Perchlorate mixed-ligand copper(II) complexes of beta-diketone and ethylene diamine derivatives: thermal, spectroscopic and biochemical studies.

PubMed

El-Ayaan, Usama; El-Metwally, Nashwa M; Youssef, Magdy M; El Bialy, Serry A A

2007-12-31

The present work carried out a study on perchlorate mixed-ligand copper(II) complexes which have been synthesized from ethylenediamine derivatives (3a-c) and beta-diketones. These complexes, namely [Cu(DA-Cl)(acac)H(2)O]ClO(4)4, [Cu(DA-Cl)(bzac)H(2)O]H(2)O.ClO(4)5, [Cu(DA-OMe)(acac)H(2)O]ClO(4)6, [Cu(DA-OMe)(bzac)H(2)O]ClO(4)7, [Cu(DA-H)(acac)H(2)O]2H(2)O.ClO(4)8 and [Cu(DA-H)(bzac)H(2)O]ClO(4)9 (where acac, acetylacetonate and bzac, benzoylacetonate) were characterized by elemental analysis, spectral (IR and UV-vis) and magnetic moment measurements. Thermal properties and decomposition kinetics of all complexes are investigated. The interpretation, mathematical analysis and evaluation of kinetic parameters (E, A, DeltaH, DeltaS and DeltaG) of all thermal decomposition stages have been evaluated using Coats-Redfern equation. The biochemical studies showed that, the diamines 3a-c have powerful effects on degradation of DNA and protein. The antibacterial screening demonstrated that, the diamine (DA-Cl), 3b has the maximum and broad activities against Gram +ve and Gram -ve bacterial strains.

Synthesis and characterization of potential iron–platinum drugs and supplements by laser liquid photolysis

PubMed Central

Nkosi, Steven S; Mwakikunga, Bonex W; Sideras-Haddad, Elias; Forbes, Andrew

2012-01-01

Highly crystalline nanospherical iron–platinum systems were produced by 248 nm laser irradiation of a liquid precursor at different laser fluences, ranging from 100–375 mJ/cm2. The influence of laser intensity on particle size, iron composition, and structure was systematically investigated. Different nanostructures of iron–platinum alloy and chemically disordered iron–platinum L10 phase were obtained without annealing. The prepared precursor solution underwent deep photolysis to polycrystalline iron–platinum nanoalloys through Fe(III) acetylacetonate and Pt(II) acetylacetonate. Fe(II) and Pt(I) acetylacetone decomposed into Fe0 and Pt0 nanoparticles. We found that the (001) diffraction peak shifted linearly to a lower angle, with the last peak shifting in opposition to the others. This caused the face-centered cubic L10 structure to change its composition according to laser fluence. The nanostructures were shown to contain iron and platinum only by energy-dispersive spectroscopy at several spots. The response of these iron–platinum nanoparticles to infrared depends on their stoichiometric composition, which is controlled by laser fluence. PMID:24198494

Synthesis, spectral characterization and DNA binding of Schiff-base metal complexes derived from 2-amino-3-hydroxyprobanoic acid and acetylacetone

NASA Astrophysics Data System (ADS)

Hosny, Nasser Mohammed; Hussien, Mostafa A.; Radwan, Fatima M.; Nawar, Nagwa

2014-11-01

Four new metal complexes derived from the reaction of Cu(II), Co(II), Ni(II) and Zn(II) acetates with the Schiff-base ligand (H3L) resulted from the condensation of the amino acid 2-amino-3-hydroxyprobanoic acid (serine) and acetylacetone have been synthesized and characterized by, elemental analyses, ES-MS, IR, UV-Vis., 1H NMR, 13C NMR, ESR, thermal analyses (TGA and DTG) and magnetic measurements. The results showed that the Schiff-base ligand acts as bi-negative tridentate through the azomethine nitrogen, the deprotonated carboxylate oxygen and the enolic carbonyl oxygen. The optical band gaps measurements indicated the semi-conducting nature of these complexes. Molecular docking was used to predict the binding between the Schiff base ligand with the receptor of prostate cancer mutant H874Y. The interactions between the Cu(II) complex and calf thymus DNA (CT-DNA) have been studied by UV spectra. The results confirm that the Cu(II) complex binds to CT-DNA in an intercalative mode.

