent, by copper sulfate-oxidized LDL. Electron microscopy observations showed that oxidized LDL induced excessive autophagy and apoptosis under normoxia, which were less marked under hypoxia. Myeloperoxidase-modified LDL were more toxic and induced a higher level of apoptosis. Hypoxia markedly decreased apoptosis and cell death, as marked by caspase activation. In conclusion, the cell death pathways induced by copper sulfate-oxidized and myeloperoxidase-modified LDL are different and are differentially modulated by hypoxia. PMID:27774474

  3. N-Acetylgalactosamine 4,6-O-sulfate residues mediate binding and activation of heparin cofactor II by porcine mucosal dermatan sulfate.

    PubMed

    Halldórsdóttir, Anna Margrét; Zhang, Lijuan; Tollefsen, Douglas M

    2006-08-01

    Dermatan sulfate (DS) accelerates the inhibition of thrombin by heparin cofactor II (HCII). A hexasaccharide consisting of three l-iduronic acid 2-O-sulfate (IdoA2SO3)-->N-acetyl-D-galactosamine 4-O-sulfate (GalNAc4SO3) subunits was previously isolated from porcine skin DS and shown to bind HCII with high affinity. DS from porcine intestinal mucosa has a much lower content of this disaccharide but activates HCII with potency similar to that of porcine skin DS. Therefore, we sought to characterize oligosaccharides from porcine mucosal DS that interact with HCII. DS was partially depolymerized with chondroitinase ABC, and oligosaccharides containing 2-12 monosaccharide units were isolated. The oligosaccharides were then fractionated by anion-exchange and affinity chromatography on HCII-Sepharose, and the disaccharide compositions of selected fractions were determined. We found that the smallest oligosaccharides able to bind HCII were hexasaccharides. Oligosaccharides 6-12 units long that lacked uronic acid (UA)2SO3 but contained one or two GalNAc4,6SO3 residues bound, and binding was proportional to both oligosaccharide size and number of GalNAc4,6SO3 residues. Intact DS and bound dodecasaccharides contained predominantly IdoA but little D-glucuronic acid. Decasaccharides and dodecasaccharides containing one or two GalNAc4,6SO3 residues stimulated thrombin inhibition by HCII and prolonged the clotting time of normal but not HCII-depleted human plasma. These data support the hypothesis that modification of IdoA-->GalNAc4SO3 subunits in the DS polymer by either 2-O-sulfation of IdoA or 6-O-sulfation of GalNAc can generate molecules with HCII-binding sites and anticoagulant activity.

  4. Assessment of the Polychlorinated Biphenyl (PCB) Occurrence in Copper Sulfates and the Influential Role of PCB Levels on Grapes.

    PubMed

    Li, Xiaomin; Su, Xiaoou

    2015-01-01

    Copper sulfates (CuSO4) are widely used as the primary component of fungicides in the grape industry. The agricultural-grade CuSO4 that we collected from Chinese nationwide markets were found to be contaminated by polychlorinated dibenzo-p-dioxins and dibenzofurans and high levels of polychlorinated biphenyls (Σ19PCBs: 0.32~9.51 ng/g). In the following research, we studied the impact of CuSO4 application on PCB levels in grape products through a field experiment, and conducted a national survey to speculate the role that CuSO4 played on the occurrence of PCB in grapes. In the field experiment, an obvious increase of PCBs in grape leaves (from 174 to 250 pg/g fw) was observed after Bordeaux mixture (the main component of which is CuSO4) application. As to the main PCB congener in CuSO4, the most toxic CB 126 (toxic equivalency factor = 0.1) also increased in grape peels (from 1.66 to 2.93 pg/g fw) after pesticide spray. Both the correlation study and the principal component analysis indicated that environmental factors were dominant PCB contributors to grapes, and grapes from e-waste dismantling area containing the highest PCBs also proved the notion. It is worth noting that this report describes the first research examining PCBs in CuSO4 and its influence on agricultural products to date.

  5. Effectiveness of 5-Pyrrolidone-2-carboxylic Acid and Copper Sulfate Pentahydrate Association against Drug Resistant Staphylococcus Strains.

    PubMed

    Governa, Paolo; Miraldi, Elisabetta; De Fina, Gianna; Biagi, Marco

    2016-04-01

    Bacterial resistance is an ongoing challenge for pharmacotherapy and pharmaceutical chemistry. Staphylococcus aureus is the bacterial species which makes it most difficult to treat skin and soft tissue infections and it is seen in thousands of hospitalization cases each year. Severe but often underrated infectious diseases, such as complicated nasal infections, are primarily caused by MRSA and S. epidermidis too. With the aim of studying new drugs with antimicrobial activity and effectiveness on drug resistant Staphylococcus strains, our attention in this study was drawn on the activity of a new association between two natural products: 5-pyrrolidone-2-carboxylic acid (PCA), naturally produced by certain Lactobacillus species, and copper sulfate pentahydrate (CS). The antimicrobial susceptibility test was conducted taking into account 12 different Staphylococcus strains, comprising 6 clinical isolates and 6 resistant strains. PCA 4%, w/w, and CS 0.002%, w/w, association in distilled water solution was found to have bactericidal activity against all tested strains. Antimicrobial kinetics highlighted that PCA 4%, w/w, and CS 0.002% association could reduce by 5 log10 viable bacterial counts of MRSA and oxacillin resistant S. epidennidis in less than 5 and 3 minutes respectively. Microscopic investigations suggest a cell wall targeting mechanism of action. Being very safe and highly tolerated, the natural product PCA and CS association proved to be a promising antimicrobial agent to treat Staphylococcus related infections.

  6. Relative roles of acetic acid, dodecyl sulfate and benzotriazole in chemical mechanical and electrochemical mechanical planarization of copper

    NASA Astrophysics Data System (ADS)

    Goonetilleke, P. C.; Roy, D.

    2008-02-01

    The efficiency of chemical mechanical or electrochemical mechanical planarization (CMP or ECMP) carried out in the fabrication of integrated circuits is largely governed by the functional chemicals used in these processes. In this work, we study the individual and combined chemical and electrochemical effects of a selected set of such chemicals that can potentially support both CMP and ECMP of copper. These chemicals include acetic acid (HAc) as a complexing agent, H2O2 as an oxidizer, and ammonium dodecyl sulfate (ADS) as a dissolution inhibitor. Surface passivating effects of ADS under both CMP (open circuit) and ECMP (voltage activated) conditions are compared with those of a standard dissolution inhibitor for Cu, benzotriazole (BTAH), and the combined effects of a BTAH-ADS mixture also are explored. The experiments are performed in the absence of mechanical polishing using static and rotating Cu disc electrodes, and electro-dissolution of Cu for ECMP is activated using a voltage pulse modulation technique. A mechanism of surface reactions is proposed to describe the relative roles of HAc, H2O2, ADS and BTAH as electrolyte components for CMP and ECMP of Cu.

  7. Effects of propionic acid and of copper sulfate on the nutritional value of diets containing moldy corn for broiler chicks.

    PubMed

    Bartov, I

    1983-11-01

    Diets containing moldy corn (in which fat levels were restored or not restored by soybean oil) were supplemented with either propionic acid (PA) or copper sulfate (CS), and their nutritional value for young broiler chicks was evaluated. The fat content of a diet containing good quality grains decreased slightly, whereas that of diets containing moldy grains decreased markedly, during the 30 days of the experiment. The PA (.3%), but not CS (600 ppm), almost completely prevented this decrease. Dietary metabolizable energy (ME), retention of dry matter and protein, and the performance of the chicks fed the diet containing the moldy corn were markedly depressed. Neither CS, nor soybean oil supplementation, nor a combination of the two, counteracted these effects. Supplementation with PA however, significantly (P less than .05) increased dietary ME, increased retention of dry matter and protein, and improved performance of chicks fed the moldy grains. The combination of PA and soybean oil supplementation yielded essentially the same results as the diet containing the good corn. It is concluded, therefore, that the nutritional value of diets containing moldy grains can be completely restored if their fat content is increased in proportion to the amount lost in the moldy grains and an efficient fungistat is used.

  8. Assessment of the Polychlorinated Biphenyl (PCB) Occurrence in Copper Sulfates and the Influential Role of PCB Levels on Grapes

    PubMed Central

    Li, Xiaomin; Su, Xiaoou

    2015-01-01

    Copper sulfates (CuSO4) are widely used as the primary component of fungicides in the grape industry. The agricultural-grade CuSO4 that we collected from Chinese nationwide markets were found to be contaminated by polychlorinated dibenzo-p-dioxins and dibenzofurans and high levels of polychlorinated biphenyls (Σ19PCBs: 0.32~9.51 ng/g). In the following research, we studied the impact of CuSO4 application on PCB levels in grape products through a field experiment, and conducted a national survey to speculate the role that CuSO4 played on the occurrence of PCB in grapes. In the field experiment, an obvious increase of PCBs in grape leaves (from 174 to 250 pg/g fw) was observed after Bordeaux mixture (the main component of which is CuSO4) application. As to the main PCB congener in CuSO4, the most toxic CB 126 (toxic equivalency factor = 0.1) also increased in grape peels (from 1.66 to 2.93 pg/g fw) after pesticide spray. Both the correlation study and the principal component analysis indicated that environmental factors were dominant PCB contributors to grapes, and grapes from e-waste dismantling area containing the highest PCBs also proved the notion. It is worth noting that this report describes the first research examining PCBs in CuSO4 and its influence on agricultural products to date. PMID:26658158

  9. Copper(II)-8-hydroxquinoline coprecipitation system for preconcentration and separation of cobalt(II) and manganese(II) in real samples.

    PubMed

    Soylak, Mustafa; Kaya, Betul; Tuzen, Mustafa

    2007-08-25

    A separation-preconcentration procedure based on the coprecipitation of cobalt(II) and manganese(II) ions with copper(II)-8-hydroxquinoline system has been developed. The analytical parameters including pH, amount of copper(II) as carrier element, amount of 8-hydroxquinoline, sample volume, etc., was investigated for the quantitative recoveries of Co(II) and Mn(II). No interferic effects were observed from the concomitant ions which are present in real samples. The detection limits for analyte ions by three sigma criteria were 0.86microgL(-1) for cobalt and 0.98microgL(-1) for manganese. The validation of the presented preconcentration procedure was performed by the analysis of NIST SRM 2711 Montana soil and GBW 07605 Tea certified reference materials. The procedure presented was applied to the analyte contents of real samples including natural waters and some food samples with successfully analytical results.

  10. Reactivity of mononuclear alkylperoxo copper(II) complex. O-O bond cleavage and C-H bond activation.

    PubMed

    Kunishita, Atsushi; Ishimaru, Hirohito; Nakashima, Satoru; Ogura, Takashi; Itoh, Shinobu

    2008-04-02

    A detailed reactivity study has been carried out for the first time on a new mononuclear alkylperoxo copper(II) complex, which is generated by the reaction of copper(II) complex supported by the bis(pyridylmethyl)amine tridentate ligand containing a phenyl group at the 6-position of the pyridine donor groups and cumene hydroperoxide (CmOOH) in CH3CN. The cumylperoxo copper(II) complex thus obtained has been found to undergo homolytic cleavage of the O-O bond and induce C-H bond activation of exogenous substrates, providing important insights into the catalytic mechanism of copper monooxygenases.

  11. Selective total encapsulation of the sulfate anion by neutral nano-jars.

    PubMed

    Fernando, Isurika R; Surmann, Stuart A; Urech, Alexander A; Poulsen, Alexander M; Mezei, Gellert

    2012-07-11

    Nano-sized toroidal copper(II)-hydroxide/pyrazolate assemblies, lined by H-bond donors on the inside and hydrophobic on the outside, selectively extract sulfate from mixtures with nitrate or perchlorate. Tetrabutylammonium "lids" seal the "nano-jars" and render the encapsulated sulfate anion completely buried and inaccessible, so that it is not precipitated by Ba(2+) ions.

  12. Static renewal tests using Anodonta imbecillis (freshwater mussels). Anodonta imbecillis copper sulfate reference toxicant/food test, Clinch River-Environmental Restoration Program (CR-ERP)

    SciTech Connect

    Simbeck, D.J.

    1993-12-31

    Reference toxicant testing using juvenile freshwater mussels was conducted as part of the CR-ERP biomonitoring study of Clinch River sediments to assess the sensitivity of test organisms and the overall performance of the test. Tests were conducted using moderately hard synthetic water spiked with known concentrations of copper as copper sulfate. Two different foods, phytoplankton and YCT-Selenastrum (YCT-S), were tested in side by side tests to compare food quality. Toxicity testing of copper sulfate reference toxicant was conducted from July 6--15, 1993. The organisms used for testing were juvenile fresh-water mussels (Anodonta imbecillis). Although significant reduction in growth, compared to the phytoplankton control, was seen in all treatments, including the YCT-S Control, the consequence of this observation has not been established. Ninety-day testing of juvenile mussels exhibited large variations in growth within treatment and replicate groups. Attachments to this report include: Toxicity test bench sheets and statistical analyses; and Copper analysis request and results.

  13. A highly selective and sensitive fluorescence assay for determination of copper(II) and cobalt(II) ions in environmental water and toner samples.

    PubMed

    Tsai, Chia-Yi; Lin, Yang-Wei

    2013-02-21

    In this study, a highly selective and sensitive fluorescence assay has been proposed for the determination of copper(II) and cobalt(II) ions in environmental water and toner samples. In the presence of hydrogen peroxide, copper(II) reacted with a new fluorescence reagent Amplex® UltraRed (AUR), forming a fluorescence product only at pH 7.0, while the fluorescence product of cobalt(II) with AUR formed only at pH 9.0. The fluorescence signal obtained was linear with respect to the copper(II) concentration over the range of 1.6-12.0 μM (R(2) = 0.988) and was linear with respect to the cobalt(II) concentration over the range of 45.0 nM to 1.0 μM (R(2) = 0.992). The limits of detection (at a signal-to-noise ratio of 3) for copper(II) and cobalt(II) were 0.17 μM and 14.0 nM, respectively. Our present approach is simpler, faster, and more cost-effective than other techniques for the detection of copper(II) and cobalt(II) ions in environmental water samples and that of copper(II) ions in toner samples.

  14. Magnetic Interactions in the Copper Complex (L-Aspartato)(1,10-phenanthroline)copper(II) Hydrate. An Exchange-Coupled Extended System with Two Dissimilar Copper Ions.

    PubMed

    Brondino, Carlos D.; Calvo, Rafael; Atria, Ana María; Spodine, Evgenia; Nascimento, Otaciro R.; Peña, Octavio

    1997-07-02

    We report EPR measurements in single-crystal samples at the microwave frequencies 9.8 and 34.3 GHz and magnetic susceptibility measurements in polycrystalline samples for the ternary complex of copper with aspartic acid and phenanthroline, (L-aspartato)(1,10-phenanthroline)copper(II) hydrate. The crystal lattice of this compound is composed of two dissimilar copper ions identified as Cu(A) and Cu(B), which are in two types of copper chains called A and B, respectively, running parallel to the b crystal axis. The copper ions in the A chains are connected by the aspartic acid molecule, and those in the B chains by a chemical path that involves a carboxylate bridge and a hydrogen bond. Both chains are held together by a complex network of hydrogen bonds and by hydrophobic interactions between aromatic amines. Magnetic susceptibility data indicate a Curie-Weiss behavior in the studied temperature range (2-300 K). The EPR spectra at 9.8 GHz display a single exchange collapsed resonance for any magnetic field orientation, in the so-called strong exchange regime. Those at 34.3 GHz are within the so-called weak exchange regime and display two resonances which belong to each type of copper ion chain. The decoupling of the spectra at 34.3 GHz using a theory based on Anderson's model for the case of two weakly exchange coupled spins S = (1)/(2) allows one to obtain the angular variation of the squares of the g-factor and the peak-to-peak line width of each resonance. This model also allows one to evaluate the exchange parameter |J(AB)/k| = 2.7(6) mK associated with the chemical path connecting dissimilar copper ions. The line width data obtained for each component of the spectra at 34.3 GHz are analyzed in terms of a model based on Kubo and Tomita's theory, to obtain the exchange parameters |J(A)/k| = 0.77(2) K and |J(B)/k| = 1.44(2) K associated with the chemical paths connecting the similar copper ions of types A and B, respectively.

  15. The Unusual Colour of Copper Deposited on a Graphite Electrode in an Aqueous Solution of CuSO[subscript 4

    ERIC Educational Resources Information Center

    Petrusevski, Vladimir M.; Stojanovska, Marina

    2010-01-01

    The colour of the copper layer deposited on a graphite electrode during electrolysis of an aqueous solution of copper(II) sulfate looks whitish-grey when inspected in situ. Taking the electrode out of the solution reveals the familiar orange-red colour of deposited copper. The explanation is found in terms of the almost ideal complementary colours…

  16. Low-temperature atomic layer deposition of copper(II) oxide thin films

    SciTech Connect

    Iivonen, Tomi Hämäläinen, Jani; Mattinen, Miika; Popov, Georgi; Leskelä, Markku; Marchand, Benoît; Mizohata, Kenichiro; Kim, Jiyeon; Fischer, Roland A.

    2016-01-15

    Copper(II) oxide thin films were grown by atomic layer deposition (ALD) using bis-(dimethylamino-2-propoxide)copper [Cu(dmap){sub 2}] and ozone in a temperature window of 80–140 °C. A thorough characterization of the films was performed using x-ray diffraction, x-ray reflectivity, UV‐Vis spectrophotometry, atomic force microscopy, field emission scanning electron microscopy, x-ray photoelectron spectroscopy, and time-of-flight elastic recoil detection analysis techniques. The process was found to produce polycrystalline copper(II) oxide films with a growth rate of 0.2–0.3 Å per cycle. Impurity content in the films was relatively small for a low temperature ALD process.

  17. Cytotoxic activity, X-ray crystal structures and spectroscopic characterization of cobalt(II), copper(II) and zinc(II) coordination compounds with 2-substituted benzimidazoles.

    PubMed

    Sánchez-Guadarrama, Obdulia; López-Sandoval, Horacio; Sánchez-Bartéz, Francisco; Gracia-Mora, Isabel; Höpfl, Herbert; Barba-Behrens, Noráh

    2009-09-01

    Herein we present the synthesis, structural and spectroscopic characterization of coordination compounds of cobalt(II), copper(II) and zinc(II) with 2-methylbenzimidazole (2mbz), 2-phenylbenzimidazole (2phbz), 2-chlorobenzimidazole (2cbz), 2-benzimidazolecarbamate (2cmbz) and 2-guanidinobenzimidazole (2gbz). Their cytotoxic activity was evaluated using human cancer cell lines, PC3 (prostate), MCF-7 (breast), HCT-15 (colon), HeLa (cervic-uterine), SKLU-1 (lung) and U373 (glioblastoma), showing that the zinc(II) and copper(II) compounds [Zn(2mbz)(2)Cl(2)].0.5H(2)O, [Zn(2cmbz)(2)Cl(2)].EtOH, [Cu(2cmbz)Br(2)].0.7H(2)O and [Cu(2gbz)Br(2)] had significant cytotoxic activity. The isostructural cobalt(II) complexes showed not significant activity. The cytotoxic activity is related to the presence of halides in the coordination sphere of the metal ion. Recuperation experiments with HeLa cells, showed that the cells recuperated after removing the copper(II) compounds and, on the contrary, the cells treated with the zinc(II) compounds did not. These results indicate that the mode of action of the coordination compounds is different.

  18. Spectroscopic characterization, antioxidant and antitumour studies of novel bromo substituted thiosemicarbazone and its copper(II), nickel(II) and palladium(II) complexes

    NASA Astrophysics Data System (ADS)

    Jagadeesh, M.; Lavanya, M.; Kalangi, Suresh K.; Sarala, Y.; Ramachandraiah, C.; Varada Reddy, A.

    2015-01-01

    A new, slightly distorted octahedral complex of copper(II), square planar complexes of nickel(II) and palladium(II) with 2,4‧-dibromoacetophenone thiosemicarbazone (DBAPTSC) are synthesized. The ligand and the complexes are characterized by FT-IR, FT-Raman, powder X-ray diffraction studies. The IR and Raman data are correlated for the presence of the functional groups which specifically helped in the confirmation of the compounds. In addition, the free ligand is unambiguously characterized by 1H and 13C NMR spectroscopy while the copper(II) complex is characterized by electron paramagnetic resonance spectroscopy (EPR). The g values for the same are found to be 2.246 (g1), 2.012 (g2) and 2.005 (g3) which suggested rhombic distortions. The HOMO-LUMO band gap calculations for these compounds are found to be in between 0.5 and 4.0 eV and these compounds are identified as semiconducting materials. The synthesized ligand and its copper(II), nickel(II) and palladium(II) complexes are subjected to antitumour activity against the HepG2 human hepatoblastoma cell lines. Among all the compounds, nickel(II) complex is found to exert better antitumour activity with 57.6% of cytotoxicity.

  19. Fe(III)EDTA and Fe(II)EDTA-NO reduction by a sulfate reducing bacterium in NO and SO₂ scrubbing liquor.

    PubMed

    Chen, Mingxiang; Zhou, Jiti; Zhang, Yu; Wang, Xiaojun; Shi, Zhuang; Wang, Xiaowei

    2015-03-01

    A viable process concept, based on NO and SO2 absorption into an alkaline Fe(II)EDTA (EDTA: ethylenediaminetetraacetic acid) solution in a scrubber combined with biological reduction of the absorbed SO2 utilizing sulfate reducing bacteria (SRB) and regeneration of the scrubbing liquor in a single bioreactor, was developed. The SRB, Desulfovibrio sp. CMX, was used and its sulfate reduction performances in FeEDTA solutions and Fe(II)EDTA-NO had been investigated. In this study, the detailed regeneration process of Fe(II)EDTA solution, which contained Fe(III)EDTA and Fe(II)EDTA-NO reduction processes in presence of D. sp. CMX and sulfate, was evaluated. Fe(III)EDTA and Fe(II)EDTA-NO reduction processes were primarily biological, even if Fe(III)EDTA and Fe(II)EDTA-NO could also be chemically convert to Fe(II)EDTA by biogenic sulfide. Regardless presence or absence of sulfate, more than 87 % Fe(III)EDTA and 98 % Fe(II)EDTA-NO were reduced in 46 h, respectively. Sulfate and Fe(III)EDTA had no affection on Fe(II)EDTA-NO reduction. Sulfate enhanced final Fe(III)EDTA reduction. Effect of Fe(III)EDTA on Fe(II)EDTA-NO reduction rate was more obvious than effect of sulfate on Fe(II)EDTA-NO reduction rate before 8 h. To overcome toxicity of Fe(II)EDTA-NO on SRB, Fe(II)EDTA-NO was reduced first and the reduction of Fe(III)EDTA and sulfate occurred after 2 h. First-order Fe(II)EDTA-NO reduction rate and zero-order Fe(III)EDTA reduction rate were detected respectively before 8 h.

  20. MICS-Asia II: Model intercomparison and evaluation of particulate sulfate, nitrate and ammonium

    NASA Astrophysics Data System (ADS)

    Hayami, Hiroshi; Sakurai, T.; Han, Z.; Ueda, H.; Carmichael, G. R.; Streets, D.; Holloway, T.; Wang, Z.; Thongboonchoo, N.; Engardt, M.; Bennet, C.; Fung, C.; Chang, A.; Park, S. U.; Kajino, M.; Sartelet, K.; Matsuda, K.; Amann, M.

    Eight chemical transport models participate in a model intercomparison study for East Asia, MICS-Asia II. This paper analyzes calculated results for particulate matter of sulfate, nitrate and ammonium through comparisons with each other and with monthly measurements at EANET (the acid deposition monitoring network in East Asia) and daily measurements at Fukue, Japan. To the EANET measurements, model ensemble means better agree with model individual results for sulfate and total ammonium, although total nitrate is consistently and considerably underestimated. To measurements at Fukue, the models show better agreement than for the EANET measurements. This is likely because Fukue is centered in many of the model domains, whereas the EANET stations are mostly in Southeast Asia and Russia. Moreover, it would be important that Fukue is in Northeast Asia, where the emission inventory is more reliable than Southeast Asia. The model-model comparisons are made in view of the total amount in the atmosphere, vertical profile, coefficient of variation in surface concentrations, and transformation changes with distance. All the models show reasonable tendencies in vertical profiles and composition ratios. However, total amounts in the atmosphere are discrepant among the models. The consistency of the total amount in the atmosphere would influence source-receptor analysis. It seems that model results would be consistent, if the models take into account the primitive processes like emission, advection/diffusion, chemical transformation and dry/wet deposition, no matter the processes are modeled simply or comprehensively. Through the comparison study, we learned that it would be difficult to find any problems from one comparison (model-observation comparison with one data or many but at one station or in a short period). Modelers tend to examine model performances only from model-observation comparisons. However, taking budget in a certain or whole model domain would be important

  1. Copper(II) binding to alpha-synuclein, the Parkinson's protein.

    PubMed

    Lee, Jennifer C; Gray, Harry B; Winkler, Jay R

    2008-06-04

    Variations in tryptophan fluorescence intensities confirm that copper(II) interacts with alpha-synuclein, a protein implicated in Parkinson's disease. Trp4 fluorescence decay kinetics measured for the F4W protein show that Cu(II) binds tightly (Kd 100 nM) near the N-terminus at pH 7. Work on a F4W/H50S mutant indicates that a histidine imidazole is not a ligand in this high-affinity site.

  2. Copper (II) complexes possessing alkyl-substituted polypyridyl ligands: Structural characterization and in vitro antitumor activity.

    PubMed

    Angel, Noah R; Khatib, Raneen M; Jenkins, Julia; Smith, Michelle; Rubalcava, Justin M; Le, Brian Khoa; Lussier, Daniel; Chen, Zhuo Georgia; Tham, Fook S; Wilson, Emma H; Eichler, Jack F

    2017-01-01

    In an effort to find alternatives to the antitumor drug cisplatin, a series of copper (II) complexes possessing alkyl-substituted polypyridyl ligands have been synthesized. Eight new complexes are reported herein: μ-dichloro-bis{2,9-di-sec-butyl-1,10-phenanthrolinechlorocopper(II)} {[((di-sec-butyl)phen)ClCu(μ-Cl)2CuCl((di-sec-butyl)phen)]}(1), 2-sec-butyl-1,10-phenanthrolinedichlorocopper(II) {([mono-sec-butyl)phen) CuCl2} (2), 2,9-di-n-butyl-1,10-phenanthrolinedichlorocopper(II) {[(di-n-butyl)phen) CuCl2}(3), 2-n-butyl-1,10-phenanthrolinedichlorocopper(II) {[(mono-n-butyl)phen) CuCl2} (4), 2,9-di-methyl-1,10-phenanthrolineaquadichlorocopper(II) {[(di-methyl)phen) Cu(H2O)Cl2}(5), μ-dichloro-bis{6-sec-butyl-2,2'-bipyridinedichlorocopper(II)} {((mono-sec-butyl)bipy) ClCu(μ-Cl)2CuCl((mono-sec-butyl)bipy)} (6), 6,6'-di-methyl-2,2'-bipyridinedichlorocopper(II) {(6,6'-di-methyl)bipy) CuCl2} (7), and 4,4'-dimethyl-2,2'-bipyridinedichlorocopper(II) {(4,4'-di-methyl)bipy) CuCl2} (8). These complexes have been characterized via elemental analysis, UV-vis spectroscopy, and mass spectrometry. Single crystal X-ray diffraction experiments revealed the complexes synthesized with the (di-sec-butyl)phen ligand (1) and (mono-sec-butyl)bipy ligand (6) crystallized as dimers in which two copper(II) centers are bridged by two chloride ligands. Conversely, complexes 2, 7, and 8 were isolated as monomeric species possessing distorted tetrahedral geometries, and the [((di-methyl)phen)Cu(H2O)Cl2] (5) complex was isolated as a distorted square pyramidal monomer possessing a coordinating aqua ligand. Compounds 1-8 were evaluated for their in vitro antitumor efficacy. Compounds 1, 5, and 7 in particular were found to exhibit remarkable activity against human derived lung cancer cells, yet this class of copper(II) compounds had minimal cytotoxic effect on non-cancerous cells. In vitro control experiments indicate the activity of the copper(II) complexes most likely does not arise from the

  3. Loss of seasonal variability in a lake resulting from copper sulfate algaecide treatment

    NASA Astrophysics Data System (ADS)

    Song, L.; Marsh, T. L.; Voice, T. C.; Long, D. T.

    Vertical profiles of selected biogeochemical parameters were measured temporally in two lakes to help understand the influence of the additions of CuSO 4 to control algal growth. Our working hypothesis is that the temporal variability of biogeochemical parameters in the treated lake will be less than in the untreated one. The study lakes are in the southern portion of the Lower Peninsula of Michigan. Hawk Island, a groundwater fed lake, was treated with periodic additions of CuSO 4. It has a large lake to watershed area ratio and its land-use is characterized by a public park that has a combination of woods and grassland with fertilizer additions. Muskrat Lake has a smaller lake to watershed ratio, is a flow-through lake, and in a dominantly agricultural landscape. Temporal measurements include total dissolved copper, pH, temperature, conductivity, dissolved oxygen, turbidity, chlorophyll a, dissolved organic carbon, percent aromaticity, total dissolved nitrogen and total dissolved phosphorous. A novel aspect of the data is a set of samples taken just after a major rain event. The results show that lakes have some similarities (e.g., same pH’s and temperatures and are well mixed). However, there are differences in some biogeochemical (e.g., DO) and physical (e.g., turbidity) parameters that can be observed as a function of sampling time and response to the rain events. Physical and biogeochemical parameters have less seasonal variability in Hawk Island Lake than in Muskrat Island Lake. The impact of the rain event (i.e., biogeochemical change and recovery) was different for each lake which is attributed in part to the influence of the CuSO 4 addition as well as to the difference in the lake hydrology. These results support the working hypothesis by showing that addition of the algaecide CuSO 4 changes the biogeochemical structure of a lake, and that with the loss of algae, seasonal variations in biogeochemical parameters are reduced. While CuSO 4 additions may be

  4. Neutral (bis-beta-diketonato) iron(III), cobalt(II), nickel(II), copper(II) and zinc(II) metallocycles: structural, electrochemical and solvent extraction studies.

    PubMed

    Clegg, Jack K; Bray, David J; Gloe, Kerstin; Gloe, Karsten; Hayter, Michael J; Jolliffe, Katrina A; Lawrance, Geoffrey A; Meehan, George V; McMurtrie, John C; Lindoy, Leonard F; Wenzel, Marco

    2007-05-07

    Neutral dimeric metallocyclic complexes of type [M(2)(L(1))(2)B(n)] (where M = cobalt(II), nickel(II) and zinc(II), L(1) is the doubly deprotonated form of a 1,3-aryl linked bis-beta-diketone ligand of type 1,3-bis(RC(O)CH(2)C(O))C(6)H(4) (R=Me, n-Pr, t-Bu) and B is pyridine (Py) or 4-ethylpyridine (EtPy)) have been synthesised, adding to similar complexes already reported for copper(II). New lipophilic ligand derivatives with R = octyl or nonyl were also prepared for use in solvent extraction experiments. Structural, electrochemical and solvent extraction investigations of selected metal complex systems from the above series are reported, with the X-ray structures of [Co(2)(L(1))(2)(Py)(4)] x 2.25CHCl(3) x 0.5H(2)O (R=Pr), [Co(2)(L(1))(2)(EtPy)(4)] (R=t-Bu), [Ni(2)(L(1))(2)(EtPy)(4)] (R=t-Bu), [Zn(2)(L(1))(2)(EtPy)(2)] (R=Me) and [Zn(2)(L(1))(2)(EtPy)(4)] (R=t-Bu) being presented. The electrochemistry of H(2)L(1) (R=t-Bu) and of [Fe(2)(L(1))(3)], [Co(2)(L(1))(2)(Py)(4)], [Ni(2)(L(1))(2)(Py)(4)], [Cu(2)(L(1))(2)] and [Zn(2)(L(1))(2)(Py)(2)] has been examined. Oxidative processes for the complexes are dominantly irreversible, but several examples of quasireversible behaviour were observed and support the assignment of an anodic process, seen between +1.0 and +1.6 V, as a metal-centred oxidation. The reduction processes for the respective metal complexes are not simple, and irreversible in most cases. Solvent extraction studies (water/chloroform) involving variable concentrations of metal, bis-beta-diketone and heterocyclic base have been performed for cobalt(II) and zinc(II) using a radiotracer technique to probe the stoichiometries of the extracted species in each case. Synergism was observed when 4-ethylpyridine was added to the bis-beta-diketone ligand in the chloroform phase. Competitive extraction studies show a clear uptake preference for copper(II) over cobalt(II), nickel(II), zinc(II) and cadmium(II).

  5. Exafs and comparative studies of copper (II) complexes

    NASA Astrophysics Data System (ADS)

    Mishra, A.; Mishra, S.

    2016-10-01

    The present paper deals with the synthesis of transition metal Schiff base complexes of copper by chemical root method. The synthesized metal complexes were characterized by Extended X-ray absorption fine structure (EXAFS) is a technique that has been used for determining the metal ligand bond length using conventional X-ray source and also by EXAFS analysis using IFEFFIT programming. Bond lengths determined from these data analysis methods are compared with the bond lengths obtained from LSS, Levy's and Lytle's methods. Bond lengths of the complexes are in good agreement obtained by theoretical and experimental method.

  6. Delineation of vagal emetic pathways: intragastric copper sulfate-induced emesis and viral tract tracing in musk shrews

    PubMed Central

    Meyers, Kelly; Lim, Audrey; Dye, Matthew; Pak, Diana; Rinaman, Linda; Yates, Bill J.

    2014-01-01

    Signals from the vestibular system, area postrema, and forebrain elicit nausea and vomiting, but gastrointestinal (GI) vagal afferent input arguably plays the most prominent role in defense against food poisoning. It is difficult to determine the contribution of GI vagal afferent input on emesis because various agents (e.g., chemotherapy) often act on multiple sensory pathways. Intragastric copper sulfate (CuSO4) potentially provides a specific vagal emetic stimulus, but its actions are not well defined in musk shrews (Suncus murinus), a primary small animal model used to study emesis. The aims of the current study were 1) to investigate the effects of subdiaphragmatic vagotomy on CuSO4-induced emesis and 2) to conduct preliminary transneuronal tracing of the GI-brain pathways in musk shrews. Vagotomy failed to inhibit the number of emetic episodes produced by optimal emetic doses of CuSO4 (60 and 120 mg/kg ig), but the effects of lower doses were dependent on an intact vagus (20 and 40 mg/kg). Vagotomy also failed to affect emesis produced by motion (1 Hz, 10 min) or nicotine administration (5 mg/kg sc). Anterograde transport of the H129 strain of herpes simplex virus-1 from the ventral stomach wall identified the following brain regions as receiving inputs from vagal afferents: the nucleus of the solitary tract, area postrema, and lateral parabrachial nucleus. These data indicate that the contribution of vagal pathways to intragastric CuSO4-induced emesis is dose dependent in musk shrews. Furthermore, the current neural tracing data suggest brain stem anatomical circuits that are activated by GI signaling in the musk shrew. PMID:24430885

  7. Delineation of vagal emetic pathways: intragastric copper sulfate-induced emesis and viral tract tracing in musk shrews.

    PubMed

    Horn, Charles C; Meyers, Kelly; Lim, Audrey; Dye, Matthew; Pak, Diana; Rinaman, Linda; Yates, Bill J

    2014-03-01

    Signals from the vestibular system, area postrema, and forebrain elicit nausea and vomiting, but gastrointestinal (GI) vagal afferent input arguably plays the most prominent role in defense against food poisoning. It is difficult to determine the contribution of GI vagal afferent input on emesis because various agents (e.g., chemotherapy) often act on multiple sensory pathways. Intragastric copper sulfate (CuSO4) potentially provides a specific vagal emetic stimulus, but its actions are not well defined in musk shrews (Suncus murinus), a primary small animal model used to study emesis. The aims of the current study were 1) to investigate the effects of subdiaphragmatic vagotomy on CuSO4-induced emesis and 2) to conduct preliminary transneuronal tracing of the GI-brain pathways in musk shrews. Vagotomy failed to inhibit the number of emetic episodes produced by optimal emetic doses of CuSO4 (60 and 120 mg/kg ig), but the effects of lower doses were dependent on an intact vagus (20 and 40 mg/kg). Vagotomy also failed to affect emesis produced by motion (1 Hz, 10 min) or nicotine administration (5 mg/kg sc). Anterograde transport of the H129 strain of herpes simplex virus-1 from the ventral stomach wall identified the following brain regions as receiving inputs from vagal afferents: the nucleus of the solitary tract, area postrema, and lateral parabrachial nucleus. These data indicate that the contribution of vagal pathways to intragastric CuSO4-induced emesis is dose dependent in musk shrews. Furthermore, the current neural tracing data suggest brain stem anatomical circuits that are activated by GI signaling in the musk shrew.

  8. Apparent copper(II)-accelerated azide-alkyne cycloaddition.

    PubMed

    Brotherton, Wendy S; Michaels, Heather A; Simmons, J Tyler; Clark, Ronald J; Dalal, Naresh S; Zhu, Lei

    2009-11-05

    Cu(II) salts accelerate azide-alkyne cycloaddition reactions in alcoholic solvents without reductants such as sodium ascorbate. Spectroscopic observations suggest that Cu(II) undergoes reduction to catalytic Cu(I) species via either alcohol oxidation or alkyne homocoupling, or both, during an induction period. The reactions involving 2-picolylazide are likely facilitated by its chelation to Cu(II). The highly exothermic reaction between 2-picolylazide and propargyl alcohol completes within 1-2 min in the presence of as low as 1 mol % Cu(OAc)(2).

  9. Copper(II) complexes of prion protein PEG11-tetraoctarepeat fragment: spectroscopic and voltammetric studies.

    PubMed

    Bonomo, Raffaele P; Di Natale, Giuseppe; Rizzarelli, Enrico; Tabbì, Giovanni; Vagliasindi, Laura I

    2009-04-14

    Spectroscopic (UV-Vis and EPR) and voltammetric studies have been carried out on the copper(II) complexes with the Ac-PEG11-(PHGGGWGQ)4-NH2 (L) polypeptide. In the ratios Cu : L 3 : 1 and 4 : 1, the two [Cu3(L)H(-6)] and [Cu4(L)H(-8)] complex species have been characterized at neutral pH values. All the copper atoms occupy similar coordination sites formed by imidazole, peptidic nitrogen atoms and carbonyl oxygen atoms in a square base pyramidal geometry. Voltammetric measurements on these systems point out the cooperativity in the electron transfer processes among the copper(II) sites during their reduction. NO interaction with these polynuclear copper species is characterized by the reduction of the copper sites through the formation of two different intermediate complex species. When an excess of the Ac-PEG11-(PHGGGWGQ)4-NH2 ligand is considered, frozen solution EPR parameters and UV-Vis spectroscopic data identify the [Cu(N(im))4]2+ chromophore, which does not interact with NO.

  10. Redox Activity of Copper(II) Complexes with NSFRY Pentapeptide and Its Analogues

    PubMed Central

    Wiloch, Magdalena Zofia; Wawrzyniak, Urszula Elżbieta; Ufnalska, Iwona; Piotrowski, Grzegorz; Bonna, Arkadiusz; Wróblewski, Wojciech

    2016-01-01

    The influence of cation-π interactions on the electrochemical properties of copper(II) complexes with synthesized pentapeptide C-terminal fragment of Atrial Natriuretic Factor (ANF) hormone was studied in this work. Molecular modeling performed for Cu(II)-NSFRY-NH2 complex indicated that the cation-π interactions between Tyr and Cu(II), and also between Phe-Arg led to specific conformation defined as peptide box, in which the metal cation is isolated from the solvent by peptide ligand. Voltammetry experiments enabled to compare the redox properties and stability of copper(II) complexes with NSFRY-NH2 and its analogues (namely: NSFRA-NH2, NSFRF-NH2, NSAAY-NH2, NSAAA-NH2, AAAAA-NH2) as well as to evaluate the contribution of individual amino acid residues to these properties. The obtained results led to the conclusion, that cation-π interactions play a crucial role in the effective stabilization of copper(II) complexes with the fragments of ANF peptide hormone and therefore could control the redox processes in other metalloproteins. PMID:27517864

  11. Spin control in ladderlike hexanuclear copper(II) complexes with metallacyclophane cores.

    PubMed

    Pardo, Emilio; Bernot, Kevin; Julve, Miguel; Lloret, Francesc; Cano, Joan; Ruiz-García, Rafael; Delgado, Fernando S; Ruiz-Pérez, Catalina; Ottenwaelder, Xavier; Journaux, Yves

    2004-05-03

    Two new hexanuclear oxamatocopper(II) complexes 3 and 4 have been synthesized from the binuclear copper(II) complexes of the meta- and para-phenylenebis(oxamate) ligands, respectively. Complexes 3 and 4 possess an overall ladderlike structure made up of two oxamate-bridged linear trinuclear units ("rails") connected through two phenylenediamidate bridges ("rungs") between the central copper atoms to give metallacyclic cores of the meta- and para-cyclophane type, respectively. They show different ground spin states, S = 1 (3) or S = 0 (4), depending on the substitution pattern in the aromatic spacers. The triplet state molecule 3 containing two spin doublet Cu(II)3 units connected by two m-phenylenediamidate bridges represents a successful extension of the concept of "ferromagnetic coupling units" to metal complexes, which is a well-known approach toward high spin organic radicals.

  12. Doubly chloro bridged dimeric copper(II) complex: magneto-structural correlation and anticancer activity.

    PubMed

    Sikdar, Yeasin; Modak, Ritwik; Bose, Dipayan; Banerjee, Saswati; Bieńko, Dariusz; Zierkiewicz, Wiktor; Bieńko, Alina; Das Saha, Krishna; Goswami, Sanchita

    2015-05-21

    We have synthesized and structurally characterized a new doubly chloro bridged dimeric copper(II) complex, [Cu2(μ-Cl)2(HL)2Cl2] (1) based on a Schiff base ligand, 5-[(pyridin-2-ylmethylene)-amino]-pentan-1-ol). Single crystal X-ray diffraction shows the presence of dinuclear copper(II) centres in a square pyramidal geometry linked by obtuse double chloro bridge. The magnetic study illustrated that weak antiferromagnetic interactions (J = -0.47 cm(-1)) prevail in complex 1 which is well supported by magneto-structural correlation. This compound adds to the library of doubly chloro bridged copper(ii) complexes in the regime of spin state cross over. DFT calculations have been conducted within a broken-symmetry (BS) framework to investigate the exchange interaction further which depicts that the approximate spin projection technique yields the best corroboration of the experimental J value. Spin density plots show the presence of an ∼0.52e charge residing on the copper atom along with a substantial charge on bridging and peripheral chlorine atoms. The potential of complex1 to act as an anticancer agent is thoroughly examined on a series of liver cancer cell lines and screening shows the HepG2 cell line exhibits maximum cytotoxicity by phosphatidyl serine exposure in the outer cell membrane associated with ROS generation and mitochondrial depolarization with increasing time in the in vitro model system.

  13. Kinetic behaviour of Duolite ES 468 in the cosorption of non-ionic surfactant and copper(II).

    PubMed

    Kauspediene, D; Snukiskis, J; Gefeniene, A

    2003-05-30

    Kinetic behaviour of the hydrogen form of Duolite ES 468 polyacrylic acid-functionalised cation exchanger with respect to the sorption of non-ionic surfactant alkylmonoethers (ALM-10) and copper(II) has been investigated; kinetic curves have been obtained, using spectrophotometric determination for ALM-10 and complexometric one for copper(II). Kinetic coefficient (B), intraparticle diffusion coefficient (D; m(2)s(-1)) and overall rate constant (k(o); s(-1)) for non-ionic surfactant and copper(II) depend on the solution composition, pH and the maximum sorption at the equilibrium. On increasing the solution acidity from pH 5 to pH 3 a decrease in both D and the equilibrium sorption for copper(II) although an increase in D for ALM-10 is observed. The action of copper(II) results in an increase in both D for ALM-10 and the maximum sorption at the equilibrium, whereas the action of ALM-10 leads to a decrease in the corresponding parameters for copper(II). Hydrogen form of Duolite ES 468 polyacrylic acid-functionalised cation exchanger is suitable for the simultaneous removal of non-ionic surfactant and copper(II) from waste water.

  14. Copper(II) ions and the Alzheimer's amyloid-β peptide: Affinity and stoichiometry of binding

    NASA Astrophysics Data System (ADS)

    Tõugu, Vello; Friedemann, Merlin; Tiiman, Ann; Palumaa, Peep

    2014-10-01

    Deposition of amyloid beta (Aβ) peptides into amyloid plaques is the hallmark of Alzheimer's disease. According to the amyloid cascade hypothesis this deposition is an early event and primary cause of the disease, however, the mechanisms that cause this deposition remain elusive. An increasing amount of evidence shows that the interactions of biometals can contribute to the fibrillization and amyloid formation by amyloidogenic peptides. From different anions the copper ions deserve the most attention since it can contribute not only toamyloid formation but also to its toxicity due to the generation of ROS. In this thesis we focus on the affinity and stoichiometry of copper(II) binding to the Aβ molecule.

  15. Antitubercular and fluorescence studies of copper(II) complexes with quinolone family member, ciprofloxacin

    NASA Astrophysics Data System (ADS)

    Kharadi, G. J.

    2011-09-01

    Four new mixed-ligand complexes of Cu(II) with ciprofloxacin (Cip) and uninegative bidentate ligands have been synthesized and characterized. The structure of mixed-ligand complexes was investigated using spectroscopic method, physicochemical and elemental analyses. The fluorescence spectra of complexes show red shift, which may be due to the chelation by the ligands to the metal ion. It enhances ligand ability to accept electrons and decreases the electron transition energy. Antimycobacterial screening of ligand and its copper compound against Mycobacterium tuberculosis shows clear enhancement in the antitubercular activity upon copper complexation.

