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Sample records for copper ii ions

  1. Preparation and characterization of microgels sensitive toward copper II ions.

    Science.gov (United States)

    Muratalin, Marat; Luckham, Paul F

    2013-04-15

    An emulsion polymerization technique has been used to prepare chemically crosslinked microgels in aqueous suspension that are sensitive to the presence of copper ions. Poly(N-isopropylacrylamide) (PNIPAM) was copolymerized with different amounts of 1-vinylimidazole (VI), and the resultant microgels exhibited multi-responsive behavior being sensitive to changes in temperature, pH and to the presence of metal ions, particularly copper. These swelling properties of the microgel particles were characterized using dynamic light scattering (DLS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The effect of temperature showed that the microgel particles shrunk continuously as the temperature was raised, up to a temperature of 50°C, and the volume phase transition temperature, VPTT, has been shifted to higher temperatures (in the range of 35-45°C) compared to pure PNIPAM microgels where the VPTT≈30-35°C. The particle size of these microgels was also investigated as a function of pH; the microgel particles became swollen at low pH and collapsed at high pH, due to the ionization of the VI component of the microgels. Most interesting, however, was the effect of the copper ion concentration in solution. The PNIPAM-co-VI microgels were found to swell with increasing concentration of Cu(2+) up to 0.3g/l of Cu(2+) due to adsorption of the cations inside the particle, which leads to charging up the internal phase of the microgel. However, at higher concentrations of added copper (II) ions, the binding forces of complexation lead to conformational changes to the microgel resulting in weaker polymer-solvent interaction and consequential shrinkage again of the polymer. In addition, the copper (II) uptake was calculated, and the uptake was found to be well described by the Langmuir adsorption isotherm, with up to 2g of copper II being taken up by 1g of microgel. Copyright © 2013 Elsevier Inc. All rights reserved.

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

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    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).

  3. Effect of Phosphorylation and Copper(II or Iron(II Ions Enrichment on Some Physicochemical Properties of Spelt Starch

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    Jacek Rożnowski

    Full Text Available ABSTRACT: This paper provides an assessment of the effect of saturation of spelt starch and monostarch phosphate with copper or iron ions on selected physicochemical properties of the resulting modified starches. Native and modified spelt starch samples were analyzed for selected mineral element content using Atomic Absorption Spectroscopy (AAS. Thermodynamic properties were measured using DSC, and pasting properties by RVA. Flow curves of 5% pastes were plotted and described using the Herschel-Bulkley model. The structure recovery ratio was measured. AAS analysis established the presence of iron(II and copper(II ions in the samples of modified starches and that potassium and magnesium ions had leached from them. In comparison to unfortified samples, enriching native starch with copper(II ions decreases value of all temperatures of phase transformation about 1.3-2.7 °C, but in case of monostarch phosphates bigger changes (2.8-3.7 °C were observed. Fortified native spelt starch with copper(II ions caused increasing the final viscosity of paste from 362 to 429 mPa·s. However, presence iron(II ions in samples caused reduced its final viscosity by 170 (spelt starch and 103 mPa·s (monostarch phosphate. Furthermore, enriching monostarch phosphate contributed to reduce degree of structure recovery of pastes from 70.9% to 66.6% in case of copper(II ions and to 59.9% in case of iron(II ions.

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

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    Kai Rückriem

    2016-06-01

    Full Text Available 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.

  5. Removal of Copper(II and Zinc(II Ions From Aqueous Solution by Chemical Treatment of Coal Fly Ash

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    Eleonora Sočo

    2015-12-01

    Full Text Available The aim of this study was to investigate the chemical modifications of coal fly ash (CFA treated with HNO3 or ammonium acetate (AcNH4 or NaOH or sodium diethyldithiocarbamate (NaDDTC as an adsorbent for the removal of copper(II and zinc(II ions from aqueous solution. The morphology of fly ash grains before and after modification was examined via X-ray diffraction (XRD and images of scanning electron microscope (SEM. Adsorption of copper(II and zinc(II ions was conducted under batch process at different duration, concentrations and temperature of the suspension. Equilibrium experiments shows that the selectivity of CFA-NaOH nanoparticles towards Cu(II ions is greater than that of Zn(II ions, which is related to their hydrated ionic radius and first hydrolysis equilibrium constant. The adsorption isotherms were described by Langmuir and Freundlich models. Kinetic data revealed that the adsorption fits well by the pseudo-second-order rate model with high regression coefficients. Thermodynamic parameters suggested that the immobilization Cu(II and Zn(II ions onto CFA-NaOH is a spontaneous process. Results demonstrated that the treating coal fly ash with alkaline solution was a promising way to enhance Cu(II and Zn(II ions adsorption.

  6. The ligational behavior of an isatinic quinolyl hydrazone towards copper(II- ions

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    Mousa Marwa A

    2011-04-01

    Full Text Available Abstract Background The importance of the isatinic quinolyl hydrazones arises from incorporating the quinoline ring with the indole ring. Quinoline ring has therapeutic and biological activities whereas, the indole ring occurs in Jasmine flowers and Orange blossoms. As a ligand, the isatin moiety is potentially ambidentate and can coordinate the metal ions either through its lactam or lactim forms. In a previous study, the ligational behavior of a phenolic quinolyl hydrazone towards copper(II- ions has been studied. As continuation of our interest, the present study is planned to check the ligational behavior of an isatinic quinolyl hydrazone. Results New homo- and heteroleptic copper(II- complexes were obtained from the reaction of an isatinic quinolyl hydrazone (HL with several copper(II- salts viz. Clˉ, Brˉ, NO3ˉ, ClO4-, SO42- and AcO-. The obtained complexes have Oh, Td and D4h- symmetry and fulfill the strong coordinating ability of Clˉ, Brˉ, NO3ˉ and SO42- anions. Depending on the type of the anion, the ligand coordinates the copper(II- ions either through its lactam (NO3ˉ and ClO4- or lactim (the others forms. Conclusion The effect of anion for the same metal ion is obvious from either the geometry of the isolated complexes (Oh, Td and D4h or the various modes of bonding. Also, the obtained complexes fulfill the strong coordinating ability of Clˉ, Brˉ, NO3ˉ and SO42- anions in consistency with the donor ability of the anions. In case of copper(II- acetate, a unique homoleptic complex (5 was obtained in which the AcO- anion acts as a base enough to quantitatively deprotonate the hydrazone. The isatinic hydrazone uses its lactim form in most complexes.

  7. Effect of copper (II) ion against elongation behavior of amyloid {beta} fibrils on liposome membranes

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    Shimanouchi, T.; Onishi, R.; Kitaura, N.; Umakoshi, H.; Kuboi, R. [Division of Chemical Engineering, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama-cho, Toyonaka, Osaka (Japan)

    2012-01-15

    The fibril growth behavior of amyloid {beta} protein (A{beta}) on cell membranes is relating to the progression of Alzheimer's disease. This growth behavior of A{beta} fibrils is sensitively affected by the metal ions, neurotransmitters, or bioreactive substrate. The inhibitory effect of those materials was quantitatively estimated from the viewpoints of ''crystal growth''. In a bulk aqueous solution, copper (II) ion showed the strong inhibitory effect on the growth of A{beta} fibrils. Meanwhile, the addition of a closed-phospholipid bilayer membrane (liposome) could reduce the above inhibitory effect of copper (II) ion. (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

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

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    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.

  9. Extraction of copper(II) ions from aqueous solutions with a methimazole-based ionic liquid.

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    Reyna-González, Juan M; Torriero, Angel A J; Siriwardana, Amal I; Burgar, Iko M; Bond, Alan M

    2010-09-15

    The recently synthesized ionic liquid (IL) 2-butylthiolonium bis(trifluoromethanesulfonyl)amide, [mimSBu][NTf(2)], has been used for the extraction of copper(II) from aqueous solution. The pH of the aqueous phase decreases upon addition of [mimSBu](+), which is attributed to partial release of the hydrogen attached to the N(3) nitrogen atom of the imidazolium ring. The presence of sparingly soluble water in [mimSBu][NTf(2)] also is required in solvent extraction studies to promote the incorporation of Cu(II) into the [mimSBu][NTf(2)] ionic liquid phase. The labile copper(II) system formed by interacting with both the water and the IL cation component has been characterized by cyclic voltammetry as well as UV-vis, Raman, and (1)H, (13)C, and (15)N NMR spectroscopies. The extraction process does not require the addition of a complexing agent or pH control of the aqueous phase. [mimSBu][NTf(2)] can be recovered from the labile copper-water-IL interacting system by washing with a strong acid. High selectivity of copper(II) extraction is achieved relative to that of other divalent cobalt(II), iron(II), and nickel(II) transition-metal cations. The course of microextraction of Cu(2+) from aqueous media into the [mimSBu][NTf(2)] IL phase was monitored in situ by cyclic voltammetry using a well-defined process in which specific interaction with copper is believed to switch from the ionic liquid cation component, [mimSBu], to the [NTf(2)] anion during the course of electrochemical reduction from Cu(II) to Cu(I). The microextraction-voltammetry technique provides a fast and convenient method to determine whether an IL is able to extract electroactive metal ions from an aqueous solution.

  10. Two different modes for copper(II ion coordination to quinine-type ligands

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    Rey Nicolás A.

    2006-01-01

    Full Text Available Three new copper(II complexes with the ligands quinuclidine [Cu(C7H13N2(OH2Cl]Cl.2H 2O (1, quinine [Cu(C20H23O2N2(OH 22]ClO4 (2, and hydroquinidine [Cu(C20H27O2N2(OH 2 Cl2]Cl.fraction one-halfH2O (3 have been isolated and characterized. The binding sites were assigned on the basis of vibrational spectroscopy, electron paramagnetic resonance, and thermal analysis results. The possibility of the involvement of the quinuclidinic nitrogen in the coordination was evidenced in complex 1, in which copper(II is coordinated to two quinuclidine molecules. In the case of quinine-type ligands, if the starting material is deprotonated in both nitrogens, copper(II coordination occurs through the quinuclidinic nitrogen, as in complex 2. In contrast, if the starting material is protonated in the quinuclidinic nitrogen the binding site is the quinolinic nitrogen, as in complex 3. Therefore, both nitrogens of quinine-type ligands constitute binding sites for copper(II ions.

  11. Determination of copper(I) and copper(II) ions after complexation with bicinchoninic acid by CE.

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    Basheer, Chanbasha; Lee, Hian Kee

    2007-10-01

    A facile, sensitive, and selective method was developed for the simultaneous separation and determination of copper(I) [Cu(+)] and copper(II) [Cu(2+)] ions using CE with direct UV detection. The copper ions were complexed with a 1.5 mM bicinchoninic acid disodium salt solution at pH 8.7 prior to analysis. Acetate buffer (2 mM) was used as the CE running buffer. Parameters affecting CE separation such as sample pH, applied voltage, concentration of complexing agent, nature of the buffer solution, and interferences by other metal ions, were evaluated. The LODs for Cu(+) and Cu(2+) were 3.0 and 2.5 microg/mL (S/N = 3), respectively. The developed method allows the simultaneous determination of Cu(+) and Cu(2+) in less than 5 min with RSDs of between 5.3 and 9.5% for migration time and between 3.4 and 9.7% for peak areas, respectively. At optimum conditions, the percentage recoveries of Cu(+) and Cu(2+) were found to be 99.4 and 99.5%.

  12. Mathematical modeling of copper(II) ion inhibition on COD removal in an activated sludge unit.

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    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.

  13. Flotation of traces of silver and copper(II) ions with a methyl cellosolve solution of dithizone.

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    Hiraide, M; Mizuike, A

    1975-06-01

    Microgram quantities of silver and copper(II) ions in aqueous solutions are collected on dithizone precipitates, which are then floated with the aid of small nitrogen bubbles. This separation technique has been successfully applied to the atomic-absorption spectrophotometric determination of down to a tenth ppm of silver and copper in high-purity lead and zinc metals.

  14. Removal of copper (II), iron (III) and lead (II) ions from Mono ...

    African Journals Online (AJOL)

    EJIRO

    The adsorption of Pb (II) was found to be maximum (94%±3.2) at pH 5, temperature of 100°C, metal ion concentration of ... Key words: Metal ions, adsorption, simulated effluent, coconut husk. INTRODUCTION ..... activated carbon and zeolite.

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

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    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.

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

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    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.

  17. Biosorption of copper (II) ions from synthetic aqueous solutions by drying bed activated sludge

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    Benaissa, H., E-mail: ho_benaissa@yahoo.fr [Laboratory of Sorbent Materials and Water Treatment, Department of Chemistry, Faculty of Sciences, University of Tlemcen, P.O. Box 119, 13000 Tlemcen (Algeria); Elouchdi, M.A. [Laboratory of Sorbent Materials and Water Treatment, Department of Chemistry, Faculty of Sciences, University of Tlemcen, P.O. Box 119, 13000 Tlemcen (Algeria)

    2011-10-30

    Highlights: {yields} Dried activated sludge has been investigated for the removal of copper ions from aqueous synthetic solutions, in batch conditions. {yields} Copper uptake was time contact, initial copper concentration, initial pH solution and copper salt type dependent. {yields} Maximum copper uptake obtained was q{sub m} = 62.50 mg/g (0.556 mmol/g) under the investigated experimental conditions. - Abstract: In the present work, the usefulness of dried activated sludge has been investigated for the removal of copper ions from synthetic aqueous solutions. Kinetic data and equilibrium sorption isotherm were measured in batch conditions. The influence of some parameters such as: contact time, initial copper concentration, initial pH of solution and copper salt nature on copper biosorption kinetics has been studied. Copper uptake was time contact, initial copper concentration, initial pH solution and copper salt type dependent. Maximum copper sorption was found to occur at initial pH 5. Two simplified kinetic models including a first-order rate equation and a pseudo second-order rate equation were selected to describe the biosorption kinetics. The process followed a pseudo second-order rate kinetics. The process mechanism was found to be complex, consisting of external mass transfer and intraparticle mass transfer diffusion. Copper biosorption process was particle-diffusion-controlled, with some predominance of some external mass transfer at the initial stages for the different experimental parameters studied. Langmuir and Freundlich models were used to describe sorption equilibrium data at natural pH of solution. Results indicated that the Langmuir model gave a better fit to the experimental data than the Freundlich model. Maximum copper uptake obtained was q{sub m} = 62.50 mg/g (0.556 mmol/g) under the investigated experimental conditions. Scanning electron microscopy coupled with X-ray energy dispersed analysis for copper-equilibrated dried activated sludge

  18. Adsorption of copper (II), chromium (III), nickel (II) and lead (II) ions from aqueous solutions by meranti sawdust.

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    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.

  19. Study of the interaction mechanism in the biosorption of copper(II) ions onto posidonia oceanica and peat

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    Izquierdo, Marta; Marzal, Paula; Gabaldon, Carmen [Departamento de Ingenieria Quimica, Escuela Tecnica Superior de Ingenieria, Universitat de Valencia, Valencia (Spain); Silvetti, Margherita; Castaldi, Paola [Dipartimento di Scienze Ambientali e Agrarie e Biotecnologie Agro-Alimentari, Sez. Chimica Agraria ed Ambientale, University of Sassari, Sassari (Italy)

    2012-04-15

    A systematic approach was used to characterize the biosorption of copper(II) onto two biosorbents, Posidonia oceanica and peat, focusing on the interaction mechanisms, the copper(II) sorption-desorption process and the thermal behavior of the biosorbents. Sorption isotherms at pH 4-6 were obtained and the experimental data were fitted to the Langmuir model with a maximum uptake (q{sub max}) at pH 6 of 85.78 and 49.69 mg g{sup -1}, for P. oceanica and peat, respectively. A sequential desorption (SD) with water, Ca(NO{sub 3}){sub 2}, and EDTA was applied to copper-saturated biosorbents. Around 65-70% copper(II) were desorbed with EDTA, indicating that this heavy metal was strongly bound. The reversibility of copper(II) sorption was obtained by desorption with HCl and SD. Fourier transform IR spectroscopy (FTIR) analysis detected the presence of peaks associated with OH groups in aromatic and aliphatic structures, CH, CH{sub 2}, and CH{sub 3} in aliphatic structures, COO{sup -} and COOH groups and unsaturated aromatic structures on the surface of both biosorbents, as well as peaks corresponding to Si-O groups on the surface of peat. The results of SEM-EDX and FTIR analysis of copper-saturated samples demonstrated that ion exchange was one of the mechanisms involved in copper(II) retention. Thermal analysis of biosorbent samples showed that copper(II) sorption-desorption processes affected the thermal stability of the biosorbents. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. Femtomole level photoelectrochemical aptasensing for mercury ions using quercetin-copper(II) complex as the DNA intercalator.

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    Li, Hongbo; Xue, Yan; Wang, Wei

    2014-04-15

    An ultrasensitive and selective photoelectrochemical (PEC) aptasensor for mercury ions was first fabricated based on perylene-3, 4, 9, 10-tetracarboxylic acid/graphene oxide (PTCA/GO) heterojunction using quercetin-copper(II) complex intercalated into the poly(dT)-poly(dA) duplexes. Both the PTCA/GO heterojunction and the quercetin-copper(II) complex are in favor of the sensitivity for the fabricated PEC aptasensor due to band alignment and strong reduction capability, respectively. And they efficiently promote the separation of photoexcited carriers and enhance the photocurrent. The formation of thymine-Hg(2+)-thymine coordination chemistry resulted in the dehybridization of poly(dT)-poly(dA) duplexes and then the intercalator quercetin-copper(II) complex broke away from the surface of the PEC aptasensor. As the concentration of mercury ions increased, the photocurrent gradually decreased. The electrode response for mercury ions detection was in the linear range from 0.01 pmol L(-1) to 1.00 pmol L(-1) with the detection limit of 3.33 fmol L(-1). The label-free PEC aptasensor has excellent performances with ultrasensitivity and good selectivity besides the advantage of economic and facile fabrication. The strategy of quercetin-copper(II) complex as a novel DNA intercalator paves a new way to improve the performances for PEC sensors. © 2013 Published by Elsevier B.V.

  1. Rat liver mitochondrial dysfunction by addition of copper(II) or iron(III) ions.

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    Saporito-Magriñá, Christian; Musacco-Sebio, Rosario; Acosta, Juan M; Bajicoff, Sofía; Paredes-Fleitas, Paola; Boveris, Alberto; Repetto, Marisa G

    2017-01-01

    Increased copper (Cu) and iron (Fe) levels in liver and brain are associated to oxidative stress and damage with increased phospholipid oxidation process. The aim of this work was to assess the toxic effects of Cu(2+) and Fe(3+) addition to rat liver mitochondria by determining mitochondrial respiration in states 3 (active respiration) and 4 (resting respiration), and phospholipid peroxidation. Both, Cu(2+) and Fe(3+) produced decreases in O2 consumption in a concentration-dependent manner in active state 3: both ions by 42% with malate-glutamate as complex I substrate (concentration for half maximal response (C50) 60μM Cu(2+) and 1.25mM Fe(3+)), and with succinate as complex II substrate: 64-69% with C50 of 50μM Cu(2+) and with C50 of 1.25mM of Fe(3+). Respiratory control decreased with Cu(2+) (C50 50μM) and Fe(3+) (C50 1.25-1-75mM) with both substrates. Cu(2+) produced a 2-fold increase and Fe(3+) a 5-fold increase of thiobarbituric acid-reactive substances (TBARS) content from 25μM Cu(2+) (C50 40μM) and from 100μM Fe(3+) (C50 1.75mM). Supplementations with Cu(2+) and Fe(3+) ions induce mitochondrial dysfunction with phospholipid peroxidation in rat liver mitochondria. Although is proved that a Fenton/Haber Weiss mechanism of oxidative damage occurs in metal-ion induced mitochondrial toxicity, slightly different responses to the metal ions suggest some differences in the mechanism of intracellular toxicity. The decreased rates of mitochondrial respiration and the alteration of mitochondrial function by phospholipid and protein oxidations lead to mitochondrial dysfunction, cellular dyshomeostasis and cell death.

  2. Cloud point extraction and flame atomic absorption spectrometry combination for copper(II) ion in environmental and biological samples

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    Shokrollahi, Ardeshir [Chemistry Department, Yasouj University, Yasouj 75914-353 (Iran, Islamic Republic of)], E-mail: ashokrollahi@mail.yu.ac.ir; Ghaedi, Mehrorang [Chemistry Department, Yasouj University, Yasouj 75914-353 (Iran, Islamic Republic of)], E-mail: m_ghaedi@mail.yu.ac.ir; Hossaini, Omid; Khanjari, Narges [Chemistry Department, Yasouj University, Yasouj 75914-353 (Iran, Islamic Republic of); Soylak, Mustafa [Chemistry Department, University of Erciyes, 38039 Kayseri (Turkey)

    2008-12-30

    A cloud point extraction procedure was presented for the preconcentration of copper(II) ion in various samples. After complexation by 4-(phenyl diazenyl) benzene-1,3-diamine (PDBDM) (chrysoidine), copper(II) ions were quantitatively recovered in Triton X-114 after centrifugation. 0.5 ml of methanol acidified with 1.0 mol L{sup -1} HNO{sub 3} was added to the surfactant-rich phase prior to its analysis by flame atomic absorption spectrometry (FAAS). The influence of analytical parameters including ligand, Triton X-114 and HNO{sub 3} concentrations, bath temperature, heating time, centrifuge rate and time were optimized. The effect of the matrix ions on the recovery of copper(II) ions was investigated. The detection limit (3S.D.{sub b}/m, n = 10) of 0.6 ng mL{sup -1} along with preconcentration factor of 30 and enrichment factor of 41.1 with R.S.D. of 1.0% for Cu was achieved. The proposed procedure was applied to the analysis of various environmental and biological samples.

  3. CYCLIC VOLTAMMETRY STUDIES OF COPPER (II AND TELLURIUM (IV IONS IN ACIDIC AQUEOUS SOLUTIONS FOR THIN FILM DEPOSITION

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    SARAVANAN NAGALINGAM

    2014-05-01

    Full Text Available Cyclic voltammetry studies of copper (II and tellurium (IV ions in acidic aqueous solutions were carried out to determine the optimum condition for copper telluride thin film deposition. The voltammetry studies include reversible scans at different solution pH. Based on the voltammogram, suitable deposition conditions was determined to be in the range of -0.35 V to -0.45 V versus Ag/AgCl at pH values between 2.0 to 2.2 under non diffusion-limited conditions.

  4. Simultaneous and sensitive analysis of aliphatic carboxylic acids by ion-chromatography using on-line complexation with copper(II) ion.

    Science.gov (United States)

    Kemmei, Tomoko; Kodama, Shuji; Yamamoto, Atsushi; Inoue, Yoshinori; Hayakawa, Kazuichi

    2015-01-02

    A new approach to ion chromatography is proposed to improve the UV detection of aliphatic carboxylic acids separated by anion-exchange chromatography. When copper(II) ion added to the mobile phase, it forms complexes with carboxylic acids that can be detected at 240 nm. The absorbance was found to increase with increasing copper(II) ion concentration. The retention times of α-hydroxy acids were also found to depend on the copper(II) ion concentration. Addition of acetonitrile to the mobile phase improved the separation of aliphatic carboxylic acids. The detection limits of the examined carboxylic acids (formate, glycolate, acetate, lactate, propionate, 3-hydroxypropionate, n-butyrate, isobutyrate, n-valerate, isovalerate, n-caproate) calculated at S/N=3 ranged from 0.06 to 3 μM. The detector signal was linear over three orders of magnitude of carboxylic acid concentration. The proposed method was successfully applied to analyze aliphatic carboxylic acids in rainwater and bread.

  5. Acid-base characterization, coordination properties towards copper(II) ions and DNA interaction studies of ribavirin, an antiviral drug.

    Science.gov (United States)

    Nagaj, Justyna; Starosta, Radosław; Jeżowska-Bojczuk, Małgorzata

    2015-01-01

    We have studied processes of copper(II) ion binding by ribavirin, an antiviral agent used in treating hepatitis C, which is accompanied usually by an increased copper level in the serum and liver tissue. Protonation equilibria and Cu(II) binding were investigated using the UV-visible, EPR and NMR spectroscopic techniques as well as the DFT (density functional theory) calculations. The spectroscopic data suggest that the first complex is formed in the water solution at pH as low as 0.5. In this compound Cu(II) ion is bound to one of the nitrogen atoms from the triazole ring. Above pH6.0, the metal ion is surrounded by two nitrogen and two oxygen atoms from two ligand molecules. The DFT calculations allowed to determine the exact structure of this complex. We found that in the lowest energy isomer two molecules of the ligand coordinate via O and N4 atoms in trans positions. The hypothetical oxidative properties of the investigated system were also examined. It proved not to generate plasmid DNA scission products. However, the calf thymus (CT)-DNA binding studies showed that it reacts with ribavirin and its cupric complex. Moreover, the interaction with the complex is much more efficient.

  6. Biological Role of Cobalt(II), Copper(II) and Nickel(II) Metal Ions on the Antibacterial Properties of Some Nicotinoyl-Hydrazine Derived Compounds

    OpenAIRE

    Chohan, Zahid H.; Sherazi, Syed K. A.

    1997-01-01

    Several cobalt(II), copper(II) and nickel(II) complexes of nicotinoylhydrazine-derived compounds were prepared and characterised by physical, spectral and analytical data. These compounds and their complexes have proven to be antibacterial. The screening data show the metal complexes to be more potential/bactericidal than the uncomplexed compounds against one or more bacterial species.

  7. EPR study of complex formation between copper (II) ions and sympathomimetic amines in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Preoteasa, E.A. [Inst. of Atomic Physics, IFIN, Bucharest (Romania); Duliu, O.G.; Grecu, V.V. [Bucharest, Univ. (Romania). Dept. of Atomic and Nuclear Physics

    1997-07-01

    The complex formation between sympathomimetic amines (SA): adrenaline (AD), noradrenaline (NA), dopamine (DA), ephedrine (ED) and p-tyramine (pTA), and Cu(II) ion in aqueous solution has been studied by X-band EPR at room temperature. Excepting pTA, all investigated SA yielded two types of complexes in different pH domains. All complexes consistent with a ligand fields having a distorted octahedral symmetry, i.e., hexacoordination of Cu(II). The covalence coefficient calculated from the isotropic g and A values has shown strong ionic sigma-type ligand bonds. A structural model with the Cu(II) ion bound by four catecholic O(hydroxy) atoms for the low pH complexes of AD, NA and DA is proposed. For the high pH complexes of the former compounds as well as for both Ed complexes, the authors suppose Cu(II) bound by two N (amino) and two O (hydroxy) atoms. The spectra are consistent to water binding on the longitudinal octahedron axis in all compounds excepting the high pH complex of Ed, where OH2- ions are bound. Possible implications for the SA-cell receptors interactions are discussed.

  8. New dinuclear copper(II) and zinc(II) complexes for the investigation of sugar-metal ion interactions.

    Science.gov (United States)

    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.

  9. Synthesis, characterization, and catalytic properties of cationic hydrogels containing copper(II) and cobalt(II) ions.

    Science.gov (United States)

    Lombardo Lupano, Lucía Victoria; Lázaro Martínez, Juan Manuel; Piehl, Lidia Leonor; Rubín de Celis, Emilio; Torres Sánchez, Rosa María; Campo Dall' Orto, Viviana

    2014-03-18

    Here, we report the synthesis and characterization of a hydrogel based on ethylene glycol diglycidyl ether (EGDE) and 1,8-diamino-3,6-dioxaoctane (DA). Chemically stable Co(II) and Cu(II) coordination complexes were prepared with this nonsoluble polyelectrolyte, poly(EGDE-DA), and studied by ss-NMR, FT-IR, thermogravimetry, and microscopy. Mesopores were found in all the samples, the thermal stability of the polymer matrix was highly affected by the presence of metal ions, and the (13)C CP-MAS spectrum for the Cu(II)-complex evidenced a significant increase in the reticulation degree by Cu(II) ions. The catalytic activity of these materials on H2O2 activation was studied by electron spin resonance (ESR). The Co(II)-poly(EGDE-DA)/H2O2 heterogeneous system produced O2, an anion superoxide (O2(•)¯), and a hydroxyl radical (OH(•)), which diffused into the solution at the time that a decrease in pH was detected. In the same way, the Cu(II)-poly(EGDE-DA)/H2O2 heterogeneous system produced O2 and OH(•). H2O2 activation by the poly(EGDE-DA) complexes with Co(II) and Cu(II) were applied on the decolorization of solutions of the azo-dye methyl orange (MO). In the presence of 63 mM H2O2, 87% of MO was removed in 10 min with Cu(II)-poly(EGDE-DA) and in 110 min with Co(II)-poly(EGDE-DA). In addition, the pharmaceutical product epinephrine was partially oxidized to adrenochrome by the O2(•)¯ released from the Co(II)-poly(EGDE-DA)/H2O2 heterogeneous system.

  10. Biosorption of copper(II) ions onto powdered waste sludge in a completely mixed fed-batch reactor: estimation of design parameters.

    Science.gov (United States)

    Pamukoglu, Yunus; Kargi, Fikret

    2007-04-01

    Biosorption of Cu(II) ions onto pre-treated powdered waste sludge (PWS) was investigated using a fed-batch operated completely mixed reactor. Fed-batch adsorption experiments were performed by varying the feed flow rate ( 0.075-0.325 l h(-1)), feed copper (II) ion concentrations (50-300 mg l(-1)) and the amount of adsorbent (1-6 g PWS) using fed-batch operation. Breakthrough curves describing the variations of effluent copper ion concentrations with time were determined for different operating conditions. Percent copper ion removals from the aqueous phase decreased, but the biosorbed (solid phase) copper ion concentrations increased with increasing the feed flow rate and Cu(II) concentration. A modified Bohart-Adams equation was used to determine the biosorption capacity of PWS and the rate constant for Cu(II) ion biosorption. Adsorption rate constant in fed-batch operation was an order of magnitude larger than those obtained in adsorption columns because of elimination of mass transfer limitations encountered in the column operations while the biosorption capacity of PWS was comparable with powdered activated (PAC) in column operations. Therefore, a completely mixed reactor operated in fed-batch mode was proven to be more advantageous as compared to adsorption columns due to better contact between the phases yielding faster adsorption rates.

  11. Copper(II) ions interactions in the systems with triamines and ATP. Potentiometric and spectroscopic studies.

    Science.gov (United States)

    Hoffmann, S K; Goslar, J; Bregier-Jarzebowska, R; Gasowska, A; Zalewska, A; Lomozik, L

    2017-09-09

    The mode of interaction and thermodynamic stability of complexes formed in binary and ternary Cu(II)/ATP/triamines systems were studied using potentiometric and spectroscopic (NMR, EPR, UV-Vis) methods. It was found that in binary metal-free systems ATP/HxPA species are formed (PA: Spd=spermidine or 3,3-tri=1,7-diamino-4-azaheptane) where the phosphate groups from nucleotides are preferred negative centers and protonated amine groups of amines are positive centers of reaction. In the ternary systems Cu/ATP/Hx(PA) as well as Cu/(ATP)(PA) species are formed. The type of the formed Cu(II) complexes depends on pH of the solution. For a low pH value the complexation appears between Cu(II) and ATP molecules via oxygen atoms of phosphate groups. For a very high pH value, where ATP is hydrolyzed, the Cu(II) ions are bound to the nitrogen atoms of polyamine molecules. We did not detect any direct coordination of the N7 nitrogen atom of adenosine to Cu(II) ions. It means that the CuN7 interaction is an indirect type and can be due to noncovalent interplay including water molecule. EPR studies were performed at glassy state (77K) after a fast freezing both for binary and ternary systems. The glassy state EPR spectra do not reflect species identified in titration studies indicating significant effect of rapid temperature decrease on equilibrium of Cu(II) complexes. We propose the molecular structure of all the studied complexes at the glassy state deduced from EPR and optical spectroscopy results. Copyright © 2017 Elsevier Inc. All rights reserved.

  12. Multipath colourimetric assay for copper(II) ions utilizing MarR functionalized gold nanoparticles

    Science.gov (United States)

    Wang, Yulong; Wang, Limin; Su, Zhenhe; Xue, Juanjuan; Dong, Jinbo; Zhang, Cunzheng; Hua, Xiude; Wang, Minghua; Liu, Fengquan

    2017-02-01

    We use the multiple antibiotic resistance regulator (MarR), as a highly selective biorecognition elements in a multipath colourimetric sensing strategy for the fast detection of Cu2+ in water samples. The colourimetric assay is based on the aggregation of MarR-coated gold nanoparticles in the presence of Cu2+ ions, which induces a red-to-purple colour change of the solution. The colour variation in the gold nanoparticle aggregation process can be used for qualitative and quantitative detection of Cu2+ by the naked eye, and with UV–vis and smartphone-based approaches. The three analysis techniques used in the multipath colourimetric assay complement each other and provide greater flexibility for differing requirements and conditions, making the assay highly applicable for Cu2+ detection. Under optimal conditions, the Cu2+ concentration was quantified in less than 5 min with limits of detection for the naked eye, UV–vis and smartphone-based approaches of 1 μM, 405 nM and 61 nM, respectively. Moreover, the sensing system exhibited excellent selectivity and practical application for Cu2+ detection in real water samples. Thus, our strategy has great potential for application in on-site monitoring of Cu2+, and the unique response of MarR towards copper ions may provide a new approach to Cu2+ sensing.

  13. Multipath colourimetric assay for copper(II) ions utilizing MarR functionalized gold nanoparticles

    Science.gov (United States)

    Wang, Yulong; Wang, Limin; Su, Zhenhe; Xue, Juanjuan; Dong, Jinbo; Zhang, Cunzheng; Hua, Xiude; Wang, Minghua; Liu, Fengquan

    2017-01-01

    We use the multiple antibiotic resistance regulator (MarR), as a highly selective biorecognition elements in a multipath colourimetric sensing strategy for the fast detection of Cu2+ in water samples. The colourimetric assay is based on the aggregation of MarR-coated gold nanoparticles in the presence of Cu2+ ions, which induces a red-to-purple colour change of the solution. The colour variation in the gold nanoparticle aggregation process can be used for qualitative and quantitative detection of Cu2+ by the naked eye, and with UV–vis and smartphone-based approaches. The three analysis techniques used in the multipath colourimetric assay complement each other and provide greater flexibility for differing requirements and conditions, making the assay highly applicable for Cu2+ detection. Under optimal conditions, the Cu2+ concentration was quantified in less than 5 min with limits of detection for the naked eye, UV–vis and smartphone-based approaches of 1 μM, 405 nM and 61 nM, respectively. Moreover, the sensing system exhibited excellent selectivity and practical application for Cu2+ detection in real water samples. Thus, our strategy has great potential for application in on-site monitoring of Cu2+, and the unique response of MarR towards copper ions may provide a new approach to Cu2+ sensing. PMID:28155905

  14. Use of Composite Sorbents for the Removal of Copper (II ions from Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Rebecca Oyedoyin Adeeyo

    2015-01-01

    Full Text Available Composite adsorbents are synthesized from two or more materials with different chemical and physical properties in order to increase their selectivity and the reusability. Researchers have developed and applied several novel composite materials for enhancing the removal of heavy metal. In this review, extensive list of composites developed via advanced technologies with specified characteristics for the removal of Cu (II ion are discussed. Emphases on their adsorption capacities, reusability, desorption and regeneration with improved mechanical strengths are presented. Conclusively, prospects and other challenges to be checked and addressed in future are outlined.

  15. MODIFICATION OF KELUD VOLCANIC ASH 2014 AS SELECTIVE ADSORBENT MATERIAL FOR COPPER(II METAL ION

    Directory of Open Access Journals (Sweden)

    Susila Kristianingrum

    2017-01-01

      This research aims to prepare an adsorbent from Kelud volcanic ash for better Cu(II adsorption efficiency than Kiesel gel 60G E'Merck. Adsorbent synthesis was done by dissolving 6 grams of volcanic ash activated 700oC 4 hours and washed with HCl 0.1 M into 200 ml of 3M sodium hydroxide with stirring and heating of 100 °C for 1 hour. The filtrate sodium silicate was then neutralized using sulfuric acid. The mixture was allowed to stand for 24 hours then filtered and washed with aquaDM, then dried and crushed. The procedure is repeated for nitric acid, acetic acid and formic acid with a contact time of 24 hours. The products were then characterized using FTIR and XRD, subsequently determined acidity, moisture content, and tested for its adsorption of the ion Cu (II with AAS. The results showed that the type of acid that produced highest rendemen is AK-H2SO4-3M ie 36.93%, acidity of the adsorbent silica gel synthesized similar to Kiesel gel 60G E'Merck ie adsorbent AK-CH3COOH-3M and the water content of the silica gel adsorbent synthesized similar to Kiesel gel 60G E'Merck ie adsorbent AK-H2SO4-2 M. The character of the functional groups of silica gel synthesized all have similarities with Kiesel gel 60G E'Merck as a comparison. Qualitative analysis by XRD for all modified adsorbent showed a dominant peak of SiO2 except adsorbent AK-H2SO4 amorphous and chemical bonds with FTIR indicates that it has formed a bond of Si-O-Si and Si-OH. The optimum adsorption efficiency of the metal ions Cu(II obtained from AK-H2SO4-5M adsorbent that is equal to 93.2617% and the optimum adsorption capacity of the Cu(II metal ions was obtained from the adsorbent AK-CH3COOH-3M is equal to 2.4919 mg/ g.   Keywords: adsorbents, silica gel, adsorption, kelud volcanic ash

  16. Trapping of muscle relaxant methocarbamol degradation product by complexation with copper(II) ion: Spectroscopic and quantum chemical studies

    Science.gov (United States)

    Mansour, Ahmed M.; Shehab, Ola R.

    2014-07-01

    Structural properties of methocarbamol (Mcm) were extensively studied both experimentally and theoretically using FT IR, 1H NMR, UV-Vis., geometry optimization, Mulliken charge, and molecular electrostatic potential. Stability arises from hyper-conjugative interactions, charge delocalization and H-bonding was analyzed using natural bond orbital (NBO) analysis. Mcm was decomposed in ethanol/water mixture at 80 °C to guaifenesin [(RS)-3-(2-methoxyphenoxy)propane-1,2-diol] and carbamate ion [NH2COO-], where the degradation mechanism was explained by trapping the carbamate ion via the complexation with copper(II) ion. The structure of the isolated complex ([Cu(NH2COO)2(H2O)]ṡ4H2O) was elucidated by spectral, thermal, and magnetic tools. Electronic spectra were discussed by TD-DFT and the descriptions of frontier molecular orbitals and the relocations of the electron density were determined. Calculated g-tensor values showed best agreement with experimental values from EPR when carried out using both the B3LYP and B3PW91 functional.

  17. Non-noble metal graphene oxide-copper (II) ions hybrid electrodes for electrocatalytic hydrogen evolution reaction

    KAUST Repository

    Muralikrishna, S.

    2015-08-25

    Non-noble metal and inexpensive graphene oxide-copper (II) ions (GO-Cu2+) hybrid catalysts have been explored for the hydrogen evolution reaction (HER). We were able to tune the binding abilities of GO toward the Cu2+ ions and hence their catalytic properties by altering the pH. We have utilized the oxygen functional moieties such as carboxylate, epoxide, and hydroxyl groups on the edge and basal planes of the GO for binding the Cu2+ ions through dative bonds. The GO-Cu2+ hybrid materials were characterized by cyclic voltammetry in sodium acetate buffer solution. The morphology of the hybrid GO-Cu2+ was characterized by atomic force microscopy. The GO-Cu2+ hybrid electrodes show good electrocatalytic activity for HER with low overpotential in acidic solution. The Tafel slope for the GO-Cu2+ hybrid electrode implies that the primary discharge step is the rate determining step and HER proceed with Volmer step. © 2015 American Institute of Chemical Engineers Environ Prog.

  18. Thermodynamics of the formation of complexes of copper(II) ions and glycylglycine in aqueous solutions at 298 K according to calorimetry data

    Science.gov (United States)

    Kochergina, L. A.; Emel'yanov, A. V.

    2015-04-01

    Heat effects of the interaction between glycylglycine and copper(II) nitrate solutions are measured by direct calorimetry at a [metal] : [ligand] ratio of 1 : 5 and at different pH values of the solution. The measurements are made at a temperature of 298.15 K and ionic strengths of 0.25, 0.50, and 0.75. KNO3 is used as a background electrolyte. The thermodynamic characteristics of complex formation by the peptide and copper(II) ions in aqueous solutions are determined. Standard enthalpies of the formation of complex particles in aqueous solutions are calculated.

  19. Cadmium Sulphide-Reduced Graphene Oxide-Modified Photoelectrode-Based Photoelectrochemical Sensing Platform for Copper(II Ions.

    Directory of Open Access Journals (Sweden)

    I Ibrahim

    Full Text Available A photoelectrochemical (PEC sensor with excellent sensitivity and detection toward copper (II ions (Cu2+ was developed using a cadmium sulphide-reduced graphene oxide (CdS-rGO nanocomposite on an indium tin oxide (ITO surface, with triethanolamine (TEA used as the sacrificial electron donor. The CdS nanoparticles were initially synthesized via the aerosol-assisted chemical vapor deposition (AACVD method using cadmium acetate and thiourea as the precursors to Cd2+ and S2-, respectively. Graphene oxide (GO was then dip-coated onto the CdS electrode and sintered under an argon gas flow (50 mL/min for the reduction process. The nanostructured CdS was adhered securely to the ITO by a continuous network of rGO that also acted as an avenue to intensify the transfer of electrons from the conduction band of CdS. The photoelectrochemical results indicated that the ITO/CdS-rGO photoelectrode could facilitate broad UV-visible light absorption, which would lead to a higher and steady-state photocurrent response in the presence of TEA in 0.1 M KCl. The photocurrent decreased with an increase in the concentration of Cu2+ ions. The photoelectrode response for Cu2+ ion detection had a linear range of 0.5-120 μM, with a limit of detection (LoD of 16 nM. The proposed PEC sensor displayed ultra-sensitivity and good selectivity toward Cu2+ ion detection.

  20. Bioinspired, direct synthesis of aqueous CdSe quantum dots for high-sensitive copper(II) ion detection.

    Science.gov (United States)

    Bu, Xiaohai; Zhou, Yuming; He, Man; Chen, Zhenjie; Zhang, Tao

    2013-11-21

    Luminescent CdSe semiconductor quantum dots (QDs), which are coated with a denatured bovine serum albumin (dBSA) shell, have been directly synthesized via a bioinspired approach. The dBSA coated CdSe QDs are ultrasmall (d CdSe QDs. The luminescent QDs are used for copper(II) ion detection due to their highly sensitive and selective fluorescence quenching response to Cu(2+). The concentration dependence of the quenching effect can be best described by the typical Stern-Volmer equation in a linearly proportional concentration of Cu(2+) ranging from 10 nM to 7.5 μM with a detection limit of 5 nM. As confirmed by various characterization results, a possible quenching mechanism is given: Cu(2+) ions are first reduced to Cu(+) by the dBSA shell and then chemical displacement between Cu(+) and Cd(2+) is performed at the surface of the ultrasmall metallic core to impact the fluorescence performance.

  1. Removal of Copper (II Ions from Aqueous Solutions by Adsorption with Low Cost Acid Activated Cynodon Dactylon Carbon

    Directory of Open Access Journals (Sweden)

    U. Gayathri

    2011-01-01

    Full Text Available The main purpose of this work was to exploit low cost and efficient sorbents for the removal of copper from aqueous solution using Cynodon dactylon carbon. It was observed from the experimental results that almost 90-100% copper can be removed from the aqueous solution. Adsorption kinetics and equilibrium have been investigated as a function of initial copper ion concentration. pH, contact time and adsorbent dosage. Kinetics studies suggested that the adsorption allowed first order reaction. Equilibrium data were analyzed using Langmuir and Freundlich isotherm models. On the basis of experimental results and the model parameters, it can be concluded that the carbonaceous Cynodon dactylon is effective for the removal of copper ion from aqueous solution.

  2. Coumarin-Based Fluorescent Probes for Dual Recognition of Copper(II and Iron(III Ions and Their Application in Bio-Imaging

    Directory of Open Access Journals (Sweden)

    Olimpo García-Beltrán

    2014-01-01

    Full Text Available Two new coumarin-based “turn-off” fluorescent probes, (E-3-((3,4-dihydroxybenzylideneamino-7-hydroxy-2H-chromen-2-one (BS1 and (E-3-((2,4-dihydroxybenzylideneamino-7-hydroxy-2H-chromen-2-one (BS2, were synthesized and their detection of copper(II and iron(III ions was studied. Results show that both compounds are highly selective for Cu2+ and Fe3+ ions over other metal ions. However, BS2 is detected directly, while detection of BS1 involves a hydrolysis reaction to regenerate 3-amino-7-hydroxycoumarin (3 and 3,4-dihydroxybenzaldehyde, of which 3 is able to react with copper(II or iron(III ions. The interaction between the tested compounds and copper or iron ions is associated with a large fluorescence decrease, showing detection limits of ca. 10−5 M. Preliminary studies employing epifluorescence microscopy demonstrate that Cu2+ and Fe3+ ions can be imaged in human neuroblastoma SH-SY5Y cells treated with the tested probes.

  3. Coumarin-based fluorescent probes for dual recognition of copper(II) and iron(III) ions and their application in bio-imaging.

    Science.gov (United States)

    García-Beltrán, Olimpo; Cassels, Bruce K; Pérez, Claudio; Mena, Natalia; Núñez, Marco T; Martínez, Natalia P; Pavez, Paulina; Aliaga, Margarita E

    2014-01-13

    Two new coumarin-based "turn-off" fluorescent probes, (E)-3-((3,4-dihydroxybenzylidene)amino)-7-hydroxy-2H-chromen-2-one (BS1) and (E)-3-((2,4-dihydroxybenzylidene)amino)-7-hydroxy-2H-chromen-2-one (BS2), were synthesized and their detection of copper(II) and iron(III) ions was studied. Results show that both compounds are highly selective for Cu²⁺ and Fe³⁺ ions over other metal ions. However, BS2 is detected directly, while detection of BS1 involves a hydrolysis reaction to regenerate 3-amino-7-hydroxycoumarin (3) and 3,4-dihydroxybenzaldehyde, of which 3 is able to react with copper(II) or iron(III) ions. The interaction between the tested compounds and copper or iron ions is associated with a large fluorescence decrease, showing detection limits of ca. 10⁻⁵ M. Preliminary studies employing epifluorescence microscopy demonstrate that Cu²⁺ and Fe³⁺ ions can be imaged in human neuroblastoma SH-SY5Y cells treated with the tested probes.

  4. Biodynamics of copper oxide nanoparticles and copper ions in an oligochaete - Part II: Subcellular distribution following sediment exposure

    Science.gov (United States)

    Thit, Amalie; Ramskov, Tina; Croteau, Marie-Noele; Selck, Henriette

    2016-01-01

    The use and likely incidental release of metal nanoparticles (NPs) is steadily increasing. Despite the increasing amount of published literature on metal NP toxicity in the aquatic environment, very little is known about the biological fate of NPs after sediment exposures. Here, we compare the bioavailability and subcellular distribution of copper oxide (CuO) NPs and aqueous Cu (Cu-Aq) in the sediment-dwelling worm Lumbriculus variegatus. Ten days (d) sediment exposure resulted in marginal Cu bioaccumulation in L. variegatus for both forms of Cu. Bioaccumulation was detected because isotopically enriched 65Cu was used as a tracer. Neither burrowing behavior or survival was affected by the exposure. Once incorporated into tissue, Cu loss was negligible over 10 d of elimination in clean sediment (Cu elimination rate constants were not different from zero). With the exception of day 10, differences in bioaccumulation and subcellular distribution between Cu forms were either not detectable or marginal. After 10 d of exposure to Cu-Aq, the accumulated Cu was primarily partitioned in the subcellular fraction containing metallothionein-like proteins (MTLP, ≈40%) and cellular debris (CD, ≈30%). Cu concentrations in these fractions were significantly higher than in controls. For worms exposed to CuO NPs for 10 d, most of the accumulated Cu was partitioned in the CD fraction (≈40%), which was the only subcellular fraction where the Cu concentration was significantly higher than for the control group. Our results indicate that L. variegatus handle the two Cu forms differently. However, longer-term exposures are suggested in order to clearly highlight differences in the subcellular distribution of these two Cu forms.

  5. Engineering Short Preorganized Peptide Sequences for Metal Ion Coordination: Copper(II) a Case Study.

    Science.gov (United States)

    Lima, L M P; Iranzo, O

    2016-01-01

    Peptides are multidentate chiral ligands capable of coordinating different metal ions. Nowadays, they can be obtained with high yield and purity, thanks to the advances on peptide/protein chemistry as well as in equipment (peptide synthesizers). Based on the identity and length of their amino acid sequences, peptides can present different degrees of flexibility and folding. Although short peptide sequences (ion coordination. Based on our experience, we present a general scheme for the design, synthesis, and characterization of these peptidic scaffolds and provide protocols for the study of their metal ion coordination properties.

  6. Polyacrylamide-phytic acid-polydopamine conducting porous hydrogel for rapid detection and removal of copper (II) ions.

    Science.gov (United States)

    Zhao, Zhen; Chen, Hongda; Zhang, Hua; Ma, Lina; Wang, Zhenxin

    2017-05-15

    In this work, a conducting porous polymer hydrogel-based electrochemical sensor has been developed for rapid detection of copper (II) ions (Cu(2+)). The polymer (termed as PAAM/PA/PDA) hydrogel is prepared through multi-interactions of the monomers dopamine (DA), acrylamide (AAM) and phytic acid (PA) under mild ambient conditions: the AAM polymerizes through free-radical polymerization, DA occurs poly coupling reaction, and PA crosslinks polydopamine (PDA) and polyacrylamide (PAAM) by hydrogen bonds. The three dimensional (3D) network nanostructured PAAM/PA/PDA hydrogel not only provides a large surface area for increasing the amount of immobilized molecules/ions, but also exhibits a good conductivity. The PAAM/PA/PDA hydrogel-based electrochemical sensor exhibits a low detection limit (1nmolL(-)(1), S/N=3) and wide linear range (from 1nmolL(-)(1) to 1µmolL(-1)) for Cu(2+) detection in aqueous samples. Furthermore, the Cu(2+) can be sensitively detected by the electrochemical sensor in different sample matrices, indicating that the electrochemical sensor could be used to monitor Cu(2+) with reasonable assay performance in practical samples. The PAAM/PA/PDA hydrogel also exhibits a good capacity to remove Cu(2+)(231.36±4.70mgg(-1)), which is superior to those of other adsorption materials reported in the literature. The facile synthesized PAAM/PA/PDA hydrogel provides a novel and regenerable platform for monitoring and removing Cu(2+) in real samples. Copyright © 2016 Elsevier B.V. All rights reserved.

  7. H4octapa: highly stable complexation of lanthanide(III) ions and copper(II).

    Science.gov (United States)

    Kálmán, Ferenc Krisztián; Végh, Andrea; Regueiro-Figueroa, Martín; Tóth, Éva; Platas-Iglesias, Carlos; Tircsó, Gyula

    2015-03-02

    The acyclic ligand octapa(4-) (H4octapa = 6,6'-((ethane-1,2-diylbis((carboxymethyl)azanediyl))bis(methylene))dipicolinic acid) forms stable complexes with the Ln(3+) ions in aqueous solution. The stability constants determined for the complexes with La(3+), Gd(3+), and Lu(3+) using relaxometric methods are log KLaL = 20.13(7), log KGdL = 20.23(4), and log KLuL = 20.49(5) (I = 0.15 M NaCl). High stability constants were also determined for the complexes formed with divalent metal ions such as Zn(2+) and Cu(2+) (log KZnL = 18.91(3) and log KCuL = 22.08(2)). UV-visible and NMR spectroscopic studies and density functional theory (DFT) calculations point to hexadentate binding of the ligand to Zn(2+) and Cu(2+), the donor atoms of the acetate groups of the ligand remaining uncoordinated. The complexes formed with the Ln(3+) ions are nine-coordinated thanks to the octadentate binding of the ligand and the presence of a coordinated water molecule. The stability constants of the complexes formed with the Ln(3+) ions do not change significantly across the lanthanide series. A DFT investigation shows that this is the result of a subtle balance between the increased binding energies across the 4f period, which contribute to an increasing complex stability, and the parallel increase of the absolute values of the hydration free energies of the Ln(3+) ions. In the case of the [Ln(octapa)(H2O)](-) complexes the interaction between the amine nitrogen atoms of the ligand and the Ln(3+) ions is weakened along the lanthanide series, and therefore the increased electrostatic interaction does not overcome the increasing hydration energies. A detailed kinetic study of the dissociation of the [Gd(octapa)(H2O)](-) complex in the presence of Cu(2+) shows that the metal-assisted pathway is the main responsible for complex dissociation at pH 7.4 and physiological [Cu(2+)] concentration (1 μM).

  8. A New Rhodamine B Derivative As a Colorimetric Chemosensor for Recognition of Copper(II) Ion

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Lijun; Li, Fangfang; Liu, Minghui [Bohai University, Jinzhou (China); Nandhakumar, Raju [Karunya University, TamilNadu (India)

    2010-11-15

    A new rhodamine-based sensor 1 was designed and synthesized by incorporating rhodamine B and benzimidazole moieties. Sensor 1 exhibits high selectivity and sensitivity to Cu{sup 2+} in CH{sub 3}CN-water solution (HEPES buffer, pH = 7.0) with an obvious color change from colorless to pink. Other metal ions such as Hg{sup 2+}, Ag{sup +}, Pb{sup 2+}, Sr{sup 2+}, Ba{sup 2+}, Cd{sup 2+}, Ni{sup 2+}, Co{sup 2+}, Fe{sup 2+}, Mn{sup 2+}, Cu{sup 2+}, Zn{sup 2+}, Ce{sup 3+}, Mg{sup 2+}, K{sup +} and Na{sup +} had no such color change and have no significant influence on Cu{sup 2+} recognition process. The interaction of Cu{sup 2+} and sensor 1 was proven to adopt a 1:1 binding stoichiometry and the recognition process is reversible.

  9. Binding selectivity of vitamin K3 based chemosensors towards nickel(II) and copper(II) metal ions

    Science.gov (United States)

    Patil, Amit; Lande, Dipali N.; Nalkar, Archana; Gejji, Shridhar P.; Chakrovorty, Debamitra; Gonnade, Rajesh; Moniz, Tânia; Rangel, Maria; Pereira, Eulália; Salunke-Gawali, Sunita

    2017-09-01

    The vitamin K3 derivatives 2-methyl-3-[(pyridin-2-ylmethyl)-amino]-1,4-naphthoquinone (M-1), 2-methyl-3-[(pyridin-2-ylethyl)-amino]-1,4-naphthoquinone (M-2), 2-methyl-3-((2-(thiophen-2-yl)methyl)amino)naphthalene-1,4-dione (M-3) and 2-methyl-3-((2-(thiophen-2-yl)ethyl)amino)naphthalene-1,4-dione (M-4) have been synthesized, characterized and studied for their chemosensor abilities towards transition metal ions. Crystal structures of M-1 to M-4 revealed a variety of Nsbnd H⋯O, Csbnd H⋯O, Csbnd H⋯π and π⋯π interactions. Minor variations in such interactions by chemical stimuli such as metal ions, results in change in color that can be visualized by naked eyes. It has been shown that electronic structure and 1H NMR, vibrational as well as electronic spectra from the density functional theory agree well with the experiments. The metal ion binding in ethanol, ethanol-water and in mild base triethylamine brings forth recognizing ability of M-1 toward Ni2+ whereas M-2 exhibits large sensing ability for Cu2+ ion. Interestingly M-1 display varying metal ion binding specificity in different solvents with the association constant in ethanol being 11,786 M-1 for Ni2+ compared to 9462 M-1 for the Cu2+. A reversal in preferential binding of M-2 with the respective association constants being 4190 M-1 and 6370 M-1 is discernible.

  10. Removal of copper (II) from aqueous solutions by flotation using polyaluminum chloride silicate (PAX-XL60 S) as coagulant and carbonate ion as activator.

    Science.gov (United States)

    Ghazy, S E; Mahmoud, I A; Ragab, A H

    2006-01-01

    Flotation is a separation technology for removing toxic heavy metal ions from aqueous solutions. Here a simple and rapid flotation procedure is presented for the removal of copper(II) from aqueous solutions. It is based on the use of polyaluminum chloride silicate (PAX-XL60 S) as coagulant and flocculent, carbonate ion as activator and oleic acid (HOL) as surfactant. Both ion and precipitate flotation are included depending on the solution pH. Ion and precipitate flotation in the aqueous HOL-PAX-XL60 S-Cu2+-CO3(2-) system gave powerful preferential removal of Cu2+ (F -100%) over the HOL-PAX-XL60 S-Cu2+ system containing no CO3(2+) ion (F approximately 86%). The role of CO3(2-) ion is also evident from decreasing the dose of PAX-XL60 S from 700 mg l(-1) to 200 mg l(-1). The other parameters, influencing the flotation process, namely: metal ion, surfactant and PAX-XL60 S concentrations, ionic strength, temperature and foreign ions were examined. Moreover, the procedure was successfully applied to recover Cu2+ ions from different volumes up to 11 and from natural water samples.

  11. Coordination modes of a schiff base pentadentate derivative of 4-aminoantipyrine with cobalt(II), nickel(II) and copper(II) metal ions: synthesis, spectroscopic and antimicrobial studies.

    Science.gov (United States)

    Chandra, Sulekh; Jain, Deepali; Sharma, Amit Kumar; Sharma, Pratibha

    2009-01-01

    Transition metal complexes of Co(II), Ni(II) and Cu(II) metal ions with general stoichiometry [M(L)X]X and [M(L)SO(4)], where M = Co(II), Ni(II) and Cu(II), L = 3,3'-thiodipropionic acid bis(4-amino-5-ethylimino-2,3-dimethyl-1-phenyl-3-pyrazoline) and X = NO(3)(-), Cl(-) and OAc(-), have been synthesized and structurally characterized by elemental analyses, molar conductance measurements, magnetic susceptibility measurements and spectral techniques like IR, UV and EPR. The nickel(II) complexes were found to have octahedral geometry, whereas cobalt(II) and copper(II) complexes were of tetragonal geometry. The covalency factor (beta) and orbital reduction factor (k) suggest the covalent nature of the complexes. The ligand and its complexes have been screened for their antifungal and antibacterial activities against three fungi, i.e. Alternaria brassicae, Aspergillus niger and Fusarium oxysporum and two bacteria, i.e. Xanthomonas compestris and Pseudomonas aeruginosa.

  12. Integrated miniature fluorescent probe to leverage the sensing potential of ZnO quantum dots for the detection of copper (II) ions.

    Science.gov (United States)

    Ng, Sing Muk; Wong, Derrick Sing Nguong; Phung, Jane Hui Chiun; Chin, Suk Fun; Chua, Hong Siang

    2013-11-15

    Quantum dots are fluorescent semiconductor nanoparticles that can be utilised for sensing applications. This paper evaluates the ability to leverage their analytical potential using an integrated fluorescent sensing probe that is portable, cost effective and simple to handle. ZnO quantum dots were prepared using the simple sol-gel hydrolysis method at ambient conditions and found to be significantly and specifically quenched by copper (II) ions. This ZnO quantum dots system has been incorporated into an in-house developed miniature fluorescent probe for the detection of copper (II) ions in aqueous medium. The probe was developed using a low power handheld black light as excitation source and three photo-detectors as sensor. The sensing chamber placed between the light source and detectors was made of 4-sided clear quartz windows. The chamber was housed within a dark compartment to avoid stray light interference. The probe was operated using a microcontroller (Arduino Uno Revision 3) that has been programmed with the analytical response and the working algorithm of the electronics. The probe was sourced with a 12 V rechargeable battery pack and the analytical readouts were given directly using a LCD display panel. Analytical optimisations of the ZnO quantum dots system and the probe have been performed and further described. The probe was found to have a linear response range up to 0.45 mM (R(2)=0.9930) towards copper (II) ion with a limit of detection of 7.68×10(-7) M. The probe has high repeatable and reliable performance.

  13. Preparation of chitosan/poly(acrylic acid) magnetic composite microspheres and applications in the removal of copper(II) ions from aqueous solutions.

    Science.gov (United States)

    Yan, Han; Yang, Lingyun; Yang, Zhen; Yang, Hu; Li, Aimin; Cheng, Rongshi

    2012-08-30

    In this current work, the magnetic composite microspheres (MCM), consisting of Fe(3)O(4) nanoparticles and poly(acrylic acid) (PAA) blended chitosan (CS), were prepared successfully by a simple method, co-precipitation of the compounds in alkaline solution. SEM, FTIR and TG techniques have been applied to investigate the structures of the MCM materials. The vibrating-sample magnetometer (VSM) measurement illustrated a paramagnetic property as well as a fast magnetic response, which indicated the significant separability of the MCM in the aqueous suspensions. Then, the MCM materials were employed as absorbents for removal of copper(II) (Cu(II)) ions from aqueous solutions. The fundamental adsorption behaviors of MCM were studied also. Experimental results revealed that the CS/PAA-MCM had greater adsorption capacity than CS-MCM, and PAA played an important role for the adsorption of Cu(II) ions. Moreover, the adsorption isotherms were all well described by the Langmuir model, while the adsorption kinetics followed the pseudo-second order equation. Furthermore, the adsorbent could be easily regenerated at lower pH and reused almost without any loss of adsorption capacity. On the contrary, the Cu(II) ions loaded CS-MCM and CS/PAA-MCM were stable enough at pH higher than 4.0, and both exhibited efficient phosphate removal with maximal uptakes around 63.0 and 108.0 mg Pg(-1), respectively. Copyright © 2012 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  16. Coordination Modes of a Schiff Base Derived from Substituted 2-Aminothiazole with Chromium(III, Manganese(II, Iron(II, Cobalt(II, Nickel(II and Copper(II Metal Ions: Synthesis, Spectroscopic and Antimicrobial Studies

    Directory of Open Access Journals (Sweden)

    Ambit Thakar

    2011-01-01

    Full Text Available Transition metal complexes of Cr(III, Mn(II, Fe(II, Co(II, Ni(II and Cu(II metal ions with general stoichiometry [ML2.2H2O] and [ML3], where M= Mn(II, Cr(III, Fe(II, Co(II, Ni(II and Cu(II, L= Schiff base derived from the condensation of 2-amino-4(4’-phenyl/methylphenyl-5-methyl-thiazole with 4-acetyl-1(3-chloro phenyl-3-methyl-2-pyrazoline-5-ones, have been synthesized and structurally characterized by elemental analysis, molar conductance measurements, magnetic susceptibility measurements and spectral techniques like IR, UV, 1H NMR, 13C NMR and Mass Spectra. All the complexes were found to be octahedral geometry. The ligand and its complexes have been screened for their antifungal and antibacterial activities against three fungi, i.e. Alternaria brassicae, Aspergillus niger and Fesarium oxysporum and two bacteria, i.e. Xanthomonas compestris and Pseudomonas aeruginosa.

  17. A 9,10-anthraquinone derivative having two propenyl arms as a neutral ionophore for highly selective and sensitive membrane sensors for copper(II) ion.

    Science.gov (United States)

    Shamsipur, Mojtaba; Avanes, Armen; Javanbakht, Mehran; Ganjali, Mohammad Reza; Sharghi, Hashem

    2002-08-01

    New polymeric membrane (PME) and coated graphite (CGE) copper(II)-selective electrodes based on 1-hydroxy-2-(prop-2'-enyl)-4-(prop-2'-enyloxy)-9,10-anthraquinone were prepared. The electrodes reveal linear emf-pCu2+ responses over wide concentration ranges (1.0 x 10(-5)-1.0 x 10(-1) M with a slope of 27.3 mV decade-1 for PME and 8.0 x 10(-8)-5.0 x 10(-2) M with a slope of 29.1 mV decade-1 for CGE) and very low limits of detection (8.0 x 10(-6) M for PME and 5.0 x 10(-8) M for CGE). The potentiometric response is independent of the pH of the test solution in the pH range 3.0-6.0. The proposed electrodes possess very good selectivities over a wide variety of other cations, including alkali, alkaline earth, transition and heavy metal ions, the selectivity coefficients for the CGE being much improved over those for the PME. The electrodes were used as indicator electrodes in the potentiometric titration of Cu2+ and in the recovery of copper ions from wastewater.

  18. The formation of copper sulphide semiconductors inside Langmuir–Blodgett films of Cu(II) ion complexes

    NARCIS (Netherlands)

    Werkman, P.J.; Wieringa, R.H.; Schouten, A.J.

    1998-01-01

    The fabrication of layers of copper sulphide within multilayers of copper complexes of the amphiphile 4-(10,12-pentacosadiynamido methyl pyridine, by diffusion of H2S into the multilayers, was studied by UV–VIS spectroscopy. XPS measurements revealed that copper sulphides can be synthesised which di

  19. On the interaction of copper(II) with disulfiram.

    Science.gov (United States)

    Lewis, David J; Deshmukh, Parikshit; Tedstone, Aleksander A; Tuna, Floriana; O'Brien, Paul

    2014-11-11

    In combination with copper(II) ions, disulfiram (DSF) has been reported to be a potentially potent anticancer agent based on in vitro results. The interaction of DSF with copper(II) chloride in solution has been studied using a range of spectroscopic techniques. There is strong evidence for the rapid formation of the bis(N,N-diethyl dithiocarbamato)copper(II) complex in situ. Kinetic experiments were used to determine rate laws for the reaction that give insight into the mechanism of the process which may help to explain the observed in vitro cytotoxicity.