ESI-MS studies of the reactions of novel platinum(II) complexes containing O,O'-chelated acetylacetonate and sulfur ligands with selected model proteins.

PubMed

Marzo, Tiziano; De Pascali, Sandra A; Gabbiani, Chiara; Fanizzi, Francesco P; Messori, Luigi; Pratesi, Alessandro

2017-08-01

A group of mixed-ligand Pt(II) complexes bearing acetylacetonate and sulphur ligands were recently developed in the University of Lecce as a new class of prospective anticancer agents that manifested promising pharma-cological properties in preliminary in vitro and in vivo tests. Though modelled on the basis of cisplatin, these Pt(II) complexes turned out to exhibit a profoundly distinct mode of action as they were found to act mainly on non-genomic targets rather than on DNA. Accordingly, we have explored here their reactions with two representative model proteins through an established ESI-MS procedure with the aim to describe their general interaction mechanism with protein targets. A pronounced reactivity with the tested proteins was indeed documented; the nature of the resulting metallodrug-protein interactions could be characterised in depth in the various cases. Preferential binding to protein targets compared to DNA is supported by independent ICP-OES measurements. The implications of these findings are discussed.

Synthesis, spectral, thermal and optical properties of Schiff-base complexes derived from 2(E)-2-((z)-4-hydroxypent-3-en-2-ylideneamino)-5-guanidinopentanoic acid and acetylacetone

NASA Astrophysics Data System (ADS)

Hosny, Nasser Mohammed; Hussien, Mostafa A.; Radwan, Fatima M.; Nawar, Nagwa

2017-09-01

New metal complexes derived from the in situ reaction of Cu(II), Co(II), Ni(II) and Zn(II) acetates with the Schiff-base ligand (H2L) resulted from the condensation of 2-amino-5-guanidinopentanoic acid (arginine) and acetylacetone have been synthesized. The resulting complexes have been characterized by, elemental analyses, ES-MS, IR, Raman spectra, UV-Vis., 1HNMR, ESR, thermal analyses (TGA and DTG) and magnetic measurements. The results showed that, The Schiff-base ligand acts as bi-negative tridentate coordinating via azomethine nitrogen, enolic carbonyl oxygen and carboxylate oxygen after displacement of hydrogen. The thermodynamic parameters E∗, ΔH, ΔG and ΔS of the isolated complexes have been calculated. The optical band gap (Eg) values of Cu, Co, Ni and Zn were found to be 3.3, 3.4, 3.7 and 4.3 eV, respectively, arising from direct transitions. Optical band gap measurements indicate the semi-conductivity nature of these complexes.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Michael Edward

1993-10-01

The thesis is divided into the following 4 chapters: synthesis, characterization, and reactivity of trinuclear pentamethylcyclopentadienyl cobalt and nickel clusters with triply-bridging methylidyne groups; chemical and physical properties of pentamethylcyclopentadienyl acetylacetonate complexes of Co(II) and Ni(II); synthesis, characterization, and reactivity of pentamethylcyclopentadienyl halide complexes of Co and Ni; and crystallographic studies of distortions in metallocenes with C 5-symmetrical cyclopentadienyl rings.

EFFECTS OF LASER RADIATION ON MATTER. LASER PLASMA: Selective metallisation of diamonds with the aid of laser radiation

NASA Astrophysics Data System (ADS)

Shafeev, Georgii A.; Pimenov, S. M.; Lubnin, Evgenii N.; Smolin, A. A.; Konov, Vitalii I.; Laptev, V. A.

1995-02-01

An experimental investigation was made of laser activation of diamond surfaces (single crystals and polycrystalline diamond films) prior to electroless before catalytic deposition of metals from solutions. The activation was carried out by a copper vapour laser or a KrF excimer laser in two ways: decomposition of a thin film of palladium acetylacetonate and local laser stimulated modification of the diamond surface by laser evaporation. An ohmic contact (Cu or Ni) with an adhesive strength of 3 N mm-2 was formed and the spatial resolution achieved was 10 μm.

Corrigendum to "Electronic structure and photoelectron spectra of nickel (II) acetylacetonate and its thio- and amino-substituted analogues" [J. Mol. Struct. 1099 (2015) 579-587

NASA Astrophysics Data System (ADS)

Vovna, Vitaliy I.; Korochentsev, Vladimir V.; Komissarov, Alexander A.; L'vov, Igor B.; Myshakina, Nataliya S.