  16. Experimental Investigation on the Mechanism of Chelation-Assisted, Copper(II) Acetate-Accelerated Azide-Alkyne Cycloaddition

    PubMed Central

    Kuang, Gui-Chao; Guha, Pampa M.; Brotherton, Wendy S.; Simmons, J. Tyler; Stankee, Lisa A.; Nguyen, Brian T.; Clark, Ronald J.; Zhu, Lei

    2011-01-01

    A mechanistic model is formulated to account for the high reactivity of chelating azides (organic azides capable of chelation-assisted metal coordination at the alkylated azido nitrogen position) and copper(II) acetate (Cu(OAc)2) in copper(II)-mediated azide-alkyne cycloaddition (AAC) reactions. Fluorescence and 1H NMR assays are developed for monitoring the reaction progress in two different solvents – methanol and acetonitrile. Solvent kinetic isotopic effect and pre-mixing experiments give credence to the proposed different induction reactions for converting copper(II) to catalytic copper(I) species in methanol (methanol oxidation) and acetonitrile (alkyne oxidative homocoupling), respectively. The kinetic orders of individual components in a chelation-assisted, copper(II)-accelerated AAC reaction are determined in both methanol and acetonitrile. Key conclusions resulting from the kinetic studies include (1) the interaction between copper ion (either in +1 or +2 oxidation state) and a chelating azide occurs in a fast, pre-equilibrium step prior to the formation of the in-cycle copper(I)-acetylide, (2) alkyne deprotonation is involved in several kinetically significant steps, and (3) consistent with prior experimental and computational results by other groups, two copper centers are involved in the catalysis. The X-ray crystal structures of chelating azides with Cu(OAc)2 suggest a mechanistic synergy between alkyne oxidative homocoupling and copper(II)-accelerated AAC reactions, in which both a bimetallic catalytic pathway and a base are involved. The different roles of the two copper centers (a Lewis acid to enhance the electrophilicity of the azido group and a two-electron reducing agent in oxidative metallacycle formation, respectively) in the proposed catalytic cycle suggest that a mixed valency (+2 and +1) dinuclear copper species be a highly efficient catalyst. This proposition is supported by the higher activity of the partially reduced Cu(OAc)2 in

  17. Control of size in losartan/copper(II) coordination complex hydrophobic precipitate.

    PubMed

    Denadai, Ângelo M L; Da Silva, Jeferson G; Guimarães, Pedro P G; Gomes, Leonardo Bertolini S; Mangrich, Antonio S; de Rezende, Edivaltrys I P; Daniel, Izabela M P; Beraldo, Heloísa; Sinisterra, Rubén D

    2013-10-01

    Reaction of highly soluble orally active, non-peptide antihypertensive drug losartan with copper(II) leads to the spontaneous formation of a very insoluble 2:1 covalent complex, which self assembles in a hydrophobic supramolecular structure of nanometric dimensions. Thermal analysis showed that Los/Cu(II) complex presents intermediate stability in comparison with its precursors KLos and Cu(OAc)2·H2O. Isothermal titration calorimetry indicated complexation to be a stepwise process, driven by enthalpy and entropy. Zeta potential and DLS measurements showed that it is possible to control the size and charge of nanoprecipitates by adjusting the relative concentration of Los(-) and Cu(II).

  18. Immobilization of Hg(II) by Coprecipitation in Sulfate-Cement Systems

    PubMed Central

    2012-01-01

    Uptake and molecular speciation of dissolved Hg during formation of Al- or Fe-ettringite-type and high-pH phases were investigated in coprecipitation and sorption experiments of sulfate-cement treatments used for soil and sediment remediation. Ettringite and minor gypsum were identified by XRD as primary phases in Al systems, whereas gypsum and ferrihydrite were the main products in Hg–Fe precipitates. Characterization of Hg–Al solids by bulk Hg EXAFS, electron microprobe, and microfocused-XRF mapping indicated coordination of Hg by Cl ligands, multiple Hg and Cl backscattering atoms, and concentration of Hg as small particles. Thermodynamic predictions agreed with experimental observations for bulk phases, but Hg speciation indicated lack of equilibration with the final solution. Results suggest physical encapsulation of Hg as a polynuclear chloromercury(II) salt in ettringite as the primary immobilization mechanism. In Hg–Fe solids, structural characterization indicated Hg coordination by O atoms only and Fe backscattering atoms that is consistent with inner-sphere complexation of Hg(OH)20 coprecipitated with ferrihydrite. Precipitation of ferrihydrite removed Hg from solution, but the resulting solid was sufficiently hydrated to allow equilibration of sorbed Hg species with the aqueous solution. Electron microprobe XRF characterization of sorption samples with low Hg concentration reacted with cement and FeSO4 amendment indicated correlation of Hg and Fe, supporting the interpretation of Hg removal by precipitation of an Fe(III) oxide phase. PMID:22594782

  19. Electrocatalytic water oxidation with a copper(II) polypeptide complex.

    PubMed

    Zhang, Ming-Tian; Chen, Zuofeng; Kang, Peng; Meyer, Thomas J

    2013-02-13

    A self-assembly-formed triglycylglycine macrocyclic ligand (TGG(4-)) complex of Cu(II), [(TGG(4-))Cu(II)-OH(2)](2-), efficiently catalyzes water oxidation in a phosphate buffer at pH 11 at room temperature by a well-defined mechanism. In the mechanism, initial oxidation to Cu(III) is followed by further oxidation to a formal "Cu(IV)" with formation of a peroxide intermediate, which undergoes further oxidation to release oxygen and close the catalytic cycle. The catalyst exhibits high stability and activity toward water oxidation under these conditions with a high turnover frequency of 33 s(-1).

  20. Diaqua-bis-(hydrogen tartrato)copper(II) dihydrate.

    PubMed

    Al-Dajani, Mohammad T M; Abdallah, Hassan H; Mohamed, Nornisah; Hemamalini, Madhukar; Fun, Hoong-Kun

    2010-06-16

    The title complex, [Cu(C(4)H(5)O(6))(2)(H(2)O)(2)]·2H(2)O, contains a Cu(II) ion lying on an inversion centre. The coordination geometry of the Cu(II) ion is a distorted octa-hedron with four O atoms from two hydrogen tartrate ions occupying the equatorial positions and two O atoms from two coordinated water mol-ecules occupying the axial positions. In the crystal structure, inter-molecular O-H⋯O and C-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional network.

  1. Dinuclear cobalt(II) and copper(II) complexes with a Py2N4S2 macrocyclic ligand.

    PubMed

    Núñez, Cristina; Bastida, Rufina; Lezama, Luis; Macías, Alejandro; Pérez-Lourido, Paulo; Valencia, Laura

    2011-06-20

    The interaction between Co(II) and Cu(II) ions with a Py(2)N(4)S(2)-coordinating octadentate macrocyclic ligand (L) to afford dinuclear compounds has been investigated. The complexes were characterized by microanalysis, conductivity measurements, IR spectroscopy and liquid secondary ion mass spectrometry. The crystal structure of the compounds [H(4)L](NO(3))(4), [Cu(2)LCl(2)](NO(3))(2) (5), [Cu(2)L(NO(3))(2)](NO(3))(2) (6), and [Cu(2)L(μ-OH)](ClO(4))(3)·H(2)O (7) was also determined by single-crystal X-ray diffraction. The [H(4)L](4+) cation crystal structure presents two different conformations, planar and step, with intermolecular face-to-face π,π-stacking interactions between the pyridinic rings. Complexes 5 and 6 show the metal ions in a slightly distorted square-pyramidal coordination geometry. In the case of complex 7, the crystal structure presents the two metal ions joined by a μ-hydroxo bridge and the Cu(II) centers in a slightly distorted square plane or a tetragonally distorted octahedral geometry, taking into account weak interactions in axial positions. Electron paramagnetic resonance spectroscopy is in accordance with the dinuclear nature of the complexes, with an octahedral environment for the cobalt(II) compounds and square-pyramidal or tetragonally elongated octahedral geometries for the copper(II) compounds. The magnetic behavior is consistent with the existence of antiferromagnetic interactions between the ions for cobalt(II) and copper(II) complexes, while for the Co(II) ones, this behavior could also be explained by spin-orbit coupling.

  2. Poly[diamminedi-μ3-dicyanamido-copper(II)

    PubMed Central

    Díaz, Jesús García; Albor, Atzimba García; Jaime, Espino Valencia; Vrábel, Viktor; Kožíšek, Jozef

    2012-01-01

    The asymmetric unit of the title polymeric mononuclear CuII complex, [Cu(C2N3)2(NH3)2]n, contains one half-mol­ecule, the complex being completed through inversion symmetry, with the CuII atom situated on the centre of symmetry. The coordination polyhedron around CuII is a Jahn–Teller-distorted [CuN6] octa­hedron. The terminal N atoms of two dicyanamide ligands and two ammine ligands form an approximate square plane, with N—Cu—N bite angles of 89.72 (5) and 90.28 (5)°. The coordination polyhedron is completed in the axial positions by the central amide-type N atoms of two additional dicyanamide ligands, with an elongated Cu—N distance of 2.548 (1) Å. In turn, each of the four dicyanamide ligands, acting as bidentate, link the CuII ions into a two-dimensional polymeric structure parallel to (100). The ammine H atoms are involved in inter­molecular hydrogen bonding with the free terminal N atoms of neighbouring dicyanamide ligands, yielding a three-dimensional network. PMID:23468666

  3. Catalytic wet oxidation of thiocyanate with homogeneous copper(II) sulphate catalyst.

    PubMed

    Collado, Sergio; Laca, Adriana; Díaz, Mario

    2010-05-15

    The wet oxidation of thiocyanate has been investigated in a semi-batch reactor at temperatures between 423 and 473 K and pressures between 6.1 x 10(3) and 1.0 x 10(4)kPa in the presence of copper(II) sulphate as catalyst. The effects of copper concentration, initial thiocyanate concentration, pressure and temperature on the reaction rate were analyzed and the main products of reaction were identified. A kinetic model for the Cu-catalyzed reaction is here proposed, including temperature, oxygen concentration, and the reduction of Cu(2+) to Cu(+) that gives an accurate prediction of the oxidation process under the assayed conditions. A mechanistic model based on the formation of a transition complex between a copper cation and two thiocyanate anions has been proposed for the catalytic wet oxidation.

  4. Reconstitution of Formylglycine-generating Enzyme with Copper(II) for Aldehyde Tag Conversion

    PubMed Central

    Holder, Patrick G.; Jones, Lesley C.; Drake, Penelope M.; Barfield, Robyn M.; Bañas, Stefanie; de Hart, Gregory W.; Baker, Jeanne; Rabuka, David

    2015-01-01

    To further our aim of synthesizing aldehyde-tagged proteins for research and biotechnology applications, we developed methods for recombinant production of aerobic formylglycine-generating enzyme (FGE) in good yield. We then optimized the FGE biocatalytic reaction conditions for conversion of cysteine to formylglycine in aldehyde tags on intact monoclonal antibodies. During the development of these conditions, we discovered that pretreating FGE with copper(II) is required for high turnover rates and yields. After further investigation, we confirmed that both aerobic prokaryotic (Streptomyces coelicolor) and eukaryotic (Homo sapiens) FGEs contain a copper cofactor. The complete kinetic parameters for both forms of FGE are described, along with a proposed mechanism for FGE catalysis that accounts for the copper-dependent activity. PMID:25931126

  5. Copper(II) benzoate dimers coordinated by different linear alcohols - A systematic study of crystal structures

    NASA Astrophysics Data System (ADS)

    Katzsch, Felix; Münch, Alexander S.; Mertens, Florian O. R. L.; Weber, Edwin

    2014-05-01

    Three new copper(II) benzoates coordinated by 1-propanol, [Cu2(PhCOO)4(1-PrOH)2] [Cu2(PhCOO)4(H2O)2] (3), 1-butanol, [Cu2(PhCOO)4(1-BuOH)2] (4) and 1-pentanol, [Cu2(PhCOO)4(1-PentOH)2] (5) at the available metal coordination sites, have been prepared and investigated with reference to their X-ray crystal structures. In all cases, dimeric paddle-wheel complexes where two copper(II) ions are held together by four benzoates were found. Moreover, the complexes show 1-propanol and water (3), 1-butanol (4) and 1-pentanol (5) coordinated to the free coordination sites of the Cu(II) ions. The dimeric complex units are connected with each other by strong Osbnd H⋯O hydrogen bonds to form strands linked together via weaker Csbnd H⋯O and Csbnd H⋯π interactions. Comparative discussion including the redetermined crystal structures obtained from copper(II) benzoate in the presence of methanol (1) or ethanol (2) allows to draw argumentation regarding the coordination of linear alcohols in corresponding crystals of paddle-wheel complexes.

  6. Charge-transfer photochemistry of bis(diethyl-diselenocarbamato)copper(II)

    NASA Astrophysics Data System (ADS)

    Sarova, G.; Roussanova, D.; Jeliazkova, B.; Yordanov, N. D.; Malik, M. A.; O'Brien, P.

    2000-02-01

    The photochemical reactions of bis(diethyl-diselenocarbamato)copper(II), Cu(Et 2dsc) 2, complex have been studied in toluene, CH 2Cl 2, CHCl 3 and chloroalkane/EtOH mixed solvents. Charge-transfer irradiation induces intramolecular oxidation of the ligand and reduction of copper(II) to copper(I) as evidenced by EPR and UV-Vis spectra of the complex as well as quantum yield results. When photolysis is carried out in CHCl 3 or CH 2Cl 2 or in the solvent mixture CHCl 3/EtOH resp. CH 2Cl 2/EtOH of lower than 1:1 EtOH content, the primary photoproduct Cu I(Et 2dsc) is further oxidised in a dark reaction with the chloroalkane producing the corresponding paramagnetic mixed-ligand Cu II(Et 2dsc)Cl complex in equilibrium with its chloride-bridged and EPR silent, dimeric form Cu 2(Et 2dsc) 2Cl 2. At low concentration of EtOH the equilibrium is shifted to the dimeric form whereas at higher than 1:1 EtOH content in the mixed solvent CHCl 3/EtOH it is shifted to Cu II(Et 2dsc)Cl. A reaction mechanism is proposed and the role of ethanol is discussed.

  7. Mechanism of Hg(II) Immobilization in Sediments by Sulfate-Cement Amendment.

    PubMed

    Serrano, Susana; Vlassopoulos, Dimitri; O'Day, Peggy A

    2016-04-01

    Reactive amendments such as Portland and super-sulfate cements offer a promising technology for immobilizing metalloid contaminants such as mercury (Hg) in soils and sediments through sequestration in less bioavailable solid forms. Tidal marsh sediments were reacted with dissolved Hg(II) in synthetic seawater and fresh water solutions, treated with Portland cement and FeSO4 amendment, and aged for up to 90 days. Reacted solids were analyzed with bulk sequential extraction methods and characterized by powder X-ray diffraction (XRD), electron microscopy, and synchrotron X-ray absorption spectroscopy at the Hg LIII- and S K-edge. In amended sediments, XRD, SEM and sulfur K-edge XANES indicated formation of gypsum in seawater experiments or ettringite-type (Ca6Al2(SO4)3(OH)12(.)26H2O) phases in fresh water experiments, depending on the final solution pH (seawater ∼8.5; freshwater ∼10.5). Analysis of Hg EXAFS spectra showed Cl and Hg ligands in the first- and second-coordination shells at distances characteristic of a polynuclear chloromercury(II) salt, perhaps as a nanoparticulate phase, in both seawater and fresh water experiments. In addition to the chloromercury species, a smaller fraction (∼20-25%) of Hg was bonded to O atoms in fresh water sample spectra, suggesting the presence of a minor sorbed Hg fraction. In the absence of amendment treatment, Hg sorption and resistance to extraction can be accounted for by relatively strong binding by reduced S species present in the marsh sediment detected by S XANES. Thermodynamic calculations predict stable aqueous Hg-Cl species at seawater final pH, but higher final pH in fresh water favors aqueous Hg-hydroxide species. The difference in Hg coordination between aqueous and solid phases suggests that the initial Hg-Cl coordination was stabilized in the cement hydration products and did not re-equilibrate with the bulk solution with aging. Collectively, results suggest physical encapsulation of Hg as a polynuclear

  8. Statics of molybdenum sorption from manganese(II) sulfate solutions on porous and macronetwork anion-exchange resin AN-108

    SciTech Connect

    Kholmogorov, A.G.; Kononova, O.N.; Pashkov, G.L.

    1994-11-20

    The statics have been considered of the ion-exchange equilibrium in the system R{sub 2}SO{sub 4}-MnSO{sub 4}-H{sub 2}SO{sub 4}-Mo(VI)-H{sub 2}O in recovery of molybdenum(VI) ions from sulfate solutions of manganese(II) in relation to the sulfuric acid concentration, physical and chemical structure of the ion-exchange resin, and solution temperatures.

  9. The effect of copper(II), iron(II) sulphate, and vitamin C combinations on the weak antimicrobial activity of (+)-catechin against Staphylococcus aureus and other microbes.

    PubMed

    Holloway, Andrew C; Mueller-Harvey, Irene; Gould, Simon W J; Fielder, Mark D; Naughton, Declan P; Kelly, Alison F

    2012-12-01

    Few attempts have been made to improve the activity of plant compounds with low antimicrobial efficacy. (+)-Catechin, a weak antimicrobial tea flavanol, was combined with putative adjuncts and tested against different species of bacteria. Copper(II) sulphate enhanced (+)-catechin activity against Pseudomonas aeruginosa but not Staphylococcus aureus, Proteus mirabilis or Escherichia coli. Attempts to raise the activity of (+)-catechin against two unresponsive species, S. aureus and E. coli, with iron(II) sulphate, iron(III) chloride, and vitamin C, showed that iron(II) enhanced (+)-catechin against S. aureus, but not E. coli; neither iron(III) nor combined iron(II) and copper(II), enhanced (+)-catechin activity against either species. Vitamin C enhanced copper(II) containing combinations against both species in the absence of iron(II). Catalase or EDTA added to active samples removed viability effects suggesting that active mixtures had produced H(2)O(2)via the action of added metal(II) ions. H(2)O(2) generation by (+)-catechin plus copper(II) mixtures and copper(II) alone could account for the principal effect of bacterial growth inhibition following 30 minute exposures as well as the antimicrobial effect of (+)-catechin-iron(II) against S. aureus. These novel findings about a weak antimicrobial flavanol contrast with previous knowledge of more active flavanols with transition metal combinations. Weak antimicrobial compounds like (+)-catechin within enhancement mixtures may therefore be used as efficacious agents. (+)-Catechin may provide a means of lowering copper(II) or iron(II) contents in certain crop protection and other products.

  10. Intercalation of organic molecules in 2D copper (II) nitroprusside: Intermolecular interactions and magnetic properties

    SciTech Connect

    Osiry, H.; Cano, A.; Lemus-Santana, A.A.; Rodríguez, A.; Carbonio, R.E.; Reguera, E.

    2015-10-15

    This contribution discusses the intercalation of imidazole and its 2-ethyl derivative, and pyridine in 2D copper nitroprusside. In the interlayer region, neighboring molecules remain interacting throu gh their dipole and quadrupole moments, which supports the solid 3D crystal structure. The crystal structure of this series of intercalation compounds was solved and refined from powder X-ray diffraction patterns complemented with spectroscopic information. The intermolecular interactions were studied from the refined crystal structures and low temperature magnetic measurements. Due to strong attractive forces between neighboring molecules, the resulting π–π cloud overlapping enables the ferromagnetic coupling between metal centers on neighboring layers, which was actually observed for the solids containing imidazole and pyridine as intercalated molecules. For these two solids, the magnetic data were properly described with a model of six neighbors. For the solid containing 2-ethylimidazole and for 2D copper nitroprusside, a model of four neighbors in a plane is sufficient to obtain a reliable data fitting. - Highlights: • Intercalation of organic molecules in 2D copper (II) nitroprusside. • Molecular properties of intercalation compounds of 2D copper (II) nitroprusside. • Magnetic properties of hybrid inorganic–organic solids. • Hybrid inorganic–organic 3D framework.

  11. The tachykinin peptide neurokinin B binds copper forming an unusual [CuII(NKB)2] complex and inhibits copper uptake into 1321N1 astrocytoma cells.

    PubMed

    Russino, Debora; McDonald, Elle; Hejazi, Leila; Hanson, Graeme R; Jones, Christopher E

    2013-10-16

    Neurokinin B (NKB) is a member of the tachykinin family of neuropeptides that have neuroinflammatory, neuroimmunological, and neuroprotective functions. In a neuroprotective role, tachykinins can help protect cells against the neurotoxic processes observed in Alzheimer's disease. A change in copper homeostasis is a clear feature of Alzheimer's disease, and the dysregulation may be a contributory factor in toxicity. Copper has recently been shown to interact with neurokinin A and neuropeptide γ and can lead to generation of reactive oxygen species and peptide degradation, which suggests that copper may have a place in tachykinin function and potentially misfunction. To explore this, we have utilized a range of spectroscopic techniques to show that NKB, but not substance P, can bind Cu(II) in an unusual [Cu(II)(NKB)2] neutral complex that utilizes two N-terminal amine and two imidazole nitrogen ligands (from each molecule of NKB) and the binding substantially alters the structure of the peptide. Using 1321N1 astrocytoma cells, we show that copper can enter the cells and subsequently open plasma membrane calcium channels but when bound to neurokinin B copper ion uptake is inhibited. This data suggests a novel role for neurokinin B in protecting cells against copper-induced calcium changes and implicates the peptide in synaptic copper homeostasis.

  12. Cytotoxic copper(II), cobalt(II), zinc(II), and nickel(II) coordination compounds of clotrimazole.

    PubMed

    Betanzos-Lara, Soledad; Gómez-Ruiz, Celedonio; Barrón-Sosa, Lidia R; Gracia-Mora, Isabel; Flores-Álamo, Marcos; Barba-Behrens, Noráh

    2012-09-01

    Sixteen novel mononuclear Cu(II), Co(II), Zn(II), and Ni(II) complexes of the biologically active ligand clotrimazole (clotri) of the forms [M(clotri)(2)Cl(2)]·nH(2)O (1-4), [M(clotri)(2)Br(2)]·nH(2)O (5-7), [M(clotri)(3)Br(2)] (8), [M(clotri)(3)NO(3)]NO(3)·nH(2)O (9, 11), [M(clotri)(3)(NO(3))(2)]·nH(2)O (10), and [M(clotri)(3)(OH(2))(2)NO(3)]NO(3)·nH(2)O (12) were synthesized and fully characterized. Dinuclear [Cu(2)(clotri)(4)μ(2)-Cl(4)]·2H(2)O (1a) and [Cu(2)(clotri)(4)μ(2)-Br(2)]·2H(2)O (5b) as well as tetranuclear [Cu(4)(clotri)(4)μ(4)-Br(6)μ(4)-O] (5a) complexes were also isolated. Complexes 1-7, 9, and 11 present a tetrahedral geometry; complex 8 exhibits a pentacoordinated structure; complexes 1a, 10 and 12 an octahedral geometry. X-ray crystal structures of [Cu(clotri)(2)Cl(2)](1), [Cu(clotri)(2)(EtOH)Cl(2)](1·EtOH), [Zn(clotri)(2)Cl(2)] (3), [Zn(clotri)(2)Br(2)] (7), and [Cu(4)(clotri)(4)μ(4)-Br(6)μ(4)-O] (5a) were obtained. Complexes 1-12 were tested for cytotoxic activity against the human carcinoma cell lines HeLa (cervix-uterine), PC3 (prostate), and HCT-15 (colon) displaying IC(50) values <30 μM. Confocal microscopy and nuclear dying (DAPI) for complex 1 showed condensation of cromatin and nuclear membrane fragmentation. Immunocytochemical detection/expression of biomarkers suggests that complexes 1 and 9 induce cell death via apoptosis. TUNEL assay detected DNA fragmentation in HeLa cells, resulting from apoptotic signaling cascades induced by Cu(II) complexes 1 and 9. (1)H NMR studies of the Zn(II) complexes showed that they can bind to nucleotides.

  13. Antifouling bastadin congeners target mussel phenoloxidase and complex copper(II) ions.

    PubMed

    Bayer, Mirko; Hellio, Claire; Maréchal, Jean-Philippe; Frank, Walter; Lin, Wenhan; Weber, Horst; Proksch, Peter

    2011-12-01

    Synthetically prepared congeners of sponge-derived bastadin derivatives such as 5,5'-dibromohemibastadin-1 (DBHB) that suppress the settling of barnacle larvae were identified in this study as strong inhibitors of blue mussel phenoloxidase that is involved in the firm attachment of mussels to a given substrate. The IC₅₀ value of DBHB as the most active enzyme inhibitor encountered in this study amounts to 0.84 μM. Inhibition of phenoloxidase by DBHB is likely due to complexation of copper(II) ions from the catalytic centre of the enzyme by the α-oxo-oxime moiety of the compound as shown here for the first time by structure activity studies and by X-ray structure determination of a copper(II) complex of DBHB.

  14. Chitosan-Copper (II) complex as antibacterial agent: synthesis, characterization and coordinating bond- activity correlation study

    NASA Astrophysics Data System (ADS)

    Mekahlia, S.; Bouzid, B.

    2009-11-01

    The antimicrobial activity of chitosan is unstable and sensitive to many factors such as molecular weight. Recent investigations showed that low molecular weight chitosan exhibited strong bactericidal activities compared to chitosan with high molecular weight. Since chitosan degradation can be caused by the coordinating bond, we attempt to synthesize and characterize the chitosan-Cu (II) complex, and thereafter study the coordinating bond effect on its antibacterial activity against Salmonella enteritidis. Seven chitosan-copper complexes with different copper contents were prepared and characterized by FT-IR, UV-vis, XRD and atomic absorption spectrophotometry (AAS). Results indicated that for chitosan-Cu (II) complexes with molar ratio close to 1:1, the inhibition rate reached 100%.

  15. Synthesis of four binuclear copper(II) complexes: Structure, anticancer properties and anticancer mechanism.

    PubMed

    Qi, Jinxu; Liang, Shichu; Gou, Yi; Zhang, Zhenlei; Zhou, Zuping; Yang, Feng; Liang, Hong

    2015-01-01

    Copper (Cu) compounds are a promising candidate for next generation metal anticancer drugs and have been extensively studied. Therefore, four binuclear copper(II) compounds derived from Schiff base thiosemicarbazones (L1-L4), namely [CuCl(L1)]2 (C1), [CuNO3(L2)]2 (C2), [Cu(NCS) (L3)]2 (C3) and [Cu(CH3COO) (L4)]2 (C4) were synthesized and characterized. Four of these compounds showed very high cytotoxicity to cancer cell lines in vitro. These Cu(II) compounds strongly promoted the apoptosis of BEL-7404 cells. The formation of reactive oxygen species (ROS), change in mitochondrial membrane potential and western blot analysis revealed that Cu compounds could induce cancer cell apoptosis through the intrinsic ROS-mediated mitochondrial pathway accompanied by the regulation of Bcl-2 family proteins.

  16. Breast Cancer Stem Cell Potent Copper(II)-Non-Steroidal Anti-Inflammatory Drug Complexes.

    PubMed

    Boodram, Janine N; Mcgregor, Iain J; Bruno, Peter M; Cressey, Paul B; Hemann, Michael T; Suntharalingam, Kogularamanan

    2016-02-18

    The breast cancer stem cell (CSC) potency of a series of copper(II)-phenanthroline complexes containing the nonsteroidal anti-inflammatory drug (NSAID), indomethacin, is reported. The most effective copper(II) complex in this series, 4, selectivity kills breast CSC-enriched HMLER-shEcad cells over breast CSC-depleted HMLER cells. Furthermore, 4 reduces the formation, size, and viability of mammospheres, to a greater extent than salinomycin, a potassium ionophore known to selectively inhibit CSCs. Mechanistic studies revealed that the CSC-specificity observed for 4 arises from its ability to generate intracellular reactive oxygen species (ROS) and inhibit cyclooxygenase-2 (COX-2), an enzyme that is overexpressed in breast CSCs. The former induces DNA damage, activates JNK and p38 pathways, and leads to apoptosis.

  17. Selective separation of copper(II) and nickel(II) from aqueous media using the complexation-ultrafiltration process.

    PubMed

    Molinari, Raffaele; Poerio, Teresa; Argurio, Pietro

    2008-01-01

    The polyethylenimine (PEI) as complexing agent was used to study the complexation-ultrafiltration (CP-UF) process in the selective removal of Cu(II) from Ni(II) contained in aqueous media. Preliminary tests showed that optimal chemical conditions for Cu(II) and Ni(II) complexation by the PEI polymer were pH>6.0 and 8.0, respectively, and polymer/metal weight ratio of 3.0 and 6.0, respectively. The effect of some important operating parameters on process selectivity was studied by performing UF tests at different parameters: pH, polymer/metal weight ratio, transmembrane pressure (TMP), and membrane cut-off in a batch experimental set-up. It was observed that process selectivity was achieved by choosing the pH value for obtaining a preferential copper complexation (pH 6.0), and the polymer/metal ratio needed to bound only the copper ion (3.0). The selective separation by UF tests was performed by using both a laboratory aqueous solution and a real aqueous effluent (water from Emoli torrent, Rende (CS)). The Iris 30 membrane at TMP of 200 kPa (2 bar) for both aqueous media gave the best results. A complete nickel recovery was reached, and copper recovery was the highest for this membrane (94% and 92%). Besides at this pressure, a lower water amount was needed to obtain total nickel recovery by diafiltration. A little higher membrane fouling was obtained by using the river effluent due to the presence of dissolved organic and inorganic matter.

  18. New copper(I) and heteronuclear copper(I)-ruthenium(II) complexes: Synthesis, structural characterization and cytotoxicity.

    PubMed

    Lopes, João; Alves, David; Morais, Tânia S; Costa, Paulo J; Piedade, M Fátima M; Marques, Fernanda; Villa de Brito, Maria J; Helena Garcia, M

    2017-04-01

    A new family of copper(I) complexes of general formula [Cu(dppe)(NN)](+) have been synthesized and fully characterized, with dppe=1.2-bis(diphenylphosphino)ethane and NN representing several bidentate heteroaromatic ligands: 2,2'-bipy=2.2'-bipyridine (1), Me2bpy=4.4'-dimethyl-2,2'-bipyridine (2), dpytz=3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine (3), dpp=2.3-bis(2-pyridyl)pyrazine (4), and the metallaligand [Ru(η(5)-C5H5)(PPh3)(dpp)](+) (5), yielding the bimetallic copper(I)-ruthenium(II) complex [Cu(dppe)(μ-dpp)Ru(η(5)-C5H5)(PPh3)](2+) (6). The single crystal structures of complexes (2) and (4) were determined by X-ray diffraction studies. All the complexes exhibit high cytotoxicity against the human cancer cells A2780 and MCF7 with IC50 values far lower than those found for the antitumor drug cisplatin in the same cell lines and even surpassing cisplatin resistance in the A2780cisR cells. They display IC50 values on the human embryonic kidney HEK293 non-tumoral cells of the same order of magnitude as those found for the tumoral cells. In the ovarian cells the compounds induce rapid production of reactive oxygen species (ROS) probably through mitochondrial pathways. According to the results reported here, these compounds can be considered as prospective antitumoral agents that deserve further evaluation.

  19. Interaction of gold nanoparticles and nickel(II) sulfate affects dendritic cell maturation.

    PubMed

    Deville, Sarah; Baré, Birgit; Piella, Jordi; Tirez, Kristof; Hoet, Peter; Monopoli, Marco P; Dawson, Kenneth A; Puntes, Victor F; Nelissen, Inge

    2016-12-01

    Despite many investigations have focused on the pristine toxicity of gold nanoparticles (GNPs), little is known about the outcome of co-exposure and interaction of GNPs with heavy metals which can possibly detoxify or potentiate them. Here, the combined exposure of nickel (II) sulfate (NiSO4) and GNPs on the maturation response of dendritic cells (DCs) was explored. Exposure to GNPs or NiSO4 separately induced cell activation. When cells were exposed to a mixture of both, however, the observed cell activation pattern indicated a competitive rather than an additive effect of both inducers with levels similar to those induced by NiSO4 alone. Quantification of the GNP uptake by DCs demonstrated a significant decrease in intracellular gold content during co-incubation with NiSO4. An extensive physiochemical characterization was performed to determine the interaction between GNPs and NiSO4 in the complex physiological media using nanoparticle tracking analyses, disc centrifugation, UV-visible spectroscopy, ICP-MS analyses, zeta potential measurements, electron microscopy, and proteomics. Although GNPs and NiSO4 did not directly interact with each other, the presence of NiSO4 in the physiological media resulted in changes in GNPs' charge and their associated protein corona (content and composition), which may contribute to a decreased cellular uptake of GNPs and sustaining the nickel-induced DC maturation. The presented results provide new insights in the interaction of heavy metals and NPs in complex physiological media. Moreover, this study highlights the necessity of mixture toxicology, since these combined exposures are highly relevant for human subjection to NPs and risk assessment of nanomaterials.

  20. Consolidation of Military Pay and Personnel Functions (Copper). Volume II

    DTIC Science & Technology

    1978-05-01

    Inclusi Log In 3815 Sign 3815 To T.S ToPage 11-15-A12 1 1 -1-AlICOPPER From Pago 11-15-All Log 11TL In UTL Control Log From Page 11-15-AIO Today’s saing...SIDPERS JUMPS BT Input BT Input BT (or unit SID uput) 210 211 212 To Page II 15-C17 To Page 11-15-Cll To Pago 11-15-C2 *A ’miwni SJ block" Is a block...possibility for traffic con- gestion ; equipment inadequacies and location problems; lighting, safety, and telephone problems, and problems such as the

  1. Solvent extraction separation of nickel and cobalt from a sulfate solution containing iron(II) and magnesium using versatic 10

    NASA Astrophysics Data System (ADS)

    Ichlas, Zela Tanlega; Purwadaria, Sunara

    2017-01-01

    The separation of nickel and cobalt from a synthetic sulfate solution that contains iron(II) and magnesium via solvent extraction techniques using a neodecanoic acid, Versatic 10, as extractant was explored. The extraction behavior of the metals was investigated by varying the operating pH while the stripping behavior was investigated by varying the acidity of the stripping agent which was sulfuric acid. The experimental results demonstrate that nickel, cobalt and iron(II) can be separated easily from magnesium via selective extraction using 20% Versatic 10 as extractant and 5% tri-n-butyl phosphate (TBP) as phase modifier at pH 7.0, while the nickel and cobalt in the loaded organic phase can be separated from iron(II) by selective stripping of the two metals using 0.1 mol/L sulfuric acid solution leaving iron(II) in the organic phase. Attempts to optimize the extraction and stripping processes were reported.

  2. Biosorption of lead(II), cadmium(II), copper(II) and nickel(II) by anaerobic granular biomass.

    PubMed

    Hawari, Alaa H; Mulligan, Catherine N

    2006-03-01

    Biosorption is potentially an attractive technology for treatment of wastewater for retaining heavy metals from dilute solutions. This study investigated the feasibility of anaerobic granules as a novel type of biosorbent, for lead, copper, cadmium, and nickel removal from aqueous solutions. Anaerobic sludge supplied from a wastewater treatment plant in the province of Quebec was used. Anaerobic granules are microbial aggregates with a strong, compact and porous structure and excellent settling ability. After treatment of the biomass with Ca ions, the cation exchange capacity of the biomass was approximately 111 meq/100 g of biomass dry weight which is comparable to the metal binding capacities of commercial ion exchange resins. This work investigated the equilibrium, batch dynamics for the biosorption process. Binding capacity experiments using viable biomass revealed a higher value than those for nonviable biomass. Binding capacity experiments using non-viable biomass treated with Ca revealed a high value of metals uptake. The solution initial pH value affected metal sorption. Over the pH range of 4.0-5.5, pH-related effects were not significant. Meanwhile, at lower pH values the uptake capacity decreased. Time dependency experiments for the metal ions uptake showed that adsorption equilibrium was reached almost 30 min after metal addition. It was found that the q(max) for Pb2+, Cd2+, Cu2+, and Ni2+ ions, were 255, 60, 55, and 26 mg/g respectively (1.23, 0.53, 0.87, and 0.44 mmol/g respectively). The data pertaining to the sorption dependence upon metal ion concentration could be fitted to a Langmiur isotherm model. Based on the results, the anaerobic granules treated with Ca appear to be a promising biosorbent for removal of heavy metals from wastewater due to its optimal uptake of heavy metals, its particulate shape, compact porous structure, excellent settling ability, and its high mechanical strength.

  3. Copper(II) interaction with the Human Prion 103-112 fragment - Coordination and oxidation.

    PubMed

    Csire, Gizella; Nagy, Lajos; Várnagy, Katalin; Kállay, Csilla

    2017-02-20

    The prion protein (PrP) is a membrane-anchored cell surface glycoprotein containing 231 amino acids. It has been associated with a group of neurodegenerative disorders. Copper(II) interaction with the Human Prion 103-112 fragment and its mutants has been studied with various techniques. The studied human prion fragment contains both histidine and methionine residues, while methionine residues are systematically replaced or displaced in the studied mutants. pH-potentiometric, UV-Vis and circular dicroism spectroscopic techniques were applied to study the stoichiometry, stability and structure of the copper(II) complexes, while HPLC-MS and MS/MS were used for identifying the products of copper(II) catalyzed oxidation. The complex formation reactions of the studied ligands are rather similar; only 1:1 complexes are formed, where the imidazole nitrogen of the histidine residue is the main binding site beside the amide nitrogens of the peptide chain. The only difference is, that in the peptides which contain methionine in position 109, in addition to the (Nim,N(-),N(-)) coordination mode, a weak interaction of thioether sulfur atoms can be supposed. The mutant peptide which does not contain methionine did not undergo oxidation, only the fragmentation of the peptide chain was perceived. However, in the case of methionine containing peptides, the peptide chain was not cleaved; but the oxidation of methionine to methionine sulfoxide occurred.

  4. An unusual 3D interdigitated architecture assembled from Keggin polyoxometalates and dinuclear copper(II) complexes

    SciTech Connect

    Pang, Haijun; Yang, Ming; Kang, Lu; Ma, Huiyuan; Liu, Bo; Li, Shaobin; Liu, Heng

    2013-02-15

    A novel organic-inorganic hybrid compound, [Cu{sub 2}(bipy){sub 3}({mu}{sub 1}-H{sub 2}O){sub 2}({mu}{sub 2}-H{sub 2}O)({mu}{sub 2}-OH)(H{sub 2}BW{sub 12}O{sub 40})]{center_dot}4 H{sub 2}O (1) (bipy=4,4 Prime -bipy), has been synthesized in hydrothermal condition and characterized by elemental analysis, IR spectrum, TG analysis and single-crystal X-ray diffraction. Compound 1 possesses poly-pendant layered motifs composed of 12-tungstoborates and dinuclear copper(II) complexes, in which the mono-coordinated bipy molecules are orderly appended to both sides of the layer, respectively. Adjacent layers mutually engage in a zipper-like pattern to result in a novel 3D interdigitated architecture. The variable-temperature magnetic susceptibility of 1 showed that there existed weak antiferromagnetic interaction in 1. Toward the reduction of hydrogen peroxide, 1 has good electrocatalytic activity and remarkable stability. - A new compound has been obtained, which represents the first interdigitated architecture assembled by POMs and dinuclear copper(II) complexes. Highlights: Black-Right-Pointing-Pointer The first example of interdigitated architecture assembled by POMs and dinuclear copper(II) complexes is observed. Black-Right-Pointing-Pointer A zipper-like pattern is observed in the structure. Black-Right-Pointing-Pointer The IR, TG, XRPD, magnetism and electrochemical property of the title compound were studied.

  5. Hydrolysis of phosphate diesters with copper(II) catalysts

    SciTech Connect

    Morrow, J.R.; Trogler, W.C.

    1988-09-21

    Hydrolysis of phosphate diesters (4-NO/sub 2/C/sub 6/H/sub 4/O)/sub 2/PO/sub 2/Na (1) and (4-NO/sub 2/C/sub 6/H/sub 4/O)(CH/sub 3/CH/sub 2/O)PO/sub 2/Li (2) is catalyzed by Cu(bpy)/sup 2 +/ (bpy = 2,2'-bipyridine) in aqueous solution at 75/degrees/C in the pH range 5.8-8.3. Greater than 1000 turnovers and 200 turnovers per Cu(bpy)/sup 2 +/ are observed in the hydrolysis of 1 and 2, respectively. Catalytic rate enhancements of the hydrolysis of 1 and 2 by 1 x 10/sup -3/ M Cu(bpy)/sup 2 +/ at pH 6.5 over spontaneous hydrolysis under the same conditions without catalyst are 2000 and 150, respectively. The hydrolysis of copper-bound 2 proceeds 6300-fold more rapidly (pH 7.85) than hydrolysis of 2 in the absence of catalyst. Kinetics for the Cu(bpy)/sup 2 +/-catalyzed hydrolysis of 2 are examined in detail. Reaction pathways are proposed. Labeling studies in /sup 18/OH/sub 2/ show no incorporation of /sup 18/O into p-nitrophenol. A single /sup 18/O label incorporates into the (C/sub 2/H/sub 5/O)PO/sub 3//sup 2 -/ product. Several simple transition-metal complexes promote the catalytic hydrolysis of phosphate diesters 1 and 2, although none are as effective as Cu(bpy)/sup 2 +/. Second-order rate constants for Cu(bpy)/sup 2 +/-promoted hydrolysis in the series of 4-nitrophenyl phosphate esters (triester, diester (anion), monoester (dianion)) vary by only a factor of 60 in contrast to those for the reaction of these phosphate esters with anionic nucleophiles in the absence of metal catalysts, which show large differences in second-order rate constants (> 10/sup 3/) between each ester in the series. 54 references, 5 figures, 6 tables.

  6. STUDIES ON BIOSORPTION OF ZINC(II) AND COPPER(II) ON DESULFOVIBRIO DESULFURICANS

    EPA Science Inventory

    The objectives of thes studies are to determine the equilibrium concentration and kinetics of metal sorption on sulfate-reducing bacteria (SRB) isolates. Adsorption establishes the net reversible cellular metal uptake and is related to SRB metal toxicity and the effects of enviro...

  7. Anaerobic reactions of Rhus vernicifera laccase and its type-2 copper-depleted derivatives with hexacyanoferrate(II).

    PubMed Central

    Sakurai, T

    1992-01-01

    Anaerobic reactions of Rhus vernicifera laccase and its type-2 copper-depleted derivatives with hexacyanoferrate(II) were investigated by absorption and e.s.r. spectroscopy. When native laccase was treated with excess hexacyanoferrate(II), the type-1 and type-2 coppers were immediately reduced and the e.s.r. signal due to type-3 copper was transiently observed. After incubation, a novel e.s.r. signal (g parallel = 2.31, g perpendicular = 2.08) developed together with the type-1 copper signal. Only the novel e.s.r. signal was left after the sample had been treated with ascorbate. In the corresponding absorption spectrum, a new band was observed at around 490 nm. A similar new e.s.r. signal did not appear for the type-2-copper-depleted (T2D) laccase, in which the type-3 copper had been reduced during the procedure to deplete the type-2 copper. On the other hand, the novel e.s.r. signal emerged when the type-3 copper in T2D laccase had been previously reoxidized with H2O2. The novel e.s.r. signal was not significantly saturated even by 200 mV microwave power at 4 K. Quantitative estimations and a small molecule study for CuII-FeII(CN)6 and CuII-FeIII(CN)6 systems suggested that the novel e.s.r. signal corresponds to some sort of adduct involving the type-3 copper and hexacyanoferrate(II). PMID:1320374

  8. Non-covalent interactions in 2-methylimidazolium copper(II) complex (MeImH)2[Cu(pfbz)4]: Synthesis, characterization, single crystal X-ray structure and packing analysis

    NASA Astrophysics Data System (ADS)

    Sharma, Raj Pal; Saini, Anju; Kumar, Santosh; Kumar, Jitendra; Sathishkumar, Ranganathan; Venugopalan, Paloth

    2017-01-01

    A new anionic copper(II) complex, (MeImH)2 [Cu(pfbz)4] (1) where, MeImH = 2-methylimidazolium and pfbz = pentafluorobenzoate has been isolated by reacting copper(II) sulfate pentahydrate, pentafluorobenzoic acid and 2-methylimidazole in ethanol: water mixture in 1:2:2 molar ratio. This complex 1 has been characterized by elemental analysis, thermogravimetric analysis, spectroscopic techniques (UV-Vis, FT-IR) and conductance measurements. The complex salt crystallizes in monoclinic crystal system with space group C2/c. Single crystal X-ray structure determination revealed the presence of discrete ions: [Cu(pfbz)4]2- anion and two 2-methylimidazolium cation (C4H7N2)+. The crystal lattice is stabilized by strong hydrogen bonding and F⋯F interactions between cationic-anionic and the anionic-anionic moieties respectively, besides π-π interactions.

  9. Transition metal complexes of neocryptolepine analogues. Part I: synthesis, spectroscopic characterization, and invitro anticancer activity of copper(II) complexes.

    PubMed

    Emam, Sanaa Moustafa; El Sayed, Ibrahim El Tantawy; Nassar, Nagla

    2015-03-05

    New generation of copper(II) complexes with aminoalkylaminoneocryptolepine as bidentate ligands has been synthesized and it is characterized by elemental analyses, magnetic moment, spectra (IR, UV-Vis, (1)H NMR and ESR) and thermal studies. The IR data suggest the coordination modes for ligands which behave as a bidentate with copper(II) ion. Based on the elemental analysis, magnetic studies, electronic and ESR data, binuclear square planar geometry was proposed for complexes 7a, 7b, square pyramidal for 9a, 9b and octahedral for 8a, 8b, 10a, 10b. The molar conductance in DMF solution indicates that all complexes are electrolyte except 7a and 7b. The ESR spectra of solid copper(II) complexes in powder form showed an axial symmetry with (2)B1g as a ground state and hyperfine structure. The thermal stability and degradation of the ligands and their metal complexes were studied employing DTA and TG methods. The metal-free ligands and their copper(II) complexes were tested for their in vitro anticancer activity against human colon carcinoma (HT-29). The results showed that the synthesized copper(II) complexes exhibited higher anticancer activity than their free ligands. Of all the studied copper(II) complexes, the bromo-substituted complex 9b exhibited high anticancer activity at low micromolar inhibitory concentrations (IC50=0.58μM), compared to the other complexes and the free ligands.