  20. Magnesite tailing as low-cost adsorbent for the removal of copper (II) ions from aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Kipcak, Ilker; Isiyel, Turgut Giray [Eskisehir Osmangazi University, Eskisehir (Turkmenistan)

    2015-08-15

    The removal of Cu(II) ions from aqueous solution using magnesite tailing was investigated. Batch kinetic and equilibrium experiments were conducted to study the effects of initial pH, adsorbent dosage, contact time, initial concentration and temperature. The pseudo-first-order, pseudo-second-order and intraparticle diffusion models were used to study the kinetic data. The experimental data were best fitted by the pseudo-second-order kinetic model. The linear Langmuir and Freundlich adsorption equations were applied to describe the equilibrium isotherms. The equilibrium data fit very well the Langmuir model, and the maximum adsorption capacity was estimated as 12.18mg/g at 45 .deg. C. Thermodynamic parameters such as enthalpy change (ΔH{sup o}), free energy change (ΔG{sup o}) and entropy change (ΔS{sup o}) were calculated, and it was found that the adsorption process was spontaneous and endothermic. The results showed that magnesite tailing is a suitable adsorbent for the removal of Cu(II) ions from aqueous solutions.

  1. Synthesis and characterization of novel ion-imprinted polymeric nanoparticles for very fast and highly selective recognition of copper(II) ions.

    Science.gov (United States)

    Shamsipur, Mojtaba; Besharati-Seidani, Abbas; Fasihi, Javad; Sharghi, Hashem

    2010-12-15

    This work reports the preparation of new Cu(2+) ion-imprinted polymeric nanoparticles using 1-hydroxy-4-(prop-2'-enyloxy)-9,10-anthraquinone (AQ) as a vinylated chelating agent. The Cu(2+) ion found to form a stable 1:1 complex with AQ in methanol solution. The resulting Cu(2+)-AQ complex was copolymerized with ethyleneglycol dimethacrylate, as a cross-linking monomer, via precipitation polymerization method. The imprint copper ion was removed from the polymeric matrix using a 0.1 mol L(-1) HNO(3) solution. The Cu(2+)-imprinted polymeric nanoparticles were characterized by IR spectroscopy, scanning electron microscopy (SEM) and N(2) adsorption-desorption isotherms. The SEM micrographs showed colloidal nanoparticles of 60-100 nm in diameter and slightly irregular in shape. Optimum pH for maximum sorption was 7.0. Sorption and desorption of Cu(2+) ion on the IIP nanoparticles were quite fast and achieved completely over entire investigated time periods of 2-30 min. Maximum sorbent capacity and enrichment factor of the prepared IIP for Cu(2+) were 73.8 μmol g(-1) and 56.5, respectively. The relative standard deviation and limit of detection (C(LOD)=3S(b)/m) of the method were evaluated as 2.6% and 0.1 ng mL(-1), using inductively coupled plasma-atomic emission spectrometry, respectively. It was found that the imprinting technology results in increased affinity of the prepared material toward Cu(2+) ion over other metal ions with the same charge and close ionic radius. The relative standard deviations for six and twenty replicates with the same nanoparticles were found to be 1.7% and 2.1%, respectively. Copyright © 2010 Elsevier B.V. All rights reserved.

  2. Copper(II)-mediated thermolysis of alginates: a model kinetic study on the influence of metal ions in the thermochemical processing of macroalgae.

    Science.gov (United States)

    Rowbotham, J S; Dyer, P W; Greenwell, H C; Selby, D; Theodorou, M K

    2013-02-06

    Thermochemical processing methods such as pyrolysis are of growing interest as a means of converting biomass into fuels and commodity chemicals in a sustainable manner. Macroalgae, or seaweed, represent a novel class of feedstock for pyrolysis that, owing to the nature of the environments in which they grow coupled with their biochemistry, naturally possess high metal contents. Although the impact of metals upon the pyrolysis of terrestrial biomass is well documented, their influence on the thermochemical conversion of marine-derived feeds is largely unknown. Furthermore, these effects are inherently difficult to study, owing to the heterogeneous character of natural seaweed samples. The work described in this paper uses copper(II) alginate, together with alginic acid and sodium alginate as model compounds for exploring the effects of metals upon macroalgae thermolysis. A thermogravimetric analysis-Fourier transform infrared spectroscopic study revealed that, unusually, Cu(2+) ions promote the onset of pyrolysis in the alginate polymer, with copper(II) alginate initiating rapid devolatilization at 143°C, 14°C lower than alginic acid and 61°C below the equivalent point for sodium alginate. Moreover, this effect was mirrored in a sample of wild Laminaria digitata that had been doped with Cu(2+) ions prior to pyrolysis, thus validating the use of alginates as model compounds with which to study the thermolysis of macroalgae. These observations indicate the varying impact of different metal species on thermochemical behaviour of seaweeds and offer an insight into the pyrolysis of brown macroalgae used in phytoremediation of metal-containing waste streams.

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

    Science.gov (United States)

    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.

  4. Application of artificial neural network to simultaneous potentiometric determination of silver(I), mercury(II) and copper(II) ions by an unmodified carbon paste electrode.

    Science.gov (United States)

    Shamsipur, Mojtaba; Tashkhourian, Javad; Hemmateenejad, Bahram; Sharghi, Hashem

    2004-10-20

    The response characteristics and selectivity coefficients of an unmodified carbon paste electrode (CPEs) towards Ag(+), Cu(2+) and Hg(2+) were evaluated. The electrode was used as an indicator electrode for the simultaneous determination of the three metal ions in their mixtures via potentiometric titration with a standard thiocyanate solution. A three-layered feed-forward artificial neural network (ANN) trained by back-propagation learning algorithm was used to model the complex non-linear relationship between the concentration of silver, copper and mercury in their different mixtures and the potential of solution at different volumes of the added titrant. The network architecture and parameters were optimized to give low prediction errors. The optimized networks were able to precisely predict the concentrations of the three cations in synthetic mixtures.

  5. Coordination mode of pentadentate ligand derivative of 5-amino-1,3,4-thiadiazole-2-thiol with nickel(II) and copper(II) metal ions: synthesis, spectroscopic characterization, molecular modeling and fungicidal study.

    Science.gov (United States)

    Chandra, Sulekh; Gautam, Seema; Kumar, Amit; Madan, Molly

    2015-02-01

    Complexes of nickel(II), and copper(II) were synthesized with pantadentate ligand i.e. 3,3'-thiodipropionicacid-bis(5-amino-1,3,4-thiadiazole-2-thiol) (L). The ligand was synthesized by the condensation of thiodipropionic acid and 5-amino-1,3,4-thiadiazole-2-thiol in 1:2 ratio, respectively. Synthesized ligand was characterized by elemental analysis, mass, (1)H NMR, IR, and molecular modeling. All the complexes were characterized by elemental analysis, molar conductance, magnetic moment, IR, electronic spectra, ESR, and molecular modeling. The newly synthesized complexes possessed general composition [M(L)X2] where M = Ni(II), Cu(II), L = pantadentate ligand and X = Cl(-), CH3COO(-). The IR spectral data indicated that the ligand behaved as a pantadentate ligand and coordinated to the metal ion through N2S3 donor atoms. The molar conductance value of Ni(II), and Cu(II) complexes in DMSO corresponded to their electrolytic behavior. On the basis of spectral study, octahedral and tetragonal geometry was assigned for Ni(II) and Cu(II) complexes, respectively. In vitro fungicidal study of ligand and its complexes was investigated against fungi Candida albicans, Candida parapsilosis, Candidia krusei, and Candida tropicalis by means of well diffusion method.

  6. Application of L-Aspartic Acid-Capped ZnS:Mn Colloidal Nanocrystals as a Photosensor for the Detection of Copper (II Ions in Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Jungho Heo

    2016-04-01

    Full Text Available Water-dispersible ZnS:Mn nanocrystals (NCs were synthesized by capping the surface with polar L-aspartic acid (Asp molecules. The obtained ZnS:Mn-Asp NC product was optically and physically characterized using the corresponding spectroscopic methods. The ultra violet-visible (UV-VIS absorption spectrum and photoluminescence (PL emission spectrum of the NCs showed broad peaks at 320 and 590 nm, respectively. The average particle size measured from the obtained high resolution-transmission electron microscopy (HR-TEM image was 5.25 nm, which was also in accordance with the Debye-Scherrer calculations using the X-ray diffraction (XRD data. Moreover, the surface charge and degree of aggregation of the ZnS:Mn-Asp NCs were determined by electrophoretic and hydrodynamic light scattering methods, respectively. These results indicated the formation of agglomerates in water with an average size of 19.8 nm, and a negative surface charge (−4.58 mV in water at ambient temperature. The negatively-charged NCs were applied as a photosensor for the detection of specific cations in aqueous solution. Accordingly, the ZnS:Mn-Asp NCs showed an exclusive luminescence quenching upon addition of copper (II cations. The kinetic mechanism study on the luminescence quenching of the NCs by the addition of the Cu2+ ions proposed an energy transfer through the ionic binding between the two oppositely-charged ZnS:Mn-Asp NCs and Cu2+ ions.

  7. The Mechanism of the Copper Ion Catalyzed Autoxidation of Cysteine in Alkaline Medium

    NARCIS (Netherlands)

    Koningsberger, D.C.; Zwart, J.; Wolput, J.H.M.C. van

    1981-01-01

    Quantitative e.s.r. measurements carried out during the copper catalysed alkaline autoxidation of cysteine show that the Cu(II)-dicysteine complex represents almost the total amount of copper. Only a small fraction (<2%) of the copper ions might be present in a state which is not detectable by e.s.r

  8. New Magnetic and Structural Results for Uniformly Spaced, Alternatingly Spaced, and Ladder-Like Copper(II) Linear Chain Compounds.

    Science.gov (United States)

    1980-12-15

    ligands are dig- cussed, including the quasi-linear chain compound bia(dimethyldithio- carbamato )copper(II) in which the copper(II) ions are...sample of the linear chain compound bis(dimethyldithio- adequate to permit a correlation between the magnetic carbamato )copper(II) is plotted as a

  9. Detection of Copper(II) Ions Using Glycine on Hydrazine-Adsorbed Gold Nanoparticles via Raman Spectroscopy

    Science.gov (United States)

    Ly, Nguyễn Hoàng; Seo, Chulhun; Joo, Sang-Woo

    2016-01-01

    A facile, selective, and sensitive detection method for the Cu2+ ions in environmental and biological solutions has been newly developed by observing the unique CN stretching peaks at ~2108 cm−1 upon the dissociative adsorption of glycine (GLY) in hydrazine buffer on gold nanoparticles (AuNPs). The relative abundance of Cu species on AuNPs was identified from X-ray photoelectron spectroscopy analysis. UV-Vis spectra also indicated that the Au particles aggregated to result in the color change owing to the destabilization induced by the GLY-Cu2+ complex. The CN stretching band at ~2108 cm−1 could be observed to indicate the formation of the CN species from GLY on the hydrazine-covered AuNP surfaces. The other ions of Fe3+, Fe2+, Hg2+, Mg2+, Mn2+, Ni2+, Zn2+, Cr3+, Co2+, Cd2+, Pb2+, Ca2+, NH4+, Na+, and K+ at high concentrations of 50 µM did not produce such spectral changes. The detection limit based on the CN band for the determination of the Cu2+ ion could be estimated to be as low as 500 nM in distilled water and 1 µM in river water, respectively. We attempted to apply our method to estimate intracellular ion detection in cancer cells for more practical purposes. PMID:27792178

  10. Copper(II) ions increase plasminogen activator inhibitor type 1 dynamics in key structural regions that govern stability

    DEFF Research Database (Denmark)

    Bucci, Joel C; Trelle, Morten Beck; McClintock, Carlee S;

    2016-01-01

    demonstrated that Cu(II) and other transition metals modulate the stability of PAI-1, exhibiting effects that are dependent on the presence or absence of the somatomedin B (SMB) domain of VN. The study presented here dissects the changes in molecular dynamics underlying the destabilizing effects of Cu...... effects are not a result of coordination of Cu(II) to these histidine residues. Finally, addition of Cu(II) results in an acceleration of the local unfolding kinetics of PAI-1 presumed to be on pathway to the latency conversion. The effect of ligands on the dynamics of PAI-1 adds another intriguing......Plasminogen activator inhibitor type 1 (PAI-1) regulates the fibrinolysis pathway by inhibiting the protease activity of plasminogen activators. PAI-1 works in concert with vitronectin (VN), an extracellular protein that aids in localization of active PAI-1 to tissues. The Peterson laboratory...

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

    Science.gov (United States)

    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

  12. Copper(II) complex of 3-cinnamalideneacetylacetone: Synthesis and characterisation

    Indian Academy of Sciences (India)

    A Veeraraj; P Sami; N Raman

    2000-10-01

    A bidentate ligand derived from cinnamaldehyde and acetylacetone and its copper(II) complex have been synthesized and characterized by elemental analysis, UV-Vis, IR, ESR and magnetic susceptibility measurements. Magnetic susceptibility measurements, ESR and electronic spectral data indicate the presence of six coordinated Cu(II) ion. The ligand and complex are tested for antibacterial activity against Pseudomonas aeroginosa. They are found to show the antibacterial activity

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

    Science.gov (United States)

    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.

  14. Removal of copper (II) ion from aqueous solution using zeolite Y synthesized from rice husk ash: Equilibrium and kinetic study

    Science.gov (United States)

    Tuyen, Nguyen Thi Kim; Nhan, Do Nguyen Thanh; Nhat, Trieu Thi; An, Ngo Thanh; Long, Nguyen Quang

    2017-09-01

    Zeolite Y was synthesized from silica of rice-husk ash using hydrothermal process. The crystalline structure FAU of zeolite Y was characterized by X-ray diffraction (XRD). Surface's area of the catalyst was determined by physic-adsorption method using BET model. The zeolite was examined for possibility of Cu2+ adsorbent by an ion-exchange mechanism. Various adsorption isotherm models, such as Langmuir, Freundlich and Dubinin-Radushkevich were tested for equilibrium study. The integration method was applied to find out the possible kinetic equation of the Cu2+ adsorption on the zeolite Y which obtained from cheap and locally available rice husk ash.

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

    Energy Technology Data Exchange (ETDEWEB)

    Bakovets, Vladimir V., E-mail: becambe@niic.nsc.ru [Nikolaev Institute of Inorganic Chemistry SB RAS, 630090 Novosibirsk, Prospekt Akademika Lavrent’eva 3 (Russian Federation); Nadolinnii, Vladimir A.; Kovalenko, Ekaterina A.; Plyusnin, Pavel E.; Dolgovesova, Irina P. [Nikolaev Institute of Inorganic Chemistry SB RAS, 630090 Novosibirsk, Prospekt Akademika Lavrent’eva 3 (Russian Federation); Zaikovskii, Vladimir I. [Boreskov Institute of Catalysis SB RAS, 630090 Novosibirsk, Pospekt Akademika Lavrent’eva 5 (Russian Federation)

    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

  16. Synthetic, spectral and solution studies on imidazolate-bridged copper(II)-copper(II) and copper(II)-zinc(II) complexes

    Indian Academy of Sciences (India)

    Subodh Kumar; R N Patel; P V Khadikar; K B Pandeya

    2001-02-01

    Synthesis, spectral and solution studies on 2-ethyl imidazolate-bridged (2-EtIm) homo-binuclear copper(II)-copper(II) and hetero-binuclear copper(II)-zinc(II) homologue are described. Magnetic moment values of homo-binuclear complexes indicate that the imidazolate group can mediate antiferromagnetic interactions. Optical spectra of hetero-binuclear complex at varying H values suggest that the imidazolate-bridged complex is stable over the H-range 7 15-10 0.

  17. A Solid-Contact Ion Selective Electrode for Copper(II Using a Succinimide Derivative as Ionophore

    Directory of Open Access Journals (Sweden)

    Mihaela Dana Tutulea-Anastasiu

    2013-04-01

    Full Text Available All-solid-state sensors with polyvinyl chloride (PVC-based membranes using off-the-shelf N-hydroxysuccinimide (NHS and succinimide (Succ ionophores were prepared using DOP (dioctyl phthalate and NPOE (ortho-nitrophenyloctyl ether as plasticizers. Good responses were obtained when NHS was used. The potentiometric response of the proposed electrode is independent of pH over the range 2–6. The electrode shows a fast response time of 0.25 s. The electrode exhibits a Super-Nernstian response, with 37.5 mV/decade, with a potentiometric detection limit of 4.4 µM. The proposed sensor revealed good selectivity towards a group of transition metal ions.

  18. Interactions of catechins with copper ions

    OpenAIRE

    Řihošková, Petra

    2014-01-01

    Charles University in Prague Faculty of Pharmacy in Hradec Králové Department of Pharmaceutical botanic and ecology Candidate: Mgr. Petra Řihošková Supervisor: PharmDr. Jana Karlíčková, Ph.D. Title of Thesis: Interactions of catechins with copper ions Keywords: catechins, chelating activity, copper, bathocuproine, hematoxylin, antioxidants Flavonoids are a class of plant polyphenols with significant antioxidant activity, which positively affects human health. Flavonoids are able to chelate me...

  19. Efficient On-Off Ratiometric Fluorescence Probe for Cyanide Ion Based on Perturbation of the Interaction between Gold Nanoclusters and a Copper(II)-Phthalocyanine Complex.

    Science.gov (United States)

    Shojaeifard, Zahra; Hemmateenejad, Bahram; Shamsipur, Mojtaba

    2016-06-22

    A new ratiometric fluorescent sensor was developed for the sensitive and selective detection of cyanide ion (CN(-)) in aqueous media. The ratiometric sensing system is based on CN(-) modulated recovery of copper(II) phthalocyanine (Cu(PcTs)) fluorescence signal at the expense of diminished fluorescence intensity of gold nanoclusters (AuNCs). Preliminary experiments revealed that the AuNCs and Cu(PcTs) possess a turn-off effect on each other, the interaction of which being verified through studying their interactions by principle component analysis (PCA) and multivariate cure resolution-alternating least-squares (MCR-ALS) methods. In the presence of CN(-) anion, the AuNCs and Cu(PcTs) interaction was perturbed, so that the fluorescence of Cu (PcTs), already quenched by AuNCs, was found to be efficiently recovered, while the fluorescence intensity of AuNCs was quenched via the formation of a stable [Au(CN)2](-) species. The ratiometric variation of AuNCs and Cu(PcTs) fluorescence intensities leads to designing a highly sensitive probe for CN(-) ion detection. Under the optimal conditions, CN(-) anion was detected without needing any etching time, over the concentration range of 100 nM-220 μM, with a detection limit of 75 nM, which is much lower than the allowable level of CN(-) in water permitted by the World Health Organization (WHO). Moreover, the detection of CN(-) was developed based on the CN(-) effects on the blue and red florescent colors of Cu(PcTs) and AuNCs, respectively. The designed probe displays a continuous color change from red to blue by addition of CN(-), which can be clearly observed by the naked eye in the range of 7-350 μM, under UV lamp. The prepared AuNCs/Cu(PcTs) probe was successfully utilized for the selective and sensitive determination of CN(-) anion in two different types of natural water (Rodbal dam and rainwater) and also in blood serum as a biological sample.

  20. Effect of sorption conditions on the state of copper(II) ions in the phase of AN-31 ion exchange resin, according to data from ESR and UV-vis diffuse reflectance spectroscopy

    Science.gov (United States)

    Stroganova, E. A.; Anufrienko, V. F.; Larina, T. V.; Vasenin, N. T.; Lebedev, Yu. A.; Parmon, V. N.

    2017-08-01

    It is found that the sorption recovery of copper ions from water solutions in the phase of AN-31 low basicity anion exchanger has a mixed character. It is established via diffuse reflectance spectroscopy that ions are stabilized through complexation with the participation of the functional groups of the sorbent with the formation of structures [Cu(NR3)2(OH)2(H2O)2], [Cu(NR3)3(OH)(H2O)2], and as a result of the physical adsorption of oxide dimers and planar-squared copper clusters. It is shown that increasing the ionic strength of a solution by introducing sodium chloride into the system greatly improves the capacity of the sorbent and leads to the uniform distribution of copper ions in the resin matrix. The similarity between the ESR spectrum parameters of copper-containing samples of the ion exchanger, obtained in a wider range of pH, is determined via ESR and testifies to the homogeneity of the stabilization positions of Cu2+ ions. The crystalline field of tetragonal-elongated octahedron is typical of all Cu2+ ions. All of the complexes have Cu(NO3)2 coordination nodes with the covalent bonding of Cu2+ ions and the amine groups of the sorbent.

  1. 铜(II)离子对橙皮素清除自由基作用的影响%Study on effect of copper (II) ion on radical scavenging of hesperetin

    Institute of Scientific and Technical Information of China (English)

    邹淑君; 许树军; 张蕾; 徐暘

    2015-01-01

    为探讨Cu2+存在对橙皮素( Hsp)清除自由基作用的影响.将Hsp与Cu2+混合即生成不稳定配合物(Hsp-Cu),利用UV-Vis光谱测定Hsp及Hsp-Cu对1,1-二苯基-2-三硝基苯肼自由基( DPPH·)、羟基自由基(· OH)、超氧阴离子自由基( O2-·)的清除作用.在实验条件下Hsp-Cu对DPPH·及· OH有一定的清除作用,但清除能力不如Hsp.Hsp-Cu不能有效清除O2-·,且在邻苯三酚自氧化过程中表现出促氧化作用.表明Hsp作为抗氧化剂使用时,应避免与Cu2+接触,以免影响其抗氧化能力.%To study the affection of Copper ( II ) ions on radical scavenging of hesperetin . Unstable hesperetin -copper ( II ) complex was generated when hesperetin was mixed with copper ( II ) chloride dihydrate .By the contrast tests on the scavenging reaction to DPPH radical, hydroxyl radical (· OH), and superoxide free radical (O2 -· ) of hesperetin -copper ( II) complex and hesperetin , proves that the scavenging activity of DPPH · and · OH of hesperetin-copper ( II) complex was weaker than that of hesperetin .The hesperetin-copper (II) complex can’t scavenge O2 -· showing accelerated oxidation in the process of pyrogallol autoxidation .Hesperetin was used as an antioxidant , cannot coexist with Cu 2+, so as not to affect the antioxidant capacity of hesperetin .

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  4. Electrochemical Synthesis and Structural Characterization of a Novel Mixed-valence Copper (I-copper (II Complex: {[Bis(ethylenediamine Copper (II] Bis[diiodocuprate (I]}

    Directory of Open Access Journals (Sweden)

    Mahboobeh Dashti Ardakani

    2007-07-01

    Full Text Available A novel, mixed-valent copper(I-copper(II complex, {[bis(ethylene-diaminecopper(II] bis[diiodocuprate(I]} (1, has been prepared by electrochemicaldissolution of a sacrificial copper anode in a solution of ethylenediamine (en, I2 andtetraethylammoniumperchlorate (TEAP as supporting electrolyte in acetonitrile (AcNand characterized by single-crystal X-ray structure determination. The crystal structure ofthe complex 1 shows that it consists of a CuI2 polymer formed from I- ligands bridgingCu(I ions, with a nearly square planar geometry of bivalente Cu(II atoms chelated by twoethylenediamine ligands. The results also show that direct electrosynthesis of the complexhad high current efficiency, purity and electrolysis yield.

  5. Bioactive and Antibacterial Glass Powders Doped with Copper by Ion-Exchange in Aqueous Solutions

    Directory of Open Access Journals (Sweden)

    Marta Miola

    2016-05-01

    Full Text Available In this work, two bioactive glass powders (SBA2 and SBA3 were doped with Cu by means of the ion-exchange technique in aqueous solution. SBA2 glass was subjected to the ion-exchange process by using different Cu salts (copper(II nitrate, chloride, acetate, and sulphate and concentrations. Structural (X-ray diffraction-XRD, morphological (Scanning Electron Microscopy-SEM, and compositional (Energy Dispersion Spectrometry-EDS analyses evidenced the formation of crystalline phases for glasses ion-exchanged in copper(II nitrate and chloride solutions; while the ion-exchange in copper(II acetate solutions lead to the incorporation of higher Cu amount than the ion-exchange in copper(II sulphate solutions. For this reason, the antibacterial test (inhibition halo towards S. aureus was performed on SBA2 powders ion-exchanged in copper(II acetate solutions and evidenced a limited antibacterial effect. A second glass composition (SBA3 was developed to allow a greater incorporation of Cu in the glass surface; SBA3 powders were ion-exchanged in copper(II acetate solutions (0.01 M and 0.05 M. Cu-doped SBA3 powders showed an amorphous structure; morphological analysis evidenced a rougher surface for Cu-doped powders in comparison to the undoped glass. EDS and X-ray photoelectron spectroscopy (XPS confirmed the Cu introduction as Cu(II ions. Bioactivity test in simulated body fluid (SBF showed that Cu introduction did not alter the bioactive behaviour of the glass. Finally, inhibition halo test towards S. aureus evidenced a good antimicrobial effect for glass powders ion-exchanged in copper(II acetate solutions 0.05 M.

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

    Science.gov (United States)

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

    2011-03-01

    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

  7. Sorption recovery of copper (II and zinc (II from chloride aqueous solutions

    Directory of Open Access Journals (Sweden)

    Kononova Olga N.

    2014-01-01

    Full Text Available The present investigation is devoted to simultaneous sorption recovery of copper (II and zinc (II ions on some commercial anion exchangers with different physical-chemical properties. The initial concentrations of zinc and copper were 1-3 mmol L-1 and the recovery was carried out in 0.01 M and 2 M hydrochloric acid solutions. It was shown that the investigated anion exchangers possess good sorption and kinetic properties. After the recovery of copper and zinc from strong acidic solutions, their selective elution was carried out by means of 2 M hydrochloric acid solution (zinc recovery and 2 M ammonia solution (copper recovery. In weak acidic solutions, copper and zinc were separated during sorption, as zinc sorption did not proceed in this case. The subsequent copper (II elution was carried out by 2 M ammonia solution. The anion exchangers Purolite S985, Purolite A500 and AM-2B can be recommended for zinc and copper recovery from acidic industrial solutions and waste water.

  8. Semax, an ACTH4-10 peptide analog with high affinity for copper(II) ion and protective ability against metal induced cell toxicity.

    Science.gov (United States)

    Tabbì, Giovanni; Magrì, Antonio; Giuffrida, Alessandro; Lanza, Valeria; Pappalardo, Giuseppe; Naletova, Irina; Nicoletti, Vincenzo Giuseppe; Attanasio, Francesco; Rizzarelli, Enrico

    2015-01-01

    Heptapeptide Semax, encompassing the sequence 4-7 of N-terminal domain of the adrenocorticotropic hormone (ACTH) and a C-terminal Pro-Gly-Pro tripeptide, belongs to a short regulatory peptides family. This compound has been found to affect learning processes and to exert marked neuroprotective activities on cognitive brain functions. Dys-homeostasis of metal ions is involved in several neurodegenerative disorders and growing evidences have showed that brain is a specialized organ able to concentrate metal ions. In this work, the metal binding ability and protective activity of Semax and its metal complexes were studied. The equilibrium study clearly demonstrated the presence of three complex species. Two minor species [CuL] and [CuLH-1]- co-exist together with the [CuLH-2]2- in the pH range from 3.6 to 5. From pH5 the [CuLH-2]2- species becomes predominant with the donor atoms around copper arranged in a 4N planar coordination mode. Noteworthy, a reduced copper induced cytotoxicity was observed in the presence of Semax by MTT [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide] assay on a SHSY5Y neuroblastoma and RBE4 endothelial cell lines.

  9. Removal of Pb(II) ions from aqueous solution by a waste mud from copper mine industry: equilibrium, kinetic and thermodynamic study.

    Science.gov (United States)

    Ozdes, Duygu; Gundogdu, Ali; Kemer, Baris; Duran, Celal; Senturk, Hasan Basri; Soylak, Mustafa

    2009-07-30

    The objective of this study was to assess the adsorption potential of a waste mud (WM) for the removal of lead (Pb(II)) ions from aqueous solutions. The WM was activated with NaOH in order to increase its adsorption capacity. Adsorption studies were conducted in a batch system as a function of solution pH, contact time, initial Pb(II) concentration, activated-waste mud (a-WM) concentration, temperature, etc. Optimum pH was specified as 4.0. The adsorption kinetic studies indicated that the overall adsorption process was best described by pseudo-second-order kinetics. The equilibrium adsorption capacity of a-WM was obtained by using Langmuir and Freundlich isotherm models and both models fitted well. Adsorption capacity for Pb(II) was found to be 24.4 mg g(-1) for 10 g L(-1) of a-WM concentration. Thermodynamic parameters including the Gibbs free energy (Delta G degrees), enthalpy (Delta H degrees), and entropy (DeltaS degrees) indicated that the adsorption of Pb(II) ions on the a-WM was feasible, spontaneous and endothermic, at temperature range of 0-40 degrees C. Desorption studies were carried out successfully with diluted HCl solutions. The results indicate that a-WM can be used as an effective and no-cost adsorbent for the treatment of industrial wastewaters contaminated with Pb(II) ions.

  10. Green Synthesis of Silver Nanoparticles Stabilized with Mussel-Inspired Protein and Colorimetric Sensing of Lead(II and Copper(II Ions

    Directory of Open Access Journals (Sweden)

    Ja Young Cheon

    2016-11-01

    Full Text Available This articles reports a simple and green method for preparing uniform silver nanoparticles (AgNPs, for which self-polymerized 3,4-dihydroxy-l-phenylalanine (polyDOPA is used as the reducing and stabilizing agent in aqueous media. The AgNPs functionalized by polyDOPA were analyzed by UV–Vis spectroscopy, high-resolution transmission electron microscopy (HR-TEM, Fourier transform infrared spectroscopy (FT-IR, thermogravimetric analysis (TGA, Raman spectrophotometry, and X-ray diffraction (XRD techniques. The results revealed that the polyDOPA-AgNPs with diameters of 25 nm were well dispersed due to the polyDOPA. It was noted that the polyDOPA-AgNPs showed selectivity for Pb2+ and Cu2+ detection with the detection limits for the two ions as low as 9.4 × 10−5 and 8.1 × 10−5 μM, respectively. Therefore, the polyDOPA-AgNPs can be applied to both Pb2+ and Cu2+ detection in real water samples. The proposed method will be useful for colorimetric detection of heavy metal ions in aqueous media.

  11. Green Synthesis of Silver Nanoparticles Stabilized with Mussel-Inspired Protein and Colorimetric Sensing of Lead(II) and Copper(II) Ions

    Science.gov (United States)

    Cheon, Ja Young; Park, Won Ho

    2016-01-01

    This articles reports a simple and green method for preparing uniform silver nanoparticles (AgNPs), for which self-polymerized 3,4-dihydroxy-l-phenylalanine (polyDOPA) is used as the reducing and stabilizing agent in aqueous media. The AgNPs functionalized by polyDOPA were analyzed by UV–Vis spectroscopy, high-resolution transmission electron microscopy (HR-TEM), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), Raman spectrophotometry, and X-ray diffraction (XRD) techniques. The results revealed that the polyDOPA-AgNPs with diameters of 25 nm were well dispersed due to the polyDOPA. It was noted that the polyDOPA-AgNPs showed selectivity for Pb2+ and Cu2+ detection with the detection limits for the two ions as low as 9.4 × 10−5 and 8.1 × 10−5 μM, respectively. Therefore, the polyDOPA-AgNPs can be applied to both Pb2+ and Cu2+ detection in real water samples. The proposed method will be useful for colorimetric detection of heavy metal ions in aqueous media. PMID:27916894

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

    Science.gov (United States)

    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.

  13. Determination of stability constants of 5-(2-hydroxybenzylidene)-2-thioxodihydropyrimidine-4,6(1H,5H)-dione with copper(II) and mercury(II) ions

    OpenAIRE

    Bahram,Morteza; Pesyan, Nader Noroozi

    2011-01-01

    In this work, a hard model chemometric method was used to determine the stability constants of copper(II) and mercury(II) complexes with the newly synthesized ligand 5-(2-hydroxybenzylidene)- 2-thioxodihydropyrimidine-4,6(1H,5H)-dione in acetonitrile by UV-Vis spectrophotometry. The ligand forms stable complexes with both metal cations. The protonation constants of the ligand were also measured in an ethanol-water (1:1) mixture.

  14. Sorption recovery of platinum (II, IV in presence of copper (II and zinc (II from chloride solutions

    Directory of Open Access Journals (Sweden)

    Kononova Olga N.

    2015-01-01

    Full Text Available The sorption preconcentration of platinum (II, IV ions was investigated in presence of accompanying copper (II and zinc (II ions from chloride solutions on the new ion exchangers CYBBER (Russia, previously unexplored. The initial concentrations of platinum and accompanying ions were 0.25 mmol L-1 and 2.0 mmol L-1, respectively, and the acidity of medium was 0.001 - 4.0 mol L-1. It was shown that the resins investigated - strong and weak basic anion exchangers as well as chelate ion exchangers - possess good sorption and kinetic properties. The simultaneous sorption of investigated ions results in the complete recovery of platinum, while the non-ferrous metal ions are sorbed at less than 20%. Followed by the selective elution of platinum by thiourea (80 g L-1 solution in 0.3 M H2SO4, the quantitative isolation of platinum was achieved (more than 90%. Therefore, the studied ion exchangers can be recommended for recovery and separation of Pt(II,IV, Cu(II and Zn(II ions.

  15. Base Catalytic Approach: A Promising Technique for the Activation of Biochar for Equilibrium Sorption Studies of Copper, Cu(II Ions in Single Solute System

    Directory of Open Access Journals (Sweden)

    Sharifah Bee Abdul Hamid

    2014-04-01

    Full Text Available This study examines the feasibility of catalytically pretreated biochar derived from the dried exocarp or fruit peel of mangostene with Group I alkali metal hydroxide (KOH. The pretreated char was activated in the presence of carbon dioxide gas flow at high temperature to upgrade its physiochemical properties for the removal of copper, Cu(II cations in single solute system. The effect of three independent variables, including temperature, agitation time and concentration, on sorption performance were carried out. Reaction kinetics parameters were determined by using linear regression analysis of the pseudo first, pseudo second, Elovich and intra-particle diffusion models. The regression co-efficient, R2 values were best for the pseudo second order kinetic model for all the concentration ranges under investigation. This implied that Cu(II cations were adsorbed mainly by chemical interactions with the surface active sites of the activated biochar. Langmuir, Freundlich and Temkin isotherm models were used to interpret the equilibrium data at different temperature. Thermodynamic studies revealed that the sorption process was spontaneous and endothermic. The surface area of the activated sample was 367.10 m2/g, whereas before base activation, it was only 1.22 m2/g. The results elucidated that the base pretreatment was efficient enough to yield porous carbon with an enlarged surface area, which can successfully eliminate Cu(II cations from waste water.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  18. Complexometric determination, Part II: Complexometric determination of Cu2+-ions

    Directory of Open Access Journals (Sweden)

    Rajković Miloš B.

    2002-01-01

    Full Text Available A copper-selective electrode of the coated wire type based on sulphidized copper wire was applied successfully for determining Cu(II ions by complexometric titration with the disodium salt of EDTA (complexon III. By the formation of internal complex compounds with the Cu(II ion, the copper concentration in the solution decreases, and all this is followed by a change of potential of the indicator system Cu-DWISE (or Cu-EDWISE/SCE. At the terminal point of titration, when all the Cu(II ions are already utilized for the formation of the complex with EDTA, there occurs a steep rise of potential, thus enabling us, through the first or second derivative to note the quantity of copper that is present in the solution. Copper-selective electrode showed a responsivity towards titration with EDTA as a complexing agent, with the absence of "fatigue" due to a great number of repeated measurings. Errors occurring during quantitative measurements were more a characteristic of the overall procedure which involve, because of the impossibility of the complete absence of subjectivity, a constant error, and the reproducibility of the results confirmed this fact. The disodium salt of EDTA appeared as a very efficient titrant in all titrations and with various concentrations ot Cu(II ions in the solution, with somewhat weaker response at lower concentrations in the solution.

  19. Exploiting 1,2,3-Triazolium Ionic Liquids for Synthesis of Tryptanthrin and Chemoselective Extraction of Copper(II Ions and Histidine-Containing Peptides

    Directory of Open Access Journals (Sweden)

    Hsin-Yi Li

    2016-10-01

    Full Text Available Based on a common structural core of 4,5,6,7-tetrahydro[1,2,3]triazolo[1,5-a]pyridine, a number of bicyclic triazolium ionic liquids 1–3 were designed and successfully prepared. In our hands, this optimized synthesis of ionic liquids 1 and 2 requires no chromatographic separation. Also in this work, ionic liquids 1, 2 were shown to be efficient ionic solvents for fast synthesis of tryptanthrin natural product. Furthermore, a new affinity ionic liquid 3 was tailor-synthesized and displayed its effectiveness in chemoselective extraction of both Cu(II ions and, for the first time, histidine-containing peptides.

  20. Exploiting 1,2,3-Triazolium Ionic Liquids for Synthesis of Tryptanthrin and Chemoselective Extraction of Copper(II) Ions and Histidine-Containing Peptides.

    Science.gov (United States)

    Li, Hsin-Yi; Chen, Chien-Yuan; Cheng, Hui-Ting; Chu, Yen-Ho

    2016-10-13

    Based on a common structural core of 4,5,6,7-tetrahydro[1,2,3]triazolo[1,5-a]pyridine, a number of bicyclic triazolium ionic liquids 1-3 were designed and successfully prepared. In our hands, this optimized synthesis of ionic liquids 1 and 2 requires no chromatographic separation. Also in this work, ionic liquids 1, 2 were shown to be efficient ionic solvents for fast synthesis of tryptanthrin natural product. Furthermore, a new affinity ionic liquid 3 was tailor-synthesized and displayed its effectiveness in chemoselective extraction of both Cu(II) ions and, for the first time, histidine-containing peptides.

  1. In situ reduction and functionalization of graphene oxide with l-cysteine for simultaneous electrochemical determination of cadmium(ii), lead(ii), copper(ii), and mercury(ii) ions

    KAUST Repository

    Muralikrishna, S. N.

    2014-01-01

    One pot reduction and functionalization of graphene oxide (GO) with l-cysteine (l-cys-rGO) at the edges and basal planes of the carbon layers are presented. The l-cys-rGO was characterized by X-ray diffraction studies (XRD), X-ray photoelectron spectroscopy (XPS), attenuated infrared spectroscopy (ATIR), and Raman spectroscopy. The surface morphology was studied by scanning electron microscopy (SEM) and transmittance electron microscopy (TEM). The l-cys-rGO was further utilized for the simultaneous electrochemical quantification of environmentally harmful metal ions such as, Cd2+, Pb2+, Cu2+ and Hg2+. Detection limits obtained for these metal ions were 0.366, 0.416, 0.261 and 1.113 μg L-1 respectively. The linear range obtained for Cd2+, Cu2+ and Hg2+ was 0.4 to 2.0 μM and for Pb2+ was 0.4 to 1.2 μM. The detection limits were found to be less than the World Health Organization (WHO) limits. The developed protocol was applied for the determination of the above metal ions in various environmental samples and the results obtained were validated by atomic absorption spectroscopy (AAS). This journal is

  2. Copper ion liquid-like thermoelectrics

    Science.gov (United States)

    Liu, Huili; Shi, Xun; Xu, Fangfang; Zhang, Linlin; Zhang, Wenqing; Chen, Lidong; Li, Qiang; Uher, Ctirad; Day, Tristan; Snyder, G. Jeffrey

    2012-05-01

    Advanced thermoelectric technology offers a potential for converting waste industrial heat into useful electricity, and an emission-free method for solid state cooling. Worldwide efforts to find materials with thermoelectric figure of merit, zT values significantly above unity, are frequently focused on crystalline semiconductors with low thermal conductivity. Here we report on Cu2-xSe, which reaches a zT of 1.5 at 1,000 K, among the highest values for any bulk materials. Whereas the Se atoms in Cu2-xSe form a rigid face-centred cubic lattice, providing a crystalline pathway for semiconducting electrons (or more precisely holes), the copper ions are highly disordered around the Se sublattice and are superionic with liquid-like mobility. This extraordinary ‘liquid-like’ behaviour of copper ions around a crystalline sublattice of Se in Cu2-xSe results in an intrinsically very low lattice thermal conductivity which enables high zT in this otherwise simple semiconductor. This unusual combination of properties leads to an ideal thermoelectric material. The results indicate a new strategy and direction for high-efficiency thermoelectric materials by exploring systems where there exists a crystalline sublattice for electronic conduction surrounded by liquid-like ions.

  3. Evaluation of immobilized metal-ion affinity chromatography and electrospray ionization tandem mass spectrometry for recovery and identification of copper(II-binding ligands in seawater using the model ligand 8-hydroxyquinoline

    Directory of Open Access Journals (Sweden)

    Richard L Nixon

    2016-11-01

    Full Text Available Complexation by organic ligands dominates the speciation of iron (Fe, copper (Cu, and other bioactive trace metals in seawater, controlling their bioavailability and distribution in the marine environment. Several classes of high-affinity Fe-binding ligands (siderophores have been identified in seawater but the chemical structures of marine Cu-complexing ligands remain unknown. Immobilized metal-ion affinity chromatography (IMAC allows Cu ligands to be isolated from bulk dissolved organic matter (DOM in seawater and separated into fractions which can be characterized independently using electrochemical and spectroscopic techniques. Attempts have been made to combine IMAC with electrospray ionization mass spectrometry (ESI-MS to characterize marine Cu ligands, but results have proven inconclusive due to the lack of tandem mass spectrometry (MS/MS data to confirm ligand recovery. We used 8-hydroxyquinoline (8-HQ, a well-characterized model ligand that forms strong 1:2 metal:ligand complexes with Cu2+ at pH 8 (log β2 = 18.3, to evaluate Cu(II-IMAC and ESI-MS/MS for recovery and identification of copper(II-complexing ligands in seawater. One-litre samples of 0.45µm-filtered surface seawater were spiked with 8-HQ at low concentrations (up to 100 nM and fractionated by IMAC. Fractions eluted with acidified artificial seawater were desalted and re-suspended in methanol via solid-phase extraction (SPE to obtain extracts suitable for ESI-MS analysis. Recovery of 8-HQ by Cu(II-IMAC was confirmed unambiguously by MS/MS and found to average 81% based upon accurate quantitation via multiple reaction monitoring (MRM. Cu(II-IMAC fractionation of unspiked seawater using multiple UV detection wavelengths suggests an optimal fraction size of 2 mL for isolating and analyzing Cu ligands with similar properties.

  4. Building reactive copper centers in human carbonic anhydrase II.

    Science.gov (United States)

    Song, He; Weitz, Andrew C; Hendrich, Michael P; Lewis, Edwin A; Emerson, Joseph P

    2013-08-01

    Reengineering 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 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 enzymatic systems. Human carbonic anhydrase II is known to bind two Cu(2+) ions; these binding events were explored using modern isothermal titration calorimetry techniques that have become a proven method to accurately measure metal-binding thermodynamic parameters. The two Cu(2+)-binding events have different affinities (K a approximately 5 × 10(12) and 1 × 10(10)), and both are enthalpically driven processes. Reconstituting these Cu(2+) sites under a range of conditions has allowed us to assign the Cu(2+)-binding event to the three-histidine, native, metal-binding site. Our initial efforts to characterize these Cu(2+) 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.

  5. Copper Ion as a New Leakage Tracer

    Directory of Open Access Journals (Sweden)

    Modaresi J.

    2013-12-01

    Full Text Available Statement of Problem: Most failures of root canal treatments are caused by bacteria. Studies showed that the most common cause of endodontic failures were the incomplete obturation of the root canal and the lack of adequate apical seal. Some in-vitro methods are used to estimate sealing quality, generally by measuring microleakage that allows the tracer agent to penetrate the filled canal.Purpose: Conventional methods of evaluating the seal of endodontically treated teeth are complicated and have some drawbacks. We used copper ion diffusion method to assess the leakage and the results were compared to dye penetration method.Materials and Method: The crowns of 21 extracted teeth were cut off at the CEJ level. After preparing the canals, the teeth were placed in tubes containing saline. They were divided randomly into 15 experimental cases; 3 positive and 3 negative controls. Positive controls were filled by single cone without sealer while the experimental and the negative control groups were filled by lateral technique. The coronal portion of gutta was removed and 9mm was left. The external surface of each tooth was coated with nail polish. Two millimeters of apical portion was immersed into 9ml of distilled water and 0.3ml of CuSO4 solution was injected into the coronal portion. After 2 days, copper sulfate was measured by an atomic absorption spectrophotometer. The teeth were then immersed in 2% methylene blue for 24 hours, sectioned and the extent of dye penetration was measured by a stereomicroscope.Results: The maximum and minimum recorded copper ion concentrations for the experimental group were 18.37 and 2.87ppm respectively. The maximum and minimum recorded dye penetrations for the experimental group were 8.5 and 3.5mm respectively. The statistical analysis, adopting paired samples test, showed poor correlation between average recorded results of two methods.Conclusion: Based on our results, there was no significant correlation between

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

    Science.gov (United States)

    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.

  7. Strategy for copper speciation in white wine by differential pulse anodic stripping voltammetry, potentiometry with an ion-selective electrode and kinetic photometric determination

    Energy Technology Data Exchange (ETDEWEB)

    Wiese, C. [Inst. fuer Anorganische und Analytische Chemie, Technische Univ. Clausthal, Clausthal-Zellerfeld (Germany); Schwedt, G. [Inst. fuer Anorganische und Analytische Chemie, Technische Univ. Clausthal, Clausthal-Zellerfeld (Germany)

    1997-07-01

    Differential pulse anodic stripping voltammetry (DPASV), potentiometry with a copper ion-selective electrode and a kinetic photometric method were used to determine copper species in white wines. The kinetic method is based on the catalytic effect of labile copper(II) species on the oxidation of 3-hydroxybenzaldehyde azine by potassium peroxidisulfate in an ammonical medium at room temperature. The total copper concentrations were determined by flame atomic absorption spectrometry. Free copper(II) ions, labile and tightly bound copper species could be quantified in 16 non pre-treated wine samples. (orig.). With 3 figs., 5 tabs.

  8. Mechanistic studies of copper(II)-mediated oxidation of vic-dioxime to furoxan

    Indian Academy of Sciences (India)

    Oindrila Das; Tapan Kanti Paine

    2012-11-01

    The oxidation of vic-dioximes to furoxans by copper(II) perchlorate in acetonitrile as the oxidant has been discussed. This method was found to be applicable for a broad range of vic-dioximes. Copper complexes of 1,10-phenanthroline derived furoxans were isolated by oxidation of the corresponding copper(II) complexes of 1,10-phenanthroline based dioximes. In exploring the mechanism of copper(II)-mediated oxidative cyclization of vic-dioxime, a transient blue species was observed in the reaction pathway. Based on the spectroscopic signatures and reactivity patterns, the intermediate was proposed to be a dioximatecopper(II)-dinitrosoalkene complex. These results along with the role of metal ion and solvent in the oxidative transformation reaction are discussed in this review.

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

    Science.gov (United States)

    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. Surface Structures Formed by a Copper(II Complex of Alkyl-Derivatized Indigo

    Directory of Open Access Journals (Sweden)

    Akinori Honda

    2016-10-01

    Full Text Available Assembled structures of dyes have great influence on their coloring function. For example, metal ions added in the dyeing process are known to prevent fading of color. Thus, we have investigated the influence of an addition of copper(II ion on the surface structure of alkyl-derivatized indigo. Scanning tunneling microscope (STM analysis revealed that the copper(II complexes of indigo formed orderly lamellar structures on a HOPG substrate. These lamellar structures of the complexes are found to be more stable than those of alkyl-derivatized indigos alone. Furthermore, 2D chirality was observed.

  11. Synthesis of copper nanoparticles in polycarbonate by ion implantation

    Indian Academy of Sciences (India)

    Annu Sharma; Suman Bahniwal; Sanjeev Aggarwal; S Chopra; D Kanjilal

    2011-07-01

    Copper nanoparticles have been synthesized in polycarbonate by 75 KeV Cu– ion implantation with various doses ranging from 6.4 × 1015 to 1.6 × 1017 ions/cm2 with a beam current density of 800 nA/cm2. The composites formed were structurally characterized using Ultraviolet-Visible (UV-Visible) absorption spectroscopy. The appearance of particle plasmon resonance peak, characteristic of copper nanoparticles at 603 nm in absorption spectra of polycarbonate implanted to a dose of 1.6 × 1017 ions/cm2, indicates towards the formation of copper nanoparticles in polycarbonate. Transmission electron microscopy further confirms the formation of copper nanoparticles having size ∼ 3.15 nm. The formation of copper nanoparticles in the layers carbonized by Cu– implantation has been discussed. The synthesized copper-polycarbonate nanocomposite has been found to be more conducting than polycarbonate as ascertained using current–voltage characteristics.

  12. Two novel Krebs-type polyoxoanions [Cu I2(WO 2) 2(β-XW 9O 33) 2] 12- (X = Sb III, Bi III) resulting in 2D layer structures linked by copper(I) ions and copper(II) complex groups

    Science.gov (United States)

    Zhang, Wei; Liu, Shuxia; Feng, Dan; Zhang, Chundan; Sun, Ping; Ma, Fengji

    2009-11-01

    Two sandwich-type organic-inorganic hybrid polyoxotungstates [enH 2] 5[Cu II(en) 2][Cu I2(WO 2) 2(β-SbW 9O 33) 2]·16H 2O ( 1) and [enH 2] 5[Cu II(en) 2][Cu I2(WO 2) 2(β-BiW 9O 33) 2]·22H 2O ( 2) (en = ethylenediamine) have been synthesized hydrothermally and structurally characterized by elemental analyses, IR spectra, thermal stability analyses, X-ray powder diffraction, and single-crystal X-ray diffraction. The polyoxoanions in 1 and 2 are composed of two trivacant (B-β-XW 9O 33) 9- (X = Sb III ( 1), Bi III ( 2)) subunits joined together by two Cu(I) ions and two W(VI) ions resulting in two novel Krebs-type sandwich structures. These polyoxoanions are further connected by Cu(I) ions and [Cu II(en) 2] 2+ coordination cations, and afford the first copper(I)-linked 2D layer structure constructed from Krebs-type polyoxotungstates. Additionally, the electrochemical behavior and electrocatalysis of 1 and 2 modified carbon paste electrodes (CPEs) have been studied. The results indicate that they have good electrocatalytic activities toward the reduction of nitrite.

  13. Release behavior of copper ion in a novel contraceptive composite.

    Science.gov (United States)

    Li, Juan; Suo, Jinping; Huang, Xunbin; Ye, Chang; Wu, Xiwang

    2007-09-01

    The universally used contraceptive method, the Cu-IUD, an effective contraceptive, is being increasingly used worldwide for family planning. To avoid abnormal bleeding, pain, partial and complete expulsion associated with the burst release of copper during the first few days, a novel cross-linked composite based on poly vinyl alcohol (PVA) that contains copper ions, but not metallic copper, was synthesized. PVA, well known for its good processability, high strength, long-term temperature and pH stability and biocompatibility, was used as the matrix material. The corrosion products and the release rate of copper ions after soaking in simulated body fluid (SBF) for different time spans were studied by environmental scanning electron microscopy, X-ray energy dispersive spectroscopy, X-ray diffraction and atomic absorption spectrophotometer. No significant change on time dependence for the release rate of copper ions in the composite compared with that of metallic copper was found. Moreover, no other new elements, such as P, Cl and Ca, appeared on the surface of the composite and no Cu(2)O formed after immersing in SBF for 90 days. Burst release of copper ions can be avoided by loading copper ions in this polymer material. Release channels would not be obstructed by the deposition of corrosion products and nearly all of the copper loaded in the composites could be an effective contraceptive.

  14. Restricted accessed material-copper(II) ion imprinted polymer solid phase extraction combined with inductively coupled plasma-optical emission spectrometry for the determination of free Cu(II) in urine and serum samples.

    Science.gov (United States)

    Cui, Chao; He, Man; Chen, Beibei; Hu, Bin

    2013-11-15

    A novel restricted accessed material (RAM)-Cu(II) ion imprinted polymer (IIP) was synthesized by the surface imprinted-emulsion method, and possessed a high selectivity to Cu(II) and good macromolecules exclusion property. And a novel method of RAM-IIP packed microcolumn solid phase extraction (SPE) combined with inductively coupled plasma-optical emission spectrometry (ICP-OES) was developed for the determination of trace free Cu(II) in human body fluids. Under the optimized conditions, the adsorption capacity of RAM-IIP for Cu(II) was 15.9 mg g(-1). With a preconcentration factor of 30, the limit of detection was 0.17 µg L(-1), and the relative standard deviation was 2.2% (n=7, c=1 µg L(-1)). The developed method was validated by the analysis of two Certified Reference Materials, and the determined values were in good agreement with the certified values. This method was also successfully applied for the direct analysis of free Cu(II) in human urine and serum samples. While the total Cu can be determined by the proposed method after microwave digestion. The concentrations of free Cu(II) were much lower than that of total Cu, indicating that Cu is mainly coordinated with macromolecules in these biological samples. From this point of view, the developed method exhibits application potential in speciation of free metal ions and metallic complex molecules in biological samples. © 2013 Elsevier B.V. All rights reserved.

  15. Disulfiram and Copper Ions Kill Mycobacterium tuberculosis in a Synergistic Manner.

    Science.gov (United States)

    Dalecki, Alex G; Haeili, Mehri; Shah, Santosh; Speer, Alexander; Niederweis, Michael; Kutsch, Olaf; Wolschendorf, Frank

    2015-08-01

    Tuberculosis is a severe disease affecting millions worldwide. Unfortunately, treatment strategies are hampered both by the prohibitively long treatment regimen and the rise of drug-resistant strains. Significant effort has been expended in the search for new treatments, but few options have successfully emerged, and new treatment modalities are desperately needed. Recently, there has been growing interest in the synergistic antibacterial effects of copper ions (Cu(II/I)) in combination with certain small molecular compounds, and we have previously reported development of a drug screening strategy to harness the intrinsic bactericidal properties of Cu(II/I). Here, we describe the copper-dependent antimycobacterial properties of disulfiram, an FDA-approved and well-tolerated sobriety aid. Disulfiram was inhibitory to mycobacteria only in the presence of Cu(II/I) and exerted its bactericidal activity well below the active concentration of Cu(II/I) or disulfiram alone. No other physiologically relevant bivalent transition metals (e.g., Fe(II), Ni(II), Mn(II), and Co(II)) exhibited this effect. We demonstrate that the movement of the disulfiram-copper complex across the cell envelope is porin independent and can inhibit intracellular protein functions. Additionally, the complex is able to synergistically induce intracellular copper stress responses significantly more than Cu(II/I) alone. Our data suggest that by complexing with disulfiram, Cu(II/I) is likely allowed unfettered access to vulnerable intracellular components, bypassing the normally sufficient copper homeostatic machinery. Overall, the synergistic antibacterial activity of Cu(II/I) and disulfiram reveals the susceptibility of the copper homeostasis system of Mycobacterium tuberculosis to chemical attacks and establishes compounds that act in concert with copper as a new class of bacterial inhibitors.

  16. ESR, zero-field splitting, and magnetic exchange of exchange-coupled copper(II)-copper(II) pairs in copper(II) tetraphenylporphyrin N-oxide.

    Science.gov (United States)

    Yang, Fuh-An; Guo, Chih-Wei; Chen, Yao-Jung; Chen, Jyh-Horung; Wang, Shin-Shin; Tung, Jo-Yu; Hwang, Lian-Pin; Elango, Shanmugam

    2007-01-22

    The crystal structures of the dimer form of copper(II) tetraphenylporphyrin N-oxide, [Cu(tpp-N-O)]2 (3-dimer), and zinc(II) tetraphenylporphyrin N-oxide, [Zn(tpp-N-O)]2 (4-dimer), were established. The geometry at the copper ion in 3-dimer is essentially square-pyramidal with one oxygen bridge [O(1A)] occupying the apical site, giving a much larger Cu-O bond distance compared to those at the basal plane. The respective Cu...Cu distance and Cu-O-Cu angle in the core of 3-dimer are 3.987(4) A and 148.1(3) degrees. The Zn(1) atom in 4-dimer has a distorted square-pyramidal [4 + 1] coordination geometry that gives a tau-value of 0.19. The respective Zn...Zn distance and Zn-O-Zn angle in the dimeric unit of 4-dimer are 4.025(3) A and 148.1(2) degrees. The 3-dimer displays axial X-band electron paramagnetic resonance spectral features (Es = 0) in the powder state at 4 K, giving g parallel = 2.51 (A(parallel,s) = (9.6 +/- 0.2) x 10-3 cm(-1)) and g(perpendicular) = 2.11 and in the same powder state at 293 K giving Ds = 0.0731 cm(-1) (as derived from DeltaMs = 1 lines) or 0.0743 cm(-1) (as derived from the DeltaMs = 2 lines). In addition, 3-dimer displays a DeltaMs = 2 transition at g = 4.17 indicating the presence of spin-exchange coupling. The anisotropic exchange interaction (Ds(ex)= 0.132 cm(-1)) gives the main contribution to Ds in 3-dimer. The theoretical fit of the susceptibility and effective magnetic moment data of 3-dimer in the temperature range of 5-300 K gives 2J = 68 cm(-1), g = 2.01, p = 0.06, and a temperature-independent paramagnetism of 10(-6) cm3 mol(-1). This magnetic susceptibility data indicates that the copper(II) ions in 3-dimer are coupled in a ferromagnetic manner with the ground-spin triplet stabilized by 68 cm(-1) with regard to the singlet.

  17. Electrochemical Synthesis and Structural Characterization of a Novel Mixed-valence Copper (I)-copper (II) Complex: {[Bis(ethylenediamine) Copper (II)] Bis[diiodocuprate (I)]}

    OpenAIRE

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

    2007-01-01

    A novel, mixed-valent copper(I)-copper(II) complex, {[bis(ethylene-diamine)copper(II)] bis[diiodocuprate(I)]} (1), has been prepared by electrochemicaldissolution of a sacrificial copper anode in a solution of ethylenediamine (en), I2 andtetraethylammoniumperchlorate (TEAP) as supporting electrolyte in acetonitrile (AcN)and characterized by single-crystal X-ray structure determination. The crystal structure ofthe complex 1 shows that it consists of a CuI2 polymer formed from I- ligands bridgi...

  18. Absorption of copper(II) by creosote bush (Larrea tridentata): use of atomic and x-ray absorption spectroscopy.

    Science.gov (United States)

    Gardea-Torresdey, J L; Arteaga, S; Tiemann, K J; Chianelli, R; Pingitore, N; Mackay, W

    2001-11-01

    Larrea tridentata (creosote bush), a common North American native desert shrub, exhibits the ability to take up copper(II) ions rapidly from solution. Following hydroponic studies, U.S. Environmental Protection Agency method 200.3 was used to digest the plant samples, and flame atomic absorption spectroscopy (FAAS) was used to determine the amount of copper taken up in different parts of the plant. The amount of copper(II) found within the roots, stems, and leaves was 13.8, 1.1, and 0.6 mg/g, respectively, after the creosote bush was exposed to a 63.5-ppm copper(II) solution for 48 h. When the plant was exposed to a 635-ppm copper(II) solution, the roots, stems, and leaves contained 35.0, 10.5, and 3.8 mg/g, respectively. In addition to FAAS analysis, x-ray microfluorescence (XRMF) analysis of the plant samples provided further confirmation of copper absorption by the various plant parts. X-ray absorption spectroscopy (XAS) elucidated the oxidation state of the copper absorbed by the plants. The copper(II) absorbed from solution remained as copper(II) bound to oxygen-containing ligands within the plant samples. The results of this study indicate that creosote bush may provide a useful and novel method of removing copper(II) from contaminated soils in an environmentally friendly manner.

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

    Science.gov (United States)

    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.

  20. Changes in magnetic properties from solid state to solution in a trinuclear linear copper(II) complex

    NARCIS (Netherlands)

    Koval, I.A.; Akhideno, H.; Tanase, S.; Belle, C.; Duboc, C.; Saint-Aman, E.; Gamez, P.; Tooke, D.M.; Spek, A.L.; Pierre, J.-L.; Reedijk, J.

    2007-01-01

    A linear trinuclear copper(II) complex containing phenoxido- and alkoxido-bridges between the metal centers has been isolated and structurally characterized. The complex cation consists of a linear array of three copper ions, assembled by means of two doubly deprotonated ligands. The octahedral coor

  1. Samarium(III) as luminescent probe for copper(II)

    Energy Technology Data Exchange (ETDEWEB)

    Jiménez, José A., E-mail: jose.jimenez@unf.edu

    2015-05-15

    Lanthanide-based luminescent sensing of copper(II) is currently an active area of research given the need for determining trace amounts of the analyte in environmental and biological matrices. Moreover, the increasing interest of Cu-doped materials for a variety of applications (e.g. luminescent and plasmonic) calls for appropriate measures for the assessment of residual Cu{sup 2+} in the solid state. In this work, Sm{sup 3+} ions are investigated as luminescent probes for Cu{sup 2+} within a glass matrix as model system based on Sm{sup 3+}→Cu{sup 2+} energy transfer. The Cu{sup 2+} concentration dependence of the Sm{sup 3+} emission quenching and decay rates of the {sup 4}G{sub 5/2} excited state allow for establishing calibration curves useful for determining Cu{sup 2+}. The luminescence-based approaches are employed for estimating residual Cu{sup 2+} in a Cu{sup +}/Sm{sup 3+} co-doped glass as ‘unknown’, the results being compared with the spectrophotometric method based on Cu{sup 2+} absorption in the visible. Remarkably, the approaches appeared in good agreement. Thus, the present work demonstrates the potential of Sm{sup 3+} ions for optical sensing of copper(II), opening research avenues extending from materials to liquid phase systems with relevance to biological and environmental sciences. - Highlights: • Sm{sup 3+}→Cu{sup 2+} energy transfer investigated in glass as model matrix in context of analytical applications. • Sm{sup 3+} photoluminescence and emission decay dynamics correlated with Cu{sup 2+} concentration. • Potential of Sm{sup 3+} ions for optical sensing of Cu{sup 2+} demonstrated.

  2. Copper(II) complexes with aroylhydrazones

    Indian Academy of Sciences (India)

    Samudranil Pal

    2002-08-01

    The coordination chemistry of copper(II) with tridentate aroylhydrazones is briefly discussed in this article. Two types of aroylhydrazones derived from aroylhydrazines and ortho-hydroxy aldehydes or 2-pyridine-carboxaldehyde have been used. The characterization of the complexes has been performed with the help of various physico-chemical techniques. Solid state structural patterns have been established by X-ray crystallography. In the solid state, structural varieties of these complexes are seen to range from monomeric, dimeric, polymeric and onedimensional self-assembly via hydrogen bonds and - interactions. EPR spectroscopy and variable temperature magnetic susceptibility measurements have been used to reveal the nature of the coordination geometry and magnetic characteristics of these complexes.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  5. Geometry and Framework Interactions of Zeolite-Encapsulated Copper(II)-Histidine Complexes

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Grommen, R.; Manikandan, P.; Gao, Y.; Shane, T.; Shane, J.J.; Schoonheydt, R.A.; Goldfarb, D.

    2000-01-01

    The coordination geometry of zeolite-encapsulated copper(II)-histidine (CuHis) complexes, prepared by ion exchange of the complexes from aqueous solutions into zeolite NaY, was determined by a combination of UV-vis-NIR diffuse reflectance spectroscopy (DRS), X-band EPR, electron-spin-echo envelope m

  6. Geometry and Framework Interactions of Zeolite-Encapsulated Copper(II)-Histidine Complexes

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Grommen, R.; Manikandan, P.; Gao, Y.; Shane, T.; Shane, J.J.; Schoonheydt, R.A.; Goldfarb, D.

    2000-01-01

    The coordination geometry of zeolite-encapsulated copper(II)-histidine (CuHis) complexes, prepared by ion exchange of the complexes from aqueous solutions into zeolite NaY, was determined by a combination of UV-vis-NIR diffuse reflectance spectroscopy (DRS), X-band EPR, electron-spin-echo envelope m

  7. Measurement of Electron-Ion Relaxation in Warm Dense Copper

    Science.gov (United States)

    Cho, B. I.; Ogitsu, T.; Engelhorn, K.; Correa, A. A.; Ping, Y.; Lee, J. W.; Bae, L. J.; Prendergast, D.; Falcone, R. W.; Heimann, P. A.

    2016-01-01

    Experimental investigation of electron-ion coupling and electron heat capacity of copper in warm and dense states are presented. From time-resolved x-ray absorption spectroscopy, the temporal evolution of electron temperature is obtained for non-equilibrium warm dense copper heated by an intense femtosecond laser pulse. Electron heat capacity and electron-ion coupling are inferred from the initial electron temperature and its decrease over 10 ps. Data are compared with various theoretical models.