2016-01-01

The authors regret to inform that it was given erroneous spelling of Vitaliy I. Vovna author name in the published version of the article. It was written "Vitaliy V. Vovna" instead of "Vitaliy I. Vovna".

One-Step Facile Synthesis of Cobalt Phosphides for Hydrogen Evolution Reaction Catalysts in Acidic and Alkaline Medium.

PubMed

Sumboja, Afriyanti; An, Tao; Goh, Hai Yang; Lübke, Mechthild; Howard, Dougal Peter; Xu, Yijie; Handoko, Albertus Denny; Zong, Yun; Liu, Zhaolin

2018-05-09

Catalysts for hydrogen evolution reaction are in demand to realize the efficient conversion of hydrogen via water electrolysis. In this work, cobalt phosphides were prepared using a one-step, scalable, and direct gas-solid phosphidation of commercially available cobalt salts. It was found that the effectiveness of the phosphidation reaction was closely related to the state of cobalt precursors at the reaction temperature. For instance, a high yield of cobalt phosphides obtained from the phosphidation of cobalt(II) acetate was related to the good stability of cobalt salt at the phosphidation temperature. On the other hand, easily oxidizable salts (e.g., cobalt(II) acetylacetonate) tended to produce a low amount of cobalt phosphides and a large content of metallic cobalt. The as-synthesized cobalt phosphides were in nanostructures with large catalytic surface areas. The catalyst prepared from phosphidation of cobalt(II) acetate exhibited an improved catalytic activity as compared to its counterpart derived from phosphidation of cobalt(II) acetylacetonate, showing an overpotential of 160 and 175 mV in acidic and alkaline electrolytes, respectively. Both catalysts also displayed an enhanced long-term stability, especially in the alkaline electrolyte. This study illustrates the direct phosphidation behavior of cobalt salts, which serve as a good vantage point in realizing the large-scale synthesis of transition-metal phosphides for high-performance electrocatalysts.

Analysis of transition-metal acetylacetonate complexes by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

PubMed

Wyatt, Mark F; Havard, Stephen; Stein, Bridget K; Brenton, A Gareth

2008-01-01

Transition-metal acetylacetonate complexes of the form Metal(acac)(2), where Metal = Fe(II), Co(II), Ni(II), Cu(II), and Zn(II), and Metal(acac)(3), where Metal = V(III), Cr(III), Mn(III), Fe(III), and Co(III), were investigated by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). The data was acquired using the aprotic, electron transfer matrix, 2-[(2E)-3-(4-tert-butylphenyl)-2-methylprop-2-enylidene]malononitrile (DCTB), and the observation of positive radical ions is shown clearly to depend on the metal element and the oxidation state it occupies. The ionization energy of DCTB was calculated to be 8.08 eV by density functional theory methods, which is notably lower than the experimental value, but within the range of other computational values. This value is very close to those of the analytes, so the existing electron transfer mechanism which is based on the ionization energies of the matrix and analyte, cannot be used predictively. Similarly, the data neither proves nor disproves the validity of the existing electron transfer ionization mechanism, with respect to metal coordination complexes without strong chromophores. In this case, periodic trends may be more useful in explaining the observed species and the prediction of species from sets of similar complexes. The addition of a sodium salt benefits the MALDI-TOFMS characterization of certain compounds studied, but the benefit of the addition of ammonium or silver salts is negligible.

Growth behavior and properties of atomic layer deposited tin oxide on silicon from novel tin(II)acetylacetonate precursor and ozone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kannan Selvaraj, Sathees; Feinerman, Alan; Takoudis, Christos G., E-mail: takoudis@uic.edu