  10. Transition metal complexes of neocryptolepine analogues. Part I: Synthesis, spectroscopic characterization, and invitro anticancer activity of copper(II) complexes

    NASA Astrophysics Data System (ADS)

    Emam, Sanaa Moustafa; El Sayed, Ibrahim El Tantawy; Nassar, Nagla

    2015-03-01

    New generation of copper(II) complexes with aminoalkylaminoneocryptolepine as bidentate ligands has been synthesized and it is characterized by elemental analyses, magnetic moment, spectra (IR, UV-Vis, 1H NMR and ESR) and thermal studies. The IR data suggest the coordination modes for ligands which behave as a bidentate with copper(II) ion. Based on the elemental analysis, magnetic studies, electronic and ESR data, binuclear square planar geometry was proposed for complexes 7a, 7b, square pyramidal for 9a, 9b and octahedral for 8a, 8b, 10a, 10b. The molar conductance in DMF solution indicates that all complexes are electrolyte except 7a and 7b. The ESR spectra of solid copper(II) complexes in powder form showed an axial symmetry with 2B1g as a ground state and hyperfine structure. The thermal stability and degradation of the ligands and their metal complexes were studied employing DTA and TG methods. The metal-free ligands and their copper(II) complexes were tested for their in vitro anticancer activity against human colon carcinoma (HT-29). The results showed that the synthesized copper(II) complexes exhibited higher anticancer activity than their free ligands. Of all the studied copper(II) complexes, the bromo-substituted complex 9b exhibited high anticancer activity at low micromolar inhibitory concentrations (IC50 = 0.58 μM), compared to the other complexes and the free ligands.

  11. Di- versus Trinuclear Copper(II) Cryptate for the Uptake of Dicarboxylate Anions.

    PubMed

    Esteves, Catarina V; Mateus, Pedro; André, Vânia; Bandeira, Nuno A G; Calhorda, Maria José; Ferreira, Liliana P; Delgado, Rita

    2016-07-18

    Searching for receptors selective for the binding of dicarboxylate anions, the copper(II) complexes of the known ditopic octaazacryptand (t2pN8), derived from bistren [tren = tris(2-aminoethyl)amine] linked by p-xylyl spacers, were re-examined, with the expectation of observing a selective binding of oxalate or malonate by bridging the two copper centers of the [Cu2(t2pN8)(H2O)2](4+) receptor. Solution studies involving the supramolecular species formed by the receptor and oxalate (oxa(2-)), malonate (mal(2-)), and succinate (suc(2-)) anions are reported. The determined association constants revealed the unexpected formation of a 3:1:1 Cu/t2pN8/anion stoichiometry for the cascade species with oxa(2-) and mal(2-), and the single crystal X-ray structural characterization confirmed the presence of tricopper(II) complexes, with an unusual binding mode for the dicarboxylate anions. Each of the two copper atoms binds four nitrogen donor atoms of the t2pN8 cryptand and one additional hydroxide group, which bridges to the third copper. The square planar environment of this one is complete with two oxygen atoms from the oxalate (or the malonate). The two copper centers bound to the tren heads are ∼6.5 Å apart, each one at about 3.5 Å from the third Cu center. These studies were complemented by SQUID magnetization measurements and DFT calculations. The magnetic susceptibility measurements of the oxalate cascade complex showed a strong magnetic coupling (J = - 210 cm(-1)) between the Cu centers at a short distance (3.5 Å), while the coupling between the two equivalent Cu atoms (∼6.5 Å) was only -70 cm(-1). This result was well reproduced by DFT calculations.

  12. New dinuclear copper(II) and zinc(II) complexes for the investigation of sugar-metal ion interactions.

    PubMed

    Bera, Manindranath; Patra, Ayan

    2011-10-18

    We have studied the binding interactions of biologically important carbohydrates (D-glucose, D-xylose and D-mannose) with the newly synthesized five-coordinate dinuclear copper(II) complex, [Cu(2)(hpnbpda)(μ-OAc)] (1) and zinc(II) complex, [Zn(2)(hpnbpda)(μ-OAc)] (2) [H(3)hpnbpda=N,N'-bis(2-pyridylmethyl)-2-hydroxy-1,3-propanediamine-N,N'-diacetic acid] in aqueous alkaline solution. The complexes 1 and 2 are fully characterized both in solid and solution using different analytical techniques. A geometrical optimization was made of the ligand H(3)hpnbpda and the complexes 1 and 2 by molecular mechanics (MM+) method in order to establish the stable conformations. All carbohydrates bind to the metal complexes in a 1:1 molar ratio. The binding events have been investigated by a combined approach of FTIR, UV-vis and (13)C NMR spectroscopic techniques. UV-vis spectra indicate a significant blue shift of the absorption maximum of complex 1 during carbohydrate coordination highlighting the sugar binding ability of complex 1. The apparent binding constants of the substrate-bound copper(II) complexes have been determined from the UV-vis titration experiments. The binding ability and mode of binding of these sugar substrates with complex 2 are indicated by their characteristic coordination induced shift (CIS) values in (13)C NMR spectra for carbon atoms C1, C2, and C3 of sugar substrates.

  13. Crystallization and preliminary X-ray analysis of chondroitin sulfate ABC lyases I and II from Proteus vulgaris.

    PubMed

    Huang, W; Matte, A; Suzuki, S; Sugiura, N; Miyazono, H; Cygler, M

    2000-07-01

    Chondroitin sulfate ABC lyases (E.C. 4.2.2.4) are broad-specificity glycosaminoglycan-degrading enzymes. Their preferred substrates are chondroitin sulfate and dermatan sulfate, which are broken down to short oligosaccharides. Proteus vulgaris produces two such lyases, ABC lyase I and II, with molecular weights of 112-113 kDa. Diffraction-quality crystals of both enzymes have been obtained by the hanging-drop vapour-diffusion method. ABC lyase I crystallizes in space group P2(1)2(1)2(1), with unit-cell parameters a = 49.3, b = 95.1, c = 230.0 A, Z = 4, and diffracts to 1.9 A resolution. Crystals of ABC lyase II belong to space group P1, with unit-cell parameters a = 64.2, b = 64.3, c = 142.1 A, alpha = 95.7, beta = 98. 1, gamma = 95.5 degrees, Z = 2; diffraction extends to at least 2.1 A.

  14. Joint toxicity of tetracycline with copper(II) and cadmium(II) to Vibrio fischeri: effect of complexation reaction.

    PubMed

    Tong, Fei; Zhao, Yanping; Gu, Xueyuan; Gu, Cheng; Lee, Charles C C

    2015-03-01

    Co-contamination of antibiotic and heavy metals commonly occurs in the environment. Tetracycline (TC), a common antibiotic, can behave as an efficient organic ligand to complex with cations. In this paper, the joint toxicity of TC with two commonly existing metals, copper(II) and cadmium(II), towards a luminescent bacteria, Vibrio fischeri, are investigated. Results showed that coexistence of TC and Cu(II) showed a significant antagonistic effect, while TC and Cd(II) showed a synergistic effect. The aqueous speciation of TC with two metal cations was calculated using a chemical equilibrium software Visual MINTEQ and results indicated that a strong complexation exist between TC and Cu(II), while much weaker interaction between TC and Cd(II). Traditional joint toxicity prediction model based on independent action failed to predict the combined toxicity of TC with metals. A new method based on speciation calculation was used to evaluate the joint toxicity of ligands and cations. It is assumed that the metal-ligand complexes are non-toxic to V. fischeri and the joint toxicity is determined by the sum of toxic unit of free metal-ions and free organic ligands. It explained the joint toxicity of the mixed systems reasonably well. Meanwhile, citric acid (CA) and fulvic acid (FA) were also introduced in this study to provide a benchmark comparison with TC. Results showed it is also valid for mixed systems of CA and FA with metals except for the Cd-CA mixture.

  15. The structures of the crystalline phase and columnar mesophase of rhodium (II) heptanoate and of its binary mixture with copper (II) heptanoate probed by EXAFS

    NASA Astrophysics Data System (ADS)

    Inb-Elhaj, M.; Guillon, D.; Skoulios, A.; Maldivi, P.; Giroud-Godquin, A. M.; Marchon, J.-C.

    1992-12-01

    EXAFS was used to investigate the local structure of the polar spines of rhodium (II) soaps in the columnar liquid crystalline state. It was also used to ascertain the degree of blending of the cores in binary mixtures of rhodium (II) and copper (II) soaps. For the pure rhodium soaps, the columns are shown to result from the stacking of binuclear metal-metal bonded dirhodium tetracarboxylate units bonded to one another by apical ligation of the metal atom of each complex with one of the oxygen atoms of the adjacent molecule. Mixtures of rhodium (II) and copper (II) soaps give a hexagonal columnar mesophase in which pure rhodium and pure copper columns are randomly distributed.

  16. DNA breakage induced by piceatannol and copper(II): Mechanism and anticancer properties

    PubMed Central

    LI, ZHENSHENG; YANG, XIAOZHAN; DONG, SHIWU; LI, XIAOHUI

    2012-01-01

    Piceatannol (3,3′,4,5′-tetrahydroxy-trans-stilbene; Pice), found in a variety of plant sources including grapes, red wine, peanuts and rhubarb, is known as a metabolite and analog of Resveratrol (3,5,4′-trihydroxy-trans-stilbene; Res) and has higher bioactivity than Res. To explore the mechanism of DNA damage induced by Pice in the presence of copper (Cu)(II), gel electrophoresis, UV-visible spectroscopy, fluorescence spectroscopy and Fourier transform infrared spectroscopy were used. The results of gel electrophoresis demonstrated that the hydroxyl radical played a critical role in DNA cleavage. Spectroscopy confirmed that the mechanism of DNA cleavage induced by Pice-Cu(II) involves the Haber Weiss and Fenton reactions. Pice chelates with Cu(II) as a bidentate ligand, and the Pice-Cu(II) complex undergoes intramolecular electron transfer to form the semiquinone radical anion and Cu(I), which may be reoxidated by O2 to form Cu(II) with hydroxyl radical generation. In brief, the formation of the hydroxyl radical and the Cu(II)/Cu(I) redox cycle play a key role in inducing DNA damage. In this process, Pice demonstrated pro-oxidant properties. Oxidative product(s) of Pice, semiquinone, was formed and Cu(I) was reoxidized to Cu(II). The redox cycling of copper generated reactive oxygen species, which induced DNA cleavage, the hallmark of cell apoptosis. The mechanism of DNA breakage induced by Pice-Cu(II) may be a significant pathway through which cancer cells are killed. PMID:22783397

  17. Copper(I/II), α/β-Synuclein and Amyloid-β: Menage à Trois?

    PubMed

    De Ricco, Riccardo; Valensin, Daniela; Dell'Acqua, Simone; Casella, Luigi; Hureau, Christelle; Faller, Peter

    2015-11-02

    Copper binding to α-synuclein (aS) and to amyloid-β (Ab) has been connected to Parkinson's and Alzheimer's disease (AD), respectively, because Cu ions can modulate the peptide aggregation, and these Cu ⋅ peptide complexes can catalyse the production of reactive oxygen species (ROS). In a significant proportion of AD brains, aggregation of aS and Ab has been detected, and it was proposed that Ab and aS interact with each other. Thus, we investigated the potential interactions of Ab and aS through their binding of copper(I) and copper(II). Additionally, β-synuclein (bS) was investigated, due to its additional methionine residue, a potential Cu(I) ligand. We found that: 1) the peptides containing the Cu-binding domains Ab1-16, aS1-15 and bS1-15 have similar affinities towards Cu(II) and towards Cu(I), with Ab1-16 being slightly stronger, 2) in the case of Cu(I), the additional Met residue in bS1-15 increased the affinity slightly, 3) the exchange of Cu(I/II) between the two peptides is rapid (≤ ms), 4) a/bS1-15 and Ab1-16 form a heterodimeric complex with Cu(II), 5) Cu(I) probably promotes a transient ternary complex, 6) the different Cu(I/II) coordination of Ab1-16, aS1-15 and bS1-15 impacts the capacity to produce ROS and to oxidise catechol, and 7) when Ab1-16, aS1-15 and Cu are present, the ROS production more closely resembles that by Ab1-16. The work gives insights into the coordination chemistry of these related peptides, and the relevance of coordination differences, the ternary complex and ROS production are discussed.

  18. Biosorption of copper (II) from aqueous solution using non-living Mesorhizobium amorphae strain CCNWGS0123.

    PubMed

    Mohamad, Osama Abdalla; Hao, Xiuli; Xie, Pin; Hatab, Shaimaa; Lin, Yanbing; Wei, Gehong

    2012-01-01

    The mining industry generates huge amounts of wastewater, containing toxic heavy metals. Treatment to remove heavy metals is necessary and recent work has been focused on finding more environmentally friendly materials for removing heavy metals from wastewater. Biosorption can be an effective process for heavy metal removal from aqueous solutions. Our objectives were to investigate the removal of copper (II) from aqueous solutions using dead cells of Mesorhizobium amorphae CCNWGS0123 under differing levels of pH, agitation speed, temperature, initial copper concentration, biosorbent dose and contact time using flame atomic absorption spectroscopy for metal estimation. The maximum copper removal rate was achieved at pH 5.0, agitation speed 150×g, temperature 28°C and initial Cu (II) concentration of 100 mg L(-1). Maximum biosorption capacity was at 0.5 g L⁻¹ and equilibrium was attained within 30 min. Langmuir and Freundlich isotherms showed correlation coefficients of 0.958 and 0.934, respectively. Fourier transform-infrared spectroscopy (FT-IR) analysis indicated that many functional groups, such as O-H, N-H, C-H, C=O, -NH, -CN, C-N, C-O, amide -I, -II, -III and unsaturated alkenes, alkyls and aromatic groups on the cell surface were involved in the interaction between CCNWGS0123 and Cu. Scanning electron microscope and energy dispersive X-ray scanning results showed deformation, aggregation, and cell-surface damage due to the precipitation of copper on the cell surface. Dead cells of CCNWGS0123 showed potential as an efficient biosorbent for the removal of Cu²⁺ from aqueous solutions.

  19. Biosorption of Copper (II) from Aqueous Solution Using Non-Living Mesorhizobium amorphae Strain CCNWGS0123

    PubMed Central

    Mohamad, Osama Abdalla; Hao, Xiuli; Xie, Pin; Hatab, Shaimaa; Lin, Yanbing; Wei, Gehong

    2012-01-01

    The mining industry generates huge amounts of wastewater, containing toxic heavy metals. Treatment to remove heavy metals is necessary and recent work has been focused on finding more environmentally friendly materials for removing heavy metals from wastewater. Biosorption can be an effective process for heavy metal removal from aqueous solutions. Our objectives were to investigate the removal of copper (II) from aqueous solutions using dead cells of Mesorhizobium amorphae CCNWGS0123 under differing levels of pH, agitation speed, temperature, initial copper concentration, biosorbent dose and contact time using flame atomic absorption spectroscopy for metal estimation. The maximum copper removal rate was achieved at pH 5.0, agitation speed 150×g, temperature 28°C and initial Cu (II) concentration of 100 mg L−1. Maximum biosorption capacity was at 0.5 g L−1 and equilibrium was attained within 30 min. Langmuir and Freundlich isotherms showed correlation coefficients of 0.958 and 0.934, respectively. Fourier transform-infrared spectroscopy (FT-IR) analysis indicated that many functional groups, such as O-H, N-H, C-H, C=O, -NH, -CN, C-N, C-O, amide -I, -II, -III and unsaturated alkenes, alkyls and aromatic groups on the cell surface were involved in the interaction between CCNWGS0123 and Cu. Scanning electron microscope and energy dispersive X-ray scanning results showed deformation, aggregation, and cell-surface damage due to the precipitation of copper on the cell surface. Dead cells of CCNWGS0123 showed potential as an efficient biosorbent for the removal of Cu2+ from aqueous solutions. PMID:22353770

  20. Effect of copper(II) on natural organic matter removal during drinking water coagulation using aluminum-based coagulants.

    PubMed

    Liu, Guojing; Zhang, Xiangru; Talley, Jeffrey W

    2007-06-01

    Coagulation has been proposed as a best available technology for controlling natural organic matter (NOM) during drinking water treatment. The presence of heavy metals such as copper(II) in source water, which may form copper-NOM complexes and/or interact with a coagulant, may pose a potential challenge on the coagulation of NOM. In this work, the effect of copper(II) on NOM removal by coagulation using alum or PAX-18 (a commercial polymerized aluminum chloride from Kemiron Inc., Bartow, Florida) was examined. The results show that the presence of 1 to 10 mg/L of copper(H) in the simulated waters improved the total organic carbon (TOC) removal by up to 25% for alum coagulation and by up to 22% for PAX-18 coagulation. The increased NOM removal with the presence of copper(II) in the waters can most likely be ascribed to the formation copper-NOM complexes that may be more adsorbable on aluminum precipitates and to the formation of copper(II) co-precipitates that may also adsorb NOM. The presence of 1 to 5 mg/L of copper(I) in the waters containing 3 mg/L NOM as carbon was reduced below the maximum contaminant level goal (1.3 mg/L as copper) using either coagulant. The results suggest that the presence of copper(H) in source water may not adversely affect the NOM removal by coagulation. A good linear correlation was observed between the TOC removal efficiency and the log-total moles of the precipitated metals, which include the metal ion from a coagulant and the divalent metal ion(s) in source water.

  1. A doppel alpha-helix peptide fragment mimics the copper(II) interactions with the whole protein.

    PubMed

    La Mendola, Diego; Magrì, Antonio; Campagna, Tiziana; Campitiello, Maria Anna; Raiola, Luca; Isernia, Carla; Hansson, Orjan; Bonomo, Raffaele P; Rizzarelli, Enrico

    2010-06-01

    The doppel protein (Dpl) is the first homologue of the prion protein (PrP(C)) to be discovered; it is overexpressed in transgenic mice that lack the prion gene, resulting in neurotoxicity. The whole prion protein is able to inhibit Dpl neurotoxicity, and its N-terminal domain is the determinant part of the protein function. This region represents the main copper(II) binding site of PrP(C). Dpl is able to bind at least one copper ion, and the specific metal-binding site has been identified as the histidine residue at the beginning of the third helical region. However, a reliable characterization of copper(II) coordination features has not been reported. In a previous paper, we studied the copper(II) interaction with a peptide that encompasses only the loop region potentially involved in metal binding. Nevertheless, we did not find a complete match between the EPR spectroscopic parameters of the copper(II) complexes formed with the synthesized peptide and those reported for the copper(II) binding sites of the whole protein. Herein, the synthesis of the human Dpl peptide fragment hDpl(122-139) (Ac-KPDNKLHQQVLWRLVQEL-NH(2)) and its copper(II) complex species are reported. This peptide encompasses the third alpha helix and part of the loop linking the second and the third helix of human doppel protein. The single-point-mutated peptide, hDpl(122-139)D124N, in which aspartate 124 replaces an asparagine residue, was also synthesized. This peptide was used to highlight the role of the carboxylate group on both the conformation preference of the Dpl fragment and its copper(II) coordination features. NMR spectroscopic measurements show that the hDpl(122-139) peptide fragment is in the prevailing alpha-helix conformation. It is localized within the 127-137 amino acid residue region that represents a reliable conformational mimic of the related protein domain. A comparison with the single-point-mutated hDpl(122-139)D124N reveals the significant role played by the aspartic

  2. Building reactive copper center(s) in human carbonic anhydrase II

    PubMed Central

    Song, He; Weitz, Andrew C.; Hendrich, Michael P.; Lewis, Edwin A.; Emerson, Joseph P.

    2014-01-01

    Re-engineering metalloproteins to generate new biologically relevant metal centers is an effective a way to test our understanding of the structural and mechanistic features that steer chemical transformations in biological systems. Here we report thermodynamic data characterizing the formation of two type-2 (T2) copper sites in carbonic anhydrase and experimental evidence showing one of these new copper centers has characteristics similar to a variety of well-characterized copper centers in synthetic models and in enzymatic systems. Human CA II is known to bind two Cu2+ ions; herein, these binding events are explored using modern isothermal titration calorimetry (ITC) techniques that have become a proven method to accurately measure metal-binding thermodynamic parameters. The two Cu2+-binding events have different affinities (Ka ∼ 5 × 1012 and 1 × 1010) and both are enthalpically driven processes. Reconstituting these Cu2+ sites under a range of conditions has allowed us to assign the Cu2+-binding event to the three-histidine, native, metal binding site. Our initial efforts to characterize these Cu2+ sites have yielded data that show distinctive (and noncoupled) EPR signals associated with each copper-binding site, and that this reconstituted enzyme can activate hydrogen peroxide to catalyze the oxidation of 2-aminophenol. PMID:23744511

  3. Effect of excess dietary iron as ferrous sulfate and excess dietary ascorbic acid on liver zinc, copper and sulfhydryl groups and the ovary

    SciTech Connect

    Edwards, C.H.; Adkins, J.S.; Harrison, B.

    1986-03-05

    Female guinea pigs of the NIH 13/N strain, weighing between 475 and 512 g, were fed diets supplemented with 50 to 2500 mg of iron per kg of diet as ferrous sulfate and 0.2 to 8.0 g of ascorbic acid per kg of diet. A significant effect was observed on tissue copper and zinc, ovary weight and liver protein sulfhydryl groups. The mean ovary weight for guinea pigs fed 2500 mg of iron was significantly less than that of animals fed 50 mg of iron, 0.045 +/- 0.012 g and 0.061 +/- 0.009 g, respectively. Liver zinc content of animals fed 2500 mg of iron and 200 mg of ascorbic acid per kg of diet was significantly less than that of animals fed 50 mg of iron and 200 mg of ascorbic acid, 16.3 +/- 3.3 ..mu..g and 19.6 +/- 1.6 ..mu..g, respectively. There was no difference in liver copper due to dietary iron, but when dietary ascorbic acid was increased to 8 g per kg of diet, there was a significant decrease (from 22.8 +/- 8.1 ..mu..g to 10.5 +/- 4.8 ..mu..g) in liver copper. Excess dietary ascorbic acid decreased ovarian zinc significantly when increased to 8 g per kg of diet, 2929 +/- 919 ..mu..g vs 1661 +/- 471 ..mu..g, respectively, when compared to the control group.

  4. Subneurotoxic copper(II)-induced NF-κB-dependent microglial activation is associated with mitochondrial ROS

    SciTech Connect

    Hu, Zhuqin; Yu, Fengxiang; Gong, Ping; Qiu, Yu; Zhou, Wei; Cui, Yongyao; Li, Juan Chen, Hongzhuan

    2014-04-15

    Microglia-mediated neuroinflammation and the associated neuronal damage play critical roles in the pathogenesis of neurodegenerative disorders. Evidence shows an elevated concentration of extracellular copper(II) in the brains of these disorders, which may contribute to neuronal death through direct neurotoxicity. Here we explored whether extracellular copper(II) triggers microglial activation. Primary rat microglia and murine microglial cell line BV-2 cells were cultured and treated with copper(II). The content of tumor necrosis factor-α (TNF-α) and nitric oxide in the medium was determined. Extracellular hydrogen peroxide was quantified by a fluorometric assay with Amplex Red. Mitochondrial superoxide was measured by MitoSOX oxidation. At subneurotoxic concentrations, copper(II) treatment induced a dose- and time-dependent release of TNF-α and nitric oxide from microglial cells, and caused an indirect, microglia-mediated neurotoxicity that was blocked by inhibition of TNF-α and nitric oxide production. Copper(II)-initiated microglial activation was accompanied with reduced IkB-α expression as well as phosphorylation and translocation of nuclear factor-κB (NF-κB) p65 and was blocked by NF-κB inhibitors (BAY11-7082 and SC-514). Moreover, copper(II) treatment evoked a rapid release of hydrogen peroxide from microglial cells, an effect that was not affected by NADPH oxidase inhibitors. N-acetyl-cysteine, a scavenger of reactive oxygen species (ROS), abrogated copper(II)-elicited microglial release of TNF-α and nitric oxide and subsequent neurotoxicity. Importantly, mitochondrial production of superoxide, paralleled to extracellular release of hydrogen peroxide, was induced after copper(II) stimulation. Our findings suggest that extracellular copper(II) at subneurotoxic concentrations could trigger NF-κB-dependent microglial activation and subsequent neurotoxicity. NADPH oxidase-independent, mitochondria-derived ROS may be involved in this activation

  5. Surface Alteration of Activated Carbon for Detoxification of Copper (ii) from Industrial Effluents

    NASA Astrophysics Data System (ADS)

    Bhutto, Sadaf; Khan, M. Nasiruddin

    2013-04-01

    The low-cost modified activated carbons were prepared from Thar and Lakhra (Pakistan) coals by activation with sulfuric acid and further modified with citric, tartaric and acetic acids for the selective adsorption of Cu(II) from aqueous solution. The original carbon obtained from activated Thar and Lakhra coals at pH 3.0 displayed significant adsorption capacity for lead and insignificant capacity values (0.880 and 0.830 mgṡg-1) for copper. However, after modification with citric, tartaric and acetic acid the copper adsorption capacities enhanced in the range of 5.56-21.85 and 6.05-44.61 times, respectively. The Langmuir, Freundlich and Temkin adsorption isotherms were used to elucidate the observed sorption phenomena. The isotherm equilibrium data was well fitted by the Langmuir and sufficiently fitted to the Freundlich models. The calculated thermodynamic parameters such as change in Gibbs free energy (ΔG°), enthalpy (ΔH°) and entropy (ΔS°) inferred that the investigated adsorption was spontaneous and endothermic in nature. Based on the results, it was concluded that the surface alteration with citric and tartaric acid, Thar and Lakhra activated carbons had significant potential for selective removal of copper(II) from industrial wastewater.

  6. Cytotoxicity of copper(II) complexes of N-salicylidene-L-glutamate: modulation by ascorbic acid.

    PubMed

    Paulikova, H; Kadlecikova, E; Suchanova, M; Valkova, Z; Rauko, P; Hudecova, D; Valent, A

    2008-01-01

    Cytotoxic/cytostatic activity of N-salicylidene-L-glutamato diaqua copper(II) complex (CuC) against mice leukemia cells L1210 has been estimated and their bioactivity was enhanced by addition of ascorbic acid. The Cu-complex with isoquinoline ligand (IQ-CuC) had stronger cytostatic effect (IC50 =15.6 microM) than parental complex (CuC) and its cytotoxicity several times increased in the presence of 0.1 mM ascorbic acid (IC50 =1.0 microM). The cytotoxicity has been caused by oxidative stress, enhanced creation of TBARS has been confirmed, and formation of 2',7'-dichlorofluorescein from 2',7'- dichlorodihydrofluorescein has been observed, also. Some hallmarks of apoptotic/necrotic death of L1210 cells have been observed by fluorescent microscopy after dyeing of cell with propidium iodide and Hoechst 33342. In addition, it was confirmed that both complexes in the presence of ascorbic acid cleavaged of pDNA. Although these copper complexes were initially prepared as substances with antioxidant properties we have showed that combined treatment of L1210 cells with IQCuC and ascorbic acid induced strong oxidative stress and death of cells. Our results confirmed that physiological concentration of ascorbic acid increases the cytostatic/cytotoxic efficiency of N-salicylidene-L-glutamato diaqua copper(II) complexes.

  7. Enantiopure copper(II) complex of natural product rosin derivative: DNA binding, DNA cleavage and cytotoxicity.

    PubMed

    Fei, Bao-Li; Yin, Bin; Li, Dong-Dong; Xu, Wu-Shuang; Lu, Yang

    2016-12-01

    To develop chiral anticancer drug candidates for molecular target DNA, the synthesis and characterization of a novel enantiomerically pure copper(II) complex [Cu 1 Cl 2 ] (2) of an optically pure ligand N-(pyridin-2-ylmethylene) dehydroabietylamine (1) was carried out. The coordination geometry of the copper center is a distorted square-planar arrangement. The interactions of 1 and 2 with salmon sperm DNA were investigated by viscosity measurements, UV, fluorescence and circular dichroism (CD) spectroscopic techniques. All the results reveal that 1 and 2 interacted with DNA through intercalation and 2 exhibited a higher DNA binding ability. Further, 1 and 2 could cleave supercoiled pBR322 DNA by single strand and 2 displayed stronger cleavage ability in the presence of ascorbic acid. In vitro cytotoxicity of 1 and 2 against HeLa, SiHa, HepG-2 and A431 cancer cell lines was studied using CCK-8 assay. The results indicate that 2 had a superior cytotoxicity than 1 and the widely used drug cisplatin under identical conditions. Flow cytometry analysis demonstrates 2 produced death of HeLa cancer cells through an apoptotic pathway. Cell cycle analysis shows that 2 mainly arrested HeLa cells at the S phase. A novel enantiomerically pure copper(II) complex [Cu 1 Cl 2 ] (2) of an optically pure ligand N-(pyridin-2-ylmethylene) dehydroabietylamine (1), based on natural product rosin has been synthesized. 2 has the potential to act as effective anticancer drug.

  8. Copper(II) and lead(II) removal from aqueous solution by water treatment residues.

    PubMed

    Castaldi, Paola; Silvetti, Margherita; Garau, Giovanni; Demurtas, Daniela; Deiana, Salvatore

    2015-01-01

    In this study, we investigated the ability of Fe- and Al-based water treatment residues (Fe- and Al-WTR) to accumulate Pb(II) and Cu(II) at pH 4.5. The role of the inorganic and organic fractions of WTRs in metals sorption was also assessed. Sorption isotherms showed a higher sorption of Pb(II) by both WTRs with respect to Cu(II) (e.g. 0.105 and 0.089 mmol g(-1) of Pb(II) and Cu(II) respectively sorbed by Fe-WTR). Fe-WTR revealed a stronger sorbent for both metals than Al-WTR. The amount of Pb(II) and Cu(II) sorbed by Fe-WTR was about the 69% and 63% higher than that sorbed by the Al-WTR. The organic matter of Fe- and Al-WTR contributed to about 26% and 8.5% respectively in the sorption of both metals. The sequential extraction procedure showed that the greatest amount of metals sorbed by both WTRs were tightly bound and not extractable, and this was particularly apparent for Cu(II). The FT-IR spectra indicated the formation of inner-sphere complexes between the Fe(Al)-O nucleus and Pb(II) and Cu(II). Moreover, the FT-IR spectra also suggested that the humic fraction of WTRs interacted, through the carboxylate groups, with Cu(II) and Pb(II) by forming mainly monodentate and bidentate complexes, respectively.

  9. Synthesis, characterization and antibacterial studies of a copper(II) levofloxacin ternary complex.

    PubMed

    Sousa, Isabel; Claro, Vasco; Pereira, João Lino; Amaral, Ana Luísa; Cunha-Silva, Luís; de Castro, Baltazar; Feio, Maria J; Pereira, Eulália; Gameiro, Paula

    2012-05-01

    Solution behavior of levofloxacin (lvx) complexes with copper(II) in the presence and absence of phen was studied in aqueous solution, by potentiometry. The results obtained show that under physiological conditions (micromolar concentration range and pH 7.4) only copper(II):lvx:phen ternary complexes are stable. Hence, a novel copper(II) ternary complex of fluoroquinolone levofloxacin with nitrogen donor heterocyclic ligand phen was synthesized and characterized by means of UV-Visible and IR spectroscopy, elemental analysis and X-Ray crystallography. In the synthesized complex (1), [Cu(lvx)(phen)(H(2)O)](NO(3)).2H(2)O, levofloxacin acts as a bidentate ligand coordinating to the metal, in its anionic form, through the carbonyl and carboxyl oxygens and phen coordinates through two N-atoms forming the equatorial plane of a distorted square-pyramidal geometry. The fifth ligand of the penta-coordinated Cu(II) centre is occupied axially by an oxygen atom from a water molecule. Minimum inhibitory concentration (MIC) determinations of the complex and comparison with free levofloxacin in various E. coli strains indicated that the Cu-complex is as efficient an antimicrobial as the free antibiotic (both in the case of the dissolved synthesized complex and the complex formed following stoichiometric mixture of the individual components in solution). Moreover, results strongly suggest that the cell intake route of both species is different supporting, therefore, the complex's suitability as a candidate for further biological testing in fluoroquinolone-resistant microorganisms.

  10. Synthesis, characterization and antibacterial studies of a copper(II) lomefloxacin ternary complex.

    PubMed

    Fernandes, Patrícia; Sousa, Isabel; Cunha-Silva, Luís; Ferreira, Mariana; de Castro, Baltazar; Pereira, Eulália F; Feio, Maria J; Gameiro, Paula

    2014-02-01

    Solution behavior of lomefloxacin (lmx) complexes with copper(II) in the presence and absence of 1,10-phenanthroline (phen) was studied in aqueous solution, by potentiometry. The results obtained showed that under physiological conditions (micromolar concentration range and pH7.4) only copper(II):lmx:phen ternary complexes are stable. Hence, a novel copper(II) ternary complex of lomefloxacin with the nitrogen donor heterocyclic ligand phen was synthesized and characterized by means of UV-visible and IR spectroscopy, elemental analysis and X-ray crystallography. In the synthesized complex (1), [Cu(lmx)(phen)(NO3)]·5H2O, lmx acts as a bidentate ligand coordinating the metal cation, in its anionic form, through the carbonyl and carboxyl oxygens and phen coordinates through two N-atoms forming the equatorial plane of a distorted square-pyramidal geometry. The fifth ligand of the penta-coordinated Cu(II) center is occupied axially by an oxygen atom from the nitrate ion. Minimum inhibitory concentration (MIC) determinations of the complex and comparison with free lomefloxacin in various E. coli strains indicated that the Cu-complex is an antimicrobial which is as efficient as the free antibiotic but strongly suggest that the cell intake route of both species is different. Moreover, spectrophotometric stability studies suggest that the solution of the complex synthesized is considerably more photostable than the free fluoroquinolone supporting, therefore, the complex's suitability as a candidate for further biological testing in fluoroquinolone-resistant microorganisms with possible reduced side-effects.

  11. Copper in organic proteinate or inorganic sulfate form is equally bioavailable for broiler chicks fed a conventional corn-soybean meal diet.

    PubMed

    Liu, Songbai; Lu, Lin; Li, Sufen; Xie, Jingjing; Zhang, Liyang; Wang, Runlian; Luo, Xugang

    2012-06-01

    An experiment was conducted to investigate the bioavailability of organic copper (Cu) proteinate relative to inorganic Cu sulfate for broiler chicks fed a conventional corn-soybean meal basal diet. A total of 320 day-old Arbor Acres commercial male chicks were assigned to one of five treatments in a completely randomized design involving a 2 × 2 factorial arrangement with two levels of added Cu (125 or 250 mg Cu/kg) and two Cu sources (Cu proteinate and Cu sulfate) plus a control with no added Cu for an experimental phase of 42 days. Plasma and liver tissue samples were collected at both 21 and 42 days of age, and bile samples were also obtained at 42 days of age for Cu analyses. The Cu concentrations in liver and bile increased linearly (P < 0.001) on both days 21 and 42 as dietary Cu levels increased. No significant (P > 0.17) linear regression relationships were observed between plasma Cu concentrations on days 21 and 42 or log10 liver Cu concentration on day 21 and daily analyzed Cu intake. Therefore, based on the slope ratios from multiple linear regressions of log10 liver and bile Cu concentrations with daily analyzed Cu intake on day 42, when Cu sulfate was set as 100%, the estimated relative bioavailability values of Cu proteinate were 78.8% for log10 liver Cu concentration and 79.3% for log10 bile Cu concentration, respectively. There was no significant (P > 0.08) difference in bioavailability between Cu proteinate and Cu sulfate for broilers chicks in this experiment.

  12. Unusual Recognition and Separation of Hydrated Metal Sulfates [M2(μ-SO4)2(H2O)n, M = Zn(II), Cd(II), Co(II), Mn(II)] by a Ditopic Receptor.

    PubMed

    Ghosh, Tamal Kanti; Dutta, Ranjan; Ghosh, Pradyut

    2016-04-04

    A ditopic receptor L1, having metal binding bis(2-picolyl) donor and anion binding urea group, is synthesized and explored toward metal sulfate recognition via formation of dinuclear assembly, (L1)2M2(SO4)2. Mass spectrometric analysis, (1)H-DOSY NMR, and crystal structure analysis reveal the existence of a dinuclear assembly of MSO4 with two units of L1. (1)H NMR study reveals significant downfield chemical shift of -NH protons of urea moiety of L1 selectively with metal sulfates (e.g., ZnSO4, CdSO4) due to second-sphere interactions of sulfate with the urea moiety. Variable-temperature (1)H NMR studies suggest the presence of intramolecular hydrogen bonding interaction toward metal sulfate recognition in solution state, whereas intermolecular H-bonding interactions are observed in solid state. In contrast, anions in their tetrabutylammonium salts fail to interact with the urea -NH probably due to poor acidity of the tertiary butyl urea group of L1. Metal sulfate binding selectivity in solution is further supported by isothermal titration calorimetric studies of L1 with different Zn salts in dimethyl sulfoxide (DMSO), where a binding affinity is observed for ZnSO4 (Ka = 1.23 × 10(6)), which is 30- to 50-fold higher than other Zn salts having other counteranions in DMSO. Sulfate salts of Cd(II)/Co(II) also exhibit binding constants in the order of ∼1 × 10(6) as in the case of ZnSO4. Positive role of the urea unit in the selectivity is confirmed by studying a model ligand L2, which is devoid of anion recognition urea unit. Structural characterization of four MSO4 [M = Zn(II), Cd(II), Co(II), Mn(II)] complexes of L1, that is, complex 1, [(L1)2(Zn)2(μ-SO4)2]; complex 2, [(L1)2(H2O)2(Cd)2(μ-SO4)2]; complex 3, [(L1)2(H2O)2(Co)2(μ-SO4)2]; and complex 4, [(L1)2(H2O)2(Mn)2(μ-SO4)2], reveal the formation of sulfate-bridged eight-membered crownlike binuclear complexes, similar to one of the concentration-dependent dimeric forms of MSO4 as observed in solid state

  13. Electrical conductivity of solutions of copper(II) nitrate crystalohydrate in dimethyl sulfoxide

    NASA Astrophysics Data System (ADS)

    Mamyrbekova, Aigul K.; Mamitova, A. D.; Mamyrbekova, Aizhan K.

    2016-06-01

    Conductometry is used to investigate the electric conductivity of Cu(NO3)2 ṡ 3H2O solutions in dimethyl sulfoxide in the 0.01-2.82 M range of concentrations and at temperatures of 288-318 K. The limiting molar conductivity of the electrolyte and the mobility of Cu2+ and NO 3 - ions, the effective coefficients of diffusion of copper(II) ions and nitrate ions, and the degree and constant of electrolytic dissociation are calculated for different temperatures from the experimental results. It is established that solutions containing 0.1-0.6 M copper nitrate trihydrate in DMSO having low viscosity and high electrical conductivity can be used in electrochemical deposition.

  14. Chitosan-montmorillonite biocomposite as an adsorbent for copper (II) cations from aqueous solutions.

    PubMed

    Pereira, F A R; Sousa, K S; Cavalcanti, G R S; Fonseca, M G; de Souza, Antônio G; Alves, A P M

    2013-10-01

    Chitosan-montmorillonite (KSF-CTS) beads were prepared by crosslinking with pentasodium tripolyphosphate (TPP). Montmorillonite (KSF-Na), CTS and KSF-CTS biocomposite were used to remove Cu(II) from aqueous solutions. These materials were characterized before and after copper adsorption by XRD, FTIR and thermogravimetry (TG). The data indicated that the adsorption process proceeds kinetically according to a pseudo-second-order model. The adsorption processes were adjusted to the Langmuir model for KSF-Na and CTS and to the Temkin model for KSF-CTS. The maximum adsorption capacity followed the order CTS>KSF-CTS>KSF-Na. Percentages desorption of copper ions from the KSF-CTS composite after three desorption cycles were 86%, 85% and 84%, respectively, using EDTA as regeneration agents.

  15. Copper(II)-Thymine Coordination Polymer Nanoribbons as Potential Oligonucleotide Nanocarriers.

    PubMed

    Vegas, Verónica G; Lorca, Romina; Latorre, Ana; Hassanein, Khaled; Gómez-García, Carlos J; Castillo, Oscar; Somoza, Álvaro; Zamora, Félix; Amo-Ochoa, Pilar

    2017-01-19

    The direct reaction between copper nitrate, thymine-1-acetic acid, and 4,4'-bipyridine in water leads to the formation of a blue colloid comprising uniform crystalline nanoribbons (length >1 μm; width ca. 150-185 nm; diameter ca. 15-60 nm) of a coordination polymer. The polymer displays a thymine-based structure freely available for supramolecular interactions. These nanostructures show significant selective interaction with single-stranded oligonucleotides based on adenine. Remarkably, they present low cell toxicity in three cell lines-despite the copper(II) content-and can be used as nanocarriers of oligonucleotides. These results suggest the potential of these types of nanostructures in several biological applications.

  16. Removal of copper(II) from aqueous solution by pine and base modified pine cone powder as biosorbent.

    PubMed

    Ofomaja, A E; Naidoo, E B; Modise, S J

    2009-09-15

    Pine cone, a popular agricultural waste in South Africa has been studied for its potential application as a biosorbent in its raw and sodium hydroxide modified form. Surface modification were carried out using sodium hydroxide solution of concentration ranging from 0.01 to 0.15 mol L(-1)and the samples characterized. Batch kinetics were carried out on the biosorption of copper(II) from aqueous solution using the prepared samples and varying biosorption parameters such as solution pH, dose and biosorption temperature. The results revealed that pine cone surface was modified by sodium hydroxide treatment, carboxylic and phenolic functional groups were mostly affected as seen from Boehm's titration and FTIR analysis. Surface modification reduced pH(PZC) from 7.49 to 2.55 and also increased the internal surface of pine cone powder. Copper(II) biosorption studies revealed that optimum solution pH and biosorbent dose for copper(II) removal was pH 5 and 8.0g L(-1), for the untreated and treated samples. Copper(II) uptake followed the pseudo-second order kinetic model and the intraparticle diffusion model. Copper(II) removal increased with NaOH modification and higher NaOH concentration. Biosorption temperature was found to increase copper(II) uptake for all samples indicating that copper(II) biosorption is endothermic in nature. Activation energy computed from the pseudo-second order rate constant increased with NaOH modification from 18.22 to 21.39 kJ mol(-1). The thermodynamic parameters of activation (DeltaG*, DeltaH* and DeltaS*) were computed using Erying equation and the results show that the reorientation step is mostly entropy controlled at the activation state and the contribution of entropy to the reorientation step of activation tends to decrease with NaOH washing and with increase in NaOH concentration.

  17. Copper

    Integrated Risk Information System (IRIS)

    Copper ; CASRN 7440 - 50 - 8 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effects )

  18. a Study of the Structural, Magnetic, Optical, and Electronic Properties of Several New Copper(ii) Halide and Copper(ii, i) Halide Compounds in the Solid State.

    NASA Astrophysics Data System (ADS)

    Scott, Brian Lindley

    Robin and Day classification scheme. A series of compounds of the stoichiometry (paraquat)Cu _2X_4 (X = Cl, Br, I) are investigated using x-ray crystallographic, EPR, magnetic susceptibility, differential scanning calorimetry, and electrical conductivity techniques. X-ray results show all three compounds to be pure copper(I) in character. Magnetic susceptibility results show small copper(II) contributions in the chloride and bromide analogs. In the chloride salt the copper(II) ions appear to be incorporated into the (Cu_2Cl_4) _infty chain, with accompanying vacancies to provide for charge balance. In the bromide salt a Cu_2Br_6^ {2-} dimer appears to be incorporated into the chain structure. The chloride and iodide salts show insulating behavior, but the bromide salt shows enhanced conductivity.

  19. Synthesis, characterization, and photoactivated DNA cleavage by copper (II)/cobalt (II) mediated macrocyclic complexes.

    PubMed

    Naik, H R Prakash; Naik, H S Bhojya; Aravinda, T; Lamani, D S

    2010-01-01

    We report the synthesis of new photonuclease consisting of two Co(II)/Cu(II) complexes of macrocyclic fused quinoline. Metal complexes are [MLX(2)], type where M = Co(II) (5), Cu(II) (6), and X = Cl, and are well characterized by elemental analysis, Fourier transform infrared spectroscopy, (1)H-NMR and electronic spectra. We have shown that photocleavage of plasmid DNA is markedly enhanced when this ligand is irradiated in the presence of Cu(II), and more so than that of cobalt. The chemistry of ternary and binary Co(II) complexes showing efficient light induced (360 nm) DNA cleavage activity is summarized. The role of the metal in photoinduced DNA cleavage reactions is explored by designing complex molecules having macrocyclic structure. The mechanistic pathways are found to be concentration dependent on Co(II)/Cu(II) complexes and the photoexcitation energy photoredox chemistry. Highly effective DNA cleavage ability of 6 is attributed to the effective cooperation of the metal moiety.

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

    SciTech Connect

    Ryabova, I.N.