  8. Copper(II) complexes encapsulated in human red blood cells.

    Science.gov (United States)

    Bonomo, R P; De Flora, A; Rizzarelli, E; Santoro, A M; Tabbí, G; Tonetti, M

    1995-09-01

    Copper(II) complexes were encapsulated in human red blood cells in order to test their possible use as antioxidant drugs by virtue of their labile character. ESR spectroscopy was used to verify whether encapsulation in red blood cells leads to the modification of such complexes. With copper(II) complexes bound to dipeptides or tripeptides, an interaction with hemoglobin was found to be present, the hemoglobin having a strong coordinative site formed by four nitrogen donor atoms. Instead, with copper(II) complexes with TAD or PheANN3, which have the greatest stability. ESR spectra always showed the original species. Only the copper(II) complex with GHL gave rise to a complicated behavior, which contained signals from iron(III) species probably coming from oxidative processes. Encapsulation of all copper(II) complexes in erythrocytes caused a slight oxidative stress, compared to the unloaded and to the native cells. However, no significant differences were observed in the major metabolic properties (GSH, glycolytic rate, hexose monophosphate shunt, Ca(2+)-ATPase) of erythrocytes loaded with different copper(II) complexes, with the exception of methemoglobin levels, which were markedly increased in the case of [Cu(GHL)H-1] compared to [Cu(TAD)]. This latter finding suggests that methemoglobin formation can be affected by the type of complex used for encapsulation, depending on the direct interaction of the copper(II) complex with hemoglobin.

  9. 1D μ-glycine-briged copper (II) chain in complex [Cu(μ-Gly)Im(ClO4)]n and ferromagnetic interactions among copper (II)

    Science.gov (United States)

    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.

  10. (II) and Pb (II) ions from aqueous media using Sta

    African Journals Online (AJOL)

    Joshua Konne

    Removal of Ni (II), Co (II) and Pb (II) ions from aqueous media using Starch. Stabilized Magnetic ... initial metal concentration and contact time on the removal processes was investigated. The results .... India) supplied NaOH and the Fe salts.

  11. trans-Bis(perchlorato-κOtetrakis(1H-pyrazole-κN2copper(II

    Directory of Open Access Journals (Sweden)

    Viktor Zapol'skii

    2008-10-01

    Full Text Available The title compound, [Cu(ClO42(C3H4N24], was obtained unexpectedly by the reaction of copper(II perchlorate hexahydrate with equimolar amounts of 1-chloro-1-nitro-2,2,2-tripyrazolylethane in methanol solution. The crystal structure comprises octahedrally coordinated Cu2+ ions, located on an inversion centre, with four pyrazole ligands in the equatorial plane. The average Cu—N distance is 2.000 (1 Å. Two perchlorate ions are coordinated to copper in trans positions [Cu—O = 2.4163 (11 Å].

  12. Bis(hexamethylenetetramine)bis(trichloroacetato)copper(II)

    OpenAIRE

    Li-Min Li; Fang-Fang Jian; Yu-Feng Li

    2009-01-01

    In the title compound, [Cu(C2Cl3O2)2(C6H12N4)2], the CuII ion (site symmetry 2) is coordinated by two trichloroacetate anions and two hexamethylenetetramine molecules, resulting in a distorted CuN2O2 geometry that is intermediate between tetrahedral and square planar. The Cl atoms are disordered over two sets of sites, with relative occupancies of 0.749 (7) and 0.251 (7). In the crystal, the packing is consolidated by intermolecular C—H...O interactions.

  13. Biosorption of lead (II and copper (II by biomass of some marine algae

    Directory of Open Access Journals (Sweden)

    Chaisuksant, Y.

    2004-09-01

    Full Text Available Biosorption of heavy metal ions by algae is a potential technology for treating wastewater contaminated with heavy metals. Adsorption of lead (II and copper (II in aqueous solutions by some marine algae available in large quantities in Pattani Bay including Gracilaria fisheri, Ulva reticulata and Chaetomorpha sp. were investigated. The effect of pH on metal sorption of the algal biomass and the metal uptake capacity of the algal biomass comparing to that of synthetic adsorbents including activated carbon and siliga gel were studied by using batch equilibrium experiments. Each dried adsorbent was stirred in metal ions solutions with different pH or different concentration at room temperature for 24 hours and the residual metal ions were analysed using atomic absorption spectrophotometer. The initial concentrations of lead and copper ionswere 70 µg/l and 20 mg/l, respectively. It was found that the effect of pH on metal sorption was similar in each algal biomass. The metal uptake capacity increased as pH of the solution increased from 2.0 to 4.0 and reached a plateau at pH 5.0-7.0. The metal uptake capacities of each algal biomass were similar. At low concentrations of metal ions, the metal adsorption occurred rapidly while at higher metal concentration less metal adsorption by each algal biomass was observed. The metal adsorption of activated carbon and silica gel occurred gradually and was less than those of algal biomass. The equilibrium data of copper and lead ions fitted well to the Langmuir and Freundlich isotherm models. The maximum sorption capacity (Qm values (mean±SD of Chaetomorpha sp., U. reticulata, G. fisheri, activated carbon and silica gel for lead ions were 1.26±0.14, 1.19±0.14, 1.18±0.15, 1.14±0.11 and 1.15±0.12 mg/g, respectively. For copper adsorption, the Qm values for G. fisheri, U. reticulata and Chaetomorpha biomass were 15.87±1.03, 14.71±1.02 and 12.35± 1.03 mg/g, respectively. While those of activated carbon and

  14. Biosorption of copper (II) from aqueous solution by mycelial pellets ...

    African Journals Online (AJOL)

    Syvia

    2012-01-19

    Jan 19, 2012 ... A stock solution of copper (II) was prepared by dissolving required amount of ... Reagent Co., Ltd, Shanghai, China) in double distilled water to obtain a .... through sharing or exchange of electrons between adsorbent and ...

  15. Metallic copper corrosion rates, moisture content, and growth medium influence survival of copper ion-resistant bacteria

    DEFF Research Database (Denmark)

    Elguindi, J; Moffitt, S; Hasman, Henrik

    2010-01-01

    The rapid killing of various bacteria in contact with metallic copper is thought to be influenced by the influx of copper ions into the cells, but the exact mechanism is not fully understood. This study showed that the kinetics of contact killing of copper surfaces depended greatly on the amount...... of moisture present, copper content of alloys, type of medium used, and type of bacteria. We examined antibiotic- and copper ion-resistant strains of Escherichia coli and Enterococcus faecium isolated from pig farms following the use of copper sulfate as feed supplement. The results showed rapid killing...... of both copper ion-resistant E. coli and E. faecium strains when samples in rich medium were spread in a thin, moist layer on copper alloys with 85% or greater copper content. E. coli strains were rapidly killed under dry conditions, while E. faecium strains were less affected. Electroplated copper...

  16. MECHANISM OF THE OXIDATION OF HEMOGLOBIN BY COPPER (II COMPLXES

    Directory of Open Access Journals (Sweden)

    M. BAYATI

    1994-07-01

    Full Text Available An outer sphere electron transfer mechanism by which human hemoglobin reduces the complexes of copper(II and, in turn, is oxidized to methemoglobin has been characterized. We have found that the rate of oxidation of hemoglobin is a function of pH, temperature, concentration of copper(II, and the environment of the hemoglobin. Prior to oxidation, copper(II complex binds to specific sites on the surface of the protein by losing one or more of its ligands, forming a ternary complex. This process is followed by electron transfer between the Cu(II and Fe(H with the Cu(II-deoxyhemoglobin being the active intermediate. The dominant factors which govern the rate of oxidation of hemoglobin by coppcr(I I complexes seem to be the stability constant of the Cu(II complexes and the overall redox potential of the ternary complex.

  17. Simultaneous Platinum and Copper Ion Attachment to a Human Copper Chaperone Protein

    Science.gov (United States)

    Hodak, Miroslav; Cvitkovic, John; Yu, Corey; Dmitriev, Oleg; Kaminski, George; Bernholc, Jerry

    2015-03-01

    Cisplatin is a potent anti-cancer drug based on a platinum ion. However, its effectiveness is decreased by cellular resistance, which involves cisplatin attaching to copper transport proteins. One of such proteins is Atox1, where cisplatin attaches to the copper binding site. Surprisingly, it was shown that both cisplatin and copper can attach to Atox1 at the same time. To study this double metal ion attachment, we use the KS/FD DFT method, which combines Kohn-Sham DFT with frozen-density DFT to achieve efficient quantum-mechanical description of explicit solvent. Calculations have so far investigated copper ion attachment to CXXC motifs present in Atox1. The addition of the platinum ion and the competition between the two metals is currently being studied. These calculations start from a molecular mechanics (MM) structural model, in which glutathione groups provide additional ligands to the Pt ion. Our goals are to identify possible Cu-Pt structures and to determine whether copper/platinum attachment is competitive, independent, or cooperative. Results will be compared to the 1H, N1 5 -HSQC NMR experiments, in which binding of copper and cisplatin to Atox1 produces distinct secondary chemical shift signatures, allowing for kinetic studies of simultaneous metal binding.

  18. [Atomic absorption spectrophotometry study of copper ion release by copper-bearing intrauterine devices].

    Science.gov (United States)

    Berthou, J; Chrétien, F C; Driguez, P A

    1998-11-01

    Copper release from copper-bearing IUD's was studied in vitro and in vivo using atomic absorption spectrophotometry in deionized water, normal saline solution and normal ovulatory cervical mucus. In these media, copper release from a 375 mm2 DIU occurs without latency, showing comparable amounts for identical time intervals. Daily copper release was shown to be respectively 8 and 11 times higher in cervical mucus and normal saline solution than in deionized water. Although copper ions are detectable in ovulatory cervical mucus under physiological conditions, the copper content appears 5 to 6 times higher in women bearing a copper IUD. Obviously, the copper amount is dependent on the copper exposed surface: the daily in vitro release from a 250 mm2 IUD is 18% inferior to that observed from a 375 mm2 model. In vivo, the daily copper release in ovulatory mucus of 380 or 200 mm2 IUD users is respectively 5 and 3.5 times higher than in controls.

  19. Simultaneous removal of methylene blue and copper(II) ions by photoelectron catalytic oxidation using stannic oxide modified iron(III) oxide composite electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Qi, Jinqiu [College of Water Conservancy and Civil Engineering, Shandong Agricultural University, Tai' an, Shandong 271018 (China); Li, Xiaochen, E-mail: lixiaochen02@163.com [College of Water Conservancy and Civil Engineering, Shandong Agricultural University, Tai' an, Shandong 271018 (China); Zheng, Hao [College of Water Conservancy and Civil Engineering, Shandong Agricultural University, Tai' an, Shandong 271018 (China); Li, Peiqiang; Wang, Huying [College of Chemistry and Material Science, Shandong Agricultural University, Tai' an, Shandong 271018 (China)

    2015-08-15

    Highlights: • Photoelectron catalytic oxidation was used for methylene blue and Cu{sup 2+} removal. • SnO{sub 2}/Fe{sub 2}O{sub 3} was prepared and characterized for use as photoanodes and photocathodes. • Optimal reaction conditions were determined for methylene blue and Cu{sup 2+} removal. • Methylene blue removal followed the Langmuir–Freundlich–Hinshelwood kinetic model. • Cu{sup 2+} removal followed the first-order rate model. - Abstract: Stannic oxide modified Fe(III) oxide composite electrodes (SnO{sub 2}/Fe{sub 2}O{sub 3}) were synthesized for simultaneously removing methylene blue (MB) and Cu(II) from wastewater using photoelectron catalytic oxidation (PEO). The SnO{sub 2}/Fe{sub 2}O{sub 3} electrodes were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), and photoelectrochemical techniques. The removal of MB and Cu(II) by PEO using the SnO{sub 2}/Fe{sub 2}O{sub 3} composite electrodes was studied in terms of reaction time, electric current density, and pH of the electrolyte. The kinetics of the reactions were investigated using batch assays. The optimal reaction time, pH, and electric current density of the PEO process were determined to be 30 min, 6.0, and 10 mA/cm{sup 2}, respectively. The removal rates of MB from wastewater treated by PEO and electron catalytic oxidation process were 84.87% and 70.64%, respectively, while the recovery rates of Cu(II) were 91.75% and 96.78%, respectively. The results suggest that PEO is an effective method for the simultaneous removal of MB and Cu(II) from wastewater, and the PEO process exhibits a much higher removal rate for MB and Cu(II) compared to the electron catalytic oxidation process. Furthermore, the removal of MB was found to follow the Langmuir–Freundlich–Hinshelwood kinetic model, whereas the removal of Cu(II) fitted well to the first-order reaction model.

  20. Iron(III) and copper(II) complexes of trans-bis(ferrocenyl)porphyrin: Effect of metal ions on long-range electronic communication

    Indian Academy of Sciences (India)

    Dipankar Sahoo; Sankar Prasad Rath

    2015-02-01

    A series of complex with a general formula of M(Fc2Ph2P) [Fc2Ph2P = 5, 10-bisferrocenyl-15,20-bisphenylporphyrin (2−); M = Fe(III)Cl Fe(III)(ClO4) and Cu(II)] have been synthesized and characterized. The single crystal X-ray structure of CuII(Fc2Ph2P) has been reported in which two ferrocene moieties are in anti form with respect to each other. The ferrocenyl groups of CuII(Fc2Ph2P) are more easily oxidized via a single two-electron quasi-reversible process compared to the free base ligand in which two 1e-oxidative response separated by 0.23 V are observed. Electrochemical study of FeIII(Fc2Ph2P)Cl revealed ferrocenebased two-electron quasi-reversible oxidation at 0.72 V indicating no observable coupling of the ferrocene moieties. The higher oxidation state of Fe(III) reduces the electron releasing tendency of the porphyrin ring and thus make the ferrocene oxidation difficult. The porphyrin, however, lack substituents at the -pyrrolic positions, and the ferrocenyl moieties are therefore free to rotate. The observed electrochemical analyses thus demonstrate that the oxidation of the ferrocene subunit is strongly affected by porphyrin ring as well as the central metal through extended -conjugation.

  1. An Angular Overlap Model for Cu(II) Ion in the AMOEBA Polarizable Force Field.

    Science.gov (United States)

    Xiang, Jin Yu; Ponder, Jay W

    2014-01-01

    An extensible polarizable force field for transition metal ion was developed based on AMOEBA and the angular overlap model (AOM) with consistent treatment of electrostatics for all atoms. Parameters were obtained by fitting molecular mechanics (MM) energies to various ab initio gas-phase calculations. The results of parameterization were presented for copper (II) ion ligated to water and model fragments of amino acid residues involved in the copper binding sites of type 1 copper proteins. Molecular dynamics (MD) simulations were performed on aqueous copper (II) ion at various temperatures, as well as plastocyanin (1AG6) and azurin (1DYZ). Results demonstrated that the AMOEBA-AOM significantly improves the accuracy of classical MM in a number of test cases when compared to ab initio calculations. The Jahn-Teller distortion for hexa-aqua copper (II) complex was handled automatically without specifically designating axial and in-plane ligands. Analyses of MD trajectories resulted in a 6-coordination first solvation shell for aqueous copper (II) ion and a 1.8ns average residence time of water molecules. The ensemble average geometries of 1AG6 and 1DYZ copper binding sites were in general agreement with X-ray and previous computational studies.

  2. Removal of copper, nickel, and zinc ions from electroplating rinse water

    Energy Technology Data Exchange (ETDEWEB)

    Revathi, Meyyappan; Saravanan, Mohan; Velan, Manickam [Department of Chemical Engineering, AC Tech, Anna University, Chennai, Tamil Nadu (India); Chiya, Ahmed Basha [Department of Chemical Engineering, Industrial Liaison Research Institute, Kyang Hee University, Gyeonggi (Korea, Republic of)

    2012-01-15

    Removal of copper, nickel, and zinc ions from synthetic electroplating rinse water was investigated using cationic exchange resin (Ceralite IR 120). Batch ion exchange studies were carried out to optimize the various experimental parameters (such as contact time, pH, and dosage). Influence of co-existing cations, chelating agent EDTA on the removal of metal ion of interest was also studied. Sorption isotherm data obtained at different experimental conditions were fitted with Langmuir, Freundlich, Redlich-Peterson, and Toth models. A maximum adsorption capacity of 164 mg g{sup -1} for Cu(II), 109 mg g{sup -1} for Ni(II), and 105 mg g{sup -1} for Zn(II) was observed at optimum experimental conditions according to Langmuir model. The kinetic data for metal ions adsorption process follows pseudo second-order. Presence of EDTA and co-ions markedly alters the metal ion removal. Continuous column ion exchange experiments were also conducted. The breakeven point of the column was obtained after recovering effectively several liters of rinse water. The treated rinse water could be recycled in rinsing operations. The Thomas and Adams-Bohart models were applied to column studies and the constants were evaluated. Desorption of the adsorbed metal ions from the resin column was studied by conducting a model experiments with Cu(II) ions loaded ion exchange resin column using sulfuric acid as eluant. A novel lead oxide coated Ti substrate dimensionally stable (DSA) anode was prepared for recovery of copper ions as metal foil from regenerated liquor by electro winning at different current densities (50-300 A cm{sup -2}). (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  3. Development of a four-zone carousel process packed with metal ion-imprinted polymer for continuous separation of copper ions from manganese ions, cobalt ions, and the constituent metal ions of the buffer solution used as eluent.

    Science.gov (United States)

    Jo, Se-Hee; Park, Chanhun; Yi, Sung Chul; Kim, Dukjoon; Mun, Sungyong

    2011-08-19

    A three-zone carousel process, in which Cu(II)-imprinted polymer (Cu-MIP) and a buffer solution were employed as adsorbent and eluent respectively, has been developed previously for continuous separation of Cu²⁺ (product) from Mn²⁺ and Co²⁺ (impurities). Although this process was reported to be successful in the aforementioned separation task, the way of using a buffer solution as eluent made it inevitable that the product stream included the buffer-related metal ions (i.e., the constituent metal ions of the buffer solution) as well as copper ions. For a more perfect recovery of copper ions, it would be necessary to improve the previous carousel process such that it can remove the buffer-related metal ions from copper ions while maintaining the previous function of separating copper ions from the other 2 impure heavy-metal ions. This improvement was made in this study by proposing a four-zone carousel process based on the following strategy: (1) the addition of one more zone for performing the two-step re-equilibration tasks and (2) the use of water as the eluent of the washing step in the separation zone. The operating conditions of such a proposed process were determined on the basis of the data from a series of single-column experiments. Under the determined operating conditions, 3 runs of carousel experiments were carried out. The results of these experiments revealed that the feed-loading time was a key parameter affecting the performance of the proposed process. Consequently, the continuous separation of copper ions from both the impure heavy-metal ions and the buffer-related metal ions could be achieved with a purity of 91.9% and a yield of 92.8% by using the proposed carousel process based on a properly chosen feed-loading time.

  4. Catalytic activation of copper (II) salts on the reaction of peroxynitrite with propofol in alkaline medium.

    Science.gov (United States)

    Kohnen, Stephan; Halusiak, Emilie; Mouithys-Mickalad, Ange; Deby-Dupont, Ginette; Deby, Carol; Hans, Pol; Lamy, Maurice; Noels, Alfred F

    2005-06-01

    We report here on the role of copper (II) salts on the acceleration of peroxynitrite (ONOO-) decomposition and ONOO- reaction with the anaesthetic agent propofol (2,6-diisopropylphenol) in alkaline medium. We observed a strong acceleration of the ONOO- decomposition in alkaline medium in the presence of copper (I and II) salts. After 18 h of ONOO- reaction with propofol, we observed nitrosated, nitrated, and oxidized (quinone and diphenylquinone) derivatives of propofol, but in the presence of Cu(II) (20% molar vs ONOO-), the yields of quinone and nitrosopropofol strongly increased. We also observed that the temperature and the atmosphere influenced the effects of Cu(II) on ONOO- reactions with propofol: low temperatures promoted nitrosation and high temperatures promoted oxidation; O2 atmosphere increased the general reactivity and the yield of nitrated and oxidized products. We highlighted the influence of Cu(II) salts on the radical character of the reaction by direct EPR technique. The exact mechanism of the Cu(II) catalysis remains unexplained, but we suggest the formation of a copper complex with propofol or, more probably, the oxidation of ONOO- into ONOO. by copper ions promoting the formation of quinone and nitrosopropofol according to a previously reported mechanism [M. Cudic, C. Ducrocq, Transformations of 2,6-diisopropylphenol by NO-derived nitrogen oxides, particularly peroxynitrite, Nitric Oxide 4 (2000) 147-156].

  5. Spectrophotometric determination of copper(II) in pharmaceutical, biological and water samples by 4-(2'-benzothiazolylazo)-salicylic acid

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  7. Activation of peroxyl and molecular oxygen using bis-benzimidazole diamide copper (II) compounds

    Indian Academy of Sciences (India)

    Pavan Mathur

    2006-11-01

    New tetradentate bis-benzimidazole ligands have been synthesized and utilized to prepare copper (II) complexes. Some of these copper (II) complexes have been characterized structurally. The copper (II) in these complexes is found to possess varying geometries. A distorted octahedral geometry is found with a highly unsymmetrical bidentate nitrate group. An unusual polymeric one-dimensional structure is observed where copper (II) is in a distorted square pyramidal geometry with a monodentate nitrate ion, having long Cu-O bond, while a distorted triagonal bipyramidal geometry is found with two carbonyl O atoms and a Cl atom in the equatorial plane, and two benzimidazole imine N atoms occupy the axial position. These compounds are found to activate the cumylperoxyl group, and this has been utilized in the facile oxidation of aromatic alcohols to aldehydes, where they act as catalysts with large turnovers. The yields of the respective products vary from 32 to 65%. The role of molecular oxygen has been studied and an attempt has been made to identify the "active copper species”. Activation of molecular oxygen has also been observed and has been used for oxidative dealkylation of a hindered phenol, producing di-butyl quinones with yields of 20-25% and 10-12 fold catalytic turnover. Dihydroxybenzenes and substituted catechols are also readily oxidized to the corresponding quinones, in oxygen-saturated solvents. Yields of 84% have been observed with 34-fold catalyst turnover, with di--butylcatechol. The activity of these copper (II) - bis-benzmidazolediamide compounds is reminiscent of the functioning of copper centres in galactose oxidase, tyrosinase and catechol oxidase.

  8. Synthesis, Characterization and DNA Cleavage of Copper(II ...

    African Journals Online (AJOL)

    (UV) light. Results: ATR-FTIR confirmed the formation of copper(II) complex with DTT by binding through thiol group based on the .... DNA cleavage detection ... The infrared spectra of pure DTT and its Cu(II) .... and iron complexes. J Phys Conf ...

  9. Three ion-pair complexes containing bis(maleonitriledithiolate)copper(II) anion and substituted 2-aminopyridinium cations: Syntheses, crystal structures, and magnetic properties

    Science.gov (United States)

    Liu, Yin; Ou, Shu-Hua; Li, Jin-Ni; Liao, Xiao-Lan; Zheng, Xiao-Xu; Luo, Cui-Ping; Yang, Le-Min; Zhou, Jia-Rong; Ni, Chun-Lin

    2016-04-01

    Three new ion-pair complexes, [2-ClBz-2‧-NH2Py]2[Cu(mnt)2](1), [2-Cl-4-ClBz-2-NH2Py]2[Cu(mnt)2](2) and [2-Cl-4-BrBz-2‧-NH2Py]2[Cu(mnt)2]·C2H5OH(3) ([2-Cl-4-RBz-2‧-NH2Py]+ = 1-(2‧-chloro-4‧-Rbenzyl)-2-aminopyridinium, R = H, Cl, Br; mnt2- = maleonitriledithiolate), were synthesized and characterized by elemental analyses, IR, UV-visible, single crystal X-ray diffraction and magnetic measurements. Both 1 and 2 crystallize in the monoclinic space group P2(1)/c, and the [Cu(mnt)2]2- anions and the cations form a 1D network structure through the N-HṡṡṡN hydrogen bonds. While the anions in 3 form a ladder-like chain through the C-HṡṡṡN interactions between the [Cu(mnt)2]2- anions and CH3CH2OH molecules. Some weak interactions such as πṡṡṡπ, CuṡṡṡN, ClṡṡṡC, and C-HṡṡṡCl, O-HṡṡṡCl, C-HṡṡṡS, N-HṡṡṡO, N-HṡṡṡN and C-HṡṡṡN hydrogen bonds in three molecular solids generate further a 3D network structure. The magnetic measurement reveals that 1 shows a very weak ferromagnetic interaction, and 2 exhibits a transition from ferromagnetic to antiferromagnetic coupling about 15 K, while 3 shows an antiferromagnetic coupling feature with θ = -12.51 K when the temperature is lowered.

  10. Adsorpsi Ion Logam Cu(II Menggunakan Lignin dari Limbah Serbuk Kayu Gergaji

    Directory of Open Access Journals (Sweden)

    Lelifajri Lelifajri

    2010-06-01

    Full Text Available Adsorption of heavy metal ion Cu(II onto modified lignin from sawdust waste have been presented. The ability of lignin from sawdust waste to adsorb the copper ion has been evaluated by varying adsorption time, pH of solution, and adsorption capacity. The concentration of copper ion was measured by atomic adsorption spectrometer. The result showed that the optimum condition of ion Cu(II by lignin were achieved at adsorption time of 15 minutes, pH of solution of 6, and copper concentration of 20 mg/L with adsorption efficiency of 99,3 %. In this study, the maximum capacity of 15,43 mg/g and equilibrium constant of 754,96 were achieved. Keywords: adsorpsi, ion tembaga, lignin, limbah serbuk kayu gergaji

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

    Science.gov (United States)

    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.

  12. EVALUATION OF APPLICATION OF COAGULANTS CONTAINING DIVALENT AND TRIVALENT IRON TO ENHANCE REMOVAL OF ORGANIC COMPOUNDS AND COMPLEXED COPPER AND TIN IONS FROM INDUSTRIAL EFFLUENTS

    Directory of Open Access Journals (Sweden)

    Maciej Thomas

    2014-10-01

    Full Text Available The article presents the issues concerning physical and chemical parameters of raw sewage from the production of printed circuit boards and the composition of the bath used technology in terms of meeting the requirements for the introduction of treated wastewater into surface waters, ground or the municipal sewage system. Showed test results for the removal of organic compounds and ions complexed copper (II and tin (II and (IV using coagulants containing ions of Fe (II and Fe (III. The studies showed the high efficiency of removal of organic compounds and tin compounds. Explained the possible causes of the difficulties of precipitation complexed copper ions (II.

  13. Erosion of Copper Target Irradiated by Ion Beam

    CERN Document Server

    Polosatkin, S V; Grishnyaev, E S; Konstantinov, S G; Shoshin, A A

    2012-01-01

    Erosion of copper target irradiated by deuterium ion beam with ultimate fluence is studied. The target originally destined for neutron generation represents bulk copper substrate covered by 3-\\mum titanium layer. The target was irradiated by deuterium ion beam generated in Bayard-Alpert type ion source with energy of ions 17.5 keV/nuclear. Maximal fluence in the center of the target achieves 2.5x10^23atoms/cm^2. Measurements of the profile of irradiated target and estimation of fluence shows that physical sputtering is a dominating process that determines the target erosion Most interesting feature is growth of \\mum-size tadpole-shaped structures, localized in the cracks of the surface. RFA analysis of these structures showed extremely large (up to 60%at.) carbon content.

  14. Photocleavage of DNA by copper(II) complexes

    Indian Academy of Sciences (India)

    Akhil R Chakravarty

    2006-11-01

    The chemistry of ternary and binary copper(II) complexes showing efficient visible lightinduced DNA cleavage activity is summarized in this article. The role of the metal in photo-induced DNA cleavage reactions is explored by designing complex molecules having a variety of ligands. Ternary copper(II) complexes with amino acid like L-methionone or L-lysine and phenanthroline base are efficient photocleavers of DNA. Complexes of formulation [Cu(L)(phen)](ClO4) with NSO-donor Schiff base (HL) and NN-donor heterocyclic base 1,10-phenanthroline (phen) show significant cleavage of supercoiled (SC) DNA on exposure to red light at ≈ 700 nm. The - and CT electronic bands of the copper(II) complexes play important roles in DNA cleavage reactions. The mechanistic pathways are found to be dependent on the types of ligands present in the copper(II) complexes and the photo-excitation energy. While UV exposure generally proceeds via a type-II process forming singlet oxygen as the reactive species, red-light exposure leads to DNA cleavage following different mechanistic pathways, viz. type-I, type-II and photo-redox pathways. Ternary copper(II) complexes with phen as DNA binder and Schiff base with a thiomethyl group as photosensitizer, cleave SC DNA to its nicked circular (NC) form in a type-II process in red-light. The binary complex [Cu(dpq)2(H2O)](ClO4)2 (dpq, dipyridoquinoxaline) cleaves DNA by photo-redox pathway at 694 nm. The binuclear complex [Cu$^{\\text{II}}_{2}$(RSSR)2], where H2RSSR is a Schiff base derived from 2-(thioethyl)salicylaldimine, cleaves SC DNA at 632.8 nm (CW He-Ne laser) and 694 nm (ruby laser) involving sulphide (type-I process) and hydroxyl radicals (photo-redox pathway) as the reactive species.

  15. Seeding of silicon by copper ion implantation for selective electroless copper plating

    Energy Technology Data Exchange (ETDEWEB)

    Bhansali, S.; Sood, D.K.; Zmood, R.B. [Microelectronic and Materials Technology Centre, Royal Melbourne Institute of Technolgy, Melbourne, VIC (Australia)

    1993-12-31

    We report on the successful use of copper(self) ion implantation into silicon to seed the electroless plating of copper on silicon (100) surfaces. Copper ions have been implanted to doses of 5E14-6.4E16 ions/cm{sup 2} using a MEEVA ion implanter at extraction voltage of 40kV. Dose was varied in fine steps to determine the threshold dose of 2E15 Cu ions/cm{sup 2} for `seed` formation of copper films on silicon using a commercial electroless plating solution. Plated films were studied with Rutherford backscattering spectrometry, scanning electron microscopy, EDX and profilometry . The adhesion of films was measured by `scotch tape test`. The adhesion was found to improve with increasing dose. However thicker films exhibited rather poor adhesion and high internal stress. SEM results show that the films grow first as isolated islands which become larger and eventually impinge into a continuous film as the plating time is increased. (authors). 5 refs., 1 tab., 3 figs.

  16. Experimental investigation on the mechanism of chelation-assisted, copper(II) acetate-accelerated azide-alkyne cycloaddition.

    Science.gov (United States)

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

    2011-09-07

    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 (1)H NMR assays are developed for monitoring the reaction progress in two different solvents, methanol and acetonitrile. Solvent kinetic isotopic effect and premixing 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. Silver(I) and copper(II)-imidazolium carboxylates: Efficient catalysts in Ullmann coupling reactions

    Indian Academy of Sciences (India)

    GANESAN PRABUSANKAR; CHATLA NAGA BABU; GEMBALI RAJU; NATARAJAN SAMPATH

    2017-05-01

    The silver(I) and copper(II)-imidazolium carboxylate coordination assemblies were derived from the reaction between corresponding carboxylic acid ligands and metal salts. These new metal derivatives depict a novel structural motif with variable chemical and thermal properties. These metal complexes act as potentialcatalysts in Ullmann coupling reactions. The imidazolium linker present in these complexes plays a role as both ligand and counter ion to balance the metal charge.

  18. Electrical conductivity of solutions of copper(II) nitrate crystalohydrate in dimethyl sulfoxide

    Science.gov (United States)

    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.

  19. Binding of copper(II) ions to the polyproline II helices of PEVK modules of the giant elastic protein titin as revealed by ESI-MS, CD, and NMR.

    Science.gov (United States)

    Ma, Kan; Wang, Kuan

    2003-10-01

    Titin, a family of giant elastic proteins, constitutes an elastic sarcomere matrix in striated muscle. In the I-band region of the sarcomere, the titin PEVK segment acts as a molecular spring to generate elasticity as well as sites of adhesion with parallel thin filaments. Previously, we reported that PEVK consists of tandem repeats of 28 residue modules and that the "polyproline II-coil" motif is the fundamental conformational motif of the PEVK module. In order to characterize the factors that may affect and alter the PPII-coil conformational motifs, we have initiated a systematic study of the interaction with divalent cations (Cu2+, Ca2+, Zn2+, and Ni2+) and a conformational profile of PEVK peptides (a representative 28-mer peptide PR: PEPPKEVVPEKKAPVAPPKKPEVPPVKV and its subfragments PR1: kvPEPPKEVVPE, PR2: VPEKKAPVAPPK, PR3: KPEVPPVKV). UV-Vis absorption difference spectra and CD spectra showed that Cu2+ bound to PR1 with high affinity (20 microM), while its binding to PR2 and PR3 as well as the binding of other cations to all four peptides were of lower affinity (>100 microM). Conformational studies by CD revealed that Cu2+ binding to PR1 resulted in a polyproline II to turn transition up to a 1:2 PR1/Cu2+ ratio and a coil to turn transition at higher Cu2+ concentration. ESI-MS provided the stoichiometry of PEVK peptide-Cu2+ complexes at both low and high ion strength, confirming the specific high affinity binding of Cu2+ to PR1 and PR. Furthermore, NMR and ESI-MS/MS fragmentation analysis elucidated the binding sites of the PEVK peptide-Cu2+ complexes at (-2)KVPE2, 8VPE10, 13APV15, and 22EVP24. A potential application of Cu2+ binding in peptide sequencing by mass spectrometry was also revealed. We conclude that Cu2+ binds and bends PEVK peptides to a beta-turn-like structure at specific sites. The specific targeting of Cu2+ towards PPII is likely to be of significant value in elucidating the roles of PPII in titin elasticity as well as in interactions of

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  2. Bis[2-(cyclopentyliminomethyl-5-methoxyphenolato]copper(II

    Directory of Open Access Journals (Sweden)

    Xiao-Hui Ji

    2010-08-01

    Full Text Available The title compound, [Cu(C13H16NO22], is a mononuclear copper(II complex derived from the Schiff base ligand 2-(cyclopentyliminomethyl-5-methoxyphenol and copper acetate. The CuII atom is four-coordinated by the phenolate O atoms and imine N atoms from two Schiff base ligands, in a highly distorted square-planar geometry. The O- and N-donor atoms are mutually trans and the dihedral angle between the two benzene rings is 55.8 (3°.

  3. Visual Observation of Dissolution of Copper Ions from a Copper Electrode

    Science.gov (United States)

    Ikemoto, Isao; Saitou, Kouichi

    2013-01-01

    During electrolysis, to visually observe the conversion of a metal to its cation, either the cation or its complex ion should have a distinct color while the electrolyte solution must be colorless and transparent. A demonstration is described in which copper is used as the electrodes and sodium polyacrylate (a superabsorbent polymer) solution is…

  4. Visual Observation of Dissolution of Copper Ions from a Copper Electrode

    Science.gov (United States)

    Ikemoto, Isao; Saitou, Kouichi

    2013-01-01

    During electrolysis, to visually observe the conversion of a metal to its cation, either the cation or its complex ion should have a distinct color while the electrolyte solution must be colorless and transparent. A demonstration is described in which copper is used as the electrodes and sodium polyacrylate (a superabsorbent polymer) solution is…

  5. An experimental and theoretical approach of spectroscopic and structural properties of a new chelidamate copper (II) complex.

    Science.gov (United States)

    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).

  6. Crystal structure, characterization and magnetic properties of a 1D copper(II) polymer incorporating a Schiff base with carboxylate side arm

    Indian Academy of Sciences (India)

    SHYAMAPADA SHIT; MADHUSUDAN NANDY; CORRADO RIZZOLI; CÉDRIC DESPLANCHES; SAMIRAN MITRA

    2016-06-01

    A new 1D polymeric copper(II) complex [{Cu(L)$(CF_{3}COO)}2]_{n}$ has been synthesized using apotentially tetradentate Schiff base ligand, HL, ((E)-2-((pyridin-2-yl)methyleneamino)-5-chlorobenzoic acid)and characterized by different spectroscopic methods. Single crystal X-ray structural characterization revealsthat the side arm carboxylate group of the coordinated Schiff base exhibits a $μ_{1,3}$ -bridging mode and connectsthe neighbouring copper(II) ions leading to a zigzag 1D chain structure where the copper(II) ions displaydistorted square pyramidal geometries. Variable temperature magnetic susceptibility measurement reveals aweak antiferromagnetic exchange (J = −0.47±0.01 $cm_{−1}) prevails between copper(II) ions in the chainmediated by the bridging carboxylate group, is also supported by the room temperature EPR spectral study.Electrochemical property of the complex is also reported.

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

    Science.gov (United States)

    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.

  8. Microwaves initiated synthesis of activated carbon-based composite hydrogel for simultaneous removal of copper(II) ions and direct red 80 dye: A multi-component adsorption system

    OpenAIRE

    Oladipo, Akeem Adeyemi; Gazi, Mustafa

    2015-01-01

    We present a novel microwave initiated preparation of polyacrylamide/activated carbon hydrogel (PAAm-FAc) in this article and characterized by FT-IR, pHzpc and Boehm titration. The adsorbent was assessed for competitive adsorption of copper(II) and direct red 80 from a binary mixture in a single-staged batch process as a function of volume of binary mixture/mass of adsorbent (V0/M0) ratio at varying orders of second pollutant concentration. A competitive, multi-component Langmuir isotherm was...

  9. Copper(II) coordination properties of the integrin ligand sequence PHSRN and its new β-cyclodextrin conjugates.

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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)

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

    Science.gov (United States)

    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.

  13. Inhibition of respiratory complex I by copper(ii)-bis(thiosemicarbazonato) complexes.

    Science.gov (United States)

    Djoko, Karrera Y; Donnelly, Paul S; McEwan, Alastair G

    2014-12-01

    Several copper(ii) complexes of bis(thiosemicarbazones) [Cu(btsc)s] show promise as therapeutics for the treatment of neurological diseases, cancers and bacterial infections. These complexes are thought to act primarily as copper ionophores or "copper boosting" agents, whereby the Cu(II) centre is reduced by cytosolic reductants and Cu(I) is released as "free" or "bioavailable" ion. It is then assumed that the dissociated Cu(I) ion is the species responsible for many of the observed biological effects of Cu(btsc)s. We recently showed that Cu(btsc) complexes inhibited NADH dehydrogenases in the bacterial respiratory chain. In this work, we demonstrate that Cu(btsc) complexes also inhibit mitochondrial respiration and that Complex I in the mitochondrial electron transport chain is a specific target of inhibition. However, bioavailable Cu ions do not appear to contribute to the action of Cu(btsc) as a respiratory inhibitor. Instead, an intact Cu(btsc) molecule may bind reversibly and competitively to the site of ubiquinone binding in Complex I. Our results add to the growing body of evidence that the intact complex may be important in the overall cellular activity of Cu(btsc) complexes and further the understanding of their biological effects as a potential therapeutic.

  14. Synthesis and Crystal Structure of Copper(II) Complex with Mixed Bipyridine and 2-Hydroxy-1-naphthaldehyde Ligands

    Institute of Scientific and Technical Information of China (English)

    卜平宇; 程鹏; 赵斌; 阎世平; 瘳代正; 姜宗慧; 刘松岩; 姚心侃; 王宏根

    2002-01-01

    A mononuclear copper(II) complex, [Cu(bipy)(naph)(ClO4)] (where bipy is bipyridine and naph is 2-hydroxy-1-naphthaldehyde), was synthesized and characterized by X-ray single-crystal structure analysis. The crystal is triclinic, space group P ī with a = 9.245(4), b = 9.962(4), c = 10.809(7) A, α = 84.83(5), β =82.35(4), γ = 81.02(4)°, V = 972.1 >3, C21H15ClCuN2O6 Mr = 490.36, Z = 2, F(000) = 498, Dx = 1.68 g/cm3, μ = 13.05 cm-1, R = 0.078, Rw = 0.081 for 2295 observed reflections with I > 3σ(I). The copper(II) ion is coordinated by two nitrogen atoms of bipy and two oxygen atoms of naph in the equatorial plane, with an axial perchlorate oxygen-copper(II) bond to copper(II) ion to form square-pyramidal coordination geometry. The coordination environment of copper(II) is similar to the active site of galactose oxidase and this compound may also be considered as the structural model of galactose oxidase.

  15. Enantioseparation of Amino Acids by Micelle-Enhanced Ultrafiltration : Experimental and Theoretical Studies of Copper(II) Amino Acid Interactions

    NARCIS (Netherlands)

    Bruin, de T.J.M.

    2000-01-01

    A micelle-enhanced ultrafiltration system, which can potentially be used for large scale separations, has been used to investigate the resolution of amino acid enantiomers. For this purpose amino acid derivatives were synthesized, which in combination with copper(II) ions were used as chiral selecto

  16. Synthesis, crystal structure and magnetic properties of terephthalate-isophthalete- and phthalate-bridged copper (II) dinuclear complexes

    Energy Technology Data Exchange (ETDEWEB)

    Cano, J.; De Munno, G.; Sanz, J.L.; Ruiz, R.; Lloret, F.; Faus, J.; Julve, M.

    1997-09-01

    The ability of the dianions of the terephthalic (H{sub 2}ta), isophthalic (H{sub 2} ita) and phthalic (H{sub 2} phta) acids both to act as bridges between copper (II) ions and to mediate intramolecular exchange interactions has been investigated by single crystal X-ray diffraction and variable-temperature magnetic susceptibility measurements. (Author) 31 refs.

  17. Synthesis and characteristics of a novel artificial hapten using the copper mercaptide of penicillenic acid from penicillin G for immunoassay of heavy metal ions.

    Science.gov (United States)

    Xu, Wu; Xie, Peng; Fan, Liuyin; Cao, Chengxi; Xi, Tao; Zhou, Pei

    2011-09-01

    In this paper, we describe the synthesis of a novel copper ion hapten using the copper mercaptide of penicillenic acid (CMPA) derived from penicillin. Results from tests with immune rabbits indicate that: (i) A new antigen synthesized with CMPA has good stability and is safe for immunizing animals with no toxic phenomena being found in animal experiments; (ii) the immunogenic antigen (CMPA-BSA) can stimulate the immune system to produce specific antibodies with high titrations, up to 150000; and (iii) antibodies in antisera showed higher affinity to OVA-GSH-CuCl than OVA-GSH, which indicates that the antibodies have specific affinity towards copper ions. These results confirm that the novel hapten and relevant antigen for copper ion have been successfully synthesized, giving progress towards an immunoassay for copper ions in environmental and food samples.

  18. Can copper(II) mediate Hoogsteen base-pairing in a left-handed DNA duplex? A pulse EPR study.

    Science.gov (United States)

    Santangelo, Maria Grazia; Antoni, Philipp M; Spingler, Bernhard; Jeschke, Gunnar

    2010-02-22

    Pulse EPR spectroscopy is used to investigate possible structural features of the copper(II) ion coordinated to poly(dG-dC).poly(dG-dC) in a frozen aqueous solution, and the structural changes of the polynucleotide induced by the presence of the metal ion. Two different copper species were identified and their geometry explained by a molecular model. According to this model, one species is exclusively coordinated to a single guanine with the N7 nitrogen atom forming a coordinative bond with the copper. In the other species, a guanine and a cytosine form a ternary complex together with the copper ion. A copper crosslink between the N7 of guanine and N3 of cytosine is proposed as the most probable coordination site. Moreover, no evidence was found for an interaction of either copper species with a phosphate group or equatorial water molecules. In addition, circular dichroism (CD) spectroscopy showed that the DNA of the Cu(II)-poly(dG-dC).poly(dG-dC) adducts resembles the left-handed Z-form. These results suggest that metal-mediated Hoogsteen base pairing, as previously proposed for a right-handed DNA duplex, can also occur in a double-stranded left-handed DNA.

  19. Removal of copper ions from electroplating rinse water using electrodeionization

    Institute of Scientific and Technical Information of China (English)

    Xiao FENG; Jun-song GAO; Zu-cheng WU

    2008-01-01

    An improved configuration of the membrane stack was adopted in the electrodeionization (EDI)cell to prevent precipitation of bivalent metal hydroxide during the running.The operational parameters that influenced the removal of copper ions from the dilute solution were optimized.The result showed that a moderate decrease in the inlet pH value and a moderate increase in the applied voltage could achieve a better removaI effect.The steady process of electroplating wastewater treatment could be achieved with a removal efficiency ofmore than 99.5%and an enrichment factor of 5~14.The concentration of copper in purlfled water was less than 0.23 mg/L.This demonstrated the applicability of recovering heavy metal ions and purifled water from electroplating effluent for industrial reuse.

  20. Biosorption of copper(II) by nonliving lichen biomass of Cladonia rangiformis hoffm

    Energy Technology Data Exchange (ETDEWEB)

    Ekmekyapar, Fatma [Engineering Faculty, Department of Environmental Engineering, Atatuerk University, Erzurum 25240 (Turkey)]. E-mail: fyapar@atauni.edu.tr; Aslan, Ali [Education Faculty, Department of Biology, Atatuerk University, Erzurum 25240 (Turkey); Bayhan, Y. Kemal [Engineering Faculty, Department of Environmental Engineering, Atatuerk University, Erzurum 25240 (Turkey); Cakici, Avni [Engineering Faculty, Department of Environmental Engineering, Atatuerk University, Erzurum 25240 (Turkey)

    2006-09-01

    Biosorption of heavy metals can be an effective process for the removal of heavy metal ions from aqueous solutions. In this study, the adsorption properties of lichen biomass of Cladonia rangiformis hoffm. for copper(II) were investigated by using batch adsorption techniques. The effects of initial metal ion concentration, initial pH, biosorbent concentration, stirring speed and contact time on biosorption efficiency were studied. In the experiments the optimum pH value was found out 5.0 which was the native pH value of solution. The experimental adsorption data were fitted to the Langmuir adsorption model. The highest metal uptake was calculated from Langmuir isotherm and found to be 7.6923 mg Cu(II)/g inactivated lichen at 15 deg. C. The results indicated that the biomass of C. rangiformis is a suitable biosorbent for removing Cu(II) from aqueous solutions.

  1. A one-dimensional carboxylate-bridged helical copper(II) complex containing (quinolin-8-yloxy)acetate.

    Science.gov (United States)

    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.

  2. Theoretical Studies on the Spin Exchange Interaction in Copper(II) Complexes Coordinated with Nitronyl Nitroxide

    Institute of Scientific and Technical Information of China (English)

    Jie REN; Hai Yan WEI; Qi Hua ZHAO; Zhi Da CHEN

    2003-01-01

    Nitronyl nitroxide radical 1, NIT (4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl-1-oxyl-3-oxide) and copper(II) chloride complexes with nitronyl nitroxide 2, [Cu(NITPh)2Cl2] (NITPh=2-phenyl-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide) were studied with density functional theory (DFT). The magnetic orbital analysis reveals that the antiferromagnetic coupling for complex 2 is due to the antibonding σ*-orbital overlap between (Cu) and π* (NO) orbitals. Also, spin population and atomic charge distribution analysis suggest that for AFS of complex 2 the antiferromagnetic coupling between the radical ligands and the copper(II) ion originates from the spin delocalization induced by the α electron transfer from π*(NO) to (Cu) orbital.

  3. Dispersion of chitosan on perlite for enhancement of copper(II) adsorption capacity.

    Science.gov (United States)

    Hasan, Shameem; Ghosh, Tushar K; Viswanath, Dabir S; Boddu, Veera M

    2008-04-01

    Chitosan coated perlite beads were prepared by drop-wise addition of slurry, made of chitosan dissolved in oxalic acid and perlite, to an alkaline bath (0.7 M NaOH). The beads that contained 32% chitosan enhanced the accessibility of OH and amine groups present in chitosan for adsorption of copper ions. The experiments using Cu(II) ions were carried out in the concentration range of 50-4100 mg/L (0.78-64.1 mmol/L). Adsorption capacity for Cu(II) was pH dependent and a maximum uptake of 104 mg/g of beads (325 mg/g of chitosan) was obtained at pH 4.5 when its equilibrium concentration in the solution was 812.5 mg/L at 298 K. The XPS and TEM data suggested that copper was mainly adsorbed as Cu(II) and was attached to amine groups. The adsorption data could be fitted to one-site Langmuir adsorption model. Anions in the solution had minimal effect on Cu(II) adsorption by chitosan coated perlite beads. EDTA was used effectively for the regeneration of the bed. The diffusion coefficient of Cu(II) onto chitosan coated beads was calculated from the breakthrough curve and was found to be 2.02 x 10(-8) cm(2)/s.

  4. A doppel alpha-helix peptide fragment mimics the copper(II) interactions with the whole protein.

    Science.gov (United States)

    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

  5. Comparison and distribution of copper oxide nanoparticles and copper ions in activated sludge reactors.

    Science.gov (United States)

    Zhang, Dongqing; Trzcinski, Antoine P; Oh, Hyun-Suk; Chew, Evelyn; Tan, Soon Keat; Ng, Wun Jern; Liu, Yu

    2017-05-12

    Copper oxide nanoparticles (CuO NPs) are being increasingly applied in the industry which results inevitably in the release of these materials into the hydrosphere. In this study, simulated waste-activated sludge experiments were conducted to investigate the effects of Copper Oxide NPs at concentrations of 0.1, 1, 10 and 50 mg/L and to compare it with its ionic counterpart (CuSO4). It was found that 0.1 mg/L of CuO NPs had negligible effects on Chemical Oxygen Demand (COD) and ammonia removal. However, the presence of 1, 10 and 50 mg/L of CuO NPs decreased COD removal from 78.7% to 77%, 52.1% and 39.2%, respectively (P copper ions were more toxic towards microorganisms compared to CuO NPs. CuO NPs were removed effectively (72-93.2%) from wastewater due to a greater biosorption capacity of CuO NPs onto activated sludge, compared to the copper ions (55.1-83.4%). The SEM images clearly showed the accumulation and adsorption of CuO NPs onto activated sludge. The decrease in Live/dead ratio after 5 h of exposure of CuO NPs and Cu(2+) indicated the loss of cell viability in sludge flocs.

  6. Incorporation of copper ions into crystals of T2 copper-depleted laccase from Botrytis aclada

    Energy Technology Data Exchange (ETDEWEB)

    Osipov, E. M., E-mail: e.m.osipov@gmail.com [A. N. Bach Institute of Biochemistry, Leninsky pr. 33, Moscow 119071 (Russian Federation); Polyakov, K. M. [A. N. Bach Institute of Biochemistry, Leninsky pr. 33, Moscow 119071 (Russian Federation); Engelhardt Institute of Molecular Biology, Vavilova str. 32, Moscow 119991 (Russian Federation); Tikhonova, T. V. [A. N. Bach Institute of Biochemistry, Leninsky pr. 33, Moscow 119071 (Russian Federation); Kittl, R. [BOKU – University of Natural Resources and Life Sciences, Muthgasse 18, 1190 Wien (Austria); Dorovatovskii, P.V. [RSC ‘Kurchatov Institute’, Acad. Kurchatov sq. 1, Moscow 123182 (Russian Federation); Shleev, S. V.; Popov, V. O. [A. N. Bach Institute of Biochemistry, Leninsky pr. 33, Moscow 119071 (Russian Federation); RSC ‘Kurchatov Institute’, Acad. Kurchatov sq. 1, Moscow 123182 (Russian Federation); Ludwig, R. [BOKU – University of Natural Resources and Life Sciences, Muthgasse 18, 1190 Wien (Austria)

    2015-11-18

    The restoration of the native form of laccase from B. aclada from the type 2 copper-depleted form of the enzyme was investigated. Copper ions were found to be incorporated into the active site after soaking the depleted enzyme in a Cu{sup +}-containing solution. Laccases belong to the class of multicopper oxidases catalyzing the oxidation of phenols accompanied by the reduction of molecular oxygen to water without the formation of hydrogen peroxide. The activity of laccases depends on the number of Cu atoms per enzyme molecule. The structure of type 2 copper-depleted laccase from Botrytis aclada has been solved previously. With the aim of obtaining the structure of the native form of the enzyme, crystals of the depleted laccase were soaked in Cu{sup +}- and Cu{sup 2+}-containing solutions. Copper ions were found to be incorporated into the active site only when Cu{sup +} was used. A comparative analysis of the native and depleted forms of the enzymes was performed.

  7. Conclusion on the peer review of the pesticide risk assessment of confirmatory data submitted for the active substance Copper (I, copper (II variants namely copper hydroxide, copper oxychloride, tribasic copper sulfate, copper (I oxide, Bordeaux mixture

    Directory of Open Access Journals (Sweden)

    European Food Safety Authority

    2013-06-01

    Full Text Available The conclusions of the European Food Safety Authority (EFSA following the peer review of the initial risk assessment carried out by the competent authority of the rapporteur Member State France, for the pesticide active substance copper (I, copper (II variants (formerly referred to as copper compounds are reported. The context of the peer review was that requested by the European Commission following the submission and evaluation of confirmatory environmental fate and behaviour and ecotoxicology data. The conclusions were reached on the basis of the evaluation of the representative uses of copper (I, copper (II variants as a fungicide/bactericide on grapes and tomatoes. The reliable endpoints concluded as being appropriate for use in regulatory risk assessment, derived from the available studies and literature in the dossier peer reviewed, are presented. Concerns are identified.

  8. Redox properties of a mononuclear copper(II)-superoxide complex.

    Science.gov (United States)

    Tano, Tetsuro; Okubo, Yuri; Kunishita, Atsushi; Kubo, Minoru; Sugimoto, Hideki; Fujieda, Nobutaka; Ogura, Takashi; Itoh, Shinobu

    2013-09-16

    Redox properties of a mononuclear copper(II) superoxide complex, (L)Cu(II)-OO(•), supported by a tridentate ligand (L = 1-(2-phenethyl)-5-[2-(2-pyridyl)ethyl]-1,5-diazacyclooctane) have been examined as a model compound of the putative reactive intermediate of peptidylglycine α-hydroxylating monooxygenase (PHM) and dopamine β-monooxygenase (DβM) (Kunishita et al. J. Am. Chem. Soc. 2009, 131, 2788-2789; Inorg. Chem. 2012, 51, 9465-9480). On the basis of the reactivity toward a series of one-electron reductants, the reduction potential of (L)Cu(II)-OO(•) was estimated to be 0.19 ± 0.07 V vs SCE in acetone at 298 K (cf. Tahsini et al. Chem.-Eur. J. 2012, 18, 1084-1093). In the reaction of TEMPO-H (2,2,6,6-tetramethylpiperidine-N-hydroxide), a simple HAT (hydrogen atom transfer) reaction took place to give the corresponding hydroperoxide complex LCu(II)-OOH, whereas the reaction with phenol derivatives ((X)ArOH) gave the corresponding phenolate adducts, LCu(II)-O(X)Ar, presumably via an acid-base reaction between the superoxide ligand and the phenols. The reaction of (L)Cu(II)-OO(•) with a series of triphenylphosphine derivatives gave the corresponding triphenylphosphine oxides via an electrophilic ionic substitution mechanism with a Hammett ρ value as -4.3, whereas the reaction with thioanisole (sulfide) only gave a copper(I) complex. These reactivities of (L)Cu(II)-OO(•) are different from those of a similar end-on superoxide copper(II) complex supported by a tetradentate TMG3tren ligand (1,1,1-Tris{2-[N(2)-(1,1,3,3-tetramethylguanidino)]ethyl}amine (Maiti et al. Angew. Chem., Int. Ed. 2008, 47, 82-85).

  9. EPR of Cu(II) in sarcosine cadmium chloride: probe into dopant site - symmetry and copper-sarcosine interaction

    CERN Document Server

    Pathinettam-Padiyan, D; Murugesan, R

    2000-01-01

    The electron paramagnetic resonance spectra of Cu(II) doped sarcosine cadmium chloride single crystals have been investigated at room temperature. Experimental results reveal that the Cu(II) ion enters the lattice interstitially. The observed superhyperfine lines indicate the superposition of two sets of quintet structure with interaction of nitrogen atoms and the two isotopes of copper. The spin Hamiltonian parameters are evaluated by Schonland method and the electric field symmetry around the copper ion is rhombic. An admixture of d sub z sup 2 orbital with the d sub x sub sup 2 sub - sub y sub sup 2 ground state is observed. Evaluation of MO coefficients reveals that the in-plane interaction between copper and nitrogen is strong in this lattice.

  10. Interaction of copper (II) complexes by bovine serum albumin: spectroscopic and calorimetric insights.

    Science.gov (United States)

    Singh, Namrata; Pagariya, Darshana; Jain, Surbhi; Naik, Sunil; Kishore, Nand

    2017-07-28

    Serum albumins being the most abundant proteins in the blood and cerebrospinal fluid are significant carriers of essential transition metal ions in the human body. Studies of copper (II) complexes have gained attention because of their potential applications in synthetic, biological, and industrial processes. Study of binding interactions of such bioinorganic complexes with serum albumins improves our understanding of biomolecular recognition process essential for rational drug design. In the present investigation, we have applied quantitative approach to explore interactions of novel synthesized copper (II) complexes viz. [Cu(L(1))(L(2))ClO4] (complex I), [Cu(L(2))(L(3))]ClO4] (complex II) and [Cu(L(4))2(H2O)2] (complex III) with bovine serum albumin (BSA) to evaluate their binding characteristics, site and mode of interaction. The fluorescence quenching of BSA initiated by complexation has been observed to be static in nature. The binding interactions are endothermic driven by entropic factors as confirmed by high sensitivity isothermal titration calorimetry. Changes in secondary and tertiary structure of protein have been studied by circular dichroism and significant reduction in α-helical content of BSA was observed upon binding. Site marking experiments with warfarin and ibuprofen indicated that copper complexes bind at site II of the protein.

  11. Fundamental features of copper ion precipitation using sulfide as a precipitant in a wastewater system.

    Science.gov (United States)

    Choi, Jung-Yoon; Kim, Dong-Su; Lim, Joong-Yeon

    2006-01-01

    We have investigated the precipitation features of copper ion using sulfide as a precipitant by varying the mole ratio of sulfide to copper ion, pH, temperature and the kind and concentration of complexing agent. In the precipitation of copper ion by sulfide, sludge is produced as cupric sulfide; thus, there is a possibility for its recycled use in photochemical and ceramic processes. When the ratio of the concentration of copper ion to sulfide was increased to more than 1.0, the extent of precipitation was very high. As the ratio was increased, nucleation time was decreased and crystal growth rate was raised. The higher the pH, the greater the amount of precipitated copper ion due to lowered solubility of cupric sulfide. When temperature changed from 25 degrees C to 55 degrees C, the precipitation of copper ion was increased a little. On the basis of estimated thermodynamic parameters such as Gibbs free energy and enthalpy, the precipitation reaction was spontaneous and endothermic. The precipitation of copper ion was lowered in the presence of complexing agent and it was affected by the stability of the copper complex. The feasibility test for the application of precipitation treatment to actual wastewater containing copper ion showed, although there was a little decrease in the removal of copper, the precipitation extent of copper was higher than 90% compared with that for artificial wastewater.

  12. Electrochemical determination of copper ions in spirit drinks using carbon paste electrode modified with biochar.

    Science.gov (United States)

    Oliveira, Paulo Roberto; Lamy-Mendes, Alyne C; Rezende, Edivaltrys Inayve Pissinati; Mangrich, Antonio Sálvio; Marcolino, Luiz Humberto; Bergamini, Márcio F

    2015-03-15

    This work describes for first time the use of biochar as electrode modifier in combination with differential pulse adsorptive stripping voltammetric (DPAdSV) techniques for preconcentration and determination of copper (II) ions in spirit drinks samples (Cachaça, Vodka, Gin and Tequila). Using the best set of the experimental conditions a linear response for copper ions in the concentration range of 1.5 × 10(-6) to 3.1 × 10(-5) mol L(-1) with a Limit of Detection (LOD) of 4.0 × 10(-7) mol L(-1). The repeatability of the proposed sensor using the same electrode surface was measured as 3.6% and 6.6% using different electrodes. The effect of foreign species on the voltammetric response was also evaluated. Determination of copper ions content in different samples of spirit drinks samples was also realized adopting inductively coupled plasma optical emission spectroscopy (ICP-OES) and the results achieved are in agreement at a 95% of confidence level.

  13. Probing the copper(II) binding features of angiogenin. Similarities and differences between a N-terminus peptide fragment and the recombinant human protein.

    Science.gov (United States)

    La Mendola, Diego; Farkas, Daniel; Bellia, Francesco; Magrì, Antonio; Travaglia, Alessio; Hansson, Örjan; Rizzarelli, Enrico

    2012-01-02

    The angiogenin protein (hAng) is a potent angiogenic factor and its cellular activities may be affected by copper ions even if it is yet unknown how this metal ion is able to produce this effect. Among the different regions of hAng potentially able to bind copper ions, the N-terminal domain appears to be an ideal candidate. Copper(II) complexes of the peptide fragments encompassing the amino acid residues 4-17 of hAng protein were characterized by potentiometric, UV-vis, CD, and EPR spectroscopic methods. The results show that these fragments have an unusual copper(II) binding ability. At physiological pH, the prevailing complex species formed by the peptide encompassing the protein sequence 4-17 is [CuHL], in which the metal ion is bound to two imidazole and two deprotonated amide nitrogen atoms disposed in a planar equatorial arrangement. Preliminary spectroscopic (UV-vis, CD, and EPR) data obtained on the copper(II) complexes formed by the whole recombinant hAng protein, show a great similarity with those obtained for the N-terminal peptide fragments. These findings indicate that within the N-terminal domain there is one of the preferred copper(II) ions anchoring site of the whole recombinant hAng protein.

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

    Science.gov (United States)

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

    Science.gov (United States)

    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.

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

    OpenAIRE

    Lucas, Heather R.; Lee, Jennifer C.

    2011-01-01

    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. Adsorption of lead and copper ions from aqueous effluents on rice husk ash in a dynamic system

    Directory of Open Access Journals (Sweden)

    M. G. A. Vieira

    2014-06-01

    Full Text Available This study evaluated the kinetic adsorption of Pb and Cu ions using rice husk ash as adsorbent in a fixed bed. The maximum adsorption capacities obtained for lead and copper ions in the fixed bed were 0.0561 and 0.0682 mmol/g (at 20 ºC, respectively. The thermodynamic studies indicated that the lead adsorption process was exothermic and spontaneous, while the copper adsorption process was endothermic and spontaneous. Characterization results indicated the presence of several functional groups, amorphous silica and a fibrous and longitudinal structure of rice husks. Rice husk ash (RHA from northern Brazil can be used as a bioadsorbent for the individual removal of Pb(II and Cu(II ions from metal-containing effluents.

  18. Copper ions inactivate S-ade-nosylhomocysteine hydrolase

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    S-adenosylhomocysteine (AdoHcy) hydrolase isan enzyme that regulates biomethylation and some otherphysiological processes. Recombinant AdoHcy hydrolase wasoverexpressed in E. coli JM109 and purified with ion ex-change and gel filtration chromatographies. The effects ofcopper ions (Cu2+) on the activity of AdoHcy hydrolase wereinvestigated and the results showed that Cu2+ inhibited theenzyme's activity by a concentration and time-dependentprocess. The inhibition constant (Ki) and the apparent rateconstant (kapp) were calculated to be (14 + 4) nmol @ L-1 and(1.08 + 0.15) min-1, respectively. The existence of the naturalsubstrate Ado could to some extent prevent Cu2+ from inac-tivating the enzyme, suggesting that copper ions possiblycould compete with the natural substrate on enzyme's sub-strate binding site. Further studies on the mechanism of in-hibition are being carried out.

  19. The role of copper ions in pathophysiology and fluorescent sensors for the detection thereof.

    Science.gov (United States)

    Verwilst, Peter; Sunwoo, Kyoung; Kim, Jong Seung

    2015-04-04

    Copper ions are indispensible to life and maintaining tight control over the homeostasis of copper ions in the body is a prerequisite to sustaining health. Aberrations in normal copper levels, both systemic as well as on a tissue or cellular scale, are implicated in a wide range of diseases, such as Menkes disease, Wilson's disease, Alzheimer's disease, Parkinson's disease and transmissible spongiform encephalopathy (prion diseases). The current understanding of how copper influences these diseases is described. The field of fluorescent copper sensors both functioning via a reaction based mechanism as well as by directly binding copper ions has known an inflation in recent years, and the importance of this field to elucidating the role of copper in cell biology is pointed out. Progress in these tightly interwoven fields has resulted in a better understanding of a number of diseases related to copper imbalances and current developments might open the path for novel and innovating therapies to address these diseases.

  20. Rapid determination of trace level copper in tea infusion samples by solid contact ion selective electrode

    Directory of Open Access Journals (Sweden)

    Aysenur Birinci

    2016-07-01

    Full Text Available A new solid contact copper selective electrode with a poly (vinyl chloride (PVC membrane consisting of o-xylylenebis(N,N-diisobutyldithiocarbamate as ionophore has been prepared. The main novelties of constructed ion selective electrode concept are the enhanced robustness, cheapness, and fastness due to the use of solid contacts. The electrode exhibits a rapid (< 10 seconds and near-Nernstian response to Cu2+ activity from 10−1 to 10−6 mol/L at the pH range of 4.0–6.0. No serious interference from common ions was found. The electrode characterizes by high potential stability, reproducibility, and full repeatability. The electrode was used as an indicator electrode in potentiometric titration of Cu(II ions with EDTA and for the direct assay of tea infusion samples by means of the calibration graph technique. The results compared favorably with those obtained by the atomic absorption spectroscopy (AAS.