In this work, a novel liquid tin(II) precursor, tin(II)acetylacetonate [Sn(acac){sub 2}], was used to deposit tin oxide films on Si(100) substrate, using a custom-built hot wall atomic layer deposition (ALD) reactor. Three different oxidizers, water, oxygen, and ozone, were tried. Resulting growth rates were studied as a function of precursor dosage, oxidizer dosage, reactor temperature, and number of ALD cycles. The film growth rate was found to be 0.1 ± 0.01 nm/cycle within the wide ALD temperature window of 175–300 °C using ozone; no film growth was observed with water or oxygen. Characterization methods were used to study the composition, interface quality, crystallinity, microstructure,more » refractive index, surface morphology, and resistivity of the resulting films. X-ray photoelectron spectra showed the formation of a clean SnO{sub x}–Si interface. The resistivity of the SnO{sub x} films was calculated to be 0.3 Ω cm. Results of this work demonstrate the possibility of introducing Sn(acac){sub 2} as tin precursor to deposit conducting ALD SnO{sub x} thin films on a silicon surface, with clean interface and no formation of undesired SiO{sub 2} or other interfacial reaction products, for transparent conducting oxide applications.« less

Self-assembly of a constitutional dynamic library of Cu(II) coordination polygons and reversible sorting by crystallization.

PubMed

Rancan, Marzio; Tessarolo, Jacopo; Zanonato, Pier Luigi; Seraglia, Roberta; Quici, Silvio; Armelao, Lidia

2013-06-07

A small coordination constitutional dynamic library (CDL) is self-assembled from Cu(2+) ions and the ortho bis-(3-acetylacetone)benzene ligand. Two coordination polygons, a rhomboid and a triangle, establish a dynamic equilibrium. Quantitative sorting of the rhomboidal polygon is reversibly obtained by crystallization. Thermodynamic and kinetic aspects ruling the CDL system have been elucidated.

Synthesis of Nanometric-Sized Barium Titanate Powders Using Acetylacetone as the Chelating Agent in a Sol-Precipitation Process

NASA Astrophysics Data System (ADS)

Hung, Kun Ming; Hsieh, Ching Shieh; Yang, Wein Duo; Tsai, Hui Ju

2007-03-01

Nanometric-sized barium titanate powders were prepared by using titanium isopropoxid as the raw material and acetylacetone as a chelating agent, in a strong alkaline solution (pH > 13) through the sol-precipitation method. The preparatory variables affect the extent of cross-linking in the structure, change the mode of condensation of the gels, and even control the particle size of the powder. The reaction rate of forming powder, at a higher temperature such as 100°C and more water content (the molar ratio of water to titanium isopropoxide is 25) or fewer acetylacetone (the molar ratio of acetylacetone to titanium isopropoxide is 1), is rapid and the particle size formed is finer at 60 80 nm. On the contrary, that of forming powder, at lower temperature (40°C) and less water content (molar ratio of water/titanium isopropoxide = 5) or higher acetylacetone (acetylacetone/titanium isopropoxide = 7), is slow and the particle size of the powder is larger. The optimal preparatory conditions were obtained by using the experimental statistical method; as a result, nanometric-sized BaTiO3 powder with an average particle size of about 50 nm was prepared.

Monodisperse gold-palladium alloy nanoparticles and their composition-controlled catalysis in formic acid dehydrogenation under mild conditions.

PubMed

Metin, Önder; Sun, Xiaolian; Sun, Shouheng

2013-02-07

Monodisperse 4 nm AuPd alloy nanoparticles with controlled composition were synthesized by co-reduction of hydrogen tetrachloroaurate(III) hydrate and palladium(II) acetylacetonate with a borane-morpholine complex in oleylamine. These NPs showed high activity (TOF = 230 h(-1)) and stability in catalyzing formic acid dehydrogenation and hydrogen production in water at 50 °C without any additives.

Aerosol-assisted chemical vapor deposition of ultra-thin CuOx films as hole transport material for planar perovskite solar cells

NASA Astrophysics Data System (ADS)

Zhang, Zhixin; Chen, Shuqun; Li, Pingping; Li, Hongyi; Wu, Junshu; Hu, Peng; Wang, Jinshu

This paper reports on the fabrication of CuOx films to be used as hole transporting layer (HTL) in CH3NH3PbI3 perovskite solar cells (PSCs). Ultra-thin CuOx coatings were grown onto FTO substrates for the first time via aerosol-assisted chemical vapor deposition (AACVD) of copper acetylacetonate in methanol. After incorporating into the PSCs prepared at ambient air, a highest power conversion efficiency (PCE) of 8.26% with HTL and of 3.34% without HTL were achieved. Our work represents an important step in the development of low-cost CVD technique for fabricating ultra-thin metal oxide functional layers in thin film photovoltaics.