    2008-01-15

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

  1. Synthesis, characterization and cyclic voltammetric study of copper(II) and nickel(II) polymer chelates.

    PubMed

    Azmeera, Venkanna; Rastogi, Pankaj Kumar; Adhikary, Pubali; Ganesan, Vellaichamy; Krishnamoorthi, S

    2014-09-22

    Graft copolymers based on dextran (Dx) and 2-acrylamido-2-methyl-1-propane sulphonic acid (AMPS) were synthesized by free radical initiated solution polymerization technique using ceric ammonium nitrate as initiator. These graft copolymers were used to prepare Cu(II) and Ni(II) chelates by reactions with Cu(II) and Ni(II) metal ions respectively. Graft copolymer and metal chelates were characterized by elemental analysis, intrinsic viscosity, FT-IR, scanning electron microscopy (SEM), atomic force microscopy (AFM), thermogravimetric analysis (TGA) and powder X-ray diffraction (XRD). Elemental analysis, intrinsic viscosity and FT-IR studies revealed the incorporation of metal ions to form metal chelates. SEM studies showed the change in morphology due to metal incorporation. From AFM studies it was observed that there was increase in Root mean square (RMS) roughness values in case of metal complexes. Metal chelates were observed to be thermally more stable than graft copolymer from TGA. UV-vis spectroscopy study revealed increase in absorbance values and cyclic voltammetric (CV) studies showed more than tenfold increase in redox current due to formation of Cu(II) and Ni(II) metal chelates. The binding constants of each complex determined by using UV-visible spectroscopy revealed that Cu(II) has more binding ability than Ni(II).

  2. Synthesis and structural characterisation of iron(II) and copper(II) diphosphates containing flattened metal oxotetrahedra

    SciTech Connect

    Keates, Adam C.; Wang, Qianlong; Weller, Mark T.

    2014-02-15

    Single crystal and bulk polycrystalline forms of K{sub 2}MP{sub 2}O{sub 7} (M=Fe(II), Cu(II)) have been synthesised and their structures determined from single crystal X-ray diffraction data. Both compounds crystallize in the tetragonal system, space group P-42{sub 1}m. Their structures are formed from infinite sheets of linked oxopolyhedra of the stoichiometry [MP{sub 2}O{sub 7}]{sup 2−} with potassium cations situated between the layers. The MO{sub 4} tetrahedra share oxygen atoms with [P{sub 2}O{sub 7}]{sup 4−} diphosphate groups and the potassium ions have KO{sub 8} square prismatic geometry. In both compounds the M(II) centre has an unusual strongly flattened, tetrahedral coordination to oxygen, as a result of the Jahn–Teller (JT) effect for the high spin d{sup 6} Fe(II) and p-orbital mixing or a second order JT effect for d{sup 9} Cu(II) centres in four fold coordination. The uncommon transition metal ion environments found in these materials are reflected in their optical absorption spectra and magnetism data. - Graphical abstract: The structures of the tetragonal polymorphs of K{sub 2}MP{sub 2}O{sub 7}, M=Cu(II), Fe(II), consist of infinite sheets of stoichiometry [MP{sub 2}O{sub 7}]{sup 2−}, formed from linked pyrophosphate groups and MO{sub 4} tetrahedra, separated by potassium ions. In both compounds the unusual tetrahedral coordination of the M(II) centre is strongly flattened as a result of Jahn–Teller (JT) effects for high spin, d{sup 6} Fe(II) and p-orbital mixing and second-order JT effects for d{sup 9} Cu(II). Display Omitted - Highlights: • Tetrahedral copper and iron(II) coordinated by oxygen. • New layered phosphate structure. • Jahn–Teller and d{sup 10} distorted coordinations.

  3. METHANOGENESIS AND SULFATE REDUCTION IN CHEMOSTATS: II. MODEL DEVELOPMENT AND VERIFICATION

    EPA Science Inventory

    A comprehensive dynamic model is presented that simulates methanogenesis and sulfate reduction in a continuously stirred tank reactor (CSTR). This model incorporates the complex chemistry of anaerobic systems. A salient feature of the model is its ability to predict the effluent ...

  4. Amine nitrosation via NO reduction of the polyamine copper(II) complex Cu(DAC)2+.

    PubMed

    Khin, Chosu; Lim, Mark D; Tsuge, Kiyoshi; Iretskii, Alexei; Wu, Guang; Ford, Peter C

    2007-10-29

    The reaction of the fluorescent macrocyclic ligand 1,8-bis(anthracen-9-ylmethyl)-1,4,8,11-tetraazacyclotetradecane with copper(II) salts leads to formation of the Cu(DAC)2+ cation (I), which is not luminescent. However, when aqueous methanol solutions of I are allowed to react with NO, fluorescence again develops, owing to the formation of the strongly luminescent N-nitrosated ligand DAC-NO (II), which is released from the copper center. This reaction is relatively slow in neutral media, and kinetics studies show it to be first order in the concentrations of NO and base. In these contexts, it is proposed that the amine nitrosation occurs via NO attack at a coordinated amine that has been deprotonated and that this step occurs with concomitant reduction of the Cu(II) to Cu(I). DFT computations at the BP/LACVP* level support these mechanistic arguments. It is further proposed that such nitrosation of electron-rich ligands coordinated to redox-active metal centers is a mechanistic pathway that may find greater generality in the biochemical formation of nitrosothiols and nitrosoamines.

  5. Bis(dipyridophenazine)copper(II) complex as major groove directing synthetic hydrolase.

    PubMed

    Gupta, Tarkeshwar; Dhar, Shanta; Nethaji, Munirathinam; Chakravarty, Akhil R

    2004-06-21

    The copper(II) complex [Cu(dppz)(2)Cl]Cl () has been prepared, structurally characterized and its DNA binding and cleavage properties studied (dppz, dipyridophenazine). Crystal structure of 1xdppzxH(2)O shows the presence of the monocationic copper(II) complex containing two dppz ligands and one chloride in the five coordinate structure. While one bidentate chelating dppz ligand occupies the basal plane, the other dppz ligand shows an axial/equatorial mode of bonding. The chloride ligand binds at the basal plane. The complex crystallizes with dppz and water as lattice molecules. The dppz moieties in the metal-bound and free forms are involved in pi-pi stacking interactions. The one-electron paramagnetic complex shows a visible spectral d-d band at 707 nm in DMF and displays quasireversible cyclic voltammetric response for the Cu(II)/Cu(I) couple near 0.1 V vs. SCE in DMF-0.1 M TBAP. The complex which is an avid binder to calf thymus DNA giving a binding constant (K(b)) value of 2.0 x 10(4) M(-1) in DMF-Tris buffer, cleaves supercoiled pUC19 DNA in an oxidative manner in the presence of mercaptopropionic acid (MPA) as a reducing agent or on photo irradiation at 312 nm. Control experiments show major groove binding and DNA cleavage via the formation of hydroxyl radical in the presence of MPA and by singlet oxygen in the photocleavage reaction. The complex exhibits significant hydrolytic cleavage of DNA in the dark in the absence of any additives at a rate of approximately 3.0 h(-1). The hydrolytic nature of the DNA cleavage is evidenced from the T4 ligase experiments converting the nicked circular form to its original supercoiled form quantitatively. Complex presents a rare example of copper-based major groove directing efficient synthetic hydrolase.

  6. Synthesis, structure, and magnetic properties of regular alternating μ-bpm/di-μ-X copper(II) chains (bpm = 2,2'-bipyrimidine; X = OH, F).

    PubMed

    Marino, Nadia; Armentano, Donatella; De Munno, Giovanni; Cano, Joan; Lloret, Francesc; Julve, Miguel

    2012-04-02

    The preparation and X-ray crystal structure of four 2,2'-bipyrimidine (bpm)-containing copper(II) complexes of formula {[Cu(2)(μ-bpm)(H(2)O)(4)(μ-OH)(2)][Mn(H(2)O)(6)](SO(4))(2)}(n) (1), {[Cu(2)(μ-bpm)(H(2)O)(4)(μ-OH)(2)]SiF(6)}(n) (2), {Cu(2)(μ-bpm)(H(2)O)(2)(μ-F)(2)F(2)}(n) (3), and [Cu(bpm)(H(2)O)(2)F(NO(3))][Cu(bpm)(H(2)O)(3)F]NO(3)·2H(2)O (4) are reported. The structures of 1-3 consist of chains of copper(II) ions with regular alternation of bis-bidentate bpm and di-μ-hydroxo (1 and 2) or di-μ-fluoro (3) groups, the electroneutrality being achieved by either hexaaqua manganese(II) cations plus uncoordinated sulfate anions (1), uncoordinated hexafluorosilicate anions (2), or terminally bound fluoride ligands (3). Each copper(II) ion in 1-4 is six-coordinated in elongated octahedral surroundings. 1 and 2 show identical, linear chain motifs with two bpm-nitrogen atoms and two hydroxo groups building the equatorial plane at each copper(II) ion and the axial position being filled by water molecules. In the case of 3, the axial sites at the copper atom are occupied by a bpm-nitrogen atom and a bis-monodentate fluoride anion, producing a "step-like" chain motif. The values of the angle at the hydroxo and fluoro bridges are 94.11(6) (1), 94.75(4) (2), and 101.43(4)° (3). In each case, the copper-copper separation through the bis-bidentate bpm [5.428(1) (1), 5.449(1) (2), and 5.9250(4) Å (3)] is considerably longer than that through the di-μ-hydroxo [2.8320(4) (1) and 2.824(1) Å (2)] or di-μ-fluoro [3.3027(4) Å (3)] bridges. Compound 4 is a mononuclear species whose structure is made up of neutral [Cu(bpm)(H(2)O)(2)F(NO(3))] units, [Cu(bpm)(H(2)O)(3)F](+) cations, uncoordinated nitrate anions, and crystallization water molecules, giving rise to a pseudo-helical, one-dimensional (1D) supramolecular motif. The magnetic properties of 1-3 have been investigated in the temperature range 1.9-300 K. Relatively large, alternating antiferro- [J = -149 (1) and

  7. The toxicity of copper(II) species to marine algae, with particular reference to macroalgae

    SciTech Connect

    Gledhill, M.; Nimmo, M.; Hill, S.J.; Brown, M.T.

    1997-02-01

    Ambient concentrations of dissolved copper(II) in seawater are very low. However, levels can increase as a result of natural and anthropogenic sources. Such increase can have profound effects on organisms in the vicinity resulting in inhibition of growth, reduced fecundity, and even death. This paper highlights the importance of pecieation when considering the toxic effects of cooper, with particular reference to macroalgae in a marine environment, and to encourage more biologists to take account of this in their studies of metal pollution. 104 refs., 2 figs., 4 tabs.

  8. Copper(II)-catalyzed hydroxylation of aryl halides using glycolic acid as a ligand.

    PubMed

    Xiao, Yan; Xu, Yongnan; Cheon, Hwan-Sung; Chae, Junghyun

    2013-06-07

    Copper(II)-catalyzed hydroxylation of aryl halides has been developed to afford functionalized phenols. The protocol utilizes the reagent combination of Cu(OH)2, glycolic acid, and NaOH in aqueous DMSO, all of which are cheap, readily available, and easily removable after the reaction. A broad range of aryl iodides and activated aryl bromides were transformed into the corresponding phenols in excellent yields. Moreover, it has been shown that C-O(alkyl)-coupled product, instead of phenol, can be predominantly formed under similar reaction conditions.

  9. Correlation between the molecular structure and the kinetics of decomposition of azamacrocyclic copper(ii) complexes.

    PubMed

    Acosta-Rueda, Laura; Delgado-Pinar, Estefanía; Pitarch-Jarque, Javier; Rodríguez, Alexis; Blasco, Salvador; González, Jorge; Basallote, Manuel G; García-España, Enrique

    2015-05-07

    The formation of copper(ii) complexes with symmetrical dinucleating macrocyclic ligands containing two either monomethylated () or trimethylated () diethylenetriamine (Medien or Me3dien) subunits linked by pyridine spacers has been studied by potentiometry. Potentiometric studies show that has larger basicity than as well as higher stability of its mono- and binuclear complexes. The crystal structures of ·6HCl (), [Cu2(L1)Cl2](CF3SO3)2 (), [Cu2(L1)(OH)](ClO4)3·3H2O () and [Cu(L1)](ClO4)2 () show that adopts different coordination modes when bound to copper(ii). Whereas in , each copper(ii) is bound to one Medien subunit and to one pyridine group, in each metal center is coordinated to one 2,6-di(aminomethyl)pyridine moiety (damp) and to one aminomethyl group. The mononuclear complex shows pseudo-octahedral coordination with two weakly coordinated axial nitrogens. Kinetic studies indicate that complex decomposition is strongly dependent on the coordination mode of . Upon addition of an acid excess, all the species except [Cu2(L1)](4+) convert very rapidly to an intermediate that decomposes more slowly to copper(ii) and a protonated ligand. In contrast, [Cu2(L1)](4+) decomposes directly without the formation of any detectable intermediate. These results can be rationalized by considering that the crystal structures are maintained in solution and that the weakest Cu-N bonds are broken first, thus indicating that kinetic measurements on complex decomposition can be used to provide information about structural reorganizations in the complexes. In any case, complete decomposition of the complexes takes place in a maximum of two kinetically resolvable steps. However, minor changes in the structure of the complexes can lead to drastic changes in the kinetics of decomposition and the complexes decompose with polyphasic kinetics in which up to four different steps associated with the successive breaking of the different Cu-N bonds can be resolved.

  10. Sulfated chitosan/PVA absorbent membrane for removal of copper and nickel ions from aqueous solutions-Fabrication and sorption studies.

    PubMed

    Abu-Saied, M A; Wycisk, Ryszard; Abbassy, Moustafa M; El-Naim, G Abd; El-Demerdash, F; Youssef, M E; Bassuony, H; Pintauro, Peter N

    2017-06-01

    Novel absorbents for the removal of Cu(2+) and Ni(2+) ions from aqueous solutions were prepared from solution cast sulfated chitosan/polyvinyl alcohol membranes (SCS/PVA) and their properties were investigated. FTIR, SEM, XRD and TGA analyses were used to determine membrane structure. The effect of environmental parameters on absorption was studied, including pH, contact time, temperature and the initial concentration of Ni(2+) and Cu(2+) ions. Freundlich and Langmuir absorption isotherms were fitted to experimental data and a pseudo-second order rate equation was employed to model the kinetics of uptake for several copper and nickel ion concentrations. The results indicate that the affinity of an SCS/PVA membrane for Cu(2+) ions was higher than that for Ni(2+) ions. The study demonstrated that the SCS/PVA system can be utilized as highly efficient sorbents, to extract Ni(2+) and Cu(2+) from aqueous feed solutions.

  11. Ultraviolet spectrophotometric characterization of copper(II) complexes with imidazole N-methyl derivatives of ?-histidine in aqueous solution

    NASA Astrophysics Data System (ADS)

    Prenesti, Enrico; Berto, Silvia; Daniele, Pier Giuseppe

    2003-01-01

    In this study we considered π-methyl- L-histidine (π-methis) and τ-methyl- L-histidine (τ-methis) as ligands for copper(II) ion, in order to clarify, by means of ultraviolet (UV) spectroscopy in aqueous solution ( T=25 °C, I=0.1 M), some aspects of the co-ordination mode with respect to other ligands of a previous study in which copper(II) complexes of L-histidine, N-acetyl- L-histidine, histamine, L-histidine methyl ester or carnosine were investigated. Particularly, UV spectra (300-400 nm) were recorded on solutions at various pH values, containing each binary system Cu-L; afterwards, an UV absorption spectrum for single complexes was calculated, taking into account the chemical model previously assessed, in order to fulfil a correct spectrum-structure correlation. The problem related to the eventual superimposition of the CT shoulder (≈330 nm) to copper(II) of OH - and imidazole pyridine nitrogen groups were now solved by means of a comparison of the UV spectra of dimer species formed by both π-methis or τ-methis. Finally, copper(II) complex formation with 2,2'-bipyridine was taken into account to compare the behaviour of pyridine (from 2,2'-bipyridine) and pyridine imidazole nitrogens (from π-methis or τ-methis) with respect to the UV charge transfer process to copper(II) ion.

  12. Impact of DIC, Sulfate and Chloride on Pb(II) Solubility

    EPA Science Inventory

    Corrosion of lead and the subsequent release of lead into drinking water distribution systems pose a concern to public health. Consequently, the U.S. Environmental Protection Agency’s (U.S. EPA) Lead and Copper rule established an action level for lead at the consumer’s tap of 0....

  13. USING RESPIROMETRY TO MEASURE HYDROGEN UTILIZATION IN SULFATE REDUCING BACTERIA IN THE PRESENCE OF COPPER AND ZINC

    EPA Science Inventory

    A respirometric method has been developed to measure hydrogen utilization by sulfate reducing bacteria (SRB). One application of this method has been to test inhibitory metals effects on the SRB culture used in a novel acid mine drainage treatment technology. As a control param...

  14. Evaluation of copper-labeled Cu(II) bis(thiosemicarbazone) complexes as blood flow tracers for positron emission tomography

    SciTech Connect

    Bott, A.J.

    1990-01-01

    Positron emmision tomography (PET) is an imaging technique not widely available for clinical diagnosis due to the costs of producing positron-emitting radiolabels. The development of radiotracers labeled with generator-produced positron emitters would facilitate the use of PET by eliminating the need for an in-house cyclotron. Copper-62 is a generator-produced positron emitter potentially useful for labeling PET radiopharmaceuticals. Copper-62 labeled Cu(II) pyruvaldehyde bis(N[sup 4]-methylthiosemicarbazone), Cu(PTSM), is a proposed PET perfusion tracer of the brain, heart, and kidneys. After IV injection in animals, copper-labeled Cu(PTSM) affords high initial uptake followed by prolonged retention of radiocopper in these organs. This retention is thought to be a result of reductive decomposition of the copper-labeled copper(II) complex by intracellular glutathione, GSH. To validate copper-62 labeled Cu(PTSM) as a myocardial and renal perfusion tracer, the regional radiocopper level afforded by intravenous copper-67 labeled Cu(PTSM) was compared to the absolute blood flow measured with labeled microspheres in normal dog kidneys and surgically infarcted myocardia. In the heart and randomly sectioned kidneys, an excellent correlation resulted. In kidneys dissected to separate anatomical regions, radiocopper levels increased montonically with increasing blood flows for individual dogs, but a linear correlation was observed when data from 12 animals was combined. Should the distribution of Cu(PTSM) vary with naturally occuring GSH fluctuations, the clinical utility of this radiotracer would be limited. Therefore, to validate further copper-62 labeled Cu(PTSM), the biodistribution of copper-67 labeled (PTSM) was determined in GSH-depleted rats. Relatively large GSH reductions in the experimental animals caused only slight changes in the distribution of Cu(PTSM). Another 23 copper-67 labeled compounds were tested.

  15. Sorption of lead (II), cobalt (II) and copper (II) ions from aqueous solutions by γ-MnO2 nanostructure

    NASA Astrophysics Data System (ADS)

    Chung Le, Ngoc; Van Phuc, Dinh

    2015-01-01

    Manganese dioxide γ-MnO2 was synthesized via the reduction-oxidation reaction between KMnO4 and C2H5OH at room temperature and characterized with x-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Brunauer-Emmet-Teller nitrogen adsorption (BET-N2 adsorption). The results showed that γ-MnO2 was about 10-18 nm in size and the BET surface area was about 65 m2 g-1. The feasibility of γ-MnO2 used as a low cost adsorbent for the adsorption of Pb(II), Co(II) and Cu(II) from aqueous solutions was explored. During the adsorption process, batch technique was used, and the effects of contact time and pH on adsorption efficiency under room temperature were studied. The adsorption data showed that the Freundlich, Langmuir and Redlich-Peterson isotherms are a good model for the sorption of Co(II) and Cu(II), while the Langmuir and Redlich-Peterson isotherms provide a reasonable fit to the experimental data for Pb(II). By using the Langmuir isotherm, the adsorption capacities for Pb(II), Co(II) and Cu(II) are found to be 200 mg g-1, 90.91 mg g-1 and 83.33 mg g-1, respectively. The effectiveness of γ-MnO2 in the sorption of the three metal ions from aqueous system has the order Pb(II) > Co(II) > Cu(II). Kinetic studies showed that a pseudo-second-order model was more suitable than the pseudo-first-order model. Also, the intra-particle diffusion models were used to ascertain the mechanism of the sorption process. It is concluded that γ-MnO2 can be used as an effective adsorbent for removing Pb(II), Co(II) and Cu(II) from aqueous solutions.

  16. New masking procedure for selective complexometric determination of copper(II).

    PubMed

    Singh, R P

    1972-11-01

    A study has been made of a new masking procedure for highly selective complexometric determination of copper(II), based on decomposition of the copper-EDTA complex at pH 5-6. Among the various combinations of masking agents tried, ternary masking mixtures comprising a main complexing agent (thiourea), a reducing agent (ascorbic acid) and an auxiliary complexing agent (thiosemicarbazide or a small amount of 1,10-phenanthroline or 2,2'-dipyridyl) have been found most suitable. An excess of EDTA is added and the surplus EDTA is back-titrated with lead (or zinc) nitrate with Xylenol Orange as indicator (pH 5-6). A masking mixture is then added to decompose the copper-EDTA complex and the liberated EDTA is again back-titrated with lead (or zinc) nitrate. The following cations do not interfere: Ag(+), Hg(2+), Pb(2+), Ni(2+), Bi(3+), As(3+), Al(3+), Sb(3+), Sn(4+), Cd(2+), Co(2+), Cr(3+) and moderate amounts of Fe(3+) and Mn(2+). The notable feature is that consecutive determination of Hg(2+) and Cu(2+) can be conveniently carried out in the presence of other cations.

  17. Synthesis, physico-chemical studies of manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) complexes with some p-substituted acetophenone benzoylhydrazones and their antimicrobial activity.

    PubMed

    Singh, Vinod P; Singh, Shweta; Katiyar, Anshu

    2009-04-01

    Complexes of the type [M(pabh)(H2O)Cl], [M(pcbh)(H2O)Cl] and [M(Hpabh)(H2O)2 (SO4)] where, M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II); Hpabh = p-amino acetophenone benzoyl hydrazone and Hpcbh = p-chloro acetophenone benzoyl hydrazone have been synthesized and characterized with the help of elemental analyses, electrical conductance, magnetic susceptibility measurements, electronic, ESR and IR spectra, thermal (TGA & DTA) and X-ray diffraction studies. Co(II), Ni(II) and Cu(II) chloride complexes are square planar, whereas their sulfate complexes have spin-free octahedral geometry. ESR spectra of Cu(II) complexes with Hpabh are axial and suggest d(x(2)-y(2) as the ground state. The ligand is bidentate bonding through > C = N--and deprotonated enolate group in all the chloro complexes, whereas, >C = N and >C = O groups in all the sulfato complexes. Thermal studies (TGA & DTA) on [Cu(Hpabh)(H2O)2(SO4)] indicate a multistep decomposition pattern, which are both exothermic and endothermic in nature. X-ray powder diffraction parameters for [Co(pabh)(H2O)Cl] and [Ni(Hpabh)(H2O)2(SO4)] correspond to tetragonal and orthorhombic crystal lattices, respectively. The ligands as well as their complexes show a significant antifungal and antibacterial activity. The metal complexes are more active than the ligand.

  18. Sensitive and selective capillary electrophoretic analysis of proteins by zirconia nanoparticle-enhanced copper (II)-catalyzed luminol-hydrogen peroxide chemiluminescence.

    PubMed

    Liu, Qingchun; Wu, Jingqing; Tian, Jing; Zhang, Chenling; Gao, Jingjie; Latep, Nurgul; Ge, Ying; Qin, Weidong

    2012-08-15

    We report herein a sensitive, selective, convenient CE determination of heme proteins in complex matrices by a sodium-dodecyl-sulfate-assisted, zirconia nanoparticle-enhanced copper (II)-catalyzed luminol-hydrogen peroxide chemiluminescence (CCLHPCL). Introducing a segment of sodium dodecyl sulfate to the capillary after sample injection not only rendered selective detection by quenching the luminescence signals from the non-heme proteins but also owning to the suppressed protein adsorption, led to significant improvement in separation efficiency and detection sensitivity. The signals were further improved by addition of ZrO(2) nanoparticles to the chemiluminescence solution. Compared with the conventional CCLHPCL, the detection limits (S/N=3) were improved by 10.2-22.0 folds, with 7.8×10(-9), 3.3×10(-9) and 1.5×10(-9) M for three model proteins, viz, myoglobin, hemoglobin and cytochrome C, respectively. Because the method did not require sophisticated pretreatment, it was convenient to analyze heme proteins in complex matrices, as demonstrated, hemoglobin in human blood and spiked human urine samples.

  19. Dinuclear cadmium(II), zinc(II), and manganese(II), trinuclear nickel(II), and pentanuclear copper(II) complexes with novel macrocyclic and acyclic Schiff-base ligands having enantiopure or racemic camphoric diamine components.

    PubMed

    Jiang, Jue-Chao; Chu, Zhao-Lian; Huang, Wei; Wang, Gang; You, Xiao-Zeng

    2010-07-05

    Four novel [3 + 3] Schiff-base macrocyclic ligands I-IV condensed from 2,6-diformyl-4-substituted phenols (R = CH(3) or Cl) and enantiopure or racemic camphoric diamines have been synthesized and characterized. Metal-ion complexations of these enantiopure and racemic [3 + 3] macrocyclic ligands with different cadmium(II), zinc(II), manganese(II), nickel(II), and copper(II) salts lead to the cleavage of Schiff-base C horizontal lineN double bonds and subsequent ring contraction of the macrocyclic ligands due to the size effects and the spatial restrictions of the coordination geometry of the central metals, the steric hindrance of ligands, and the counterions used. As a result, five [2 + 2] and one [1 + 2] dinuclear cadmium(II) complexes (1-6), two [2 + 2] dinuclear zinc(II) (7 and 8), and two [2 + 2] dinuclear manganese(II) (9 and 10) complexes together with one [1 + 1] trinuclear nickel(II) complex (11) and one [1 + 2] pentanuclear copper(II) complex (12), bearing enantiopure or racemic ligands, different substituent groups in the phenyl rings, and different anionic ligands (Cl(-), Br(-), OAc(-), and SCN(-)), have been obtained in which the chiral carbon atoms in the camphoric backbones are arranged in different ways (RRSS for the enantiopure ligands in 1, 2, 4, 5, and 7-10 and RSRS for the racemic ligands in 3, 6, 11, and 12). The steric hindrance effects of the methyl group bonded to one of the chiral carbon atoms of camphoric diamine units are believed to play important roles in the formation of the acyclic [1 + 1] trinuclear complex 11 and [1 + 2] dinuclear and pentanuclear complexes 6 and 12. In dinuclear cadmium(II), zinc(II), and manganese(II) complexes 1-10, the sequence of separations between the metal centers is consistent with that of the ionic radii shortened from cadmium(II) to manganese(II) to zinc(II) ions. Furthermore, UV-vis, circular dichroism, (1)H NMR, and fluorescence spectra have been used to characterize and compare the structural

  20. Spectrophotometric determination of copper(II) in pharmaceutical, biological and water samples by 4-(2'-benzothiazolylazo)-salicylic acid

    NASA Astrophysics Data System (ADS)

    Hashem, E. Y.; Seleim, M. M.; El-Zohry, A. M.

    2011-09-01

    A highly sensitive method is proposed to determine copper(II) ions by forming a stable complex through their interaction with 4-(2'-benzothiazolylazo)-salicylic acid (BTAS) at room temperature and pH of about 5.0. The complex gave a maximum absorption at λ = 485 nm with a molar absorptivity coefficient of 2.35·104 l/(mol·cm). The linear range for the copper determination is 0.63-5.04 mg/l. The method can be applied to determine copper ions in different biological specimens like some drugs and water samples.

  1. Assessing the combination of iron sulfate and organic materials as amendment for an arsenic and copper contaminated soil. A chemical and ecotoxicological approach.

    PubMed

    Fresno, Teresa; Moreno-Jiménez, Eduardo; Peñalosa, Jesús M

    2016-12-01

    The efficiency of combining iron sulfate and organic amendments (paper mill sludge, olive mill waste compost and olive tree pruning biochar) for the remediation of an As- and Cu-contaminated soil was evaluated. Changes in As and Cu fractionation and solubility due to the application of the amendments was explored by leachate analysis, single and sequential extractions. Also, the effects on Arrhenatherum elatius growth, germination of Lactuca sativa and toxicity to the bacteria Vibrio fischeri were assessed. The combination of iron sulfate and the organic amendments efficiently reduced As solubility and availability through the formation of amorphous iron oxides, while organic matter did not seem to mobilize As. At the same time, copper fractionation was strongly affected by soil pH and organic matter addition. The soil pH significantly influenced both As and Cu mobility. Within all the amendments tested, FeSO4 in combination with compost showed to be the most suitable treatment for the overall remediation process, as it reduced As and Cu availability andenhanced soil nutrient concentrations and plant growth. In sipte of contradictory trends between chemical analyses and ecotoxicity tests, we can still conclude that the application of organic amendments in combination with reactive iron salts is a suitable approach for the remediation of soils contaminated by Cu and As.

  2. Benthic sulfate reduction along the Chesapeake Bay central channel. II. Temporal controls

    USGS Publications Warehouse

    Marvin-DiPasquale, M. C.; Boynton, W.R.; Capone, D.G.

    2003-01-01

    Seasonal and interannual controls of benthic sulfate reduction (SR) were examined at 3 sites (upper [UB], mid- [MB] and lower [LB] bay) along the Chesapeake Bay central channel, from early spring through fall, for 6 yr (1989 to 1994). The combined influences of temperature, sulfate, organic loading and bioturbation affected seasonal SR rates differently in the 3 regions. Consistently low SR rates at UB resulted from low overlying-water sulfate concentrations and the dominance of refractory organic terrestrial material. Combined seasonal variation in temperature and sulfate accounted for 50% of the annual variability in 0 to 2 cm depth interval SR rates, while sediment organic content had no significant seasonal influence. In contrast, MB and LB sites had high rates of SR fostered by high levels of overlying water SO42- and organic input dominated by labile phytoplankton detritus. New organic loading (measured as chl a) stimulated 0 to 2 cm SR during spring at both sites. Combined organic quantity (as particulate C and/or N) and temperature accounted for > 75% of the variability in 0 to 2 cm SR at MB during spring and fall. Molecular diffusion supplied 25 to 45% of the SO 42- needed to fuel 0 to 12 cm depth interval SR at MB, with the balance presumably supplied by S-recycling. Interannual differences in summertime SR rates were linked to the extent of freshwater flow during spring, with high-flow years associated with high SR rates at UB and MB, and low rates at LB. The negative trend between benthic SR and river flow at LB may result from the up-estuary transport of senescing organic matter in bottom water, which increases in the lower reach of the estuary with increasing freshwater inflow.

  3. Electrodeposition of copper selenide films from acidic bath and their properties

    NASA Astrophysics Data System (ADS)

    Mane, Rajaram S.; Shaikh, Arif V.; Joo, Oh-Shim; Han, Sung-Hwan; Pathan, Habib M.

    2012-06-01

    Copper selenide thin films are successfully deposited using electrodeposition method by combining copper sulfate and sodiumseleno sulfate precursors at room temperature in acidic bath. The chemical composition was a key factor in preparing high-quality uniform and smooth thin films of the copper selenide. We present indium-tin-oxide as a substrate for depositing copper selenide films which usually exists as copper (I) selenide or copper (II) selenide. Obtained brownish films of copper selenide are examined for their structural, morphological, compositional and optical properties by means of X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis and optical absorption measurement techniques, respectively for the structural, morphological and optical analysis.

  4. Effect of Copper Sulfate on Expression of Endogenous L1 Retrotransposons in HepG2 Cells (Hepatocellular Carcinoma).

    PubMed

    Karimi, Abbas; Majidzadeh-A, Keivan; Madjd, Zahra; Akbari, Abolfazl; Habibi, Laleh; Akrami, Seyed Mohammad

    2015-06-01

    The long interspersed element-1 (LINE-1 or L1) constitutes approximately 17% of human genome. The expression of these elements is deregulated upon exposure to environmental exposures resulting to genomic instability and cancer promotion. The effect of copper as essential elements in regulation of L1 expression remained to be elucidated. Using non-cytotoxic concentrations of the copper, the expression of endogenous L1 was analyzed by qPCR after 6 days of copper pretreatment in human hepatocellular carcinoma cells (HepG2). The results indicated that the expression of active L1 elements are significantly downregulated at concentrations of 12.5, 25, and 50 μM (p < 0.005). Our data imply that low-level copper exposure may have a protective effect to suppress the induction of L1 activity and decrease incidence of cancer-associated L1 mutagenesis. If this achievement is confirmed by further studies, it can be applied in the long-term goals of cancer prevention.

  5. Mathematical modeling of copper(II) ion inhibition on COD removal in an activated sludge unit.

    PubMed

    Pamukoglu, M Yunus; Kargi, Fikret

    2007-07-19

    A mathematical model was developed to describe the Cu(II) ion inhibition on chemical oxygen demand (COD) removal from synthetic wastewater containing 15 mg l(-1) Cu(II) in an activated sludge unit. Experimental data obtained at different sludge ages (5-30 days) and hydraulic residence times (HRT) (5-25 h) were used to determine the kinetic, stoichiometric and inhibition constants for the COD removal rate in the presence and absence of Cu(II) ions. The inhibition pattern was identified as non-competitive, since Cu(II) ion inhibitions were observed both on maximum specific substrate removal rate (k) and on the saturation constant (Ks) with the inhibition constants of 97 and 18 mg l(-1), respectively, indicating more pronounced inhibition on Ks. The growth yield coefficient (Y) decreased and the death rate constant (b) increased in the presence of Cu(II) ions due to copper ion toxicity on microbial growth with inhibition constants of 29 and 200 mg l(-1), respectively indicating more effective inhibition on the growth yield coefficient or higher maintenance requirements. The mathematical model with the predetermined kinetic constants was able to predict the system performance reasonably well especially at high HRT operations.

  6. Spectroscopic, structural and theoretical studies of copper(II) complexes of tridentate NOS Schiff bases

    NASA Astrophysics Data System (ADS)

    Olalekan, Temitope E.; Ogunlaja, Adeniyi S.; VanBrecht, Bernardus; Watkins, Gareth M.

    2016-10-01

    Two newly synthesized Schiff bases (L4 and L5) were derived from the condensation reaction of 2-(methylthiomethyl)anilines and 4-methoxysalicylaldehyde. Coordination complexes of these and four previously reported NOS Schiff bases, Cu(L1)2-Cu(L6)2, were synthesized via the reflux reaction of the various Schiff base ligands with CuCl2·2H2O. The compounds were characterized by means of elemental analysis, FTIR and UV-Vis. The crystal structures of Cu(L1)2 and Cu(L2)2 were obtained by X-ray diffraction. The Schiff bases were coordinated to copper ion as monobasic tridentate ligands through the phenolic oxygen, azomethine nitrogen and thioether sulfur. The microanalyses of the coordination complexes were agreeable with bimolar binding of the ligands to the copper metal ion. The crystal structures of the copper complexes confirmed an octahedral geometry around the metal centre and showed they are mononuclear. The magnetic moment values indicated the presence of a lone electron in each copper(II) orbital and confirmed the mononuclearity of the complexes. The electronic spectra of the coordination compounds consist of the intraligand, charge transfer and d→d bands. Molecular modeling studies on the complexes (Cu(L1)2-Cu(L6)2) by employing DFT revealed that complex Cu(L5)2 possessed the smallest optimization energy as well as a small HOMO-LUMO energy gap which may best explain its higher polarizability as well as reactivity in comparison to the other complexes.

  7. Dimeric (isoquinoline)(N-salicylidene-D,L-glutamato)copper(II) ethanol solvate.

    PubMed

    Langer, Vratislav; Gyepesová, Dalma; Kohútová, Mária; Valent, Aladár

    2009-05-01

    The title racemic complex, bis[mu-N-(2-oxidobenzylidene)-D,L-glutamato(2-)]bis[(isoquinoline)copper(II)] ethanol disolvate, [Cu(2)(C(12)H(11)NO(5))(2)(C(9)H(7)N)(2)].2C(2)H(6)O, adopts a square-pyramidal Cu(II) coordination mode with a tridentate N-salicylideneglutamato Schiff base dianion and an isoquinoline ligand bound in the basal plane. The apex of the pyramid is occupied by a phenolic O atom from the adjacent chelate molecule at an apical distance of 2.487 (3) A, building a dimer located on the crystallographic inversion center. The Cu...Cu spacing within the dimers is 3.3264 (12) A. The ethanol solvent molecules are hydrogen bonded to the dimeric complex molecules, forming infinite chains in the a direction. The biological activity of the title complex has been studied.

  8. XAFS Study of the Ferro- and Antiferromagnetic Binuclear Copper(II) Complexes of Azomethine Based Tridentate Ligands

    SciTech Connect

    Vlasenko, Valery G.

    2007-02-02

    Binuclear copper complexes are known to be models for metalloenzymes containing copper active sites, and some of them are of considerable interest due to their magnetic and charge transfer properties. The reactions of the complex formation of bibasic tridentate heterocyclic imines with copper acetate leads to two types of chelates with mono deprotonated ligands and with totally deprotonated ligands. Cu K-edge EXAFS has been applied to determine the local structure around the metal center in copper(II) azomethine complexes with five tridentate ligands: 1-(salycilideneimino)- or 1-(2-tosylaminobenzilideneimino)-2-amino(oxo, thio)benzimidazoles. It has been found that some of the chelates studied are bridged binuclear copper complexes, and others are mononuclear complexes. The copper-copper interatomic distances in the bridged binuclear copper complexes were found to be 2.85-3.01 A. Variable temperature magnetic susceptibility data indicate the presence of both ferromagnetic and antiferromagnetic interactions within the dimer, the former is dominating at low temperatures and the latter at high temperatures.

  9. Formation of a new copper(II) dimer through heterocyclic ligand ring opening reaction: Supramolecular features and magnetic properties

    NASA Astrophysics Data System (ADS)

    Gonçalves, Bruna Lisboa; Gervini, Vanessa Carratu; Flores, Alex Fabiani Claro; Junior, Jorge Luiz Pimentel; Bortoluzzi, Adailton João; Burrow, Robert Alan; Duarte, Rafael; da Silva, Robson Ricardo; Vicenti, Juliano Rosa de Menezes

    2017-01-01

    Two new compounds were synthesized and characterized in this work: the heterocycle (Z)-1-(4-(hydroxyimino)-3,5-dimethyl-1-(methylcarbamothioyl)-4,5-dihydro-1H-pyrazol-5-yl)-4-methylthiosemicarbazide and a copper(II) thiosemicarbazonato dimeric complex. Green prismatic single crystals of the dimer were obtained by the reaction of the heterocycle with copper(II) chloride dihydrate. Both compounds were essentially characterized by spectroscopic methods and X-ray diffraction crystallography. The crystal structures revealed molecules connected through supramolecular hydrogen bond interactions and copper(II) centers in a slightly distorted square-pyramidal environment. SQUID magnetometry performed for the dimer revealed both ferromagnetic and antiferromagnetic interactions in the studied complex, presenting a critical temperature of 19 K.

  10. Reaction of a copper(II)-nitrosyl complex with hydrogen peroxide: phenol ring nitration through a putative peroxynitrite intermediate.

    PubMed

    Kalita, Apurba; Deka, Ramesh C; Mondal, Biplab

    2013-10-07

    Copper(II) complex, 1, with the histidine-derived ligand L (L = methyl 2-(2-hydroxybenzylamino)-3-(1H-imidazol-5-yl)propanoate) has been synthesized and characterized. Single-crystal structure determination reveals a diphenolato-bridged dicopper(II) core in 1. Addition of (•)NO to an acetonitrile solution of 1 affords the corresponding mononuclear copper(II)-nitrosyl complex, 2. In the presence of H2O2, 2 results in formation of the corresponding copper(I)-peroxynitrite. Formation of peroxynitrite ((-)OONO) intermediate is evident from its characteristic phenol ring nitration reaction which resembles the tyrosine nitration in biological systems. Further, isolation of nitrate (NO3(-)) as the decomposition product from 2 at room temperature also supports the involvement of (-)OONO intermediate.

  11. Oxidation of substituted phenols using copper(II) metallatriangles formed through ligand sharing.

    PubMed

    Mahiya, Kuldeep; Kumar, Ravinder; Lloret, Francisco; Mathur, Pavan

    2014-12-10

    Reaction of N(2),N(2')-bis-[(1-butyl-benzimidazol-2yl)methyl]biphenyl-2,2'-dicarboxamide (L) with CuX2⋅nH2O in methanol leads to the assembly of four trinuclear Cu(II) complexes with the general formula [Cu3(L)3X3]⋅3X⋅nH2O⋅mMeCN, where X=Cl(-), Br(-), NO3(-) and C6H5COO(-) and n=0-5, m=0-8 (compounds 1-4, respectively). The structure of one of the complex contains three Cu(II) metal ions at the corners of an equilateral triangle. Each of the copper(II) are coordinated through two benzimidazolyl imine N-atoms and two amide carbonyl O-atoms and the apical position is occupied by an anionic nitrate ion, leading to a distorted square pyramidal environment. The magnetic susceptibility data were analyzed through Hamiltonian H=-J (S1S2+S2S3+S1S3) obtaining -J=0.16, 0.12, 0.15 and 0.14cm(-1) for 1-4, respectively. X-Band EPR spectra typically show a broad single line at 120K with g∼2.11. Oxidation of phenols was studied homogeneously using copper(II) metallatriangles (1-3) as catalyst in acetonitrile. The oxidation of 2,4,6-tri-tert-butyl phenol yields the corresponding quinone after oxidative dealkylation. The oxidation of 2-amino-5-methyl phenol yields the corresponding phenoxazinone while the oxidation of 2-amino-4-tert-butyl phenol yields the phenoxazine instead of phenoxazinone. The products so obtained were analyzed by NMR and X-ray single crystallography.

  12. Uranyl-copper(II) heterometallic oxalate complexes: coordination polymers and frameworks.

    PubMed

    Thuéry, Pierre; Rivière, Eric

    2013-08-07

    Five oxalate complexes containing both uranyl and copper(II) ions and 2,2′-bipyridine (bipy), 2,2′-bipyrimidine (bipym) or 1,10-phenanthroline (phen) as co-ligands have been synthesized under hydrothermal conditions and their crystal structures were determined. [UO2Cu(C2O4)(NO3)2(bipy)(H2O)] (1) is a molecular complex in which the two cations are connected by the bis-chelating oxalate. A one-dimensional uranyl oxalate ribbon is formed in [UO2Cu(C2O4)2(bipym)(H2O)] (2), with uranyl ions bound to two chelating anions and to a third, monodentate oxalate which holds the decorating [Cu(bipym)(H2O)]2+ groups. Complex [(UO2)2Cu2(C2O4)2(bipym)3(OH)2]·2NO3 (3) is a two-dimensional assembly in which uranyl oxalate chains are linked to one another by [Cu2(bipym)3]4+ dinuclear units through bridging hydroxide ions. Finally, [UO2Cu(C2O4)2(bipy)] (4) and [UO2Cu(C2O4)2(phen)] (5) display identical three-dimensional arrangements containing uranyl oxalate sheets connected to one another by copper oxalate dinuclear units. The magnetic properties of compounds 2 and 4 have been investigated. Weak inter-chain antiferromagnetic interactions between copper(II) atoms are present in 2, while 4 displays strong oxalate-mediated antiferromagnetic exchange (J = -335 cm(-1)). These complexes are the first uranyl-d block metal oxalate complexes to be reported.

  13. New discrete and polymeric supramolecular architectures derived from dinuclear (bis-beta-diketonato)copper(II) metallocycles.

    PubMed

    Clegg, Jack K; Gloe, Karsten; Hayter, Michael J; Kataeva, Olga; Lindoy, Leonard F; Moubaraki, Boujemaa; McMurtrie, John C; Murray, Keith S; Schilter, David

    2006-09-07

    New examples of adducts between di- (and, in one instance, tetra-) functional nitrogen ligands and planar 'platform-like' dinuclear copper(II) complexes, [Cu2L2], incorporating the 1,3-aryl linked bis-beta-diketonato bridging ligand 1,1'-(1,3-phenylene)-bis(4,4-dimethylpentane-1,3-dione) (H2L) have been synthesised. The X-ray structures of six adduct species are reported. The interaction of [Cu2(L)2] with the ditopic ligand aminopyrazine (apyz) yielded the sandwich-like tetranuclear species [(Cu2L2(apyz))2]. A variable-temperature magnetochemical investigation of this product indicated weak antiferromagnetic coupling between the (five-coordinate) copper centres, mediated by the 2-aminopyrazine linkers. An analogous structure, [(Cu2L2(dabco))2] (dabco=1,4-diazabicyclo[2.2.2]octane), was generated when dabco was substituted for aminopyrazine while use of 4,4'-dipyridyl sulfide (dps) and 4,4'-(1,3-xylylene)-bis(3,5-dimethylpyrazole) (xbp) as the ditopic 'spacer' ligands resulted in polymeric species of type [Cu2L2(dps)]n and [Cu2L2(xbp)]n, respectively. These latter species exist as one-dimensional chain structures in which copper(II) centres on different dinuclear platforms are linked in a 'zigzag' fashion. In contrast, with 2,2'-dipyridylamine (dpa) a discrete complex of type [Cu2L2(dpa)2] formed in which one potential pyridyl donor from each 2,2'-dipyridylamine ligand remains uncoordinated. The use of the potentially quadruply-bridging hexamethylenetetramine (hmt) ligand as the linker unit was found to give rise to an unusual two-dimensional polymeric motif of type [(Cu2(L2)2)3(hmt)2]n. The product takes the form of a (6,3) network, incorporating triply bridging hexamethylenetetramine units.

  14. Synthetic, crystallographic, and computational study of copper(II) complexes of ethylenediaminetetracarboxylate ligands.