  1. Simultaneous photoreductive removal of copper (II) and selenium (IV) under visible light over spherical binary oxide photocatalyst

    Energy Technology Data Exchange (ETDEWEB)

    Aman, Noor [ACC Division, National Metallurgical Laboratory, CSIR (Council of Scientific and Industrial Research), Jamshedpur-831007 (India); Mishra, T., E-mail: drtmishra@yahoo.com [ACC Division, National Metallurgical Laboratory, CSIR (Council of Scientific and Industrial Research), Jamshedpur-831007 (India); Hait, J.; Jana, R.K. [ACC Division, National Metallurgical Laboratory, CSIR (Council of Scientific and Industrial Research), Jamshedpur-831007 (India)

    2011-02-15

    Graphical abstract: Spherical zirconia mixed titania materials can reduce 100 ppm of Cu(II) and Se(VI) mixture within 40 min of reaction under visible light. - Abstract: 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.

  2. Removal of adsorbent particles od copper ions by Jet flotation; Remocion de particulas adsorbentes de iones cobre por flotacion Jet

    Energy Technology Data Exchange (ETDEWEB)

    Santander, M.; Tapia, P.; Pavez, O.; Valderrama, L.; Guzman, D.

    2009-07-01

    The present study shows the results obtained on the removal of copper ions from synthetic effluents by using the adsorbent particles flotation technique (APF) in a Jet flotation cell (Jameson type). In a typical experimental run, a mineral with high quartz content was used as adsorbent particles in the adsorption and flotation experiments, to determine optimal pH conditions, adsorbent particles concentration; flotation reagents dosage and air/effluent flow ratio for applying in the Jet cell to maximize the efficiency of copper ions adsorptions and the removal of particles adsorbents containing the absorbed copper ions. The results indicate the at pH>7 and at adsorbent particles concentration of 2 kg.m{sup -}3, 99% of copper ions is adsorbed and, when the air/effluent flow ratio applied in the Jet cell is 0,2, 98% of absorbent particles containing the adsorbed copper ions is removed. (Author) 39 refs.

  3. Dynamics of reactive oxygen species generation in the presence of copper(II)-histidine complex and cysteine.

    Science.gov (United States)

    Ząbek-Adamska, Anna; Drożdż, Ryszard; Naskalski, Jerzy W

    2013-01-01

    Histidine-copper(II) complex (Cu-His2) is a form of bound copper necessary for cellular copper uptake. Due to the high affinity of histidine to copper(II) ions, the binding of copper(II) by histidine is considered a substantial part of plasma antioxidative defense. Also cysteine plays a role in the antioxidative system. However, we show here that in the presence of oxygen the histidine-copper(II) complex plus cysteine produces reactive oxygen species (ROS). Cysteine concentration was assayed using a thiol specific silver-mercury electrode. Hydrogen peroxide was assayed amperometrically using platinum electrode. ROS formation was followed by chemiluminescence of luminol-fluoresceine-enhanced system. Addition of cysteine to Cu-His2 solution at pH 7.4 in the presence of atmospheric oxygen initiates the synthesis of H2O2 and generation of ROS, which manifests as a burst of chemiluminescence. The reaction has two stages; in the first stage, cysteine is utilized for the synthesis of an unstable intermediary product which becomes a substrate for ROS formation. Anaerobic conditions inhibit ROS formation. Increased cysteine concentration enhances the lag phase of the oxidative burst without influencing the amount of ROS. The synthesis of ROS (measured by chemiluminescence) is proportional to the concentration of Cu-His2 employed. ROS production can be repetitively initiated by further additions of cysteine to the reaction medium. The study suggests that Cu-His2 catalyzes cysteine-dependent reduction of oxygen to superoxide employing an intermediary cysteine-copper(I) complex and enabling Fenton reaction with copper and hydrogen peroxide produced as a secondary product. In effect, Cu-His2 with cysteine may be a source of ROS in biological media.

  4. Copper(II)-selective membrane electrode based on a recently synthesized naphthol-derivative Schiff's base

    Energy Technology Data Exchange (ETDEWEB)

    Alizadeh, N.; Ershad, S. [Dept. of Chemistry, Tarbiat Moderres Univ., Tehran (Iran); Naeimi, H.; Sharghi, H. [Dept. of Chemistry, Shiraz Univ. (Iran); Shamsipur, M. [Dept. of Chemistry, Razi Univ., Kermanshah (Iran)

    1999-11-01

    A PVC membrane electrode for copper(II) ions based on a recently synthesized naphthol-derivative Schiff's base as membrane carrier was prepared. The sensor exhibits a Nernstian response for Cu{sup 2+} ions over a wide concentration range (5.0 x 10{sup -6}-5.0 x 10{sup -2} mol/L) with a detection limit of 3.1 x 10{sup -6} mol/L (0.2 {mu}g/mL). It has a very short response time of about 5 s and can be used for 3 months without any divergence in potential. The proposed electrode revealed good selectivities over a wide variety of other cations including alkali, alkaline earth, transition and heavy metal ions and could be used in a pH range of 4.0-7.0. It was successfully applied to the direct determination and potentiometric titration of copper ion. (orig.)

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

    Science.gov (United States)

    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).

  6. The Formation of Polycomplexes of Poly(Methyl Vinyl Ether-Co-Maleic Anhydride and Bovine Serum Albumin in the Presence of Copper Ions

    Directory of Open Access Journals (Sweden)

    Karahan Mesut

    2014-09-01

    Full Text Available The binary and ternary complex formations of poly(methyl vinyl ether-co-maleic anhydride (PMVEMA with copper ions and with bovine serum albumin (BSA in the presence of copper ions in phosphate buffer solution at pH = 7 were examined by the techniques of UV-visible, fluorescence, dynamic light scattering, atomic force microscopy measurements. In the formation of binary complexes of PMVEMA-Cu(II, the addition of copper ions to the solution of PMVEMA in phosphate buffer solution at pH = 7 forms homogeneous solutions when the molar ratio of Cu(II/MVEMA is 0.5. Then the formations of ternary complexes of PMVEMA-Cu(II-BSA were examined. Study analysis revealed that the toxicities of polymer-metal and polymer-metal-protein mixture solutions depend on the nature and ratio of components in mixtures.

  7. Biosorption of copper(II), lead(II), iron(III) and cobalt(II) on Bacillus sphaericus-loaded Diaion SP-850 resin.

    Science.gov (United States)

    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.

  8. Guanine-containing copper(II) complexes: synthesis, X-ray structures and magnetic properties.

    Science.gov (United States)

    Mastropietro, Teresa F; Armentano, Donatella; Grisolia, Ettore; Zanchini, Claudia; Lloret, Francesc; Julve, Miguel; De Munno, Giovanni

    2008-01-28

    Three new compounds of formula {[Cu(gua)(H(2)O)(3)](BF(4))(SiF(6))(1/2)}(n) (1), {[Cu(gua)(H(2)O)(3)](CF(3)SO(3))(2).H(2)O}(n) (2) and [Cu(gua)(2)(H(2)O)(HCOO)]ClO(4).H(2)O.1/2HCOOH] (3) [gua = 2-amino-1H-purin-6(9H)-one] showing the unprecedented coordination of neutral guanine, have been synthesised and structurally characterized. The structures of the compounds 1 and 2 contain uniform copper(II) chains of formula [Cu(gua)(H(2)O)(3)](n)(2n+), where the copper atoms are bridged by guanine ligands coordinated via N(3) and N(7). The electroneutrality is achieved by uncoordinated tetrafluoroborate and hexafluorosilicate (1) and triflate (2). Each copper atom in 1 and 2 is five-coordinated in a distorted square pyramidal environment: two water molecules in trans positions and the N(3) and N(7a) nitrogen atoms of two guanine ligands build the basal plane whereas a water molecule fills the axial position. The values of the copper-copper separation across the bridging guanine ligand are 7.183(1) (1) and 7.123(1) A (2). is an ionic salt whose structure is made up of mononuclear [Cu(gua)(2)(H(2)O)(HCOO)](+) cations and perchlorate anions plus water and formic acid as crystallization molecules. The two guanine ligands in the cation are coordinated to the copper centre through the N(9) atom. The copper atom in 3 is four-coordinated with two monodentate guanine molecules in the trans position, a water molecule and a monodenate formate ligand building a quasi square planar surrounding. Magnetic susceptibility measurements for 1 and 2 in the temperature range 1.9-300 K show the occurrence of significant intrachain antiferromagnetic interactions between the copper(ii) ions across the guanine bridge [J = -9.6(1) (1) and -10.3(1) cm(-1) (2) with H = -J summation operator(i)S(i).S(i+1)].

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

    Science.gov (United States)

    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.

  10. Texture coefficient analysis of ion beam irradiated copper nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Rana, Pallavi, E-mail: prana.phy@gmail.com; Chaudhary, Ritika, E-mail: chauhanrpc@gmail.com; Chauhan, R. P. [Department of Physics, National Institute of Technology, Kurukshetra-136119 (India)

    2016-05-23

    Radiation may deteriorate physical properties of the materials and leave negative as well as positive impacts especially on crystalline materials. The energy deposited by ions to the grains and grain boundaries could also influence other properties of grains like: strain, reflection of charge carriers from grain boundaries, in addition to their grain size and orientation. The intensity of a peak in the XRD spectra is the direct reflection of orientation of a miller plane in the crystal. The increased intensity symbolizes the crystalline behavior due to defects annealing, while decreased intensity portray the defects formation and slender amorphisation. Orientation distribution function is a probability distribution function that quantified the texture of a polycrystalline material. The coefficients of harmonic expansion of orientation distribution function is the measurement of the texture coefficient ‘TC’. This study focused on the investigation of effect of ion beam irradiation on the preffered orientation of the planes of copper nanowires.

  11. Di(2-ethylhexyl)phosphoric acid-coconut oil supported liquid membrane for the separation of copper ions from copper plating wastewater

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Permeation of Cu(II) from its aqueous solution through a supported liquid membrane (SLM) containing di(2-ethylhexyl)phosphoric acid (D2EHPA) carrier dissolved in coconut oil has been studied. The effects of Cu(II), pH (in feed), H2SO4 (stripping) and D2EHPA (in membrane) concentrations have been investigated. The stability of the D2EHPA-coconutoil has also been evaluated. High Cu(II) concentration in the feed leads to an increase in flux from 4.1 × 10-9 to 8.9 × 10-9 mol/(m2·s) within the Cu(II) concentration range 7.8×10-4-78.6×10-4 mol/L at pH of 4.0 in the feed and 12.4 × 10-4 mol/L D2EHPA in the membrane phase. Increase in H2SO4 concentration in strip solution leads to an increase in copper ions flux up to 0.25 mol/L H2SO4, providing a maximum flux of 7.4 × 10-9 mol/(m2·s). The optimum conditions for Cu(II) transport are, pH of feed 4.0, 0.25 mol/L H2SO4 in strip phase and 12.4 × 10-4 mol/L D2EHPA (membrane) in 0.5 (m pore size polytetrafluoroethylene (PTFE) membrane. It has been observed that Cu(II) flux across the membrane tends to increase with the concentration of copper ions. Application of the method developed to copper plating bath rinse solutions has been found to be successful in the recovery of Cu(II). rane. It

  12. Simultaneous photoreductive removal of copper (II) and selenium (IV) under visible light over spherical binary oxide photocatalyst.

    Science.gov (United States)

    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.

  13. Copper(I/II), α/β-Synuclein and Amyloid-β: Menage à Trois?

    Science.gov (United States)

    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.

  14. Solid-phase extraction of copper, iron and zinc ions on Bacillus thuringiensis israelensis loaded on Dowex optipore V-493

    Energy Technology Data Exchange (ETDEWEB)

    Tuzen, Mustafa; Melek, Esra [Gaziosmanpasa University, Faculty of Science and Arts, Chemistry Department, 60250 Tokat (Turkey); Soylak, Mustafa [Erciyes University, Faculty of Science and Arts, Chemistry Department, 38039 Kayseri (Turkey)], E-mail: msoylak@gmail.com

    2008-11-30

    Bacillus thuringiensis israelensis loaded on Dowex optipore V-493 as new adsorbent for the separation-preconcentration of heavy metal ions has been proposed. The analytical conditions for the quantitative recoveries of copper(II), iron(III) and zinc(II) including pH, amounts of adsorbent, sample volume, etc. were investigated. The influences of alkaline and earth alkaline ions were also reported. The recovery values for the analytes are generally higher than 95%. The preconcentration factor was 37. The limit of detections of the analyte ions (k = 3, N = 21) were 1.14 {mu}g L{sup -1} for copper, 2.01 {mu}g L{sup -1} for iron and 0.14 {mu}g L{sup -1} for zinc. The relative standard deviations of the determinations were found to be lower than 9%. The procedure was validated by analyzing copper, iron and zinc contents in two certified reference materials, NRCC-SLRS-4 Riverine water and NIST SRM 1515 Apple leaves. Agreements between the obtained results and the certified values were achieved. The developed preconcentration method was applied in the flame atomic absorption spectrometric determination of copper, iron and zinc in several samples including a multivitamin-multimineral tablet, dialysis solutions, natural waters and some food samples.

  15. Photoluminescence quenching/recovery kinetics of [Ru(bpy)2(tatp)]2+ and [Ru(bpy)2(dmtatp)]2+ intercalated within DNA by copper(II) ions and EDTA.

    Science.gov (United States)

    Ji, Shibo; Chen, Miaojing; Gan, Guilian; Li, Hong; Li, Weishan

    2012-03-01

    The quenching and recovery kinetics of photoluminescence of [Ru(bpy)(2)(tatp)](2+) (Ru1) and [Ru(bpy)(2)(dmtatp)](2+) (Ru2) intercalated within DNA (where bpy=2,2'-bipyridine, tatp=1,4,8,9-tetra-aza-triphenylene and dmtatp=2,3-dimethyl-1,4,8,9-tetra-aza-triphenylene) have been investigated by steady-state and time-resolved methods performed at various temperatures (293-333K). Two complexes Ru1 and Ru2 show a single-exponential luminescence decay with τ(Ru1)=246.0 ns and τ(Ru2)=513.5 ns, whose luminescence upon intercalating into DNA exhibits very consistent bi-exponential decay changes. The addition of Cu(2+) ions is found to dynamically quench the luminescence of both DNA-bound Ru(II) complexes, involving a spontaneous exothermic process. The sequential addition of EDTA can partially recover the luminescence quenched by Cu(2+), however depending on methyl substituents of the intercalative ligand. The chemical conversion and luminescence control mechanism of the two DNA-bound Ru(II) complexes is discussed in detail. The present results should be of value for better understanding chemical modulation of DNA-bound Ru(II) complexes as luminescence probes. Copyright © 2011 Elsevier B.V. All rights reserved.

  16. SETUP AND PERFORMANCE OF THE RHIC INJECTOR ACCELERATORS FOR THE 2005 RUN WITH COPPER IONS.

    Energy Technology Data Exchange (ETDEWEB)

    AHRENS, L.; ALESSI, J.; GARDNER, C.J.

    2005-05-16

    Copper ions for the 2005 run [1] of the Relativistic Heavy Ion Collider (RHIC) at Brookhaven National Laboratory (BNL) are accelerated in the Tandem, Booster and AGS prior to injection into RHIC. The setup and performance of these accelerators with copper are reviewed in this paper.

  17. Reactive oxygen species generation by copper(II) oxide nanoparticles determined by DNA damage assays and EPR spectroscopy.

    Science.gov (United States)

    Angelé-Martínez, Carlos; Nguyen, Khanh Van T; Ameer, Fathima S; Anker, Jeffrey N; Brumaghim, Julia L

    2017-03-01

    Copper(II) oxide nanoparticles ((NP)CuO) have many industrial applications, but are highly cytotoxic because they generate reactive oxygen species (ROS). It is unknown whether the damaging ROS are generated primarily from copper leached from the nanoparticles, or whether the nanoparticle surface plays a significant role. To address this question, we separated nanoparticles from the supernatant containing dissolved copper, and measured their ability to damage plasmid DNA with addition of hydrogen peroxide, ascorbate, or both. While DNA damage from the supernatant (measured using an electrophoresis assay) can be explained solely by dissolved copper ions, damage by the nanoparticles in the presence of ascorbate is an order of magnitude higher than can be explained by dissolved copper and must, therefore, depend primarily upon the nanoparticle surface. DNA damage is time-dependent, with shorter incubation times resulting in higher EC50 values. Hydroxyl radical ((•)OH) is the main ROS generated by (NP)CuO/hydrogen peroxide as determined by EPR measurements; (NP)CuO/hydrogen peroxide/ascorbate conditions generate ascorbyl, hydroxyl, and superoxide radicals. Thus, (NP)CuO generate ROS through several mechanisms, likely including Fenton-like and Haber-Weiss reactions from the surface or dissolved copper ions. The same radical species were observed when (NP)CuO suspensions were replaced with the supernatant containing leached copper, washed (NP)CuO, or dissolved copper solutions. Overall, (NP)CuO generate significantly more ROS and DNA damage in the presence of ascorbate than can be explained simply from dissolved copper, and the (NP)CuO surface must play a large role.

  18. Joint toxicity of tetracycline with copper(II) and cadmium(II) to Vibrio fischeri: effect of complexation reaction.

    Science.gov (United States)

    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.

  19. Aromatic C-nitrosation by a copper(II)-nitrosyl complex.

    Science.gov (United States)

    Rout, Kanhu Charan; Mondal, Biplab

    2015-01-28

    Copper(II) complex of 4-amino-3-hydroxy-1-sulphonic acid was synthesized and characterized. Upon addition of nitric oxide, the copper(II) center of the complex in methanol was found to undergo reduction through an unstable copper(II)-nitrosyl intermediate. The formation of the intermediate was confirmed by UV-visible and FT-IR spectroscopy. The reduction of the copper(II) center was accompanied with a simultaneous C-nitrosation of the aromatic ring of the ligand. The C-nitrosation product was isolated and characterized by various spectroscopic analyses.

  20. Investigation of peptide based surface functionalization for copper ions detection using an ultrasensitive mechanical microresonator

    DEFF Research Database (Denmark)

    Cagliani, Alberto; Fischer, Lee MacKenzie; Rasmussen, Jakob Lyager

    2011-01-01

    In the framework of developing a portable label-free sensor for multi arrayed detection of heavy metals in drinking water, we present a mechanical resonator-based copper ions sensor, which uses a recently synthesized peptide Cysteine–Glycine–Glycine–Histidine (CGGH) and the l-Cysteine (Cys) peptide...... devices to detect a concentration of 10μM of copper in water, we regenerate the surface by removing the copper ions from the functionalization layer using EDTA....

  1. Voltammetric determination of copper(II) using antimony film electrodes

    OpenAIRE

    Ashrafi, Amir Mansoor; Husáková, Lenka; Vytřas, Karel

    2012-01-01

    Possibility of determination of Cu(II) at antimony modified carbon paste electrode and its application in determination of trace amount of copper in real sample has been investigated. According to obtained results, it was found that SbF-CPE can be used for these purposes successfully. Both detection limit of 1.45 ppb (evaluated as 3σ) and RSD 4.8 (for 10 ppb Cu and 10 different measurements) were also evaluated. Antimony-based electrodes are environmentally friendly which is their most import...

  2. Copper(II) complex formation with a linear peptide encompassing the putative cell binding site of angiogenin.

    Science.gov (United States)

    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.

  3. Polymeric networks of copper(II) phenylmalonate with heteroaromatic n-donor ligands: synthesis, crystal structure, and magnetic properties.

    Science.gov (United States)

    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. Fluorescent sensing and determination of mercury (II) ions in water

    African Journals Online (AJOL)

    2011-11-28

    Nov 28, 2011 ... towards the mercury (II) ion among various alkali, alkaline earth, and transition metal ions. The mercury (II) .... the metal stock solution was added to 13 separate test tubes. The test ..... positive curvature in Stern-Volmer plots.

  5. Copper(II)-Mediated Self-Assembly of Hairpin Peptides and Templated Synthesis of CuS Nanowires.

    Science.gov (United States)

    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.

  6. 3-Pyridylmethanol vs. N,N‧-diethylnicotinamide in copper(II) complex formation - A comparative EPR study

    Science.gov (United States)

    Husáriková, L.; Repická, Z.; Valigura, D.; Valko, M.; Mazúr, M.

    2013-10-01

    Copper(II) complexes, formed from 4-chlorosalicylic acid anion A (A = 4-Clsal-), different copper(II) salts (Cu(ac)2 or CuSO4) and different N-donor ligands B (B = 3-pyridylmethanol (ron) or N,N'-diethylnicotinamide (denia)) with varying N-donor ligand-to-metal ratio (x), were studied by EPR spectroscopy in the frozen water/methanol (1:3 v/v) solutions. The number of ligand B molecules coordinated to Cu(II) central ion was determined from the nitrogen perpendicular and parallel superhyperfine splitting multiplets of Cu(II) EPR spectra. It was found for both N-donor ligands: (i) At lower ligand B concentrations (x = 1, 2), [CuB] and/or [CuB2] species having one and/or two molecules of ligands B in equatorial position were dominant. The dominant ternary complex particles were [CuA2B2] species. (ii) At higher ligand B concentrations (x ⩾ 4) the formation of [CuB3] and/or [CuB4] species having three and/or four molecules of ligands B in equatorial position was confirmed. Such information is not possible to get from Cu(II) EPR spectra of powdered samples of given copper(II) complexes.

  7. 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.

    Science.gov (United States)

    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

  8. Synthesis, characterization and antibacterial studies of a copper(II) lomefloxacin ternary complex.

    Science.gov (United States)

    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.

  9. Correlation between Copper Ion Concentration in Cervical Mucus and Fllbrinolytic Activity in Menstrual Blood in Copper-releasiag IUD Users

    Institute of Scientific and Technical Information of China (English)

    林建华; 潘家骧; 严隽鸿

    1993-01-01

    In the present study, 44 women using TCu220c-IUD or inert-IUD were asked to make follow-ups before insertion and at the 1st., 3rd., 6th, 9th and 12th month after insertion The mean menstrual blood loss, the fibrinalytic activity including the activation of tissue-plasminogen activator (t-PA) and the amount of plasminogen PIG) and fibrinogen-fibrin degradation products (FDP) in menstrual blood and the copper ion concentration in cervical mucus were determined. The correlation between the copper ion concentration and the fibrinalytic activity was considered. It was found that the change of the copper ion concentration was positively correlated with that of the activition of t-PA and the amount of FDP. On the contrary, the change ofthe copper ion concentration was inversely related to the change of PLG value. It is concluded that the high copper ion level can enhance the activation of fibrinolytic system in human endometrium and induce the increase of menorrhagia.

  10. Spectroscopic, structural and theoretical studies of copper(II) complexes of tridentate NOS Schiff bases

    Science.gov (United States)

    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.

  11. Syntheses and structural characterization of iron(II) and copper(II) coordination compounds with the neutral flexible bidentate N-donor ligands

    Science.gov (United States)

    Beheshti, Azizolla; Lalegani, Arash; Bruno, Giuseppe; Rudbari, Hadi Amiri

    2014-08-01

    Two new coordination compounds [Fe(bib)2(N3)2]n(1) and [Cu2(bpp)2(N3)4] (2) with azide and flexible ligands 1,4-bis(imidazolyl)butane (bib) and 1,3-bis(3,5-dimethylpyrazolyl)propane (bpp) were prepared and structurally characterized. In the 2D network structure of 1, the iron(II) ion lies on an inversion center and exhibits an FeN6 octahedral arrangement while in the dinuclear structure of 2, the copper(II) ion adopts an FeN5 distorted square pyramid geometry. In the complex 1, each μ2-bib acts as bridging ligand connecting two adjacent iron(II) ions while in the complex 2, the bpp ligand is coordinated to copper(II) ion in a cyclic-bidentate fashion forming an eight-membered metallocyclic ring. Coordination compounds 1 and 2 have been characterized by infrared spectroscopy, elemental analyses and single-crystal X-ray diffraction. Thermal analysis of polymer 1 was also studied.

  12. cis-Aquadichlorido[pyrimidin-2(1H-one-κN3]copper(II

    Directory of Open Access Journals (Sweden)

    A. Guy Orpen

    2008-07-01

    Full Text Available In the title compound, [CuCl2(C4H4N2O(H2O], the CuII cation is coordinated by two chloride anions, one pyrimidin-2-one N atom and one water molecule, giving a slightly distorted square-planar geometry. In the crystal structure, the pyrimidin-2-one rings stack along the b axis, with an interplanar distance of 3.306 Å, as do the copper coordination planes (interplanar spacing = 2.998 Å. The coordination around the Jahn–Teller-distorted CuII ion is completed by long Cu...O [3.014 (5 Å] and Cu...Cl [3.0194 (15 Å] interactions with adjacent molecules involved in this stacking. Several N—H...Cl, O—H...Cl and O—H...O intermolecular hydrogen bonds form a polar three-dimensional network.

  13. Preparation and thermal decomposition of copper(II, zinc(II and cadmium(II chelates with 8-hydroxyquinoline

    Directory of Open Access Journals (Sweden)

    Crespi Marisa S.

    1999-01-01

    Full Text Available When the compounds are heated in an inert atmosphere it can be verified the consecutive partial sublimation, fusion, partial volatilization and partial thermal decomposition of the anhydrous complexes. When in an oxidating atmosphere the above process is only verified to Cu(II chelates. Anhydrous copper(II complexes present a monoclinic structure in the b form and the volatilized compound in a a form. Zinc(II and cadmium(II hydrated complexes are isomorphous and they present different cell dimensions from those reported previously.

  14. Novel copper-based therapeutic agent for anti-inflammatory: synthesis, characterization, and biochemical activities of copper(II) complexes of hydroxyflavone Schiff bases.

    Science.gov (United States)

    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.

  15. Copper ion-exchanged channel waveguides optimization for optical trapping.

    Science.gov (United States)

    Reshak, A H; Khor, K N; Shahimin, M M; Murad, S A Z

    2013-08-01

    Optical trapping of particles has become a powerful non-mechanical and non-destructive technique for precise particle positioning. The manipulation of particles in the evanescent field of a channel waveguide potentially allows for sorting and trapping of several particles and cells simultaneously. Channel waveguide designs can be further optimized to increase evanescent field prior to the fabrication process. This is crucial in order to make sure that the surface intensity is sufficient for optical trapping. Simulation configurations are explained in detail with specific simulation flow. Discussion on parameters optimization; physical geometry, optical polarization and wavelength is included in this paper. The effect of physical, optical parameters and beam spot size on evanescent field has been thoroughly discussed. These studies will continue toward the development of a novel copper ion-exchanged waveguide as a method of particle sorting, with biological cell propulsion studies presently underway.

  16. Morphology of gold and copper ion-plated coatings

    Science.gov (United States)

    Spalvins, T.

    1978-01-01

    Copper and gold films (0.2 to 2 microns thick) were ion plated onto polished 304-stainless-steel, glass, mica surfaces. These coatings were examined by SEM for defects in their morphological growth. Three types of defects were distinguished: nodular growth, abnormal or runaway growth, and spits. The cause for each type of defect was investigated. Nodular growth is due to inherent substrate microdefects, abnormal or runaway growth is due to external surface inclusions, and spits are due to nonuniform evaporation (ejection of droplets). All these defects induce stresses and produce porosity in the coatings and thus weaken their mechanical properties. During surface rubbing, large nodules are pulled out, leaving vacancies in the coatings.

  17. Effects of nano-copper(II) oxide and nanomagnesium oxide particles on activated sludge.

    Science.gov (United States)

    Liu, Guoqiang; Wang, Jianmin

    2012-07-01

    Effects of nano-copper(II) oxide (nano-CuO) and nanomagnesium oxide (nano-MgO) particles on activated sludge endogenous respiration (aerobic digestion), biochemical oxygen demand (BOD) biodegradation, and nitrification were investigated through respiration rate measurement. For comparison, the effects of Cu(II) and Mg(II) ions on activated sludge were also studied. Results indicated that soluble Cu(II) has half maximum inhibitory concentration (IC50) values of 19, 5.5, 53, and 117 mg Cu/L for endogenous respiration, BOD biodegradation, ammonium oxidation, and nitrite oxidation, respectively. However, nano-CuO only inhibited BOD biodegradation at 240 mg Cu/L or more, and its associated toxicity was primarily caused by soluble Cu(II). In contrast, soluble Mg(II) was not toxic to activated sludge in the experimental concentration range, but nano-MgO inhibited BOD biodegradation and nitrification with IC50 values of 70 and 143 mg Mg/L, respectively. Further study indicated that the toxicity of nano-MgO resulted primarily from increased pH following MgO hydrolysis.

  18. Copper(II) interaction with peptide fragments of histidine-proline-rich glycoprotein: Speciation, stability and binding details.

    Science.gov (United States)

    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.

  19. Binding of transition metal ions [cobalt, copper, nickel and zinc] with furanyl-, thiophenyl-, pyrrolyl-, salicylyl- and pyridyl-derived cephalexins as potent antibacterial agents.

    Science.gov (United States)

    Chohan, Zahid H; Pervez, Humayun; Khan, Khalid Mohammed; Rauf, A; Supuran, Claudiu T

    2004-02-01

    A method is described for the preparation of novel cephalexin-derived furanyl-, thiophenyl-, pyrrolyl-, salicylyl- and pyridyl-containing compounds showing potent antibacterial activity. The binding of these newly synthesized antibacterial agents with metal ions such as cobalt(II), copper(II), nickel(II) and zinc(II) has been studied and their inhibitory properties against various bacterial species such as Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, and Klebsiella pneumoniae are also reported. These results suggest that metal ions to possess an important role in the designing of metal-based antibacterials and that such complexes are more effective against infectious diseases compared to the uncomplexed drugs.

  20. The removal of hydrogen sulfide from gas streams using an aqueous metal sulfate absorbent : Part II. the regeneration of copper sulfide to copper oxide - An experimental study

    NARCIS (Netherlands)

    Ter Maat, H.; Hogendoorn, J. A.; Versteeg, G. F.

    2005-01-01

    Aim of this study was to investigate the possibilities for a selective and efficient method to convert copper(II) sulfide (CuS) into copper(II) oxide (CuO). The oxidation of copper sulfide has been studied experimentally using a thermogravimetric analyzer (TGA) at temperatures ranging from 450 to 75

  1. The removal of hydrogen sulfide from gas streams using an aqueous metal sulfate absorbent: Part II. The regeneration of copper sulfide to copper oxide—an experimental study

    NARCIS (Netherlands)

    Maat, ter H.; Hogendoorn, J.A.; Versteeg, G.F.

    2005-01-01

    Aim of this study was to investigate the possibilities for a selective and efficient method to convert copper(II) sulfide (CuS) into copper(II) oxide (CuO). The oxidation of copper sulfide has been studied experimentally using a thermogravimetric analyzer (TGA) at temperatures ranging from 450 to 75

  2. The removal of hydrogen sulfide from gas streams using an aqueous metal sulfate absorbent : Part II. the regeneration of copper sulfide to copper oxide - An experimental study

    NARCIS (Netherlands)

    Ter Maat, H.; Hogendoorn, J. A.; Versteeg, G. F.

    2005-01-01

    Aim of this study was to investigate the possibilities for a selective and efficient method to convert copper(II) sulfide (CuS) into copper(II) oxide (CuO). The oxidation of copper sulfide has been studied experimentally using a thermogravimetric analyzer (TGA) at temperatures ranging from 450 to

  3. Investigation of the interaction of copper(II) oxide and electron beam irradiation crosslinkable polyethylene

    Energy Technology Data Exchange (ETDEWEB)

    Bee, Soo-Tueen, E-mail: direct.beest@gmail.com [Department of Chemical Engineering, Lee Kong Chian Faculty of Engineering and Science, Universiti Tunku Abdul Rahman, Jalan Sungai Long, Bandar Sungai Long, Cheras, 43000 Kajang, Selangor (Malaysia); Sin, Lee Tin, E-mail: direct.tinsin@gmail.com [Department of Chemical Engineering, Lee Kong Chian Faculty of Engineering and Science, Universiti Tunku Abdul Rahman, Jalan Sungai Long, Bandar Sungai Long, Cheras, 43000 Kajang, Selangor (Malaysia); Ratnam, C.T. [Radiation Processing Technology Division, Malaysian Nuclear Agency, Bangi, 43000 Kajang, Selangor (Malaysia); Haraveen, K.J.S.; Tee, Tiam-Ting [Department of Chemical Engineering, Lee Kong Chian Faculty of Engineering and Science, Universiti Tunku Abdul Rahman, Jalan Sungai Long, Bandar Sungai Long, Cheras, 43000 Kajang, Selangor (Malaysia); Rahmat, A.R. [Department of Polymer Engineering, Faculty of Chemical Engineering, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor (Malaysia)

    2015-10-01

    In this study, the effects of electron beam irradiation on the properties of copper(II) oxide when added to low-density polyethylene (LDPE) blends were investigated. It was found that the addition of low loading level of copper(II) oxide (⩽2 phr) to LDPE results in significantly poorer gel content and hot set results. However, the incorporation of higher loading level of copper(II) oxide (⩾3 phr) could slightly increase the degree of crosslinking in all irradiated LDPE composites. This is due to the fact that higher amounts of copper(II) oxide could slightly induce the formation of free radicals in LDPE matrix. Besides, increasing irradiation doses was also found to gradually increase the gel content of LDPE composites by generating higher amounts of free radicals. As a consequence, these higher amounts of free radicals released in the LDPE matrix could significantly increase the degree of crosslinking. The addition of copper(II) oxide could reduce the tensile strength and fracture strain (elongation at break) of LDPE composites because of poorer interfacial adhesion effect between copper(II) oxide particles and LDPE matrix. Meanwhile, increasing irradiation doses on all copper(II) oxide added LDPE composites could marginally increase the tensile strength. In addition, increasing irradiation dose could enhance the thermal stability of LDPE composites by increasing the decomposition temperature. The oxidation induction time (OIT) analysis showed that, because of the crosslinking network in the copper(II) oxide added LDPE composites, oxidation reaction is much delayed.

  4. Structures of dioxobipyridil-12-crown-4 and its complexes with silver (I) and copper (II) cations

    Science.gov (United States)

    Starova, Galina L.; Denisova, Anna S.; Dem'yanchuk, Evgeniya M.

    2008-02-01

    The structures of dioxobipyridil-12-crown-4 ( bpy-CO-crown) and its complexes with copper (II) and silver (I) cations have been determined using single crystal X-ray-diffraction. The results have been compared with the literature data on the complexes of dcmbpy and its complex with silver (I) and copper (II) cations.

  5. Copper electrodeposition from cuprous chloride solutions containing lead, zinc or iron ions

    Institute of Scientific and Technical Information of China (English)

    M. Tchoumou; M. Roynette Ehics

    2005-01-01

    Cuprous chloride hydrochloric acid solutions were electrolysed in a two compartments cell without agitation for copper extraction. It is found that the current density affects the colour and the size of copper deposits. During electrodeposition of copper from cuprous solution in the presence of various concentrations of lead, zinc or iron ions at different current densities, it is observed that lead is codeposited with copper by increasing current density.In all experiments, the current efficiency for the copper deposition reaction fluctuates between 88.50% and 95.50%.

  6. Calculation and optimization of the copper (II sulphate monohydrate from copper (II sulphate pentahydrate production process in a fluidized bed dryer

    Directory of Open Access Journals (Sweden)

    Kaluđerović-Radoičić Tatjana

    2015-01-01

    Full Text Available In this paper the process of the copper (II sulphate monohydrate from copper (II sulphate pentahydrate (also known as a Blue vitriol or Bluestone production was analyzed. Copper (II sulphate pentahydrate is one of the most important copper salts which has been known since the ancient Egyptians. In the nineteenth century its application as a fungicide was discovered which provoked wide industrial production. Molecule of the copper (II sulphate pentahydrate is a crystalohydrate with five water molecules linked by chemical bonds to a molecule of the copper (II sulphate. Copper (II sulphate exists as a series of compounds that differ in their degree of hydratation. The anhydrous form is a pale green or gray-white powder, whereas the pentahydrate (CuSO4•5H2O, the most commonly encountered salt, is bright blue. In order to obtain copper (II sulphate monohydrate from copper (II sulphate pentahydrate four water molecules need to be removed. To determine the optimum temperature and time required for the removal of four water molecules from a molecule of pentahydrate in this work thermogravimetric (TGA analysis was performed. Thermogravimetric (TGA analysis - dehydration of copper (II sulphate pentahydrate is done using simultaneous TG-DSC thermal analyzer DTG-Q600 SDT from TA Instruments. Analyzes was carried out for two type of samples, the sample containing particles of the average diameter equal to 0.17 mm and the particles of the average diameter 0.5 mm. In addition, fluidization and drying curve was determined using a semi-industrial fluidization column. On top, the industrial fluidization column aimed to produce 300 tones per month of copper (II sulphate monohydrate was designed. Material and energy calculations were performed using software packages Simprosys 3.0 and SuperPro Designer 5.1. Simprosys 3.0 is a software package designed for the modeling and simulation of a drying process as well as for 20 different unit operations. Super

  7. 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.

    Science.gov (United States)

    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.

  8. A novel Schiff-base as a Cu(II) ion fluorescent sensor in aqueous solution.

    Science.gov (United States)

    Gündüz, Z Yurtman; Gündüz, C; Özpınar, C; Urucu, O Aydın

    2015-02-05

    A new fluorescent Cu(II) sensor (L) obtained from the Schiff base of 5,5'-methylene-bis-salicylaldehyde with amidol (2,4-diaminophenol) was synthesized and characterized by FT-IR, MS, (1)H NMR, (13)C NMR techniques. In the presence of pH 6.5 (KHPO4-Na2HPO4) buffer solutions, copper reacted with L to form a stable 2:1 complex. Fluorescence spectroscopic study showed that Schiff base is highly sensitive towards Cu(II) over other metal ions (K(+), Na(+), Al(3+), Ni(2+), Co(2+), Fe(3+), Zn(2+), Pb(2+)) in DMSO/H2O (30%, v/v). The sensor L was successfully applied to the determination of copper in standard reference material. The structural properties and molecular orbitals of the complex formed between L and Cu(2+) ions were also investigated using quantum chemical computations.

  9. Surface adsorption and self-assembly of Cu(II) ions on TEMPO-oxidized cellulose nanofibers in aqueous media.

    Science.gov (United States)

    Liu, Peng; Oksman, Kristiina; Mathew, Aji P

    2016-02-15

    TEMPO-mediated oxidized cellulose nanofibers (TOCNFs) have shown potential in the bioremediation of metal ions from contaminated water due to their interaction with positively charged metal ions via electrostatic interactions involving surface carboxyl groups. Copper is one of the most common pollutants in industrial effluents and is thus the target metal in the current study. The specific surface adsorption of Cu(II) was similar for TOCNFs with different degrees of functionalization and directly impacted the zeta potential. SEM imaging of the TOCNF after Cu(II) adsorption revealed interesting nanostructured clusters that were attributable to Cu(II) ions first being adsorbed by carboxylate groups on the TOCNF and subsequently being reduced and self-assembled to Cu(0) nanoparticles (NPs) or copper oxide NPs by microprecipitation. TOCNF turned superhydrophilic and resulted in faster water filtration after copper adsorption due to the stronger polarity of the copper ions or the self-assembled Cu(0) NPs creating voids or highly water-permeable channels at the interface between the interconnected TEMPO-oxidized nanofibers. Thus, the adsorption of Cu(II) ions and self-assembly into the Cu NPs on TOCNF favors a faster water purification process and provides a viable route to reuse/recycle TOCNFs studded with Cu nanoparticles as biocidal materials.

  10. Als1 and Als3 regulate the intracellular uptake of copper ions when Candida albicans biofilms are exposed to metallic copper surfaces.

    Science.gov (United States)

    Zheng, Sha; Chang, Wenqiang; Li, Chen; Lou, Hongxiang

    2016-05-01

    Copper surfaces possess efficient antimicrobial effect. Here, we reported that copper surfaces could inactivate Candida albicans biofilms within 40 min. The intracellular reactive oxygen species in C. albicans biofilms were immediately stimulated during the contact of copper surfaces, which might be an important factor for killing the mature biofilms. Copper release assay demonstrated that the copper ions automatically released from the surface of 1 mm thick copper coupons with over 99.9% purity are not the key determinant for the copper-mediated killing action. The susceptibility test to copper surfaces by using C. albicans mutant strains, which were involved in efflux pumps, adhesins, biofilms formation or osmotic stress response showed that als1/als1 and als3/als3 displayed higher resistance to the copper surface contact than other mutants did. The intracellular concentration of copper ions was lower in als1/als1 and als3/als3 than that in wild-type strain. Transcriptional analysis revealed that the expression of copper transporter-related gene, CRP1, was significantly increased in als1/als1, als3/als3, suggesting a potential role of ALS1 and ALS3 in absorbing ions by regulating the expression of CRP1 This study provides a potential application in treating pathogenic fungi by using copper surfaces and uncovers the roles of ALS1 and ALS3 in absorbing copper ions for C. albicans.

  11. Manganese Coated Sand for Copper (II Removal from Water in Batch Mode

    Directory of Open Access Journals (Sweden)

    Nidal Hilal

    2013-09-01

    Full Text Available Removal of heavy metals, such as copper ions, from water is important to protect human health and the environment. In this study, manganese coated sand (MCS was used as an adsorbent to remove copper ions in a batch system. Equilibrium data were determined at a temperature of 25.6 °C and the Langmuir model was used to describe the experimental data. Mn-coating improved the removal of copper ions by 70% as compared to uncoated sand. Based on a kinetics study, the adsorption of copper ions on MCS was found to occur through a chemisorption process and the pseudo-second-order model was found to fit the kinetics experimental data well. Due to particle interactions, the equilibrium uptake was reduced as the ratio of sand to volume of solution increased. pH affected the removal of copper ions with lowest uptakes found at pH 3 and pHs >7, whilst at pHs in the range of 4 to 7, the uptake was highest and almost constant at the value of 0.0179 mg/g ± 4%. This study has also revealed that copper ions removal was dissolved oxygen (DO dependent with the highest removal occurring at ambient DO concentration, which suggests that DO should be carefully studied when dealing with copper ions adsorption.

  12. Mixed-ligand binuclear copper(II) complex of 5-methylsalicylaldehyde and 2,2'-bipyridyl: Synthesis, crystal structure, DNA binding and nuclease activity

    Indian Academy of Sciences (India)

    Perumal Gurumoorthy; Jayaram Ravichandran; Aziz Kalilur Rahiman

    2014-05-01

    A new mixed-ligand binuclear copper(II) complex [Cu(MS)(bpy)]2.(ClO4)2, built of 5-methylsalicylaldehyde and 2,2'-bipyridyl has been synthesized and characterized by using elemental analysis, IR and UV-Vis spectroscopy. Crystal structure of the complex shows that copper(II) ion lies in a square pyramidal coordination environment. The structure consists of two symmetrical half units in which the copper(II) ion of one half unit connected with the phenolate oxygen atom of other half unit along with one perchlorate anion in the crystal lattice as free molecule. Presence of uncoordinated perchlorate anion was also confirmed by IR spectroscopy. Absorption spectroscopy exhibits d-d transition at 628 nm, which further supports the square pyramidal geometry around the copper(II) ions. EPR spectrum of the copper(II) complex at room temperature shows a broad signal without any splitting pattern at ∥ = 2.26, ⊥ = 2.03 and the magnetic moment (eff = 1.31 BM) obtained at room temperature indicate an antiferromagnetic interaction between the two copper(II) ions through phenoxide-bridge. Binding studies reveal that the complex possesses good binding propensity (b = 5.2 ± 1.7 × 104 M-1) and bind to nitrogenous bases of DNA through intercalation. Nuclease activity of the complex with pBR322 DNA shows that the effect of hydrolytic cleavage is dose-dependent and the oxidative cleavage indicates the involvement of hydroxyl radical and singlet-oxygen as reactive oxygen species.

  13. Supramolecular control of a mononuclear biomimetic copper(II) center: bowl complexes vs funnel complexes.

    Science.gov (United States)

    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.

  14. A new copper containing MALDI matrix that yields high abundances of [peptide + Cu]+ ions.

    Science.gov (United States)

    Wu, Zhaoxiang; Fernandez-Lima, Francisco A; Perez, Lisa M; Russell, David H

    2009-07-01

    The dinuclear copper complex (alpha-cyano-4-hydroxycinnamic acid (CHCA) copper salt (CHCA)(4)Cu(2)), synthesized by reacting CHCA with copper oxide (CuO), yields increased abundances of [M + xCu - (x-1)H](+) (x = 1-6) ions when used as a matrix for matrix-assisted laser desorption ionization (355 nm Nd:YAG laser). The yield of [M + xCu - (x-1)H](+) (x = 1 to approximately 6) ion is much greater than that obtained by mixing peptides with copper salts or directly depositing peptides onto oxidized copper surfaces. The increased ion yields for [M + xCu - (x-1)H](+) facilitate studies of biologically important copper binding peptides. For example, using this matrix we have investigated site-specific copper binding of several peptides using fragmentation chemistry of [M + Cu](+) and [M + 2Cu - H](+) ions. The fragmentation studies reveal interesting insight on Cu binding preferences for basic amino acids. Most notable is the fact that the binding of a single Cu(+) ion and two Cu(+) ions are quite different, and these differences are explained in terms of intramolecular interactions of the peptide-Cu ionic complex.

  15. Biosorption of binary mixtures of Cr(III and Cu(II ions by Sargassum sp

    Directory of Open Access Journals (Sweden)

    Silva E.A.

    2003-01-01

    Full Text Available The adsorption of two metal ions, Cr(III and Cu(II, in single-component and binary systems by Sargassum sp., a brown alga, was studied. Equilibrium batch sorption studies were carried out at 30ºC and pH 3.5. Kinetic tests were done for a binary mixture (chromium + copper for a contact time of 72 hours to guarantee that equilibrium was reached. The monocomponent equilibrium data obtained were analyzed using the Langmuir and Freundlich isotherms. The binary equilibrium data obtained were described using four Langmuir-type and Freundlich isotherms. The F-test showed a statistically significant fit for all binary isotherm models. The parameters for isotherms of the Langmuir-type were used to determine the affinity of one metal for the biosorbent in the presence of another metal. The chromium ion showed a greater affinity for Sargassum sp. than the copper ion.

  16. Effects of Excess Copper Ions on Decidualization of Human Endometrial Stromal Cells.

    Science.gov (United States)

    Li, Ying; Kang, Zhen-Long; Qiao, Na; Hu, Lian-Mei; Ma, Yong-Jiang; Liang, Xiao-Huan; Liu, Ji-Long; Yang, Zeng-Ming

    2017-05-01

    The aim of this study was to investigate the effects of copper ions on decidualization of human endometrial stromal cells (HESCs) cultured in vitro. Firstly, non-toxic concentrations of copper D-gluconate were screened in HESCs based on cell activity. Then, the effects of non-toxic concentrations of copper ions (0~250 μM) were examined on decidualization of human endometrial stromal cells. Our data demonstrated that the mRNA expressions of insulin-like growth factor binding protein (IGFBP-1), prolactin (PRL), Mn-SOD, and FOXO1were down-regulated during decidualization following the treatments with 100 or 250 μM copper ions. Meanwhile, the amount of malonaldehyde (MDA) in the supernatant of HESCs was increased. These results showed that in vitro decidualization of HESCs was impaired by copper treatment.

  17. Peculiar reactivity of a di-imine copper(II) complex regarding its binding to albumin protein.

    Science.gov (United States)

    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.

  18. The role of copper(II) and zinc(II) in the degradation of human and murine IAPP by insulin-degrading enzyme.

    Science.gov (United States)

    Bellia, Francesco; Grasso, Giuseppe

    2014-04-01

    Amylin or islet amyloid polypeptide (IAPP) is a 37-residue peptide hormone secreted from the pancreatic islets into the blood circulation and is cleared by peptidases in the kidney. IAPP aggregates are strongly associated with β-cell degeneration in type 2 diabetes, as demonstrated by the fact that more than 95% of patients exhibit IAPP amyloid upon autopsy. Recently, it has been reported that metal ions such as copper(II) and zinc(II) are implicated in the aggregation of IAPP as well as able to modulate the proteolytic activity of IAPP degrading enzymes. For this reason, in this work, the role of the latter metal ions in the degradation of IAPP by insulin-degrading enzyme (IDE) has been investigated by a chromatographic and mass spectrometric combined method. The latter experimental approach allowed not only to assess the overall metal ion inhibition of the human and murine IAPP degradation by IDE but also to have information on copper- and zinc-induced changes in IAPP aggregation. In addition, IDE cleavage site preferences in the presence of metal ions are rationalized as metal ion-induced changes in substrate accessibility.

  19. Reagents for selective extraction of nickel(II), cobalt(II) and copper(II) from highly acidic sulfate feeds containing iron

    OpenAIRE

    Roebuck, James William

    2015-01-01

    This thesis focuses on development of new regents which are suitable for recovering nickel, cobalt and copper from laterite leach solutions, specifically focusing on reagent requirements for novel base metal flowsheets developed by Anglo American. The work aims to design reagents which can extract nickel(II), cobalt(II) and copper(II) from a highly acidic aqueous sulfate solutions whilst showing selectivity over iron(II) and iron(III). Chapter 1 reviews current extractive metallur...

  20. Synthesis, Crystal Structure, and Characterization of Ternary Copper(II Complex Derived from N-(salicylidene-L-valine

    Directory of Open Access Journals (Sweden)

    Sundaramurthy Santha Lakshmi

    2016-01-01

    Full Text Available Ternary Schiff base copper(II complex [CuL(tmpda] (where H2L is N-(salicylidene-L-valine; tmpda is N,N,N′,N′-tetramethyl-1,3-propanediamine has been characterized by UV-Vis., FTIR, and single crystal XRD. The crystal structure displays a distorted square pyramidal geometry in which Schiff base is bonded to the Cu(II ion via phenolate oxygen, imine nitrogen, and an oxygen atom of the carboxylate group through the basal plane and the chelating diamine, N,N,N′,N′-tetramethyl-1,3-propanediamine, displays an axial and equatorial mode of binding via NN-donor atoms.

  1. Synthesis and structure of copper(II) complexes: Potential cyanide sensor and oxidase model'

    Indian Academy of Sciences (India)

    PALASH MONDAL; SANKAR PRASAD PARUA; POULAMI PATTANAYAK; UTTAM DAS; SURAJIT CHATTOPADHYAY

    2016-05-01

    The new complexes of compositions $[(L_{a})_{2}Cu]$ and $[(L_{b})_{2}Cu]$ were prepared by treating with2-hydroxy-5-methyl-3-(2-aryldiazenyl)phenylimino) methyl) benzaldehyde $(HL_{a})$ and ethyl-2-cyano-3-(2-hydroxy-5-methyl-3-(-(2-aryldiazenyl) phenylimino) methyl) phenyl) acrylate $(HL_{b})$ ligands [where aryl isphenyl for $HL_{a}^{1}$ and $HL_{b}^{1}$ ; p-methyl phenyl for $HL_{a}^{2}$ and $HL_{b}^{2}$ ; and p-chloro phenyl for $HL_{a}^{3}$ and $HL_{b}^{3}$ ] with $Cu(OAc)_{2}.H_{2}O$, respectively. Both the bis copper(II) complexes consist of tridentate (N,N,O) anionic ligands, $L^{-}_a$ or $L^{-}_b$ . X-ray structures of the representative complexes $[(L^{1}_{a})_{2}Cu]$ and $[(L^{2}_{b})_{2}Cu]$ were determined toconfirm the molecular species unequivocally. The molecular structure of copper complexes exhibited tetragonallydistorted (Jahn-Teller) geometry consistent with the $d^{9}$ configuration of Cu(II) metal ion. Oxidation ofbenzyl alcohols using the newly synthesized complexes as catalyst has been studied. Photoluminescence propertiesof $[(L^{2}_{a})_{2}Cu]$ and $[(L^{2}_{b})_{2}Cu]$ were exploited for selective cyanide recognition. The $[(L_{b})_{2}Cu], complexesdisplayed antibacterial activity toward gram positive and gram negative bacteria

  2. Determination of copper(II) in the dairy product by an electrochemical sensor based on click chemistry.

    Science.gov (United States)

    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.

  3. Copper-based nanoparticles prepared from copper (II acetate bipyridine complex

    Directory of Open Access Journals (Sweden)

    Lastovina Tatiana A.

    2016-01-01

    Full Text Available We report the synthesis of CuO, Cu/Cu2O and Cu2O/CuO nanoparticles (NPs from the single copper (II acetate bipyridine complex by three different methods:microwave-assisted, solvothermal and borohydride. Presence of bipyridine ligand in the copper complex would impose no need in additional stabilization during synthesis. The phases of formed NPs were identified by X-ray diffraction. CuO NPs of ~11 nm were obtained via solvothermal synthesis from alkaline solution at 160°C. The Cu/Cu2O NPs of ~80 nm were produced via microwave-assisted polyol procedure at 185-200°C, where ethylene glycol can play a triple role as a solvent, a reducing agent and a surfactant. The Cu2O/CuO NPs of ~16 nm were synthesized by a borohydride method at room temperature. Interplanar spacing calculated from the selected-area electron diffraction data confirmed the formation of Cu, CuO and Cu2O phases in respective samples. All NPs are stable and can be used for various applications including biomedicine.

  4. Structural, spectroscopic, magnetic and electrochemical studies of monomer N-substituted-sulfanilamide copper (II) complex with 2,2'-bipyridine.

    Science.gov (United States)

    Öztürk, Filiz; Bulut, İclal; Bulut, Ahmet

    2015-03-05

    A novel copper (II) complex of sulfamethazine (4-amino-N-[4,6-dimethyl-2-pyrimidinyl] benzene sulfonamide, Hsmz) ([Cu(smz)2bipy]⋅0.8H2O; bipy: 2,2'-bipyridine) has been synthesized and characterized by single crystal X-ray diffraction, EPR, IR, UV-vis and electrochemical methods. The single crystal X-ray analysis indicated that the compound crystallizes in the monoclinic space group P21/c with Z=4. The central copper (II) ion is coordinated by two bidentate sulfamethazine anions through the nitrogen atoms together with one bidentate 2,2'-bipyridine ligand forming the octahedral geometry. The characteristic vibration bands support the X-ray analysis results. The EPR spectral analysis has led to that the ground state wave function of the unpaired electron of copper ion is [Formula: see text] ((2)B1g state) and also indicated that the metal ions are located in distorted octahedral sites (D4h) elongated along the z-axis. The electrochemical studies of the complex were also carried out to determine the active sites of the ligands. The cyclic and square wave voltammetric techniques have been used to determine the complex.

  5. Synthesis, crystal structures and properties of two novel macrocyclic nickel(II) and copper(II) complexes

    Science.gov (United States)

    Su, Yan-Hui; Liu, Jie; Li, Jia; Si, Xue-Zhi

    2007-06-01

    Two new 14-membered hexaaza macrocyclic complexes with the formulae [NiL](ClO 4) 2·CH 3COCH 3 ( 1) and [CuL](ClO 4) 2·CH 3COCH 3 ( 2), where L = 3,10-bis(2-thiophenemethyl)-1,3,5,8,10,12-hexaazacyclotetradecane, have been synthesized and characterized by elemental analyses, single-crystal X-ray diffraction analyses, electronic spectra, IR and TG-DTA. In 1, the nickel(II) ion is four-coordinated with four nitrogen atoms from the macrocycle and forms a square-planar coordination geometry. In 2, the copper(II) ion is six-coordinated with four nitrogen atoms from the macrocyclic ligand in the equatorial plane and two oxygen atoms from the perchlorate anions in the axial position exhibiting an elongated octahedron coordination geometry. The two complexes present two different molecular arrangements in which the [ML] 2+ (M = Ni, Cu) cation arrays in the manner of M(1)M(2)M(1)… in sequence. The pendant thiophene groups of the neighboring macrocycles have no π⋯π interactions. All the ClO4- anions and acetone molecules are involved in hydrogen-bonding interactions with the macrocyclic ligand.

  6. X-ray and DFT studies of a mono- and binuclear copper(II) ionic compound containing a Schiff base.

    Science.gov (United States)

    Langer, Vratislav; Mach, Pavol; Gyepesová, Dalma; Andrezálová, Lucia; Kohútová, Mária

    2012-11-01

    In the structure of trans-bis(ethanol-κO)tetrakis(1H-imidazole-κN(3))copper(II) bis[μ-N-(2-oxidobenzylidene)-D,L-glutamato]-κ(4)O(1),N,O(2'):O(2');κ(4)O(2'):O(1),N,O(2')-bis[(1H-imidazole-κN(3))cuprate(II)], [Cu(C(3)H(4)N(2))(4)(C(2)H(6)O)(2)][Cu(2)(C(15)H(14)N(3)O(5))(2)], both ions are located on centres of inversion. The cation is mononuclear, showing a distorted octahedral coordination, while the anion is a binuclear centrosymmetric dimer with a square-pyramidal copper(II) coordination. An extensive three-dimensional hydrogen-bonding network is formed between the ions. According to B3LYP/6-31G* calculations, the two equivalent components of the anion are in doublet states (spin density located mostly on Cu(II) ions) and are coupled as a triplet, with only marginal preference over an open-shell singlet.

  7. Kinetics of copper ion absorption by cross-linked calcium polyacrylate membranes

    Science.gov (United States)

    Philipp, W. H.; May, C. E.

    1983-01-01

    The absorption of copper ions from aqueous copper acetate solutions by cross-linked calcium acrylate membranes was found to obey parabolic kinetics similar to that found for oxidation of metals that form protective oxide layers. For pure calcium polyacrylate membranes the rate constant was essentially independent of copper acetate concentration and film thickness. For a cross-linked copolymer film of polyvinyl alcohol and calcium polyacrylate, the rate constant was much greater and dependent on the concentration of copper acetate. The proposed mechanism in each case involves the formation of a copper polyacrylate phase on the surface of the membrane. The diffusion of the copper ion through this phase appears to be the rate controlling step for the copolymer film. The diffusion of the calcium ion is apparently the rate controlling step for the calcium polyacrylate. At low pH, the copper polyacrylate phase consists of the normal copper salt; at higher pH, the phase appears to be the basic copper salt.

  8. Copper diffusivity in boron-doped silicon wafer measured by dynamic secondary ion mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Koh, Songfoo [S.E.H (M) Sdn. Bhd., Lot 2, Lorong Enggang 35, Ulu Klang FTZ, 54200 Selangor (Malaysia); You, Ahheng [Faculty of Engineering and Technology, Multimedia University, Jalan Ayer Keroh Lama, Bukit Beruang, 75450 Melaka (Malaysia); Tou, Teckyong, E-mail: tytou@mmu.edu.my [Faculty of Engineering, Multimedia Univesity, Jalan Multimedia, 63100 Cyberjaya (Malaysia)

    2013-03-20

    Highlights: ► Effective copper diffusivity in boron-doped silicon wafer was measured. ► Dynamic secondary ion mass spectrometry was used. ► Interstitial copper ions were first drifted to surface region and allowed to back-diffuse. ► Boron concentration largely influenced the effect copper diffusivity. -- Abstract: The effective copper diffusivity (D{sub eff}) in boron-doped silicon wafer was measured using a Dynamic Secondary Ion Mass Spectrometry (D-SIMS) that was incorporated with an out-drift technique. By this technique, positive interstitial copper ions (Cu{sub I}{sup +}) migrated to the surface region when a continuous charge of electrons showered on the oxidized silicon wafer, which was also bombarded by primary O{sub 2}{sup +} ions. The Cu{sub I}{sup +} ions at the surface region diffused back to the bulk when the electron showering stopped. The D-SIMS recorded the real-time distribution of Cu{sub I}{sup +} ions, generating depth profiles for in-diffusion of copper for silicon-wafer samples with different boron concentrations. These were curve-fitted using the standard diffusion expressions to obtain different D{sub eff} values, and compared with other measurement techniques.

  9. Structural characterization of a high affinity mononuclear site in the copper(II)-α-synuclein complex.

    Science.gov (United States)

    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.

  10. Copper(I)- and copper(0)-promoted homocoupling and homocoupling-hydrodehalogenation reactions of dihalogenoclathrochelate precursors for C-C conjugated iron(II) bis-cage complexes.

    Science.gov (United States)

    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. Studying the Adsorption Behavior of Copper Ions in Industrial Wastewater, Using Modified Electrospun Polymeric Nano Fiber

    Directory of Open Access Journals (Sweden)

    Davood Kaviani

    2016-09-01

    Full Text Available Background & Aims of the Study:  Soil and water pollution to heavy metals is a serious threat for environment and human health. Finding an effective way for refining water from these metals is very important. The aim of this study was modifying electrospun polymeric nano fibers and studying its efficiency for copper ion omission in water solutions. Materials & Methods: In this study, nano fiber was produced by solution electrospun polystyrene in DMF/THF solvent and produced nano fiber was used for copper pre-concentration in waste water sample. In this study, an investigation of primary PH of solution, adsorption particle size, cleaning solvent volume, salt supply, contact time duration of adsorption material on copper ion adsorption supply was done, using modified nano fiber. Results: According to this study, copper adsorption process with correlation coefficient of (R2 in scope of 0.986 by Langmuir and Freundlich are describable. Findings show that, pH optimized amount for isolating copper ion on absorbent level is 7, absorbent particle size is 0.006 g/l, salt 1.3, potassium nitrate and the contact time of absorbent material on copper ion adsorption is 10 minutes. Copper ion adsorbate was cleaned, using 0.7 ml methanol. Most of obtrusive ions didn't have any inconvenience for copper ion isolation and measuring. The mean of the method was 2.7 µg/l and standard deviation was lower than %4. Conclusions: this method was done on actual samples which findings show that, this method has the ability of cooper adsorption and can use this method for measuring heavy metals like copper in different tissues. This method because of having the privilege for isolating and pre concentrating different kind of mineral and organic is used successfully in different samples.

  12. Syntheses, crystal structures, spectral and DFT studies of copper(II) and nickel(II) complexes with N‧-(pyridine-2-ylmethylene)acetohydrazide

    Science.gov (United States)

    Patel, Ram N.; Singh, Yogendra Pratap; Singh, Yogendra; Butcher, Ray J.; Zeller, Matthias; Singh, R. K. Bhubon; U-wang, Oinam

    2017-05-01

    Three new metal(II) complexes (copper(II)/nickel(II)) with N'-(pyridine-2-ylmethylene) acetohydrazide [Cu(HL)2]·(ClO4)21, [Ni(HL)2]·NO3·ClO4·0.5H2O 2 and [Cu(μ-CH3COO)(L)]2·4H2O 3 have been synthesized form N‧-(pyridine-2-ylmethylene) acetohydrazide (HL/L). The synthesized complexes were characterized by means of elemental analysis, spectroscopic, magnetic susceptibility and cyclic voltammetric measurements. Single crystal X-ray analysis of complexes has revealed the presence of a distorted octahedral geometry around mononuclear copper(II) and nickel(II) complex (1 and 2) and distorted square pyramidal geometry around copper(II) centers of complex 3. In the solid state Schiff base remains in its keto-tautomeric form. On complexation with Cu(II)/Ni(II) ions in natural or slightly acidic medium it coordinates through ketonic oxygen (keto form, HL) whereas in basic medium it acts as monoprotic (enol form, L) ligand. Variable-temperature magnetic susceptibility data of the compound 3 indicates the presence of weak antiferromagnetic interaction with J = -12.3 cm-1. The cyclic voltammograms of homobinuclear complex 3 in DMSO gave two irreversible waves which correspond to the Cu(II,II)/Cu(II,I) and Cu(II,I)/Cu(I,I) redox processes. On the other hand, the mononuclear complex 1 exhibited M(II)/M(I) quasireversible wave E1/2 = 0.06 V vs Ag/AgCl. X-band electron paramagnetic resonance (epr) data of copper(II) mononuclear and binuclear complexes 1 and 3 have been collected to investigate magnetic properties of the complexes in detail. The electronic structures, spectral properties of the ligands and the complexes have been explained by DFT and TD-DFT calculations. In addition, biological activity ranking of present complexes 1-3 are investigated theoretically. Complexes catalyzed the dismutation of superoxide (O2▪-) at biological pH in alkaline nitroblue tetrazolium chloride assay and IC50 values were evaluated.

  13. Preparation of poly(chitosan-acrylamide) flocculant using gamma radiation for adsorption of Cu(II) and Ni(II) ions

    Science.gov (United States)

    Saleh, Alaaeldine Sh.; Ibrahim, Ahmed G.; Abdelhai, Farag; Elsharma, Emad M.; Metwally, Essam; Siyam, Tharwat

    2017-05-01

    Poly(chitosan-acrylamide), P(CTS-AAm), flocculant was prepared using gamma radiation and used for the adsorption of copper(II) and nickel(II) from aqueous solutions. The effect of reaction parameters, such as acetic acid, monomer and polymer concentrations, and absorbed dose, on the conversion percentage and intrinsic viscosity of P(CTS-AAm) was investigated. The prepared polymer was characterized by Fourier-transform infrared and Thermogravimetric analysis. The factors influencing copper(II) and nickel(II) adsorption on P(CTS-AAm), such as contact time, solution pH, polymer and metal ion concentrations, were also studied. The sorption capacity of P(CTS-AAm) was 196.84 mg/g and 63.15 mg/g for Cu(II) and Ni(II), respectively.

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

    Science.gov (United States)

    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.