Biosorption characteristics of copper (II), chromium (III), nickel (II), and lead (II) from aqueous solutions by Chara sp. and Cladophora sp.

PubMed

Elmaci, Ayşe; Yonar, Taner; Ozengin, Nihan

2007-09-01

The aim of this research was to expose individual removals of copper, chromium, nickel, and lead from aqueous solutions via biosorption using nonliving algae species, Chara sp. and Cladophora sp. Optimum pH values for biosorption of copper (II), chromium (III), nickel (II), and lead (II) from aqueous solutions were determined to be 6, 7, 7, and 3 for Cladophora sp. and 5, 3, 5, and 4 for Chara sp. respectively. Maximum adsorption capacities of Chara sp. [10.54 for chromium (III) and 61.72 for lead (II)] and Cladophora sp. [6.59 for chromium (III) and 16.75 and 23.25 for lead (II)] for chromium (III) and lead (II) are similar. On the other hand, copper (II) and nickel (II) biosorption capacity of Cladophora sp. [14.28 for copper (II) and 16.75 for nickel (II)] is greater than Chara sp. [6.506 for copper (II) and 11.76 for nickel (II)]. Significantly high correlation coefficients indicated for the Langmuir adsorption isotherm models can be used to describe the equilibrium behavior of copper, chromium, nickel, and lead adsorption onto Cladophora sp. and Chara sp.

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

ERIC Educational Resources Information Center

Montangero, Marc

2015-01-01

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

Development of Novel DNA Cleavage Systems Based on Copper Complexes. Synthesis and Characterisation of Cu(II) Complexes of Hydroxyflavones

PubMed Central

el Amrani, F. Ben-Allal; Perelló, L.; Torres, L.

2000-01-01

Copper(II) complexes of several hydroxyflavones were prepared and characterised through their physico-chemical properties. The nuclease activity of three synthesised complexes is reported. These copper(II) complexes present more nuclease activity than the ligands and the copper(II) ion. PMID:18475969

Application of the zone-melting technique to metal chelate systems-VI A new apparatus for zone-melting chromatography.

PubMed

Maeda, S; Kobayashi, H; Ueno, K

1973-07-01

An improved apparatus has been constructed for zone-melting chromatography. An essential feature of the apparatus is that the length of the molten zone can be kept constant during a zone-melting operation, by employing heating and cooling compartments which are separated from each other by double partition plates. Each compartment is heated or cooled with jets of hot or cold air. The apparatus is suitable for organic materials melting in the range between 40 degrees and 180 degrees . The distribution of metal ion along the column after zone melting of copper acetylacetonate in 2-methoxynaphthalene was a smooth curve. The plot of the position of maximum concentration, x(max), against the number of zone passes, n, gave a relationship in accordance with theoretical prediction.

Subneurotoxic copper(II)-induced NF-κB-dependent microglial activation is associated with mitochondrial ROS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Zhuqin; Yu, Fengxiang; Gong, Ping

2014-04-15

Microglia-mediated neuroinflammation and the associated neuronal damage play critical roles in the pathogenesis of neurodegenerative disorders. Evidence shows an elevated concentration of extracellular copper(II) in the brains of these disorders, which may contribute to neuronal death through direct neurotoxicity. Here we explored whether extracellular copper(II) triggers microglial activation. Primary rat microglia and murine microglial cell line BV-2 cells were cultured and treated with copper(II). The content of tumor necrosis factor-α (TNF-α) and nitric oxide in the medium was determined. Extracellular hydrogen peroxide was quantified by a fluorometric assay with Amplex Red. Mitochondrial superoxide was measured by MitoSOX oxidation. At subneurotoxicmore » concentrations, copper(II) treatment induced a dose- and time-dependent release of TNF-α and nitric oxide from microglial cells, and caused an indirect, microglia-mediated neurotoxicity that was blocked by inhibition of TNF-α and nitric oxide production. Copper(II)-initiated microglial activation was accompanied with reduced IkB-α expression as well as phosphorylation and translocation of nuclear factor-κB (NF-κB) p65 and was blocked by NF-κB inhibitors (BAY11-7082 and SC-514). Moreover, copper(II) treatment evoked a rapid release of hydrogen peroxide from microglial cells, an effect that was not affected by NADPH oxidase inhibitors. N-acetyl-cysteine, a scavenger of reactive oxygen species (ROS), abrogated copper(II)-elicited microglial release of TNF-α and nitric oxide and subsequent neurotoxicity. Importantly, mitochondrial production of superoxide, paralleled to extracellular release of hydrogen peroxide, was induced after copper(II) stimulation. Our findings suggest that extracellular copper(II) at subneurotoxic concentrations could trigger NF-κB-dependent microglial activation and subsequent neurotoxicity. NADPH oxidase-independent, mitochondria-derived ROS may be involved in this activation. - Highlights: • Subneurotoxic copper(II) triggers NF-κB-dependent microglial activation. • This activation leads to hippocampal neuronal death. • This activation may involve mitochondria-derived reactive oxygen species.« less