    PubMed

    Matović, Zoran D; Miletić, Vesna D; Ćendić, Marina; Meetsma, Auke; van Koningsbruggen, Petra J; Deeth, Robert J

    2013-02-04

    Copper(II) complexes of hexadentate ethylenediaminetetracarboxylic acid type ligands H(4)eda3p and H(4)eddadp (H(4)eda3p = ethylenediamine-N-acetic-N,N',N'-tri-3-propionic acid; H(4)eddadp = ethylenediamine-N,N'-diacetic-N,N'-di-3-propionic acid) have been prepared. An octahedral trans(O(6)) geometry (two propionate ligands coordinated in axial positions) has been established crystallographically for the Ba[Cu(eda3p)]·8H(2)O compound, while Ba[Cu(eddadp)]·8H(2)O is proposed to adopt a trans(O(5)) geometry (two axial acetates) on the basis of density functional theory calculations and comparisons of IR and UV-vis spectral data. Experimental and computed structural data correlating similar copper(II) chelate complexes have been used to better understand the isomerism and departure from regular octahedral geometry within the series. The in-plane O-Cu-N chelate angles show the smallest deviation from the ideal octahedral value of 90°, and hence the lowest strain, for the eddadp complex with two equatorial β-propionate rings. A linear dependence between tetragonality and the number of five-membered rings has been established. A natural bonding orbital analysis of the series of complexes is also presented.

  15. Biosorption of copper(II) by Marrubium globosum subsp. globosum leaves powder: effect of chemical pretreatment.

    PubMed

    Yazici, Hüseyin; Kiliç, Mehmet; Solak, Murat

    2008-03-01

    The study was aimed at determining the effect of chemical pretreatment on copper(II) biosorption by Marrubium globosum subsp. globosum leaves. The uptake capacity of the biomass was increased by chemical pretreatment when compared with the raw biomass. The results of biosorption experiments, carried out at the conditions of 50 mg l(-1) initial metal concentration and pH 5.5, showed that pretreating the biomass with alkali solutions (laundry detergent, sodium hydroxide and sodium bicarbonate, 0.5 M) improved the biosorption capacity of biomass (45.90, 45.78 and 43.91%, respectively) compared with raw biomass. Pretreatment with sulfuric and nitric acid solutions, 0.5 M, increased the biosorption capacity of biomass by 11.82 and 10.18%, respectively, while there was no considerable change in the biosorption capacity of biomass (0.35%) after pretreatment with formic acid solution, 0.5 M. Furthermore, sodium chloride and calcium chloride, 0.5 M, pretreatments resulted in the improvement in biosorption capacity of biomass (31.38 and 26.69%, respectively). FT-IR analysis revealed that hydroxyl and carboxyl functional groups were mainly responsible for copper(II) biosorption.

  16. Kinetics and mechanism of the oxidation of arsine by halide complexes of copper(II)

    SciTech Connect

    Dorfman, Y.A.; Abdreimova, R.R.; Emel'yanova, V.S.; Kel'man, I.V.; Polimbetova, G.S.

    1985-11-01

    This paper studies the kinetics of the oxidation of arsine by copper (II) halides. It is shown that within the investigated region of concentrations of the components of the system CuX/sub 2/-HX-LiX-H/sub 2/O, /SUB C/ the oxidation of AsH/sub 3/ proceeds to As(O). First order with respect to /SUB Cu/ X/sub 2/ is observed; the order with respect to C /SUB As/ H/sub 3/ is close to first. With regard to activity in the reaction with arsine, copper(II) halides are distributed in the series. CuCl /SUB 3aq/ -

  17. Highly efficient visual detection of trace copper(II) and protein by the quantum photoelectric effect.

    PubMed

    Wang, Peng; Lei, Jianping; Su, Mengqi; Liu, Yueting; Hao, Qing; Ju, Huangxian

    2013-09-17

    This work presented a photocurrent response mechanism of quantum dots (QDs) under illumination with the concept of a quantum photoelectric effect. Upon irradiation, the photoelectron could directly escape from QDs. By using nitro blue tetrazolium (NBT) to capture the photoelectron, a new visual system was proposed due to the formation of an insoluble reduction product, purple formazan, which could be used to visualize the quantum photoelectric effect. The interaction of copper(II) with QDs could form trapping sites to interfere with the quantum confinement and thus blocked the escape of photoelectron, leading to a "signal off" visual method for sensitive copper(II) detection. Meanwhile, by using QDs as a signal tag to label antibody, a "signal on" visual method was also proposed for immunoassay of corresponding protein. With meso-2,3-dimercaptosuccinic-capped CdTe QDs and carcino-embryonic antigen as models, the proposed visual detection methods showed high sensitivity, low detection limit, and wide detectable concentration ranges. The visualization of quantum photoelectric effect could be simply extended for the detection of other targets. This work opens a new visual detection way and provides a highly efficient tool for bioanalysis.

  18. Spectroscopic and molecular docking studies on the interaction of human serum albumin with copper(II) complexes

    NASA Astrophysics Data System (ADS)

    Guhathakurta, Bhargab; Pradhan, Ankur Bikash; Das, Suman; Bandyopadhyay, Nirmalya; Lu, Liping; Zhu, Miaoli; Naskar, Jnan Prakash

    2017-02-01

    Two osazone based ligands, butane-2,3-dione bis(2‧-pyridylhydrazone) (BDBPH) and hexane-3,4-dione bis(2‧-pyridylhydrazone) (HDBPH), were synthesized out of the 2:1 M Schiff base condensation of 2-hydrazino pyridine respectively with 2,3-butanedione and 3,4-hexanedione. The X-ray crystal structures of both the ligands have been determined. The copper(II) complex of HDBPH has also been synthesized and structurally characterized. HDBPH and its copper(II) complex have thoroughly been characterized through various spectroscopic and analytical techniques. The X-ray crystal structure of the copper complex of HDBPH shows that it is a monomeric Cu(II) complex having 'N4O2' co-ordination chromophore. Interaction of human serum albumin (HSA) with these ligands and their monomeric copper(II) complexes have been studied by various spectroscopic means. The experimental findings show that the ligands as well as their copper complexes are good HSA binders. Molecular docking investigations have also been done to unravel the mode of binding of the species with HSA.

  19. Spectroscopic and molecular docking studies on the interaction of human serum albumin with copper(II) complexes.

    PubMed

    Guhathakurta, Bhargab; Pradhan, Ankur Bikash; Das, Suman; Bandyopadhyay, Nirmalya; Lu, Liping; Zhu, Miaoli; Naskar, Jnan Prakash

    2017-02-15

    Two osazone based ligands, butane-2,3-dione bis(2'-pyridylhydrazone) (BDBPH) and hexane-3,4-dione bis(2'-pyridylhydrazone) (HDBPH), were synthesized out of the 2:1M Schiff base condensation of 2-hydrazino pyridine respectively with 2,3-butanedione and 3,4-hexanedione. The X-ray crystal structures of both the ligands have been determined. The copper(II) complex of HDBPH has also been synthesized and structurally characterized. HDBPH and its copper(II) complex have thoroughly been characterized through various spectroscopic and analytical techniques. The X-ray crystal structure of the copper complex of HDBPH shows that it is a monomeric Cu(II) complex having 'N4O2' co-ordination chromophore. Interaction of human serum albumin (HSA) with these ligands and their monomeric copper(II) complexes have been studied by various spectroscopic means. The experimental findings show that the ligands as well as their copper complexes are good HSA binders. Molecular docking investigations have also been done to unravel the mode of binding of the species with HSA.

  20. Copper(II) coordination properties of the integrin ligand sequence PHSRN and its new β-cyclodextrin conjugates.

    PubMed

    Magrì, Antonio; D'Alessandro, Franca; Distefano, Donatella A; Campagna, Tiziana; Pappalardo, Giuseppe; Impellizzeri, Giuseppe; La Mendola, Diego

    2012-08-01

    The peptide sequence PHSRN is the second cell binding site of the human fibronectin protein, a glycoprotein which plays a critical adhesive role during development, tissue repair and angiogenesis. The copper(II) complexes with the peptide fragment PHSRN were characterized by potentiometric and UV-visible, CD, EPR spectroscopic methods. Thermodynamic and spectroscopic evidences indicate that at physiological pH, only one copper(II) complex species, [CuLH(-2)], is present and the metal ion is bound to one imidazole and two amide nitrogen atoms (N(Im), 2N(-)) in a tetrahedral distorted square planar coordination. Two new β-cyclodextrin-ethylendiamino derivatives with the PHSRN covalently attached were synthesized as multitargeting molecules, able to have a site-specific recognition sequence, to interact with copper(II) ions and to be a potential carrier of hydrophobic drugs. Copper(II) complexes with these β-cyclodextrin derivatives were characterized by means of potentiometric and spectroscopic techniques. The comparison of the experimental parameters determined at different pH values with those obtained for the parent peptide complex species, shows that at physiological pH the ethylendiamino-β-CD moiety does not influence the peptide interaction with copper ions and the β-CD hydrophobic cavity is not blocked, being available to host hydrophobic drugs such as naproxen.

  1. Copper (II) and zinc (II) complexes with flavanone derivatives: Identification of potential cholinesterase inhibitors by on-flow assays.

    PubMed

    Sarria, André Lucio Franceschini; Vilela, Adriana Ferreira Lopes; Frugeri, Bárbara Mammana; Fernandes, João Batista; Carlos, Rose Maria; da Silva, Maria Fátima das Graças Fernandes; Cass, Quezia Bezerra; Cardoso, Carmen Lúcia

    2016-11-01

    Metal chelates strongly influence the nature and magnitude of pharmacological activities in flavonoids. In recent years, studies have shown that a promising class of flavanone-metal ion complexes can act as selective cholinesterase inhibitors (ChEIs), which has led our group to synthesize a new series of flavanone derivatives (hesperidin, hesperetin, naringin, and naringenin) complexed to either copper (II) or zinc (II) and to evaluate their potential use as selective ChEIs. Most of the synthesized complexes exhibited greater inhibitory activity against acetylcholinesterase (AChE) than against butyrylcholinesterase (BChE). Nine of these complexes constituted potent, reversible, and selective ChEIs with inhibitory potency (IC50) and inhibitory constant (Ki) ranging from 0.02 to 4.5μM. Copper complexes with flavanone-bipyridine derivatives afforded the best inhibitory activity against AChE and BChE. The complex Cu(naringin)(2,2'-bipyridine) (11) gave IC50 and Ki values of 0.012±0.002 and 0.07±0.01μM for huAChE, respectively, which were lower than the inhibitory values obtained for standard galanthamine (IC50=206±30.0 and Ki=126±18.0μM). Evaluation of the inhibitory activity of this complex against butyrylcholinesterase from human serum (huBChE) gave IC50 and Ki values of 8.0±1.4 and 2.0±0.1μM, respectively. A Liquid Chromatography-Immobilized Capillary Enzyme Reactor by UV detection (LC-ICER-UV) assay allowed us to determine the IC50 and Ki values and the type of mechanism for the best inhibitors.

  2. Copper(II)-EDTA sorption onto chitosan and its regeneration applying electrolysis.

    PubMed

    Gyliene, O; Nivinskiene, O; Razmute, I

    2006-10-11

    Cu(II)-EDTA (ethylendiaminetetraacetate) complexes are widely used in the manufacture of printed circuit boards. In order to avoid the outlet into the environment the sorption of complexes onto chitosan is proposed. The uptake of both Cu(II) and EDTA proceeds in weakly acidic (pH 3-5) and strongly alkaline (pH > 12) solutions. In acidic solutions EDTA sorption prevails. FT-IR investigations have shown that in acidic solutions the amide bonds between -COOH groups of EDTA and -NH2 groups of chitosan were formed. In alkaline solutions the single EDTA sorption does not proceed. In this media the sorption is enhanced by Cu(II) ions. The possible sorption mechanisms are discussed. The uptake of both Cu(II) and EDTA by chitosan depends on the ratio between them in solutions. EDTA sorption in acidic solutions increases with increase in its concentration while that of Cu(II) decreases. In alkaline solutions the sorption of both Cu(II) and EDTA increases with increase in Cu(II) concentration. The use of electrolysis enables to regenerate chitosan and to reuse it. During electrolysis copper is deposited onto the cathode and EDTA is oxidized onto the anode. The current efficiency depends on the current intensity, the load of chitosan and the pH of the background electrolyte. Electrolysis under the most favorable conditions ensures the 10-cycles regeneration without considerable changes in the sorption properties of chitosan. FT-IR spectra of the initial and regenerated chitosans are similar.

  3. Copper(II) complex formation with a linear peptide encompassing the putative cell binding site of angiogenin.

    PubMed

    La Mendola, Diego; Magrì, Antonio; Vagliasindi, Laura I; Hansson, Örjan; Bonomo, Raffaele P; Rizzarelli, Enrico

    2010-11-28

    Angiogenin is one of the more potent angiogenic factors known, whose activity may be affected by the presence of copper ions. Copper(II) complexes with the peptides encompassing the putative endothelial cell binding domain of angiogenin, Ac-KNGNPHREN-NH(2) and Ac-PHREN-NH(2), have been characterized by potentiometric, UV-vis, CD and EPR spectroscopic methods. The coordination features of all the copper complex species derived by both peptides are practically the same, as predictable because of the presence of a proline residue within their aminoacidic sequence. In particular, Ac-PHREN-NH(2) is really the aminoacidic sequence involved in the binding to copper(II). Thermodynamic and spectroscopic evidence are given that side chain oxygen donor atom of glutamyl residue is involved in the copper binding up to physiological pH. EPR parameters suggest that the carboxylate group is still involved also in the predominant species [Cu(L)H(-2)], the metal coordination environment being probably formed by N(Im), 2N(-), H(2)O in equatorial plane and an oxygen atom from COO(-) in apical position, or vice versa, with the carboxylate oxygen atom in the copper coordination plane and the water molecule confined to one of the apical positions. Moreover, the comparison with the thermodynamic and spectroscopic results in the case of the copper(ii) complex species formed by the single point mutated peptide, Ac-PHRQN-NH(2), provides further evidence of the presence of carboxylate oxygen atom in the copper coordination sphere.

  4. Quinolones and non-steroidal anti-inflammatory drugs interacting with copper(II), nickel(II), cobalt(II) and zinc(II): structural features, biological evaluation and perspectives.

    PubMed

    Psomas, George; Kessissoglou, Dimitris P

    2013-05-14

    The structural features of copper(II), nickel(II), cobalt(II) and zinc(II) complexes with the antimicrobial drugs quinolones and non-steroidal anti-inflammatory drugs (NSAIDs) as ligands are discussed. The binding properties of these complexes to biomolecules (calf-thymus DNA, bovine or human serum albumin) are presented and evaluated. The biological activity (antimicrobial, antioxidant and antiproliferative) of selected complexes is investigated. Further perspectives concerning the synthesis and the biological activity of novel complexes with quinolones or NSAIDs attractive to synthetic chemists, biochemists and/or biologists are presented.

  5. Copper exposure interferes with the regulation of the uptake, distribution and metabolism of sulfate in Chinese cabbage.

    PubMed

    Shahbaz, Muhammad; Tseng, Mei Hwei; Stuiver, C Elisabeth E; Koralewska, Aleksandra; Posthumus, Freek S; Venema, Jan Henk; Parmar, Saroj; Schat, Henk; Hawkesford, Malcolm J; De Kok, Luit J

    2010-04-15

    Exposure of Chinese cabbage (Brassica pekinensis) to enhanced Cu(2+) concentrations (1-10 microM) resulted in leaf chlorosis, a loss of photosynthetic capacity and lower biomass production at > or = 5 microM. The decrease in pigment content was likely not the consequence of degradation, but due to hindered chloroplast development upon Cu exposure. The Cu content of the root increased with the Cu(2+) concentration (up to 40-fold), though only a minor proportion (4%) was transferred to the shoot. The nitrate uptake by the root was substantially reduced at > or = 5 microM Cu(2+). The nitrogen content of the root was affected little at lower Cu(2+) levels, whereas that in the shoot was decreased at > or = 5 microM Cu(2+). Cu affected the uptake, distribution and metabolism of sulfate in Chinese cabbage. The total sulfur content of the shoot was increased at > or = 2 microM Cu(2+), which could be attributed mainly to an increase in sulfate content. Moreover, there was a strong increase in water-soluble non-protein thiol content in the root and, to a lesser extent, in the shoot at > or = 1 microM, which could only partially be ascribed to a Cu-induced enhancement of the phytochelatin content. The nitrate uptake by the root was substantially reduced at > or = 5 microM Cu(2+), coinciding with a decrease in biomass production. However, the activity of the sulfate transporters in the root was slightly enhanced at 2 and 5 microM Cu(2+), accompanied by enhanced expression of the Group 1 high affinity transporter Sultr1;2, and the Group 4 transporters Sultr4;1 and Sultr4;2. In the shoot, there was an induction of expression of Sultr4;2 at 5 and 10 microM Cu(2+). The expression of APS reductase was affected little in the root and shoot up to 10 microM Cu(2+). The upregulation of the sulfate transporters may be due not only to greater sulfur demand at higher Cu levels, but also the consequence of interference by Cu with the signal transduction pathway regulating the expression

  6. Structural characterization of a high affinity mononuclear site in the copper(II)-α-synuclein complex.

    PubMed

    Bortolus, Marco; Bisaglia, Marco; Zoleo, Alfonso; Fittipaldi, Maria; Benfatto, Maurizio; Bubacco, Luigi; Maniero, Anna Lisa

    2010-12-29

    Human α-Synuclein (aS), a 140 amino acid protein, is the main constituent of Lewy bodies, the cytoplasmatic deposits found in the brains of Parkinson's disease patients, where it is present in an aggregated, fibrillar form. Recent studies have shown that aS is a metal binding protein. Moreover, heavy metal ions, in particular divalent copper, accelerate the aggregation process of the protein. In this work, we investigated the high affinity binding mode of truncated aS (1-99) (aS99) with Cu(II), in a stoichiometric ratio, to elucidate the residues involved in the binding site and the role of copper ions in the protein oligomerization. We used Electron Paramagnetic Resonance spectroscopy on the Cu(II)-aS99 complex at pH 6.5, performing both multifrequency continuous wave experiments and pulsed experiments at X-band. The comparison of 9.5 and 95 GHz data showed that at this pH only one binding mode is present. To identify the nature of the ligands, we performed Electron Spin Echo Envelope Modulation, Hyperfine Sublevel Correlation Spectroscopy, and pulsed Davies Electron-Nuclear Double Resonance (Davies-ENDOR) experiments. We determined that the EPR parameters are typical of a type-II copper complex, in a slightly distorted square planar geometry. Combining the results from the different pulsed techniques, we obtained that the equatorial coordination is {N(Im), N(-), H(2)O, O}, where N(im) is the imino nitrogen of His50, N(-) a deprotonated amido backbone nitrogen that we attribute to His50, H(2)O an exchangeable water molecule, and O an unidentified oxygen ligand. Moreover, we propose that the free amino terminus (Met1) participates in the complex as an axial ligand. The MXAN analysis of the XAS k-edge absorption data allowed us to independently validate the structural features proposed on the basis of the magnetic parameters of the Cu(II)-aS99 complex and then to further refine the quality of the proposed structural model.

  7. Novel copper-based therapeutic agent for anti-inflammatory: synthesis, characterization, and biochemical activities of copper(II) complexes of hydroxyflavone Schiff bases.

    PubMed

    Joseph, J; Nagashri, K

    2012-07-01

    Four hydroxyflavone derivatives have been synthesized with the aim of obtaining a good model of superoxide dismutase. Better to mimic the natural metalloenzyme, copper complexes have been designed. The Cu(II) complexes of general formulae, [CuL] where L = 5-hydroxyflavone-o-phenylenediamine (L¹H₂)/m-phenylenediamine (L²H₂) and 3-hydroxyflavone-o-phenylenediamine (L³H₂)/m-phenylenediamine (L⁴H₂) have been synthesized. The structural features have been determined from their analytical and spectral data. All the Cu(II) complexes exhibit square planar geometry. Redox behavior of copper complexes was studied and the present ligand systems stabilize the unusual oxidation state of the copper ion during electrolysis. The in vitro antimicrobial activities of the investigated compounds were tested against the bacterial species Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Proteus vulgaris, and Pseudomonas aeruginosa and fungal species Aspergillus niger, Rhizopus stolonifer, Aspergillus flavus, Rhizoctonia bataicola, and Candida albicans. Superoxide dismutase and anti-inflammatory activities of the copper complexes have also been measured and discussed.

  8. [MORPHOFUNCTIONAL ADJUSTMENT VASCULAR AND CELLULAR COMPONENTS OF THE CEREBELLAR CORTEX IN EXPOSURE TO BODY SULFATES OF COPPER, ZINC AND IRON].

    PubMed

    Grintsova, N; Vasko, L; Kiptenko, L; Gortinsky, A; Murenets, N

    2015-09-01

    In order to analyze the morphological and morphometric reconstructions of the vascular bed, and Purkinje cells of the cerebellar cortex of rats in long-term action (for 90 days) on the body of sulphates of copper, zinc and iron, an experiment was conducted on 48 adult white male rats weighing 200-250 g in age 5-7 months. We used anatomical, morphometric, statistical and common methods of microanatomical research. It was found that the combined effect on the body of sulphates of copper and zinc, and iron in the cerebellum has enough expressive toxicity, which affects the condition of the vascular bed, and Purkinje cells. The degree of morphological transformations is in direct proportion to the duration of the experiment. In the pathogenesis of violations leading role played by hypoxia, develop signs of swelling of the cerebellar cortex with signs hemorrhagic infiltration, the severity of which is maximum on the 60th day of the experiment.

  9. Crystal structures of copper(II) and nickel(II) nitrate and chloride complexes with 4-bromo-2-[(2-hydroxyethylimino)-methyl]phenol

    SciTech Connect

    Chumakov, Yu. M.; Tsapkov, V. I.; Filippova, I. G.; Bocelli, G.; Gulea, A. P.

    2008-07-15

    The crystal structures of {l_brace}4-bromo-2-[(2-hydroxyethylimino)-methyl]phenolo{r_brace}aquacopper(II) nitrate hemihydrate (I), chloro-{l_brace}4-bromo-2-[(2-hydroxyethylimino)-methyl]phenolo{r_brace}copper hemihydrate (II), and chloro-{l_brace}4-bromo-2-[(2-hydroxyethylimino)-methyl]phenolo{r_brace}aquanickel (III) are determined using X-ray diffraction. Crystals of compound I are formed by cationic complexes, nitrate ions, and solvate water molecules. In the cation, the copper atom coordinates the singly deprotonated molecule of tridentate azomethine and the water molecule. The copper complexes are joined into centrosymmetric dimers by the O{sub w}-H...O hydrogen bonds. The crystal structure of compound II is composed of binuclear copper complexes and solvate water molecules. The copper atom coordinates the O,N,O ligand molecule and the chlorine ion, which fulfills a bridging function. The coordination polyhedron of the metal atom is a distorted tetragonal bipyramid in which the vertex is occupied by the chlorine atom of the neighboring complex in the dimer. Compound III is a centrosymmetric dimer complex. The coordination polyhedra of two nickel atoms related via the inversion center are distorted octahedra shared by the edge.

  10. Copper(I)- and copper(0)-promoted homocoupling and homocoupling-hydrodehalogenation reactions of dihalogenoclathrochelate precursors for C-C conjugated iron(II) bis-cage complexes.

    PubMed

    Varzatskii, Oleg A; Shul'ga, Sergey V; Belov, Alexander S; Novikov, Valentin V; Dolganov, Alexander V; Vologzhanina, Anna V; Voloshin, Yan Z

    2014-12-28

    Iron(II) dibromo- and diiodoclathrochelates undergo copper(I)-promoted reductive homocoupling in HMPA at 70-80 °C leading to C-C conjugated dibromo- and diiodo-bis-clathrochelates in high yields. Under the same conditions, their dichloroclathrochelate analog does not undergo the same homocoupling reaction, so the target dichloro-bis-cage product was obtained in high yield via dimerization of its heterodihalogenide iodochloromonomacrobicyclic precursor. The use of NMP as a solvent at 120-140 °C gave the mixture of bis-clathrochelates resulting from a tandem homocoupling-hydrodehalogenation reaction: the initial acetonitrile copper(I) solvato-complex at a high temperature underwent re-solvatation and disproportionation leading to Cu(II) ions and nano-copper, which promoted the hydrodehalogenation process even at room temperature. The most probable pathway of this reaction in situ includes hydrodehalogenation of the already formed dihalogeno-bis-clathrochelate via the formation of reduced anion radical intermediates. As a result, chemical transformations of the iron(II) dihalogenoclathrochelates in the presence of an acetonitrile copper(I) solvato-complex were found to depend both on the nature of halogen atoms in their ribbed chelate fragments and on reaction conditions (i.e. solvent and temperature). The C-C conjugated iron(II) dihalogeno-bis-clathrochelates easily undergo nucleophilic substitution with various N,S-nucleophiles giving ribbed-functionalized bis-cage species. These iron(II) complexes were characterized by elemental analysis, MALDI-TOF mass spectrometry, IR, UV-Vis, (1)H and (13)C NMR spectroscopy, and by X-ray diffraction; their electrochemical properties were studied by cyclic voltammetry. The isomeric shift values in (57)Fe Mössbauer spectra of such cage compounds allowed identifying them as low-spin iron(II) complexes, while those of the quadrupole splitting are the evidence for a significant TP distortion of their FeN6-coordination polyhedra

  11. An experimental and theoretical approach of spectroscopic and structural properties of a new chelidamate copper (II) complex.

    PubMed

    Vural, Hatice; Uçar, İbrahim; Soylu, M Serkan

    2014-03-25

    The crystal structure of new chelidamate complex of copper (II) ion, [Cu(chel)H2O(pym)]·H2O [chel: chelidamate or 4-hydroxypyridine-2,6-dicarboxylate; pym: 2-Pyridylmethanol] has been determined by single crystal X-ray crystallographic method. The complex was characterized by IR and UV-Vis spectroscopic techniques. The magnetic environment of copper (II) ion has been defined by electron paramagnetic technique (EPR). The central copper (II) ion is six-coordinate with a distorted octahedral geometry, which exhibits Jahn-Teller distortions along one of the O-Cu-O axes with tetragonality of 0.81. Chelidamate behaved as a tridentate ligand was bonded to Cu(II) ion through carboxyl oxygens with nitrogen. The crystal structure is stabilized by O-H⋯O hydrogen bond and π-π interactions. Theoretical calculations have been carried out by using the DFT method. The modeling of copper (II) complex was made by geometric optimization. The geometry optimization and EPR study were carried out using the following unrestricted hybrid density functionals: LSDA, BPV86, B3LYP, B3PW91, MPW1PW91 and HCTH. Frontier molecular orbital energies, absorption wavelengths and excitation energy were computed by time dependent DFT (TD-DFT) method with polarizable continuum model. IR spectra were discussed and compared to other relevant complexes together with theoretical results. The natural charges on the atoms and second-order interaction energies were derived from natural bond orbital analysis (NBO).

  12. The haem-copper oxygen reductase of Desulfovibrio vulgaris contains a dihaem cytochrome c in subunit II.

    PubMed

    Lobo, Susana A L; Almeida, Claúdia C; Carita, João N; Teixeira, Miguel; Saraiva, Lígia M

    2008-12-01

    The genome of the sulphate reducing bacterium Desulfovibrio vulgaris Hildenborough, still considered a strict anaerobe, encodes two oxygen reductases of the bd and haem-copper types. The haem-copper oxygen reductase deduced amino acid sequence reveals that it is a Type A2 enzyme, which in its subunit II contains two c-type haem binding motifs. We have characterized the cytochrome c domain of subunit II and confirmed the binding of two haem groups, both with Met-His iron coordination. Hence, this enzyme constitutes the first example of a ccaa3 haem-copper oxygen reductase. The expression of D. vulgaris haem-copper oxygen reductase was found to be independent of the electron donor and acceptor source and is not altered by stress factors such as oxygen exposure, nitrite, nitrate, and iron; therefore the haem-copper oxygen reductase seems to be constitutive. The KCN sensitive oxygen reduction by D. vulgaris membranes demonstrated in this work indicates the presence of an active haem-copper oxygen reductase. D. vulgaris membranes perform oxygen reduction when accepting electrons from the monohaem cytochrome c553, thus revealing the first possible electron donor to the terminal oxygen reductase of D. vulgaris. The physiological implication of the presence of the oxygen reductase in this organism is discussed.

  13. Antibacterial, antibiofilm and antioxidant screening of copper(II)-complexes with some S-alkyl derivatives of thiosalicylic acid. Crystal structure of the binuclear copper(II)-complex with S-propyl derivative of thiosalicylic acid

    NASA Astrophysics Data System (ADS)

    Bukonjić, Andriana M.; Tomović, Dušan Lj.; Nikolić, Miloš V.; Mijajlović, Marina Ž.; Jevtić, Verica V.; Ratković, Zoran R.; Novaković, Slađana B.; Bogdanović, Goran A.; Radojević, Ivana D.; Maksimović, Jovana Z.; Vasić, Sava M.; Čomić, Ljiljana R.; Trifunović, Srećko R.; Radić, Gordana P.

    2017-01-01

    The spectroscopically predicted structure of the obtained copper(II)-complex with S-propyl derivative of thiosalicylic acid was confirmed by X-ray structural study. The binuclear copper(II)-complex with S-propyl derivative of thiosalicylic acid crystallized in two polymorphic forms with main structural difference in the orientation of phenyl rings relative to corresponding carboxylate groups. The antibacterial activity was tested determining the minimum inhibitory concentration (MIC) and the minimum bactericidal concentration (MBC) by using microdilution method. The influence on bacterial biofilm formation was determined by tissue culture plate method. In general, the copper(II)-complexes manifested a selective and moderate activity. The most sensitive bacteria to the effects of Cu(II)-complexes was a clinical isolate of Pseudomonas aeruginosa. For this bacteria MIC and biofilm inhibitory concentration (BIC) values for all tested complexes were in the range or better than the positive control, doxycycline. Also, for the established biofilm of clinical isolate Staphylococcus aureus, BIC values for the copper(II)-complex with S-ethyl derivative of thiosalicylic acid,[Cu2(S-et-thiosal)4(H2O)2] (C3) and copper(II)-complex with S-butyl derivative of thiosalicylic acid, [Cu2(S-bu-thiosal)4(H2O)2] (C5) were in range or better than the positive control. All the complexes acted better against Gram-positive bacteria (Staphylococcus aureus and Staphylococcus aureus ATCC 25923) than Gram-negative bacteria (Proteus mirabilis ATCC 12453, Pseudomonas aeruginosa, and P. aeruginosa ATCC 27855). The complexes showed weak antioxidative properties tested by two methods (1,1-diphenyl-2-picrylhydrazyl (DPPH) and reducing power assay).

  14. 2,4-Dinitrophenylhydrazine functionalized sodium dodecyl sulfate-coated magnetite nanoparticles for effective removal of Cd(II) and Ni(II) ions from water samples.

    PubMed

    Sobhanardakani, Soheil; Zandipak, Raziyeh

    2015-07-01

    2,4-Dinitrophenylhydrazine immobilized on sodium dodecyl sulfate (SDS)-coated magnetite and was used for removal of Cd(II) and Ni(II) ions from aqueous solution. The prepared product was characterized by X-ray diffraction (XRD) analysis, Fourier transform infrared spectroscopy (FT-IR), and scanning electron microscopy (SEM). The size of the nanoparticles according to SEM was obtained around 20-35 nm. In batch tests, the effects of pH, contact time, initial metal concentration, and temperature were studied. The kinetic and equilibrium data were modeled with recently developed models. The adsorption kinetics and isotherms were well fitted by the fractal-like pseudo-second-order model and Langmuir-Freundlich model, respectively. Maximum adsorption capacity by this adsorbent is 255.1 mg g(-1) for Cd(II) ion and 319.6 mg g(-1) for Ni(II) ion at pH 7.0 and 25 °C. The method was successfully applied to the removal of metal cations in real samples (tap water, river water, and petrochemical wastewater).

  15. Crystal structure of bis-(di-methyl-ammonium) hexa-aqua-nickel(II) bis-(sulfate) dihydrate.

    PubMed

    Held, Peter

    2014-11-01

    In the title salt, (C2H8N)2[Ni(H2O)6)](SO4)2·2H2O, the Ni(II) cation is located on a centre of inversion and exhibits a slightly distorted octa-hedral arrangement of water mol-ecules. The Ni-O bond lengths in the complex [Ni(H2O)6](2+) cation show a distribution as in the related Tutton salt (NH4)2[Ni(H2O)6](SO4)2, but are longer in average [2.056 (13) versus 2.037 (12) Å]. The noncoordinating water mol-ecules and di-methyl-ammonium cations connect the sulfate and [Ni(H2O)6](2+) octa-hedra via O-H⋯O and N-H⋯O hydrogen bonds from weak up to medium strength into a three-dimensional framework whereby the complex metal cations and sulfate anions are arranged in sheets parallel (001).

  16. 2,6-Bis(2,6-diethylphenyliminomethyl)pyridine coordination compounds with cobalt(II), nickel(II), copper(II), and zinc(II): synthesis, spectroscopic characterization, X-ray study and in vitro cytotoxicity.

    PubMed

    Martinez-Bulit, Pablo; Garza-Ortíz, Ariadna; Mijangos, Edgar; Barrón-Sosa, Lidia; Sánchez-Bartéz, Francisco; Gracia-Mora, Isabel; Flores-Parra, Angelina; Contreras, Rosalinda; Reedijk, Jan; Barba-Behrens, Norah

    2015-01-01

    Coordination compounds with cobalt(II), nickel(II), copper(II) and zinc(II) and the ligand 2,6-bis(2,6-diethylphenyliminomethyl)pyridine (L) were synthesized and fully characterized by IR and UV-Vis-NIR spectroscopy, elemental analysis, magnetic susceptibility and X-ray diffraction for two representative cases. These novel compounds were designed to study their activity as anti-proliferative drugs against different human cancer cell lines. The tridentate ligand forms heptacoordinated compounds from nitrate metallic salts, where the nitrate acts in a chelating form to complete the seven coordination positions. In vitro cell growth inhibition was measured for Co(II), Cu(II) and Zn(II) complexes, as well as for the free ligand. Upon coordination, the IC50 value of the transition-metal compounds is improved compared to the free ligand. The copper(II) and zinc(II) compounds are the most promising candidates for further in vitro and in vivo studies. The activity against colon and prostate cell lines merits further research, in views of the limited therapeutic options for such cancer types.

  17. Glucosamine sulfate

    MedlinePlus

    ... Glucosamine Sulphate KCl, Glucosamine-6-Phosphate, GS, Mono-Sulfated Saccharide, Poly-(1->3)-N-Acetyl-2-Amino- ... Sulfate de Glucosamine, Sulfate de Glucosamine 2KCl, SG, Sulfated Monosaccharide, Sulfated Saccharide, Sulfato de Glucosamina. Glucosamine Hydrochloride ...

  18. Stability of bromine, iodine monochloride, copper (II) chloride, and nickel (II) chloride intercalated pitch-based graphite fibers

    NASA Technical Reports Server (NTRS)

    Gaier, James R.; Slabe, Melissa E.; Shaffer, Nanette

    1987-01-01

    Four different grades of pitch-based graphite fibers (Amoco P-55, P-75, P-100. and P-120) were intercalated with each of four different intercalates: bromine (Br2), iodine monochloride (ICl), copper (II) chloride (CuCl2), and nickel (II) chloride (NiCl2). The P-55 fibers did not react with Br2 or NiCl2, and the P-75 did not react with NiCl2. The stability of the electrical resistance of the intercalated fibers was monitored over long periods of time in ambient, high humidity (100 percent at 60 C), vacuum (10 to the -6 torr), and high temperature (up to 400 C) conditions. Fibers with lower graphitization form graphite intercalation compounds (GIC's) which are more stable than those with higher graphitization (i.e., P-55 (most stable) greater than P-75 greater than P-100 greater than P-120 (least stable). Br2 formed the most stable GIC's followed in order of decreasing stability by ICl, CuCl2, and NiCl2. While Br2 GIC's had the most stability, ICl had the advantages of forming GIC's with slightly greater reduction in resistance (by about 10%) than Br2, and the ability to intercalate P-55 fiber. Transition metal chlorides are susceptible to water vapor and high temperature. The stability of fibers in composites differs.

  19. Rare configuration of tautomeric benzimidazolecarboxylate ligands in cadmium(II) and copper(II) coordination polymers

    SciTech Connect

    Wu, Jing-Yun; Yang, Ciao-Wei; Chen, Hui-Fang; Jao, Yu-Chen; Huang, Sheng-Ming; Tsai, Chiitang; Tseng, Tien-Wen; Lee, Gene-Hsiang; Peng, Shie-Ming; Lu, Kuang-Lieh

    2011-07-15

    Two Cd(HBimc)-based isomers, [Cd(HBimc{sup N})(HBimc{sup T})(H{sub 2}O)].3.5H{sub 2}O.EtOH (1a.3.5H{sub 2}O.EtOH, H{sub 2}Bimc=1H-benzimidazole-5-carboxylic acid) and [Cd(HBimc{sup N})(HBimc{sup T})(H{sub 2}O)] (1b), and two Cu(HMBimc)-based coordination polymers, [Cu(HMBimc{sup N}){sub 2}(H{sub 2}O)].1/2H{sub 2}O (2.1/2H{sub 2}O, H{sub 2}MBimc=2-methyl-1H-benzimidazole-5-carboxylic acid) and [Cu(HMBimc{sup T}){sub 2}].2THF.H{sub 2}O (3.2THF.H{sub 2}O), were self-assembled from Cd(ClO{sub 4}){sub 2}.6H{sub 2}O/H{sub 2}Bimc and Cu(ClO{sub 4}){sub 2}.6H{sub 2}O/H{sub 2}MBimc systems, respectively. Compound 1a adopts a ladder-like chain structure, comprised of a hydrogen-bond-stabilized Cd{sub 2}(HBimc{sup N}){sub 2}-metallocyclic stair and a 1D straight -(Cd-HBimc{sup T}){sub n}- edge, whereas compound 1b exhibits a 2D (4,4)-rhombus layered structure, intercrossed by 1D -(Cd-HBimc{sup N}){sub n}- chains and -(Cd-HBimc{sup T}){sub n}- chains. Compound 2 shows a 1D double-stranded wave-like chain from two single-stranded wave-like -(Cu-HMBimc{sup N}){sub n}- chains and compound 3 adopts a 2D (4,4)-topological layer structure, intercrossed by subunits of 1D -(Cu-HMBimc{sup T}){sub n}- chains. Interestingly, a pair of tautomeric HBimc building blocks-normal (N or HBimc{sup N}) and tautomer (T or HBimc{sup T})-is simultaneously included in the structures of 1a and 1b, whilst the N- and T-configured HMBimc building blocks are present as separate entities in Cu species, 2 and 3, respectively. The existence of only a tautomer (T) mode of the benzimidazolecarboxylate-based ligand in a Cu(II) network is observed for the first time. - Graphical abstract: A pair of tautomeric HBimc building blocks (normal (N) and tautomer (T)) is found simultaneously in two Cd(II) networks, whereas, the normal and tautomer modes of HMBimc are present as separate entities in two Cu(II) frameworks. The isolation of a Cu(II) network with only a tautomer (T) mode of the benzimidazolecarboxylate

  20. Ternary complexes of copper(II) and cobalt(II) involving nitrite/pyrazole and tetradentate N4-coordinate ligand: Synthesis, characterization, structures and antimicrobial activity

    NASA Astrophysics Data System (ADS)

    Solanki, Ankita; Sadhu, Mehul H.; Kumar, Sujit Baran

    2015-12-01

    Five new mononuclear mixed ligand complexes of the type [Cu(NCCH3)(dbdmp)](ClO4)2, [M(ONO)(dbdmp)]ClO4, [M(pz) (dbdmp)](ClO4)2 where M = Cu(II) and Co(II), pz = 3,5-dimethylpyrazole and dbdmp = N,N-diethyl-N‧,N‧-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)ethane-1,2-diamine have been synthesized and characterized by physico-chemical and spectroscopy studies. The crystal structures of three copper(II) complexes [Cu(NCCH3)(dbdmp)](ClO4)2, [Cu(ONO)(dbdmp)]ClO4 and [Cu(pz)(dbdmp)](ClO4)2 have been determined by single crystal X-ray diffraction studies. Structural analyses reveal the geometry of [Cu(pz)(dbdmp)](ClO4)2 is distorted square pyramidal and other two copper(II) complexes have distorted trigonal bipyramidal geometry. Molecular composition of cobalt(II) complexes have been determined by mass spectral data. The EPR spectra of copper(II) complexes in frozen acetonitrile solution exhibit axial spectra, characteristic of dx2-y2 ground state. Electrochemical studies of copper(II) complexes using glassy carbon as working electrode in acetonitrile solution show Cu(II)/Cu(I) couple with quasi reversible electron transfer versus Ag/Ag+ reference electrode. Antimicrobial activity of all the synthesized complexes were investigated against two Gram positive and two Gram negative bacterial strains.

  1. Adsorption of copper (II), chromium (III), nickel (II) and lead (II) ions from aqueous solutions by meranti sawdust.

    PubMed

    Rafatullah, M; Sulaiman, O; Hashim, R; Ahmad, A

    2009-10-30

    The present study proposed the use of meranti sawdust in the removal of Cu(II), Cr(III), Ni(II) and Pb(II) ions from synthetic aqueous solutions. Batch adsorption studies showed that meranti sawdust was able to adsorb Cu(II), Cr(III), Ni(II) and Pb(II) ions from aqueous solutions in the concentration range 1-200mg/L. The adsorption was favoured with maximum adsorption at pH 6, whereas the adsorption starts at pH 1 for all metal ions. The effects of contact time, initial concentration of metal ions, adsorbent dosage and temperature have been reported. The applicability of Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) isotherm was tried for the system to completely understand the adsorption isotherm processes. The adsorption kinetics tested with pseudo-first-order and pseudo-second-order models yielded high R(2) values from 0.850 to 0.932 and from 0.991 to 0.999, respectively. The meranti sawdust was found to be cost effective and has good efficiency to remove these toxic metal ions from aqueous solution.

  2. Optical, thermal, mechanical and dielectric properties of hexakis(urea)cobalt(II) sulfate monohydrate: A semiorganic crystal

    NASA Astrophysics Data System (ADS)

    Muthu, K.; Rajasekar, M.; Meenakshisundaram, SP.

    2013-04-01

    Single crystals of hexakis(urea)cobalt(II) sulfate monohydrate have been grown by slow evaporation solution growth technique at room temperature. The single crystal X-ray diffraction study reveals that the crystal belongs to orthorhombic system with noncentrosymmetric space group Pca21 and the cell parameters are, a=15.0549(6) Å, b=7.2105(3) Å, c=20.0284(9) Å, V=2174.15 (16) Å3 and Z=4. The functional groups of the metal-urea complex were confirmed by Fourier transform infrared spectroscopy. The powder X-ray diffraction study reveals the crystallinity of the as-grown material. The band-gap energy of the specimen is estimated by Kubelka-Munk algorithm. The dielectric results indicate an increase in dielectric and conductivity parameters with an increase of temperature at all frequencies. The crystal is further characterized by mechanical and thermal analysis.

  3. Polymeric networks of copper(II) phenylmalonate with heteroaromatic n-donor ligands: synthesis, crystal structure, and magnetic properties.

    PubMed

    Pasán, Jorge; Sanchiz, Joaquín; Ruiz-Pérez, Catalina; Lloret, Francesc; Julve, Miguel

    2005-10-31

    Two new phenylmalonate-bridged copper(II) complexes with the formulas [Cu(4,4'-bpy)(Phmal)](n).2nH(2)O (1) and [Cu(2,4'-bpy)(Phmal)(H(2)O)](n)() (2) (Phmal = phenylmalonate dianion, 4,4'-bpy = 4,4'-bipyridine, 2,4'-bpy = 2,4'-bipyridine) have been synthesized and characterized by X-ray diffraction. Complex 1 crystallizes in monoclinic space group P2(1), Z = 4, with unit cell parameters of a = 9.0837(6) Angstroms, b = 9.3514(4) Angstroms, c = 11.0831(8) Angstroms, and beta = 107.807(6) degrees , whereas complex 2 crystallizes in orthorhombic space group C2cb, Z = 8, with unit cell parameters of a = 10.1579(7) Angstroms, b = 10.3640(8) Angstroms, and c = 33.313(4) Angstroms. The structures of 1 and 2 consist of layers of copper(II) ions with bridging bis-monodentate phenylmalonate (1 and 2) and 4,4'-bpy (1) ligands and terminal monodentate 2,4'-bpy (2) groups. Each layer in 1 contains rectangles with dimensions of 11.08 x 4.99 Angstroms(2), the edges being defined by the Phmal and 4,4'-bpy ligands. The intralayer copper-copper separations in 1 through the anti-syn equatorial-apical carboxylate-bridge and the 4,4'-bpy molecule are 4.9922(4) and 11.083(1) Angstroms, respectively. The anti-syn equatorial-equatorial carboxylate bridge links the copper(II) atoms in complex 2 within each layer with a mean copper-copper separation of 5.3709(8) Angstroms. The presence of 2,4'-bpy as a terminal ligand accounts for the large interlayer separation of 15.22 Angstroms. The copper(II) environment presents a static pseudo-Jahn-Teller disorder which has been studied by EPR and low-temperature X-ray diffraction. Magnetic susceptibility measurements of both compounds in the temperature range 2-290 K show the occurrence of weak antiferromagnetic [J = -0.59(1) cm(-1) (1)] and ferromagnetic [J = +0.77(1) cm(-1) (2)] interactions between the copper(II) ions. The conformation of the phenylmalonate-carboxylate bridge and other structural factors, such as the planarity of the exchange

  4. Hexadentate bispidine derivatives as versatile bifunctional chelate agents for copper(II) radioisotopes.

    PubMed

    Juran, Stefanie; Walther, Martin; Stephan, Holger; Bergmann, Ralf; Steinbach, Jörg; Kraus, Werner; Emmerling, Franziska; Comba, Peter

    2009-02-01

    The preparation and use of bispidine derivatives (3,7-diazabicyclo[3.3.1]nonane) as chelate ligands for radioactive copper isotopes for diagnosis (64Cu) or therapy (67Cu) are reported. Starting from the hexadentate bispidine-based bis(amine)tetrakis(pyridine) ligand 1 with a keto and two ester substituents, the corresponding mono-ol 2 and two dicarboxylic acid derivatives 3 and 5 have been synthesized. A range of techniques, including single-crystal X-ray structure analysis, UV/vis spectroscopy, cyclic voltammetry, thin-layer- (TLC), and high-performance liquid chromatography (HPLC), have been used to characterize the structure and stability of the copper(II)-bispidine complexes. A rapid formation (within 1 min) of stable copper(II)-bispidine complexes under mild conditions (ambient temperature, aqueous solution) has been observed. Challenge experiments of these complexes in the presence of a high excess of competing ligands, such as glutathione, cyclam, or superoxide dismutase (SOD), as well as in rat plasma, gave no evidence of demetalation or transchelation. The bifunctional bispidine derivative 5 can be readily functionalized with biologically active molecules at the pendant carboxylate groups. The coupling of a bombesin analogue betahomo-Glu-betaAla-betaAla-[Cha(13),Nle(14)]BBN(7-14), by condensation of a carboxylate of the bispidine backbone with the N-terminus of the peptide produced the bifunctional ligand 6. The radiocopper(II) complex of this bombesin-bispidine conjugate has a considerable hydrophilicity (log D(o/w) < -2.4), and this leads to a very fast blood clearance (blood: 0.28 +/- 0.02 SUV, 1 h p.i.), low liver tissue accumulation (liver: 1.20 +/- 0.27 SUV, 1 h p.i.), and rapid renal-urinary excretion (kidneys: 6.06 +/- 2.96 SUV, 1 h p.i.) as shown by biodistribution studies of 64Cu-6 in Wistar rats. Preliminary in vivo studies of 64Cu-6 in NMRI nu/nu mice, bearing the human prostate tumor PC-3 showed an accumulation of the conjugate in the tumor (2

  5. Role of Fe(II), phosphate, silicate, sulfate, and carbonate in arsenic uptake by coprecipitation in synthetic and natural groundwater.