  15. Structures and Magnetic Properties of Monomeric Copper(II) Bromide Complexes with a Pyridine-Containing Tridentate Schiff Base

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Sung Kwon [Chungnam National Univ., Daejeon (Korea, Republic of); Yong, Soon Jung; Song, Young Kwang; Kim, Young Inn [Pusan National Univ., Busan (Korea, Republic of)

    2013-12-15

    Two novel copper(II) bromide complexes with pyridine containing Schiff base ligands, Cu(pmed)Br{sub 2} and Cu(dpmed)Br{sub 2} where pmed = N'-((pyridin-2-yl)methylene)ethane-1,2-diamine (pmed) and dpmed = N,N-diethyl-N'-((pyridin-2-yl)methylene)ethane-1,2-diamine (dpmed) were synthesized and characterized using Xray single crystal structure analysis, optical and magnetic susceptibility measurements. Crystal structural analysis of Cu(pmed)Br{sub 2} showed that the copper(II) ion has a distorted square-pyramidal geometry with the trigonality index of τ = 0.35 and two intermolecular hydrogen bonds, which result in the formation of two dimensional networks in the ab plane. On the other hand, Cu(dpmed)Br{sub 2} displayed a near square-pyramidal geometry with the value of τ = 0.06. In both compounds, the NNN Schiff base and one Br atom occupy the basal plane, whereas the fifth apical position is occupied by the other Br atom at a greater Cu-Br apical distance. The reported complexes show g{sub Π} > g{sub Τ} > 2.0023 with a d{sub x2-y2} ground state and a penta-coordinated square pyramidal geometry. Variable temperature magnetic susceptibility measurements showed that the developed copper(II) complexes follow the Curie-Weiss law, that is there are no magnetic interactions between the copper(II) ions since the Cu--Cu distance is too far for magnetic contact.

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

    Science.gov (United States)

    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).

  17. Effective inhibition of the early copper ion burst release with ultra-fine grained copper and single crystal copper for intrauterine device application.

    Science.gov (United States)

    Xu, X X; Nie, F L; Wang, Y B; Zhang, J X; Zheng, W; Li, L; Zheng, Y F

    2012-02-01

    To solve the main problems of existing coarse grained copper (CG Cu) intrauterine devices (IUD)-namely burst release and a low transfer efficiency of the cupric ions during usage-ultra-fine grained copper (UFG Cu) and single crystal copper (SC Cu) have been investigated as potential substitutes. Their corrosion properties with CG Cu as a control have been studied in simulated uterine fluid (SUF) under different conditions using electrochemical measurement methods. Long-term immersion of UFG Cu, SC Cu and CG Cu samples in SUF at 37 °C have been studied for 300 days. A lower copper ion burst release and a higher efficiency release of cupric ions were observed for UFG Cu and SC Cu compared with CG Cu in the first month of immersion and 2 months later. The respective corrosion mechanisms for UFG Cu, SC Cu and CG Cu in SUF are proposed. In vitro biocompatibility tests show a better cellular response to UFG Cu and SC Cu than CG Cu. In terms of instantaneous corrosion behavior, long-term corrosion performance and in vitro biocompatibility, the three pure copper materials follow the order: UFG Cu>SC Cu>CG Cu, which indicates that UFG Cu could be the most suitable candidate material for intrauterine devices.

  18. Biosorption of copper (II) onto immobilized cells of Pycnoporus sanguineus from aqueous solution: Equilibrium and kinetic studies

    Energy Technology Data Exchange (ETDEWEB)

    Yus Azila Yahaya [School of Chemical Engineering, Universiti Sains Malaysia, Seri Ampangan, 14300 Nibong Tebal, Seberang Prai Selatan, Pulau Pinang (Penang) (Malaysia); Mashitah Mat Don [School of Chemical Engineering, Universiti Sains Malaysia, Seri Ampangan, 14300 Nibong Tebal, Seberang Prai Selatan, Pulau Pinang (Penang) (Malaysia)], E-mail: chmashitah@eng.usm.my; Subhash Bhatia [School of Chemical Engineering, Universiti Sains Malaysia, Seri Ampangan, 14300 Nibong Tebal, Seberang Prai Selatan, Pulau Pinang (Penang) (Malaysia)

    2009-01-15

    The ability of white-rot fungus, Pycnoporus sanguineus to adsorb copper (II) ions from aqueous solution is investigated in a batch system. The live fungus cells were immobilized into Ca-alginate gel to study the influence of pH, initial metal ions concentration, biomass loading and temperature on the biosorption capacity. The optimum uptake of Cu (II) ions was observed at pH 5 with a value of 2.76 mg/g. Biosorption equilibrium data were best described by Langmuir isotherm model followed by Redlich-Peterson and Freundlich models, respectively. The biosorption kinetics followed the pseudo-second order and intraparticle diffusion equations. The thermodynamic parameters enthalpy change (10.16 kJ/mol) and entropy change (33.78 J/mol K) were determined from the biosorption equilibrium data. The FTIR analysis showed that -OH, -NH, C-H, C=O, -COOH and C-N groups were involved in the biosorption of Cu (II) ions onto immobilized cells of P. sanguineus. The immobilized cells of P. sanguineus were capable of removing Cu (II) ions from aqueous solution.

  19. Copper(II)-EDTA sorption onto chitosan and its regeneration applying electrolysis.

    Science.gov (United States)

    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.

  20. Synthesis, characterization and cyclic voltammetric study of copper(II) and nickel(II) polymer chelates.

    Science.gov (United States)

    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).

  1. A new copper(II) complex with 2-thenoyltrifluoroacetone and 2,2-bipyridine: Crystal structure, spectral properties and cytotoxic activity

    Science.gov (United States)

    Lopes, P. S.; Paixão, D. A.; de Paula, F. C. S.; Ferreira, A. M. D. C.; Ellena, J.; Guilardi, S.; Pereira-Maia, E. C.; Guerra, W.

    2013-02-01

    This work reports the synthesis and characterization of a new copper(II) complex with 2-thenoyltrifluoroacetone (HTTA) and 2,2-bipyridine (bipy). The complex was characterized by elemental analysis, UV-Vis, IR and EPR. The crystal structure was determined by single-crystal X-ray diffraction. The copper ion has a distorted square-pyramidal geometry and is coordinated to two bidentate ligands (HTTA and bipy) and a perchlorate ion weakly bonded in the apical position. The crystal packing is stabilized by non-classical hydrogen bonds and weak interactions π-π stacking. In the copper complex, the metal ion binds to HTTA via the oxygen atoms of the β-diketone group and to bipy via its two heterocyclic nitrogens. The title compound inhibits the growth of K562 cells with an IC50 value equal to 28.2 μmol L-1.

  2. DNA degradation by aqueous extract of Aloe vera in the presence of copper ions.

    Science.gov (United States)

    Naqvi, Shoa; Ullah, M F; Hadi, S M

    2010-06-01

    The plant Aloe vera has long been used in medicine, as dietary supplements and for cosmetic purposes. Aloe vera extracts are a rich source of polyphenols, such as aloin and aloe emodin and have shown a wide range of pharmacological properties, including anti-inflammatory and anti-cancer properties. The bioactive component aloe emodin has been reported to induce apoptosis in various cancer cell lines. Many of the biological activities of Aloe vera have been attributed to its antioxidant properties. However, most plant-derived polyphenols that are also present in Aloe vera may exhibit pro-oxidant properties either alone or in the presence of transition metals, such as copper. Previous reports from this laboratory have implicated the pro-oxidant action as one of the mechanisms for their anti-cancer properties. In the present paper, we show that aqueous extract of Aloe vera is also able to cause DNA degradation in the presence of copper ions. Further, the extract is also able to reduce Cu(II) to Cu(I) and generate reactive oxygen species, such as superoxide anion and hydroxyl radicals in a dose-dependent manner, which correlates with ability of the extract to cause DNA breakage. Thus, the study shows that in addition to antioxidant activity, Aloe vera extract also possess pro-oxidant properties, leading to oxidative DNA breakage.

  3. Recovery of copper ion by flotation with potassium amylxanthate; Recuperacion de iones cobre por flotacion con amilxantato de potasio

    Energy Technology Data Exchange (ETDEWEB)

    Ramirez-Serrano, B.; Coello-Velazquez, A. L.; Bernardo, A.; Afif, E.; Menendez-Aguado, J. M.

    2012-11-01

    In this paper a study about the column flotation process of copper ion employing potassium amylxanthate as collector reagent is carried out. The effect on the recovery of copper ion by the modification of variables such as collector/metal relation and surface velocity of gas and liquid was determined experimentally by the analysis of the statistic-mathematical model of the copper flotation process, as well as the physico-chemical phenomena that take place, showing the effect of the collector/metal relation in the process. The effect of pH as the main properties of the chemical system in the recovery and the kinetic of the flotation process is made too. The experimental results shows that the recovery of copper in the pH range of 4,5 - 12 is possible with prevalence of precipitate flotation. (Author) 43 refs.

  4. Visible-light-induced water oxidation by a hybrid photocatalyst consisting of bismuth vanadate and copper(II) meso-tetra(4-carboxyphenyl)porphyrin.

    Science.gov (United States)

    Nakashima, Shu; Negishi, Ryo; Tada, Hiroaki

    2016-03-04

    Copper(II) meso-tetra(4-carboxyphenyl)porphyrin surface-modified monoclinic scheelite bismuth vanadate (CuTCPP/BiVO4) has been synthesized via a two-step route involving chemisorption of TCPP on BiVO4 and successive Cu(II) ion incorporation into the TCPP, and the surface modification drastically enhances the water oxidation to oxygen (O2) under visible-light irradiation (λ > 430 nm).

  5. The two spin states of an end-on copper(II)-superoxide mimic.

    Science.gov (United States)

    Askari, Mohammad S; Girard, Brigitte; Murugesu, Muralee; Ottenwaelder, Xavier

    2011-07-28

    The reaction of nitrosobenzene with copper(I) complexes of a tetradentate ligand led to two novel species that are best described as copper(II) complexes of an O-bonded nitrosobenzyl radical anion, in either the singlet or the triplet spin-state. Both states were characterized by crystal structures, magnetic measurements and DFT calculations.

  6. New insights into single-compound and binary adsorption of copper and lead ions on a treated sea mango shell: experimental and theoretical studies.

    Science.gov (United States)

    Sellaoui, Lotfi; Edi Soetaredjo, Felycia; Ismadji, Suryadi; Cláudio Lima, Éder; Dotto, Guilherme L; Ben Lamine, Abdelmottaleb; Erto, Alessandro

    2017-09-21

    Herein, adsorption isotherms of Pb(ii) and Cu(ii) ions on treated sea mango fruit in both single-compound and binary systems were experimentally realized at different temperatures in the range of 30-50 °C. Experimental results show that adsorption of Pb(ii) was more as compared to that of Cu(ii) ions; however, for both ions, a significant reduction in the adsorption capacity was observed in the binary system as compared to that in the single-compound systems. Moreover, under all the investigated conditions, adsorption seems to be promoted by an increase in temperature. To understand and interpret the experimental evidences, the Hill and competitive Hill models developed on the basis of the grand canonical ensemble were applied for the analysis of adsorption equilibrium data. These models contain some physicochemical parameters that allow an exhaustive analysis of the dynamics of single-compound and binary adsorptions. Based on the fitting results, in particular, through the evaluation of the number of ions bonded per site (n and ni), it was found that lead and copper ions interacted by inclined and horizontal positions on treated sea mango in single-compound and binary systems, respectively. In addition, based on the same parameters, a significant interaction between ions was retrieved. A study focused on the saturation adsorption capacity in single-compound and binary systems affirmed that the adsorbent was more selective for lead than for copper. The reduction of the adsorbed capacity ratio between the binary and single-compound systems (i.e. Qb/Qs) explained and confirmed that an inhibition effect between copper and lead ions at the same receptor site occurred. Finally, based on the energetic investigations, it was deduced that the adsorption energy represented the dominant factor promoting the greater adsorption of lead than that of copper in both systems.

  7. Silica nanoparticles functionalized with polyamidoamine (PAMAM) dendrimers as platforms for photoluminescence (PL) sensing of copper and cyanide ions.

    Science.gov (United States)

    Gerrans, Kateryna; Luhrs, Alicia; Feider, Clara; Margerum, Lawrence D

    2016-05-15

    Functionalized nanoparticles for photoluminescence (PL) applications are a promising technology for biomedical imaging and as sensors for small molecules. This work presents a new method to modify silica nanoparticles (SNP) using the bifunctional linker 1,1'-carbonyldiimidazole (CDI) with a series of polyamidoamine (PAMAM) dendrimer molecules followed by grafting of fluorescein isothiocyanate (FITC) or rhodamine B isothiocyanate (RITC) to create platforms for photoluminescence (PL) sensors. A dendrimer size and charge-variable response to only copper(II) ions confirmed the prediction of a selective turn-off sensor via proximity quenching. Both dye density and Cu(2+) quenching efficiency peaked with SNP-dendrimer generation 4 (64 terminal amines). In addition, changing the terminal dendrimer arms to carboxylic acid end groups increased the copper quenching suggesting that more metal ion binding sites were created in close proximity to the dyes. Of the small anions tested for a turn-off sensor, only cyanide ion fully restored the PL when reaching a 2:1 CN(-):Cu(2+) ratio, while EDTA was not as effective at the same ratio. Therefore, dendrimer size and surface charge on the nanoparticles controlled the dye loading and copper quenching efficiency, while creating multiple binding sites for cyanide over other metal binding anions. Copyright © 2016 Elsevier Inc. All rights reserved.

  8. 乙二胺改性木屑黄原酸盐对水溶液中Cu(II)和Ni(II)离子吸附平衡及动力学%Kinetics and equilibrium adsorption of copper(II) and nickel(II) ions from aqueous solution using sawdust xanthate modified with ethanediamine

    Institute of Scientific and Technical Information of China (English)

    夏璐; 胡伊旭; 张博涵

    2014-01-01

    Sawdust xanthate modified with ethanediamine was used for the removal of Cu(II) and Ni(II) from aqueous solution. The influence of various operating parameters such temperature and adsorbent dosage on the adsorption isotherms of modified sawdust was investigated. Thermodynamic parameters, namely Gibbs free energy (∆GΘ), enthalpy (∆HΘ) and entropy (∆SΘ) of Cu(II) and Ni(II) adsorption process were calculated, showing that the adsorption is a spontaneous and exothermic process. The modified extended Langmuir equation approaches provide excellent prediction of the binary adsorption. In single and binary systems, the overall adsorption data were best described by the pseudo-second order kinetic model, then the calculated values of activation energy of Cu(II) and Ni(II) adsorption process were 59.12 and 55.92 kJ/mol respectively. The results show that the affinity of each metal ion onto the modified sawdust surface is influenced by the presence of the other one.%使用乙二胺改性的木屑黄原酸盐对水溶液中的Cu(II)、Ni(II)离子进行吸附。在单离子体系中,考虑影响因素(温度、投加量)对Cu(II)、Ni(II)单离子吸附等温线的影响;并计算Cu(II)、Ni(II)离子吸附的热力学参数:吸附吉布斯自由能(∆GΘ)、吸附过程的焓变(∆HΘ)以及熵变(∆SΘ),表明此吸附是一个放热自发的过程。在 Cu(II)和Ni(II)双离子体系中,采用修正后的拓展Langmuir模型对体系的吸附情况可以进行很好的预测。在单离子体系和双离子体系中,吸附过程的数据均可通过准二级动力学模型进行描述;计算得到其对Cu(II)和Ni(II)单离子的吸附活化能分别为59.12和55.92 kJ/mol。结果表明,金属离子在改性木屑表面的吸附效果会受到另一离子存在的影响。

  9. Electrochemical removal of copper ions from dilute solutions using packed bed electrode. Part ІІ

    Directory of Open Access Journals (Sweden)

    I.A. Khattab

    2013-06-01

    Full Text Available Conversion of soluble precious copper ions into a solid form in dilute wastewater effluents for further reuse was studied by using a packed-bed cell. The cathode packing consisted of graphite particles that have an average particle size of 0.125 cm. The effects of electrolysis time and initial copper concentration were studied. The cell was found to be effective in reducing metal ion concentration to less than 0.05% of the initial concentration and maximum current efficiency reached upto 96.2% for dilute copper solution (100 mg/l. It was observed that using this cell was effective in reducing copper ion concentration from 100 mg/l to less than 4 mg/l.

  10. Mechanistic studies of copper(II)-aminoglycoside mediated DNA damage and magnesium catalyzed nuclease activity of hammerhead ribozyme

    Science.gov (United States)

    Patwardhan, Anjali A.

    The antibacterial activity of aminoglycosides stems from their high affinity binding to the 16S rRNA in bacteria resulting in inhibition of protein synthesis. Used to treat acute bacterial infections these antibiotics have limited applications due to their high dosage requirements and the emergence of resistant strains. We have synthesized and characterized Cu(II) derivatives of the aminoglycosides, kanamycin A, tobramycin, neamine, kanamycin B, neomycin B, and paromomycin. The first three exhibit preferential and tight binding to Cu(II) as against neomycin B and kanamycin B and paromomycin. EPR of frozen solutions and UV-visible spectroscopy suggest a change in geometry around the Cu(II) but the stabilities of the complexes in water differ. These copper derivatives efficiently cleave plasmid DNA at micromolar concentrations (hydrolytic) and at nanomolar concentrations in the presence co-reactants like hydrogen peroxide or ascorbic acid. Hydrolysis is multi turnover and exhibits Michelis-Menten kinetics with enzyme-like behavior whereas oxidative cleavage is highly specific with C-4' H abstraction resulting in characteristic base propenal and nucleotide base products. Hydroxyl radicals generated are copper based and are generated in close proximity of the substrate. Hammerhead ribozymes are selectively hydrolyzed in the presence of divalent ions with Mg2+ being the metal ion of choice in vivo . Our studies with complex ions like cobalt hexaammine and fac-triamminetriaquochromium(III) establish outer sphere interactions of Mg2+ with the hammerhead in the catalytic site. There are two sets of sites, one structural and one catalytic. Complex ions in the catalytic site and divalent ions in the structural site result in a slow but active hammerhead ribozyme suggesting that the complex ions are not inhibitory, contrary to what was suggested previously.

  11. Zn(II) ions substantially perturb Cu(II) ion coordination in amyloid-β at physiological pH.

    Science.gov (United States)

    Silva, K Ishara; Saxena, Sunil

    2013-08-15

    The interaction of Cu(II) and Zn(II) ions with amyloid-β (Aβ) plays an important role in the etiology of Alzheimer's disease. We describe the use of electron spin resonance (ESR) to measure metal-binding competition between Cu(II) and Zn(II) in amyloid-β at physiological pH. Continuous wave ESR measurements show that the affinity of Cu(II) toward Aβ(1-16) is significantly higher than that of Zn(II) at physiological pH. Importantly, of the two known Cu(II) coordination modes in Aβ, component I and component II, Zn(II) displaces Cu(II) only from component I. Our results indicate that at excess amounts of Zn(II) component II becomes the most dominant coordination mode. This observation is important as Aβ aggregates in the brain contain a high Zn(II) ion concentration. In order to determine details of the metal ion competition, electron spin echo envelope modulation experiments were carried out on Aβ variants that were systematically (15)N labeled. In the presence of Zn(II), most peptides use His 14 as an equatorial ligand to bind Cu(II) ions. Interestingly, Zn(II) ions completely substitute Cu(II) ions that are simultaneously coordinated to His 6 and His 13. Furthermore, in the presence of Zn(II), the proportion of Cu(II) ions that are simultaneously coordinated to His 13 and His 14 is increased. On the basis of our results we suggest that His 13 plays a critical role in modulating the morphology of Aβ aggregates.

  12. Styrene Oxidation by Copper(II) Complexes Salen-Type Encapsulated into Nay Zeolite

    National Research Council Canada - National Science Library

    I. Kuźniarska-Biernacka; M.A. Carvalho; I. Correia Neves; A. M. Fonseca; A. Lisińska-Czekaj; D. Czekaj

    2013-01-01

    The copper(II) complex with a Schiff-base salen-type ligand has been encapsulated in the nanopores of a NaY zeolite by using two different methodologies, the flexible ligand and in situ complex preparation methods...

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

    Energy Technology Data Exchange (ETDEWEB)

    Mahjoub, Omima Abdalla; Farina, Yang [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor (Malaysia)

    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.

  14. The crystal structure of paramagnetic copper(ii) oxalate (CuC2O4):

    DEFF Research Database (Denmark)

    Christensen, Axel Nørlund; Lebech, Bente; Andersen, Niels Hessel

    2014-01-01

    Synthetic copper(ii) oxalate, CuC2O4, was obtained in a precipitation reaction between a copper(ii) solution and an aqueous solution of oxalic acid. The product was identified from its conventional X-ray powder patterns which match that of the copper mineral Moolooite reported to have the composi...

  15. Mechanism of copper(II)-induced misfolding of Parkinson's disease protein.

    Science.gov (United States)

    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.

  16. Highly cytotoxic DNA-interacting copper(II) coordination compounds.

    Science.gov (United States)

    Brissos, Rosa F; Torrents, Ester; dos Santos Mello, Francyelli Mariana; Carvalho Pires, Wanessa; Silveira-Lacerda, Elisângela de Paula; Caballero, Ana B; Caubet, Amparo; Massera, Chiara; Roubeau, Olivier; Teat, Simon J; Gamez, Patrick

    2014-10-01

    Four new Schiff-base ligands have been designed and prepared by condensation reaction between hydrazine derivatives (i.e. 2-hydrazinopyridine or 2-hydrazinoquinoline) and mono- or dialdehyde (3-tert-butyl-2-hydroxybenzaldehyde and 5-tert-butyl-2-hydroxyisophthalaldehyde, respectively). Six copper(II) coordination compounds of various nuclearities have been obtained from these ligands, which are formulated as [Cu(L1)Cl](CH3OH) (1), [Cu(L2)NO3] (2), [Cu2(L3)(ClO4)2(CH3O)(CH3OH)](CH3OH) (3), [Cu2(L4)(ClO4)(OH)(CH3OH)](ClO4) (4), [Cu8(L3)4(NO3)4(OH)5](NO3)3(CH3OH)5(H2O)8 (5) and [Cu3(HL2')4Cl6](CH3OH)6 (6), as revealed by single-crystal X-ray studies. Their DNA-interacting abilities have been investigated using different characterization techniques, which suggest that the metal complexes act as efficient DNA binders. Moreover, cytotoxicity assays with several cancer cell lines show that some of them are very active, as evidenced by the sub-micromolar IC50 values achieved in some cases.

  17. Antimicrobial evaluation of copper sulfate (II) on strains of Enterococcus faecalis. In vitro study.

    OpenAIRE

    Marisol Sierra; Aldo Sanhueza; Rául Alcántara; Gabriela Sánchez

    2013-01-01

    ABSTRACT Introduction: Controlling Enterococcus faecalis is of vital importance in endodontics, as this pathogen is associated with endodontic failure. Experimental evidence has shown that copper has antibacterial activity against other pathogens with similar characteristics. The objective of this study was to determine the antimicrobial activity of copper (II) or cupric (SC-II) sulfate on strains of Enterococcus faecalis and to compare it with the most commonly used antimicrobials. Methodol...

  18. Antioxidant Promotion of Tyrosine Nitration in the Presence of Copper(II)

    OpenAIRE

    Qiao, Liang; Liu, Baohong; Girault, Hubert

    2013-01-01

    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 β-amyloid peptide and angiotensin I. These stu...

  19. Photophysical studies of the interactions of poly(amidoamine) generation zero (PAMAM G0) with copper and zinc ions

    Energy Technology Data Exchange (ETDEWEB)

    López-Cabaña, Z.E. [Laboratory of Asymmetric Synthesis, Chemistry Institute of Natural Resources, University of Talca (Chile); Valdés, O. [Nanobiotechnology Division at University of Talca, Fraunhofer Chile Research Foundation – Center for Systems Biotechnology, FCR-CSB, P.O. Box 747 Talca (Chile); Vergara, C.E. [Laboratory of Asymmetric Synthesis, Chemistry Institute of Natural Resources, University of Talca (Chile); Camarada, M.B. [Universidad Andrés Bello, Facultad de Biología, Center for Bioinformatics and Integrative Biology (CBIB), República 239, Santiago (Chile); Fundación Fraunhofer Chile Research, M. Sánchez Fontecilla 310 piso 14, Las Condes (Chile); Nachtigall, F.M. [Nanobiotechnology Division at University of Talca, Fraunhofer Chile Research Foundation – Center for Systems Biotechnology, FCR-CSB, P.O. Box 747 Talca (Chile); González-Nilo, F.D. [Universidad Andrés Bello, Facultad de Biología, Center for Bioinformatics and Integrative Biology (CBIB), República 239, Santiago (Chile); Fundación Fraunhofer Chile Research, M. Sánchez Fontecilla 310 piso 14, Las Condes (Chile); Santos, Leonardo S., E-mail: lssantos@utalca.cl [Laboratory of Asymmetric Synthesis, Chemistry Institute of Natural Resources, University of Talca (Chile); Nanobiotechnology Division at University of Talca, Fraunhofer Chile Research Foundation – Center for Systems Biotechnology, FCR-CSB, P.O. Box 747 Talca (Chile)

    2015-08-15

    This study reports the photophysical behavior of poly(amidoamine) generation zero (PAMAM G0) in the presence of Cu(II) and Zn(II) ions in aqueous solutions using absorption and fluorescence spectroscopy. Theoretical and experimental results confirmed the presence of a strong covalent metal–ligand interaction between PAMAM G0 and copper ion that favored the formation of a ligand–metal charge transfer band coordination complex. In the case of Zn(II), no complex formation with PAMAM G0 was registered. Structure analysis identified the presence of aggregate like PAMAM G0–Zn moieties that generated an enhancement in the fluorescence emission of PAMAM G0. - Highlights: • Photophysical behavior of PAMAM G0 dendrimer with Cu and Zn ions was studied. • Strong covalent metal–ligand interaction was confirmed between PAMAM G0–Cu(II). • No complex formation with PAMAM G0 was registered in the case of Zn(II). • Dendrimer aggregate generated an enhancement in fluorescence emission.

  20. Mixed matrix membranes for efficient adsorption of copper ions from aqueous solutions

    NARCIS (Netherlands)

    Tetala, K.K.R.; Stamatialis, Dimitrios

    2013-01-01

    This work presents adsorption of copper (Cu2+) ions from aqueous solutions using mixed matrix membrane (MMM) and its elution afterwards. The developed flat sheet MMM, comprises of chitosan beads incorporated in Ethylene vinyl alcohol (EVAL) polymer porous matrix and exhibits static Cu2+ ion

  1. Ligand-assisted, copper(II) acetate-accelerated azide-alkyne cycloaddition.

    Science.gov (United States)

    Michaels, Heather A; Zhu, Lei

    2011-10-04

    Polytriazole ligands such as the widely used tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine (TBTA), are shown to assist copper(II) acetate-mediated azide-alkyne cycloaddition (AAC) reactions that involve nonchelating azides. Tris(2-{4-[(dimethylamino)methyl]-1H-1,2,3-traizol-1-yl}ethyl)amine (DTEA) outperforms TBTA in a number of reactions. The satisfactory solubility of DTEA in a wide range of polar and nonpolar solvents, including water and toluene, renders it advantageous under copper(II) acetate-mediated conditions. The copper(II) acetate-mediated formation of the three triazolyl groups in a tris(triazolyl)-based ligand occurs sequentially with an inhibitory effect in the last step. The kinetic investigations of the ligand-assisted reactions reveal an interesting mechanistic dependence on the relative affinity of azide and alkyne to copper (II). In addition to expanding the scope of the copper(II) acetate-mediated AAC reactions to include nonchelating azides, this work offers evidence for the mechanistic synergy between the title reaction and the alkyne oxidative homocoupling reaction. The elucidation of the structural details of the polytriazole-ligand-bound reactive species in copper(I/II)-mediated AAC reactions, however, awaits further characterization of the metal coordination chemistry of polytriazole ligands. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Fabrication of interfacial functionalized porous polymer monolith and its adsorption properties of copper ions.

    Science.gov (United States)

    Han, Jiaxi; Du, Zhongjie; Zou, Wei; Li, Hangquan; Zhang, Chen

    2014-07-15

    The interfacial functionalized poly (glycidyl methacrylate) (PGMA) porous monolith was fabricated and applied as a novel porous adsorbent for copper ions (Cu(2+)). PGMA porous material with highly interconnected pore network was prepared by concentrated emulsion polymerization template. Then polyacrylic acid (PAA) was grafted onto the interface of the porous monolith by the reaction between the epoxy group on PGMA and a carboxyl group on PAA. Finally, the porous monolith was interfacial functionalized by rich amount of carboxyl groups and could adsorb copper ions effectively. The chemical structure and porous morphology of the porous monolith were measured by Fourier transform infrared spectroscopy and scanning electron microscopy. Moreover, the effects of pore size distribution, pH value, co-existing ions, contacting time, and initial concentrations of copper ions on the adsorption capacity of the porous adsorbents were studied.

  3. Ligand effects on the structures and magnetic properties of tricyanomethanide-containing copper(II) complexes.

    Science.gov (United States)

    Yuste, Consuelo; Bentama, Abdeslem; Stiriba, Salah-Eddine; Armentano, Donatella; De Munno, Giovanni; Lloret, Francesc; Julve, Miguel

    2007-11-28

    The preparation, crystal structure and magnetic properties of four heteroleptic copper(II) complexes with the tricyanomethanide (tcm(-)) and the heterocyclic nitrogen donors 3,6-bis(2-pyridyl)pyridazine (dppn), 2,5-bis(2-pyridyl)pyrazine (2,5-dpp), 2,3-bis(2-pyridyl)pyrazine (2,3-dpp) and 2,3-bis(2-pyridyl)quinoxaline (2,3-dpq) are reported, {[Cu(2)(dppn)(OH)(tcm)(2)] x tcm}(n) (1), {[Cu(2,5-dpp)(tcm)] x tcm}(n) (2), {[Cu(2)(2,3-dpp)(2)(tcm)(3)(H(2)O)(0.5)] x tcm x 0.5H(2)O}(n) (3) and [Cu(2,3-dpq)(tcm)(2)](n) (4). 1 has a ladder-like structure with single mu-1,5-tcm ligands forming the sides and a bis-bidentate dppn and a single mu-hydroxo providing the rung. Each copper atom in 1 exhibits a distorted square pyramidal CuN(4)O surrounding: the basal plane is built by the hydroxo-oxygen, a nitrile-nitrogen atom from a tcm group and one pyrazine and a pyridyl nitrogen atoms from the dppn whereas the apical position is filled by a nitrile-nitrogen atom from a symmetry-related tcm ligand. The structures of 2-4 consists of zig-zag (2 and 3)/linear (4) chains of copper(II) ions which are bridged by either bis-bidentate 2,5-dpp (2) and 2,3-dpp (3) molecules or single mu-1,5-tcm (4) groups. The copper atoms in 2 and 4 are five coordinated with distorted trigonal bipyramidal (2) and square pyramidal (4) CuN(5) surroundings. The axial positions in 2 are occupied by two pyridyl-nitrogen atoms from two 2,5-dpp ligands whereas the trigonal plane is built by a nitrile-nitrogen from a terminally bound tcm group and two pyrazine nitrogen atoms from two 2,5-dpp molecules. The basal plane in 4 is defined by a pyridyl and a pyrazine nitrogen atoms from the bidentate 2,3-dpq ligand and two nitrile nitrogen atoms from two tcm groups (one terminal and the other bridging) whereas the apical position is filled by a nitrile nitrogen from another tcm ligand. The crystallographically independent copper atoms in 3 [Cu(1) and Cu(2)] exhibit elongated octahedral geometries being defined by four

  4. Mechanism of Formation of Copper(II) Chloro Complexes Revealed by Transient Absorption Spectroscopy and DFT/TDDFT Calculations.

    Science.gov (United States)

    Mereshchenko, Andrey S; Olshin, Pavel K; Karabaeva, Kanykey E; Panov, Maxim S; Wilson, R Marshall; Kochemirovsky, Vladimir A; Skripkin, Mikhail Yu; Tveryanovich, Yury S; Tarnovsky, Alexander N

    2015-07-16

    Copper(II) complexes are extremely labile with typical ligand exchange rate constants on the order of 10(6)-10(9) M(-1) s(-1). As a result, it is often difficult to identify the actual formation mechanism of these complexes. In this work, using UV-vis transient absorption when probing in a broad time range (20 ps to 8 μs) in conjunction with DFT/TDDFT calculations, we studied the dynamics and underlying reaction mechanisms of the formation of extremely labile copper(II) CuCl4(2-) chloro complexes from copper(II) CuCl3(-) trichloro complexes and chloride ions. These two species, produced via photochemical dissociation of CuCl4(2-) upon 420 nm excitation into the ligand-to-metal-charge-transfer electronic state, are found to recombine into parent complexes with bimolecular rate constants of (9.0 ± 0.1) × 10(7) and (5.3 ± 0.4) × 10(8) M(-1) s(-1) in acetonitrile and dichloromethane, respectively. In dichloromethane, recombination occurs via a simple one-step addition. In acetonitrile, where [CuCl3](-) reacts with the solvent to form a [CuCl3CH3CN](-) complex in less than 20 ps, recombination takes place via ligand exchange described by the associative interchange mechanism that involves a [CuCl4CH3CN](2-) intermediate. In both solvents, the recombination reaction is potential energy controlled.

  5. Chelation-assisted, copper(II)-acetate-accelerated azide-alkyne cycloaddition.

    Science.gov (United States)

    Kuang, Gui-Chao; Michaels, Heather A; Simmons, J Tyler; Clark, Ronald J; Zhu, Lei

    2010-10-01

    We described in a previous communication a variant of the popular Cu(I)-catalyzed azide-alkyne cycloaddition (AAC) process where 5 mol % of Cu(OAc)(2) in the absence of any added reducing agent is sufficient to enable the reaction. 2-Picolylazide (1) and 2-azidomethylquinoline (2) were found to be by far the most reactive carbon azide substrates that convert to 1,2,3-triazoles in as short as a few minutes under the discovered conditions. We hypothesized that the abilities of 1 and 2 to chelate Cu(II) contribute significantly to the observed high reaction rates. The current work examines the effect of auxiliary ligands near the azido group other than pyridyl for Cu(II) on the efficiency of the Cu(OAc)(2)-accelerated AAC reaction. The carbon azides capable of binding to the catalytic copper center at the alkylated azido nitrogen in a chelatable fashion were indeed shown to be superior substrates under the reported conditions. The chelation between carbon azide 11 and Cu(II) was demonstrated in an X-ray single-crystal structure. In a limited set of examples, the ligand tris(benzyltriazolylmethyl)amine (TBTA), developed by Fokin et al. for assisting the original Cu(I)-catalyzed AAC reactions, also dramatically enhances the Cu(OAc)(2)-accelerated AAC reactions involving nonchelating azides. This observation leads to the hypothesis of an additional effect of chelating azides on the efficiencies of Cu(OAc)(2)-accelerated AAC reactions, which is to facilitate the rapid reduction of Cu(II) to highly catalytic Cu(I) species. Mechanistic studies on the AAC reactions with particular emphasis on the role of carbon azide/copper interactions will be conducted based on the observations reported in this work. Finally, the immediate utility of the product 1,2,3-triazole molecules derived from chelating azides as multidentate metal coordination ligands is demonstrated. The resulting triazolyl-containing ligands are expected to bind with transition metal ions via the N(2) nitrogen of

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

    Science.gov (United States)

    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.

  7. Kinetic and equilibrium studies for the adsorption process of cadmium(II) and copper(II) onto Pseudomonas aeruginosa using square wave anodic stripping voltammetry method

    Energy Technology Data Exchange (ETDEWEB)

    Kong Bo; Tang Biyu; Liu Xiaoying; Zeng Xiandong; Duan Haiyan [State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Hunan, Changsha 410082 (China); Luo Shenglian, E-mail: kongbo2136@163.com [State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Hunan, Changsha 410082 (China); Wei Wanzhi [State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Hunan, Changsha 410082 (China)

    2009-08-15

    A novel method for the simultaneous determination of cadmium(II) and copper(II) during the adsorption process onto Pseudomonas aeruginosa was developed. The concentration of the free metal ions was successfully detected by square wave anodic stripping voltammetry (SWASV) on the mercaptoethane sulfonate (MES) modified gold electrode, while the P. aeruginosa was efficiently avoided approaching to the electrode surface by the MES monolayer. And the anodic stripping peaks of Cd{sup 2+} and Cu{sup 2+} appear at -0.13 and 0.34 V respectively, at the concentration range of 5-50 {mu}M, the peak currents of SWASV present linear relationships with the concentrations of cadmium and copper respectively. As the determination of Cd{sup 2+} and Cu{sup 2+} was in real time and without pretreatment, the kinetic characteristics of the adsorption process were studied and all the corresponding regression parameters were obtained by fitting the electrochemical experimental data to the pseudo-second-order kinetic model. Moreover, Langmuir and Freundlich models well described the biosorption isotherms. And there were some differences in the amount of metal ion adsorbed at equilibrium (q{sub e}) and other kinetics parameters when the two ions coexisted were compared with the unaccompanied condition, which were also discussed in this paper. The proposed electrode system provides excellent platform for the simultaneous determination of trace metals in complex biosorption process.

  8. The role of terminal amino group and histidine at the fourth position in the metal ion binding of oligopeptides revisited: Copper(II) and nickel(II) complexes of glycyl-glycyl-glycyl-histamine and its N-Boc protected derivative.

    Science.gov (United States)

    Jancsó, Attila; Selmeczi, Katalin; Gizzi, Patrick; Nagy, Nóra V; Gajda, Tamás; Henry, Bernard

    2011-01-01

    Copper(II) and nickel(II) binding properties of two pseudo tetrapeptides, N-Boc-Gly-Gly-Gly-Histamine (BGGGHa) and Gly-Gly-Gly-Histamine (GGGHa) have been investigated by pH-potentiometric titrations, UV-visible-, EPR-, NMR- and ESI-HRMS (electrospray ionization high resolution MS) spectroscopies, in order to compare the role of N-terminal amino group and imidazole moiety at the fourth position in the complex formation processes. Substantially higher stabilities were determined for the ML complexes of GGGHa, compared to those of BGGGHa, supporting the coordination of the terminal amino group and the histamine imidazole of the non-protected ligand. A dimeric Cu(2)H(-2)L(2) species, formed through the deprotonation of peptide groups of the ligands, was found in the GGGHa-copper(II) system. Deprotonation and coordination of further amide nitrogens led to CuH(-2)L and, above pH~10, CuH(-3)L. Experimental data supports a {NH(2), 2 × N(amide),N(im)} macrochelate structure in CuH(-2)L whereas a {NH(2), 3 × N(amide)} coordination environment in CuH(-3)L. The first two amide deprotonation processes were found to be strongly cooperative with nickel(II) and spectroscopic studies proved the transformation of the octahedral parent complexes to square planar, yellow, diamagnetic species, NiH(-2)L and above pH~9, NiH(-3)L. In the basic pH-range deprotonation and coordination of the amide groups also took place in the BGGGHa containing systems, leading to complexes with a {3 × N(amide),N(im)} donor set, and in parallel the re-dissolving of precipitate. Above pH~11, a further proton release from the pyrrolic NH group of the imidazole ring of BGGGHa occurred providing an additional proof for the different binding modes of the two ligands. Copyright © 2010 Elsevier Inc. All rights reserved.

  9. Copper(II and lead(II complexation by humic acid and humic-like ligands

    Directory of Open Access Journals (Sweden)

    IVANA KOSTIĆ

    2011-09-01

    Full Text Available The stability of metal–humate complexes is an important factor determining and predicting speciation, mobility and bioavailability of heavy metals in the environment. A comparative investigation of the complexation of Cu(II and Pb(II with humic acid and humic-like ligands, such as benzoic and salicylic acid, was performed. The analysis was realized at pH 4.0, a temperature of 25 °C and at an ionic strength of 0.01 mol dm-3 (NaCl using the Schubert ion-exchange method and its modified form. The stability constants were calculated from the experimental data by the Schubert method for complexes with benzoic and humic acid. A modified Schubert method was used for the determination of the stability constants of the complexes with salicylic acid. It was found that Cu(II and Pb(II form mononuclear complexes with benzoic and humic acid while with salicylic acid both metals form polynuclear complexes. The results indicate that Pb(II has a higher binding ability than Cu(II to all the investigated ligands. The Cu(II–salicylate and Pb(II–salicylate complexes showed noticeable higher stability constants compared with their complexes with humic acid, while the stabilities of the complexes with benzoic acid differed less. Salicylic and benzoic acids as humic-like ligands can be used for setting the range of stability constants of humic complexes with Cu(II and Pb(II.

  10. Study of coagulation processes of selected humic acids under copper ions influence*

    Science.gov (United States)

    Boguta, Patrycja; Sokolowska, Zofia

    2013-04-01

    Humic acids have limited sorption capacity and big dose of metal or other mineral component which can be sorbed on humic acids, can cause saturation of negative, surface charge of humic acids leading to destabilization of dissolved humic acids compounds. Destabilisation can be observed as coagulation and floculation proces of humic acids. However there are a lot of mechanisms which causing precipitation of humic acids. Thereby, in order to full description of coagulation process, different methods should be applied. Ordinarily, humic acids coagulation is studied by measurement of absorbance, transmittance or carbon loss in solution. Meanwhile, very significant information is also variation of metal content in soil solution and information whether metal goes to precipitate together with humic acids or stays in dissolved form in solution. So, that, from one side, processes of stronger accumulation of metal can lead to soil degradation and micronutrient deficiency for plants. However, there is also possibility to stay metal in solution in toxic and bioavailable form for plants. Main aim of this paper was to study coagulation process of different humic acids extracted from mucking peats under copper ions influence at adjusted pH to 5. In order to this, four peaty-muck soils were taken from selected places in east part of Poland (meadows and river valleys). These soils differed by humification degree, secondary transformation, density and pH. At next step, humic acids were extracted from soils using sodium hydroxide (NaOH) extractant. After exact purification by washing with HF-HCl mixture and water, humic acids were liofilized. Solutions of humic acids were prepared at concentration 40 mg/dm3 with addition of different amount of copper ions to obtain final concentration of Cu(II) ranged from 0-40mg/dm3. After 24 hours solutions were investigated using measurements of absorbance at 470nm (UV-VIS spectrometer Jasco V-530), measurements of organic carbon in solution

  11. Novel copper(II) complexes with hydrazides and heterocyclic bases: Synthesis, structure and biological studies.

    Science.gov (United States)

    Paixão, Drielly A; Marzano, Ivana M; Jaimes, Edgar H L; Pivatto, Marcos; Campos, Débora L; Pavan, Fernando R; Deflon, Victor M; Maia, Pedro Ivo da S; Da Costa Ferreira, Ana M; Uehara, Isadora A; Silva, Marcelo J B; Botelho, Françoise V; Pereira-Maia, Elene C; Guilardi, Silvana; Guerra, Wendell

    2017-07-01

    Five new copper(II) complexes of the type [Cu(NO)(NN)(ClO4)2], in which NO=4-fluorophenoxyacetic acid hydrazide (4-FH) or 4-nitrobenzoic hydrazide (4-NH) and NN=1,10-phenanthroline (phen), 4-4'-dimethoxy-2-2'-bipyridine (dmb) or 2,2-bipyridine (bipy) were synthesized and characterized using various spectroscopic methods. The X-ray structural analysis of one representative compound indicates that the geometry around the copper ion is distorted octahedron, in which the ion is coordinated to hydrazide via the terminal nitrogen and the carbonyl oxygen, and to heterocyclic bases via their two nitrogen atoms. Two perchlorate anions occupy the apical positions, completing the coordination sphere. The cytotoxic activity of compounds was investigated in three tumor cell lines (K562, MDA-MB-231 and MCF-7). Concerning K562 cell line, the complexes with 1,10-phenanthroline exhibit high cytotoxic activity and are more active than carboplatin, free ligands and [Cu(phen)2](2+). Considering the cytotoxicity results, further investigations for the compounds [Cu(4-FH)(phen)(ClO4)2] I and [Cu(4-NH)(phen)(ClO4)2]∙H2O III were performed. Flow cytometric analysis revealed that these complexes induce apoptotic cell death in MDA-MB-231 cell line and bind to DNA with K values of 4.38×10(4) and 2.62×10(4), respectively. These compounds were also evaluated against wild type Mycobacterium tuberculosis (ATCC 27294) and exhibited antimycobacterial activity, displayed MIC values lower than those of the corresponding free ligands. Copyright © 2017 Elsevier Inc. All rights reserved.

  12. Detection and investigation of the molecular nature of low-molecular-mass copper ions in isolated rheumatoid knee-joint synovial fluid.

    Science.gov (United States)

    Naughton, D P; Knappitt, J; Fairburn, K; Gaffney, K; Blake, D R; Grootveld, M

    1995-03-20

    Low-molecular-mass copper(II) species have been detected and quantified in ultrafiltrates (n = 7) of rheumatoid synovial fluid (SF) by a highly-sensitive HPLC-based assay system with the ability to determine Cu(II) concentrations of ultrafiltrates resulted in complexation by histidine > alanine > formate > threonine > lactate > tyrosine > phenylalanine, their effectiveness in this context being in the given order. CD spectra of Cu(II)-treated samples of intact SF exhibited absorption bands typical of copper(II)-albumin complexes, in addition to a band attributable to a low-molecular-mass histidinate complex (lambda min 610 nm). Since both albumin and histidine are potent radical scavengers, these results indicate that any .OH radical generated from bound copper ions will be 'site-specifically' scavenged. Hence, low-molecular-mass copper complexes with the ability to promote the generation of .OH radical which can then escape from the metal ion co-ordination sphere (and in turn, cause damage to critical biomolecules) appear to be absent from inflammatory SF.

  13. Effect of Lithium Ions on Copper Nanoparticle Size, Shape, and Distribution

    Directory of Open Access Journals (Sweden)

    Kyung-Deok Jang

    2012-01-01

    Full Text Available Copper nanoparticles were synthesized using lithium ions to increase the aqueous electrical conductivity of the solution and precisely control the size, shape, and size distribution of the particles. In this study, the conventional approach of increasing particle size by the concentration of copper ions and PGPPE in a copper chloride solution was compared to increasing the concentration of lithium chloride when the copper chloride concentration was held constant. Particle size and shape were characterized by TEM, and the size distribution of the particles at different concentrations was obtained by particle size analysis. Increasing the concentration of copper ion in the solution greatly increased the aqueous electric conductivity and the size of the particles but led to a wide size distribution ranging from 150 nm to 400 nm and rough particle morphology. The addition of lithium ions increased the size of the particles, but maintains them in a range of 250 nm. In addition the particles exhibited spherical shape as determined by TEM. The addition of lithium ions to the solution has the potential to synthesize nanoparticles with optimal characteristics for printing applications by maintaining a narrow size range and spherical shape.

  14. Thermodynamics of the complex formation of copper(II) with L-phenylalanine in aqueous ethanol solutions

    Science.gov (United States)

    Burov, D. M.; Ledenkov, S. F.; Vandyshev, V. N.

    2013-05-01

    Constants of the acid dissociation and complexation of L-phenylalanine (HPhe) with copper(II) ions are determined by potentiometry in aqueous ethanol solutions containing 0 to 0.7 molar fraction of alcohol. Changes in the Gibbs energy for the transfer from water to a binary solvent of L-phenylalanine, Phe- anion, and [CuPhe]+ complex are calculated. It is found that the weakening of solvation of the ligand donor groups in solvents with high ethanol contents is accompanied by an increase in the stability of [CuPhe]+ complex.

  15. Bis(6-meth-oxy-2-{[tris-(hydroxy-meth-yl)-meth-yl]-imino-meth-yl}phenolato)-copper(II) dihydrate.

    Science.gov (United States)

    Zhang, Xiutang; Wei, Peihai; Dou, Jianmin; Li, Bin; Hu, Bo

    2009-01-08

    In the title compound, [Cu(C(12)H(16)NO(5))(2)]·2H(2)O, the Cu(II) ion adopts a trans-CuN(2)O(4) octa-hedral geometry arising from two N,O,O'-tridentate 6-meth-oxy-2-{[tris-(hydroxy-meth-yl)meth-yl]-imino-meth-yl}phenolate ligands. The Jahn-Teller distortion of the copper centre is unusally small. In the crystal structure, O-H⋯O hydrogen bonds, some of which are bifurcated, link the component species.

  16. [Electrooptical properties of soil nitrogen-fixing bacterium Azospirillum brasilense: effect of copper ions].

    Science.gov (United States)

    Ignatov, O V; Kamnev, A A; Markina, L N; Antoniuk, L P; Kolina, M; Ignatov, V V

    2001-01-01

    The effects of copper ions on the uptake of some essential metals in the biomass and the electrooptical properties of cell suspensions of the nitrogen-fixing soil bacterium Azospirillum brasilense sp. 245 were studied. Copper cations were shown to be effectively taken up by the cell biomass from the culture medium. The addition of copper ions increased the rate of uptake of some other metals present in the culture medium. This was accompanied by changes in the electrooptical characteristics of cell suspension as measured within the orienting electric field frequency range of 10 to 10,000 kHz. The effects observed during short-term incubation of A. brasilense in the presence of copper cations were less significant than during long-term incubation. These results can be used for rapid screening of microbial cultures for enhanced efficiency of sorption and uptake of metals.

  17. Evaluation of copper ion of antibacterial effect on Pseudomonas aeruginosa, Salmonella typhimurium and Helicobacter pylori and optical, mechanical properties

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Young-Hwan [School of Materials Science and Engineering, University of Yonsei, Seoul (Korea, Republic of); Choi, Yu-ri; Kim, Kwang-Mahn [Department and Research Institute of Dental Biomaterials and Bioengineering, College of Dentistry, University of Yonsei, Seoul (Korea, Republic of); Choi, Se-Young, E-mail: sychoi@yonsei.ac.kr [School of Materials Science and Engineering, University of Yonsei, Seoul (Korea, Republic of)

    2012-02-01

    Antibacterial effect on Pseudomonas aeruginosa, Salmonella typhimurium and Helicobacter pylori of copper ion was researched. Also, additional effects of copper ion coating on optical and mechanical properties were researched as well. Copper ion was coated on glass substrate as a thin film to prevent bacteria from growing. Cupric nitrate was used as precursors for copper ion. The copper ion contained sol was deposited by spin coating process on glass substrate. Then, the deposited substrates were heat treated at the temperature range between 200 Degree-Sign C and 250 Degree-Sign C. The thickness of deposited copper layer on the surface was 63 nm. The antibacterial effect of copper ion coated glass on P. aeruginosa, S. typhimurium and H. pylori demonstrated excellent effect compared with parent glass. Copper ion contained layer on glass showed a similar value of transmittance compared with value of parent glass. The 3-point bending strength and Vickers hardness were 209.2 MPa, 540.9 kg/mm{sup 2} which were about 1.5% and 1.3% higher than the value of parent glass. From these findings, it is clear that copper ion coating on glass substrate showed outstanding effect not only in antibacterial activity but also in optical and mechanical properties as well.

  18. Evaluation of copper ion of antibacterial effect on Pseudomonas aeruginosa, Salmonella typhimurium and Helicobacter pylori and optical, mechanical properties

    Science.gov (United States)

    Kim, Young-Hwan; Choi, Yu-ri; Kim, Kwang-Mahn; Choi, Se-Young

    2012-02-01

    Antibacterial effect on Pseudomonas aeruginosa, Salmonella typhimurium and Helicobacter pylori of copper ion was researched. Also, additional effects of copper ion coating on optical and mechanical properties were researched as well. Copper ion was coated on glass substrate as a thin film to prevent bacteria from growing. Cupric nitrate was used as precursors for copper ion. The copper ion contained sol was deposited by spin coating process on glass substrate. Then, the deposited substrates were heat treated at the temperature range between 200 °C and 250 °C. The thickness of deposited copper layer on the surface was 63 nm. The antibacterial effect of copper ion coated glass on P. aeruginosa, S. typhimurium and H. pylori demonstrated excellent effect compared with parent glass. Copper ion contained layer on glass showed a similar value of transmittance compared with value of parent glass. The 3-point bending strength and Vickers hardness were 209.2 MPa, 540.9 kg/mm2 which were about 1.5% and 1.3% higher than the value of parent glass. From these findings, it is clear that copper ion coating on glass substrate showed outstanding effect not only in antibacterial activity but also in optical and mechanical properties as well.

  19. Copper(II) ion catalytic oxidation of o-phenylenediamine and characterization, X-ray crystal structure and solution studies of the final product [DAPH][H3O][Cu(dipic)2]·3H2O

    Science.gov (United States)

    Ghasemi, Khaled; Rezvani, Ali Reza; Shokrollahi, Ardeshir; Abdul Razak, Ibrahim; Refahi, Masoud; Moghimi, Abolghasem; Rosli, Mohd Mustaqim

    2015-09-01

    The complex [DAPH][H3O][Cu(dipic)2]·3H2O, (1) (dipicH2 = 2,6-pyridinedicarboxylic acid and DAP = 2,3-diaminophenazine) was prepared from the reaction of Cu(NO3)2·2H2O with mixture of o-phenylenediamine (OPD) and 2,6-pyridinedicarboxylic acid in water. The complex was characterized by FTIR, elemental analysis, UV-Vis and the single-crystal X-ray diffraction. The crystal system is monoclinic with the space group P21/c. This complex is stabilized in the solid state by an extensive network of hydrogen bonds between crystallized water, anionic and cationic fragments, which form a three-dimensional network. Furthermore, hydrogen bonds, π⋯π and Csbnd O⋯π stacking interactions seem to be effective in stabilizing the crystal structures. The protonation constants of dipic (L) and DAP (Q), the equilibrium constants for the dipic-DAP proton transfer system and the stoichiometry and stability constants of binary complexes including each of ligands (dipic, DAP) in presence Cu2+ ion, ternary complexes including, both of ligands (dipic-DAP) in presence of metal ion were calculated in aqueous solutions by potentiometric pH titration method using the Hyperquad2008 program. The stoichiometry of the most complexes species in solution was found to be very similar to the solid-state of cited metal ion complex.

  20. Synthesis, characterization, spectroscopic and theoretical studies of new zinc(II), copper(II) and nickel(II) complexes based on imine ligand containing 2-aminothiophenol moiety

    Science.gov (United States)

    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.

  1. SOURCES OF COPPER IONS AND SELECTED METHODS OF THEIR REMOVAL FROM WASTEWATER FROM THE PRINTED CIRCUITS BOARD PRODUCTION

    Directory of Open Access Journals (Sweden)

    Maciej Thomas

    2014-10-01

    Full Text Available This paper presents the issues related to the presence and removal of copper compounds from industrial effluents with including wastewater from plants involved in the production of printed circuit boards. Characterized the toxicological properties of selected copper compounds, described the applicable technological processes, sources of copper ions in the effluents and selected methods for their removal.

  2. Structural and Spectroscopic Aspects of Schiff Base Metal Complexes of Cobalt(II, Nickel(II and Copper(II

    Directory of Open Access Journals (Sweden)

    B.K. Rai

    2014-09-01

    Full Text Available The complexes of Co(II, Ni(II and Cu(II with Schiff base 2-butyl thioquinazoline 4(3H thiosemicarbazone were synthesized. The general formulae of the complexes are of the type {M(L2X2], L=2 – butyl thioquinazoline 4(3H thiosemicarbazone; x = Cl-, Br-, I- and NO3-. Elemental analyses and spectral (IR, electronic studies of the synthesized complexes suggest the presence of octahedral, environment around the central metal ion. These complexes were also subjected to study their antimicrobial screening against, Gram positive bacteria Candida albicans and gram negative bacteria Escherichia coli by disc diffusion technique.

  3. Biosorption Performance of Encapsulated Candida krusei for the removal of Copper(II).

    Science.gov (United States)

    Luk, Chi Him Jim; Yip, Joanne; Yuen, Chun Wah Marcus; Pang, Siu Kwong; Lam, Kim Hung; Kan, Chi Wai

    2017-05-19

    The use of microorganisms in biosorption is one of the most promising ways to remove trace amounts of heavy metal ions. Nevertheless, the enhancement of the successful removal of heavy metal ions by using different combinations of biosorbents is not generally guaranteed which leaves room to explore the application of the technique. In this study, the performance of free and immobilized forms of a yeast strain, Candida krusei (C. krusei), and calcium alginate (CaAlg) are evaluated for their ability to remove copper(II). Infrared spectroscopy, studies on the effects of pH and temperature, and kinetics and isotherm modelling are carried out to evaluate the biosorption. The infrared spectroscopy shows that the primary biosorption sites on the biosorbents are carboxylate groups. In addition, a higher pH and higher temperatures promote biosorption while a decline in biosorption ability is observed for C. krusei at 50 °C. The kinetics study shows that C. krusei, CaAlg and immobilized C. krusei (MCaAlg) conform with good correlation to pseudo-second order kinetics. MCaAlg and CaAlg fit well to the Langmuir isotherm while C. krusei fits well to the Temkin isotherm. From the experimental data, encapsulating C. krusei showed improved biosoprtion and address clogging in practical applications.

  4. Synthesis, structure, spectroscopic and electrochemical properties of bis(histamine-saccharinate) copper(II) complex

    Science.gov (United States)

    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.

  5. An electron paramagnetic resonance study of the behaviour of copper (II) in ageing catechin-based model wines

    Energy Technology Data Exchange (ETDEWEB)

    Mitri, M.; Scollary, G.R. [The University of Melbourne, Parkville, VIC (Australia). School of Chemistry; Troup, G.J.; Hutton, D.R.; Hunter, C.A.; Hewitt, D.G. [Monash University, Clayton, VIC (Australia). Depts of Physics, Anatomy and Chemistry

    1996-12-31

    This poster reports an electron paramagnetic resonance (EPR) study of copper in a model white wine. The model consists of a saturated 12% ethanol solution of potassium hydrogen tartrate solution (the `wine base`) containing copper and catechin as the oxidizable substrate. Ascorbic acid, as a supposed anti-oxidant, was added to some solutions. A Varian E-12 EPR spectrometer ({approx}9.1 GHz frequency) with quartz sample tubes was used and spectra were recorded at liquid nitrogen temperature to avoid polar water losses. Solutions were examined on four successive days whilst kept at room temperature and subsequently every third day when stored at 45 degree C. Variations in signal intensity, linewidth and form will be shown and the changes related to the degree of browning, as measured by visible absorption spectroscopy at 440 nm. The ESP spectra of the brown deposits reveal that the copper (II) ion is in a low symmetry site and a well defined free radical signal was also observed. No free radical signal was found in solutions containing copper and catechin, indicating that a high degree of polymerization of the oxidized catechin is required to stabilize the free radical species Truncated abstract. 1 fig.

  6. Removal of Zn(II) and Pb (II) ions Using Rice Husk in Food Industrial ...

    African Journals Online (AJOL)

    Michael Horsfall

    Removal of Zn(II) and Pb (II) ions Using Rice Husk in Food Industrial Wastewater. *ASRARI, ELHAM; TAVALLALI ... Payame Noor University (PNU), Shiraz, 711955 -1368, Iran ... need to reconsider consumption patterns and the way resources ...

  7. Tetranuclear zinc(II-oxy (benzothiazole-2-thiolate aggregate and copper(I phenylthiolate aggregate

    Directory of Open Access Journals (Sweden)

    Abir Goswami

    2015-12-01

    Full Text Available A tetranuclear zinc-oxy (benzothiazole-2-thiolate aggregate whose structure has a C3-axis passing through ZnO unit relating three other zinc ions and a tetranuclear copper(I phenylthiolate aggregate having each thiphenolate ligand bridging three copper ions are reported. These aggregates were prepared by hydrothermal reactions of 2,2′-dithiobis-(benzothiazole with zinc nitrate or copper(I iodide, respectively. The reaction of zinc nitrate passed through in situ abstraction of a oxy ligand from moisture to form a Zn4O core holding six 2-benzothiazolethiolate ligands, and during the formation of the aggregate, cleavage of S–S bond of 2,2′-dithiobis-(benzothiazole took place. Whereas, an aggregate formed by self-assembling of copper(I phenylthiolate was formed after extensive degradation of 2,2′-dithiobis-(benzothiazole during solvothermal reaction.

  8. Combined effects of water temperature and copper ion concentration on catalase activity in Crassostrea ariakensis

    Science.gov (United States)

    Wang, Hui; Yang, Hongshuai; Liu, Jiahui; Li, Yanhong; Liu, Zhigang

    2015-07-01

    A central composite experimental design and response surface method were used to investigate the combined effects of water temperature (18-34°C) and copper ion concentration (0.1-1.5 mg/L) on the catalase (CAT) activity in the digestive gland of Crassostrea ariakensis. The results showed that the linear effects of temperature were significant ( P0.05), and the quadratic effects of copper ion concentration were significant ( P0.05), and the effect of temperature was greater than that of copper ion concentration. A model equation of CAT enzyme activity in the digestive gland of C. ariakensis toward the two factors of interest was established, with R 2, Adj. R 2 and Pred. R 2 values as high as 0.943 7, 0.887 3 and 0.838 5, respectively. These findings suggested that the goodness of fit to experimental data and predictive capability of the model were satisfactory, and could be practically applied for prediction under the conditions of the study. Overall, the results suggest that the simultaneous variation of temperature and copper ion concentration alters the activity of the antioxidant enzyme CAT by modulating active oxygen species metabolism, which may be utilized as a biomarker to detect the effects of copper pollution.

  9. Dissociations of copper(II)-containing complexes of aromatic amino acids: radical cations of tryptophan, tyrosine, and phenylalanine.

    Science.gov (United States)

    Siu, Chi-Kit; Ke, Yuyong; Guo, Yuzhu; Hopkinson, Alan C; Siu, K W Michael

    2008-10-14

    The dissociations of two types of copper(II)-containing complexes of tryptophan (Trp), tyrosine (Tyr), or phenylalanine (Phe) are described. The first type is the bis-amino acid complex, [Cu(II)(M)(2)].(2+), where M = Trp, Tyr, or Phe; the second [Cu(II)(4Cl-tpy)(M)].(2+), where 4Cl-tpy is the tridendate ligand 4'-chloro-2,2':6',2''-terpyridine. Dissociations of the Cu(ii) bis-amino acid complexes produce abundant radical cation of the amino acid, M.(+), and/or its secondary products. By contrast, dissociations of the 4Cl-tpy-bearing ternary complexes give abundant M.(+) only for Trp. Density functional theory (DFT) calculations show that for Tyr and Phe, amino-acid displacement reactions by H(2)O and CH(3)OH (giving [Cu(II)(4Cl-tpy)(H(2)O)].(2+) and [Cu(II)(4Cl-tpy)(CH(3)OH)].(2+)) are energetically more favorable than dissociative electron transfer (giving M.(+) and [Cu(I)(4Cl-tpy)](+)). The fragmentation pathway common to all these [Cu(II)(4Cl-tpy)(M)].(2+) ions is the loss of NH(3). DFT calculations show that the loss of NH(3) proceeds via a "phenonium-type" intermediate. Dissociative electron transfer in [Cu(II)(4Cl-tpy)(M-NH(3))].(2+) results in [M-NH(3)].(+). The [Phe-NH(3)] (+) ion dissociates facilely by eliminating CO(2) and giving a metastable phenonium-type ion that rearranges readily into the styrene radical cation.

  10. Synthesis, spectroscopic characterization, crystallographic studies and antibacterial assays of new copper(II) complexes with sulfathiazole and nimesulide

    Science.gov (United States)

    Nunes, Julia Helena Bormio; de Paiva, Raphael Enoque Ferraz; Cuin, Alexandre; da Costa Ferreira, Ana Maria; Lustri, Wilton Rogério; Corbi, Pedro Paulo

    2016-05-01

    New ternary copper(II) complexes of sulfathiazole (SFT, C9H8N3O2S2) or nimesulide (NMS, C13H11N2O5S) and 2,2‧-bipyridine (bipy) were synthesized, and characterized by chemical and spectroscopic techniques. Elemental analyses indicated a 2:1:1 sulfonamide/copper/bipy composition for both complexes. Mass spectrometric measurements permitted identifying the molecular ions [Cu(SFT)2(bipy)+H]+ and [Cu(NMS)2(bipy)+H]+ at m/z 728 and 835, respectively, confirming the proposed compositions. Crystal structure of the [Cu(SFT)2(bipy)] complex was solved by powder X-ray diffraction analysis (PXRD), attesting that the Cu(II) ion is hexacoordinated in a distorted octahedral geometry. Each SFT molecule coordinates to the metal ion by the nitrogen atoms of the SO2-N group and of the heterocyclic ring. The coordination sphere is completed by a bipyridine. Electronic paramagnetic resonance (EPR) studies were carried out for the [Cu(NMS)2(bipy)] complex, indicating a tetragonal environment around the metal ion. It was suggested that NMS coordinates to Cu(II) by the nitrogen and oxygen atoms of the SO2-N group, which was confirmed by infrared spectroscopic studies. Biological studies showed the antibacterial activity of both Cu-SFT and Cu-NMS complexes, with the minimum inhibitory concentration (MIC) values ranging from 0.10 to 0.84 mmol L-1 against Gram-negative bacteria for [Cu(SFT)2(bipy)], and from 1.50 to 3.00 mmol L-1 against Gram-positive and -negative bacteria for [Cu(NMS)2(bipy)].

  11. Removal of copper(II) from some environmental samples by sorptive-flotation using powdered marble wastes as sorbents and oleic acid as surfactant.

    Science.gov (United States)

    Ghazy, S E; Samra, S E; Mahdy, A F M; El-Morsy, S M

    2004-11-01

    A simple and economic experimental sorptive -flotation procedure is presented for the removal of copper(II) species from aqueous solutions. It is based on using powdered marble wastes (PMW), which are widespread and inexpensive and may represent an environmental problem, as the effective inorganic sorbent and oleic (HOL) as the surfactant. The main parameters (i.e. initial solution pH, sorbent, surfactant and copper concentrations, stirring times, ionic strength, temperature and the presence of foreign ions) influencing the flotation of PMW and /or Cu(II) were examined. Nearly, 100% of PMW and Cu(II) were removed from aqueous solutions at pH7 after stirring for 10 min and at room temperature, (approximately 25 degrees C). The procedure was successfully applied to recover Cu(II) spiked to some natural water samples. A mechanism for sorption and flotation is suggested.

  12. Preparation of a DNA-bound [Ru(bpy)2(mbpibH2)]2+ film and its two-mode luminescence tuning by copper(II) ions and EDTA

    Science.gov (United States)

    Gan, Gui-Lian; Chao, Hui; Ji, Shi-Bo; Chen, Lin-Lin; Li, Hong

    2012-11-01

    An imidazophenanthroline-containing ruthenium(II) complex [Ru(bpy)2(mbpibH2)]2+ (bpy = 2,2'-bipyridine, mbpibH2 = 1,3-bis([1,10]phenanthroline[5,6-d]imidazol-2-yl)benzene) can bind DNA through groove-binding and/or non-classical intercalation modes, revealed by spectrophotometric methods, viscosity measurements and variable ionic strength experiments. On the basis of binding interactions between cationic [Ru(bpy)2(mbpibH2)]2+ and anionic DNA at a molar ratio of 1:1, a yellow transparent cast film has been assembled on an indium-tin oxide (ITO) surface using a solution-based self-standing method. The prepared DNA-[Ru(bpy)2(mbpibH2)]2+ film shows a bi-exponential luminescence decay with τ1 = 62.1 ns (8.0%) and τ2 = 594.5 ns (92.0%), whose lifetimes become much shorter than those of DNA-bound [Ru(bpy)2(mbpibH2)]2+ in buffer solutions. The Ru(II) complex with a free bi-dentate coordination site in the DNA cast film shows tunable luminescence, quenched dynamically by Cu2+ and restored by using EDTA to eliminate two modes of Cu2+-binding. The results from this study provide a significant foundation for better understanding the fabrication and modulation of a DNA-based solid luminescence device using the Ru(II) complexes as DNA-concentrating and signal-sensing agents.

  13. Physico-chemical characterization and anti- microbial activity of copper(II complexes with 2-amino and 2-methylbenzimidazole derivatives

    Directory of Open Access Journals (Sweden)

    Podunavac-Kuzmanović Sanja O.

    2004-01-01

    Full Text Available Copper(II chloride, in warm ethanolic solution, reacted with 2-amino and 2-methylbenzimidazole derivatives to give complexes of the formula CuL2Cl2·nH2O, where L=1-benzyl-2-aminobenzimidazole 1-(4-methylbenzyl-2-aminobenzimidazole, 1-benzyl-2-methylbenzimidazole and 1-(4-methylbenzyl-2-methylbenzimidazole( n=1 or 2. The complexes were characterized by elemental analysis of the metal, molar conductivity magnetic susceptibility measurements and IR spectra. The molar conductivities of copper(IIcomplexes in dimethyl formamide (DMF corresponding to a 1:1 type of electrolyte indicate that in all the complexes one of the coordinated chloride ions has been replaced by DMF molecule. The room temperature effective magnetic moments and IR data of the complexes suggest that all Cu(II complexes have a tetrahedral configuration, which is realized by participation of the pyridine nitrogen of two organic ligand molecules and two chloride anions. The antimicrobial activity of the ligands and their complexes against Pseudomonas aeruginosa, Bacillus sp. Staphylococcus aureus, Sarcina lutea and Saccharomyces cerevisiae was investigated. The effect of copper complexation on the ligand antimicrobial activity is discussed.

  14. Synthesis, characterization, electrochemical studies and DFT calculations of amino acids ternary complexes of copper (II) with isonitrosoacetophenone. Biological activities

    Science.gov (United States)

    Tidjani-Rahmouni, Nabila; Bensiradj, Nour el Houda; Djebbar, Safia; Benali-Baitich, Ouassini

    2014-10-01

    Three mixed complexes having formula [Cu(INAP)L(H2O)2] where INAP = deprotonated isonitrosoacetophenone and L = deprotonated amino acid such as histidine, phenylalanine and tryptophan have been synthesized. They have also been characterized using elemental analyses, molar conductance, UV-Vis, IR and ESR spectra. The value of molar conductance indicates them to be non-electrolytes. The spectral studies support the binding of the ligands with two N and two O donor sites to the copper (II) ion, giving an arrangement of N2O2 donor groups. Density Functional Theory (DFT) calculations were applied to evaluate the cis and trans coordination modes of the two water molecules. The trans form was shown to be energetically more stable than the cis one. The ESR data indicate that the covalent character of the metal-ligand bonding in the copper (II) complexes increases on going from histidine to phenylalanine to tryptophan. The electrochemical behavior of the copper (II) complexes was determined by cyclic voltammetry which shows that the chelate structure and electron donating effects of the ligands substituent are among the factors influencing the redox potentials of the complexes. The antimicrobial activities of the complexes were evaluated against several pathogenic microorganisms to assess their antimicrobial potentials. The copper complexes were found to be more active against Gram-positive than Gram-negative bacteria. Furthermore, the antioxidant efficiencies of the metal complexes were determined by 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activity. The antioxidant activity of the complexes indicates their moderate scavenging activity against the radical DPPH.

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

    Science.gov (United States)

    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.

  16. Formation of a dinuclear copper(II) complex through the cleavage of CN bond of 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole

    Science.gov (United States)

    Shardin, Rosidah; Pui, Law Kung; Yamin, Bohari M.; Kassim, Mohammad B.

    2014-09-01

    A simple mononuclear octahedral copper(II) complex was attempted from the reaction of three moles of 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole and one mole of copper(II) perchlorate hexahydrate in methanol. However, the product of the reaction was confirmed to be a dinuclear copper(II) complex with μ-{3-(pyridin-2-yl)-pyrazolato} and 3-(pyridin-2-yl)-1H-pyrazole ligands attached to each of the Cu(II) centre atom. The copper(II) ion assisted the cleavage of the CbenzoylN bond afforded a 3-(pyridin-2-yl)-1H-pyrazole molecule. Deprotonation of the 3-(pyridin-2-yl)-1H-pyrazole gave a 3-(pyridin-2-yl)-pyrazolato, which subsequently reacted with the Cu(II) ion to give the {3-(pyridin-2-yl)-pyrazolato}{3-(pyridin-2-yl)-1H-pyrazole}Cu(II) product moiety. The structure of the dinuclear complex was confirmed by x-ray crystallography. The complex crystallized in a monoclinic crystal system with P2(1)/n space group and cell dimensions of a = 12.2029(8) Å, b = 11.4010(7) Å, c = 14.4052(9) Å and β = 102.414(2)°. The compound was further characterized by mass spectrometry, CHN elemental analysis, infrared and UV-visible spectroscopy and the results concurred with the x-ray structure. The presence of d-d transition at 671 nm (ɛ = 116 dm3 mol-1 cm-1) supports the presence of Cu(II) centres.

  17. N,N,O and N,O,N Meridional cis Coordination of Two Guanines to Copper(II) by d(CGCGCG)2.

    Science.gov (United States)

    Rohner, Melanie; Medina-Molner, Alfredo; Spingler, Bernhard

    2016-06-20

    Many research groups study the generation of supramolecular n-dimensional arrays by combining metals with DNA building blocks. Most of the time, the natural nucleobases are modified to obtain higher-affinity metal binding sites. Using unmodified nucleobases avoids a potentially difficult synthesis; however, they have the possible disadvantage of a less defined and/or weaker coordination mode of the metal. Structural studies on the behavior of copper(II) as a linking metal and guanine as the natural ligand for metals in unmodified DNA are reported. Previously, the ability of mono- and dinuclear metal complexes to induce Z-DNA has been explored [Medina-Molner, A.; Spingler, B. Chem. Commun. 2012, 48, 1961; Medina-Molner, A.; Rohner, M.; Pandiarajan, D.; Spingler, B. Dalton Trans. 2015, 44, 3664]. Herein, X-ray crystallographic studies of the structures resulting from the combination of copper(II) ions with DNA hexamers of the general sequence d(CG)3 are presented. Three different packing motifs were observed in three crystal structures with resolutions ranging from 2.15 to 1.45 Å. The motifs are dependent upon other cations being present and/or the crystallization conditions. The first examples of intramolecular O6,N7-chelates of a neutral purine nucleobase to copper(II) were obtained as well as the first meridional N,N,O and N,O,N coordination modes of two guanines to copper(II). The fascinating coordination chemistry of copper(II) complexes generated by the Z-DNA oligonucleotides and the differences to simple nucleobases complexes with copper(II) are discussed in detail.

  18. Template Syntheses, Crystal Structures and Supramolecular Assembly of Hexaaza Macrocyclic Copper(II) Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Taehyung; Kim, Ju Chang [Pukyong National Univ., Busan (Korea, Republic of); Lough, Alan J. [Univ. of Toronto, Toronto (Canada)

    2013-06-15

    Two new hexaaza macrocyclic copper(II) complexes were prepared by a template method and structurally characterized. In the solid state, they were self-assembled by intermolecular interactions to form the corresponding supramolecules 1 and 2, respectively. In the structure of 1, the copper(II) macrocycles are bridged by a tp ligand to form a macrocyclic copper(II) dimer. The dimer extends its structure by intermolecular forces such as hydrogen bonds and C-H···π interactions, resulting in the formation of a double stranded 1D supramolecule. In 2, the basic structure is a monomeric copper(II) macrocycle with deprotonated imidazole pendants. An undulated 1D hydrogen bonded array is achieved through hydrogen bonds between imidazole pendants and secondary amines, where the imidazole pendants act as a hydrogen bond acceptor. The 1D hydrogen bonded supramolecular chain is supported by C-H···π interactions between the methyl groups of acetonitrile ligands and imidazole pendants of the copper(II) macrocycles. In both complexes, the introduction of imidazoles to the macrocycle as a pendant plays an important role for the formation of supramolecules, where they act as intermolecular hydrogen bond donors and/or acceptors, C-H···π and π-π interactions.

  19. Copper(II) and zinc(II) complexes of the peptides Ac-HisValHis-NH2 and Ac-HisValGlyAsp-NH2 related to the active site of the enzyme CuZnSOD.

    Science.gov (United States)

    Bóka, Beáta; Myari, Alexandra; Sóvágó, Imre; Hadjiliadis, Nick

    2004-01-01

    Copper(II) and zinc(II) complexes of the peptides Ac-HisValHis-NH2 and Ac-HisValGlyAsp-NH2 related to the active site of the enzyme CuZnSOD were studied by potentiometric and spectroscopic (UV-Vis, CD and EPR) techniques. The results reveal that both ligands have effective metal binding sites, but the tripeptide is a much stronger complexing agent than the tetrapeptide. The formation of a macrochelate via the coordination of the imidazolyl residues is suggested in the copper(II)-Ac-HisValHis-NH2 system in the acidic pH range, while a 4N complex predominates at physiological pH. The interaction of Ac-HisValHis-NH2 with zinc(II) results in the formation of a precipitate indicating polynuclear complex formation. Both copper(II)-Ac-HisValHis-NH2 and copper(II)-HisValHis systems exhibit catalytic activity toward the dismutation of superoxide anion at physiological pH, but the saturated coordination sphere of the metal ions in both systems results in low reactivity as compared to the native enzyme.

  20. Adsorption efficiencies of calcium (II ion and iron (II ion on activated carbon obtained from pericarp of rubber fruit

    Directory of Open Access Journals (Sweden)

    Orawan Sirichote

    2008-03-01

    Full Text Available Determination of adsorption efficiencies of activated carbon from pericarp of rubber fruit for calcium (II ion and iron (II ion has been performed by flowing the solutions of these ions through a column of activated carbon. The weights of activated carbon in 500 mL buret column (diameter 3.2 cm for flowing calcium (II ion and iron (II ion solutions were 15 g and 10 g, respectively. The initial concentration of calcium ion was prepared to be about eight times more diluted than the true concentration found in the groundwater from the lower part of southern Thailand. Calcium (II ion concentrations were analysed by EDTA titration and its initial concentration was found to be 23.55 ppm. With a flow rate of 26 mL/min, the adsorption efficiency was 11.4 % with passed through volume 4.75 L. Iron (II ion concentrations were analysed by spectrophotometric method; its initial concentration was found to be 1.5565 ppm. At a flow rate of 22 mL/min, the adsorption efficiency was 0.42 % with passed through volume of 34.0 L.

  1. Preconcentration of Pb(II), Cr(III), Cu(II), Ni(II) and Cd(II) ions in environmental samples by membrane filtration prior to their flame atomic absorption spectrometric determinations

    Energy Technology Data Exchange (ETDEWEB)

    Divrikli, Umit [Pamukkale University, Faculty of Arts and Science, Department of Chemistry, 20020 Denizli (Turkey)]. E-mail: udivrikli@pamukkale.edu.tr; Kartal, Aslihan Arslan [Pamukkale University, Faculty of Arts and Science, Department of Chemistry, 20020 Denizli (Turkey); Soylak, Mustafa [Erciyes University, Faculty of Arts and Science, Department of Chemistry, 38039 Kayseri (Turkey); Elci, Latif [Pamukkale University, Faculty of Arts and Science, Department of Chemistry, 20020 Denizli (Turkey)

    2007-07-16

    A method for separation-preconcentration of Pb(II), Cr(III), Cu(II), Ni(II) and Cd(II) ions by membrane filtration has been described. The method based on the collection of analyte metal ions on a cellulose nitrate membrane filter and determination of analytes by flame atomic absorption spectrometry (FAAS). The method was optimized for several parameters including of pH, matrix effects and sample volume. The recoveries of analytes were generally in the range of 93-100%. The detection limits by 3 sigma for analyte ions were 0.02 {mu}g L{sup -1} for Pb(II), 0.3 {mu}g L{sup -1} for Cr(III), 3.1 {mu}g L{sup -1} for Cu(II), 7.8 {mu}g L{sup -1} for Ni(II) and 0.9 {mu}g L{sup -1} for Cd(II). The proposed method was applied to the determination of lead, chromium, copper, nickel and cadmium in tap waters and RM 8704 Buffalo River Sediment standard reference material with satisfactory results. The relative standard deviations of the determinations were below 10%.

  2. Simultaneous removal of copper and lead ions from a binary solution by sono-sorption process

    Energy Technology Data Exchange (ETDEWEB)

    Entezari, M.H. [Department of Chemistry, Ferdowsi University of Mashhad, 91775 Mashhad (Iran, Islamic Republic of)], E-mail: moh_entezari@yahoo.com; Soltani, T. [Department of Chemistry, Ferdowsi University of Mashhad, 91775 Mashhad (Iran, Islamic Republic of)

    2008-12-15

    The aim of this work is to compare the simultaneous sorption of copper and lead ions from a binary aqueous solution in the presence and in the absence of ultrasound. The experiments under sonication were carried out by 20-kHz apparatus. Results indicated that the removal of copper and lead ions from a binary aqueous solution was greater in the presence of ultrasound than in control method. The removal of these ions was examined by varying experimental conditions such as the amount of sorbent, contact time, and temperature. In addition, the competitive sorption of ions was considered with different concentrations of each ion under the constant total concentration. The Langmuir isotherm model fits adequately the experimental data. In point of kinetics, the second-order kinetic model describes the sorption process for both ions. It was found that more than 90% of the lead and 60% of the copper ions was removed in less than 2 min from the solution under sonication. The thermodynamic parameters such as {delta}G{sup o}, {delta}H{sup o}, and {delta}S{sup o} were determined for the sorption of Cu{sup 2+} and Pb{sup 2+} from the temperature dependence of the sorption process.

  3. The Porphyromonas gingivalis HmuY haemophore binds gallium(iii), zinc(ii), cobalt(iii), manganese(iii), nickel(ii), and copper(ii) protoporphyrin IX but in a manner different to iron(iii) protoporphyrin IX.

    Science.gov (United States)

    Wójtowicz, Halina; Bielecki, Marcin; Wojaczyński, Jacek; Olczak, Mariusz; Smalley, John W; Olczak, Teresa

    2013-04-01

    Porphyromonas gingivalis, a major etiological agent of chronic periodontitis, acquires haem from host haemoproteins through a haem transporter HmuR and a haemophore HmuY. The aim of this study was to analyse the binding specificity of HmuY towards non-iron metalloporphyrins which may be employed as antimicrobials to treat periodontitis. HmuY binds gallium(iii), zinc(ii), cobalt(iii), manganese(iii), nickel(ii), and copper(ii) protoporphyrin IX but in a manner different to iron(iii) protoporphyrin IX which uses His(134) and His(166) as axial ligands. The metal ions in Ga(iii)PPIX and Zn(ii)PPIX can accept only His(166) as an axial ligand, whereas nickel(ii) and copper(ii) interact exclusively with His(134). Two forms of pentacoordinate manganese(iii) are present in the Mn(iii)PPIX-HmuY complex since the metal accepts either His(134) or His(166) as a single axial ligand. The cobalt ion is hexacoordinate in the Co(iii)PPIX-HmuY complex and binds His(134) and His(166) as axial ligands; however, some differences in their environments exist. Despite different coordination modes of the central metal ion, gallium(iii), zinc(ii), cobalt(iii), and manganese(iii) protoporphyrin IX bound to the HmuY haemophore cannot be displaced by excess haem. All of the metalloporphyrins examined bind to a P. gingivalis wild-type strain with higher ability compared to a mutant strain lacking a functional hmuY gene, thus corroborating binding of non-iron metalloporphyrins to purified HmuY protein. Our results further clarify the basis of metalloporphyrin acquisition by P. gingivalis and add to understanding of the interactions with porphyrin derivatives which exhibit antimicrobial activity against P. gingivalis.

  4. Biosorption of copper (II) from chemical mechanical planarization wastewaters.

    Science.gov (United States)

    Stanley, Leah C; Ogden, Kimberly L

    2003-11-01

    Copper Chemical Mechanical Planarization (Cu-CMP) is a critical step in integrated circuit (IC) device manufacturing. CMP and post-CMP cleaning processes are projected to account for 30-40% of the water consumed by IC manufacturers in 2003. CMP wastewater is expected to contain increasing amounts of copper as the industry switches from Al-CMP to Cu-CMP causing some IC manufacturers to run the risk of violating discharge regulations. There are a variety of treatment schemes currently available for the removal of heavy metals from CMP wastewater, however, many introduce additional chemicals to the wastewater, have large space requirements, or are expensive. This work explores the use of microorganisms for waste treatment. A Staphylococcus sp. of bacteria was isolated and studied to determine the feasibility for use in removing copper from Cu-CMP wastewater. A model Cu-CMP wastewater was developed and tested, as well as actual Cu-CMP wastes. Continuous-flow packed column experiments were performed to obtain adsorption data and show copper recovery from the waste. A predictive, empirical model was used to accurately describe Cu removal. Additionally, the immobilized cells were regenerated, allowing for the concentration and potential recovery of copper from the wastewater.

  5. A new copper(II) Schiff base complex containing asymmetrical tetradentate N2O2 Schiff base ligand: Synthesis, characterization, crystal structure and DFT study

    Science.gov (United States)

    Grivani, Gholamhossein; Baghan, Sara Husseinzadeh; Vakili, Mohammad; Khalaji, Aliakbar Dehno; Tahmasebi, Vida; Eigner, Václav; Dušek, Michal

    2015-02-01

    A new copper (II) Schiff base complex, CuL1, was prepared from the reaction of asymmetrical Schiff base ligand of L1 and Cu(OAC)2 (L1 = salicylidene imino-ethylimino-pentan-2-one). The Schiff base ligand, L1, and its copper (II) complex, CuL1, have been characterized by elemental analysis (CHN) and FT-IR and UV-vis spectroscopy. In addition, 1H NMR was employed for characterization of the ligand. Thermogrametric analysis of the CuL1 reveals its thermal stability and its decomposition pattern shows that it is finally decomposed to the copper oxide (CuO). The crystal structure of CuL1 was determined by the single crystal X-ray analysis. The CuL1 complex crystallizes in the monoclinic system, with space group P21/n and distorted square planar coordination around the metal ion. The Schiff base ligand of L1 acts as a chelating ligand and coordinates via two nitrogen and two oxygen atoms to the copper (II) ion with C1 symmetry. The structure of the CuL1 complex was also studied theoretically at different levels of DFT and basis sets. According to calculated results the Csbnd O bond length of the salicylate fragment is slightly higher than that in the acetylacetonate fragment of ligand, which could be interpreted by resonance increasing between phenyl and chelated rings in ligand in relative to the acetylacetonate fragment.

  6. DFT calculations of EPR parameters for copper(II)-exchanged zeolites using cluster models.

    Science.gov (United States)

    Ames, William M; Larsen, Sarah C

    2010-01-14

    The coordination environment of Cu(II) in hydrated copper-exchanged zeolites was explored through the use of density functional theory (DFT) calculations of EPR parameters. Extensive experimental EPR data are available in the literature for hydrated copper-exchanged zeolites. The copper complex in hydrated copper-exchanged zeolites was previously proposed to be [Cu(H(2)O)(5)OH](+) based on empirical trends in tetragonal model complex EPR data. In this study, calculated EPR parameters for the previously proposed copper complex, [Cu(H(2)O)(5)OH](+), were compared to model complexes in which Cu(II) was coordinated to small silicate or aluminosilicate clusters as a first approximation of the impact of the zeolitic environment on the copper complex. Interpretation of the results suggests that Cu(II) is coordinated or closely associated with framework oxygen atoms within the zeolite structure. Additionally, it is proposed that the EPR parameters are dependent on the Si/Al ratio of the parent zeolite.

  7. Biosorption effects of copper ions on Candida utilis under negative pressure cavitation

    Institute of Scientific and Technical Information of China (English)

    ZU Yuan-gang; ZHAO Xiu-hua; HU Mao-sheng; REN Yuan; XIAO Peng; ZHU Lei; CAO Yu-jie; ZHANG Yao

    2006-01-01

    Under the optimal condition of copper ions adsorption on yeast, we found some different effects among static adsorption,shaking adsorption and negative pressure cavitation adsorption, and the methods of yeast with different pretreatments also affect adsorption of copper ions. At the same time, the change of intercellular pH before and after adsorption of copper with BCECF was studied. The copper distribution was located by using PhenGreen (dipotassium salt and diacetate), and the surface of yeast was observed by an atomic force microscope. The results showed that negative pressure cavitation can improve bioadsorption capacity of copper ions on yeast. However, the yeasts' pretreatment has a higher effect on bioadsorption. It indicates that heavy metal bioadsorption on yeast has much relation with its cellular molecule basis. With the adsorping, the intercellular pH of yeast increased gradually and changed from acidity to alkalescence. These results may suggest that negative pressure cavitation can compel heavy metals to transfer from the cell surface into inside cell and make the surface of yeast coarse.

  8. Halogen-bonded network of trinuclear copper(II 4-iodopyrazolate complexes formed by mutual breakdown of chloroform and nanojars

    Directory of Open Access Journals (Sweden)

    Stuart A. Surmann

    2016-11-01

    Full Text Available Crystals of bis(tetrabutylammonium di-μ3-chlorido-tris(μ2-4-iodopyrazolato-κ2N:N′tris[chloridocuprate(II] 1,4-dioxane hemisolvate, (C16H36N2[Cu3(C3H2IN23Cl5]·0.5C4H8O or (Bu4N2[CuII3(μ3-Cl2(μ-4-I-pz3Cl3]·0.5C4H8O, were obtained by evaporating a solution of (Bu4N2[{CuII(μ-OH(μ-4-I-pz}nCO3] (n = 27–31 nanojars in chloroform/1,4-dioxane. The decomposition of chloroform in the presence of oxygen and moisture provides HCl, which leads to the breakdown of nanojars to the title trinuclear copper(II pyrazolate complex, and possibly CuII ions and free 4-iodopyrazole. CuII ions, in turn, act as catalyst for the accelerated decomposition of chloroform, ultimately leading to the complete breakdown of nanojars. The crystal structure presented here provides the first structural description of a trinuclear copper(II pyrazolate complex with iodine-substituted pyrazoles. In contrast to related trinuclear complexes based on differently substituted 4-R-pyrazoles (R = H, Cl, Br, Me, the [Cu3(μ-4-I-pz3Cl3] core in the title complex is nearly planar. This difference is likely a result of the presence of the iodine substituent, which provides a unique, novel feature in copper pyrazolate chemistry. Thus, the iodine atoms form halogen bonds with the terminal chlorido ligands of the surrounding complexes [mean length of I...Cl contacts = 3.48 (1 Å], leading to an extended two-dimensional, halogen-bonded network along (-110. The cavities within this framework are filled by centrosymmetric 1,4-dioxane solvent molecules, which create further bridges via C—H...Cl hydrogen bonds with terminal chlorido ligands of the trinuclear complex not involved in halogen bonding.

  9. Lithium ion beam driven hohlraums for PBFA II

    Energy Technology Data Exchange (ETDEWEB)

    Dukart, R.J.

    1994-05-06

    In our light ion inertial confinement fusion (ICF) program, fusion capsules are driven with an intense x-ray radiation field produced when an intense beam of ions penetrates a radiation case and deposits energy in a foam x-ray conversion region. A first step in the program is to generate and measure these intense fields on the Particle Beam Fusion Accelerator II (PBFA II). Our goal is to generate a 100-eV radiation temperature in lithium ion beam driven hohlraums, the radiation environment which will provide the initial drive temperature for ion beam driven implosion systems designed to achieve high gain. In this paper, we describe the design of such hohlraum targets and their predicted performance on PBFA II as we provide increasing ion beam intensities.

  10. The copper(II) and zinc(II) coordination mode of HExxH and HxxEH motif in small peptides: the role of carboxylate location and hydrogen bonding network.

    Science.gov (United States)

    Grasso, Giuseppe; Magrì, Antonio; Bellia, Francesco; Pietropaolo, Adriana; La Mendola, Diego; Rizzarelli, Enrico

    2014-01-01

    Copper(II) and zinc(II) complexes with two hexapeptides encompassing HExxH and HxxEH motif were characterized by means of a combined experimental and theoretical approach. Parallel tempering and density functional theory (DFT) investigations show the presence of different hydrogen bonding networks between the copper(II) and zinc(II) complexes with the two peptides, suggesting a significant contribution of these non-covalent interactions to the stability constant values. The glutamate carboxylate group has a direct role in metal ion binding. The location of this amino acid along the sequence of the investigated peptides is critical to determine thermodynamic and spectroscopic features of the copper(II) complex species, whereas is less relevant in the zinc(II) complexes formation. Electrospray ionization mass spectrometry (ESI-MS) characterization of the zinc(II) complex species show that in the [ZnH-2L] two deprotonated amide nitrogen atoms are involved in the metal coordination environment, an uncommon behavior in zinc(II) complexes for multi-histidine ligands.

  11. Remarkable inertness of copper(II) chelates of cyclen-based macrobicycles with two trans-N-acetate arms.

    Science.gov (United States)

    Esteves, Catarina V; Lamosa, Pedro; Delgado, Rita; Costa, Judite; Désogère, Pauline; Rousselin, Yoann; Goze, Christine; Denat, Franck

    2013-05-06

    Two cross-bridged cyclen-based macrocycles with two trans-N-acetic acid arms, one having a dibenzofuran (DBF) moiety as the bridge, H2L1, and the other a diphenyl ether (DPE) one, H2L2, were synthesized. Both compounds behave as "proton sponges." The thermodynamic stability constants for the Cu(2+), Zn(2+), Al(3+), and Ga(3+) complexes of both compounds were determined. They exhibit an excellent thermodynamic selectivity for copper(II), ensuring that metal ions largely present in the human body do not interfere with the copper(II) chelates. All complexes are very slow to form, and [CuL2] and [CuL1] are extremely inert to demetallate, especially [CuL2]. The acid-assisted dissociation of [CuL1] led to a half-life of 4.28 h in 5 M HCl at 363.2 K, while [CuL2] needed harsher conditions of 12 M HCl at 363.2 K with a half-life of 30.8 days. To the best of our knowledge, [CuL2] exhibits the highest half-life value for a copper(II) complex of a polyazamacrocycle derivative reported in the literature until now. Single crystal X-ray diffraction determined for [Cu(H2L1)](ClO4)2 showed the copper center in a distorted octahedral environment bound to the N4O donors of the macrobicycle and one oxygen atom from a carboxylic arm, while for [CuL2] it showed the copper center in a trigonal bipyramid geometry only bound to the donors of the macrobicycle and leaving the carboxylate arms away from the coordination sphere. UV-vis-NIR and X-band EPR spectra showed that in [CuL1] the copper center adopts a distorted compressed octahedral environment, which is the only structure found in solution for this complex, while in [CuL2] a similar environment was found in the first stages of its slow formation but reached a square-pyramidal geometry upon stabilization. The acetate arms play therefore an important role during the formation of the complex, as revealed by the comparison of its complexation behavior with the corresponding parent compounds.

  12. Fabrication of new carbon paste electrodes based on gold nano-particles self-assembled to mercapto compounds as suitable ionophores for potentiometric determination of copper ions

    Directory of Open Access Journals (Sweden)

    Rasoul Pourtaghavi Talemi

    2013-12-01

    Full Text Available In the present study, we investigate the potentiometric behavior of Cu2+ carbon paste electrodes based on two mercapto compounds 2-ethylmino-5-mercapto-1,3,4-thiadiazole (EAMT and 2-acetylamino-5-mercapto-1,3,4-thiadiazole (AAMT self-assembled on gold nano-paricle (GNP as ionophore. Then, the obtained results from the modified electrodes are compared. The self-assembled ionophores exhibit a high selectivity for copper ion (Cu2+, in which the sulfur and nitrogen atoms in their structure play a significant role as the effective coordination donor site for the copper ion. Among these electrodes, the best performance was obtained with the sensor with a EAMT/graphite powder/paraffin oil weight ratio of 4.0/68/28 with 200 µL of GNP which exhibits the working concentration range of 1.6×10−9 to 6.3×10−2 M and a nernstian slope of 28.9±0.4 mVdecade−1 of copper(II activity. The detection limit of electrode was 2.9(±0.2×10−10M and potential response was pH ; in other words, it was independent across the range of 2.8–6.3. The proposed electrode presented very good selectivity and sensitivity towards the Cu2+ ions over a wide variety of cations including alkali, alkaline earth, transition and heavy metal ions. Moreover, the proposed electrode was successfully applied as an indicator electrode in the potentiometric titration of Cu(II ions with EDTA and also the potentiometric determination of copper ions in spiked water samples.

  13. Metal ions to control the morphology of semiconductor nanoparticles: copper selenide nanocubes.

    Science.gov (United States)

    Li, Wenhua; Zamani, Reza; Ibáñez, Maria; Cadavid, Doris; Shavel, Alexey; Morante, Joan Ramon; Arbiol, Jordi; Cabot, Andreu

    2013-03-27

    Morphology is a key parameter in the design of novel nanocrystals and nanomaterials with controlled functional properties. Here, we demonstrate the potential of foreign metal ions to tune the morphology of colloidal semiconductor nanoparticles. We illustrate the underlying mechanism by preparing copper selenide nanocubes in the presence of Al ions. We further characterize the plasmonic properties of the obtained nanocrystals and demonstrate their potential as a platform to produce cubic nanoparticles with different composition by cation exchange.

  14. NEW SOLVATOMORPH OF TETRAKIS(μ2-ACETATO-O,O'-BIS(ISONICOTINAMIDE-N-DI-COPPER(II: SYNTHESIS, IR, TGA AND X-RAY STUDY

    Directory of Open Access Journals (Sweden)

    Diana Chisca

    2015-12-01

    Full Text Available Dinucleartetracarboxylato-bridged copper(IIsolvato-morph [Cu2(OAc4(ina2] •2dmso was prepared and studied by IR spectroscopy, TGA analysis and single crystal X-ray method. Cu(II ions are bridged by four syn,syn-η1:η1:μ carboxylates, showing a paddle-wheel cage-type with a square-pyramidal geometry.

  15. Copper ions stimulate the proliferation of hepatic stellate cells via oxygen stress in vitro.

    Science.gov (United States)

    Xu, San-qing; Zhu, Hui-yun; Lin, Jian-guo; Su, Tang-feng; Liu, Yan; Luo, Xiao-ping

    2013-02-01

    This study examined the effect of copper ions on the proliferation of hepatic stellate cells (HSCs) and the role of oxidative stress in this process in order to gain insight into the mechanism of hepatic fibrosis in Wilson's disease. LX-2 cells, a cell line of human HSCs, were cultured in vitro and treated with different agents including copper sulfate, N-acetyl cysteine (NAC) and buthionine sulfoximine (BSO) for different time. The proliferation of LX-2 cells was measured by non-radioactive cell proliferation assay. Real-time PCR and Western blotting were used to detect the mRNA and protein expression of platelet-derived growth factor receptor β subunit (PDGFβR), ELISA to determine the level of glutathione (GSH) and oxidized glutathione (GSSG), dichlorofluorescein assay to measure the level of reactive oxygen species (ROS), and lipid hydroperoxide assay to quantify the level of lipid peroxide (LPO). The results showed that copper sulfate over a certain concentration range could promote the proliferation of LX-2 cells in a time- and dose-dependent manner. The effect was most manifest when LX-2 cells were treated with copper sulfate at a concentration of 100 μmol/L for 24 h. Additionally, copper sulfate could dose-dependently increase the levels of ROS and LPO, and decrease the ratio of GSH/GSSG in LX-2 cells. The copper-induced increase in mRNA and protein expression of PDGFβR was significantly inhibited in LX-2 cells pre-treated with NAC, a precursor of GSH, and this phenomenon could be reversed by the intervention of BSO, an inhibitor of NAC. It was concluded that copper ions may directly stimulate the proliferation of HSCs via oxidative stress. Anti-oxidative stress therapies may help suppress the copper-induced activation and proliferation of HSCs.

  16. Biodynamics of copper oxide nanoparticles and copper ions in an oligochaete, Part I

    DEFF Research Database (Denmark)

    Ramskov, Tina; Thit, Amalie; Croteau, Marie-Noelle

    2015-01-01

    Copper oxide (CuO) nanoparticles (NPs) are widely used, and likely released into the aquatic environment. Both aqueous (i.e., dissolved Cu) and particulate Cu can be taken up by organisms. However, how exposure routes influence the bioavailability and subsequent toxicity of Cu remains largely...

  17. Novel copper(II)-dien-imidazole/imidazolate-bridged copper(II) complexes. Crystal structure of [Cu(dien)(Him)](ClO4)2 and of [(dien)Cu(mu-im)Cu(dien)](ClO4)3, a homobinuclear model for the copper(II) site of the CuZn-superoxide dismutase.

    Science.gov (United States)

    Patel, R N; Singh, Nripendra; Shukla, K K; Chauhan, U K

    2005-01-01

    The imidazolate-bridged binuclear copper(II)-copper(II) complex [(dien)Cu(mu-im)Cu(dien)](ClO(4))(3) and related mononuclear complexes [Cu(dien)(H(2)O)](ClO(4))(2), [Cu(dien)(Him)](ClO(4))(2) were synthesized with diethylenetriamine (dien) as capping ligand. The crystal structure of mononuclear [Cu(dien)(Him)](ClO(4))(2) and binuclear complex [(dien)Cu(mu-im)Cu(dien)](ClO(4))(3) have been determined by single crystal X-ray diffraction methods. The mononuclear complex [Cu(dien)(Him)](ClO(4))(2) crystallizes in the orthorhombic, Pca2(1) with a = 9.3420(9) A, b = 12.3750(9) A, c = 14.0830(9) A, beta = 90.000(7)(o) and Z = 4 and binuclear complex [(dien)Cu(mu-im)Cu(dien)](ClO(4))(3) crystallizes in the monoclinic space group P2(1)/a, with a = 15.017(7) A, b = 11.938(6) A, c = 15.386(6) A, beta = 110.30(4)(o) and Z = 4. The molecular structures show that copper(II) ions in an asymmetrically elongated octahedral coordination (type 4 + 1 + 1) and in binuclear complex Cu(1) atom has a asymmetrically elongated octahedral coordination (type type 4 + 1 + 1) and Cu(2) atom exhibits a square base pyramidal coordination (type 4 + 1). The bridging ligand (imidazolate ion, im) lies nearly on a straight line between two Cu(2+), which are separated by 5.812 A, slightly shorter than the value in copper-copper superoxide dismutase (Cu(2)-Cu(2)SOD). Magnetic measurements and electron spin resonance (ESR) spectroscopy of the binuclear complex have shown an antiferromagnetic exchange interaction. From pH-dependent cyclic voltametry (CV) and electronic spectroscopic studies the complex has been found to be stable over a wide pH range (7.75-12.50).

  18. Copper ions removal from water using functionalized carbon nanotubes–mullite composite as adsorbent

    Energy Technology Data Exchange (ETDEWEB)

    Tofighy, Maryam Ahmadzadeh; Mohammadi, Toraj, E-mail: torajmohammadi@iust.ac.ir

    2015-08-15

    Highlights: • CNTs–mullite composite was prepared via chemical vapor deposition (CVD) method. • The prepared composite was modified with concentrated nitric acid and chitosan. • The modified CNTs–mullite composites were used as novel adsorbents. • Copper ion removal from water by the prepared adsorbents was performed. • Langmuir and Freundlich isotherms and two kinetic models were applied to fit the experimental data. - Abstract: Carbon nanotubes–mullite composite was synthesized by direct growth of carbon nanotubes on mullite particles via chemical vapor deposition method using cyclohexanol and ferrocene as carbon precursor and catalyst, respectively. The carbon nanotubes–mullite composite was oxidized with concentrated nitric acid and functionalized with chitosan and then used as a novel adsorbent for copper ions removal from water. The results demonstrated that modification with concentrated nitric acid and chitosan improves copper ions adsorption capacity of the prepared composite, significantly. Langmuir and Freundlich isotherms and two kinetic models were applied to fit the experimental data. The carbon nanotubes growth on mullite particles to form the carbon nanotubes–mullite composite with further modification is an inherently safe approach for many promising environmental applications to avoid some concerns regarding environment, health and safety. It was found that the modified carbon nanotubes–mullite composite can be considered as an excellent adsorbent for copper ions removal from water.

  19. A copper-catalyzed bioleaching process for enhancement of cobalt dissolution from spent lithium-ion batteries.

    Science.gov (United States)

    Zeng, Guisheng; Deng, Xiaorong; Luo, Shenglian; Luo, Xubiao; Zou, Jianping

    2012-01-15

    A copper-catalyzed bioleaching process was developed to recycle cobalt from spent lithium-ion batteries (mainly LiCoO(2)) in this paper. The influence of copper ions on bioleaching of LiCoO(2) by Acidithiobacillus ferrooxidans (A.f) was investigated. It was shown that almost all cobalt (99.9%) went into solution after being bioleached for 6 days in the presence of 0.75 g/L copper ions, while only 43.1% of cobalt dissolution was obtained after 10 days without copper ions. EDX, XRD and SEM analyses additionally confirmed that the cobalt dissolution from spent lithium-ion batteries could be improved in the presence of copper ions. The catalytic mechanism was investigated to explain the enhancement of cobalt dissolution by copper ions, in which LiCoO(2) underwent a cationic interchange reaction with copper ions to form CuCo(2)O(4) on the surface of the sample, which could be easily dissolved by Fe(3+).

  20. New tridentate azo-azomethines and their copper(II) complexes: Synthesis, solvent effect on tautomerism, electrochemical and biological studies

    Science.gov (United States)

    Sarigul, Munire; Deveci, Pervin; Kose, Muhammet; Arslan, Ugur; Türk Dagi, Hatice; Kurtoglu, Mukerrem

    2015-09-01

    In this study, three azo-azomethines and their copper(II) complexes were prepared and characterized by analytical and spectroscopic methods. The complexes prepared were found to be mononuclear and the chelation of the ligands to the copper(II) ions occurs through two phenolic oxygens and a nitrogen atom of the azomethine group of the ligand. The tautomeric behaviors of the azo-azomethines in solution were studied by UV-Vis. spectra in three organic solvents with different polarity (CHCl3, DMSO and DMF) at room temperature. The redox behaviors of the azo-azomethines and their Cu(II) complexes were investigated by cyclic voltammetry (CV) in DMSO solution containing 0.1 M tetrabutylammonium tetrafluoroborate (TBATFB) as supporting electrolyte. Additionally, the antibacterial activity was also evaluated by the broth microdilution methods against Staphylococcus aureus, Enterococcus faecalis, Escherichia coli, Klebsiella pneumoniae and Pseudomonas aeruginosa. The compounds were found to be less effective against all bacteria tested than two reference antibiotics (ampicillin and gentamicin).

  1. Beam-Ion Instability in PEP-II

    Energy Technology Data Exchange (ETDEWEB)

    Heifets, S.; Kulikov, A.; Wang, Min-Huey; Wienands, U.; /SLAC

    2007-11-07

    The instability in the PEP-II electron ring has been observed while reducing the clearing gap in the bunch train. We study the ion effects in the ring summarizing existing theories of the beam-ion interaction, comparing them with observations, and estimating effect on luminosity in the saturation regime. Considering the gap instability we suggest that the instability is triggered by the beam-ion instability, and discuss other mechanisms pertinent to the instability.

  2. Methylresorcinarene: a reaction vessel to control the coordination geometry of copper(II) in pyridine N-oxide copper(II) complexes.

    Science.gov (United States)

    Beyeh, Ngong Kodiah; Puttreddy, Rakesh

    2015-06-07

    Pyridine and 2-picolinic acid N-oxides form 2 : 2 and 2 : 1 ligand : metal (L : M) discrete L2M2 and polymeric complexes with CuCl2 and Cu(NO3)2, respectively, with copper(ii) salts. The N-oxides also form 1 : 1 host-guest complexes with methylresorcinarene. In combination, the three components form a unique 2 : 2 : 1 host-ligand-metal complex. The methylresorcinarene acts as a reaction vessel/protecting group to control the coordination of copper(ii) from cis-see-saw to trans-square planar, and from octahedral to square planar coordination geometry. These processes were studied in solution and in the solid state via(1)H NMR spectroscopy and single crystal X-ray diffraction.

  3. Tailor-made ion-imprinted polymer based on functionalized graphene oxide for the preconcentration and determination of trace copper in food samples.

    Science.gov (United States)

    Liu, Yan; Qiu, Jian; Liu, Zhanchao; Ni, Liang; Jiang, Yinhua; Gong, Chongying; Meng, Xiangguo; Liu, Fangfang; Zhong, Guoxing

    2016-04-01

    A tailor-made Cu(II) ion-imprinted polymer based on large-surface-area graphene oxide sheets has been synthesized for the preconcentration and determination of trace copper from food samples by solid-phase extraction. Attributed to the ultrahigh surface area and hydrophilicity of graphene oxide, the Cu(II) ion-imprinted polymer prepared by the surface ion-imprinting technique exhibited a high binding capacity and a fast adsorption rate under the optimized experimental conditions. In the static adsorption experiments, the maximum adsorption capacity of Cu(II) ion-imprinted polymer is 109.38 mg/g at 25°C, which is much higher than that of the nonimprinted polymer (32.12 mg/g). Meanwhile, the adsorption is very rapid and equilibrium is reached after approximately 30 min. The adsorption mechanism is found to follow Langmuir adsorption model and the pseudo-second-order adsorption process. The Cu(II) ion-imprinted polymer was used for extracting and detecting Cu(II) in food samples combined with graphite flame atomic adsorption spectrometry with high recoveries in the range of 97.6-103.3%. The relative standard deviation and limit of detection of the method were evaluated as 1.2% and 0.37 μg/L, respectively. The results showed that the novel absorbent can be utilized as an effective material for the selective enrichment and determination of Cu(II) from food samples.

  4. Microanalysis of oligodeoxynucleotides by cathodic stripping voltammetry at amalgam-alloy surfaces in the presence of copper ions.

    Science.gov (United States)

    Hason, Stanislav; Vetterl, Vladimír

    2006-05-15

    The application of gold amalgam-alloy electrode (AuAE) for a sensitive voltammetric detection of different oligodeoxynucleotides (ODNs) containing the purine units within the ODN-chains in the presence of copper is described. The detection of ODNs is based on the following procedure: (i) the first step includes an acidic hydrolysis of the ODN (ahODN) samples performing the release of the purine bases from ODN-chain; (ii) the second step includes an electrochemical accumulation of the complex of the purine base residues released from ODN-chain with copper ions Cu(I) (ahODN-Cu(I) complex) at the potential of reduction of copper ions Cu(II) on the amalgam-alloy electrode surfaces; (iii) finally followed the cathodic stripping of the electrochemically accumulated ahODN-Cu(I) complex from the electrode surface. The proposed electrochemical method was used for: (a) detection of different ODN lengths containing only adenine units (the number of adenine units within the ODN-chains was changed from 10 to 80), and (b) determination of the number of purine units within the 30-mer ODNs containing a random sequence segments involving both the purine and pyrimidine units. The intensity of the cathodic stripping current density peak (j(CSP)) of the electrochemically accumulated ahODN-Cu(I) complex increased linearly with the increasing number of purine units within the ODN-chains. We observed a good correlation between the percentage content of purine units to the whole length of different 30-mer ODNs and the percentage content of the intensity of the j(CSP) of the electrochemically accumulated 30-mer ahODN-Cu(I) complexes. The detection of acid hydrolysed 80-mer (A(80)) in the bulk solution and in a 20-mul volume is possible down to 200pM and 2nM at the AuAE, respectively. For the shortest 10-mer (A(10)) a detectable value of 5nM in the bulk solution on the AuAE was observed. The sensitive detection of different ODNs containing the purine units in their chains in the presence of

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

    Science.gov (United States)

    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.

  6. Sorption of copper(II) from aqueous phase by waste biomass

    Energy Technology Data Exchange (ETDEWEB)

    Nagendra Rao, C.R. (Government Polytechnic, Anantapur (India)); Iyengar, L.; Venkobachar, C. (Indian Inst. of Tech., Kanpur (India))

    The objective of the present investigation is to compare three biomasses for copper uptake under different experimental conditions so as to choose the most suitable one for scaleup purposes. Ganoderma lucidum is a macrofungi, growing widely in tropical forests. Sorbent preparation requires its collection from the field. Asperigillus niger is obtained as a waste biomass from the fermentation industry. Activated sludge biomass is available from the biological waste treatment plants. The results of their potential to remove copper are presented. The copper uptake by biosorbents though, varied significantly, showed an increased trend in the range of pH 4 to 6. The increase in metal binding after alkali treatment was marginal for G. lucidum, significant for A. niger, and dramatic for sludge. Copper sorption capacities of M and M[sub c] were much higher than for other sorbents at pH 5.0. The effect of anionic ligands, like acetate and tartrate on copper uptake by raw and alkali treated biosorbents, was negligible as the predominant species in the presence of these ligands is divalent copper ion. Pyrophosphate, citrate, and EDTA had varying degrees of adverse effects on metal uptake. Thus, among the sorbents G. lucidum in its raw form is best suited for the practical application of copper removal from industrial effluents.

  7. Structural characterization of copper(II) binding to alpha-synuclein: Insights into the bioinorganic chemistry of Parkinson's disease.

    Science.gov (United States)

    Rasia, Rodolfo M; Bertoncini, Carlos W; Marsh, Derek; Hoyer, Wolfgang; Cherny, Dmitry; Zweckstetter, Markus; Griesinger, Christian; Jovin, Thomas M; Fernández, Claudio O

    2005-03-22

    The aggregation of alpha-synuclein (AS) is characteristic of Parkinson's disease and other neurodegenerative synucleinopathies. We demonstrate here that Cu(II) ions are effective in accelerating AS aggregation at physiologically relevant concentrations without altering the resultant fibrillar structures. By using numerous spectroscopic techniques (absorption, CD, EPR, and NMR), we have located the primary binding for Cu(II) to a specific site in the N terminus, involving His-50 as the anchoring residue and other nitrogen/oxygen donor atoms in a square planar or distorted tetragonal geometry. The carboxylate-rich C terminus, originally thought to drive copper binding, is able to coordinate a second Cu(II) equivalent, albeit with a 300-fold reduced affinity. The NMR analysis of AS-Cu(II) complexes reveals the existence of conformational restrictions in the native state of the protein. The metallobiology of Cu(II) in Parkinson's disease is discussed by a comparative analysis with other Cu(II)-binding proteins involved in neurodegenerative disorders.

  8. Development of an extractive spectrophotometric method for the determination of copper(II) in leafy vegetable and pharmaceutical samples using pyridoxal-4-phenyl-3-thiosemicarbazone (PPT).

    Science.gov (United States)

    Sarma, L Subramanyam; Kumar, J Rajesh; Reddy, K Janardhan; Reddy, A Varada

    2005-07-13

    A highly sensitive extractive spectrophotometric method has been developed for the determination of copper(II) using pyridoxal-4-phenyl-3-thiosemicarbazone(PPT) as an analytical reagent. The PPT forms reddish brown species of copper(II) at a pH range of 3.0-5.5, and the complex was extracted into n-butanol. The Cu(II)-PPT complex shows maximum absorbance at 440 nm, with molar absorptivity and Sandell's sensitivity being 2.16 x 10(4) L mol(-1) cm(-1) and 2.94 x 10(-3) microg cm(-2), respectively. The system obeys Beer's law in the range of 0.2-5.0 mg/L. The regression coefficient of the Beer's law straight line is 0.338, and the correlation coefficient is 0.96. The detection limit of the method is 0.0065 microg mL(-1). Most of the common metal ions generally found associated with copper do not interfere. The repeatability of the method was checked by finding the relative standard deviation. The developed method has been successfully employed for the determination of copper(II) in leafy vegetable and pharmaceutical samples. The method is evaluated by analyzing samples from the Bureau of Analyzed Samples (BCS 233, 266, 216/1, 207, and 179) and by intercomparison of experimental values using AAS.

  9. Synthesis and Structure of a Ternary Copper(II) Complex with Mixed Ligands of Diethylenetriamine and Picrate: DNA/Protein-Binding Property and In Vitro Anticancer Activity Studies.

    Science.gov (United States)

    Shi, Ya-Ning; Zheng, Kang; Zhu, Ling; Li, Yan-Tuan; Wu, Zhi-Yong; Yan, Cui-Wei

    2015-05-01

    Based on the importance of the design and synthesis of transition metal complexes with noncovalent DNA/protein-binding abilities in the field of metallo pharmaceuticals, a new mononuclear ternary copper(II) complex with mixed ligands of diethylenetriamine (dien) and picrate anion (pic), identified as [Cu(dien)(pic)](pic), was synthesized and characterized by elemental analysis, molar conductivity measurement, infrared spectrum, electronic spectral studies, and single-crystal X-ray diffractometry. The structure analysis reveals that the copper(II) complex crystallizes in the monoclinic space group P21 /c, and the copper(II) ion has a distorted square pyramidal coordination geometry. A two-dimensional supramolecular structure is formed through hydrogen bonds. The DNA/bovine serum albumin (BSA)-binding properties of the complex are explored, indicating that the complex can interact with herring sperm DNA via intercalation mode and bind to BSA responsible for quenching of tryptophan fluorescence by static quenching mechanism. The in vitro anticancer activity shows that the copper(II) complex is active against the selected tumor cell lines.

  10. Novel homo- and hetero-nuclear copper(II) complexes of tetradentate Schiff bases: Synthesis, characterization, solvent-extraction and catalase-like activity studies

    Energy Technology Data Exchange (ETDEWEB)

    Dede, Buelent [Sueleyman Demirel University, Department of Chemistry, Isparta, 32260 (Turkey)], E-mail: dbulent@fef.sdu.edu.tr; Karipcin, Fatma; Cengiz, Mustafa [Sueleyman Demirel University, Department of Chemistry, Isparta, 32260 (Turkey)

    2009-04-30

    Twelve homo- and hetero-nuclear copper(II) complexes of tetradentate Schiff base ligands containing N{sub 4} donor sets have been prepared by employing several steps. The characterization and nature of bonding of the complexes have been deduced from elemental analysis, FT-IR, molar conductivity, magnetic moment measurements and thermal analysis. The three Schiff base ligands were further identified using {sup 1}H and {sup 13}C NMR spectra. All copper(II) complexes are 1:2 electrolytes as shown by their molar conductivities ({lambda}{sub M}) in DMF and paramagnetic. The subnormal magnetic moment values of the di- and tri-nuclear complexes explained by a very strong anti-ferromagnetic interaction. The extraction ability of the ligands has been examined by the liquid-liquid extraction of selected transition metal (Mn{sup 2+}, Co{sup 2+}, Ni{sup 2+}, Cu{sup 2+}, Zn{sup 2+}, Pb{sup 2+}, Cd{sup 2+}, Hg{sup 2+}) cations. The ligands show strong binding ability toward copper(II) ion. Furthermore the homo- and hetero-nuclear copper(II) complexes were each tested for their ability to catalyse the disproportionation of hydrogen peroxide in the presence of the added base imidazole.

  11. Level of Copper Ion in Cervical Mucus of Various Duration after Inserting VCu200 IUD

    Institute of Scientific and Technical Information of China (English)

    刘庆喜; 黄祝姈; 潘琢如

    1996-01-01

    The purpose of the study was to test the effective period of VCu200 IUD. The concentration of copper ion was measured with non-flame atomic absorption s pectrophotometer HITACHI- 180. The average concentration of copper ion(x±sx) was 2.66±0.58 μg/g cervical mucus wet weight (μg/g · M·W·W) in the first year, then gradually decreasing to 0.91±0. 16 μg/g·M·W·W in the fifteenth-year group of VCu200 IUD. There was an average of 0.35±0.08~0. 56±0. 14 μg/g·M·W·W in the control group. It showed that the concentration of copper ion was decreasing with prolongation of use of VCu200 IUD and there was statistically significant difference between VCu200 IUD group, on the one hand, and the stainless steel ring group and the control group (P<0.05~0. 01) on the other hand. No difference was found between the stainless steel ring group and the control group (P>0. 05). It was reported in the literature that the concentration of copper ion in 1.0 μg/ml had the action of anti fertility, and it was found that the concentration of copper ion was higher than 1.0 μg/ml in the tenth year after insertion of VCu200 IUD. It suggested that effective period of VCu200 IUD was at least ten years.

  12. Spectroscopic studies on Solvatochromism of mixed-chelate copper(II) complexes using MLR technique.

    Science.gov (United States)

    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.

  13. Electrochemical Studies of Betti Base and Its Copper(II Complex by Cyclic and Elimination Voltammetry

    Directory of Open Access Journals (Sweden)

    Shardul Bhatt

    2013-01-01

    Full Text Available The electrochemical behavior of Betti base 1-(α-amino benzyl-2-naphthol (BB and its copper(II complex by cyclic and elimination voltammetry (EVLS is reported in the present study. The cyclic voltammetric studies carried out at a glassy carbon working electrode, Ag/Ag+ reference electrode (0.01 M AgNO3 in acetonitrile in DCM at 100 mV/sec, 200 mV/sec, and 400 mV/sec scan rates indicated a preceding chemical oxidation of the adsorbed BB species to form an iminium ion followed by formation of a carbanion via two-step quasireversible reduction. The suggested reaction mechanism has been supported by the elimination voltammetry. The CV and EVLS studies revealed Cu(IIBB complex to undergo a chemical or a surface reaction before electron transfer from the electrode at −0.49 V to form Cu(IBB species. The oxidation of Cu(IBB species has been observed to be CV silent.

  14. Metamagnetism in hydrophobically induced carboxylate (phenylmalonate)-bridged copper(II) layers.

    Science.gov (United States)

    Pasán, Jorge; Sanchiz, Joaquín; Ruiz-Pérez, Catalina; Campo, Javier; Lloret, Francesc; Julve, Miguel

    2006-07-21

    Self-assembly of copper(l) ions, phenylmalonate and pyrimidine yields the layered compound [Cu(pym)(Phmal)n (1) where intralayer ferro- and interlayer antiferromagnetic interactions occur with three-dimensional antiferromagnetic ordering at T(c) = 2.15 K.

  15. Syntheses and Crystal Structures of Mercury(II) and Copper(II) Complexes of an 18-Membered NS{sub 4}-Macrocycle

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Eunji; Lee, Shim Sung [Gyeongsang National University, Jinju (Korea, Republic of)

    2015-01-15

    An 18-membered NS{sub 4}-macrocycle was employed, and its complexation behaviors with hard and soft metal ions were investigated. Reactions of L with mercury(II) nitrate and thiocyanate afforded endocyclic mononuclear complexes [Hg(L)(NO{sub 3}){sub 2}] (1) and [Hg(L)(SCN){sub 2}] (2), respectively, with anion coordinations. In the nitrato complex 1, the mercury(II) center is six-coordinate, being bound to three S donors and one pyridine N atom in L, and the coordination sphere is completed by two monodentate nitrate ions from both sides of the macrocyclic plane adopting a distorted octahedral geometry. The thiocyanato complex 2, which contains two crystallographically independent but almost isostructural complex units is five-coordinate, being bound to NS{sub 2} donors in L and two monodentate thiocyanate ions on the same side of the bound macrocycle unlike 1, adopting a distorted square pyramidal geometry. Reaction of L with CuCl{sub 2} 2H{sub 2}O yielded a dark-green bis(macrocycle) trinuclear complex, [Cu{sub 3}(L){sub 2}Cl{sub 6}] 0.5CH{sub 2}Cl{sub 2} (3), in which two endocyclic monocopper (II) complex units are linked by an exocyclic one Cu and two bridging Cl atoms. In 3, interestingly, the local coordination environments of the three copper(II) atoms are different, with four, five, or six coordination, adopting a distorted square pyramidal, tetrahedral, or octahedral geometry, respectively. From these results, it is found that the ditopic ligand L reacts with both soft and hard metal-ion species to give diverse types of endocyclic complexes whose structures are also dependent on the anions used.

  16. Ion-beam-induced modifications in the structural and electrical properties of copper oxide selenite nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Rana, Pallavi, E-mail: prana.phy@gmail.com; Chauhan, R.P.

    2015-04-15

    Highlights: •Nanowires were synthesized via template-assisted electrodeposition method. •Copper oxide selenite nanowires were irradiated with 160 MeV, Ni{sup +12} ion beam. •XRD confirmed no change in phase of irradiated nanowires. •Electrical resistivity of nanowires was found to decrease with the ion fluence. -- Abstract: Irradiation with swift heavy ions (SHIs) with energy in the MeV range is a unique tool for engineering the properties of materials. In this context, the objective of the present work is to study the conduction of charge carriers in pre- and post-ion-irradiated semiconducting nanowires. Copper oxide selenite nanowires were synthesized using a template-assisted electrodeposition technique from an aqueous solution of 0.8 M CuSO{sub 4}·5H{sub 2}O and 8 mM SeO{sub 2}. The synthesized nanowires were observed to have a monoclinic structure with linear I–V characteristics (IVC). The effect of irradiation with 160 MeV Ni{sup +12} ions on the properties of the copper oxide selenite nanowires was investigated for fluences varying from 10{sup 11} to 10{sup 13} ions/cm{sup 2}. XRD spectra confirmed no change in the phase of the swift-heavy-ion-irradiated nanowires, but a modification in the orientation of the planes was observed that depended on the ion fluence. The electrical resistivity of the semiconducting nanowires also varied with the ion fluence. Simultaneous irradiation-induced modifications to the electro-chemical potential gradient and the granular properties of the material may have been the origin of the alteration in the structural and electrical properties of the nanowires.

  17. New Class of Antimicrobial Agents: SBA-15 Silica Containing Anchored Copper Ions

    Directory of Open Access Journals (Sweden)

    Lukasz Laskowski

    2017-01-01

    Full Text Available The paper is about a new class of antimicrobial functional nanomaterials. Proposed compounds are based on SBA-15 porous silica matrices and contain anchored copper ions. Thanks to the immobilization of functional groups the compounds are safer for environment than commonly used disinfectant agents. We prepared and examined silica based materials containing two concentrations of copper-containing groups: 10 and 5%. For the reference we prepared samples containing free-standing CuO molecules in the structure and checked their antimicrobial properties. Antibacterial effect of considered SBA-15-Cu material was tested on Escherichia coli bacteria. Antimicrobial tests were applied for the pure form of the material and as modifying agents for plastics. The obtained results showed that the sample with lower concentration of active copper-containing groups has stronger antimicrobial properties than the one with higher concentration of copper. Interestingly, silica containing free-standing CuO molecules has no antimicrobial properties. Considering the obtained results, we can conclude that the most probable antimicrobial mechanism in this case is an oxidation stress. When a plastic modifier is applied the material is enriched with bacterial inhibitory properties. It seems that SBA-15 silica containing low concentration of anchored copper ions is promising in terms of its antibacterial property and biomaterial potential for commercial use.

  18. The first salen-type ligands derived from 3',5'-diamino-3',5'-dideoxythymidine and -dideoxyxylothymidine and their corresponding copper(II complexes

    Directory of Open Access Journals (Sweden)

    Koth Daniel

    2006-08-01

    Full Text Available Abstract Background There are many nucleoside metal complexes known. According to observations made, only very few of them reveal their central ion to be co-ordinated by the sugar part of their molecules. The regio- and stereospecific exchange of the hydroxyl groups at the sugar moiety by chelating units improves its complexation ability and should give access to a new class of chiral ligands. Results In this paper we present the synthesis of 3',5'-diamino substituted thymidines with ribo- as well as xylo-configuration and the preparation of copper(II complexes derived from their corresponding Schiff bases. Starting from thymidine, the amino derivatives were prepared in a three and four step reaction sequence respectively. The absolute configuration of the ligands was proved by the three-bond 1H-1H spin spin coupling constants 3J obtained by NMR-studies. Condensation of the amino derivatives with salicylic aldehydes resulted in the corresponding diimines, which represent a new class of chiral salen-type ligands. All ligands formed uncharged stable copper(II complexes. The structure of 3',5'-bis(3,5-di-tert-butylsalicylaldiminato-3',5'-dideoxyxylothymidine-copper(II could be determined by single crystal X-ray structure analysis. The copper centre in this complex has distorted tetrahedral coordination geometry. Conclusion For the synthesis of 3',5'-diamino-3',5'-dideoxy thymidines with xylo- as well as ribo-configuration an effective synthesis pathway has been developed. Their corresponding salicylidene imines form stable coordination compounds with copper(II ions. They represent the first salen type complexes of nucleosides with this substitution pattern.

  19. Salicylaldimine Copper(II) complex catalyst: Pioneer for ring opening Polymerization of Lactide

    Indian Academy of Sciences (India)

    ANITA ROUTARAY; NIBEDITA NATH; TUNGABIDYA MAHARANA; PRATAP KUMAR SAHOO; JAYA PRAKASH DAS; ALEKHA KUMAR SUTAR

    2016-06-01

    Salicylaldimine copper complex has been synthesized and its reactivity for the ring-opening polymerization(ROP) of lactide has been studied. This monomeric copper complex was prepared by the reaction ofcopper(II) solution with one molar equivalent of salicylaldimine Schiff-base ligand in methanol under nitrogenatmosphere. This copper complex has been characterized by different spectroscopic methods, which showedsquare planar geometry. The molecular structure of the salicylaldimine Schiff-base has been determined byX-ray diffraction studies. The complex was tested as the initiator for the ring-opening polymerization of lactide,with variation in diamine group in ligand. The rate of polymerization is dependent on the diamine groupin the following order: ethylene > propylene > phenyl. The salicylaldimine copper complex allows controlledring-opening polymerization as indicated by the linear relationship between the percentage conversion and thenumber-average molecular weight. On the basis of literature reports, a mechanism for ROP of lactide has beenproposed.

  20. Effect of copper ions on the degradation of thiram in aqueous solution: identification of degradation products by HPLC-MS/MS.

    Science.gov (United States)

    Filipe, Olga M S; Santos, Sónia A O; Domingues, M Rosário M; Vidal, Maria M; Silvestre, Armando J D; Santos, Eduarda B H

    2014-08-30

    The aim of this work was to examine the effect of Cu(II) on the degradation of thiram (Thi) in aqueous solutions, since the literature focused on this effect is scarce and copper based fungicides can be applied together with thiram or during the same season to agricultural crops. The effect of Cu(II) on the degradation of thiram was followed by both UV-vis and HPLC-MS/MS. When thiram is dissolved in pure water its degradation occurs very slowly, being negligible during the first 7 days. However, the presence of Cu(II) has a strong influence on the thiram degradation in aqueous solutions along time. In the presence of an excess of Cu(II), a [CuThi](2+) complex is initially formed which degrades into a complex formed between the dimethyldithiocarbamate anion (DMDTC) and Cu(II) ion, [Cu(DMDTC)](+). This complex further degrades leading to other copper complexes which were identified for the first time, by MS(n). The results obtained in the present work also demonstrated that a redox reaction involving DMDTC anions and Cu(II) ions gives rise to the formation of a Thi-Cu(I) complex. Finally, some of the complexes resulting from the degradation of [CuThi](2+) are quite persistent in solution for long periods of time (>1 month).