    PubMed

    Ciardelli, Mark C; Xu, Huifang; Sahai, Nita

    2008-02-01

    Competitive effects of phosphate, silicate, sulfate, and carbonate on As(III) and As(V) removal at pH approximately 7.2 have been investigated to test the feasibility of Fe(II)(aq) and hydroxylapatite crystals as inexpensive and potentially efficient agents for remediation of contaminated well-water, using Bangladesh as a type study. Arsenic(III) removal approximately 50-55% is achieved, when Fe(II)(aq) oxidizes to Fe(III) and precipitates as Fe(OH)3 at 25 degrees C and 3h reaction time, in the presence of all the oxyanion. Similar results were obtained for well-water samples from two sites in Bangladesh. Heating at 95 degrees C for 24h results in 70% As(III) uptake due to precipitation of magnesian calcite. A two-step process, Fe(II) oxidation and Fe(OH)3 precipitation at 25 degrees C for 2h, followed by magnesian calcite precipitation at 95 degrees C for 3h, yields approximately 65% arsenic removal while reducing the expensive heating period. In the absence of silicate, up to 70% As(III) uptake occurs at 25 degrees C. In all cases, As(III) was oxidized to As(V) in solution by dissolved oxygen and the reaction rate was probably promoted by intermediates formed during Fe(II) oxidation. Iron-catalyzed oxidation of As(III) by oxygen and hydrogen peroxide is pH-dependent with formation of oxidants in the Fenton reaction. Buffering pH at near-neutral values by dissolved carbonate and hydroxylapatite seeds is important for faster Fe(II) oxidation kinetics ensuring rapid coprecipitation of As as As(V) in the ferric phases.

  6. Simultaneous photoreductive removal of copper (II) and selenium (IV) under visible light over spherical binary oxide photocatalyst.

    PubMed

    Aman, Noor; Mishra, T; Hait, J; Jana, R K

    2011-02-15

    Waste water of copper mines and copper processing plant contains both copper and selenium ions with other contaminants. In this paper simultaneous photoreductive removal of copper (II) and selenium (IV) is studied for the first time using spherical binary oxide photocatalysts under visible light. All the synthesized materials are found to be mesoporous in nature with reasonably high surface area. Among a range of hole scavengers, only EDTA (ethylene diamine tetraacetic acid) and formic acid are found to be the most active for the reduction reaction. A comparative study is carried out using both the hole scavengers varying reaction time, concentration, pH etc. For a single contaminant, EDTA is found to be the best for Cu(II) reduction whereas formic acid is the best for Se(IV) reduction. In a mixed solution both EDTA and formic acid perform very well under visible light irradiation. Highest photocatalytic reduction in a mixed solution is observed at pH 3. Among all the synthesized materials, TiZr-10 performs as the best photocatalyst for both Cu(II) and Se(IV) reduction. However under UV light, Degussa P25 performs slightly better than TiZr-10. Present study shows that 100 ppm of mixed solution can be removed under visible light in 40 min of reaction using TiZr-10 as catalyst. Photodeposited material is found to be copper selenide rather than pure copper and selenium metal. This indicates that the waste water containing copper and selenium ions can be efficiently treated under visible or solar light.

  7. Electronic Structure of a Cu(II)-Alkoxide Complex Modeling Intermediates in Copper-Catalyzed Alcohol Oxidations.

    PubMed

    Hayes, Ellen C; Porter, Thomas R; Barrows, Charles J; Kaminsky, Werner; Mayer, James M; Stoll, Stefan

    2016-03-30

    In the copper-catalyzed oxidation of alcohols to aldehydes, a Cu(II)-alkoxide (Cu(II)-OR) intermediate is believed to modulate the αC-H bond strength of the deprotonated substrate to facilitate the oxidation. As a structural model for these intermediates, we characterized the electronic structure of the stable compound Tp(tBu)Cu(II)(OCH2CF3) (Tp(tBu) = hydro-tris(3-tert-butyl-pyrazolyl)borate) and investigated the influence of the trifluoroethoxide ligand on the electronic structure of the complex. The compound exhibits an electron paramagnetic resonance (EPR) spectrum with an unusually large gzz value of 2.44 and a small copper hyperfine coupling Azz of 40 × 10(-4) cm(-1) (120 MHz). Single-crystal electron nuclear double resonance (ENDOR) spectra show that the unpaired spin population is highly localized on the copper ion (≈68%), with no more than 15% on the ethoxide oxygen. Electronic absorption and magnetic circular dichroism (MCD) spectra show weak ligand-field transitions between 5000 and 12,000 cm(-1) and an intense ethoxide-to-copper charge transfer (LMCT) transition at 24,000 cm(-1), resulting in the red color of this complex. Resonance Raman (rR) spectroscopy reveals a Cu-O stretch mode at 592 cm(-1). Quantum chemical calculations support the interpretation and assignment of the experimental data. Compared to known Cu(II)-thiolate and Cu(II)-alkylperoxo complexes from the literature, we found an increased σ interaction in the Cu(II)-OR bond that results in the spectroscopic features. These insights lay the basis for further elucidating the mechanism of copper-catalyzed alcohol oxidations.

  8. Electronic Structure of a CuII-Alkoxide Complex Modeling Intermediates in Copper-Catalyzed Alcohol Oxidations

    PubMed Central

    Hayes, Ellen C.; Porter, Thomas R.; Barrows, Charles J.; Kaminsky, Werner; Mayer, James M.; Stoll, Stefan

    2016-01-01

    In the copper-catalyzed oxidation of alcohols to aldehydes, a CuII-alkoxide (CuII-OR) intermediate is believed to modulate the αC-H bond strength of the deprotonated substrate to facilitate the oxidation. As a structural model for these intermediates, we characterized the electronic structure of the stable compound TptBuCuII(OCH2CF3) (TptBu = (hydro-tris (3-tert-butyl-pyrazolyl) borate) and investigated the influence of the trifluoroethoxide ligand on the electronic structure of the complex. The compound exhibits an electron paramagnetic resonance (EPR) spectrum with an unusually large gzz value of 2.44 and a small copper hyperfine coupling Azz of 40·10−4 cm−1 (120 MHz). Single-crystal electron nuclear double resonance (ENDOR) spectra show that the unpaired spin population is highly localized on the copper ion (≈ 68 %), with no more than 15 % on the ethoxide oxygen. Electronic absorption and magnetic circular dichroism (MCD) spectra show weak ligand-field transitions between 5000 and 12000 cm−1 and an intense ethoxide-to-copper charge transfer (LMCT) transition at 24000 cm−1, resulting in the red color of this complex. Resonance Raman (rR) spectroscopy reveals a Cu-O stretch mode at 592 cm−1. Quantum chemical calculations support the interpretation and assignment of the experimental data. Compared to known CuII-thiolate and CuII-alkylperoxo complexes from the literature, we found an increased σ interaction in the CuII-OR bond that results in the spectroscopic features. These insights lay the basis for further elucidating the mechanism of copper-catalyzed alcohol oxidations. PMID:26907976

  9. Synthesis, crystallographic characterization and electrochemical property of a copper(II) complex of the anticancer agent elesclomol.

    PubMed

    Vo, Nha Huu; Xia, Zhiqiang; Hanko, Jason; Yun, Tong; Bloom, Steve; Shen, Jianhua; Koya, Keizo; Sun, Lijun; Chen, Shoujun

    2014-01-01

    Elesclomol is a novel anticancer agent that has been evaluated in a number of late stage clinical trials. A new and convenient synthesis of elesclomol and its copper complex is described. X-ray crystallographic characterization and the electrochemical properties of the elesclomol copper(II) complex are discussed. The copper(II) cation is coordinated in a highly distorted square-planar geometry to each of the sulphur and amide nitrogen atoms of elesclomol. Electrochemical measurements demonstrate that the complex undergoes a reversible one-electron reduction at biologically accessible potentials. In contrast the free elesclomol is found electrochemically inactive. This evidence is in strong support of the mechanism of action we proposed for the anticancer activity of elesclomol.

  10. Anion-induced structural transformation of a sulfate-incorporated 2D Cd(II)–organic framework

    SciTech Connect

    Lee, Li-Wei; Luo, Tzuoo-Tsair; Wang, Chih-Min; Lee, Gene-Hsiang; Peng, Shie-Ming; Liu, Yen-Hsiang; Lee, Sheng-Long; Lu, Kuang-Lieh

    2016-07-15

    A Cd(II)–organic framework {[Cd_2(tpim)_4(SO_4)(H_2O)_2]·(SO_4)·21H_2O}{sub n} (1) was synthesized by reacting CdSO{sub 4}·8/3H{sub 2}O and 2,4,5-tri(4-pyridyl)imidazole (tpim) under hydrothermal conditions. A structural analysis showed that compound 1 adopts a layered structure in which the [Cd(tpim){sub 2}]{sub n} chains are linked by sulfate anions. These 2D layers are further packed into a 3D supramolecular framework via π–π interactions. The structure contains two types of SO{sub 4}{sup 2−} anions, i.e., bridging SO{sub 4}{sup 2−} and free SO{sub 4}{sup 2−} anions, the latter of which are included in the large channels of the framework. Compound 1 exhibits interesting anion exchange behavior. In the presence of SCN{sup −} anions, both the bridging and free SO{sub 4}{sup 2−} anions in 1 were completely exchanged by SCN{sup −} ligands to form a 1D species [Cd(tpim){sub 2}(SCN){sub 2}] (1A), in which the SCN{sup –} moieties function as a monodentate ligand. On the other hand, when compound 1 was ion exchanged with N{sub 3}{sup −} anions in aqueous solution, the bridging SO{sub 4}{sup 2−} moieties remained intact, and only the free guest SO{sub 4}{sup 2−} were replaced by N{sub 3}{sup −} anions. The gas adsorption behavior of the activated compound 1 was also investigated. - Highlights: • An interesting anion-induced structural transformation of a sulfate-incorporated 2D Cd(II)–organic framework is reported. • The sulfate-incorporated 2D layer compound exhibits very different anion exchange behavior with respect to SCN{sup −} and N{sub 3}{sup −}. • Both the bridging and free SO{sub 4}{sup 2−} anions in the 2D structure were completely exchanged by SCN{sup −} ligands, resulting in the formation of a 1D species. However, in the case of N{sub 3}{sup −} anions, only the free guest SO{sub 4}{sup 2−} in the structure was replaced.

  11. Interaction of a copper (II) complex containing an artificial sweetener (aspartame) with calf thymus DNA.

    PubMed

    Shahabadi, Nahid; Khodaei, Mohammad Mehdi; Kashanian, Soheila; Kheirdoosh, Fahimeh

    2014-01-01

    A copper (II) complex containing aspartame (APM) as ligand, Cu(APM)2Cl2⋅2H2O, was synthesized and characterized. In vitro binding interaction of this complex with native calf thymus DNA (CT-DNA) was studied at physiological pH. The interaction was studied using different methods: spectrophotometric, spectrofluorometric, competition experiment, circular dichroism (CD) and viscosimetric techniques. Hyperchromicity was observed in UV absorption band of Cu(APM)2Cl2⋅2H2O. A strong fluorescence quenching reaction of DNA to Cu(APM)2Cl2⋅2H2O was observed and the binding constants (Kf) and corresponding numbers of binding sites (n) were calculated at different temperatures. Thermodynamic parameters, enthalpy change (ΔH) and entropy change (ΔS) were calculated to be+89.3 kJ mol(-1) and+379.3 J mol(-1) K(-1) according to Van't Hoff equation which indicated that reaction is predominantly entropically driven. Experimental results from spectroscopic methods were comparable and further supported by viscosity measurements. We suggest that Cu(APM)2Cl2⋅2H2O interacts with calf thymus DNA via a groove interaction mode with an intrinsic binding constant of 8×10+4 M(-1). Binding of this copper complex to DNA was found to be stronger compared to aspartame which was studied recently.

  12. Mechanism of copper(II)-induced misfolding of Parkinson's disease protein.

    PubMed

    Rose, Frisco; Hodak, Miroslav; Bernholc, Jerzy

    2011-01-01

    α-synuclein (aS) is a natively unfolded pre-synaptic protein found in all Parkinson's disease patients as the major component of fibrillar plaques. Metal ions, and especially Cu(II), have been demonstrated to accelerate aggregation of aS into fibrillar plaques, the precursors to Lewy bodies. In this work, copper binding to aS is investigated by a combination of quantum and molecular mechanics simulations. Starting from the experimentally observed attachment site, several optimized structures of Cu-binding geometries are examined. The most energetically favorable attachment results in significant allosteric changes, making aS more susceptible to misfolding. Indeed, an inverse kinematics investigation of the configuration space uncovers a dynamically stable β-sheet conformation of Cu-aS that serves as a nucleation point for a second β-strand. Based on these findings, we propose an atomistic mechanism of copper-induced misfolding of aS as an initial event in the formation of Lewy bodies and thus in PD pathogenesis.

  13. Chiral copper(II) complex based on natural product rosin derivative as promising antitumour agent.

    PubMed

    Fei, Bao-Li; Huang, Zhi-Xiang; Xu, Wu-Shuang; Li, Dong-Dong; Lu, Yang; Gao, Wei-Lin; Zhao, Yue; Zhang, Yu; Liu, Qing-Bo

    2016-07-01

    To evaluate the biological preference of chiral drug candidates for molecular target DNA, the synthesis and characterization of a chiral copper(II) complex (2) of a chiral ligand N,N'-(pyridin-2-ylmethylene) dehydroabietylamine (1) was carried out. The interactions of 1 and 2 with salmon sperm DNA were investigated by viscosity measurements, UV, fluorescence and circular dichroism (CD) spectroscopic techniques. Absorption spectral, emission spectral and viscosity analysis reveal that 1 and 2 interacted with DNA through intercalation and 2 exhibited a higher DNA binding ability. In the absence/presence of ascorbic acid, 1 and 2 cleaved supercoiled pBR322 DNA by single-strand and 2 displayed stronger DNA cleavage ability. In addition, in vitro cytotoxicity of 1 and 2 against HeLa, SiHa, HepG-2 and A431 cancer cell lines study show that they exhibited effective cytotoxicity against the tested cell lines, notably, 2 showed a superior cytotoxicity than the widely used drug cisplatin under identical conditions, indicating it has the potential to act as effective anticancer drug. Flow cytometry analysis indicates 2 produced death of HeLa cancer cells through an apoptotic pathway. Cell cycle analysis demonstrates that 2 mainly arrested HeLa cells at the S phase. The study represents the first step towards understanding the mode of the promising chiral rosin-derivative based copper complexes as chemotherapeutics.

  14. Copper(II) complexes with phenoxyalkanoic acids and nitrogen donor heterocyclic ligands: structure and bioactivity.

    PubMed

    Dendrinou-Samara, C; Psomas, G; Raptopoulou, C P; Kessissoglou, D P

    2001-01-01

    The copper complexes with the phenoxyalkanoic acids MCPA, 2,4-D, 2,4,5-T and 2,4-DP in the presence of a nitrogen donor heterocyclic ligand, phen or bipyam, were prepared and characterized. Interaction of Cu(II) with phenoxyalkanoic acids and bipyam leads to dinuclear or uninuclear neutral complexes while in the presence of phen uninuclear neutral or cationic forms have been isolated. The crystal structure of bis(1,10-phenanthroline)(2-methyl-4-chloro-phenoxyacetato)copper(ll) chloride-methanol(1/1)-water(1/0.6), 1 has been determined and refined by least-squares methods using three-dimensional MoK, data. 1 crystallizes in space group P1, in a cell of dimensions a = 14.577(6)A, b = 1 1.665(5) A, c = 12.249(6) A, alpha = 98.38( 1)degrees, beta = 112.18( 1) degrees, gamma = 104.56(1 ) degrees, V= 1,798( 1) A3 and Z= 2. The cyclic voltammograms of uninuclear cationic complexes in dmf exhibit an extra cathodic wave due to the chloride ion. The available evidence supports an increasing antimicrobial effeciency for the cationic complexes.

  15. Synthesis and characterization of cobalt(II), nickel(II), copper(II) and zinc(II) complexes with Schiff base derived from 4-amino-3-mercapto-6-methyl-5-oxo-1,2,4-triazine.

    PubMed

    Singh, Kiran; Barwa, Manjeet Singh; Tyagi, Parikshit

    2007-03-01

    A few (1:1) and (1:2) metal complexes of cobalt(II), nickel(II), copper(II) and zinc(II) have been isolated with ligand derived from the condensation of 4-amino-3-mercapto-6-methyl-5-oxo-1,2,4-triazine with 2-acetylpyridine (L(1)) and characterized by elemental analysis, conductivity measurements, infrared, electronic, (1)H NMR spectral data, magnetic and thermogravimetric analyses. Due to insolubility in water and most of the common organic solvents and infusibility at higher temperatures, all the complexes are thought to be polymeric in nature. A square-planar geometry was suggested for copper(II) and octahedral proposed for cobalt(II), nickel(II) and zinc(II). Some of the chemically synthesized compounds have been screened in vitro against the three Gram-positive (Staphylococcus aureus, Staphylococcus epidermidis and Bacillus subtilis) and two Gram-negative (Salmonella typhi and Escherichia coli) organisms. It is observed that the coordination of metal ion has pronounced effect on the microbial activities of the ligand. The metal complexes have higher antimicrobial effect than the free ligands.

  16. Characterization of sodium dodecyl sulfate modified iron pillared montmorillonite and its application for the removal of aqueous Cu(II) and Co(II).

    PubMed

    Li, Shu-Zhen; Wu, Ping-Xiao

    2010-01-15

    Anionic surfactant modified Fe-pillared montmorillonites were prepared by Fe-hydrate solution and sodium dodecyl sulfate (SDS) solution. These organo-inorgano complex montmorillonites were divided into three types (CM1, CM2 and CM3) depending on different intercalation processes. X-ray diffraction spectra, the Fourier transform infrared (FTIR) spectra were used to analyze the structure of the raw and modified montmorillonites. X-ray photoelectron spectra of the samples have been studied to determine spectral characteristics to allow the identification of Fe(III) hydroxide. The specific surface area of the host montmorillonite (M0) is 73.2m(2)/g, while for the modified montmorillonites it is 114.0m(2)/g, 117.2m(2)/g, and 115.8m(2)/g, respectively. The mesopore volumes of the montmorillonites decrease after modification. Ions of copper and cobalt were selected as adsorbates to evaluate the adsorption performance of each montmorillonite. The adsorption data was analyzed by both Freundlich and Langmuir isotherm models and the data was well fit by the Langmuir isotherm model. The adsorption was efficient and significantly influenced by metal speciation, metal concentration, contact time, and pH. Higher adsorption capacity of the modified montmorillonites were obtained at pH 5-6. The results of desorption indicated that the metal ions were covalently bound to the modified montmorillonites.

  17. Copper(II) interaction with peptide fragments of histidine-proline-rich glycoprotein: Speciation, stability and binding details.

    PubMed

    La Mendola, Diego; Magrì, Antonio; Santoro, Anna Maria; Nicoletti, Vincenzo G; Rizzarelli, Enrico

    2012-06-01

    GHHPH is the peptide repeat present in histidine-proline rich glycoprotein (HPRG), a plasma glycoprotein involved in angiogenesis process. The copper(II) ions interaction with mono (Ac-GHHPHG-NH(2)) and its bis-repeat (Ac-GHHPHGHHPHG-NH(2)) was investigated by means of potentiometric and spectroscopic techniques. To single out the copper(II) coordination environments of different species formed with Ac-GHHPHG-NH(2), three single point mutated peptides were also synthesized and their ability to coordinate Cu(2+) investigated. Ac-GHHPHG-NH(2) binds Cu(2+) by the imidazole side chain and the amide nitrogen deprotonation that takes place towards the N-terminus. The bis-repeat is able to bind Cu(2+) more efficiently than Ac-GHHPHG-NH(2). This difference is not only due to the number of His residues in the sequence but also to the different binding sites. In fact, the comparison of the potentiometric and spectroscopic data of the copper(II) complexes with a bis-repeatPeg construct Ac-(GHHPHG)-Peg-(GHHPHG)-NH(2) and those of the metal complexes with Ac-HGHH-NH(2), indicates that the central HGHH amino acid sequence is the main copper(II) binding site.

  18. Quantitative prediction of nuclear-spin-diffusion-limited coherence times of molecular quantum bits based on copper(ii).

    PubMed

    Lenz, S; Bader, K; Bamberger, H; van Slageren, J

    2017-04-06

    We have investigated the electron spin dynamics in a series of copper(ii) β-diketonate complexes both in frozen solutions and doped solids. Double digit microsecond coherence times were found at low temperatures. We report quantitative simulations of the coherence decays solely based on the crystal structure of the doped solids.

  19. Correlation of Electronic and Geometric Structure in Mononuclear Copper(II) Superoxide Complexes

    PubMed Central

    Ginsbach, Jake W.; Peterson, Ryan L.; Cowley, Ryan E.; Karlin, Kenneth D.; Solomon, Edward I.

    2013-01-01

    The geometry of mononuclear copper(II) superoxide complexes has been shown to determine their ground state where side-on bonding leads to a singlet ground state and end-on complexes have triplet ground states. In apparent contrast to this trend, the recently synthesized (HIPT3tren)CuII–O2•− (1) was proposed to have an end-on geometry and a singlet ground state. However, re-examination of 1 with resonance Raman (rR), magnetic circular dichroism (MCD), and 2H NMR spectroscopy indicates that 1 is in fact an end-on superoxide species with a triplet ground state that results from the single CuII–O2•− bonding interaction being weaker than the spin pairing energy. PMID:24164429

  20. Magnetic properties of copper(II) complexes containing peptides. Crystal structure of [Cu(phe-leu)

    NASA Astrophysics Data System (ADS)

    Sanchiz, J.; Kremer, C.; Torre, M. H.; Facchin, G.; Kremer, E.; Castellano, E. E.; Ellena, J.

    2006-09-01

    A novel copper(II) complex containing the peptide phe-leu has been prepared and characterized. The crystal structure of [Cu(phe-leu)] ( 1) was determined by X-ray diffraction. The presence of carboxylate and amido bridges allows the formation of an extended 2D arrangement. This structure is similar to those found in [Cu(gly-val)] · 1/2H 2O ( 2), [Cu(val-gly)] ( 3), [Cu(val-phe)] ( 4), and [Cu(phe-phe)] ( 5). The magnetic properties of compounds 1- 5 were studied and analyzed comparatively. The experimental data show that the magnetic interactions are mainly transmitted through μ 2-COO - bridges, being ferromagnetic for 1 and 3, and antiferromagnetic for 2, 4 and 5.

  1. Coordination chemistry, thermodynamics and DFT calculations of copper(II) NNOS Schiff base complexes.

    PubMed

    Esmaielzadeh, Sheida; Azimian, Leila; Shekoohi, Khadijeh; Mohammadi, Khosro

    2014-12-10

    Synthesis, magnetic and spectroscopy techniques are described for five copper(II) containing tetradentate Schiff bases are synthesized from methyl-2-(N-2'-aminoethane), (1-methyl-2'-aminoethane), (3-aminopropylamino)cyclopentenedithiocarboxylate. Molar conductance and infrared spectral evidences indicate that the complexes are four-coordinate in which the Schiff bases are coordinated as NNOS ligands. Room temperature μeff values for the complexes are 1.71-1.80B.M. corresponding to one unpaired electron respectively. The formation constants and free energies were measured spectrophotometrically, at constant ionic strength 0.1M (NaClO4), at 25˚C in DMF solvent. Also, the DFT calculations were carried out to determine the structural and the geometrical properties of the complexes. The DFT results are further supported by the experimental formation constants of these complexes.

  2. EXAFS Studies of Some Copper(II) Mixed-Ligand Complexes

    SciTech Connect

    Joshi, S. K.; Katare, R. K.; Shrivastava, B. D.

    2007-02-02

    X-ray K-absorption spectroscopic studies have been carried out on copper (II) mixed-ligand complexes with glutamic acid and aspartic acid as the primary ligands, where as water, pyridine, imidazole and benz-imidazole have been used as secondary ligands. Chemical shifts obtained from the X-ray absorption data have indicated that the glutamic acid complexes are more ionic as compared to their corresponding aspartic acid complexes having similar secondary ligands. Further, we have estimated the average metal-ligand bond distances from the from structure data. For the different complexes studied under the present investigation, the studies reveal that the bonding parameter {alpha}1 decreases with the increase in the percentage covalency of the metal-ligand bond. Thus, the bonding parameter {alpha}1 may be used for the estimation of percentage covalency of the metal-ligand bond in other similar complexes.

  3. Antimalarial, antimicrobial, cytotoxic, DNA interaction and SOD like activities of tetrahedral copper(II) complexes

    NASA Astrophysics Data System (ADS)

    Mehta, Jugal V.; Gajera, Sanjay B.; Patel, Mohan N.

    2015-02-01

    The mononuclear copper(II) complexes with P, O-donor ligand and different fluoroquinolones have been synthesized and characterized by elemental analysis, electronic spectra, TGA, EPR, FT-IR and LC-MS spectroscopy. An antimicrobial efficiency of the complexes has been tested against five different microorganisms in terms of minimum inhibitory concentration (MIC) and displays very good antimicrobial activity. The binding strength and binding mode of the complexes with Herring Sperm DNA (HS DNA) have been investigated by absorption titration and viscosity measurement studies. The studies suggest the classical intercalative mode of DNA binding. Gel electrophoresis assay determines the ability of the complexes to cleave the supercoiled form of pUC19 DNA. Synthesized complexes have been tested for their SOD mimic activity using nonenzymatic NBT/NADH/PMS system and found to have good antioxidant activity. All the complexes show good cytotoxic and in vitro antimalarial activities.

  4. Zero thermal expansion in a flexible, stable framework : tetramethylammonium copper(I) zinc(II) cyanide.

    SciTech Connect

    Phillips, A. E.; Halder, G. J.; Chapman, K. W.; Goodwin, A. L.; Kepert, C. J.; Univ. Sydney; Univ. Cambridge

    2010-01-13

    Tetramethylammonium copper(I) zinc(II) cyanide, which consists of N(CH{sub 3}){sub 4}{sup +} ions trapped within a cristobalite-like metal cyanide framework, has been studied by variable-temperature powder and single-crystal X-ray diffraction. Its coefficient of thermal expansion is approximately zero over the temperature range 200-400 K and comparable with the best commercial zero thermal expansion materials. The atomic displacement parameters, apparent bond lengths, and structure of a low-temperature, low-symmetry phase reveal that the low-energy vibrational modes responsible for this behavior maintain approximately rigid Zn coordination tetrahedra but involve significant distortion of their Cu counterparts.

  5. Influence of molybdenum and sulfate supplementation and withdrawal of diets containing high copper broiler litter on tissue copper levels in ewes.

    PubMed

    Olson, K J; Fontenot, J P; Failla, M L

    1984-07-01

    Thirty-six mature, nongestating, crossbred ewes were allotted randomly to three diets for 140 d: basal (six ewes); 50% basal and 50% broiler litter, dry basis (24 ewes) and 50% basal and 50% deep stacked broiler litter with the addition of 25 ppm molybdenum (Mo) and 5 g sulfate (SO4)/kg feed (six ewes). The control diet and the broiler litter contained 8 and 257 ppm Cu, dry basis, respectively. Liver samples from six ewes in each group were obtained by biopsy initially and at 40, 80 and 120 d and at slaughter (140 d). The remaining 18 litter-fed ewes were fed the basal diet after 140 d and six were slaughtered after 30-, 60- and 120-d. Liver Cu content continually increased (P less than .01) by feeding broiler litter (404 vs 1,543 ppm, dry basis), and was decreased (962 ppm) by supplementing Mo and SO4. During the withdrawal period, liver and duodenum Cu levels were not reduced (P greater than .05). A linear increase (P less than .001) in serum glutamic oxalacetic transaminase (SGOT) was observed with time during the withdrawal period. Serum Cu decreased at 30-d withdrawal and increased thereafter (quadratic effect (P less than .05). Hepatic Cu-metallothionein levels increased 15-fold above control values in the litter-fed ewes (P less than .05).

  6. X-ray absorption edge spectroscopy of Co(II)-binding sites of copper- and zinc-containing proteins.

    PubMed

    Desideri, A; Comin, F; Morpurgo, L; Cocco, D; Calabrese, L; Mondovi, B; Maret, W; Rotilio, G

    1981-10-28

    X-ray absorption near-edge spectroscopy (XANES) of Co(II) in three derivatives of superoxide dismutase, namely [Cu(II)-Co(II)], [Cu(I)-Co(II)] and [...-Co(II)], suggests a tetrahedral coordination of the metal for all compounds. Significant differences, detected in the spectrum of the [Cu(II)-Co(II)] derivative as compared to the other species, indicate that a conformational change and/or a different charge of the imidazole bridging the two metal sites in superoxide dismutase occur in coincidence with the change of copper valence. The XANES spectra of the cobalt derivatives of alcohol dehydrogenase, carbonic anhydrase and stellacyanin show features that can be accounted for by an increasing degree of covalency in the metal first sphere of coordination, in the following order: alcohol dehydrogenase greater than stellacyanin greater than superoxide dismutase greater than or equal to carbonic anhydrase.

  7. Targeted guanine oxidation by a dinuclear copper(II) complex at single stranded/double stranded DNA junctions.

    PubMed

    Li, Lei; Murthy, Narasimha N; Telser, Joshua; Zakharov, Lev N; Yap, Glenn P A; Rheingold, Arnold L; Karlin, Kenneth D; Rokita, Steven E

    2006-09-04

    A dinuclear copper(II) complex [Cu(II)2(PD'O-)(H2O)2](ClO4)3 (5) with terminal Cu(II)-H(2)O moieties and a Cu...Cu distance of 4.13 A (X-ray structure) has been synthesized and characterized by EPR spectroscopy (ferromagnetic coupling observed) and cyclic voltammetry. Dizinc(II) and mononuclear copper(II) analogues [Zn(II)2(PD'O-)(H2O)2]3+ (7) and [Cu(II)(mPD'OH)(H2O)]2+ (6), respectively, have also been synthesized and structurally characterized. Reacting 5/MPA/O(2) (MPA = 3-mercaptopropionic acid) with DNA leads to a highly specific oxidation of guanine (G) at a junction between single- and double-stranded DNA. Mass spectrometric analysis of the major products indicates a gain of +18 and +34 amu relative to initial DNA strands. The most efficient reaction requires G at the first and second unpaired positions of each strand extending from the junction. Less reaction is observed for analogous targets in which the G cluster is farther from the junction or contains less than four Gs. Consistent with our previous systems, the multinuclear copper center is required for selective reaction; mononuclear complex 6 is not effective. Hydrogen peroxide as a substitute for MPA/O2 also does not lead to activity. Structural analysis of a [Cu(II)2(PD'O-)(G)]3+ complex (8) and dizinc analogue [Zn(II)(2)(PD'O-)(G)](ClO4)3 (9) (G = guanosine) reveals coordination of the G O6 and N7 atoms with the two copper (or zinc) centers and suggests that copper-G coordination likely plays a role in recognition of the DNA target. The Cu2-O2 intermediate responsible for guanine oxidation appears to be different from that responsible for direct-strand scission induced by other multinuclear copper complexes; the likely course of reaction is discussed.

  8. Supramolecular control of a mononuclear biomimetic copper(II) center: bowl complexes vs funnel complexes.

    PubMed

    Gout, Jérôme; Višnjevac, Aleksandar; Rat, Stéphanie; Parrot, Arnaud; Hessani, Assia; Bistri, Olivia; Le Poul, Nicolas; Le Mest, Yves; Reinaud, Olivia

    2014-06-16

    Modeling the mononuclear site of copper enzymes is important for a better understanding of the factors controlling the reactivity of the metal center. A major difficulty stems from the difficult control of the nuclearity while maintaining free sites open to coordination of exogenous ligands. A supramolecular approach consists in associating a hydrophobic cavity to a tripodal ligand that will define the coordination spheres as well as access to the metal ion. Here, we describe the synthesis of a bowl Cu(II) complex based on the resorcinarene scaffold. This study supplements a previous work on Cu(I) coordination. It provides a complete picture of the cavity-copper system in its two oxidation states. The first XRD structure of such a bowl complex was obtained, evidencing a 5-coordinate Cu(II) ion with the three imidazole donors bound to the metal (two in the base of the pyramid, one in the apical position) and with an acetate anion, completing the base of the pyramid, and deeply included in the bowl. Solution studies conducted by EPR and UV-vis absorption spectroscopies as well as cyclic voltammetry highlighted interaction with coordinating solvents, various carboxylates that can sit either in the endo or in the exo position depending on their size as well as possible stabilization of hydroxo species in a mononuclear state. A comparison of the binding and redox properties of the bowl complex with funnel complexes based on the calix[6]arene core further highlights the importance of supramolecular features defining the first, second, and third coordination sphere for control of the metal ion.

  9. Structures of chloro(glycinato)(1,10-phenanthroline)copper(II) monohydrate (I) and aqua(1,10-phenanthroline)(L-phenylalaninato)copper(II) nitrate monohydrate (II).

    PubMed

    Solans, X; Ruiz-Ramírez, L; Martinez, A; Gasque, L; Briansó, J L

    1988-04-15

    (I) [CuCl(C2H4NO2)(C12H8N2)].H2O, Mr = 371.28, orthorhombic, P2(1)2(1)2(1), a = 6.795 (3), b = 12.496 (4), c = 17.273 (5) A, V = 1467 (1) A3, Dx = 1.680 Mg m-3, Z = 4, F(000) = 756, lambda(Mo K alpha) = 0.71069 A, mu(Mo K alpha) = 1.742mm-1. Room temperature. Final R = 0.046 for 1302 unique observed reflections. (II) [Cu(C9H10NO2)(C12H8N2)(H2O)]NO3.-H2O, Mr = 505.98, monoclinic, P2(1), a = 5.782 (2), b = 20.700 (6), c = 9.355 (3) A, beta = 97.58 (2)degrees, V = 1110 (1) A3, Dx = 1.514 Mg m-3, Z = 2, F(000) = 522, lambda(Mo K alpha) = 0.71069 A, mu(Mo K alpha) = 1.076 mm-1. Room temperature. Final R = 0.069 for 1929 unique observed reflections. The Cu ion displays distorted square-pyramidal coordination in both (I) and (II), with the chlorine atom (I) or the water molecule (II) in the apical position. The Cu-N bond lengths alter according to the electronegative character of the trans atom. The conformations of the five-membered chelate rings appear to depend on H bonding and van der Waals interactions.

  10. Synthesis, characterization and X-ray structural studies of four copper (II) complexes containing dinuclear paddle wheel structures

    PubMed Central

    2013-01-01

    Background Various dinuclear copper (II) complexes with octahedral geometry have been reported. The majority of these complexes contain N containing aromatic rings as axial ligands. There are also a few cases where the solvent used in the reaction occupies the axial position of the dinuclear copper (II) complex. This may occur by planned synthesis or some times by serendipity. Here we report some four copper (II) complexes containing solvent and or N containing heterocyclic ring as the axial ligand. Results Four compounds, each containing dinuclear Copper (II) units (with the most robust, frequently occurring paddle wheel structures) were synthesized and characterised by single crystal X-ray diffraction and by IR spectroscopy. The compounds 1 & 2 have the general formula Cu2(RCOO) 4(L)2 [(for (1) RCOO= 4-Chloro Benzoate, L= Isopropanol; for 2 RCOO= Benzoate, L= 2-Amino-4,6-dimethyl pyrimidine )] while 3 & 4 have the general formula, Cu2(RCOO) 4(S)2 Cu2(RCOO) 4(L)2 [RCOO=5-Chloro-thiophene-2-carboxylate L= 2-Amino-4,6-dimethyl pyrimidine, for 3 S= ethanol; for 4 S= methanol ]. A wide range of hydrogen bonds (of the O-H…O, N-H…O and N-H…N type) and π-π stacking interactions are present in the crystal structures. Conclusions All compounds contain the dinuclear units, in which two Cu (II) ions are bridged by four syn, syn-η1:η1:μ carboxylates, showing a paddle-wheel cage type with a distorted octahedral geometry. The compounds 1 &2 contain a single dimeric unit while 3 &4 contain two dimeric units. The structures 3 and 4 are very interesting co-crystals of two paddle wheel molecules. Also it is interesting to note that the compounds 3 &4 are isostructural with similar cell parameters. Both the compounds 3 &4 differ in the solvent molecule coordinated to copper in one of the dimeric units. In all the four compounds, each of the copper dimers has an inversion centre. Every copper has a distorted octahedral centre, formed by four oxygen atoms (from different

  11. Norfloxacin and N-Donor Mixed-Ligand Copper(II) Complexes: Synthesis, Albumin Interaction, and Anti-Trypanosoma cruzi Activity

    PubMed Central

    Martins, Darliane A.; Gouvea, Ligiane R.; Muniz, Gabriel S. Vignoli; Louro, Sonia R. W.; Batista, Denise da Gama Jaen; Soeiro, Maria de Nazaré C.; Teixeira, Letícia R.

    2016-01-01

    Copper(II) complexes with the first-generation quinolone antibacterial agent norfloxacin containing a nitrogen donor heterocyclic ligand 2,2′-bipyridine (bipy) or 1,10-phenanthroline (phen) were prepared and characterized by IR, EPR spectra, molar conductivity, and elemental analyses. The experimental data suggest that norfloxacin was coordinated to copper(II) through the carboxylato and ketone oxygen atoms. The interaction of the copper(II) complexes with bovine serum albumin (BSA) and human serum albumin (HSA) was investigated using fluorescence quenching of the tryptophan residues and copper(II) EPR spectroscopy. The results of fluorescence titration revealed that copper(II) complexes have a moderate ability to quench the intrinsic fluorescence of the albumins through a static quenching mechanism. EPR experiments showed that BSA and HSA Cu(II) sites compete with NOR for Cu(II)-bipy and Cu(II)-phen to form protein mixed-ligand complexes. Copper(II) complexes, together with the corresponding ligands, were evaluated for their trypanocidal activity in vitro against Trypanosoma cruzi, the causative agent of Chagas disease. The tests performed using bloodstream trypomastigotes showed that the Cu(II)-N-donor precursors and the metal complexes were more active than the free fluoroquinolone. PMID:26924953

  12. Plant growth responses to inorganic environmental contaminants are density-dependent: experiments with copper sulfate, barley and lettuce.

    PubMed

    Hansi, Mari; Weidenhamer, Jeffrey D; Sinkkonen, Aki

    2014-01-01

    The density-dependence of terrestrial plant-plant interactions in the presence of toxins has previously been explored using biodegradable compounds. We exposed barley and lettuce to four copper concentrations at four stand densities. We hypothesized that toxin effects would decrease and Cu uptake would increase at increasing plant densities. We analyzed toxin effects by (a) comparing plant biomasses and (b) using a recent regression model that has a separate parameter for the interaction of resource competition and toxin interference. Plant response to Cu was density-dependent in both experiments. Total Cu uptake by barley increased and the dose per plant decreased as plant density increased. This study is the first to demonstrate that plant density mediates plant response to metals in soil in a predictable way. This highlights the need to explore the mechanisms for and consequences of these effects, and to integrate the use of several plant densities into standard ecotoxicological testing.

  13. Effects of ammonium sulfate aerosols on vegetation—II. Mode of entry and responses of vegetation

    NASA Astrophysics Data System (ADS)

    Gmur, Nicholas F.; Evans, Lance S.; Cunningham, Elizabeth A.

    These experiments were designed to provide information on the rates of aerosol deposition, mode of entry, and effects of deposition of submicrometer ammonium sulfate aerosols on foliage of Phaseolus vulgaris L. A deposition velocity of 3.2 × 10 3cms-1 was constant during 3-week exposures of plants to aerosol concentrations of 26mg m -3 (i.e. about two orders of magnitude above ambient episode concentrations). Mean deposition rate on foliage was 4.1 × 10 -11 μg cm -2s -1. Visible injury symptoms included leaf chlorosis, necrosis and loss of turgor. Chlorosis was most frequent near leaf margins causing epinasty and near major veins. Internal injury occurred initially in spongy mesophyll cells. Eventually abaxial epidermal and palisade parenchyma cells were injured. These results suggest that submicrometer aerosols enter abaxial stomata and affect more internal cells before affecting leaf surface cells. Exposure to aerosols decreased both abaxial and adaxial leaf resistances markedly. Although visible injury to foliage occurred, no changes in dry mass of roots and shoots or leaf area occurred. These results suggest that for the plant developmental stage studied, while leaf resistances decreased and cellular injury occurred in foliage, these factors were not significantly related to plant growth and development.

  14. Copper(II/I) Complexes of a Hexakis(bipyridyl)cyclotriveratrylene Ligand: A Redox-Induced Conformational Switch.

    PubMed

    Wytko, Jennifer A.; Boudon, Corinne; Weiss, Jean; Gross, Maurice

    1996-07-17

    A series of copper(II) and copper(I) complexes have been synthesized with ligands combining 6-methyl-2,2'-bipyridines with cyclotriveratrylene (CTV) (1) and with catechol (2). The electrochemical, (1)H NMR, and mass spectrometry characterizations of these complexes are described and discussed. The six pendant bipyridines of ligand 1 allow for the formation of two trinuclear copper(I) complexes [(1)Cu(3)](BF(4))(3) differing only in the conformation "vic" or "int" adopted by the ligand to fit the tetrahedral cuprous ions. Similarly, 1 generates two trinuclear copper(II) complexes in which the conformation of the ligand fits the square planar geometry of cupric ions. In both the cuprous and cupric complexes, a conformational equilibrium exists. Ligand 2 bearing two methylbipyridines has proven to be a useful model of the coordinating sites of ligand 1. In this case, two homologous copper(I) complexes are obtained, [(2)Cu]BF(4) and [(2)(2)Cu(2)](BF(4))(2), modeling respectively two possible coordination conformations of ligand 1. With copper(II), ligand 2 yields only one complex [(2)Cu](CF(3)SO(3))(2), which allows for the unambiguous identification of the conformations observed for ligand 1 complexes. The different coordinating modes of ligand 1 in the complexes mentioned are in exchange but exhibit different physical properties, thus representing a new bistable system based on conformational isomerism which exhibits an electrochemical potential hysteresis. An equilibrium constant and thermodynamic data were obtained for this system by variable-temperature cyclic voltammetry. The influence of coordinating vs noncoordinating solvents was also studied.

  15. In vitro DNA binding studies of the sweetening agent saccharin and its copper(II) and zinc(II) complexes.

    PubMed

    Icsel, Ceyda; Yilmaz, Veysel T

    2014-01-05

    The interactions of fish sperm DNA (FS-DNA) with the sodium salt of sweetener saccharin (sacH) and its copper and zinc complexes, namely [M(sac)2(H2O)4]·2H2O (M=Cu(II) or Zn(II)) were studied by using UV-Vis titration, fluorometric competition, thermal denaturation, viscosity and gel electrophoresis measurements. The intrinsic binding constants (Kb) obtained from absorption titrations were estimated to be 2.86 (±0.06)×10(4)M(-1) for Na(sac), 6.67 (±0.12)×10(4)M(-1) for Cu-sac and 4.01 (±0.08)×10(4)M(-1) for Zn-sac. The Cu-sac complex binds to FS-DNA via intercalation with a KA value of 50.12 (±0.22)×10(4)M(-1) as evidenced by competitive binding studies with ethidium bromide. Moreover, competition experiments with Hoechst 33258 are indicative of a groove binding mode of Na(sac) and Zn-sac with binding constants of 3.13 (±0.16)×10(4)M(-1) and 5.25 (±0.22)×10(4)M(-1), respectively. The spectroscopic measurements indicate a moderate DNA binding affinity of Na(sac) and its metal complexes. The suggested binding modes are further confirmed by the thermal denaturation and viscosity measurements. In addition, Cu-sac and Zn-sac show weak ability to damage to pBR322 supercoiled plasmid DNA.