  1. Pseudohalide copper(II) complexes derived from polypyridyl ligands: Synthesis and characterization

    Science.gov (United States)

    Mautner, Franz A.; Louka, Febee R.; LeGuet, Thibaut; Massoud, Salah S.

    2009-02-01

    A novel series of pseudohalide- ( N3- NCS -) and perchlorato-Cu(II) complexes possessing a series of ligands with pyridyl-containing donors have been investigated. These include [Cu(pmap)ClO 4)]ClO 4 ( 1), [Cu(pmap)(N 3)]ClO 4 ( 2), [Cu(pmea)(N 3)]ClO 4·H 2O ( 3), [Cu(dp-pa)(N 3)]ClO 4·½H 2O ( 4), [Cu(pzdepy)ClO 4]ClO 4 ( 5), [Cu(pzdepy)(NCS)]ClO 4 ( 6) and [Cu 2(L)(NCS) 4]·2CH 3CN ( 7) where pmap = bis[2-(2-pyridylethyl)]-(2-pyridylmethyl)amine, pmea = bis(2-pyridylmethyl)-2-(2-pyridylethyl)amine, dp-pa = N-propanamide- N, N-bis(2-pyridylmethyl)amine, pzdepy = N, N'-bis[2-(2-pyridylethyl)]piperazine and L = 3,5-bis[bis(2-pyridylmethyl)aminomethyl]-toluene. All complexes were characterized by elemental analyses, IR and UV-Visible spectroscopy. The visible spectra of all complexes reveal the square-pyramidal geometries (SP) around the central Cu 2+ ion. IR spectra confirmed the coordination of the ClO4- group in 1 and 5 and the N-donor thiocyanate group in complexes 6 and 7. The X-ray structure determination of the pseudohalide complexes 2, 6 and 7 confirmed the monodentate coordination nature of N3- and NCS - ions. The structure of 2 or 6 consists of isolated [Cu(pmap)(N 3)] + or [Cu(pzdepy)(NCS)] + cations and perchlorate counter anions. The copper centers are penta-coordinated by the four N atoms of the pmap or pzdepy and N(5) atom of the azide group in 2 and the thiocyanate group in 6. In the dinuclear unit [Cu 2(L)(NCS) 4] of 7, each copper atom forms bonds to three nitrogen atoms of the ligand L, [Cu sbnd N bonds from 2.013(2) to 2.054(2) Å], and to N(4) and N(5) atoms of the two terminal thiocyanato groups [Cu(1) sbnd N(4) = 1.954(2) Å; Cu(1) sbnd N(5) = 2.178(2) Å]. The intradimer Cu(1)...Cu(1A) distance is 5.7010(14) Å. An intramolecular π-π stacking with a ring-ring separation of 3.5991(14) Å is observed between the central benzene ring and the pyridyl rings. In the three complexes ( 2, 6 and 7), the CuN 5 chromophore may be described as an

  2. Angiotensin II and Renal Tubular Ion Transport

    Directory of Open Access Journals (Sweden)

    Patricia Valles

    2005-01-01

    Evidence for the regulation of H+-ATPase activity in vivo and in vitro by trafficking/exocytosis has been provided. An additional level of H+-ATPase regulation via protein synthesis may be important as well. Recently, we have shown that both aldosterone and angiotensin II provide such a mechanism of regulation in vivo at the level of the medullary collecting tubule. Interestingly, in this part of the nephron, the effects of aldosterone and angiotensin II are not sodium dependent, whereas in the cortical collecting duct, both aldosterone and angiotensin II, by contrast, affect H+ secretion by sodium-dependent mechanisms.

  3. Cancer Therapy by Catechins Involves Redox Cycling of Copper Ions and Generation of Reactive Oxygen Species

    Directory of Open Access Journals (Sweden)

    Mohd Farhan

    2016-02-01

    Full Text Available Catechins, the dietary phytochemicals present in green tea and other beverages, are considered to be potent inducers of apoptosis and cytotoxicity to cancer cells. While it is believed that the antioxidant properties of catechins and related dietary agents may contribute to lowering the risk of cancer induction by impeding oxidative injury to DNA, these properties cannot account for apoptosis induction and chemotherapeutic observations. Catechin (C, epicatechin (EC, epigallocatechin (EGC and epigallocatechin-3-gallate (EGCG are the four major constituents of green tea. In this article, using human peripheral lymphocytes and comet assay, we show that C, EC, EGC and EGCG cause cellular DNA breakage and can alternatively switch to a prooxidant action in the presence of transition metals such as copper. The cellular DNA breakage was found to be significantly enhanced in the presence of copper ions. Catechins were found to be effective in providing protection against oxidative stress induced by tertbutylhydroperoxide, as measured by oxidative DNA breakage in lymphocytes. The prooxidant action of catechins involved production of hydroxyl radicals through redox recycling of copper ions. We also determined that catechins, particularly EGCG, inhibit proliferation of breast cancer cell line MDA-MB-231 leading to a prooxidant cell death. Since it is well established that tissue, cellular and serum copper levels are considerably elevated in various malignancies, cancer cells would be more subject to redox cycling between copper ions and catechins to generate reactive oxygen species (ROS responsible for DNA breakage. Such a copper dependent prooxidant cytotoxic mechanism better explains the anticancer activity and preferential cytotoxicity of dietary phytochemicals against cancer cells.

  4. Effect of Some Heterocyclic Derivatives on the Removal of Copper Ions from Wastewater by Cementation

    Institute of Scientific and Technical Information of China (English)

    A.A. Taha; M.G.Marei; D.E.Abd El-khalek

    2004-01-01

    Removal of copper ions from copper sulphate solutions on a rotating zinc rod in absence and in presence of 3(2H)-furanones and 4H-pyran-4-one derivatives was investigated experimentally. Variables studied were initial copper ions concentration,rotational speed of the zinc rod, temperature and concentration of organic additives. It was found that cementation reaction is first order in presence and in absence of additives. Increasing concentration of initial copper ions, rotational speed of the zinc rod and temperature were found to increase the rate of cementation. In presence of organic additives an enhancement of the rate was observed, except in presence of methoxyfuranone the rate was found to decrease by an amount ranging from 11.74% to 33.79%. Rate acceleration or inhibition is associated mainly with changes in the structure of the additives as well as its concentration. The apparent activation energy for the cementation process in presence of different additives was estimated and was found to be ranged between 11.8 k J/mol and 25.95 k J/mol. These values suggest that the copper removal process in presence of these additives is controlled by diffusion. A scanning electron microscopy study of copper deposits obtained in presence of tolylfuranone, phenylpyrone and methoxyfuranone correlate with their behaviour during the kinetic study. Different reaction conditions and the physical properties of solutions were studied to obtain dimensionless correlation among all these parameters. It was found that on applying cementation reaction on a sample from industrial wastewater in presence of phenylpyrone about 91.9% of Cu2+ are removed.

  5. Cancer Therapy by Catechins Involves Redox Cycling of Copper Ions and Generation of Reactive Oxygen species.

    Science.gov (United States)

    Farhan, Mohd; Khan, Husain Yar; Oves, Mohammad; Al-Harrasi, Ahmed; Rehmani, Nida; Arif, Hussain; Hadi, Sheikh Mumtaz; Ahmad, Aamir

    2016-02-04

    Catechins, the dietary phytochemicals present in green tea and other beverages, are considered to be potent inducers of apoptosis and cytotoxicity to cancer cells. While it is believed that the antioxidant properties of catechins and related dietary agents may contribute to lowering the risk of cancer induction by impeding oxidative injury to DNA, these properties cannot account for apoptosis induction and chemotherapeutic observations. Catechin (C), epicatechin (EC), epigallocatechin (EGC) and epigallocatechin-3-gallate (EGCG) are the four major constituents of green tea. In this article, using human peripheral lymphocytes and comet assay, we show that C, EC, EGC and EGCG cause cellular DNA breakage and can alternatively switch to a prooxidant action in the presence of transition metals such as copper. The cellular DNA breakage was found to be significantly enhanced in the presence of copper ions. Catechins were found to be effective in providing protection against oxidative stress induced by tertbutylhydroperoxide, as measured by oxidative DNA breakage in lymphocytes. The prooxidant action of catechins involved production of hydroxyl radicals through redox recycling of copper ions. We also determined that catechins, particularly EGCG, inhibit proliferation of breast cancer cell line MDA-MB-231 leading to a prooxidant cell death. Since it is well established that tissue, cellular and serum copper levels are considerably elevated in various malignancies, cancer cells would be more subject to redox cycling between copper ions and catechins to generate reactive oxygen species (ROS) responsible for DNA breakage. Such a copper dependent prooxidant cytotoxic mechanism better explains the anticancer activity and preferential cytotoxicity of dietary phytochemicals against cancer cells.

  6. In vitro release of cupric ion from intrauterine devices: influence of frame, shape, copper surface area and indomethacin.

    Science.gov (United States)

    Zhang, Shuangshuang; Li, Ying; Yu, Panpan; Chen, Tong; Zhou, Weisai; Zhang, Wenli; Liu, Jianping

    2015-02-01

    The release of cupric ion from copper intrauterine device (Cu-IUD) in human uterus is essential for contraception. However, excessive cupric ion will cause cytotoxic effect. In this paper, we investigated the influence of device characteristics (frame, copper surface area, shape, copper type and indomethacin) on copper release for the efficacy and adverse effects vary with IUD types which may correlate to their different release behaviors. Nine types of Cu-IUDs were selected and incubated in simulated uterine fluid. They were paired for comparison based on the device properties and the release of cupric ion was determined by flame atomic absorption spectrometer for about 160 days. The result showed that there was a burst release during the first month and the release rate tends to slow down and become steady afterwards. In addition, the copper release was mainly influenced by frame, indomethacin and copper type (copper wire and copper sleeve) while the shape variation had little effect on copper release throughout the experiment. Moreover, the influence of copper surface area was only noticeable during the first month. These findings were seldom reported before and may provide some useful information for the design of Cu-IUDs.

  7. Fragmentation of copper current collectors in Li-ion batteries during spherical indentation

    Science.gov (United States)

    Wang, Hsin; Watkins, Thomas R.; Simunovic, Srdjan; Bingham, Philip R.; Allu, Srikanth; Turner, John A.

    2017-10-01

    Large, areal, brittle fracture of copper current collector foils has been observed by 3D x-ray computed tomography (XCT) of a spherically indented Li-ion cell. This fracture is hidden and non-catastrophic to a degree because the graphite layers deform plastically, and hold the materials together so that the cracks in the foils cannot be seen under optical and electron microscopy. The cracking of copper foils could not be immediately confirmed when the cell is opened for post-mortem examination. However, 3D XCT on the indented cell reveals "mud cracks" within the copper layer and an X-ray radiograph on a single foil of the Cu anode shows clearly that the copper foil has broken into multiple pieces. This failure mode of anodes in Li-ion cell has very important implications on the behavior of Li-ion cells under mechanical abuse conditions. The fragmentation of current collectors in the anode must be taken into consideration for the electrochemical responses which may lead to capacity loss and affect thermal runaway behavior of the cells.

  8. Chelation-Assisted, Copper(II) Acetate-Accelerated Azide-Alkyne Cycloaddition

    Science.gov (United States)

    Kuang, Gui-Chao; Michaels, Heather A.; Simmons, J. Tyler; Clark, Ronald J.; Zhu, Lei

    2010-01-01

    We described in a previous communication (ref. 13) a variant of the popular CuI-catalyzed azide-alkyne cycloaddition (AAC) process where 5 mol% Cu(OAc)2 in the absence of any added reducing agent is sufficient to enable the reaction. 2-Picolylazide (1) and 2-azidomethylquinoline (2) were found to be by far the most reactive carbon azide substrates that convert to 1,2,3-triazoles in as short as a few minutes under the discovered conditions. We hypothesized that the abilities of 1 and 2 to chelate CuII contribute significantly to the observed high reaction rates. The current work examines the effect of auxiliary ligands near the azido group other than pyridyl for CuII on the efficiency of the Cu(OAc)2-accelerated AAC reaction. The carbon azides capable of binding to the catalytic copper center at the alkylated azido nitrogen in a chelatable fashion were indeed shown to be superior substrates under the reported conditions. The chelation between carbon azide 11 and CuII was demonstrated in an X-ray single crystal structure. In a limited set of examples, the ligand tris(benzyltriazolylmethyl)amine (TBTA), developed by Fokin et al. for assisting the original CuI-catalyzed AAC reactions (ref. 8), also dramatically enhances the Cu(OAc)2-accelerated AAC reactions involving non-chelating azides. This observation leads to the hypothesis of an additional effect of chelating azides on the efficiencies of Cu(OAc)2-accelerated AAC reactions, which is to facilitate the rapid reduction of CuII to highly catalytic CuI species. Mechanistic studies on the AAC reactions with particular emphasis on the role of carbon azide/copper interactions will be conducted based on the observations reported in this work. Finally, the immediate utility of the product 1,2,3-triazole molecules derived from chelating azides as multidentate metal coordination ligands is demonstrated. The resulting triazolyl-containing ligands are expected to bind with transition metal ions via the N(2) nitrogen of the 1

  9. Copper(II) bromide, nitrate and perchlorate complexes with sterically demanding N-(6-methylpyridin-2-yl)acetamide ligands.

    Science.gov (United States)

    Smolentsev, Anton I

    2017-08-01

    Functionalized acid amides are widely used in biology, medicine, environmental chemistry and many other areas. Among them, pyridine-substituted amides, in particular N-(pyridin-2-yl)acetamide and its derivatives, play an important role due to their excellent chelating properties. The donor properties of these ligands can be effectively modified by introducing electron-donating substituents (e.g. alkyl groups) into the heterocycle. On the other hand, substituents in the α-position of the pyridine ring can create steric hindrance, which significantly influences the coordination number and geometry. To achieve a better understanding of these effects, copper(II) complexes with sterically demanding N-(6-methylpyridin-2-yl)acetamide ligands (L) and monoanions of different size, shape and coordination ability have been chosen as model compounds. The crystal structures of three new compounds, bromidobis[N-(6-methylpyridin-2-yl-κN)acetamide-κO]copper(II) bromide, [CuBr(C8H10N2O)]Br, (I), aquabis[N-(6-methylpyridin-2-yl-κN)acetamide-κO]copper(II) dinitrate, [Cu(C8H10N2O)(H2O)](NO3)2, (II), and aquabis[N-(6-methylpyridin-2-yl-κN)acetamide-κO]copper(II) bis(perchlorate), [Cu(C8H10N2O)(H2O)](ClO4)2, (III), have been determined by single-crystal X-ray diffraction analysis. It has been shown that the presence of the 6-methyl group results in either a distorted square-pyramidal or a distorted trigonal-bipyramidal coordination geometry around the Cu(II) centres instead of the typical octahedral geometry observed when the methyl substituent is absent or occupies any other position on the pyridine ring. Moreover, due to the steric hindrance provided by the L ligands, only the bromide ligand, the smallest of the series, enters into the first coordination sphere of the Cu(II) ion in (I). In (II) and (III), the vacant coordination site of the Cu(II) ion is occupied by a water molecule, while the nitrate and perchlorate anions are not involved in coordination to the metal centre

  10. Application of a metal ion-imprinted polymer based on salen-Cu complex to flow injection preconcentration and FAAS determination of copper.

    Science.gov (United States)

    Walas, Stanisław; Tobiasz, Anna; Gawin, Marta; Trzewik, Bartosz; Strojny, Marcin; Mrowiec, Halina

    2008-06-30

    A new Cu(II)-imprinted polymer (Cu-IIP) for preconcentration of copper by liquid-solid extraction via flow injection technique has been proposed. Cu-IIP was obtained by copolymerization of salen-Cu(II) complex with styrene and divinylbenzene using suspension polymerization technique. Granules fraction of 60-80 microm in diameter was used as a microcolumn packing. Cu(II) sorption was proved to be the most effective from solutions of pH 7, whereas similar elution effectiveness was observed when applying as eluents hydrochloric or nitric acid in the concentration range of 0.5-10% (v/v). The system exhibited good long-term stability and acid resistance. Batch sorbent capacity was found to be 0.11 mmol g(-1) of a dry polymer. Enrichment factor (EF) for 30 s loading time was 16. Preconcentration of Cu(II) and potentially interfering metal ions is strongly pH dependent. Examination of Cu(II) sorption in the presence of Pb(II), Cd(II), Zn(II) and Ag(I) showed significant influence of cadmium and zinc ions only and that was for the interferent concentrations above 0.5 mg L(-1) (Cu-IIP mass of ca. 35 mg). The interference effect was reduced with the sorbent mass increase. Fe(III) and Mn(II) ions, present in treated tap water in relatively high concentrations, did not interfere. Effective pH adjusting of the loaded solution in on-line mode, when applying diluted Clark-Lubs buffering solution, allowed accurate copper determination in tap water (compared to graphite furnace atomic absorption spectrometry, GFAAS) using standard addition or combination calibration method.

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

    Energy Technology Data Exchange (ETDEWEB)

    Iivonen, Tomi, E-mail: tomi.iivonen@helsinki.fi; Hämäläinen, Jani; Mattinen, Miika; Popov, Georgi; Leskelä, Markku [Laboratory of Inorganic Chemistry, Department of Chemistry, University of Helsinki, P.O. Box 55, FI-00014 Helsinki (Finland); Marchand, Benoît; Mizohata, Kenichiro [Division of Materials Physics, Department of Physics, University of Helsinki, P.O. Box 43, FI-00014 Helsinki (Finland); Kim, Jiyeon; Fischer, Roland A. [Chair of Inorganic Chemistry II, Ruhr-University Bochum, Universitätsstrasse 150, 44780 Bochum (Germany)

    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.

  12. Complexes cobalt(II, zinc(II and copper(II with some newly synthesized benzimidazole derivatives and their antibacterial activity

    Directory of Open Access Journals (Sweden)

    S. O. PODUNAVAC-KUZMANOVIC

    1999-05-01

    Full Text Available The preparation and properties of some complexes of cobalt(II, zinc(II and copper(II with several newly synthesized benzimidazole derivatives (L are reported. The complexes, of the general formula [MCl2L2] (M=Co(II, Zn(II and [CuCl2L(H2O], have a tetrahedral structure. The complexes were characterized by elemental analysis, molar conductivity, magnetic susceptibility measurements, IR and absorption electronic spectra. The antibacterial activitiy of the benzimidazoles and their complexes was evaluated against Erwinia carotovora subsp. carotovora and Erwinia amylovora. The complexes were found to be more toxic than the ligands.

  13. Structural, MALDI-TOF-MS, magnetic and spectroscopic studies of new dinuclear copper(II), cobalt(II) and zinc(II) complexes containing a biomimicking μ-OH bridge.

    Science.gov (United States)

    Núñez, Cristina; Bastida, Rufina; Macías, Alejandro; Valencia, Laura; Neuman, Nicolás I; Rizzi, Alberto C; Brondino, Carlos D; González, Pablo J; Capelo, José Luis; Lodeiro, Carlos

    2010-12-28

    The Py(2)N(4)S(2) octadentate coordinating ligand afforded dinuclear cobalt, copper and zinc complexes and the corresponding mixed metal compounds. The overall geometry and bonding modes have been deduced on the basis of elemental analysis data, MALDI-TOF-MS, IR, UV-vis and EPR spectroscopies, single-crystal X-Ray diffraction, conductivity and magnetic susceptibility measurements. In the copper and zinc complexes, a μ-hydroxo bridge links the two metal ions. In both cases, the coordination geometry is distorted octahedral. Magnetic and EPR data reveal weakly antiferromagnetic high spin Co(II) ions, compatible with a dinuclear structure. The magnetic characterization of the dinuclear Cu(II) compound indicates a ferromagnetically coupled dimer with weak antiferromagnetic intermolecular interactions. The intra-dimer ferromagnetic behaviour was unexpected for a Cu(II) dimer with such μ-hydroxo bridging topology. We discuss the influence on the magnetic properties of non-covalent interactions between the bridging moiety and the lattice free water molecules.

  14. Copper and Zinc Ions Specifically Promote Nonamyloid Aggregation of the Highly Stable Human γ-D Crystallin.

    Science.gov (United States)

    Quintanar, Liliana; Domínguez-Calva, José A; Serebryany, Eugene; Rivillas-Acevedo, Lina; Haase-Pettingell, Cameron; Amero, Carlos; King, Jonathan A

    2016-01-15

    Cataract is the leading cause of blindness in the world. It results from aggregation of eye lens proteins into high-molecular-weight complexes, causing light scattering and lens opacity. Copper and zinc concentrations in cataractous lens are increased significantly relative to a healthy lens, and a variety of experimental and epidemiological studies implicate metals as potential etiological agents for cataract. The natively monomeric, β-sheet rich human γD (HγD) crystallin is one of the more abundant proteins in the core of the lens. It is also one of the most thermodynamically stable proteins in the human body. Surprisingly, we found that both Cu(II) and Zn(II) ions induced rapid, nonamyloid aggregation of HγD, forming high-molecular-weight light-scattering aggregates. Unlike Zn(II), Cu(II) also substantially decreased the thermal stability of HγD and promoted the formation of disulfide-bridged dimers, suggesting distinct aggregation mechanisms. In both cases, however, metal-induced aggregation depended strongly on temperature and was suppressed by the human lens chaperone αB-crystallin (HαB), implicating partially folded intermediates in the aggregation process. Consistently, distinct site-specific interactions of Cu(II) and Zn(II) ions with the protein and conformational changes in specific hinge regions were identified by nuclear magnetic resonance. This study provides insights into the mechanisms of metal-induced aggregation of one of the more stable proteins in the human body, and it reveals a novel and unexplored bioinorganic facet of cataract disease.

  15. Oxygen and hydrogen peroxide reduction catalyses in neutral aqueous media using copper ion loaded glassy carbon electrode electrolyzed in ammonium carbamate solution

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, Hiroaki; Yamazaki, Haruhito [Department of Materials Science and Engineering, Graduate School of Engineering, Saitama Institute of Technology, 1690 Fusaiji Fukaya, Saitama 369-0293 (Japan); Wang, Xiuyun [School of Chemical Engineering, University of Science and Technology Liaoning, Anshan, Liaoning, 114051 (China); Uchiyama, Shunichi [Department of Materials Science and Engineering, Graduate School of Engineering, Saitama Institute of Technology, 1690 Fusaiji Fukaya, Saitama 369-0293 (Japan)], E-mail: uchiyama@sit.ac.jp

    2009-01-30

    An aminated glassy carbon electrode (AGCE) can be obtained by the electrode oxidation of glassy carbon electrode in ammonium carbamate solution. In the cyclic voltammetric experiments, the electrode reduction of the dissolved oxygen began from -0.15 V vs. Ag/AgCl in neutral aqueous media when the aminated glassy carbon electrode was used as a working electrode although it began from -0.40 V vs. Ag/AgCl when a polished GCE was used. The nitrogen containing groups introduced by the electrode oxidation of carbamic acid must be related with the acceleration of the electron transfer rate of oxygen. Moreover, the new reduction wave of the dissolved oxygen appeared at +0.15 V vs. Ag/AgCl when copper (II) ion was coordinated to AGCE surface. This reduction potential of oxygen coincided with that of copper (II) ion and this fact suggests that the coordinated copper ion to the aminated carbon surface works as a redox mediator of oxygen. The reduction product of oxygen was monitored by rotating platinum ring - aminated glassy carbon disk electrode, and it was found that most of oxygen was reduced to water in a potential range negative than -0.4 V vs. Ag/AgCl. By using AGCE, it was recognized that the catalytic reduction of hydrogen peroxide was also taken place as well as oxygen reduction.

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

    Science.gov (United States)

    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.

  17. Synthetic, Crystallographic, and Computational Study of Copper(II) Complexes of Ethylenediaminetetracarboxylate Ligands

    NARCIS (Netherlands)

    Matovic, Zoran D.; Miletic, Vesna D.; Cendic, Marina; Meetsma, Auke; van Koningsbruggen, Petra J.; Deeth, Robert J.; Matović, Zoran D.; Miletić, Vesna D.; Ćendić, Marina

    2013-01-01

    Copper(II) complexes of hexadentate ethylenediaminetetracarboxylic acid type ligands H(4)eda3p and Rieddadp (H(4)eda3p = ethylenediamine-N-acetic-N,N',N'-tri-3-propionic acid; ateddadp = ethylenediamine-N,N'-diaceticN,N'-di-3-propionic acid) have been prepared. An octahedral trans(O-6) geometry (two

  18. Synthetic, Crystallographic, and Computational Study of Copper(II) Complexes of Ethylenediaminetetracarboxylate Ligands

    NARCIS (Netherlands)

    Matovic, Zoran D.; Miletic, Vesna D.; Cendic, Marina; Meetsma, Auke; van Koningsbruggen, Petra J.; Deeth, Robert J.; Matović, Zoran D.; Miletić, Vesna D.; Ćendić, Marina

    2013-01-01

    Copper(II) complexes of hexadentate ethylenediaminetetracarboxylic acid type ligands H(4)eda3p and Rieddadp (H(4)eda3p = ethylenediamine-N-acetic-N,N',N'-tri-3-propionic acid; ateddadp = ethylenediamine-N,N'-diaceticN,N'-di-3-propionic acid) have been prepared. An octahedral trans(O-6) geometry (two

  19. Copper(II)–imida‐salen Complexes Encapsulated into NaY Zeolite for Oxidations Reactions

    DEFF Research Database (Denmark)

    Kuźniarska‐Biernacka, Iwona; Carvalho, M. Alice; Rasmussen, Søren Birk

    2013-01-01

    The oxidation of phenol, cychohexanol and hydroquinone has been screened in the presence of copper(II) complexes with the Schiff‐base salen ligand, 1,5‐bis[(E)‐5‐chloro‐2‐hydroxybenzylideneamino]‐1H‐imidazole‐4‐carbonitrile, and encapsulated into NaY zeolite by using two different methods. The new...

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

    Science.gov (United States)

    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

  1. Molecular Mechanics (MM) Force Fields for Modelling of Copper(II) Amino Acid Complexes in Different Environments

    Science.gov (United States)

    Sabolović, Jasmina

    2009-03-01

    New MM force field developed for modelling the properties of copper(II) complexes with aliphatic amino acid in vacuo, in crystal, and in aqueous solution was applied to study conformational properties of bis(N,N-diethylglycinato)copper(II). Two hypotheses are examined and confirmed as true: (i) the conformations which do not allow apical coordination to the copper(II) are the most stable in vacuo and in aqueous solution; (ii) MM calculations quantitatively support the supposition that the experimentally observed conformer is better suited for crystal packing than the in vacuo and in solution most stable conformers.

  2. Aqua(azido[N-(pyridin-2-ylcarbonylpyridine-2-carboxamido-κ3N,N′,N′′]copper(II

    Directory of Open Access Journals (Sweden)

    Sandra Bruda

    2013-11-01

    Full Text Available The title compound, [Cu(C12H8N3O2(N3(H2O], was formed by the air oxidation of 2-(aminomethylpyridine in 95% ethanol in the presence of copper(II nitrate and sodium azide with condensation of the resulting picolinamide molecules to generate the imide moiety. The CuII ion has a square-pyramidal coordination sphere, the basal plane being occupied by four N atoms [two pyridine (py N atoms, the imide N atom and an azide N atom] in a nearly planar array [mean deviation = 0.048 (6 Å] with the CuII ion displaced slightly from the plane [0.167 (5 Å] toward the fifth ligand. The apical position is occupied by a coordinating water molecule [Cu—O = 2.319 (4 Å]. The crystal structure is stabilized by hydrogen-bonding interactions between the water molecules and carbonyl O atoms. The inversion-related square-pyramidal complex molecules pack base-to-base with long Cu...Npy contact distances of 3.537 (9 Å, preventing coordination of a sixth ligand.

  3. A spectrophotometric method for the determination of zinc, copper, and cobalt ions in metalloproteins using Zincon.

    Science.gov (United States)

    Säbel, Crystal E; Neureuther, Joseph M; Siemann, Stefan

    2010-02-15

    Zincon (2-carboxy-2'-hydroxy-5'-sulfoformazylbenzene) has long been known as an excellent colorimetric reagent for the detection of zinc and copper ions in aqueous solution. To extend the chelator's versatility to the quantification of metal ions in metalloproteins, the spectral properties of Zincon and its complexes with Zn(2+), Cu(2+), and Co(2+) were investigated in the presence of guanidine hydrochloride and urea, two common denaturants used to labilize metal ions in proteins. These studies revealed the detection of metals to be generally more sensitive with urea. In addition, pH profiles recorded for these metals indicated the optimal pH for complex formation and stability to be 9.0. As a consequence, an optimized method that allows the facile determination of Zn(2+), Cu(2+), and Co(2+) with detection limits in the high nanomolar range is presented. Furthermore, a simple two-step procedure for the quantification of both Zn(2+) and Cu(2+) within the same sample is described. Using the prototypical Cu(2+)/Zn(2+)-protein superoxide dismutase as an example, the effectiveness of this method of dual metal quantification in metalloproteins is demonstrated. Thus, the spectrophotometric determination of metal ions with Zincon can be exploited as a rapid and inexpensive means of assessing the metal contents of zinc-, copper-, cobalt-, and zinc/copper-containing proteins.

  4. Fabrication of interfacial functionalized porous polymer monolith and its adsorption properties of copper ions

    Energy Technology Data Exchange (ETDEWEB)

    Han, Jiaxi; Du, Zhongjie; Zou, Wei; Li, Hangquan; Zhang, Chen, E-mail: zhangch@mail.buct.edu.cn

    2014-07-15

    Highlights: • Interface functionalized PGMA porous monolith was fabricated. • The adsorption capacity of Cu{sup 2+} was 35.3 mg/g. • The effects of porous structure on the adsorption of Cu{sup 2+} were studied. • The adsorption behaviors of porous monolith were studied. - Abstract: The interfacial functionalized poly (glycidyl methacrylate) (PGMA) porous monolith was fabricated and applied as a novel porous adsorbent for copper ions (Cu{sup 2+}). PGMA porous material with highly interconnected pore network was prepared by concentrated emulsion polymerization template. Then polyacrylic acid (PAA) was grafted onto the interface of the porous monolith by the reaction between the epoxy group on PGMA and a carboxyl group on PAA. Finally, the porous monolith was interfacial functionalized by rich amount of carboxyl groups and could adsorb copper ions effectively. The chemical structure and porous morphology of the porous monolith were measured by Fourier transform infrared spectroscopy and scanning electron microscopy. Moreover, the effects of pore size distribution, pH value, co-existing ions, contacting time, and initial concentrations of copper ions on the adsorption capacity of the porous adsorbents were studied.

  5. Proton conduction and long-range ferrimagnetic ordering in two isostructural Copper(II) mesoxalate metal-organic frameworks.

    Science.gov (United States)

    Gil-Hernández, Beatriz; Savvin, Stanislav; Makhloufi, Gamall; Núñez, Pedro; Janiak, Christoph; Sanchiz, Joaquín

    2015-02-16

    Two compounds of formula {(H3O)[Cu7(Hmesox)5(H2O)7]·9H2O}n (1a) and {(NH4)0.6(H3O)0.4[Cu7(Hmesox)5(H2O)7]·11H2O}n (1b) were prepared and structurally characterized by single-crystal X-ray diffraction (H4mesox = mesoxalic acid, 2-dihydroxymalonic acid). The compounds are crystalline functional metal-organic frameworks exhibiting proton conduction and magnetic ordering. Variable-temperature magnetic susceptibility measurements reveal that the copper(II) ions are strongly ferro- and antiferromagnetically coupled by the alkoxide and carboxylate bridges of the mesoxalate linker to yield long-range magnetic ordering with a Tc of 17.6 K, which is reached by a rare mechanism known as topologic ferrimagnetism. Electric conductivity, measured by impedance methods, shows values as high as 6.5 × 10(-5) S cm(-1) and occurs by proton exchange among the hydronium/ammonium and water molecules of crystallization, which fill the voids left by the three-dimensional copper(II) mesoxalate anionic network.

  6. Interaction of ions in water system containing copper-zinc alloy for boiler energy saving

    Institute of Scientific and Technical Information of China (English)

    MING Xing; LIANG Jinsheng; OU Xiuqin; TANG Qingguo; DING Yan

    2006-01-01

    Copper-zinc alloy element for boiler energy saving was put in the intake of simulated boiler system to investigate the interaction and transfer of ions in water system both theoretically and experimentally. The fouling was analyzed by scanning electron microscopy (SEM) and energy dispersive X-ray detector (EDX). The results show that the transfer of calcium and magnesium ions in heat-transfer-surface-water system is affected by zinc ions dissolved from the alloy because of primary battery reaction. Some calcium ions of calcium carbonate crystal are replaced by zinc ions, the growth of aragonite crystal nucleus is retarded, and the transition of calcium carbonate from aragonite to calcite is hampered.

  7. Structural, spectroscopic, magnetic and electrochemical studies of monomer N-substituted-sulfanilamide copper (II) complex with 2,2‧-bipyridine

    Science.gov (United States)

    Öztürk, Filiz; Bulut, İclal; Bulut, Ahmet

    2015-03-01

    A novel copper (II) complex of sulfamethazine (4-amino-N-[4,6-dimethyl-2-pyrimidinyl] benzene sulfonamide, Hsmz) ([Cu(smz)2bipy]ṡ0.8H2O; bipy: 2,2‧-bipyridine) has been synthesized and characterized by single crystal X-ray diffraction, EPR, IR, UV-vis and electrochemical methods. The single crystal X-ray analysis indicated that the compound crystallizes in the monoclinic space group P21/c with Z = 4. The central copper (II) ion is coordinated by two bidentate sulfamethazine anions through the nitrogen atoms together with one bidentate 2,2‧-bipyridine ligand forming the octahedral geometry. The characteristic vibration bands support the X-ray analysis results. The EPR spectral analysis has led to that the ground state wave function of the unpaired electron of copper ion is dx2-y2 (2B1g state) and also indicated that the metal ions are located in distorted octahedral sites (D4h) elongated along the z-axis. The electrochemical studies of the complex were also carried out to determine the active sites of the ligands. The cyclic and square wave voltammetric techniques have been used to determine the complex.

  8. Electrochemical removal of copper ions from dilute solutions using packed bed electrode. Part І

    Directory of Open Access Journals (Sweden)

    I.A. Khattab

    2013-06-01

    Full Text Available Removal of some hazardous waste like copper from effluent streams has an industrial importance. In this field, this paper is directed towards electrochemical removal of copper ions from sulfate solution using packed bed electrode. The cathode packing is in static mode, consisted of graphite particles, with mean particle size equal to 0.125 cm. The high surface area of this cell is expected to give high current efficiency and removal percent. The effect of current density and liquid flow rate were tested. Experimental results obtained indicate that the efficiencies are in direct proportional with current density while inversely proportional with liquid flow rate. It was observed that, using this cell was effective in reducing copper concentration to less than 4 mg/l with R.E of 96.2% during 30 min electrolysis time.

  9. Kr II and Xe II axial velocity distribution functions in a cross-field ion source

    Science.gov (United States)

    Lejeune, A.; Bourgeois, G.; Mazouffre, S.

    2012-07-01

    Laser induced fluorescence measurements were carried out in a cross-field ion source to examine the behaviour of the axial ion velocity distribution functions (VDFs) in the expanding plasma. In the present paper, we focus on the axial VDFs of Kr II and Xe II ions. We examine the contourplots in a 1D-phase space (x,vx) representation in front of the exhaust channel and along the centerline of the ion source. The main ion beam, whose momentum corresponds to the ions that are accelerated through the whole potential drop, is observed. A secondary structure reveals the ions coming from the opposite side of the channel. We show that the formation of the neutralized ion flow is governed by the annular geometry. The assumption of a collisionless shock or a double layer due to supersonic beam interaction is not necessary. A non-negligible fraction of slow ions originates in local ionization or charge-exchange collision events between ions of the expanding plasma and atoms of the background residual gas. Slow ions that are produced near the centerline in the vicinity of the exit plane are accelerated toward the source body with a negative velocity leading to a high sputtering of front face. On the contrary, the ions that are produced in the vicinity of the channel exit plane are partially accelerated by the extended electric field.

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

    Science.gov (United States)

    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.

  11. Highly efficient simultaneous ultrasonic-assisted adsorption of Pb(II), Cd(II), Ni(II) and Cu (II) ions from aqueous solutions by graphene oxide modified with 2,2'-dipyridylamine: Central composite design optimization.

    Science.gov (United States)

    Zare-Dorabei, Rouholah; Ferdowsi, Somayeh Moazen; Barzin, Ahmad; Tadjarodi, Azadeh

    2016-09-01

    In present work, a graphene oxide chemically modified with 2,2'-dipyridylamine (GO-DPA), was synthesized by simple, fast and low-cost process for the simultaneous adsorption of four toxic heavy metals, Pb(II), Cd(II), Ni(II) and Cu(II), from aqueous solutions. The synthesized adsorbent was characterized by FT-IR, XRD, XPS, SEM and AFM measurements. The effects of variables such as pH solution, initial ion concentrations, adsorbent dosage and sonicating time were investigated on adsorption efficiency by rotatable central composite design. The optimum conditions, specified as 8mg of adsorbent, 20mgL(-1) of each ion at pH 5 and short time of 4min led to the achievement of a high adsorption capacities. Ultrasonic power had important role in shortening the adsorption time of ions by enhancing the dispersion of adsorbent in solution. The adsorption kinetic studies and equilibrium isotherms for evaluating the mechanism of adsorption process showed a good fit to the pseudo-second order and Langmuir model, respectively. The maximum adsorption capacities (Qm) of this adsorbent were 369.749, 257.201, 180.893 and 358.824mgg(-1) for lead, cadmium, nickel and copper ions, respectively. The removal performance of adsorbent on the real wastewater samples also showed the feasibility of adsorbent for applying in industrial purposes.

  12. Free cupric ions in contaminated agricultural soils around a copper mine in eastern Nanjing City, China

    Institute of Scientific and Technical Information of China (English)

    LUO Xiao-san; ZHOU Dong-mei; WANG Yu-jun

    2006-01-01

    To determine the environmental free metal ion activity was a recent hot issue. A method to measure low-level free cupric ion activity in soil solution extracted with 0.01 mol/L KNO3 was developed by using cupric ion-selective electrode (ISE) and calibrating with Cu-buffer solution. Three copper buffers including iminodiacetic acid (IDA), ethylenediamine (EN), and glycine (Gly)were compared for calibrating the Cu-ISE curves in the range of free cupric ions (pCu2+) 7-13. The Cu-EN buffer showed the best electrode response and thus was applied as the calibration buffer. The pCu2+ of 39 contaminated agricultural soils around a copper mine was measured, ranging from 5.03 to 9.20. Most Cu in the soil solutions was found to be complexed with dissolved soil organic matters, averaging 98.1%. The proportion of free Cu2+ ions in the soil solutions decreased with the increasing of solution pH. Soluble Cu and free Cu2+ ions concentrations were analyzed by multiple linear regressions to evaluate the effects of soil properties on metal levels and speciation. The results showed that soil solution pH was the most significant factor influencing pCu2+ (with R2 value of 0.76), while not important for the soluble Cu concentration.

  13. The effect of CuII ions in L-asparagine single crystals

    Science.gov (United States)

    Santana, Ricardo C.; Gontijo, Henrique O.; Menezes, Arthur F.; Martins, José A.; Carvalho, Jesiel F.

    2016-11-01

    We report the synthesis, crystal growth, and spectroscopic characterization of L-asparagine monohydrate (LAM) single crystals doped with CuII. The crystals were successfully grown by slow cooling from a supersaturated aqueous solution up to size of 16×12×2 mm3;the effect of copper impurities in the crystals morphology was discussed. Electron Paramagnetic Resonance (EPR) was used to calculate the g and hyperfine coupling (A) tensors of the CuII ions (g1=2.044, g2=2.105, g3=2.383and A1≈0, A2=35, A3=108 Gauss). The EPR spectra for certain orientations of the magnetic field suggest that CuII ions are coordinated to two 14N atoms. Correlating the EPR and optical absorption results, the crystal field and the CuII orbital bond parameters were calculated. The results indicate that the paramagnetic center occupies interstitial rhombic distorted site and the ground orbital state for the unpaired electron is the d(x2-y2).

  14. Effects of copper oxide nanoparticles and copper ions to zebrafish (Danio rerio) cells, embryos and fry

    DEFF Research Database (Denmark)

    Thit, Amalie; Skjolding, Lars Michael; Selck, Henriette

    2017-01-01

    with similar concentration-response relationships, whereas only Cu ions affected fry mortality (24h LC50≈30μM, ≈2mgCuL-1 for Cu ions and no significant mortality observed at up to 200μM, 12.7mgCuL-1 for CuO NP). Both Cu forms increased fry swimming activity during light cycles and decreased activity during......) and fry locomotion. In the ZFL tests, no significant cytotoxicity (cell death, decreased metabolic or cell membrane integrity) was detected for either treatment, though both significantly affected reactive oxygen species (ROS) production. Embryo mortality was affected by both Cu ions and CuO NPs...... dark cycles: Cu ions had significant impact at lower concentrations than CuO NPs. The implications are that Cu ions generally are more toxic than CuO NPs to embryos and fry but there is a marked difference in toxicity among the different zebrafish model systems. Metal NPs release into the environment...

  15. A Nanostructured Lipid System as a Strategy to Improve the in Vitro Antibacterial Activity of Copper(II Complexes

    Directory of Open Access Journals (Sweden)

    Patricia B. da Silva

    2015-12-01

    Full Text Available The aim of this study was to construct a nanostructured lipid system as a strategy to improve the in vitro antibacterial activity of copper(II complexes. New compounds with the general formulae [CuX2(INH2]·nH2O (X = Cl− and n = 1 (1; X = NCS− and n = 5 (2; X = NCO− and n = 4 (3; INH = isoniazid, a drug widely used to treat tuberculosis derived from the reaction between the copper(II chloride and isoniazid in the presence or absence of pseudohalide ions (NCS− or NCO− were synthesized and characterized by infrared spectrometry, electronic absorption spectroscopy, electron paramagnetic resonance (EPR spectroscopy, elemental analysis, melting points and complexometry with 2,2′,2′′,2′′′-(Ethane-1,2-diyldinitrilotetraacetic acid (EDTA. The characterization techniques allowed us to confirm the formation of the copper(II complexes. The Cu(II complexes were loaded into microemulsion (MEs composed of 10% phase oil (cholesterol, 10% surfactant [soy oleate and Brij® 58 (1:2] and 80% aqueous phase (phosphate buffer pH = 7.4 prepared by sonication. The Cu(II complex-loaded MEs displayed sizes ranging from 158.0 ± 1.060 to 212.6 ± 1.539 nm, whereas the polydispersity index (PDI ranged from 0.218 ± 0.007 to 0.284 ± 0.034. The antibacterial activity of the free compounds and those that were loaded into the MEs against Staphylococcus aureus ATCC® 25923 and Escherichia coli ATCC® 25922, as evaluated by a microdilution technique, and the cytotoxicity index (IC50 against the Vero cell line (ATCC® CCL-81TM were used to calculate the selectivity index (SI. Among the free compounds, only compound 2 (MIC 500 μg/mL showed activity for S. aureus. After loading the compounds into the MEs, the antibacterial activity of compounds 1, 2 and 3 was significantly increased against E. coli (MIC’s 125, 125 and 500 μg/mL, respectively and S. aureus (MICs 250, 500 and 125 μg/mL, respectively. The loaded compounds were less toxic against the Vero

  16. A Nanostructured Lipid System as a Strategy to Improve the in Vitro Antibacterial Activity of Copper(II) Complexes.

    Science.gov (United States)

    Silva, Patricia B da; Bonifácio, Bruna V; Frem, Regina C G; Godoy Netto, Adelino V; Mauro, Antonio E; Ferreira, Ana M da Costa; Lopes, Erica de O; Raddi, Maria S G; Bauab, Tais M; Pavan, Fernando R; Chorilli, Marlus

    2015-12-16

    The aim of this study was to construct a nanostructured lipid system as a strategy to improve the in vitro antibacterial activity of copper(II) complexes. New compounds with the general formulae [CuX₂(INH)₂]·nH₂O (X = Cl(-) and n = 1 (1); X = NCS(-) and n = 5 (2); X = NCO(-) and n = 4 (3); INH = isoniazid, a drug widely used to treat tuberculosis) derived from the reaction between the copper(II) chloride and isoniazid in the presence or absence of pseudohalide ions (NCS(-) or NCO(-)) were synthesized and characterized by infrared spectrometry, electronic absorption spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, elemental analysis, melting points and complexometry with 2,2',2'',2'''-(Ethane-1,2-diyldinitrilo)tetraacetic acid (EDTA). The characterization techniques allowed us to confirm the formation of the copper(II) complexes. The Cu(II) complexes were loaded into microemulsion (MEs) composed of 10% phase oil (cholesterol), 10% surfactant [soy oleate and Brij® 58 (1:2)] and 80% aqueous phase (phosphate buffer pH = 7.4) prepared by sonication. The Cu(II) complex-loaded MEs displayed sizes ranging from 158.0 ± 1.060 to 212.6 ± 1.539 nm, whereas the polydispersity index (PDI) ranged from 0.218 ± 0.007 to 0.284 ± 0.034. The antibacterial activity of the free compounds and those that were loaded into the MEs against Staphylococcus aureus ATCC® 25923 and Escherichia coli ATCC® 25922, as evaluated by a microdilution technique, and the cytotoxicity index (IC50) against the Vero cell line (ATCC® CCL-81(TM)) were used to calculate the selectivity index (SI). Among the free compounds, only compound 2 (MIC 500 μg/mL) showed activity for S. aureus. After loading the compounds into the MEs, the antibacterial activity of compounds 1, 2 and 3 was significantly increased against E. coli (MIC's 125, 125 and 500 μg/mL, respectively) and S. aureus (MICs 250, 500 and 125 μg/mL, respectively). The loaded compounds were less toxic against the Vero

  17. Preparation of ethambutol-copper(II) complex and fabrication of PVC based membrane potentiometric sensor for copper.

    Science.gov (United States)

    Gupta, Vinod K; Prasad, Rajendra; Kumar, Azad

    2003-05-28

    Copper(II) complex of ethambutol (I) was prepared and used in the fabrication of Cu(2+) selective ISE membrane. The membrane having Cu(II)-ethambutol complex (I) as electroactive material, along with sodium tetraphenylborate (NaTPB) as anion discriminator, dioctylphthalate (DOP) as plasticizer in poly(vinyl chloride) (PVC) matrix in the percentage ratio 6:2:190:200 (I:NaTPB:DOP:PVC) (w/w) gave a linear response in the concentration range 7.94x10(-6) to 1.0x10(-1) M of Cu(2+) with a slope of 29.9+/-0.2 mV per decade of activity and a fast response time of 11+/-2 s. The sensor works well in the pH range 2.1-6.3 and could be satisfactorily used in presence of 40% (v/v) methanol, ethanol and acetone and is selective for copper over a large number of cations with slight interference from Na(+) and Co(2+) if present at a level 1.5x10(-5) and 6.5x10(-5) M, respectively. It works well over a period of 6 months and can also be used as indicator electrode for the end point determination in the potentiometric titration of Cu(2+) against EDTA as well as in the determination of Cu(2+) in real samples.

  18. Copper(II) Complexes of Phenanthroline and Histidine Containing Ligands: Synthesis, Characterization and Evaluation of their DNA Cleavage and Cytotoxic Activity.

    Science.gov (United States)

    Leite, Sílvia M G; Lima, Luís M P; Gama, Sofia; Mendes, Filipa; Orio, Maylis; Bento, Isabel; Paulo, António; Delgado, Rita; Iranzo, Olga

    2016-11-21

    Copper(II) complexes have been intensely investigated in a variety of diseases and pathological conditions due to their therapeutic potential. The development of these complexes requires a good knowledge of metal coordination chemistry and ligand design to control species distribution in solution and tailor the copper(II) centers in the right environment for the desired biological activity. Herein we present the synthesis and characterization of two ligands HL1 and H2L2 containing a phenanthroline unit (phen) attached to the amino group of histidine (His). Their copper(II) coordination properties were studied using potentiometry, spectroscopy techniques (UV-vis and EPR), mass spectrometry (ESI-MS) and DFT calculations. The data showed the formation of single copper complexes, [CuL1](+) and [CuL2], with high stability within a large pH range (from 3.0 to 9.0 for [CuL1](+) and from 4.5 to 10.0 for [CuL2]). In both complexes the Cu(2+) ion is bound to the phen unit, the imidazole ring and the deprotonated amide group, and displays a distorted square pyramidal geometry as confirmed by single crystal X-ray crystallography. Interestingly, despite having similar structures, these copper complexes show different redox potentials, DNA cleavage properties and cytotoxic activity against different cancer cell lines (human ovarian (A2780), its cisplatin-resistant variant (A2780cisR) and human breast (MCF7) cancer cell lines). The [CuL2] complex has lower reduction potential (Epc= -0.722 V vs -0.452 V for [CuL1](+)) but higher biological activity. These results highlight the effect of different pendant functional groups (carboxylate vs amide), placed out of the coordination sphere, in the properties of these copper complexes.

  19. Efficiency of Chitosan for the Removal of Pb (II), Fe (II) and Cu (II) Ions from Aqueous Solutions

    OpenAIRE

    Soheil Sobhanardakani; Raziyeh Zandipak; Hassan Parvizimosaed; Arash Javanshir Khoei; Mehran Moslemi; Mahsa Tahergorabi; Seyed Mehdi Hosseini; Parisa Delfieh

    2014-01-01

    Background: Heavy metals have been recognized as harmful environmental pollutant known to produce highly toxic effects on different organs and systems of both humans and animals. The aim of this paper is to evaluate the adsorption potential of chitosan for the removal of Pb(II), Fe(II) and Cu(II) ions from aqueous solutions. Methods: This study was conducted in laboratory scale. In this paper chitosan has been used as an adsorbent for the removal of Pb(II), Fe(II) and Cu(II) from aqueous s...

  20. Efficiency of Chitosan for the Removal of Pb (II, Fe (II and Cu (II Ions from Aqueous Solutions

    Directory of Open Access Journals (Sweden)

    Soheil Sobhanardakani

    2014-09-01

    Full Text Available Background: Heavy metals have been recognized as harmful environmental pollutant known to produce highly toxic effects on different organs and systems of both humans and animals. The aim of this paper is to evaluate the adsorption potential of chitosan for the removal of Pb(II, Fe(II and Cu(II ions from aqueous solutions. Methods: This study was conducted in laboratory scale. In this paper chitosan has been used as an adsorbent for the removal of Pb(II, Fe(II and Cu(II from aqueous solution. In batch tests, the effects of parameters like pH solution (1.0-8.0, initial metal concentrations (100-1000 mgL-1, contact time (5.0-150 min and adsorbent dose (1.0-7.0 g on the adsorption process were studied. Results: The results showed that the adsorption of Pb(II, Fe(II and Cu(II ions on chitosan strongly depends on pH. The experimental isothermal data were analyzed using the Langmuir and Freundlich equations and it was found that the removal process followed the Langmuir isotherm and maximum adsorption capacity for the adsorption of Pb(II, Fe(II and Cu(II ions by the chitosan were 55.5mg g−1, 71.4 mg g−1 and 59 mg g−1, respectively, under equilibrium conditions at 25±1 ºC. The adsorption process was found to be well described by the pseudo-second-order rate model. Conclusion: The obtained results showed that chitosan is a readily, available, economic adsorbent and was found suitable for removing Pb(II, Fe(II and Cu(II ions from aqueous solution.

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

    Science.gov (United States)

    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

  2. Isolation, Characterization and Antitumour Propirties of the 1,2-Popylenediaminetetraacetate trans-Diaqua-Copper (II).

    Science.gov (United States)

    Kamah, S; Vilaplana, R; Moreno, J; Akdi, K; García-Herdugo, G; González-Vílchez, F

    2000-01-01

    A trans-diaquacomplex formed by copper(II) sulphate and the sequestering polyamminopolycarboxylic ligand 1,2-propylenediaminetetraacetic acid (PDTA) has been isolated and characterized by chemical analysis, titrimetry, FT-IR and electronic spectroscopy, Potentiometric and electronic measurements identified the ligand as tetradentate, two nitrogen and two oxygen atoms being bonded to the Cu(II) in planar positions. This octahedral monomeric soluble compound, is an unusual example of a copper (II) substance showing significant in vitro antitumour activity against the human ovarian tumour cells TG (ID(50) = 2.29 muM at 48 h) and important in vivo antitumour activity against solid Sarcoma 180 with complete regression of the tumour at a dose of 12.5 mg/Kg body weight.

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

    Science.gov (United States)

    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.

  4. Biosorption of the Copper and Cadmium Ions - a Study through Adsorption Isotherms Analysis

    Directory of Open Access Journals (Sweden)

    Marcia T. Veit

    2007-10-01

    Full Text Available In this work, the biosorption process of copper-cadmium ions binary mixture by using marine algae Sargassum filipendula was investigated. A set of experiments was performed to obtain equilibrium data for the given batch operational conditions - T=30°C, pH=5. The interpretation of equilibrium data was based on the binary adsorption isotherms models in the Langmuir and Freundlich forms. To evaluate the models parameters, nonlinear identification procedure was used based on the Least Square statistical method and SIMPLEX local optimizer. An analysis of the obtained results showed that the marine algae biomass has higher affinity to copper ions than to cadmium ones. The biomass maximum adsorption capacity for the binary system was about 1.16 meq/g.

  5. Magnetic property, DFT calculation, and biological activity of bis[(μ(2)-chloro)chloro(1,10-phenanthroline)copper(II)] complex.

    Science.gov (United States)

    Mroueh, Mohammad; Daher, Costantine; Hariri, Essa; Demirdjian, Sally; Isber, Samih; Choi, Eun Sang; Mirtamizdoust, Babak; Hammud, Hassan H

    2015-04-25

    The dinuclear complex bis[(μ(2)-chloro)chloro(1,10-phenanthroline)copper(II)] (1) was synthesized, and characterized by X-ray, FTIR and thermal analysis. The fitting of magnetic susceptibility and magnetization curve of (1) indicates the occurrence of weak antiferromagnetic exchange interaction between copper(II) ions. The electronic structure has been also determined by density functional theory (DFT) method. Complex (1) displayed potent anticancer activity against B16 (Melanoma), MDA-MB-32 (Breast Adenocarcinoma), A549 (Lung Adenocarcinoma), HT-29 (Colon Adenocarcinoma) and SF (Astrocytoma) cell lines with an average IC50 value of 0.726 μg/ml compared to 4.88 μg/ml for cisplatin. Complex (1) has a better therapeutic index and toxicological profile than cisplatin, and has demonstrated a potential chemotherapeutic property.

  6. Systematic coordination chemistry and cytotoxicity of copper(II) complexes with methyl substituted 4-nitropyridine N-oxides.

    Science.gov (United States)

    Puszko, Aniela; Brzuszkiewicz, Anna; Jezierska, Julia; Adach, Anna; Wietrzyk, Joanna; Filip, Beata; Pełczynska, Marzena; Cieslak-Golonka, Maria

    2011-08-01

    Three new nitrato copper(II) complexes of dimethyl substituted 4-nitropyridine N-oxide were synthesized and characterized by elemental analysis, magnetic, spectroscopic, thermal and X-ray methods, respectively. They were isolated as trans isomers, mononuclear (μ=1.70-1.88 BM), five (1-2) and four (3) coordinate species of general formula [Cu(NO3)2(H2O)L2] where L=2,3-dimethyl-, 2,5-dimethyl-4-nitropyridine N-oxide and [Cu (NO3)2L2], L=3,5-dimethyl-4-nitropyridine N-oxide, respectively. The X-ray crystal structure of (1) (L=2,3-dimethyl-4-nitropyridine N-oxide) was determined. The organic ligands, the complexes and copper hexaqua ion as a reference were tested in vitro on the cytotoxic activity against human cancer cell lines: MCF-7 (breast), SW-707 (colon) and P-388 (murine leukemia). The complexes are relatively strong cytotoxic agents towards P-388 cell line. Comparative analysis was performed for all known copper(II) complexes containing methyl derivatives of the 4-nitropyridine N-oxide on the basis of their composition, structure and cytotoxic activities. To obtain the typical structure for these species (i.e., 4-coordinate mononuclear of the type trans-[Cu(inorganic anion)2L2]), two methyl groups must be situated on both sides of nitrogen atom(s) (i.e., NO and NO2) in the ligand. The biological activity was found to be strongly dependent upon the number of the methyl groups and the type of cell line. The best cytotoxic results were found for the complexes without substituents or with one methyl group. Generally, for all cell lines, the complexation increased cytotoxicity when compared with the free ligands.

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

    Science.gov (United States)

    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.

  8. Development of two highly sensitive immunoassays for detection of copper ions and a suite of relevant immunochemicals

    Energy Technology Data Exchange (ETDEWEB)

    Zhao Hongwei [College of Agronomy and Biotechnology, China Agricultural University, Beijing 100193 (China); Department of Molecular Biosciences and Bioengineering, University of Hawaii at Manoa, Honolulu, HI 96822 (United States); Nan Tiegui; Tan Guiyu; Gao Wei; Cao Zhen; Sun Shuo; Li Zhaohu [College of Agronomy and Biotechnology, China Agricultural University, Beijing 100193 (China); Li, Qing X., E-mail: qingl@hawaii.edu [Department of Molecular Biosciences and Bioengineering, University of Hawaii at Manoa, Honolulu, HI 96822 (United States); Wang Baomin, E-mail: wbaomin@263.com [College of Agronomy and Biotechnology, China Agricultural University, Beijing 100193 (China)

    2011-09-19

    Highlights: {center_dot} Two highly sensitive immunoassays for determination of Cu(II) at sub ppb levels. {center_dot} The heterologous competitive enzyme linked immunosorbent assay for heavy metals. {center_dot} Haptenated protein directly conjugated with HRP can reduce the loss of HRP activity. - Abstract: Availability of highly sensitive assays for metal ions can help monitor and manage the environmental and food contamination. In the present study, a monoclonal antibody against Copper(II)-ethylenediaminetetraacetic acid was used to develop two sensitive ELISAs for Cu(II) analysis. Cobalt(II)-EDTA-BSA was the coating antigen in a heterologous indirect competitive ELISA (hicELISA), whereas Co(II)-EDTA-BSA-horseradish peroxidase (HRP) was the enzyme tracer in a heterologous direct competitive ELISA (hdcELISA). Both ELISAs were validated for detecting the content of Cu(II) in environmental waters. The ELISA data agreed well with those from graphite furnace atomic absorption spectroscopy. The methods of developing the Cu(II) hicELISA and hdcELISA are potentially applicable for developing ELISAs for other metals. The chelator-protein complexes such as EDTA-BSA and EDTA-BSA-HRP can form a suite of metal complexes having the consistent hapten density, location and orientation on the conjugates except the difference of the metal core, which can be used as ideal reagents to investigate the relationship between assay sensitivity and antibody affinities for the haptens and the analytes. The strategy of conjugating a haptenated protein directly with HRP can reduce the loss of HRP activity during the conjugation reaction and thus can be applicable for the development of ELISAs for small molecules.

  9. Irradiation damage in aluminium single crystals produced by 50-keV aluminium and copper ions

    DEFF Research Database (Denmark)

    Henriksen, L.; Johansen, A.; Koch, J.

    1968-01-01

    Aluminium single crystals, thin enough to be examined by electron microscopy, have been irradiated with 50-keV aluminium and copper ions. The irradiation fluxes were in the range 1011–1014 cm−2 s−1 and the doses were from 6 × 1012 to 6 × 1014 cm−2. Irradiation along either a or a direction produc...

  10. Biosorption of Fe (II) and Cd (II) ions from aqueous solution using a ...

    African Journals Online (AJOL)

    ADOWIE PERE

    low cost adsorbent to adsorb Cd(II) and Fe(II) metal ions. ... the removal of heavy metals includes high efficiency in metal recovery, readily available, highly ..... sites and also by the decrease in positive surface charge on the adsorbents, which ...

  11. A polymorph structure of copper(II hydrogenphosphite dihydrate

    Directory of Open Access Journals (Sweden)

    Lei Yang

    2009-04-01

    Full Text Available The title compound, poly[[diaquacopper(II]-μ3-hydrogenphosphito], [Cu(HPO3(H2O2]n, (I, has been prepared by hydrothermal synthesis at 393 K. Its non-centrosymmetric polymorph structure, (II, was known previously and has been redetermined at 193 (2 K [El Bali & Massa (2002. Acta Cryst. E58, i29–i31]. The Cu atoms in (I and (II are square-pyramidal coordinated. A distorted octahedral geometry around the Cu atoms is considered by including the strongly elongated apical distances of 2.8716 (15 Å in (I and 3.000 (1 Å in (II. The Cu...Cu separation of the dimeric unit is 3.1074 (3 Å. The secondary building units (SBU (the Cu2O2 dimer and two HPO3 units in (I are inversion related and form a two-dimensional layered structure, with sheets parallel to the bc plane, whereas in the structure of (II, the chain elements are connected via screw-axis symmetry to form a three-dimensional microporous framework. In both polymorph structures, strong O—H...O hydrogen bonds are observed.

  12. Removing of Cu (II) Ion from Polluted Water: Determination of Precipitation Limit of Cu (II) Ion with β-Alanin

    OpenAIRE

    , H Koraqi; , E Behrami; , A Lajqi

    2016-01-01

    The goal of this research was to investigate the condition for removing of Cu (II) ion from water. Through precipitation method with β-Alanin as the ligand.Is this study we examined the precipitation of Cu(II) ion in water solutions of Cu(NO3)2xH2O (1x10-3 mol L-1) with β-Alanin (1x10-3molL-1,1x10-4molL-1,1x10-5 molL-1,1x10-6molL-1) in constant ionic strength of 0,1 molL-1 NaClO4.We have determined the concentration region at which Cu(II) ion start to precipitate. From precipitation diagrams ...

  13. Micronized Copper Wood Preservatives: Efficacy of Ion, Nano, and Bulk Copper against the Brown Rot Fungus Rhodonia placenta.

    Directory of Open Access Journals (Sweden)

    Chiara Civardi

    Full Text Available Recently introduced micronized copper (MC formulations, consisting of a nanosized fraction of basic copper (Cu carbonate (CuCO3·Cu(OH2 nanoparticles (NPs, were introduced to the market for wood protection. Cu NPs may presumably be more effective against wood-destroying fungi than bulk or ionic Cu compounds. In particular, Cu- tolerant wood-destroying fungi may not recognize NPs, which may penetrate into fungal cell walls and membranes and exert their impact. The objective of this study was to assess if MC wood preservative formulations have a superior efficacy against Cu-tolerant wood-destroying fungi due to nano effects than conventional Cu biocides. After screening a range of wood-destroying fungi for their resistance to Cu, we investigated fungal growth of the Cu-tolerant fungus Rhodonia placenta in solid and liquid media and on wood treated with MC azole (MCA. In liquid cultures we evaluated the fungal response to ion, nano and bulk Cu distinguishing the ionic and particle effects by means of the Cu2+ chelator ammonium tetrathiomolybdate (TTM and measuring fungal biomass, oxalic acid production and laccase activity of R. placenta. Our results do not support the presence of particular nano effects of MCA against R. placenta that would account for an increased antifungal efficacy, but provide evidence that attribute the main effectiveness of MCA to azoles.

  14. Structural studies of copper(II) complexes with 2-(2-aminoethyl)pyridine derived Schiff bases and application as precursors of thin organic-inorganic layers.

    Science.gov (United States)

    Barwiolek, Magdalena; Szlyk, Edward; Berg, Andrzej; Wojtczak, Andrzej; Muziol, Tadeusz; Jezierska, Julia

    2014-07-14

    Cu(ii) complexes with Schiff bases derived from 2-pyridin-2-ylethanamine were obtained and characterized by UV-Vis, fluorescence, and IR spectra. The X-ray crystal structures determined for [Cu(ii)(epy(di-t-Buba))Cl] × 0.042H2O and [Cu(ii)(epy(di-t-Buba))O2CCH3] revealed tetrahedral distortion of the Cu(ii) coordination sphere in the solid phase. For both molecules the Cu(ii) ions were found in tetragonal environments, as was confirmed by the values of EPR g-matrix diagonal components. The thermal properties of the complexes and the gas phase composition were studied by TG/IR techniques. Thin layers of the studied copper(ii) complexes were deposited on Si(111) by a spin coating method and characterized by scanning electron microscopy (SEM/EDS), atomic force microscopy (AFM) and fluorescence spectra. For copper(ii) layers the most intensive fluorescence band from intra-ligand transition was observed between 498 and 588 nm. The layers' fluorescence intensity was related to the rotation speed and deposition time.

  15. Synthesis and evaluation of a new colorimetric and ratiometric fluorescence probe for copper ions

    Energy Technology Data Exchange (ETDEWEB)

    Chawla, Har Mohindra, E-mail: hmchawla@chemistry.iitd.ernet.in; Munjal, Priyanka; Goel, Preeti

    2015-08-15

    Synthesis and spectroscopic evaluation of compounds 3a, 3b and 4 reveal that cone conformer of 25,27-bis(o-aminothiophenyl propyloxy) -tetra-p-tert-butylcalix[4]arene 3a can function as a highly selective ratiometric and colorimetric fluorescence probe for copper ions. - Highlights: • We have synthesized a new calixarene based receptor 3 for Cu{sup 2+}. • 3 Showed ratiometric changes with Cu{sup 2+} in emission spectrum. • Reference compound 4 showed quenching with Cu{sup 2+} in emission spectrum. • Importance of calix[4]arene platform in ion recognition.

  16. Brassica napus responses to short-term excessive copper treatment with decrease of photosynthetic pigments, differential expression of heavy metal homeostasis genes including activation of gene NRAMP4 involved in photosystem II stabilization.

    Science.gov (United States)

    Zlobin, I E; Kholodova, V P; Rakhmankulova, Z F; Kuznetsov, Vl V

    2015-08-01

    In the present study, the influence of 50 and 100 µM CuSO4 was investigated starting from 3 h till 72 h treatment of 4-weeks Brassica napus plants. High CuSO4 concentrations in nutrient medium resulted in the rapid copper accumulation in plants, especially in roots, much slower and to lower degree in leaves. Copper excess induced early decrease in the leaf water content and temporary leaf wilting. The decrease in content of photosynthetic pigments became significant to 24 h of excessive copper treatments and reached 35 % decrease to 72 h, but there were no significant changes in maximum quantum efficiency of photosystem II photochemistry. The copper excess affected the expression of ten genes involved in heavy metal homeostasis and copper detoxification. The results showed the differential and organ-specific expression of most genes. The potential roles of copper-activated genes encoding heavy metal transporters (ZIP5, NRAMP4, YSL2, and MRP1), metallothioneins (MT1a and MT2b), low-molecular chelator synthesis enzymes (PCS1 and NAS2), and metallochaperones (CCS and HIPP06) in heavy metal homeostasis and copper ion detoxification were discussed. The highest increase in gene expression was shown for NRAMP4 in leaves in spite of relatively moderate Cu accumulation there. The opinion was advanced that the NRAMP4 activation can be considered among the early reactions in the defense of the photosystem II against copper excess.

  17. Manganese-II oxidation and Copper-II resistance in endospore forming Firmicutes isolated from uncontaminated environmental sites

    Directory of Open Access Journals (Sweden)

    Cristina Dorador

    2016-04-01

    Full Text Available The accumulation of metals in natural environments is a growing concern of modern societies since they constitute persistent, non-degradable contaminants. Microorganisms are involved in redox processes and participate to the biogeochemical cycling of metals. Some endospore-forming Firmicutes (EFF are known to oxidize and reduce specific metals and have been isolated from metal-contaminated sites. However, whether EFF isolated from uncontaminated sites have the same capabilities has not been thoroughly studied. In this study, we measured manganese oxidation and copper resistance of aerobic EFF from uncontaminated sites. For the purposes of this study we have sampled 22 natural habitats and isolated 109 EFF strains. Manganese oxidation and copper resistance were evaluated by growth tests as well as by molecular biology. Overall, manganese oxidation and tolerance to over 2 mM copper was widespread among the isolates (more than 44% of the isolates exhibited Mn (II-oxidizing activity through visible Birnessite formation and 9.1% tolerate over 2 mM copper. The co-occurrence of these properties in the isolates was also studied. Manganese oxidation and tolerance to copper were not consistently found among phylogenetically related isolates. Additional analysis correlating the physicochemical parameters measured on the sampling sites and the metabolic capabilities of the isolates showed a positive correlation between in situ alkaline conditions and the ability of the strains to perform manganese oxidation. Likewise, a negative correlation between temperature in the habitat and copper tolerance of the strains was observed. Our results lead to the conclusion that metal tolerance is a wide spread phenomenon in unrelated aerobic EFF from natural uncontaminated environments.

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

    Science.gov (United States)

    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).

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

    Science.gov (United States)

    1978-05-01

    as in any system, the commander and staff must perform their roles in providing information in a timely and accurate manner. a. Concepts pertaining to...feminine genders . Exceptions to this use of the words "he" or "his" will be so noted. 8. RECOMMENDED CHANGES AND COMMENTS. Users of this manual are...II-lO-Aq3 S NO CAH TR TION NCL IN 0’ SECTION 2 co P ? PAGE YES YES II-10-A43 MAKE CORRECTIONS LOG IN OTL SEPARATE DOCUMENTS Orl, OTL DOCUMENTS ORIG

  20. Hexa-μ-chlorido-μ4-oxido-tetrakis({1-[(pyridin-2-ylmethyl]-1H-benzimidazole-κN3}copper(II

    Directory of Open Access Journals (Sweden)

    Hong Sun

    2011-10-01

    Full Text Available The title tetranuclear complex, [Cu4Cl6O(C13H11N34], features a tetrahedral arrangement of copper(II ions bonded to the central O atom (site symmetry overline{4}. Each of the six edges of the Cu4 tetrahedron is bridged by a chloride ion (one of which has site symmetry 2, so that each copper ion is linked to the other three metal ions through the central O atom and through three separate chloride-ion bridges. The fifth coordination position, located on the central Cu—O axis on the outside of the cluster, is occupied by an N atom of the monodentate 1-(pyridin-2-ylmethyl-1H-benzimidazole ligand. The resulting coordination geometry of the metal ion is a distorted trigonal bipyramid with the O and N atoms in the axial positions. The dihedral angle between the benzimidazole ring system and the pendant pyridine ring is 61.0 (2°.

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

    Energy Technology Data Exchange (ETDEWEB)

    Collado, Sergio; Laca, Adriana [Department of Chemical Engineering and Environmental Technology, University of Oviedo, c/ Julian Claveria s/n, E-33071, Oviedo (Spain); Diaz, Mario, E-mail: mariodiaz@uniovi.es [Department of Chemical Engineering and Environmental Technology, University of Oviedo, c/ Julian Claveria s/n, E-33071, Oviedo (Spain)

    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{sup 3} and 1.0 x 10{sup 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{sup 2+} to Cu{sup +} 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.

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

    Science.gov (United States)

    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.

  3. Antimicrobial evaluation of copper sulfate (II on strains of Enterococcus faecalis. In vitro study.

    Directory of Open Access Journals (Sweden)

    Marisol Sierra

    2013-12-01

    Full Text Available Introduction: Controlling Enterococcus faecalis is of vital importance in endodontics, as this pathogen is associated with endodontic failure. Experimental evidence has shown that copper has antibacterial activity against other pathogens with similar characteristics. The objective of this study was to determine the antimicrobial activity of copper (II or cupric (SC-II sulfate on strains of Enterococcus faecalis and to compare it with the most commonly used antimicrobials. Methodology: We used 33 strains of Enterococcus faecalis isolated from different clinical pictures in different Chilean hospitals. The minimum inhibitory concentration (MIC of SC-II, chlorhexidine and calcium hydroxide was determined by the broth microdilution technique, following the recommendations given by the Clinical and Laboratory Standards Institute. Results: The MIC for CHX varied in the range of 5-10µg/ml; SC-II from 1.5 to 12 µg/ml, and HC was >32mg/ml. The geometric mean of SC-II was 6µg/ml, lower than that of CHX, which was 7.29µg/ml. Conclusions: SC-II showed antimicrobial activity at lower concentrations than CHX. HC (which could have been affected by the buffer effect of the broth microdilution technique showed high values, not comparable to other compounds. We suggest carrying out further studies on the properties of SC-II, such assessing its biocompatibility and reaction with other materials to be used clinically in endodontic therapy.

  4. DNA binding and biological studies of some novel water-soluble polymer-copper(II)-phenanthroline complexes.

    Science.gov (United States)

    Kumar, Rajendran Senthil; Arunachalam, Sankaralingam; Periasamy, Vaiyapuri Subbarayan; Preethy, Christo Paul; Riyasdeen, Anvarbatcha; Akbarsha, Mohammad Abdulkader

    2008-10-01

    Some novel water-soluble polymer-copper(II)-phenanthroline complex samples, [Cu(phen)2(BPEI)]Cl(2).4H2O (phen=1,10-phenanthroline, BPEI=branched polyethyleneimine), with different degrees of copper complex content in the polymer chain have been prepared by ligand substitution method in water-ethanol medium and characterized by infrared, UV-visible, EPR spectral and elemental analysis methods. The binding of these complex samples with DNA has been investigated by electronic absorption spectroscopy, emission spectroscopy and gel retardation assay. Electrostatic interactions between DNA molecule and polymer-copper(II) complex molecule containing many high positive charges have been observed. Besides these ionic interactions, van der Waals interactions, hydrogen bonding and other partial intercalation binding modes may also exist in this system. The polymer-copper(II) complex with higher degree of copper complex content was screened for its antimicrobial activity and antitumor activity.

  5. Synthesis and synergistic antifungal activities of a pyrazoline based ligand and its copper(II) and nickel(II) complexes with conventional antifungals.

    Science.gov (United States)

    Ali, Imran; Wani, Waseem A; Khan, Amber; Haque, Ashanul; Ahmad, Aijaz; Saleem, Kishwar; Manzoor, Nikhat

    2012-08-01

    A pyrazoline based ligand; (5-(4-chlorophenyl)-3-phenyl-4, 5-dihydro-1H-pyrazole-1-carbothioamide) has been synthesized by Claisen-Schmidt condensation of acetophenone with p-chlorobenzaldehyde, followed by sodium hydroxide assisted cyclization of the resulting chalcone with thiosemicarbazide. Metal ion complexes of the synthesized ligand were prepared with Cu(II) and Ni(II) metal ions, separately and respectively. Ligand and the metal complexes were characterized by elemental analysis, FT-IR, UV-Vis, (1)HNMR, ESI-MS and (13)CNMR spectroscopic techniques. Molar conductance measurements in DMSO suggested non-electrolytic nature of the complexes. Tetragonally distorted octahedral geometry for copper and octahedral geometry for the nickel complexes was proposed on the basis of UV-Vis spectroscopic studies and magnetic moment measurements. The complexes were investigated for their ability to kill human fungal pathogen Candida by determining MICs (Minimum inhibitory concentrations), inhibition in solid media and ability to produce a possible synergism with conventional most clinically practiced antifungals by disc diffusion assay and FICI (fractional inhibitory concentration index).

  6. Solvent effects of N-nitroso, N-(2-chloroethyl), N',N'-dibenzylsulfamid and its copper(II) and cobalt(II) complexes: fluorescence studies.

    Science.gov (United States)

    Bensouilah, Nadjia; Fisli, Hassina; Dhaoui, Nabila; Benali-Cherif, Nourredine; Abdaoui, Mohamed

    2013-01-01

    The structure of N-nitroso, N-(2-chloroethyl), N',N'-dibenzylsulfamid (CENS) was established by X-ray crystallography. The atomic coordinates, factors of isotropic thermal agitation, bond lengths and valence angles were determined. The solvent effects on the electronic absorption and fluorescence spectra of CENS were investigated at room temperature. The effects of solvent polarity and of hydrogen bonding were interpreted by means of linear solvation energy relationships (LSERs). Multiple linear regression analysis indicated that the hydrogen donation properties of the solvent play an important role in determining the position of the absorption maximum, while the classical polarity of the medium is the only dominating parameter in determining the emission maximum and the Stokes' shift. Complexation of the investigated compound by two different transition metal ions was studied. Fluorescence measurements show that fluorescence quenching by cobalt(II) is more important than that by copper(II). This phenomenon can be attributed to good stereo-structural matching between the electronic configuration of the Co(2+) ion and the active site distribution of CENS in aqueous solution.

  7. REMOVAL OF COPPER IONS USING ALIQUAT 336/TBP BASED SUPPORTED LIQUID MEMBRANE

    Directory of Open Access Journals (Sweden)

    Baghdad Medjahed

    2014-03-01

    Full Text Available The sorption of copper (II present in an aqueous media using a supported liquid membrane (SLM by chloride tri-N-octylmethylammonium (Aliquat 336 and Tri-n-butylphosphate (TBP from molar ratio 1:1, with polytetrafluoroethylene (PTFE as a membrane support was studied. The effects of various parameters as initial pH, KSCN concentration and ammonium acetate concentration on the extraction yield were carried out. By a calculation program using CHEAQS V. L20.1, the determination of the percentages of the present species before and after extraction were given, in aqueous medium and on the membrane to be able to determine the relation between the nature of the extracted species and the extraction yield. The 23 factorial design achieve the best conditions of recovery procedure. The recovery of copper (II is almost quantitative (94 %, in one step.

  8. Polyacrylamide hydrogel encapsulated E. coli expressing metal-sensing green fluorescent protein as a potential tool for copper ion determination.

    Science.gov (United States)

    Tantimongcolwat, Tanawut; Isarankura-Na-Ayudhya, Chartchalerm; Srisarin, Apapan; Galla, Hans-Joachim; Prachayasittikul, Virapong

    2014-01-01

    A simple, inexpensive and field applicable metal determination system would be a powerful tool for the efficient control of metal ion contamination in various sources e.g. drinking-water, water reservoir and waste discharges. In this study, we developed a cell-based metal sensor for specific and real-time detection of copper ions. E. coli expressing metal-sensing green fluorescent protein (designated as TG1/(CG)6GFP and TG1/H6CdBP4GFP) were constructed and served as a metal analytical system. Copper ions were found to exert a fluorescence quenching effect, while zinc and cadmium ions caused minor fluorescence enhancement in the engineered bacterial suspension. To construct a user-friendly and reagentless metal detection system, TG1/H6CdBP4GFP and TG1/(CG)6GFP were encapsulated in polyacrylamide hydrogels that were subsequently immobilized on an optical fiber equipped with a fluorescence detection module. The sensor could be applied to measure metal ions by simply dipping the encapsulated bacteria into a metal solution and monitoring fluorescence changes in real time as a function of the metal concentration in solution. The sensor system demonstrated high specificity toward copper ions. The fluorescence intensities of the encapsulated TG1/(CG)6GFP and TG1/H6CdBP4GFP were quenched by approximately 70 % and 80 % by a high-dose of copper ions (50 mM), respectively. The level of fluorescence quenching exhibited a direct correlation with the copper concentration, with a linear correlation coefficient (r) of 0.99. The cell-based metal sensor was able to efficiently monitor copper concentrations ranging between 5 M and 50 mM, encompassing the maximum allowed copper contamination in drinking water (31.15 M) established by the WHO. Furthermore, the cell-based metal sensor could undergo prolonged storage for at least 2 weeks without significantly influencing the copper sensitivity.

  9. Uptake of copper ion by activated sludge and its bacterial community variation analyzed by 16S rDNA

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The effect and uptake of copper ion on SBR(sequence batch reactor) biological treatment system was studied in this paper. Special nutrient and powder activated carbon(PAC) additive were tested as uptake stimulation technique. Results showed that copper ion had higher effect on unacclimated activated sludge system than on acclimated one. The special nutrient adding could enhance the uptake of copper significantly, while PAC adding could improve the sludge settling and decrease the turbidity of effluent. The variation of bacterial community analyzed by 16S rDNA method showed the acclimation of copper could increase copper resistance species, and excess accumulation could cause some species diminish. It was confirmed that acclimation could improve the resistance and uptake ability of microorganism to heavy metal.

  10. Hydrogen bonds as structural directive towards unusual polynuclear complexes: synthesis, structure, and magnetic properties of copper(II) and nickel(II) complexes with a 2-aminoglucose ligand.

    Science.gov (United States)

    Burkhardt, Anja; Spielberg, Eike T; Simon, Sascha; Görls, Helmar; Buchholz, Axel; Plass, Winfried

    2009-01-01

    The reaction of benzyl 2-amino-4,6-O-benzylidene-2-deoxy-alpha-D-glucopyranoside (HL) with the metal salts Cu(ClO(4))(2)6 H(2)O and Ni(NO(3))(2)6 H(2)O affords via self-assembly a tetranuclear mu(4)-hydroxido bridged copper(II) complex [(mu(4)-OH)Cu(4)(L)(4)(MeOH)(3)(H(2)O)](ClO(4))(3) (1) and a trinuclear alcoholate bridged nickel(II) complex [Ni(3)(L)(5)(HL)]NO(3) (2), respectively. Both complexes crystallize in the acentric space group P2(1). The X-ray crystal structure reveals the rare (mu(4)-OH)Cu(4)O(4) core for complex 1 which is mu(2)-alcoholate bridged. The copper(II) ions possess a distorted square-pyramidal geometry with an [NO(4)] donor set. The core is stabilized by hydrogen bonding between the coordinating amino group of the glucose backbone and the benzylidene protected oxygen atom O4 of a neighboring {Cu(L)} fragment as hydrogen-bond acceptor. For complex 2 an [N(4)O(2)] donor set is observed at the nickel(II) ions with a distorted octahedral geometry. The trinuclear isosceles Ni(3) core is bridged by mu(3)-alcoholate O3 oxygen atoms of two glucose ligands. The two short edges are capped by mu(2)-alcoholate O3 oxygen atoms of the two ligands coordinated at the nickel(II) ion at the vertex of these two edges. Along the elongated edge of the triangle a strong hydrogen bond (244 pm) between the O3 oxygen atoms of ligands coordinating at the two relevant nickel(II) ions is observed. The coordinating amino groups of the these two glucose ligands are involved in additional hydrogen bonds with O4 oxygen atoms of adjacent ligands further stabilizing the trinuclear core. The carbohydrate backbones in all cases adopt the stable (4)C(1) chair conformation and exhibit the rare chitosan-like trans-2,3-chelation. Temperature dependent magnetic measurements indicate an overall antiferromagnetic behavior for complex 1 with J(1)=-260 and J(2)=-205 cm(-1) (g=2.122). Compound 2 is the first ferromagnetically coupled trinuclear nickel(II) complex with J(A)=16.4 and J

  11. Reduction of microbial pathogens during apple cider production using sodium hypochlorite, copper ion, and sonication.

    Science.gov (United States)

    Rodgers, Stephanie L; Ryser, Elliot T

    2004-04-01

    Sodium hypochlorite (100 ppm), copper ion water (1 ppm), and sonication (22 to 44 kHz and 44 to 48 kHz) were assessed individually and in combination for their ability to reduce populations of Escherichia coli O157:H7 and Listeria monocytogenes on apples and in apple cider. Commercial unpasteurized cider was inoculated to contain approximately 10(6) CFU/ml of either pathogen and then sonicated at 44 to 48 kHz, with aliquots removed at intervals of 30 to 60 s for up to 5 min and plated to determine numbers of survivors. Subsequently, whole apples were inoculated by dipping to contain approximately 10(6) CFU/g E. coli O157:H7 or L. monocytogenes, held overnight, and then submerged in 1 ppm copper ion water with or without 100 ppm sodium hypochlorite for 3 min with or without sonication at 22 to 44 kHz and examined for survivors. Treated apples were also juiced, with the resulting cider sonicated for 3 min. Populations of both pathogens decreased 1 to 2 log CFU/ml in inoculated cider following 3 min of sonication. Copper ion water alone did not significantly reduce populations of either pathogen on inoculated apples. However, when used in combination with sodium hypochlorite, pathogen levels decreased approximately 2.3 log CFU/g on apples. Sonication of this copper ion-sodium hypochlorite solution at 22 to 44 kHz did not further improve pathogen reduction on apples. Numbers of either pathogen in the juice fraction were approximately 1.2 log CFU/ml lower after being juiced, with sonication (44 to 48 kHz) of the expressed juice decreasing L. monocytogenes and E. coli O157:H7 populations an additional 2 log. Hence, a 5-log reduction was achievable for both pathogens with the use of copper ion water in combination with sodium hypochlorite followed by juicing and sonication at 44 to 48 kHz.

  12. Extraction of copper ions by supercritical carbon dioxide

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Complexation combined with supercritical fluid extraction was used to extract Cu2+ in this study. The effects of pressure, temperature, volume of CO2 on the efficiency of extraction were systematically investigated. At the optimum condition a 57.32% recovery was achieved. Addition of suitable amount of methanol(v/v = 5 % ) to the supercritical CO2 can increase in the extraction of Cu2+ (72.69 %, RSD = 2.12 %, n = 3). And the recovery can further increase in the presence of non-ionic surfactant Triton X-100 because of its function of solubilization. Surfactant was first used in the extraction of metal ions in the present study, and the results are satisfied (90.52%, RSD=2.20%, n =3).

  13. Two-step flash light sintering process for enhanced adhesion between copper complex ion/silane ink and a flexible substrate

    Energy Technology Data Exchange (ETDEWEB)

    Jeon, Eun-Beom; Joo, Sung-Jun [Department of Mechanical Convergence Engineering, Hanyang University, Haengdang-dong, Seongdong-gu, Seoul 133-791 (Korea, Republic of); Ahn, Heejoon [Department of Organic and Nano Engineering, Hanyang University, Haengdang-dong, Seongdong-gu, Seoul 133-791 (Korea, Republic of); Kim, Hak-Sung, E-mail: kima@hanyang.ac.kr [Department of Mechanical Convergence Engineering, Hanyang University, Haengdang-dong, Seongdong-gu, Seoul 133-791 (Korea, Republic of); Institute of Nano Science and Technology, Hanyang University, Seoul 133-791 (Korea, Republic of)

    2016-03-31

    A copper complex ion ink (including copper nanoparticles, a copper precursor and a silane coupling agent) was synthesized to enhance the adhesion between the copper pattern and a polyimide (PI) substrate. Oxygen plasma treatment was performed on the polyimide substrate to initiate a chemical reaction between the complex ion ink and the polyimide. Then, a two-step flash light sintering method (consisting of preheating and main sintering) was used to sinter the copper complex ion ink. The copper complex ion patterns were characterized as a function of the weight fraction of silane coupling agent using scanning electron microscopy (SEM), a four-point probe method and adhesion testing. In addition, a bending fatigue test was performed to evaluate the reliability of the conductive copper pattern under cyclic bending. The copper pattern fabricated with copper complex ion ink containing 3 wt% silane coupling agent exhibited the highest adhesion level (5B), the lowest resistivity (7.6 μΩ·cm) and a low resistance change (18%) after the bending fatigue test. The two-step sintering method used to enhance the adhesion between the copper complex ion ink and polyimide substrate was also studied using X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). - Highlights: • The copper complex ion ink with copper nanoparticles and copper precursor was fabricated. • The copper complex ion ink was sintered by two-step flash light sintering method. • The sintered copper pattern exhibited the highest adhesion level (5B). • The resistivity of sintered copper pattern was 7.6 μΩ·cm.

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

    Energy Technology Data Exchange (ETDEWEB)

    Osiry, H.; Cano, A.; Lemus-Santana, A.A.; Rodríguez, A. [Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada, Unidad Legaria, Instituto Politécnico Nacional (Mexico); Carbonio, R.E. [INFIQC-CONICET, Departamento de Físico Química, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, X5000HUA Córdoba (Argentina); Reguera, E., E-mail: edilso.reguera@gmail.com [Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada, Unidad Legaria, Instituto Politécnico Nacional (Mexico)

    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.

  15. A new stepped tetranuclear copper(II) complex: synthesis, crystal structure and photoluminescence properties.

    Science.gov (United States)

    Gungor, Elif

    2017-05-01

    Binuclear and tetranuclear copper(II) complexes are of interest because of their structural, magnetic and photoluminescence properties. Of the several important configurations of tetranuclear copper(II) complexes, there are limited reports on the crystal structures and solid-state photoluminescence properties of `stepped' tetranuclear copper(II) complexes. A new Cu(II) complex, namely bis{μ3-3-[(4-methoxy-2-oxidobenzylidene)amino]propanolato}bis{μ2-3-[(4-methoxy-2-oxidobenzylidene)amino]propanolato}tetracopper(II), [Cu4(C11H13NO3)4], has been synthesized and characterized using elemental analysis, FT-IR, solid-state UV-Vis spectroscopy and single-crystal X-ray diffraction. The crystal structure determination shows that the complex is a stepped tetranuclear structure consisting of two dinuclear [Cu2(L)2] units {L is 3-[(4-methoxy-2-oxidobenzylidene)amino]propanolate}. The two terminal Cu(II) atoms are four-coordinated in square-planar environments, while the two central Cu(II) atoms are five-coordinated in square-pyramidal environments. The solid-state photoluminescence properties of both the complex and 3-[(2-hydroxy-4-methoxybenzylidene)amino]propanol (H2L) have been investigated at room temperature in the visible region. When the complex and H2L are excited under UV light at 349 nm, the complex displays a strong blue emission at 469 nm and H2L displays a green emission at 515 nm.

  16. Removal of lead(II) and copper(II) from aqueous solution using foitite from Linshou mine in Hebei, China.

    Science.gov (United States)

    He, Dengliang; Yin, Guangfu; Dong, Faqin; Liu, Laibao; Tan, Xiaoli; He, Wangyang

    2011-01-01

    Foitite from Linshou mine in China's Hebei province was investigated as an adsorbent to remove Pb(II) and Cu(II) from aqueous solution. The results showed that foitite can readily remove heavy metal ions from aqueous solution. The data shows that the metal uptake for Pb(II) increases rapidly, accounting for 74.47% when contact time was 2 min. In contrast to Pb(ll), there was a worse capability for adsorption of Cu(II). In the first 4 min, the metal uptake accounted for 34.7%. According to the analytical results obtained from X-ray diffraction, laser Raman spectrum, X-ray energy dispersive spectrometer, and Zeta potential, the removal mechanism of Pb(II) and Cu(II) by using foitite can be explained as following: firstly, the existence of an electrostatic field around foitite particles can attract heavy metal ions and consequently combine heavy metal ions with OH; secondly, heavy metal ions in the solution are exchanged with the Fe3+ and Al3+ in the foitite.

  17. Size-Controlled Synthesis of Copper Oxide Particles on Reduced Graphene Oxide for Lithium-Ion Battery Anode Applications.

    Science.gov (United States)

    Jang, Haneul; Kim, Kyungbae; Chang, Hyejung; Kim, Jae-Hun; Choi, Hyunjoo

    2015-11-01

    Copper oxide/reduced graphene oxide (rGO) hybrids have been successfully synthesized by attaching copper ions onto the functional groups of GO by means of a solution process, which causes precipitation and agglomeration of copper oxides during subsequent thermal reduction of the GO. The resulting copper oxide/rGO hybrid exhibited improved electrochemical performance compared to monolithic CuO, which is presumed to be due to rGO acting as a mechanical support that buffers the volume change in copper oxides that occurs as a result of the conversion reaction during charge/discharge cycling. Furthermore, it was found that the size of the copper oxide particles can be optimized by adjusting the annealing time, with a hybrid annealed for 30 min achieving a reversible capacity of 544 mA h g(-1) and an initial coulombic efficiency of 62.7%.

  18. Montmorillonite modified with copper ions: Efficient adsorbent for aflatoxin B1

    Directory of Open Access Journals (Sweden)

    Daković Aleksandra

    2008-01-01

    Full Text Available In this paper, the results of preparation of material for adsorption of aflatoxin B1, based on modification of montmorillonite with copper ions (Cu-MONT, are presented. The bentonite clay from Sokolac deposit (Šipovo, Bosnia was used as the starting raw material. After modification of concentrate of montmorillonite (MONT with copper, the content of copper in Cu-MONT, was 2.65%. It was shown that MONT, as well as the Cu-MONT were efficient in adsorption of aflatoxin B1, at different mass ratios of adsorbent : toxin, and at different pH values. It was determined that for MONT, at the mass ratio adsorbent : toxin = 5000 : 1, aflatoxin B1 adsorption index was 100% at pH 3, 98% at pH 7 and 96% at pH 9. For Cu-MONT, at the same mass ratio, the following aflatoxin B1 adsorption indexes were achieved: 98% at pH 3, 98% at pH 7 and 96% at pH 9. No differences in adsorption of this toxin by both montmorillonites with decreasing the mass ratio of adsorbent : toxin (250 : 1 were observed. That means that ion exchange of inorganic cations in montmorillonite with copper ions did not cause any changes in aflatoxin B1 adsorption, at pH 3, as well as at pH 7 and 9. It was also noticed that adsorption of aflatoxin B1 by MONT and Cu-MONT was not pH dependent.

  19. Air oxygenation chemistry of 4-TBC catalyzed by chloro bridged dinuclear copper(II) complexes of pyrazole based tridentate ligands: synthesis, structure, magnetic and computational studies.

    Science.gov (United States)

    Banerjee, Ishita; Samanta, Pabitra Narayan; Das, Kalyan Kumar; Ababei, Rodica; Kalisz, Marguerite; Girard, Adrien; Mathonière, Corine; Nethaji, M; Clérac, Rodolphe; Ali, Mahammad

    2013-02-07

    Four dinuclear bis(μ-Cl) bridged copper(II) complexes, [Cu(2)(μ-Cl)(2)(L(X))(2)](ClO(4))(2) (L(X) = N,N-bis[(3,5-dimethylpyrazole-1-yl)-methyl]benzylamine with X = H(1), OMe(2), Me(3) and Cl(4)), have been synthesized and characterized by the single crystal X-ray diffraction method. In these complexes, each copper(II) center is penta-coordinated with square-pyramidal geometry. In addition to the tridentate L(X) ligand, a chloride ion occupies the last position of the square plane. This chloride ion is also bonded to the neighboring Cu(II) site in its axial position forming an SP-I dinuclear Cu(II) unit that exhibits small intramolecular ferromagnetic interactions and supported by DFT calculations. The complexes 1-3 exhibit methylmonooxygenase (pMMO) behaviour and oxidise 4-tert-butylcatechol (4-TBCH(2)) with molecular oxygen in MeOH or MeCN to 4-tert-butyl-benzoquinone (4-TBQ), 5-methoxy-4-tert-butyl-benzoquinone (5-MeO-4-TBQ) as the major products along with 6,6'-Bu(t)-biphenyl-3,4,3',4'-tetraol and others as minor products. These are further confirmed by ESI- and FAB-mass analyses. A tentative catalytic cycle has been framed based on the mass spectral analysis of the products and DFT calculations on individual intermediates that are energetically feasible.

  20. Antiangiogenic activity of mononuclear copper(II) polypyridyl complexes for the treatment of cancers.

    Science.gov (United States)

    Nagababu, Penumaka; Barui, Ayan Kumar; Thulasiram, Bathini; Devi, C Shobha; Satyanarayana, S; Patra, Chitta Ranjan; Sreedhar, Bojja

    2015-07-09

    A series of four new mononuclear copper(II) polypyridyl complexes (1-4) have been designed, developed, and thoroughly characterized by several physicochemical techniques. The CT-DNA binding properties of 1-4 have been investigated by absorption, emission spectroscopy, and viscosity measurements. All the complexes especially 1 and 4 exhibit cytotoxicity toward several cancer cell lines, suggesting their anticancer properties as observed by several in vitro assays. Additionally, the complexes show inhibition of endothelial cell (HUVECs) proliferation, indicating their antiangiogenic nature. In vivo chick embryo angiogenesis assay again confirms the antiangiogenic properties of 1 and 4. The formation of excessive intracellular ROS (H2O2 and O2(•-)) and upregulation of BAX induced by copper(II) complexes may be the plausible mechanisms behind their anticancer activities. The present study may offer a basis for the development of new transition metal complexes through suitable choice of ligands for cancer therapeutics by controlling tumor angiogenesis.

  1. Theoretical study, and infrared and Raman spectra of copper(II) chelated complex with dibenzoylmethane

    DEFF Research Database (Denmark)

    Nekoei, A.-R.; Vakili, M.; Hakimi-Tabar, M.

    2014-01-01

    There are some discrepancies in both the vibrational assignments and in the metal-ligand (M-L) bond strengths predicted in the previous studies on the copper (II) chelated complex of dibenzoylmethane, Cu(dbm)2. Also, there is a lack of theoretical structure, Raman spectrum and full vibrational...... assignment for Cu(dbm)2 in the literatures. Density functional theory (DFT) at the B3LYP level and also MP2 calculations using different basis sets, besides Natural Bond Orbital (NBO) and Atoms-in-Molecules (AIM) analyses, have been employed to investigate the effect of methyl substitution with the phenyl...... group on the stabilities of bis(acetylacetonate) copper (II), Cu(acac)2, and Cu(dbm)2 complexes and the electron delocalization in their chelated rings. Measured solid phase infrared and Raman bands for Cu(dbm)2 complex have been interpreted in terms of the calculated vibrational modes and detailed...

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

    Science.gov (United States)

    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.

  3. Fluorescent copper(II complexes: The electron transfer mechanism, interaction with bovine serum albumin (BSA and antibacterial activity

    Directory of Open Access Journals (Sweden)

    Madhumita Hazra

    2017-01-01

    Full Text Available Dinuclear copper(II complexes with formula [Cu2(L2(N32] (1 and [Cu2(L2(NCS2] (2 HL = (1-[(3-methyl-pyridine-2-ylimino-methyl]-naphthalen-2-ol were synthesized by controlling the molar ratio of Cu(OAC2·6H2O, HL, sodium azide (1 and ammonium thiocyanate (2. The end on bridges appear exclusively in azide and thiocyanate to copper complexes. The electron transfer mechanism of copper(II complexes is examined by cyclic voltammetry indicating copper(II complexes are Cu(II/Cu(I couple. The interactions of copper(II complexes towards bovine serum albumin (BSA were examined with the help of absorption and fluorescence spectroscopic tools. We report a superficial solution-based route for the synthesis of micro crystals of copper complexes with BSA. The antibacterial activity of the Schiff base and its copper complexes were investigated by the agar disc diffusion method against some species of pathogenic bacteria (Escherichia coli, Vibrio cholerae, Streptococcus pneumonia and Bacillus cereus. It has been observed that the antibacterial activity of all complexes is higher than the ligand.

  4. Electrochemical Behavior of Nano-grained Pure Copper in Dilute Alkaline Solution with Chloride Ion Trace

    Science.gov (United States)

    Fattah-Alhosseini, Arash; Imantalab, Omid; Attarzadeh, Farid Reza

    2016-10-01

    Effect of nano-grained structure on the interface behavior of pure copper in 0.01M KOH solution with chloride ion trace is investigated by various electrochemical techniques. Nano-grained structure was achieved by accumulative roll bonding (ARB) technique. Before any electrochemical measurements, microstructure was evaluated by means of optical microscopy and transmission electron microscopy (TEM). TEM observations showed that nano-grains (with an average size of below 100 nm) appeared after eight passes of ARB. Polarization curves revealed that increasing chloride ion concentration leads to a decrease in the corrosion and pitting potentials of both annealed and nano-grained pure copper samples. Electrochemical impedance spectroscopy revealed that chloride ion trace lowers passive film resistance and charge-transfer resistance in both annealed and nano-grained samples. Mott-Schottky analysis showed that the surface films formed on annealed and nano-grained samples in KOH solution with and without NaCl addition are of p-type semiconducting behavior. Moreover, this analysis showed that the acceptor density increases by increasing chloride ion concentration.

  5. Effect of Mo Ion Implantation on Stability of Nanocrystalline Copper Surface Layers

    Directory of Open Access Journals (Sweden)

    XI Yang

    2016-08-01

    Full Text Available The surface of pure copper was modified using the surface mechanical attrition treatment (SMAT method, and molybdenum ions were implanted in the nanosurface using a metal vapor vacuum arc (MEVVA. The results of the SMAT were observed by optical microscopy (OM, X-ray diffraction (XRD and scanning electron microscopy (SEM. An obvious nanocrystalline layer and a deformation region exist on the surface. The size of the nanocrystalline layer was characterized using atomic force microscopy (AFM. The results indicate remarkable suppression on grain size, the nanocrystalline layer grows to 163nm after annealing and reduces to only 72nm due to the Mo ion implantation. In addition, the hardness of the topmost surface of the material is 3.5 times that of the SMATed copper, which is about 7 times of the value of the matrix. The above improvements most likely result from the dispersion of the Mo ions and the reactions of the crystal defects due to the SMAT and ion implantation.

  6. Coordination Environment of Cu(II) Ions Bound to N-Terminal Peptide Fragments of Angiogenin Protein.

    Science.gov (United States)

    Magrì, Antonio; Munzone, Alessia; Peana, Massimiliano; Medici, Serenella; Zoroddu, Maria Antonietta; Hansson, Orjan; Satriano, Cristina; Rizzarelli, Enrico; La Mendola, Diego

    2016-08-01

    Angiogenin (Ang) is a potent angiogenic factor, strongly overexpressed in patients affected by different types of cancers. The specific Ang cellular receptors have not been identified, but it is known that Ang-actin interaction induces changes both in the cell cytoskeleton and in the extracellular matrix. Most in vitro studies use the recombinant form (r-Ang) instead of the form that is normally present in vivo ("wild-type", wt-Ang). The first residue of r-Ang is a methionine, with a free amino group, whereas wt-Ang has a glutamic acid, whose amino group spontaneously cyclizes in the pyro-glutamate form. The Ang biological activity is influenced by copper ions. To elucidate the role of such a free amino group on the protein-copper binding, we scrutinized the copper(II) complexes with the peptide fragments Ang(1-17) and AcAng(1-17), which encompass the sequence 1-17 of angiogenin (QDNSRYTHFLTQHYDAK-NH₂), with free amino and acetylated N-terminus, respectively. Potentiometric, ultraviolet-visible (UV-vis), nuclear magnetic resonance (NMR) and circular dichroism (CD) studies demonstrate that the two peptides show a different metal coordination environment. Confocal microscopy imaging of neuroblastoma cells with the actin staining supports the spectroscopic results, with the finding of different responses in the cytoskeleton organization upon the interaction, in the presence or not of copper ions, with the free amino and the acetylated N-terminus peptides.

  7. Chloride-Ion Penetrability and Mechanical Analysis of High Strength Concrete with Copper Slag

    Directory of Open Access Journals (Sweden)

    Savaş Erdem

    2014-05-01

    Full Text Available The use of waste materials and industrial by-products in high-strength concrete could increase the sustainability of the construction industry. In this study, the potential of using copper slag as coarse aggregate in high-strength concrete was experimentally investigated. The effects of replacing gravel coarse aggregate by copper slag particles on the compressive strength, chloride ion- migration, water permeability and impact resistance of high-strength concretes were evaluated. Incorporating copper slag coarse particles resulted in a compressive strength increase of about 14 % on average partly due to the low Ca/Si ratio through the interface area of this concrete (more homogenous internal structure as confirmed by the energy dispersive X-ray micro chemical analysis. It was also found that the copper slag high-strength concrete provided better ductility and had much greater load carrying capacity compared to gravel high-strength concrete under dynamic conditions. Finally, it was observed that in comparison to the high strength concrete with slag, the chloride migration coefficient from non-steady state migration was approximately 30 % greater in the gravel high-strength concrete.

  8. Immobilization of Magnetic Nanoparticles onto Amine-Modified Nano-Silica Gel for Copper Ions Remediation

    Directory of Open Access Journals (Sweden)

    Marwa Elkady

    2016-06-01

    Full Text Available A novel nano-hybrid was synthesized through immobilization of amine-functionalized silica gel nanoparticles with nanomagnetite via a co-precipitation technique. The parameters, such as reagent concentrations, reaction temperature and time, were optimized to accomplish the nano-silica gel chelating matrix. The most proper amine-modified silica gel nanoparticles were immobilized with magnetic nanoparticles. The synthesized magnetic amine nano-silica gel (MANSG was established and characterized using X-ray diffraction (XRD, transmission electron microscopy (TEM, scanning electron microscopy (SEM, Fourier transform infrared (FTIR, thermal gravimetric analysis (TGA, differential scanning calorimetry (DSC and vibrating sample magnetometry (VSM. The feasibility of MANSG for copper ions’ remediation from wastewater was examined. MANSG achieves a 98% copper decontamination from polluted water within 90 min. Equilibrium sorption of copper ions onto MANSG nanoparticles obeyed the Langmuir equation compared to the Freundlich, Temkin, Elovich and Dubinin-Radushkevich (D-R equilibrium isotherm models. The pseudo-second-order rate kinetics is appropriate to describe the copper sorption process onto the fabricated MANSG.

  9. Copper(II tetrafluoroborate as mild and versatile catalyst for the

    Directory of Open Access Journals (Sweden)

    Jihillu. S. Yadav

    2008-12-01

    Full Text Available A variety of -acetamido ketones and ketoesters are readily prepared in high yields under extremelymild conditions via a three component coupling of aromatic aldehydes, enolizable ketones or -ketoesters andnitriles in the presence of 10 mol% of copper(II tetrafluoroborate and a stoichiometric amount of acetylchloride. A solution of 10 mol% of Cu(BF42 in acetonitrile provides a convenient reaction medium to carry out athree component reaction under mild conditions

  10. Copper complexes relevant to the catalytic cycle of copper nitrite reductase: electrochemical detection of NO(g) evolution and flipping of NO2 binding mode upon Cu(II) → Cu(I) reduction.

    Science.gov (United States)

    Maji, Ram Chandra; Barman, Suman Kumar; Roy, Suprakash; Chatterjee, Sudip K; Bowles, Faye L; Olmstead, Marilyn M; Patra, Apurba K

    2013-10-07

    Copper complexes of the deprotonated tridentate ligand, N-2-methylthiophenyl-2'-pyridinecarboxamide (HL1), were synthesized and characterized as part of our investigation into the reduction of copper(II) o-nitrito complexes into the related copper nitric oxide complexes and subsequent evolution of NO(g) such as occurs in the enzyme copper nitrite reductase. Our studies afforded the complexes [(L1)Cu(II)Cl]n (1), [(L1)Cu(II)(ONO)] (2), [(L1)Cu(II)(H2O)](ClO4)·H2O (3·H2O), [(L1)Cu(II)(CH3OH)](ClO4) (4), [(L1)Cu(II)(CH3CO2)]·H2O (5·H2O), and [Co(Cp)2][(L1)Cu(I)(NO2)(CH3CN)] (6). X-ray crystal structure determinations revealed distorted square-pyramidal coordination geometry around Cu(II) ion in 1-5. Substitution of the H2O of 3 by nitrite quantitatively forms 2, featuring the κ(2)-O,O binding mode of NO2(-) to Cu(II). Reduction of 2 generates two Cu(I) species, one with κ(1)-O and other with the κ(1)-N bonded NO2(-) group. The Cu(I) analogue of 2, compound 6, was synthesized. The FTIR spectrum of 6 reveals the presence of κ(1)-N bonded NO2(-). Constant potential electrolysis corresponding to Cu(II) → Cu(I) reduction of a CH3CN solution of 2 followed by reaction with acids, CH3CO2H or HClO4 generates 5 or 3, and NO(g), identified electrochemically. The isolated Cu(I) complex 6 independently evolves one equivalent of NO(g) upon reaction with acids. Production of NO(g) was confirmed by forming [Co(TPP)NO] in CH2Cl2 (λ(max) in CH2Cl2: 414 and 536 nm, ν(NO) = 1693 cm(-1)).

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

    Science.gov (United States)

    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.

  12. Modeling Dinuclear Copper Sites of Biological Relevance : Synthesis, Molecular Structure, Magnetic Properties, and 1H NMR Spectroscopy of a Nonsymmetric Dinuclear Copper(II) Complex. Microcalorimetric Determination of Stepwise Complexation of Copper(II) by

    NARCIS (Netherlands)

    Lubben, Marcel; Hage, Ronald; Meetsma, Auke; Bÿma, Koos; Feringa, Bernard

    1995-01-01

    The new nonsymmetric dinuclear copper(II) complex [Cu2L1(OAc)2](ClO4) (7) was synthesized by complexation of Cu(OAc)2·H2O with a new nonsymmetric dinucleating ligand (5) which is formed in situ by condensation of 2-formyl-6-((4-methylpiperazin-1-yl)methyl)phenol (3a) with 2-(aminoethyl)pyridine. Com

  13. Theoretical investigation of the magnetic exchange interactions in copper(II) oxides under chemical and physical pressures.

    Science.gov (United States)

    Rocquefelte, Xavier; Schwarz, Karlheinz; Blaha, Peter

    2012-01-01

    It remains a challenge to understand the unconventional mechanisms that cause high-T(C) superconductivity in cuprate superconductors, high-T(C) multiferroicity in CuO, or low-dimensional magnetism in the spin-Peierls transition compounds such as CuGeO(3). A common feature of all these copper oxide compounds (containing Cu(2+) ions) is the presence of large magnetic superexchange interactions J. It is a general strategy to apply chemical and/or physical pressure in order to tune these exotic properties. Here we show theoretically, for the first time, the impact of physical pressure on J on CuO, for which we predict a strong enhancement of the low-dimensionality of the magnetic interactions and the spin-frustration at high-pressures. Such modifications are expected to strongly influence the multiferroic properties of CuO. We finally demonstrate that PBE0 hybrid DFT calculations provide reliable J values for a wide range of copper(II) oxides compounds, i.e. CuGeO(3), BaCu(2)Si(2)O(7), BaCu(2)Ge(2)O(7), and La(2)CuO(4).

  14. In vivo detection of copper ions by magnetic resonance imaging using a prion-based contrast agent.

    Science.gov (United States)

    Makino, Satoshi; Umemoto, Tomohiro; Yamada, Hiroshi; Yezdimer, Eric M; Tooyama, Ikuo

    2012-10-01

    Abnormal distributions of transition metals inside the body are potential diagnostic markers for several diseases, including Alzheimer's disease, Parkinson's disease, Wilson's disease, and cancer. In this article, we demonstrate that P57/Gd, a novel prion-based contrast agent, can selectively image tissues with excessive copper accumulation using magnetic resonance imaging (MRI). P57/Gd selectivity binds copper(II) over other physiologically relevant cations such as zinc, iron, manganese, and calcium. To simulate a metabolic copper disorder, we treated mice with an intraperitoneal injection of a CuSO(4) solution to induce a renal copper overload. The MRI signal intensities from the renal cortex and medulla of copper spiked animals that were administered P57/Gd were found to correlate with the ex vivo copper concentrations determined by inductively coupled plasma mass spectrometry.

  15. THE EFFECTS OF COPPER AND ZINC IONS DURING THEIR BINDING WITH HUMAN SERUM γ-GLOBULIN

    Directory of Open Access Journals (Sweden)

    S. B. Cheknev

    2006-01-01

    Full Text Available Abstract. Conformational changes of human serum γ-globulin were studied during and after its binding with copper and zinc ions, using molecular ultrafiltration and differential spectrophotometry. The contents of nonbound metals in the filtrate were evaluated, resp., with sodium diethyl thyocarbamate and o-phenanthroline. It has been shown that copper and zinc exhibited common biological properties during their interactions with protein, but the binding differed sufficiently under similar experimental conditions. E.g., it was confirmed that copper was more active at the external sites of γ-globulin molecule, whereas zinc demonstrated tropicity for the areas of protein intraglobular compartments. The metal-binding sites have been described that differ in their parameters of interactions with cations and their spatial location within globular domains. Approaches are suggested for dynamic analysis of saturation for these differently located sites by the metal ions. We discuss the issues of altered conformational state of the γ-globulin molecule during the binding of cations, as well as potential usage of these data in clinical immunology.

  16. Copper(II) binding by dissolved organic matter: importance of the copper-to-dissolved organic matter ratio and implications for the biotic ligand model.

    Science.gov (United States)

    Craven, Alison M; Aiken, George R; Ryan, Joseph N

    2012-09-18

    The ratio of copper to dissolved organic matter (DOM) is known to affect the strength of copper binding by DOM, but previous methods to determine the Cu(2+)-DOM binding strength have generally not measured binding constants over the same Cu:DOM ratios. In this study, we used a competitive ligand exchange-solid-phase extraction (CLE-SPE) method to determine conditional stability constants for Cu(2+)-DOM binding at pH 6.6 and 0.01 M ionic strength over a range of Cu:DOM ratios that bridge the detection windows of copper-ion-selective electrode and voltammetry measurements. As the Cu:DOM ratio increased from 0.0005 to 0.1 mg of Cu/mg of DOM, the measured conditional binding constant ((c)K(CuDOM)) decreased from 10(11.5) to 10(5.6) M(-1). A comparison of the binding constants measured by CLE-SPE with those measured by copper-ion-selective electrode and voltammetry demonstrates that the Cu:DOM ratio is an important factor controlling Cu(2+)-DOM binding strength even for DOM isolates of different types and different sources and for whole water samples. The results were modeled with Visual MINTEQ and compared to results from the biotic ligand model (BLM). The BLM was found to over-estimate Cu(2+) at low total copper concentrations and under-estimate Cu(2+) at high total copper concentrations.

  17. Ion exchange in KTiOPO4 crystals irradiated by copper and hydrogen ions.

    Science.gov (United States)

    Zhang, Ruifeng; Lu, Fei; Lian, Jie; Liu, Hanping; Liu, Xiangzhi; Lu, Qingming; Ma, Hongji

    2008-05-12

    Cs(+)-K+ ion exchanges were produced on KTiOPO4 crystals which is prior irradiated by Cu+ can H+ ions. The energy and dose of implanted Cu+ ions are 1.5 MeV and 0.5 x 10(14) ions/cm2, and that of H+ are 300 keV and 1 x 10(16) ions/cm2, respectively. The temperature of ions exchange is 430 degrees C, and the time range from 15 minutes to 30 minutes. The prism coupling method is used to measure the dark mode spectra of the samples. Compared with results of ion exchange on the sample without irradiations, both the number of guided mode and its corresponding effective refractive index are decreased. The experimental results indicate that the ion exchange rate closely related with the lattice damage and the damage layers formed in the depth of maximum nuclear energy deposition act as a barrier to block the ions diffuse into the sample and the concentration of defects can modify the speed of ion exchange..

  18. Nickel(II), copper(II) and zinc(II) metallo-intercalators: structural details of the DNA-binding by a combined experimental and computational investigation.

    Science.gov (United States)

    Lauria, Antonino; Bonsignore, Riccardo; Terenzi, Alessio; Spinello, Angelo; Giannici, Francesco; Longo, Alessandro; Almerico, Anna Maria; Barone, Giampaolo

    2014-04-28

    We present a thorough characterization of the interaction of novel nickel(II) (1), copper(II) (2) and zinc(II) (3) Schiff base complexes with native calf thymus DNA (ct-DNA), in buffered aqueous solution at pH 7.5. UV-vis absorption, circular dichroism (CD) and viscometry titrations provided clear evidence of the intercalative mechanism of the three square-planar metal complexes, allowing us to determine the intrinsic DNA-binding constants (K(b)), equal to 1.3 × 10(7), 2.9 × 10(6), and 6.2 × 10(5) M(-1) for 1, 2 and 3, respectively. Preferential affinity, of one order of magnitude, toward AT compared to GC base pair sequences was detected by UV-vis absorption titrations of 1 with [poly(dG-dC)]2 and [poly(dA-dT)]2. Structural details of the intercalation site of the three metal complexes within [dodeca(dA-dT)]2 were obtained by molecular dynamics (MD) simulations followed by density functional theory/molecular mechanics (DFT/MM) calculations. The calculations revealed that three major intermolecular interactions contribute to the strong affinity between DNA and the three metal complexes: (1) the electrostatic attraction between the two positively charged triethylammoniummethyl groups of the metal complexes and the negatively charged phosphate groups of the DNA backbone; (2) the intercalation of the naphthalene moiety within the four nitrogen bases of the intercalation site; (3) the metal coordination by exocyclic donor atoms of the bases, specifically the carbonyl oxygen and amine nitrogen atoms. Remarkably, the Gibbs formation free energy calculated for the intercalation complexes of 1, 2 and 3 with [dodeca(dA-dT)]2 in the implicit water solution is in agreement with the experimental Gibbs free energy values obtained from the DNA-binding constants as ΔG° = -RT ln(K(b)). In particular, the DNA-binding affinity trend, 1 > 2 > 3, is reproduced. Finally, the first shell coordination distances calculated for the intercalation complex 3/[dodeca(dA-dT)]2 are in

  19. Synthesis and characterization of a surface-grafted Cd(II) ion-imprinted polymer for selective separation of Cd(II) ion from aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Li, Min [State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081 (China); Feng, Changgen, E-mail: cgfeng@cast.org.cn [State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081 (China); Li, Mingyu; Zeng, Qingxuan; Gan, Qiang [State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081 (China); Yang, Haiyan [Research Institute of Tsinghua University in Shenzhen, Shenzhen 518057 (China)

    2015-03-30

    Highlights: • Cd(II) ion-imprinted polymer (Cd(II)-IIP) is prepared. • Cd(II)-IIP shows high stability, good selectivity and reusability. • Cd(II)-IIP can be used as a sorbent for selective removal of Cd(II) ion. - Abstract: A novel Cd(II) ion-imprinted polymer (Cd(II)-IIP) was prepared with surface imprinting technology by using cadmium chloride as a template and allyl thiourea (ATU) as a functional monomer for on-line solid-phase extraction of trace Cd(II) ion and selective separation Cd(II) ion in water samples. The Cd(II)-IIP exhibited good chemical performance and thermal stability. Kinetics studies showed that the equilibrium adsorption was achieved within 8.0 min and the adsorption process can be described by pseudo-second-order kinetic model. Compared to the Cd(II) non-imprinted polymer (Cd(II)-NIP), the Cd(II)-IIP had a higher adsorption capacity and selectivity for Cd(II) ion. The maximum adsorption capacities of the Cd(II)-IIP and Cd(II)-NIP for Cd(II) were 38.30 and 13.21 mg g{sup −1}, respectively. The relative selectivity coefficients of the adsorbent for Cd(II) in the presence of Cu{sup 2+}, Ni{sup 2+}, Co{sup 2+}, Pb{sup 2+} and Zn{sup 2+} were 2.86, 6.42, 11.50, 9.46 and 3.73, respectively. In addition, the Cd(II) ion adsorbed was easy to remove from sorbent and the Cd(II)-IIP exhibited good stability and reusability. The adsorption capacity had no obvious decrease after being used six times. The accuracy of this method was verified by the standard reference material, it was then applied for cadmium ion determination in different types of water samples.

  20. Membrane Anchoring and Ion-Entry Dynamics in P-type ATPase Copper Transport

    DEFF Research Database (Denmark)

    Grønberg, Christina; Sitsel, Oleg; Lindahl, Erik

    2016-01-01

    Cu(+)-specific P-type ATPase membrane protein transporters regulate cellular copper levels. The lack of crystal structures in Cu(+)-binding states has limited our understanding of how ion entry and binding are achieved. Here, we characterize the molecular basis of Cu(+) entry using molecular......-dynamics simulations, structural modeling, and in vitro and in vivo functional assays. Protein structural rearrangements resulting in the exposure of positive charges to bulk solvent rather than to lipid phosphates indicate a direct molecular role of the putative docking platform in Cu(+) delivery. Mutational analyses...... and simulations in the presence and absence of Cu(+) predict that the ion-entry path involves two ion-binding sites: one transient Met148-Cys382 site and one intramembranous site formed by trigonal coordination to Cys384, Asn689, and Met717. The results reconcile earlier biochemical and x-ray absorption data...

  1. Copper(II) Binding to α-Synuclein, the Parkinson’s Protein

    OpenAIRE

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

    2008-01-01

    Variations in tryptophan fluorescence intensities confirm that copper(II) interacts with α-synuclein, a protein implicated in Parkinson’s disease. Trp4 fluorescence decay kinetics measured for the F4W protein show that Cu(II) binds tightly (K d ∼ 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. Influence of copper ions on the viability and cytotoxicity of Pseudomonas aeruginosa under conditions relevant to drinking water environments.

    Science.gov (United States)

    Dwidjosiswojo, Zenyta; Richard, Jessica; Moritz, Miriam M; Dopp, Elke; Flemming, Hans-Curt; Wingender, Jost

    2011-11-01

    Copper plumbing materials can be the source of copper ions in drinking water supplies. The aim of the current study was to investigate the influence of copper ions on the viability and cytotoxicity of the potential pathogen Pseudomonas aeruginosa that presents a health hazard when occurring in building plumbing systems. In batch experiments, exposure of P. aeruginosa (10(6)cells/mL) for 24h at 20°C to copper-containing drinking water from domestic plumbing systems resulted in a loss of culturability, while total cell numbers determined microscopically did not decrease. Addition of the chelator diethyldithiocarbamate (DDTC) to copper-containing water prevented the loss of culturability. When suspended in deionized water with added copper sulfate (10 μM), the culturability of P. aeruginosa decreased by more than 6 log units, while total cell counts, the concentration of cells with intact cytoplasmic membranes, determined with the LIVE/DEAD BacLight kit, and the number of cells with intact 16S ribosomal RNA, determined by fluorescent in situ hybridization, remained unchanged. When the chelator DDTC was added to copper-stressed bacteria, complete restoration of culturability was observed to occur within 14 d. Copper-stressed bacteria were not cytotoxic towards Chinese hamster ovary (CHO-9) cells, while untreated and resuscitated bacteria caused an almost complete decrease of the concentration of viable CHO-9 cells within 24 h. Thus, copper ions in concentrations relevant to drinking water in plumbing systems seem to induce a viable but non-culturable (VBNC) state in P. aeruginosa accompanied by a loss of culturability and cytotoxicity, and VBNC cells can regain both culturability and cytotoxicity, when copper stress is abolished.

  3. Enhancing the copper(II) complexes cytotoxicity to cancer cells through bound to human serum albumin.

    Science.gov (United States)

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

    2015-03-01

    We use Schiff-base salicylaldehyde benzoylhydrazone (HL) as the ligand for copper(II), resulting in the complexes [CuCl(L)]·H2O (C1), [CuNO3(L)]·H2O (C2) and [CuBr(L)]2 (C3). We characterize the Cu(II) compounds' interactions with human serum albumin (HSA) using fluorescence spectroscopy and molecular docking. These studies revealed that Cu(II) compounds propensity bound to IIA subdomain of HSA possible by hydrophobic interactions and hydrogen bond. Cu(II) compounds produce intracellular reactive oxygen species (ROS) in cancer cells. Complexes of HSA and copper(II) compounds enhance about 2-fold cytotoxicity in cancer cells but do not raise cytotoxicity levels in normal cells in vitro. Compared with C3 alone, HSA-C3 complex promotes HepG2 cell apoptosis and has a stronger capacity to promote cell cycle arrest at the G2/M phase of HepG2.

  4. Extractive spectrophotometric determination of copper(II in water and alloy samples with 3-methoxy-4-hydroxy benzaldehyde-4-bromophenyl hydrazone (3,4-MHBBPH

    Directory of Open Access Journals (Sweden)

    D. REKHA

    2007-03-01

    Full Text Available A facile, sensitive and selective extractive spectrophotometricmethod was developed for the determination of copper(II in various water and alloy samples using a newly synthesized reagent, 3-methoxy-4-hydroxy benzaldehyde 4-bromophenyl hydrazone (3,4-MHBBPH. Copper(II forms a orange colored complex with (3,4-MHBBPH in acetate buffermedium (pH 4 which increases the sensitivity and the complexwas extracted into chloroform. Under optimum conditions, the maximum absorption of the chloroform extract was measured at 462 nm. The Beer law was obeyed in the range of 0.20 to 4.0 mg ml-1 of copper. The molar absorptivity and the Sandell's sensitivity of the complex were 2.0520 ´ 104 mol-1 cm-1 and 0.2540 mg cm-2, respectively. The detection limit was found to be 0.0270 mg mL-1. Adetailed study of various interfering ions made the method more sensitive. The method was successfully applied for the determination of Cu(II in water and alloy samples. The performance of the present method was evaluated in terms of Student 't' test and Variance ratio 'f ' test, which indicate the significance of the present method over reported methods.

  5. Development and tests of molybdenum armored copper components for MITICA ion source

    Science.gov (United States)

    Pavei, Mauro; Böswirth, Bernd; Greuner, Henri; Marcuzzi, Diego; Rizzolo, Andrea; Valente, Matteo

    2016-02-01

    In order to prevent detrimental material erosion of components impinged by back-streaming positive D or H ions in the megavolt ITER injector and concept advancement beam source, a solution based on explosion bonding technique has been identified for producing a 1 mm thick molybdenum armour layer on copper substrate, compatible with ITER requirements. Prototypes have been recently manufactured and tested in the high heat flux test facility Garching Large Divertor Sample Test Facility (GLADIS) to check the capability of the molybdenum-copper interface to withstand several thermal shock cycles at high power density. This paper presents both the numerical fluid-dynamic analyses of the prototypes simulating the test conditions in GLADIS as well as the experimental results.

  6. Development and tests of molybdenum armored copper components for MITICA ion source

    Energy Technology Data Exchange (ETDEWEB)

    Pavei, Mauro, E-mail: mauro.pavei@igi.cnr.it; Marcuzzi, Diego; Rizzolo, Andrea; Valente, Matteo [Consorzio RFX, Corso Stati Uniti, 4, I-35127 Padova (Italy); Böswirth, Bernd; Greuner, Henri [Max-Planck-Institut für Plasmaphysik, Boltzmannstrasse 2, D-85748 Garching (Germany)

    2016-02-15

    In order to prevent detrimental material erosion of components impinged by back-streaming positive D or H ions in the megavolt ITER injector and concept advancement beam source, a solution based on explosion bonding technique has been identified for producing a 1 mm thick molybdenum armour layer on copper substrate, compatible with ITER requirements. Prototypes have been recently manufactured and tested in the high heat flux test facility Garching Large Divertor Sample Test Facility (GLADIS) to check the capability of the molybdenum-copper interface to withstand several thermal shock cycles at high power density. This paper presents both the numerical fluid-dynamic analyses of the prototypes simulating the test conditions in GLADIS as well as the experimental results.

  7. Non-invasive nano-imaging of ion implanted and activated copper in silicon

    Science.gov (United States)

    Ballout, Fouad; Samson, Jean-Sébastien; Schmidt, Diedrich A.; Bründermann, Erik; Mathis, Yves-Laurent; Gasharova, Biliana; Dirk Wieck, Andreas; Havenith, Martina

    2011-07-01

    Using vibrational imaging techniques including Fourier-transform infrared (FTIR) synchrotron microscopy, Raman microscopy, and scattering scanning near-field infrared microcscopy (s-SNIM), we mapped a sample of phosphor and copper ions implanted in a high-purity silicon wafer. While Raman microscopy monitors the structural disorder within the implantation fields, the aforementionedinfrared techniques provide a detailed picture of the distribution of the free carriers. On a large scale (tens of micrometers), we visualized the channeling effects of phosphor dopants in silicon using FTIR microscopy. In comparison, using s-SNIM we were able to image, on a nanometer scale, local variations of the dielectric properties of the silicon substrate due to the activation of copper dopants.

  8. Comparative toxicity and biodistribution of copper nanoparticles and cupric ions in rats

    Directory of Open Access Journals (Sweden)

    Lee IC

    2016-06-01

    Full Text Available In-Chul Lee,1 Je-Won Ko,1 Sung-Hyeuk Park,1 Je-Oh Lim,1 In-Sik Shin,1 Changjong Moon,1 Sung-Hwan Kim,2 Jeong-Doo Heo,3 Jong-Choon Kim1 1College of Veterinary Medicine BK21 Plus Project Team, Chonnam National University, Gwangju, 2Jeonbuk Department of Inhalation Research, Korea Institute of Toxicology, Jeongeup, 3Gyeongnam Department of Environment and Toxicology, Korea Institute of Toxicology, Gyeongnam, Republic of Korea Abstract: Despite widespread use and prospective biomedical applications of copper nanoparticles (Cu NPs, their biosafety issues and kinetics remain unclear. Thus, the aim of this study was to compare the detailed in vivo toxicity of Cu NPs and cupric ions (CuCl2; Cu ions after a single oral dose. We determined the physicochemical characteristics of Cu NPs, including morphology, hydrodynamic size, zeta potential, and dissolution in gastric (pH 1.5, vehicle (pH 6.5, and intestinal (pH 7.8 conditions. We also evaluated the kinetics of Cu following a single equivalent dose (500 mg/kg of Cu NPs and Cu ions. Cu NPs had highest dissolution (84.5% only in gastric conditions when compared with complete dissolution of Cu ions under various physiological milieus. Kinetic analysis revealed that highest Cu levels in blood and tested organs of Cu NP-treated rats were 15%–25% lower than that of Cu ions. Similar to the case of Cu ions, Cu levels in the tested organs (especially liver, kidney, and spleen of Cu NP-treated rats increased significantly when compared with the vehicle control. However, delay in reaching the highest level and biopersistence of Cu were observed in the blood and tested organs of Cu NP-treated rats compared with Cu ions. Extremely high levels of Cu in feces indicated that unabsorbed Cu NPs or absorbed Cu ions were predominantly eliminated through liver/feces. Cu NPs exerted apparent toxicological effects at higher dose levels compared with Cu ions and showed sex-dependent differences in mortality, biochemistry, and

  9. A tri-copper(II) complex displaying DNA-cleaving properties and antiproliferative activity against cancer cells.

    Science.gov (United States)

    Suntharalingam, Kogularamanan; Hunt, Douglas J; Duarte, Alexandra A; White, Andrew J P; Mann, David J; Vilar, Ramon

    2012-11-19

    A new disubstituted terpyridine ligand and the corresponding tri-copper(II) complex have been prepared and characterised. The binding affinity and binding mode of this tri-copper complex (as well as the previously reported mono- and di-copper analogues) towards duplex DNA were determined by using UV/Vis spectroscopic titrations and fluorescent indicator displacement (FID) assays. These studies showed the three complexes to bind moderately (in the order of 10(4)  M(-1)) to duplex DNA (ct-DNA and a 26-mer sequence). Furthermore, the number of copper centres and the nature of the substituents were found to play a significan