  16. Determination of copper(II) in the dairy product by an electrochemical sensor based on click chemistry.

    PubMed

    Qiu, Suyan; Xie, Lidan; Gao, Sen; Liu, Qida; Lin, Zhenyu; Qiu, Bin; Chen, Guonan

    2011-11-30

    Herein, a novel sensitive electrochemical sensor for copper(II) based on Cu(I) catalyzed alkyne-azide cycloaddition reaction (CuAAC) is described. The catalyst of Cu(I) species is derived from electrochemical reduction of Cu(II) through bulk electrolysis (BE) with coulometry technique. The propargyl-functionalized ferrocene (propargyl-functionalized Fc) is covalently coupled onto the electrode surface via CuAAC reaction and forms propargyl-functionalized Fc modified gold electrode, which allows a good and stable electrochemical signal. The change of current at peak (dI), detected by differential pulse voltammetry (DPV), exhibits a linear response to the logarithm of Cu(II) concentration in the range of 1.0×10(-14)-1.0×10(-9) mol L(-1). It is also found that the proposed sensor has a good selectivity for copper(II) assay even in the presence of other common metal ions. Additionally, the proposed method has been applied to determine copper(II) in the dairy product (yoghurt) with satisfactory results.

  17. Copper(II) ions affect the gating dynamics of the 20S proteasome: a molecular and in cell study

    PubMed Central

    Santoro, Anna Maria; Monaco, Irene; Attanasio, Francesco; Lanza, Valeria; Pappalardo, Giuseppe; Tomasello, Marianna Flora; Cunsolo, Alessandra; Rizzarelli, Enrico; De Luigi, Ada; Salmona, Mario; Milardi, Danilo

    2016-01-01

    Due to their altered metabolism cancer cells are more sensitive to proteasome inhibition or changes of copper levels than normal cells. Thus, the development of copper complexes endowed with proteasome inhibition features has emerged as a promising anticancer strategy. However, limited information is available about the exact mechanism by which copper inhibits proteasome. Here we show that Cu(II) ions simultaneously inhibit the three peptidase activities of isolated 20S proteasomes with potencies (IC50) in the micromolar range. Cu(II) ions, in cell-free conditions, neither catalyze red-ox reactions nor disrupt the assembly of the 20S proteasome but, rather, promote conformational changes associated to impaired channel gating. Notably, HeLa cells grown in a Cu(II)-supplemented medium exhibit decreased proteasome activity. This effect, however, was attenuated in the presence of an antioxidant. Our results suggest that if, on one hand, Cu(II)-inhibited 20S activities may be associated to conformational changes that favor the closed state of the core particle, on the other hand the complex effect induced by Cu(II) ions in cancer cells is the result of several concurring events including ROS-mediated proteasome flooding, and disassembly of the 26S proteasome into its 20S and 19S components. PMID:27633879

  18. A one-dimensional carboxylate-bridged helical copper(II) complex containing (quinolin-8-yloxy)acetate.

    PubMed

    Wang, Yu-Hong; Lu, Fang

    2004-11-01

    The title compound, catena-poly[[bromocopper(II)]-mu-(quinolin-8-yloxy)acetato-kappa(4)N,O,O':O''], [CuBr(C(11)H(8)NO(3))](n), is a novel carboxylate-bridged one-dimensional helical copper(II) polymer. The metal ion exhibits an approximately square-pyramidal CuBrNO(3) coordination environment, with the three donor atoms of the ligand and the bromide ion occupying the basal positions, and an O atom belonging to the carboxylate group of an adjacent molecule in the apical site. Carboxylate groups are mutually cis oriented, and each anti-anti carboxylate group bridges two copper(II) ions via one apical and one basal position [Cu...Cu = 5.677 (1) A], resulting in the formation of a helical chain along the crystallographic b axis.

  19. Manganese (II) Chelate Functionalized Copper Sulfide Nanoparticles for Efficient Magnetic Resonance/Photoacoustic Dual-Modal Imaging Guided Photothermal Therapy

    PubMed Central

    Liu, Renfa; Jing, Lijia; Peng, Dong; Li, Yong; Tian, Jie; Dai, Zhifei

    2015-01-01

    The integration of diagnostic and therapeutic functionalities into one nanoplatform shows great promise in cancer therapy. In this research, manganese (II) chelate functionalized copper sulfide nanoparticles were successfully prepared using a facile hydrothermal method. The obtained ultrasmall nanoparticles exhibit excellent photothermal effect and photoaoustic activity. Besides, the high loading content of Mn(II) chelates makes the nanoparticles attractive T1 contrast agent in magnetic resonance imaging (MRI). In vivo photoacoustic imaging (PAI) results showed that the nanoparticles could be efficiently accumulated in tumor site in 24 h after systematic administration, which was further validated by MRI tests. The subsequent photothermal therapy of cancer in vivo was achieved without inducing any observed side effects. Therefore, the copper sulfide nanoparticles functionalized with Mn(II) chelate hold great promise as a theranostic nanomedicine for MR/PA dual-modal imaging guided photothermal therapy of cancer. PMID:26284144

  20. Manganese (II) Chelate Functionalized Copper Sulfide Nanoparticles for Efficient Magnetic Resonance/Photoacoustic Dual-Modal Imaging Guided Photothermal Therapy.

    PubMed

    Liu, Renfa; Jing, Lijia; Peng, Dong; Li, Yong; Tian, Jie; Dai, Zhifei

    2015-01-01

    The integration of diagnostic and therapeutic functionalities into one nanoplatform shows great promise in cancer therapy. In this research, manganese (II) chelate functionalized copper sulfide nanoparticles were successfully prepared using a facile hydrothermal method. The obtained ultrasmall nanoparticles exhibit excellent photothermal effect and photoaoustic activity. Besides, the high loading content of Mn(II) chelates makes the nanoparticles attractive T1 contrast agent in magnetic resonance imaging (MRI). In vivo photoacoustic imaging (PAI) results showed that the nanoparticles could be efficiently accumulated in tumor site in 24 h after systematic administration, which was further validated by MRI tests. The subsequent photothermal therapy of cancer in vivo was achieved without inducing any observed side effects. Therefore, the copper sulfide nanoparticles functionalized with Mn(II) chelate hold great promise as a theranostic nanomedicine for MR/PA dual-modal imaging guided photothermal therapy of cancer.

  1. Micellar-enhanced ultrafiltration of copper ions using sodium dodecyl sulfate and its mixture with Brij 35, Tween 80 and Triton X-100.

    PubMed

    Zhao, Baowei; Li, Ruirui; Zhong, Jinkui; Zhang, Li

    2013-01-01

    The performance of copper ion removal using sodium dodecyl sulfate (SDS) and its mixtures with Brij 35, Tween 80 (TW80) and Triton X-100 (TX100) by micellar-enhanced ultrafiltration (MEUF) was investigated. The effects of the molar ratio of nonionic surfactant to SDS on the critical micelle concentration (CMC) of SDS/Brij 35, SDS/TW80 and SDS/TX100, the removal efficiency of Cu(2+), the residual concentration of SDS in the permeate solution and the permeate flux were tested. The results showed that the CMCs of the mixed surfactants were sharply less than that of pure SDS. The removal efficiencies of Cu(2+) were up to the maximum values 98.3 and 95.8% when the molar ratios of Brij 35 and TW80 to SDS were 0.3, and it was 93.5% given 0.7 molar ratio of TX100 to SDS. The concentration of SDS in the permeate decreased dramatically with the addition of nonionic surfactant, and the permeate flux decreased slightly as the molar ratio increased. Compared with the performance by single SDS, the mixed SDS/Brij 35, SDS/TW80 and SDS/TX100 at an optimum composition could result in not only higher rejection of Cu(2+) but also much less dosage of surfactant and concentration of SDS in the permeate.

  2. Effects of copper sulfate, hydrogen peroxide and N-phenyl-2-naphthylamine on oxidative stress and the expression of genes involved photosynthesis and microcystin disposition in Microcystis aeruginosa.

    PubMed

    Qian, Haifeng; Yu, Shuqiong; Sun, Zhengqi; Xie, Xiucai; Liu, Weiping; Fu, Zhengwei

    2010-09-01

    Algal blooms have been increasing in prevalence all over the world, destroying ecosystems and placing other organisms at risk. Chemical remediation is one of most important methods of controlling algal bloom formation. The effects of copper sulfate, hydrogen peroxide (H(2)O(2)) and N-phenyl-2-naphthylamine on photosynthesis-related and microcystin-related gene transcription and physiological changes of Microcystis aeruginosa were analyzed. The results suggest that transcription of psaB, psbD1 and rbcL was inhibited by the three algaecides, which blocked the electron transport chain, significantly enhanced reactive oxygen species (ROS) accumulation and overwhelmed the antioxidant system. The increase in ROS destroyed pigment synthesis and membrane integrity, which inhibited or killed the algal cells. Furthermore, H(2)O(2) treatment down-regulated mcyD transcription, which indicated a decrease in the microcystin level in the cells. Our results demonstrate that H(2)O(2) has the greatest potential as an algaecide because it not only inhibits algae growth but may reduce microcystin synthesis.

  3. Synthesis, crystal structures and antitumor activities of copper(II) complexes with a 2-acetylpyrazine isonicotinoyl hydrazone ligand

    NASA Astrophysics Data System (ADS)

    Xu, Jun; Zhou, Tao; Xu, Zhou-Qing; Gu, Xin-Nan; Wu, Wei-Na; Chen, Hong; Wang, Yuan; Jia, Lei; Zhu, Tao-Feng; Chen, Ru-Hua

    2017-01-01

    Five complexes, [Cu(L)2]·4.5H2O (1), [Cu(HL)2](NO3)2·CH3OH (2) {[Cu2(L)2(NO3)(H2O)2]·(NO3)}n (3), [Cu2(HL)2(SO4)2]·2CH3OH (4) and [Cu4(L)4Cl4]·5H2O (5) based on HL (where HL = 2-acetylpyrazine isonicotinoyl hydrazone) have been synthesized and characterized by X-ray diffraction analyses. The counter anion and organic base during the synthesis procedure influence the structures of the complexes efficiently, which generate five complexes as mono-, bi-, tetra-nuclear and one-dimensional structures. The antitumor activities of the complexes 1-5 (except for complex 3 with the poor solubility) against the Patu8988 human pancreatic cancer, ECA109 human esophagus cancer and SGC7901 human gastric cancer cell lines are screened by MTT assay. The results indicate that the chelation of Cu(II) with the ligand is responsible for the observed high cytotoxicity of the copper(II) complexes and the 1:2 copper species 1 and 2 demonstrate lower antitumor activities than that of the 1:1 copper species 4 and 5. In addition, the in vitro apoptosis inducing activity of the copper(II) complex 5 against SGC7901 cell line is determined. And the results show that the complex can bring about apoptosis of the cancerous cells in vitro.

  4. Crystal structure of bis-(di-methyl-ammonium) hexa-aqua-cobalt(II) bis-(sulfate) dihydrate.

    PubMed

    Held, Peter

    2015-04-01

    The title salt, (C2H8N)2[Co(H2O)6)](SO4)2·2H2O, is isotypic with (C2H8N)2[Ni(H2O)6)](SO4)2·2H2O. The Co-O bond lengths in the [Co(H2O)6](2+) complex cation show very similar distances as in the related Tutton salt (NH4)2[Co(H2O)6)](SO4)2 [average 2.093 (17) Å], but are significantly longer than in the isotypic Ni(II) compound (Δd ≃ 0.04 Å). The cobalt cation reaches an overall bond-valence sum of 1.97 valence units. The S-O distances are nearly equal, ranging from 1.454 (4) to 1.470 (3) Å [mean 1.465 (12) Å]; however, the O-S-O angles vary clearly from 108.1 (2) to 110.2 (2)° [average bond angle 109.5 (9)°]. The non-coordinating water mol-ecules and di-methyl-ammonium cations connect the sulfate tetrahedra and the [Co(H2O)6](2+) octa-hedron via O-H⋯O and N-H⋯O hydrogen bonds of weak up to medium strength into a three-dimensional framework whereby the complex metal cations and sulfate anions are arranged in sheets parallel to (001).

  5. Structural characterization of a metal-based perfusion tracer: copper(II) pyruvaldehyde bis(N4-methylthiosemicarbazone).

    PubMed

    John, E; Fanwick, P E; McKenzie, A T; Stowell, J G; Green, M A

    1989-01-01

    Copper(II) pyruvaldehyde bis(N4-methylthiosemicarbazone), Cu(PTSM), has been obtained as a dark red crystalline solid from EtOH-DMSO solvent mixture and structurally characterized by x-ray crystallography. The molecule possesses the expected pseudo-square planar N2S2 metal coordination sphere; however, the copper center also interacts through its axial coordination site with the sulfur atom of an adjacent Cu(PTSM) molecule in the crystal lattice. The structure of this compound is compared with the structures of other metal complexes that have been proposed in the nuclear medicine literature as perfusion tracers.

  6. Biosorption of copper(II), lead(II), iron(III) and cobalt(II) on Bacillus sphaericus-loaded Diaion SP-850 resin.

    PubMed

    Tuzen, Mustafa; Uluozlu, Ozgur Dogan; Usta, Canan; Soylak, Mustafa

    2007-01-09

    The biosorption of copper(II), lead(II), iron(III) and cobalt(II) on Bacillus sphaericus-loaded Diaion SP-850 resin for preconcentration-separation of them have been investigated. The sorbed analytes on biosorbent were eluted by using 1 mol L(-1) HCl and analytes were determined by flame atomic absorption spectrometry. The influences of analytical parameters including amounts of pH, B. sphaericus, sample volume etc. on the quantitative recoveries of analytes were investigated. The effects of alkaline, earth alkaline ions and some metal ions on the retentions of the analytes on the biosorbent were also examined. Separation and preconcentration of Cu, Pb, Fe and Co ions from real samples was achieved quantitatively. The detection limits by 3 sigma for analyte ions were in the range of 0.20-0.75 microg L(-1) for aqueous samples and in the range of 2.5-9.4 ng g(-1) for solid samples. The validation of the procedure was performed by the analysis of the certified standard reference materials (NRCC-SLRS 4 Riverine Water, SRM 2711 Montana soil and GBW 07605 Tea). The presented method was applied to the determination of analyte ions in green tea, black tea, cultivated mushroom, boiled wheat, rice and soil samples with successfully results.

  7. Synthesis, characterization, spectroscopic and theoretical studies of new zinc(II), copper(II) and nickel(II) complexes based on imine ligand containing 2-aminothiophenol moiety

    NASA Astrophysics Data System (ADS)

    Shafaatian, Bita; Mousavi, S. Sedighe; Afshari, Sadegh

    2016-11-01

    New dimer complexes of zinc(II), copper(II) and nickel(II) were synthesized using the Schiff base ligand which was formed by the condensation of 2-aminothiophenol and 2-hydroxy-5-methyl benzaldehyde. This tridentate Schiff base ligand was coordinated to the metal ions through the NSO donor atoms. In order to prevent the oxidation of the thiole group during the formation of Schiff base and its complexes, all of the reactions were carried out under an inert atmosphere of argon. The X-ray structure of the Schiff base ligand showed that in the crystalline form the SH groups were oxidized to produce a disulfide Schiff base as a new double Schiff base ligand. The molar conductivity values of the complexes in dichloromethane implied the presence of non-electrolyte species. The fluorescence properties of the Schiff base ligand and its complexes were also studied in dichloromethane. The products were characterized by FT-IR, 1H NMR, UV/Vis spectroscopies, elemental analysis, and conductometry. The crystal structure of the double Schiff base was determined by single crystal X-ray diffraction. Furthermore, the density functional theory (DFT) calculations were performed at the B3LYP/6-31G(d,p) level of theory for the determination of the optimized structures of Schiff base complexes.

  8. Synthesis, structural characterization, cytotoxic properties and DNA binding of a dinuclear copper(II) complex.

    PubMed

    Ferreira, B J M Leite; Brandão, P; Meireles, M; Martel, Fátima; Correia-Branco, Ana; Fernandes, Diana M; Santos, T M; Félix, V

    2016-08-01

    In this study a novel dinuclear copper(II) complex with adenine and phenanthroline has been synthesized and its structure determined by single crystal X-ray diffraction. In the dinuclear complex [Cu₂(μ-adenine)₂(phen)₂(H2O)2](NO3)4·0.5H2O (phen=1,10-phenanthroline) (1) the two Cu(II) centres exhibit a distorted square pyramidal coordination geometry linked by two nitrogen donors from adenine bridges leading to a Cu-Cu distance of 3.242(3)Å. Intramolecular and intermolecular π⋯π interactions as well as an H-bonding network were observed. The antitumor capacity of the complex has been tested in vitro against human cancer cell lines, cervical carcinoma (HeLa) and colorectal adenocarcinoma (Caco-2), by metabolic tests, using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-tetrazolium bromide as reagent. The complex 1 has remarkable low IC50 values of 0.87±0.06μM (HeLa) and 0.44±0.06μM (Caco-2), when compared with values for cisplatin against the same cell lines. The interaction of complex 1 with calf thymus DNA (CT DNA) was further investigated by absorption and fluorescence spectroscopic methods. A binding constant of 5.09×10(5)M(-1) was obtained from UV-vis absorption studies.

  9. Crystal structures of μ-oxalato-bis­[azido­(hista­mine)­copper(II)] and μ-oxalato-bis­[(dicyan­amido)(hista­mine)­copper(II)

    PubMed Central

    Liu, Chen; Abboud, Khalil A.

    2015-01-01

    The title compounds, μ-oxalato-κ4 O 1,O 2:O 1′,O 2′-bis­[[4-(2-amino­eth­yl)-1H-imid­azole-κ2 N 3,N 4](azido-κN 1)copper(II)], [Cu2(C2O4)(N3)2(C5H9N3)2], (I), and μ-ox­al­ato-κ4 O 1,O 2:O 1′,O 2′-bis­[[4-(2-amino­eth­yl)-1H-imidazole-κ2 N 3,N 4](dicyanamido-κN 1)copper(II)], [Cu2(C2O4)(C2N3)2(C5H9N3)2], (II), are two oxalate-bridged dinuclear copper complexes. Each CuII ion adopts a five-coordinate square-pyramidal coordination sphere where the basal N2O2 plane is formed by two O atoms of the oxalate ligand and two N atoms of a bidentate chelating histamine mol­ecule. The apical coordination site in compound (I) is occupied by a monodentate azide anion through one of its terminal N atoms. The apical coordination site in compound (II) is occupied by a monodentate dicyanamide anion through one of its terminal N atoms. The mol­ecules in both structures are centrosymmetric. In the crystals of compounds (I) and (II), the dinuclear complexes are linked through N—H⋯X and C—H⋯X (X = N, O) hydrogen bonds where the donors are provided by the histamine ligand and the acceptor atoms are provided by the azide, dicyanamide, and oxalate ligands. In compound (I), the coordinatively unsaturated copper ions inter­act with the histamine ligand via a C—H⋯Cu inter­action. The coordinatively unsaturated copper ions in compound (II) inter­act via a weak N⋯Cu inter­action with the dicyanamide ligand of a neighboring mol­ecule. The side chain of the histamine ligand is disordered over three sets of sites in (II). PMID:26594515

  10. H-atom abstraction reaction for organic substrates via mononuclear copper(II)-superoxo species as a model for DbetaM and PHM.

    PubMed

    Fujii, Tatsuya; Yamaguchi, Syuhei; Hirota, Shun; Masuda, Hideki

    2008-01-07

    Hydrogen atom abstraction reactions have been implicated in oxygenation reactions catalyzed by copper monooxygenases such as peptidylglycine alpha-hydroxylating monooxygenase (PHM) and dopamine beta-monooxygenase (DbetaM). We have investigated mononuclear copper(I) and copper(II) complexes with bis[(6-neopentylamino-2-pyridyl)methyl][(2-pyridyl)methyl]amine (BNPA) as functional models for these enzymes. The reaction of [Cu(II)(bnpa)]2+ with H2O2, affords a quasi-stable mononuclear copper(II)-hydroperoxo complex, [Cu(II)(bnpa)(OOH)]+ (4) which is stabilized by hydrophobic interactions and hydrogen bonds in the vicinity of the copper(II) ion. On the other hand, the reaction of [Cu(I)(bnpa)]+ (1) with O2 generates a trans-mu-1,2-peroxo dicopper(II) complex [Cu(II)2(bnpa)2(O2(2-]2+ (2). Interestingly, the same reactions carried out in the presence of exogenous substrates such as TEMPO-H, produce a mononuclear copper(II)-hydroperoxo complex 4. Under these conditions, the H-atom abstraction reaction proceeds via the mononuclear copper(II)-superoxo intermediate [Cu(II)(bnpa)(O2-)]+ (3), as confirmed from indirect observations using a spin trap reagent. Reactions with several substrates having different bond dissociation energies (BDE) indicate that, under our experimental conditions the H-atom abstraction reaction proceeds for substrates with a weak X-H bond (BDE < 72.6 kcal mol(-1)). These investigations indicate that the copper(II)-hydroperoxo complex is a useful tool for elucidation of H-atom abstraction reaction mechanisms for exogenous substrates. The useful functionality of the complex has been achieved via careful control of experimental conditions and the choice of appropriate ligands for the complex.

  11. Facile solid-phase synthesis of sulfated tyrosine-containing peptides: total synthesis of human big gastrin-II and cholecystokinin (CCK)-39.

    PubMed

    Kitagawa, K; Aida, C; Fujiwara, H; Yagami, T; Futaki, S; Kogire, M; Ida, J; Inoue, K

    2001-01-12

    Chemical synthesis of tyrosine O-sulfated peptides is still a laborious task for peptide chemists because of the intrinsic acid-lability of the sulfate moiety. An efficient cleavage/deprotection procedure without loss of the sulfate is the critical difficulty remaining to be solved for fluoren-9-ylmethoxycarbonyl (Fmoc)-based solid-phase synthesis of sulfated peptides. To overcome the difficulty, TFA-mediated solvolysis rates of a tyrosine O-sulfate [Tyr(SO3H)] residue and two protecting groups, tBu for the hydroxyl group of Ser and 2,2,4,6,7-pentamethyldihydrobenzofuran-5-sulfonyl (Pbf) for the guanidino group of Arg, were examined in detail. The desulfation obeyed first-order kinetics with a large entropy (59.6 J.K-1.mol-1) and enthalpy (110.5 kJ.mol-1) of activation. These values substantiated that the desulfation rate of the rigidly solvated Tyr(SO3H) residue was strongly temperature-dependent. By contrast, the SN1-type deprotections were less temperature-dependent and proceeded smoothly in TFA of a high ionizing power. Based on the large rate difference between the desulfation and the SN1-type deprotections in cold TFA, an efficient deprotection protocol for the sulfated peptides was developed. Our synthetic strategy for Tyr(SO3H)-containing peptides with this effective deprotection protocol is as follows: (i) a sulfated peptide chain is directly constructed on 2-chlorotrityl resin with Fmoc-based solid-phase chemistry using Fmoc-Tyr(SO3Na)-OH as a building block; (ii) the protected peptide-resin is treated with 90% aqueous TFA at 0 degree C for an appropriate period of time for the cleavage and deprotection. Human cholecystokinin (CCK)-12, mini gastrin-II (14 residues), and little gastrin-II (17 residues) were synthesized with this method in 26-38% yields without any difficulties. This method was further applied to the stepwise synthesis of human big gastrin-II (34 residues), CCK-33 and -39. Despite the prolonged acid treatment (15-18 h at 0 degree C), the

  12. Biochemical and morphological changes in carp (Cyprinus carpio L.) liver following exposure to copper sulfate and tannic acid.

    PubMed

    Varanka, Z; Rojik, I; Varanka, I; Nemcsók, J; Abrahám, M

    2001-03-01

    As a consequence of human activity various toxicants reach the aquatic ecosystems; humics may interact with them and may change their toxicity. Many fish are exposed to a considerable concentration of humics and pollutants. Because of paucity of data on the biochemical action of tannins in the presence of the fungicide CuSO4 a comparative study was undertaken. The alterations of redox-parameters in carp liver were monitored and tissue necrosis was followed by measuring the plasma transaminase activities and by electron microscopy. Tannic acid, a representative phenolic/humic compound, exerted prooxidant effects in carp, which may be partially due to formation of prooxidant intermediates/end-products via its biotransformation. Alternatively, tannic acid may partially inhibit the antioxidant enzymes of fish. The response to CuSO4 was more severe. Although tannic acid alone acted as a prooxidant in fish, electron micrographs demonstrated that it reduced the necrotizing effect of copper, which may be due to the complexing activity of tannic acid with the biomolecules of the hepatocytes and to the H2O2-degrading activity of tannin-CuSO4 combination. Our results indicate that the heavy metal-detoxifying capacity of tannin may be significant; however, tannin-exposure alone or combined with metals may be toxic for fish due to enzyme inhibition and oxidative stress induction.

  13. Synthesis and Characterization of a Tetramethyl Furanone Functionalized Diiminedioxime, A Potential Ligand for 64Cu Radiopharmaceuticals, and its Copper(II) and Nickel(II) Complexes

    PubMed Central

    Kiani, Salma; Staples, Richard J.; Treves, S. Ted; Packard, Alan B.

    2009-01-01

    As part of our on-going effort to develop 64Cu-based radiopharmaceuticals for PET (positron emission tomography) imaging of multidrug resistance in cancer, we prepared a tetramethylfuranone-functionalized diiminedioxime ligand, TMFPreH (TMFPreH = 4-[3-(4-Hydroxyimino-2,2,5,5-dimethyl-dihydro-furan-3-ylideneamino)-propylimino]-2,2,5,5-tetramethyl-dihydro-furan-3-one oxime) and its Cu(II) and Ni(II) complexes. When the copper(II) complex was prepared from Cu(ClO4)2 in ethanol, it was isolated as a Cu(II)-bridged dimer, but when it was prepared from Cu(OAc)2 and heated in acetone, an unusual example of an acetone adduct of the ligand is formed by reduction of one of the imine double bonds by the solvent. The Ni(II) complex is square pyramidal with the perchlorate counterion at the apex. PMID:20161333

  14. Fixed-bed column studies on a modified chitosan hydrogel for detoxification of aqueous solutions from copper (II).

    PubMed

    Kavianinia, Iman; Plieger, Paul G; Kandile, Nadia G; Harding, David R K

    2012-10-01

    A new efficient, low cost chitosan based biosorbent was successfully prepared and employed for the biosorption of copper ions from an aqueous solution using a fixed bed column. Pyromellitic dianhydride crosslinked chitosan as the new adsorbent was characterized by SEM, FTIR spectroscopy, X-ray diffraction, thermogravimetric analysis and solid state (13)C NMR analysis. Scanning electron microscopy coupled with an X-ray energy dispersed analysis for the copper-equilibrated biomass confirmed the presence of Cu(II) ions on the surface of the hydrogel. Thermogravimetric analysis showed a significant improvement in the thermal stability of the new hydrogel compared to pure chitosan. Kinetic models were applied to predict the breakthrough curves. This study shows that the prepared hydrogel based on modified chitosan could be utilized as an efficient bioadsorbent for the removal of copper ions from wastewater.

  15. Characterization of Copper(II) Interactions with Sinefungin, a Nucleoside Antibiotic: Combined Potentiometric, Spectroscopic and DFT Studies

    PubMed Central

    Jaworska, Maria; Lodowski, Piotr; Mucha, Ariel; Szczepanik, Wojciech; Valensin, Gianni; Cappannelli, Massimo; Jeżowska-Bojczuk, Małgorzata

    2007-01-01

    Interactions between sinefungin and copper(II) ions were investigated. Stoichiometry and stability constants of the metal-free system and two mononuclear complexes present in solution were determined on the basis of potentiometric data analysis. The results were compared to the Cu(II)-ornithine system due to structural similarities between both molecules. Combined spectroscopic and theoretical studies allowed for determination of coordination pattern for the Cu(II)-sinefungin complexes. At acidic pH, copper is bound in “glycine-like” coordination mode, identical with that of ornithine. This involves α-amino group and the carboxyl oxygen. At higher pH, a “bis-complex” is formed by two sinefungin molecules. The second ligand binds in equatorial position displacing two water molecules, what results in the stable {2N,2O} coordination. Both axial positions are supposed to be occupied by N1 nitrogen donors of adenine moiety, what is confirmed by DFT calculations. They interact indirectly with copper(II) through water molecules as the result of dominant syn conformation of purine. PMID:18273386

  16. Nanostructured lipid carriers for incorporation of copper(II) complexes to be used against Mycobacterium tuberculosis

    PubMed Central

    Sato, Mariana R; Oshiro Junior, João A; Machado, Rachel TA; de Souza, Paula C; Campos, Débora L; Pavan, Fernando R; da Silva, Patricia B; Chorilli, Marlus

    2017-01-01

    Tuberculosis (TB) is a disease caused by Mycobacterium tuberculosis. Cessation of treatment before the recommended conclusion may lead to the emergence of multidrug-resistant strains. The aim of this study was to develop nanostructured lipid carriers (NLCs) for use in the treatment of M. tuberculosis. The NLCs comprised the following lipid phase: 2.07% polyoxyethylene 40 stearate, 2.05% caprylic/capric triglyceride, and 0.88% polyoxyl 40 hydrogenated castor oil; the following aqueous phase: 3.50% poloxamer 407 (F1–F6), and 0.50% cetyltrimethylammonium bromide (F7–F12); and incorporated the copper(II) complexes [CuCl2(INH)2]·H2O (1), [Cu(NCS)2(INH)2]·5H2O (2), and [Cu(NCO)2(INH)2]·4H2O (3) to form compounds F11.1, F11.2, and F11.3, respectively. The mean diameter of F11, F11.1, F11.2, and F11.3 ranged from 111.27±21.86 to 134.25±22.72 nm, 90.27±12.97 to 116.46±9.17 nm, 112.4±10.22 to 149.3±15.82 nm, and 78.65±6.00 to 122.00±8.70 nm, respectively. The polydispersity index values for the NLCs ranged from 0.13±0.01 to 0.30±0.09. The NLCs showed significant changes in zeta potential, except for F11.2, with F11, F11.1, F11.2, and F11.3 ranging from 18.87±4.04 to 23.25±1.13 mV, 17.03±1.77 to 21.42±1.87 mV, 20.51±1.88 to 22.60±3.44 mV, and 17.80±1.96 to 25.25±7.78 mV, respectively. Atomic force microscopy confirmed the formation of nanoscale spherical particle dispersions by the NLCs. Differential scanning calorimetry determined the melting points of the constituents of the NLCs. The in vitro activity of copper(II) complex-loaded NLCs against M. tuberculosis H37Rv showed an improvement in the anti-TB activity of 55.4, 27.1, and 41.1 times the activity for complexes 1, 2, and 3, respectively. An in vivo acute toxicity study of complex-loaded NLCs demonstrated their reduced toxicity. The results suggest that NLCs may be a powerful tool to optimize the activity of copper(II) complexes against M. tuberculosis. PMID:28356717

  17. Cytotoxicity of copper(II)-complexes with some S-alkyl derivatives of thiosalicylic acid. Crystal structure of the binuclear copper(II)-complex with S-ethyl derivative of thiosalicylic acid

    NASA Astrophysics Data System (ADS)

    Nikolić, Miloš V.; Mijajlović, Marina Ž.; Jevtić, Verica V.; Ratković, Zoran R.; Novaković, Slađana B.; Bogdanović, Goran A.; Milovanović, Jelena; Arsenijević, Aleksandar; Stojanović, Bojana; Trifunović, Srećko R.; Radić, Gordana P.

    2016-07-01

    The spectroscopically predicted structure of the obtained copper(II)-complex with S-ethyl derivative of thiosalicylic acid was confirmed by X-ray structural study and compared to previously reported crystal structure of the Cu complex with S-methyl derivative. Single crystals suitable for X-ray measurements were obtained by slow crystallization from a water solution. Cytotoxic effects of S-alkyl (R = benzyl (L1), methyl (L2), ethyl (L3), propyl (L4) and butyl (L5)) derivatives of thiosalicylic acid and the corresponding binuclear copper(II)-complexes on murine colon carcinoma cell lines, CT26 and CT26.CL25 and human colon carcinoma cell line HCT-116 were reported here. The analysis of cancer cell viability showed that all the tested complexes had low cytotoxic effect on murine colon carcinoma cell lines, but several times higher cytotoxicity on normal human colon carcinoma cells.

  18. Peculiar reactivity of a di-imine copper(II) complex regarding its binding to albumin protein.

    PubMed

    Silveira, Vivian C; Abbott, Mariana P; Cavicchioli, Maurício; Gonçalves, Marcos B; Petrilli, Helena M; de Rezende, Leandro; Amaral, Antonia T; Fonseca, David E P; Caramori, Giovanni F; Ferreira, Ana M da Costa

    2013-05-14

    A set of four di-imine copper(II) complexes containing pyridine, pyrazine and/or imidazole moieties, [Cu(apyhist)H2O](2+) 1 (apyhist = 2-(1H-imidazol-4-yl)-N-(1-(pyridin-2-yl)ethylidene)ethanamine), [Cu(apzhist)OH](+) 2 (apzhist = 2-(1H-imidazol-4-yl)-N-(1-(pyrazin-2-yl)ethylidene)ethanamine), [Cu(apyepy)OH](+) 3 (apyepy = 2-(pyridin-2-yl)-N-(1-(pyridin-2-yl)ethylidene)ethanamine), and [Cu(apzepy)H2O](2+) 4 (apzepy = N-(1-(pyrazin-2-yl)ethylidene)-2-(pyridin-2-yl)ethanamine), were investigated regarding their capability of interacting with serum albumin (human, HSA and bovine, BSA), by using spectroscopic techniques, CD, UV/Vis and EPR. Like other similar di-imine copper(II) complexes, most of them showed an expected preferential insertion of the metal ion at the primary N-terminal site of the protein, very selective for copper and characterized by a CD band at 560 nm. Further insertion of the copper ion at a secondary site is expected when using an excess of the metal. However, one of these studied complexes, [Cu(apyhist)H2O](2+) 1, exhibited anomalous behaviour interacting only at this secondary metal binding site of albumin, characterized by a CD band at 370 nm, and attributed to the coordination of copper at the Cys34 pocket. Analogous experiments with HSA previously treated with N-ethyl-maleimide (NEM), that oxidizes the protein Cys34 residue and obstructs the metal coordination, verified these results. Additional data obtained by EPR spectroscopy complemented those results. DFT calculations, considering some structural and electronic characteristics of such series of di-imine ligands and of the corresponding copper complexes, suggested molecular recognition of the apyhist ligand at the protein cavity as a feasible explanation for this unexpected and peculiar behaviour of complex 1.

  19. Chiral mobile phase in ligand-exchange chromatography of amino acids: exploring the copper(II) salt anion effect with a computational approach.

    PubMed

    Sardella, Roccaldo; Macchiarulo, Antonio; Carotti, Andrea; Ianni, Federica; Rubiño, Maria Eugenia García; Natalini, Benedetto

    2012-12-21

    With the use of a chiral ligand-exchange chromatography (CLEC) system operating with the O-benzyl-(S)-serine [(S)-OBS] [1,2] as the chiral mobile phase (CMP) additive to the eluent, the effect of the copper(II) anion type on retention (k) and separation (α) factors was evaluated, by rationally changing the following experimental conditions: salt concentration and temperature. The CLEC-CMP analysis was carried out on ten amino acidic racemates and with nine different cupric salts. While the group of analytes comprised both aliphatic (leucine, isoleucine, nor-leucine, proline, valine, nor-valine, and α-methyl-valine) and aromatic (1-aminoindan-1,5-dicarboxylic acid, phenylglycine, and tyrosine) species, representative organic (formate, methanesulfonate, and trifluoroacetate) and inorganic (bromide, chloride, fluoride, nitrate, perchlorate, and sulfate) Cu(II) salts were selected as the metal source into the eluent. This route of investigation was pursued with the aim of identifying analogies among the employed Cu(II) salts, by observing the variation profile of the selected chromatographic parameters, upon a change of the above experimental conditions. All the data were collected and analyzed through a statistical approach (PCA and k-means clustering) that revealed the presence of two behavioral classes of cupric salts, sharing the same variation profile for k and α values. Interestingly, this clustering can be explained in terms of ESP (electrostatic surface potential) balance (ESP(bal)) values, obtained by an ab initio calculation operated on the cupric salts. The results of this appraisal could aid the rational choice of the most suitable eluent system, to succeed in the enantioseparation of difficult-to-resolve compounds, along with the eventual scale-up to a semi-preparative level.

  20. Copper(II)–human amylin complex protects pancreatic cells from amylin toxicity†‡

    PubMed Central

    Lee, Elizabeth C.; Ha, Emmeline; Singh, Sanghamitra; Legesse, Linda; Ahmad, Sana; Karnaukhova, Elena; Donaldson, Robert P.

    2014-01-01

    Human amylin-derived oligomers and aggregates are believed to play an important role in the pathogenesis of type II diabetes mellitus (T2DM). In addition to amylin-evoked cell attrition, T2DM is often accompanied by elevated serum copper levels. Although previous studies have shown that human amylin, in the course of its aggregation, produces hydrogen peroxide (H2O2) in solution, and that this process is exacerbated in the presence of copper(II) ions (Cu2+), very little is known about the mechanism of interaction between Cu2+ and amylin in pancreatic β-cells, including its pathological significance. Hence, in this study we investigated the mechanism by which Cu2+ and human amylin catalyze formation of reactive oxygen species (ROS) in cells and in vitro, and examined the modulatory effect of Cu2+ on amylin aggregation and toxicity in pancreatic rat insulinoma (RIN-m5F) β-cells. Our results indicate that Cu2+ interacts with human and rat amylin to form metalo-peptide complexes with low aggregative and oxidative properties. Human and non-amyloidogenic rat amylin produced minute (nM) amounts of H2O2, the accumulation of which was slightly enhanced in the presence of Cu2+. In a marked contrast to human and rat amylin, and in the presence of the reducing agents glutathione and ascorbate, Cu2+ produced μM concentrations of H2O2 surpassing the amylin effect by several fold. The current study shows that human and rat amylin not only produce but also quench H2O2, and that human but not rat amylin significantly decreases the amount of H2O2 in solution produced by Cu2+ and glutathione. Similarly, human amylin was found to also decrease hydroxyl radical formation elicited by Cu2+ and glutathione. Furthermore, Cu2+ mitigated the toxic effect of human amylin by inhibiting activation of pro-apoptotic caspase-3 and stress-kinase signaling pathways in rat pancreatic insulinoma cells in part by stabilizing human amylin in its native conformational state. This sacrificial quenching

  1. An effective approach to artificial nucleases using copper(II) complexes bearing nucleobases.

    PubMed

    Wang, Jin-Tao; Xia, Qing; Zheng, Xiao-Hui; Chen, Huo-Yan; Chao, Hui; Mao, Zong-Wan; Ji, Liang-Nian

    2010-02-28

    Novel copper(ii) complexes bearing 2,2'-bipyridine (bpy) derivatives with adenine, thymine and uracil nucleobases [Cu(L(1))Cl(2)].2H(2)O (1), [Cu(L(2))Cl(2)] (2) and [Cu(L(3))Cl(2)].H(2)O (3) (L(1) = 5,5'-Di[N9-adenylmethyl]-2,2'-bipyridine, L(2) = 5,5'-Di[N1-thyminylmethyl]-2,2'-bipyridine and L(3) = 5,5'-Di[N1-uracilmethyl]-2,2'-bipyridine) were synthesized and characterized. Structure simulation was performed for these complexes. Circular dichroism (CD) spectra revealed the interactions between these ligands and pBR322 DNA and showed that the local DNA structure was perturbed by these ligands. Cleavage of pBR322 DNA by these complexes was carried out in 20 mM HEPES (pH 7.5) at 37 degrees C. The calculated pseudo-Michaelis-Menten kinetic parameters (k(cat)) were 14.7 +/- 0.6 and 40.4 +/- 1.3 h(-1) for and . The cleavage efficiency of was 80-fold higher than that of its simple analogue [Cu(bpy)Cl(2)] (k(cat) = 0.50 h(-1)) and very close to the catalytic rate constant of natural EcoRI endonuclease (k(cat) = 43.2 h(-1)) at similar conditions. Thus, complex might be one of the most effective artificial nucleases that could catalyze double-stranded DNA hydrolytic cleavage so far. Hydrolytic mechanisms involved in DNA cleavage were explored using radical scavengers and T4 ligase. Competitive experiments with special binding agents showed that complexes could preferentially bind to the minor groove of double-stranded DNA, suggesting specific DNA binding characteristics. Molecular docking calculations also indicated that complexes could bind to the minor groove of targeted DNA much more strongly than their simple analogues and preferentially bind at the AT region of the dodecamer. Such high DNA cleavage ability and selectivity of these copper(ii) complexes could be attributed to the synergic effects of the metal center and the pendant nucleobases.

  2. Binuclear cobalt(II), nickel(II), copper(II) and palladium(II) complexes of a new Schiff-base as ligand: synthesis, structural characterization, and antibacterial activity.

    PubMed

    Geeta, B; Shravankumar, K; Reddy, P Muralidhar; Ravikrishna, E; Sarangapani, M; Reddy, K Krishna; Ravinder, V

    2010-11-01

    A binucleating new Schiff-base ligand with a phenylene spacer, afforded by the condensation of glycyl-glycine and o-phthalaldehyde has been served as an octadentate N₄O₄ ligand in designing some binuclear complexes of cobalt(II), nickel(II), copper(II), and palladium(II). The binding manner of the ligand to the metal and the composition and geometry of the metal complexes were examined by elemental analysis, conductivity measurements, magnetic moments, IR, ¹H, ¹³C NMR, ESR and electronic spectroscopies, and TGA measurements. There are two different coordination/chelation environments present around two metal centers of each binuclear complex. The composition of the complexes in the coordination sphere was found to be [M₂(L)(H(2)O)₄] (where M=Co(II) and Ni(II)) and [M₂(L)] (where M=Cu(II) and Pd(II)). In the case of Cu(II) complexes, ESR spectra provided further information to confirm the binuclear structure and the presence of magnetic interactions. All the above metal complexes have shown moderate to good antibacterial activity against Gram-positive and Gram-negative bacteria.

  3. Synthesis and characterization of iron(III), manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) complexes of salicylidene-N-anilinoacetohydrazone (H2L1) and 2-hydroxy-1-naphthylidene-N-anilinoacetohydrazone (H2L2).

    PubMed

    AbouEl-Enein, S A; El-Saied, F A; Kasher, T I; El-Wardany, A H

    2007-07-01

    Salicylidene-N-anilinoacetohydrazone (H(2)L(1)) and 2-hydroxy-1-naphthylidene-N-anilinoacetohydrazone (H(2)L(2)) and their iron(III), manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) complexes have been synthesized and characterized by IR, electronic spectra, molar conductivities, magnetic susceptibilities and ESR. Mononuclear complexes are formed with molar ratios of 1:1, 1:2 and 1:3 (M:L). The IR studies reveal various modes of chelation. The electronic absorption spectra and magnetic susceptibility measurements show that the iron(III), nickel(II) and cobalt(II) complexes of H(2)L(1) have octahedral geometry. While the cobalt(II) complexes of H(2)L(2) were separated as tetrahedral structure. The copper(II) complexes have square planar stereochemistry. The ESR parameters of the copper(II) complexes at room temperature were calculated. The g values for copper(II) complexes proved that the Cu-O and Cu-N bonds are of high covalency.

  4. Synthesis, characterization and DNA interaction of new copper(II) complexes of Schiff base-aroylhydrazones bearing naphthalene ring.

    PubMed

    Gökçe, Cansu; Gup, Ramazan

    2013-05-05

    Two new copper(II) complexes with the condensation products of methyl 2-naphthyl ketone with 4-hydroxybenzohydrazide, 4-hydroxy-N'-[(1Z)-1-(naphthalen-2-yl)ethylidene]benzohydrazide [HL(1)] and (Z)-ethyl 2-(4-(2-(1-(naphthalen-2-yl)ethylidene)hydrazinecarbonyl)phenoxy)acetate (HL(2)) were synthesized and characterized by elemental analysis, infrared spectra, UV-Vis electronic absorption spectra, magnetic susceptibility measurements, TGA, powder XRD and SEM-EDS. The binding properties of the copper(II) complexes with calf thymus DNA were studied by using the absorption titration method. DNA cleavage activities of the synthesized copper complexes were examined by using agarose gel electrophoresis. The effect of complex concentration on the DNA cleavage reactions in the absence and presence of H2O2 was also investigated. The experimental results suggest that the copper complexes bind significantly to calf thymus DNA by both groove binding and intercalation modes and cleavage effectively pBR322 DNA. The mechanistic studies demonstrate that a hydrogen peroxide-derived species and singlet oxygen ((1)O2) are the active oxidative species for DNA cleavage.

  5. Copper(II) complex of new non-innocent O-aminophenol-based ligand as biomimetic model for galactose oxidase enzyme in aerobic oxidation of alcohols

    NASA Astrophysics Data System (ADS)

    Safaei, Elham; Bahrami, Hadiseh; Pevec, Andrej; Kozlevčar, Bojan; Jagličić, Zvonko

    2017-04-01

    Mononuclear copper(II) complex of tetra-dentate o-aminophenol-based ligand (H2LBAPP) has been synthesized and characterized. The three dentate precursor (HLBAP) of the final ligand was synthesized first, while the title four-dentate copper bound ligand was synthesized in situ, isolated only in the final copper species [CuLBAPP]. This copper coordination complex reveals a distorted square-planar geometry around the copper(II) centre by one oxygen and three nitrogen atoms from the coordinating ligand. The ligand is thus twice deprotonated via hydroxy and amine groups. The complex is red, non-typical for copper(II), but the effective magnetic moment of 1.86 B M. and a single isotropic symmetry EPR signal with g 2.059 confirm a S = 1/2 diluted spin system, without copper-copper magnetic coupling. Electrochemical oxidation of this complex yields the corresponding Cu(II)-phenyl radical species. Finally, the title complex CuLBAPP has shown good and selective catalytic activity towards alcohol to aldehyde oxidation, at aerobic room temperature conditions, for a set of different alcohols.

  6. Quantitative investigation of copper(II) and zinc(II) complexes with S-carboxymethyl-L-cysteine and computer-simulated appraisal of their potential significance in vivo.

    PubMed

    Brumas, V; Venturini, M; Filella, M; Berthon, G

    1989-12-01

    S-carboxymethyl-L-cysteine (SCC) is a mucolytic agent extensively used in the treatment of respiratory tract disorders. Some of the undesirable side effects observed during SCC therapy being reminiscent of symptoms characteristic of copper and zinc imbalances, the objective of this paper was to test the possible interference of SCC with the metabolism of these two metals. Copper(II)- and zinc(II)-SCC complex equilibria have thus been investigated under physiological conditions by means of classical potentiometry combined with computer-assisted calculation techniques. Formation constants derived from these studies have then been used to simulate 1) the potential influence of SCC on the distribution of the above metals in blood plasma and 2) the extent to which gastrointestinal interactions between the drug and each metal ion in turn are likely to affect the bioavailability of each other. The results of these simulations show that 1) plasma therapeutic levels of SCC are not likely to induce dramatic changes in the distributions of copper(II) and zinc(II) low molecular weight fractions, 2) the gastrointestinal distribution of the drug is not affected by standard dietary doses of these metals, and 3) in contrast, therapeutic concentrations of SCC are capable of mobilizing significant fractions of both metals into tissue-diffusible electrically neutral complexes. In conclusion significant depletions of neither copper nor zinc are to be expected from oral administration of SCC. While the drug may to some extent facilitate the excretion of Cu2+ and Zn2+ ions from blood plasma, its gastrointestinal influence is, on the contrary, favorable to a better absorption of these two metals.

  7. 21 CFR 184.1315 - Ferrous sulfate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Ferrous sulfate. 184.1315 Section 184.1315 Food... GRAS § 184.1315 Ferrous sulfate. (a) Ferrous sulfate heptahydrate (iron (II) sulfate heptahydrate, Fe... pale, bluish-green crystals or granules. Progressive heating of ferrous sulfate heptahydrate...

  8. 21 CFR 184.1315 - Ferrous sulfate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ferrous sulfate. 184.1315 Section 184.1315 Food and... Substances Affirmed as GRAS § 184.1315 Ferrous sulfate. (a) Ferrous sulfate heptahydrate (iron (II) sulfate... as pale, bluish-green crystals or granules. Progressive heating of ferrous sulfate...

  9. Complexation abilities of neuropeptide gamma toward copper(II) ions and products of metal-catalyzed oxidation.

    PubMed

    Pietruszka, Marta; Jankowska, Elżbieta; Kowalik-Jankowska, Teresa; Szewczuk, Zbigniew; Smużyńska, Maria

    2011-08-15

    The stability constants, stoichiometry, and solution structures of copper(II) complexes of neuropeptide gamma (NPG) (D(1)-A-G-H(4)-G-Q-I-S-H(9)-K-R-H(12)-K-T-D-S-F-V-G-L-M(21)-NH(2)) and acethyl-neuropeptide gamma (Ac-D(1)-A-G-H(4)-G-Q-I-S-H(9)-K-R-H(12)-K-T-D-S-F-V-G-L-M(21)-NH(2)) were determined in aqueous solution. For both peptides the additional deprotonations were observed; therefore, the potentiometric data calculations for NPG were only made in 2.5-7.4 pH range. For Ac-NPG one additional deprotonation was observed, likely hydroxy group of Ser residue, and the potentiometric data calculations in the 2.5-10.5 pH range may be performed. The potentiometric and spectroscopic data (UV-vis, CD, EPR) for the neuropeptide gamma show that a D(1) residue stabilizes significantly the copper(II) complexes with 1N {NH(2),β-COO(-)}, 2N {NH(2),β-COO(-),N(Im)}, and 3N {NH(2),β-COO(-),2N(Im)} coordination modes as the result of coordination through the β-carboxylate group. The Ac-NPG forms with the copper(II) ions the 3N {3N(Im)} complex in a wide 4.5-7.5 pH range. At higher pH deprotonation and coordination of the sequential amide nitrogens occur. Metal-catalyzed oxidation of proteins is mainly a site-specific process in which amino acids at metal-binding sites to the protein are preferentially oxidized. To elucidate the products of the copper(II)-catalyzed oxidation of NPG and Ac-NPG the liquid chromatography-mass spectrometry method (LC-MS) and the Cu(II)/H(2)O(2) as a model oxidizing system were employed. For solutions containing a 1:4 peptide-hydrogen peroxide molar ratio oxidation of the methionine residue to methionine sulphone was observed. For the 1:1:4 Cu(II)-NPG-H(2)O(2) system oxidation of two His residues and cleavage of the G(3)-H(4) and R(11)-H(12) peptide bonds were detected, supporting involvement of His(4) and His(12) in binding of the copper(II) ions. Oxidations of three histidine residues to 2-oxohistidines and fragmentations of Ac-NPG near the His

  10. Anion-induced structural transformation of a sulfate-incorporated 2D Cd(II)-organic framework

    NASA Astrophysics Data System (ADS)

    Lee, Li-Wei; Luo, Tzuoo-Tsair; Wang, Chih-Min; Lee, Gene-Hsiang; Peng, Shie-Ming; Liu, Yen-Hsiang; Lee, Sheng-Long; Lu, Kuang-Lieh

    2016-07-01

    A Cd(II)-organic framework {[Cd2(tpim)4(SO4)(H2O)2]·(SO4)·21H2O}n (1) was synthesized by reacting CdSO4·8/3H2O and 2,4,5-tri(4-pyridyl)imidazole (tpim) under hydrothermal conditions. A structural analysis showed that compound 1 adopts a layered structure in which the [Cd(tpim)2]n chains are linked by sulfate anions. These 2D layers are further packed into a 3D supramolecular framework via π-π interactions. The structure contains two types of SO42- anions, i.e., bridging SO42- and free SO42- anions, the latter of which are included in the large channels of the framework. Compound 1 exhibits interesting anion exchange behavior. In the presence of SCN- anions, both the bridging and free SO42- anions in 1 were completely exchanged by SCN- ligands to form a 1D species [Cd(tpim)2(SCN)2] (1A), in which the SCN- moieties function as a monodentate ligand. On the other hand, when compound 1 was ion exchanged with N3- anions in aqueous solution, the bridging SO42- moieties remained intact, and only the free guest SO42- were replaced by N3- anions. The gas adsorption behavior of the activated compound 1 was also investigated.

  11. Cobalt(II), nickel(II) and copper(II) complexes of a hexadentate pyridine amide ligand. Effect of donor atom (ether vs. thioether) on coordination geometry, spin-state of cobalt and M(III)-M(II) redox potential.

    PubMed

    Pandey, Sharmila; Das, Partha Pratim; Singh, Akhilesh Kumar; Mukherjee, Rabindranath

    2011-10-28

    Using an acyclic hexadentate pyridine amide ligand, containing a -OCH(2)CH(2)O- spacer between two pyridine-2-carboxamide units (1,4-bis[o-(pyrydine-2-carboxamidophenyl)]-1,4-dioxabutane (H(2)L(9)), in its deprotonated form), four new complexes, [Co(II)(L(9))] (1) and its one-electron oxidized counterpart [Co(III)(L(9))][NO(3)]·2H(2)O (2), [Ni(II)(L(9))] (3) and [Cu(II)(L(9))] (4), have been synthesized. Structural analyses revealed that the Co(II) centre in 1 and the Ni(II) centre in 3 are six-coordinate, utilizing all the available donor sites and the Cu(II) centre in 4 is effectively five-coordinated (one of the ether O atoms does not participate in coordination). The structural parameters associated with the change in the metal coordination environment have been compared with corresponding complexes of thioether-containing hexadentate ligands. The μ(eff) values at 298 K of 1-4 correspond to S = 3/2, S = 0, S = 1 and S = 1/2, respectively. Absorption spectra for all the complexes have been investigated. EPR spectral properties of the copper(II) complex 4 have been investigated, simulated and analyzed. Cyclic voltammetric experiments in CH(2)Cl(2) reveal quasireversible Co(III)-Co(II), Ni(III)-Ni(II) and Cu(II)-Cu(I) redox processes. In going from ether O to thioether S coordination, the effect of the metal coordination environment on the redox potential values of Co(III)-Co(II) (here the effect of spin-state as well), Ni(III)-Ni(II) and Cu(II)-Cu(I) processes have been systematically analyzed.

  12. Atelosteogenesis type II is caused by mutations in the diastrophic dysplasia sulfate-transporter gene (DTDST): Evidence for a phenotypic series involving three chondrodysplasias

    SciTech Connect

    Haestbacka, J.; Lander, E.S.; Superti-Furga, A.

    1996-02-01

    Atelosteogenesis type II (AO II) is a neonatally lethal chondrodysplasia whose clinical and histological characteristics resemble those of another chondrodysplasia, the much less severe diastrophic dysplasia (DTD). The similarity suggests a shared pathogenesis involving lesions in the same biochemical pathway and perhaps the same gene. DTD is caused by mutations in the recently identified diastrophic dysplasia sulfate-transporter gene (DTDST). Here, we report that AOII patients also have DTDST mutations, which lead to defective uptake of inorganic sulfate and insufficient sulfation of macromolecules by patient mesenchymal cells in vitro. Together with our recent observation that a third even more severe chondrodysplasia, achondrogenesis type IB, is also caused by mutations in DTDST, these results demonstrate a phenotypic series of three chondrodysplasias of increasing severity caused by lesions in a single sulfate-transporter gene. The severity of the phenotype appears to be correlated with the predicted effect of the mutations on the residual activity of the DTDST protein. 24 refs., 6 figs., 1 tab.

  13. Synthesis, characterization, antibacterial activity, SOD mimic and interaction with DNA of drug based copper(II) complexes

    NASA Astrophysics Data System (ADS)

    Patel, Mohan N.; Dosi, Promise A.; Bhatt, Bhupesh S.; Thakkar, Vasudev R.

    2011-02-01

    Novel metal complexes of the second-generation quinolone antibacterial agent enrofloxacin with copper(II) and neutral bidentate ligands have been prepared and characterized with elemental analysis reflectance, IR and mass spectroscopy. Complexes have been screened for their in-vitro antibacterial activity against two Gram (+ve)Staphylococcus aureus, Bacillus subtilis, and three Gram (-ve)Serratia marcescens, Escherichia coli and Pseudomonas aeruginosa organisms using the double dilution technique. The binding of this complex with CT-DNA has been investigated by absorption titration, salt effect and viscosity measurements. Binding constant is ranging from 1.3 × 10 4-3.7 × 10 4. The cleavage ability of complexes has been assessed by gel electrophoresis using pUC19 DNA. The catalytic activity of the copper(II) complexes towards the superoxide anion (O 2rad -) dismutation was assayed by their ability to inhibit the reduction of nitroblue tetrazolium (NBT).

  14. Copper(II)-Mediated Self-Assembly of Hairpin Peptides and Templated Synthesis of CuS Nanowires.

    PubMed

    Wang, Chengdong; Sun, Yawei; Wang, Jiqian; Xu, Hai; Lu, Jian R

    2015-09-01

    The self-assembly of peptides and proteins under well-controlled conditions underlies important nanostructuring processes that could be harnessed in practical applications. Herein, the synthesis of a new hairpin peptide containing four histidine residues is reported and the self-assembly process mediated by metal ions is explored. The work involves the combined use of circular dichroism, NMR spectroscopy, UV/Vis spectroscopy, AFM, and TEM to follow the structural and morphological details of the metal-coordination-mediated folding and self-assembly of the peptide. The results indicate that by forming a tetragonal coordination geometry with four histidine residues, copper(II) ions selectively trigger the peptide to fold and then self-assemble into nanofibrils. Furthermore, the copper(II)-bound nanofibrils template the synthesis of CuS nanowires, which display a near-infrared laser-induced thermal effect.

  15. Interaction of a copper(II)-Schiff base complexes with calf thymus DNA and their antimicrobial activity.

    PubMed

    Sabolová, D; Kožurková, M; Plichta, T; Ondrušová, Z; Hudecová, D; Simkovič, M; Paulíková, H; Valent, A

    2011-03-01

    The interaction of a copper complexes containing Schiff bases with calf thymus (CT) DNA was investigated by spectroscopic methods. UV-vis, fluorescence and CD spectroscopies were conducted to assess their binding ability with CT DNA. The binding constants K have been estimated from 0.8 to 9.1×10(4) M(-1). The percentage of hypochromism is found to be over 70% (from spectral titrations). The results showed that the copper(II) complexes could bind to DNA with an intercalative mode. Synergic action of Cu(II) complexes with ascorbic acid against Candida albicans induced the generation of free radicals and increased (more than 60 times) antimicrobial effect of these complexes.

  16. Copper(II) complexes of N-(phosphonomethyl)glycine in aqueous solution: a thermodynamic and spectrophotometric study.

    PubMed

    Daniele, P G; De Stefano, C; Prenesti, E; Sammartano, S

    1997-12-19

    Copper(II) complexes with the herbicide N-(phosphonomethyl)glycine (glyphosate) have been investigated in aqueous solution by means of pH-metric measurements at different temperatures, 5 Copper(II)-glyphosate complexes are quite stable and must be taken into account in the speciation of natural fluids.

  17. Copper(II) cubanes with a {Cu4O} core and well defined S = 1 ground state.

    PubMed

    Escuer, A; Mayans, J; Font-Bardia, M

    2016-01-28

    The reaction of 2-pyridinemethanol with copper 4-fluorobenzoate has yielded a family of type II cubanes with formula [Cu4(pymO)4(4-F-PhCOO)3(NO3)] (), [Cu4(pymO)4(4-F-PhCOO)4] () and [Cu4(pymO)4(4-F-PhCOO)4(H2O)] (). These systems exhibit an unexpected S = 1 ground state and their magnetic properties have been unambiguously characterized and rationalized as a function of the asymmetry of the {Cu4O4} cage and Cu-O-Cu bond angles. Analysis of the coupling constants was performed applying new interaction schemes. Magneto-structural correlations have been performed from the analysis of previously reported type II copper cubanes.

  18. Synthesis, characterization, and structures of copper(II)-thiosulfate complexes incorporating tripodal tetraamine ligands.

    PubMed

    Fischmann, Adam J; Warden, Andrew C; Black, Jay; Spiccia, Leone

    2004-10-18

    The reaction of [Cu(L)(H(2)O)](2+) with an excess of thiosulfate in aqueous solution produces a blue to green color change indicative of thiosulfate coordination to Cu(II) [L = tren, Bz(3)tren, Me(6)tren, and Me(3)tren; tren = tris(2-aminoethyl)amine, Bz(3)tren = tris(2-benzylaminoethyl)amine, Me(6)tren = tris(2,2-dimethylaminoethyl)amine, and Me(3)tren = tris(2-methylaminoethyl)amine]. In excess thiosulfate, only [Cu(Me(6)tren)(H(2)O)](2+) promotes the oxidation of thiosulfate to polythionates. Products suitable for single-crystal X-ray diffraction analyses were obtained for three thiosulfate complexes, namely, [Cu(tren)(S(2)O(3))].H(2)O, [Cu(Bz(3)tren)(S(2)O(3))].MeOH, and (H(3)Me(3)tren)[Cu(Me(3)tren)(S(2)O(3))](2)(ClO(4))(3). Isolation of [Cu(Me(6)tren)(S(2)O(3))] was prevented by its reactivity. In each complex, the copper(II) center is found in a trigonal bipyramidal (TBP) geometry consisting of four amine nitrogen atoms, with the bridgehead nitrogen in an axial position and an S-bound thiosulfate in the other axial site. Each structure exhibits H bonding (involving the amine ligand, thiosulfate, and solvent molecule, if present), forming either 2D sheets or 1D chains. The structure of [Cu(Me(3)tren)(MeCN)](ClO(4))(2) was also determined for comparison since no structures of mononuclear Cu(II)-Me(3)tren complexes have been reported. The thiosulfate binding constant was determined spectrophotometrically for each Cu(II)-amine complex. Three complexes yielded the highest values reported to date [K(f) = (1.82 +/- 0.09) x 10(3) M(-1) for tren, (4.30 +/- 0.21) x 10(4) M(-1) for Bz(3)tren, and (2.13 +/- 0.05) x 10(3) M(-1) for Me(3)tren], while for Me(6)tren, the binding constant was much smaller (40 +/- 10 M(-1)).

  19. Antimalarial evaluation of copper(II) nanohybrid solids: inhibition of plasmepsin II, a hemoglobin-degrading malarial aspartic protease from Plasmodium falciparum.

    PubMed

    Mohapatra, Subash Chandra; Tiwari, Hemandra Kumar; Singla, Manisha; Rathi, Brijesh; Sharma, Arun; Mahiya, Kuldeep; Kumar, Mukesh; Sinha, Saket; Chauhan, Shyam Singh

    2010-03-01

    A new class of copper(II) nanohybrid solids, LCu(CH(3)COO)(2) and LCuCl(2), have been synthesized and characterized by transmission electron microscopy, dynamic light scattering, and IR spectroscopy, and have been found to be capped by a bis(benzimidazole) diamide ligand (L). The particle sizes of these nanohybrid solids were found to be in the ranges 5-10 and 60-70 nm, respectively. These nanohybrid solids were evaluated for their in vitro antimalarial activity against a chloroquine-sensitive isolate of Plasmodium falciparum (MRC 2). The interactions between these nanohybrid solids and plasmepsin II (an aspartic protease and a plausible novel target for antimalarial drug development), which is believed to be essential for hemoglobin degradation by the parasite, have been assayed by UV-vis spectroscopy and inhibition kinetics using Lineweaver-Burk plots. Our results suggest that these two compounds have antimalarial activities, and the IC(50) values (0.025-0.032 microg/ml) are similar to the IC(50) value of the standard drug chloroquine used in the bioassay. Lineweaver-Burk plots for inhibition of plasmepsin II by LCu(CH(3)COO)(2) and LCuCl(2) show that the inhibition is competitive with respect to the substrate. The inhibition constants of LCu(CH(3)COO)(2) and LCuCl(2) were found to be 10 and 13 microM, respectively. The IC(50) values for inhibition of plasmepsin II by LCu(CH(3)COO)(2) and LCuCl(2) were found to be 14 and 17 microM, respectively. Copper(II) metal capped by a benzimidazole group, which resembles the histidine group of copper proteins (galactose oxidase, beta-hydroxylase), could provide a suitable anchoring site on the nanosurface and thus could be useful for inhibition of target enzymes via binding to the S1/S3 pocket of the enzyme hydrophobically. Both copper(II) nanohybrid solids were found to be nontoxic against human hepatocellular carcinoma cells and were highly selective for plasmepsin II versus human cathepsin D. The pivotal mechanism of

  20. Plasmid-encoded copper resistance and precipitation by Mycobacterium scrofulaceum.

    PubMed Central

    Erardi, F X; Failla, M L; Falkinham, J O

    1987-01-01

    A copper-tolerant Mycobacterium scrofulaceum strain was able to remove copper from culture medium by sulfate-dependent precipitation as copper sulfide. Such precipitation of copper sulfide was not observed in a derivative that lacks a 173-kilobase plasmid. In addition, the plasmid-carrying strain has a sulfate-independent copper resistance mechanism. PMID:3662522

  1. Tunable DNA cleavage activity promoted by copper(ii) ternary complexes with N-donor heterocyclic ligands.

    PubMed

    Bortolotto, T; Silva-Caldeira, P P; Pich, C T; Pereira-Maia, E C; Terenzi, H

    2016-06-04

    Several small molecules have the capacity to cleave DNA promptly at high yields, even under mild conditions. Usually, this activity has no constraints, occurring without external or user control. Here, we demonstrate that UV-light exposure can greatly enhance the DNA cleavage activity promoted by four ternary copper(ii) complexes. A remarkable photocontrolled activity was achieved, which may be interesting for chemical and biochemical applications.

  2. Synthesis of 2,5-disubstituted oxazoles and oxazolines catalyzed by ruthenium(II) porphyrin and simple copper salts.

    PubMed

    Zhong, Chuan Long; Tang, Bo Yang; Yin, Ping; Chen, Yue; He, Ling

    2012-05-04

    A novel and moderate synthesis of 2,5-disubstituted oxazoles and oxazolines involving ruthenium(II) porphyrin-copper chloride catalyzed cyclization was developed. These reactions using readily available benzene carboxylic acids and phenylethenes or phenylacetylenes are performed under mild conditions. The reactions proceed in series, giving rise to the formation of an intermolecular C-N bond and an intramolecular C-O bond, which yield oxazole or oxazoline derivatives simultaneously.

  3. Templated Synthesis of Silver(I) and Copper(II) Nanostructures: Solid State Reactions and Applications

    NASA Astrophysics Data System (ADS)

    Bourret, Gilles R.

    2011-12-01

    This Thesis presents the synthesis of novel 1D, 2D, and 3D Ag(I) and Cu(II) nanostructures and their use as sacrificial templates to make functional nanomaterials. New soft template methods were developed for the synthesis of AgCN and Cu(OH)2 nanostructures. Polymeric organic nanotubes were successfully used to synthesize AgCN nanowires, while the precipitation of Cu(OH)2 nanofibers was templated in water microdroplets. Both methods benefit from the versatility of soft templates and allows for a control of both the size and the morphology of the nanostructures produced. The conversion of these precursors into metallic and semi-conductive nanomaterials was achieved via chemical and electrochemical reduction, and thermolysis. Chemical reduction of the AgCN nanowires leads to the fabrication of conductive arrays on nylon filter substrates, while the thermolysis of the Cu(OH)2 spherical assemblies yields photoresponsive semi-conductive porous CuO spheres. The electrochemical reduction of the native Ag(I) and Cu(II) one-dimensional nanostructures was investigated in aqueous solution at gold/glass/gold junctions. The solid-solid conversion involved in the electrochemical reduction process was studied via cyclic voltammetry, chronoamperometry, and electronic microscopy. The strong influence of the reduction potential on the nanomaterials produced allowed for the fabrication of a range of Ag(0) nanostructures, including nanoparticles, nanoprisms, nanofibers and porous networks. Electrochemical reduction of Au/M2+/Au junctions leads to the formation of an excellent electrical contact between the two gold electrodes. This technique was expanded to include ionically-conductive Ag2S nanowires which form metallic/ionic-conductor heterojunctions. Keywords: nanostructure, nanowire, template, emulsion, electrochemistry, silver, cyanide, copper, oxide, heterojunction, sacrificial template.

  4. Exchange Coupling in the Sulfur Bridged Quasi Linear Chain Compound Bis(dimethyldithiocarbamato)Copper(II). Observations on Exchange in Sulfur-Bridge Copper(II) Compounds.

    DTIC Science & Technology

    1980-06-02

    formation . The Cu-Sb-Cu angle is 86.90. The sixth coordination site of copper is blocked by a hydrogen atom from an ethyl group of a neighboring dimer... dimethylethylenediamine , 32 3 3 2-methylpyridine,34 ,35 and tetramethylene- 36 sulfoxide. In these latter compounds the angles at the chloride bridge 33 34 range from 860

  5. Kinetic study on removal of copper(II) using goethite and hematite nano-photocatalysts.

    PubMed

    Chen, Yen-Hua; Li, Fu-An

    2010-07-15

    Goethite and hematite nanomaterials (nano-goethite and nano-hematite) can be synthesized using a coprecipitation method. Nano-hematite is synthesized via the reaction of HCl and FeCl(3) solution at 100 degrees C for 2 days, while nano-goethite is prepared by adding Fe(2)(SO(4))(3) into the 2.5 M NaOH solution for 4h, and then heated at 40 degrees C for 2 days. Afterward the photocatalytic decomposition of methylene blue solution is performed by UV-light irradiation, and the adsorption procedure is carried out by batch experiments. It is observed that both nano-hematite and nano-goethite exhibit some photocatalytic activity and possess a high adsorption capacity for copper ions. The maximum Cu(II) adsorption capacity is 149.25 and 84.46 mg/g for nano-goethite and nano-hematite, respectively. Further, the experimental data are well fitted to the pseudo-second-order equation. It also suggests that the Langmuir isotherm is more adequate than the Freundlich isotherm in simulating the adsorption isotherm of Cu(2+), and the Cu(2+) adsorption onto nanomaterials is a spontaneous process. Therefore, these findings indicate that nano-goethite and nano-hematite are effective materials for Cu(2+) removal and, together with its photocatalytic activity, may be applied in the removal of heavy metal ions from aqueous streams.

  6. Potential-modulated DNA cleavage by (N-salicylideneglycinato)copper(II) complex.

    PubMed

    Yang, Zhou-Sheng; Wang, Yan-Ling; Liu, Yun-Chun; Zhao, Guang-Chao

    2005-11-01

    The interaction of aqua (N-salicylideneglycinato)copper(II) (Cu(salgly)2+) complex with calf thymus DNA has been investigated by cyclic voltammetry. Potential-modulated DNA cleavage in the presence of Cu(salgly)2+ complex was performed at a gold electrode in a thin layer cell. DNA can be efficiently cleaved by electrochemically reducing Cu(salgly)2+ complex to Cu(salgly)+ complex at -0.7 V (vs. Ag/AgCl). When the solution was aerated with a small flow of O2 during electrolysis, the extent of DNA cleavage was dramatically enhanced, and hydroxyl radical scavengers inhibited DNA cleavage. These results suggested that O2 and hydroxyl radical were involved in potential-modulated DNA cleavage reaction. The percentage of DNA cleavage was enhanced as the working potential was shifted to more negative values and the electrolysis time was increased. It was also dependent on the ratio of Cu(salgly)2+ complex to DNA concentration. The cleaved DNA fragments were separated by high performance liquid chromatography (HPLC). The experimental results indicated that the method for potential-modulated DNA cleavage by Cu(salgly)2+ complex was simple and efficient.

  7. Synthesis, structure, spectroscopic and electrochemical properties of bis(histamine-saccharinate) copper(II) complex

    NASA Astrophysics Data System (ADS)

    Bulut, İclal; Uçar, İbrahim; Karabulut, Bünyamin; Bulut, Ahmet

    2007-05-01

    Crystal structure of [Cu(hsm) 2(sac) 2] (hsm is histamine and sac is saccharinate) complex has been determined by X-ray diffraction analyses and its magnetic environment has been identified by electron paramagnetic resonance (EPR) technique. The title complex crystallizes in the monoclinic system, space group P 21/ c with a = 7.4282(4), b = 22.5034(16), c = 8.3300(5) Å, β = 106.227(4)°, V = 1336.98(14) Å 3, and Z = 2. The structure consist of discrete [Cu(hsm) 2(sac) 2] molecules in which the copper ion is centrosymmetrically coordinated by two histamine ligands forming an equatorial plane [Cu-N hsm = 2.024(2) and Cu-N hsm = 2.0338(18) Å]. Two N atoms from the saccharinate ligands coordinate on the elongated axial positions with Cu-N sac being 2.609(5) Å. The complex is also characterized by spectroscopic (IR, UV/Vis) and thermal (TG, and TDA) methods. The cyclic voltammogram of the title complex investigated in DMSO (dimethylsulfoxide) solution exhibits only metal centred electroactivity in the potential range - 1.25-1.5 V versus Ag/AgCl reference electrode. The molecular orbital bond coefficients of Cu(II) ion in d 9 state is also calculated by using EPR and optical absorption parameters.

  8. Synthesis, characterization and biological activity of ternary copper(II) complexes containing polypyridyl ligands

    NASA Astrophysics Data System (ADS)

    Patel, R. N.; Singh, Nripendra; Shukla, K. K.; Gundla, V. L. N.; Chauhan, U. K.

    2006-01-01

    Ternary copper(II) complexes involving polypyridyl ligands in the coordination sphere of composition [Cu(tpy)(phen)](ClO4)2 (1), [Cu(tpy)(bipy)](ClO4)2 (2), [Cu(tptz)(phen)](ClO4)2 (3) and [Cu(tptz)(bipy)](BF4)2 (4) where tpy = 2,2‧:6‧,2″-terpyridine, tptz = 2,4,6-tri(2-pyridyl)-1,3,5-triazine, phen = 1,10-phenanthroline and bipy = 2,2‧-bipyridine have been synthesized and characterized by elemental analysis, magnetic susceptibility, X-band e.p.r. spectroscopy and electronic spectroscopy. Single crystal X-ray of (1) has revealed the presence of a distorted square pyramidal geometry in the complex. Magnetic susceptibility measurements at room temperature were in the range of 1.77-1.81 BM. SOD and antimicrobial activities of these complexes were also measured. Crystal data of (1): P-1, a = 9.3010(7) Å, b = 9.7900(6) Å, c = 16.4620(6) Å, Vc = 1342.73(14) Å3, Z = 4. The bond distance of Cusbnd N in square base is 2 ± 0.04 Å.

  9. Synthesis, characterization, DNA binding, cleavage activity and cytotoxicity of copper(II) complexes.

    PubMed

    Li, Mei-Jin; Lan, Tao-Yu; Cao, Xiu-Hui; Yang, Huang-Hao; Shi, Yupeng; Yi, Changqing; Chen, Guo-Nan

    2014-02-21

    Three new mononuclear copper(II) complexes, [Cu(L2)](2+) (1), [Cu(acac)(L)](+) (2), and [Cu(acac-Cl)(L)](+) (3) (L = 2-(4-pyridine)oxazo[4,5-f]1,10-phenanthroline (4-PDOP); acac = acetylacetone; acac-Cl = 3-chloroacetylacetone), have been synthesized and characterized by elemental analysis, high resolution mass spectrometry (Q-TOF), and IR spectroscopy. Two of the complexes were structurally characterized by single-crystal X-ray diffraction techniques. Their interactions with DNA were studied by UV-vis absorption and emission spectra, viscosity, thermal melting, DNA unwinding assay and CD spectroscopy. The nucleolytic cleavage activity of the compounds was carried out on double stranded pBR322 circular plasmid DNA by using a gel electrophoresis experiment in the presence and absence of an oxidant (H2O2). Active oxygen intermediates such as hydroxyl radicals and hydrogen peroxide generated in the presence of L and complexes 1-3 may act as active species for the DNA scission. The cytotoxicity of the complexes against HepG2 cancer cells was also studied.

  10. Spectroscopic studies on Solvatochromism of mixed-chelate copper(II) complexes using MLR technique.

    PubMed

    Golchoubian, Hamid; Moayyedi, Golasa; Fazilati, Hakimeh

    2012-01-01

    Mixed-chelate copper(II) complexes with a general formula [Cu(acac)(diamine)]X where acac=acetylacetonate ion, diamine=N,N-dimethyl,N'-benzyl-1,2-diaminoethane and X=BPh(4)(-), PF(6)(-), ClO(4)(-) and BF(4)(-) have been prepared. The complexes were characterized on the basis of elemental analysis, molar conductance, UV-vis and IR spectroscopies. The complexes are solvatochromic and their solvatochromism were investigated by visible spectroscopy. All complexes demonstrated the positive solvatochromism and among the complexes [Cu(acac)(diamine)]BPh(4)·H(2)O showed the highest Δν(max) value. To explore the mechanism of interaction between solvent molecules and the complexes, different solvent parameters such as DN, AN, α and β using multiple linear regression (MLR) method were employed. The statistical results suggested that the DN parameter of the solvent plays a dominate contribution to the shift of the d-d absorption band of the complexes.

  11. One-dimensional chiral copper (II) complexes with novel nano-structures and superior antitumor activity.

    PubMed

    Zhang, Wei Chuan; Tang, Xue; Lu, Xiaoming

    2016-03-01

    Three novel copper(II) compounds of formulas {[Cu(Phen)(Ala)]·NO3·H2O}n (1), {[Cu(Phen)(Ala)]·NO3}n (2) and [Cu(Ala)2]n (3) have been synthesized and determined by X-ray diffraction. 1 and 2 are shown in one dimensional long-chain chiral structures, and 3 is a two dimensional checkerboard-type structure. Both 1 and 2 displayed a higher anticancer activity than 3 against various cancer cells, even higher than the similar mononuclear complexes and clinical anticancer drug 5-fluorouracil. The noncancerous cell lines (CCC-HEL-1) have showed that complexes 1-3 have hardly any cytotoxicity. Transmission electron microscopy was studied to show the nano-structure and π function of two complexes. The ligand 1,10-phenanthroline inserted into its enantiomer lead complex 1 stable, and the π-π interaction outside the chain made complex 2 active, which is easy to crack and pile up together. In addition, the energy gaps, UV-vis, luminescent and cyclic voltammetry were experimented to show the stable one dimensional long-chain chiral structure and the π function of two complexes.

  12. Angiotensin II type 1 receptor blockers increase tolerance of cells to copper and cisplatin

    PubMed Central

    Spincemaille, Pieter; Chandhok, Gursimran; Zibert, Andree; Schmidt, Hartmut; Verbeek, Jef; Chaltin, Patrick; Cammue, Bruno P.; Cassiman, David; Thevissen, Karin

    2014-01-01

    The human pathology Wilson disease (WD) is characterized by toxic copper (Cu) accumulation in brain and liver, resulting in, among other indications, mitochondrial dysfunction and apoptosis of hepatocytes. In an effort to identify novel compounds that can alleviate Cu-induced toxicity, we screened the Pharmakon 1600 repositioning library using a Cu-toxicity yeast screen. We identified 2 members of the drug class of Angiotensin II Type 1 receptor blockers (ARBs) that could increase yeast tolerance to Cu, namely Candesartan and Losartan. Subsequently, we show that specific ARBs can increase yeast tolerance to Cu and/or the chemotherapeutic agent cisplatin (Cp). The latter also induces mitochondrial dysfunction and apoptosis in mammalian cells. We further demonstrate that specific ARBs can prevent the prevalence of Cu-induced apoptotic markers in yeast, with Candesartan Cilexetil being the ARB which demonstrated most pronounced reduction of apoptosis-related markers. Next, we tested the sensitivity of a selection of yeast knockout mutants affected in detoxification of reactive oxygen species (ROS) and Cu for Candesartan Cilexetil rescue in presence of Cu. These data indicate that Candesartan Cilexetil increases yeast tolerance to Cu irrespectively of major ROS-detoxifying proteins. Finally, we show that specific ARBs can increase mammalian cell tolerance to Cu, as well as decrease the prevalence of Cu-induced apoptotic markers. All the above point to the potential of ARBs in preventing Cu-induced toxicity in yeast and mammalian cells. PMID:28357214

  13. Human telomeric G-quadruplex DNA interactions of N-phenanthroline glycosylamine copper(II) complexes.

    PubMed

    Duskova, Katerina; Sierra, Sara; Arias-Pérez, María-Selma; Gude, Lourdes

    2016-01-01

    We report in this article the interactions of five N-(1,10-phenanthrolin-5-yl)-β-glycopyranosylamine copper(II) complexes with G-quadruplex DNA. Specifically, the interactions of these compounds with a human telomeric oligonucleotide have been assessed by fluorescence-based assays (FRET melting and G4-FID), circular dichroism and competitive equilibrium dialysis experiments. The metal complexes bind and stabilize G-quadruplex DNA structures with apparent association constants in the order of 10(4)-10(5)M(-1) and the affinity observed is dependent on the ionic conditions utilized and the specific nature of the carbohydrate moiety tethered to the 1,10-phenanthroline system. The compounds showed only a slight preference to bind G-quadruplex DNA over duplex DNA when the quadruplex DNA was folded in sodium ionic conditions. However, the binding affinity and selectivity, although modest, were notably increased when the G-quadruplex DNA was folded in the presence of potassium metal ions. Moreover, the study points towards a significant contribution of groove and/or loop binding in the recognition mode of quadruplex structures by these non-classical quadruplex ligands. The results reported herein highlight the potential and the versatility of carbohydrate bis-phenanthroline metal-complex conjugates to recognize G-quadruplex DNA structures.

  14. Immobilized copper(II) macrocyclic complex on MWCNTs with antibacterial activity

    NASA Astrophysics Data System (ADS)

    Tarlani, Aliakbar; Narimani, Khashayar; Mohammadipanah, Fatemeh; Hamedi, Javad; Tahermansouri, Hasan; Amini, Mostafa M.

    2015-06-01

    In a new approach, a copper(II) tetraaza macrocyclic complex (CuTAM) was covalently bonded on modified multi-walled carbon nanotubes (MWCNTs). To achieve this purpose, MWCNTs were converted to MWCNT-COCl and then reacted to NH groups of TAM ligand. The prepared material was characterized by Fourier Transform Infrared (FT-IR), X-ray diffraction (XRD), Raman spectroscopy, thermal gravimetric analysis (TGA), and FESEM (field emission scanning electron microscopy). FT-IR and TGA demonstrated the presence of the organic moieties, and XRD proved that the structure of MWCNTs remained intact during the three modification steps. An increase in the ID/IG ratio in Raman spectra confirmed the surface modifications. Finally, the samples were subjected to an antibacterial assessment to compare their biological activity. The antibacterial test showed that the grafted complex on the surface of the nanotube (MWCNT-CO-CuTAM) has higher antibacterial activity against Bacillus subtilis ATCC 6633 than the MWCNT-COOH and CuTAM with 1000 and 2000 μg/mL.

  15. Maps showing distribution of pH, copper, zinc, fluoride, uranium, molybdenum, arsenic, and sulfate in water, Richfield 1 degree by 2 degrees Quadrangle, Utah

    USGS Publications Warehouse

    McHugh, J.B.; Miller, W.R.; Ficklin, W.H.

    1984-01-01

    These maps show the regional distribution of copper, zinc, arsenic, molybdenum, uranium, fluoride, sulfate, and pH in surface and ground water from the Richfield 1° x 2° quadrangle. This study supplements (Miller and others, 1984a-j) the regional drainage geochemical study done for the Richfield quadrangle under the U.S. Geological Survey’s Conterminuous United States Mineral Assessment Program (CUSMAP). Regional sampling was designed to define broad geochemical patterns and trends which can be used, along with geologic and geophysical data, to assess the mineral resource potential of the Richfield quadrangle. Analytical data used in compiling this report were published previously (McHugh and others, 1981). The Richfield quadrangle in west-central Utah covers the eastern part of the Pioche-Marysvale igneous and mineral belt that extends from the vicinity of Pioche in southeastern Nevada, east-northeastward for 250 km into central Utah. The western two-thirds of the Richfield quadrangle is in the Basin and Range Province, and the eastern third in the High Plateaus of Utah subprovince of the Colorado Plateau. Bedrock in the northern part of the Richfield quadrangle consists predominantly of latest Precambrian and Paleozoic sedimentary strata that were thrust eastward during the Sevier orogeny in Cretaceous time onto an autochthon of Mesozoic sedimentary rocks in the eastern part of the quadrangle. The southern part of the quadrangle is largely underlain by Oligocene and younger volcanic rocks and related intrusions. Extensional tectonism in late Cenozoic time broke the bedrock terrane into a series of north-trending fault blocks; the uplifted mountain areas were deeply eroded and the resulting debris deposited in the adjacent basins. Most of the mineral deposits in the Pioche-Marysvale mineral belt were formed during igneous activity in the middle and late Cenozoic time.

  16. Sulfur and oxygen isotope study of the Vermont copper belt: evidence of seawater hydrothermal alteration and sulfate reduction in a high-grade metamorphic terrane

    SciTech Connect

    Shanks, W.C. III; Woodruff, L.G.; Slack, J.F.

    1985-01-01

    Massive sulfide deposits of the Orange County copper district, in east-central Vermont, consist of stratiform lenses of pyrrhotite, chalcopyrite, and minor sphalerite within amphibolite-facies rocks of Early Devonian (.) age. The deposits occur at several different stratigraphic levels. The two largest, Elizabeth and Ely, are in quartz-mica schists of the Gile Mountain Formation; the Pike Hill deposit occurs in calcareous quartz-mica schist of the underlying Waits River Formation. Two small deposits (Orange and Gove) are within the Standing Pond Volcanics, a thin tholeiitic amphibolite near the Gile Mountain-Waits River contact. The Elizabeth deposit in particularly distinctive, and contains a suite of unusual wall rocks rich in quartz, carbonate, muscovite, amphibole, phlogopite, tourmaline, spessartine, and sodic plagioclase. Sulfur isotope values at Elizabeth and Ely of 5.1 to 9.1 per thousands contrast with values for Gove (1.9 to 4.2) and Pike Hill (1.5 to 4.6). Disseminated sulfides in amphibolites of the Standing Pond Volcanics have sulfur isotope values in the range -0.1 to 1.7 per thousands, typical of MORB. These data require sulfur contributions to massive sulfide deposits both from basalt and from contemporaneous seawater sulfate sources. Whole-rock (carbonate free) oxygen isotope analyses of host lithologies range from 7.9 per thousands (Standing Pond Volcanics) to 19.9 per thousands (Waits River Formation). Detailed sampling of Elizabeth wall rocks (including those high in B, Na, Mg, Al, Si, Mn) yields a narrow range of oxygen isotope values (11.1 to 14.1); heavier values correlate with higher silica contents. Isotopically light wallrock lithologies are probably due to premetamorphic seawater hydrothermal alteration.

  17. High-field 1H T1 and T2 NMR relaxation time measurements of H2O in homeopathic preparations of quartz, sulfur, and copper sulfate

    NASA Astrophysics Data System (ADS)

    Baumgartner, Stephan; Wolf, Martin; Skrabal, Peter; Bangerter, Felix; Heusser, Peter; Thurneysen, André; Wolf, Ursula

    2009-09-01

    Quantitative meta-analyses of randomized clinical trials investigating the specific therapeutic efficacy of homeopathic remedies yielded statistically significant differences compared to placebo. Since the remedies used contained mostly only very low concentrations of pharmacologically active compounds, these effects cannot be accounted for within the framework of current pharmacology. Theories to explain clinical effects of homeopathic remedies are partially based upon changes in diluent structure. To investigate the latter, we measured for the first time high-field (600/500 MHz) 1H T1 and T2 nuclear magnetic resonance relaxation times of H2O in homeopathic preparations with concurrent contamination control by inductively coupled plasma mass spectrometry (ICP-MS). Homeopathic preparations of quartz (10 c-30 c, n = 21, corresponding to iterative dilutions of 100-10-100-30), sulfur (13 x-30 x, n = 18, 10-13-10-30), and copper sulfate (11 c-30 c, n = 20, 100-11-100-30) were compared to n = 10 independent controls each (analogously agitated dilution medium) in randomized and blinded experiments. In none of the samples, the concentration of any element analyzed by ICP-MS exceeded 10 ppb. In the first measurement series (600 MHz), there was a significant increase in T1 for all samples as a function of time, and there were no significant differences between homeopathic potencies and controls. In the second measurement series (500 MHz) 1 year after preparation, we observed statistically significant increased T1 relaxation times for homeopathic sulfur preparations compared to controls. Fifteen out of 18 correlations between sample triplicates were higher for controls than for homeopathic preparations. No conclusive explanation for these phenomena can be given at present. Possible hypotheses involve differential leaching from the measurement vessel walls or a change in water molecule dynamics, i.e., in rotational correlation time and/or diffusion. Homeopathic preparations

  18. Acid-base interactions and complex formation while recovering copper(II) ions from aqueous solutions using cellulose adsorbent in the presence of polyvinylpyrrolidone

    NASA Astrophysics Data System (ADS)

    Nikiforova, T. E.; Kozlov, V. A.; Islyaikin, M. K.

    2012-12-01

    The sorption properties of nontreated cotton cellulose and cellulose modified with polyvinylpyrrolidone with respect to copper(II) ions are investigated. It is established that modified cellulose adsorbents have high sorption capability associated with the formation of new sorption centers during treatment with nitrogen-containing polymer. A mechanism is proposed for acid-base interactions in aqueous solutions of acids, bases, and salts during copper(II) cation recovery using cellulose adsorbent with the participation of polyvinylpyrrolidone.

  19. Pyrrolidine and Piperidine Formation Via Copper(II) Carboxylate Promoted Intramolecular Carboamination of Unactivated Olefins: Diastereoselectivity and Mechanism

    PubMed Central

    Sherman, Eric S.; Fuller, Peter H.; Kasi, Dhanalakshmi; Chemler, Sherry R.

    2008-01-01

    An expanded substrate scope and in depth analysis of the reaction mechanism of the copper(II) carboxylate promoted intramolecular carboamination of unactivated alkenes is described. This method provides access to N-functionalized pyrrolidines and piperidines. Both aromatic and aliphatic γ- and δ-alkenyl N-arylsulfonamides undergo the oxidative cyclization reaction efficiently. N-Benzoyl-2-allylaniline also underwent the oxidative cyclization. The terminal olefin substrates examined were more reactive than those with internal olefins, and the latter terminated in elimination rather than carbon-carbon bond formation. The efficiency of the reaction was enhanced by the use of more organic soluble copper(II) carboxylate salts, copper(II) neodecanoate in particular. The reaction times were reduced by the use of microwave heating. High levels of diastereoselectivity were observed in the synthesis of 2,5-disubstituted pyrrolidines, wherein the cis substitution pattern predominates. The mechanism of the reaction is discussed in the context of the observed reactivity and in comparison to analogous reactions promoted by other reagents and conditions. Our evidence supports a mechanism wherein the N-C bond is formed via intramolecular syn aminocupration and the C-C bond is formed via intramolecular addition of a primary carbon radical to an aromatic ring. PMID:17428100

  20. D-penicillamine capped cadmium telluride quantum dots as a novel fluorometric sensor of copper(II).

    PubMed

    Mohammad-Rezaei, Rahim; Razmi, Habib; Abdolmohammad-Zadeh, Hossein

    2013-01-01

    D-penicillamine-capped cadmium telluride quantum dots (DPA-capped CdTe QDs) were synthesized as the new fluorescent semiconductor nanocrystal in aqueous solution. Fourier transmission infrared spectroscopy, X-ray diffraction, transmission electron microscopy, ultraviolet-visible and photoluminescence spectroscopy were used for characterization of the QDs. Based on the quenching effect of Cu(2+) ions on the fluorescence intensity of DPA-capped CdTe QDs, a new fluorometric sensor for copper(II) detection was developed that showed good linearity over the concentration range 5 × 10(-9)-3 × 10(-6) M with the detection limit 0.4 × 10(-9) M. Owing to the strong affinity of the DPA to copper(II), the sensor showed appropriate selectivity for copper(II) compared with conventional QDs. The DPA-capped CdTe QDs was successfully applied for determination of Cu(2+) concentration in river, well and tap waters with satisfactory results.