Chemical speciation and bioavailability of Cu(II). Study of the ionic copper(II) and bis(glycinate)-copper(II) accumulation by Lemna species

DOE Office of Scientific and Technical Information (OSTI.GOV)

Benda, F.; Kouba, J.

1991-03-01

In this paper, the authors examined the accumulation of copper(II) in, and its toxic effect on, duckweed, a plant which exhibits extremely high concentration factors. The effect of copper(II) was investigated by adding it to the minimal medium in two forms: CuSO{sub 4} and (Cu(Gly){sub 2}). The neutral (2:1) tetracoordinated bis(glycinate)-copper(II) complex is constituted by two five-membered rings bonded to the central copper atom with the cis configuration. This complex was chosen to model the function of a neutral species (eliminating the charge effect) involving a nontoxic ligand, for which - in contrast to the hydrated Cu{sup 2+} species -more » direct permeation through the cell wall is conceivable.« less

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

NASA Astrophysics Data System (ADS)

Bee, Soo-Tueen; Sin, Lee Tin; Ratnam, C. T.; Haraveen, K. J. S.; Tee, Tiam-Ting; Rahmat, A. R.

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.

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

NASA Astrophysics Data System (ADS)

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

2008-09-01

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

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

NASA Astrophysics Data System (ADS)

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

2013-11-01

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

Copper(II) complex of new non-innocent O-aminophenol-based ligand as biomimetic model for galactose oxidase enzyme in aerobic oxidation of alcohols

NASA Astrophysics Data System (ADS)

Safaei, Elham; Bahrami, Hadiseh; Pevec, Andrej; Kozlevčar, Bojan; Jagličić, Zvonko

2017-04-01

Mononuclear copper(II) complex of tetra-dentate o-aminophenol-based ligand (H2LBAPP) has been synthesized and characterized. The three dentate precursor (HLBAP) of the final ligand was synthesized first, while the title four-dentate copper bound ligand was synthesized in situ, isolated only in the final copper species [CuLBAPP]. This copper coordination complex reveals a distorted square-planar geometry around the copper(II) centre by one oxygen and three nitrogen atoms from the coordinating ligand. The ligand is thus twice deprotonated via hydroxy and amine groups. The complex is red, non-typical for copper(II), but the effective magnetic moment of 1.86 B M. and a single isotropic symmetry EPR signal with g 2.059 confirm a S = 1/2 diluted spin system, without copper-copper magnetic coupling. Electrochemical oxidation of this complex yields the corresponding Cu(II)-phenyl radical species. Finally, the title complex CuLBAPP has shown good and selective catalytic activity towards alcohol to aldehyde oxidation, at aerobic room temperature conditions, for a set of different alcohols.

An efficient, cost effective, sensing behaviour liquid-liquid extraction and spectrophotometric determination of copper(II) incorporated with 4-(4‧-chlorobenzylideneimino)-3-methyl-5-mercapto-1, 2, 4-triazole: Analysis of food samples, leafy vegetables, fertilizers and environmental samples

NASA Astrophysics Data System (ADS)

Barache, Umesh B.; Shaikh, Abdul B.; Lokhande, Tukaram N.; Kamble, Ganesh S.; Anuse, Mansing A.; Gaikwad, Shashikant H.

2018-01-01

The aim of the present work is to develop an efficient, simple and selective moreover cost-effective method for the extractive spectrophotometric determination of copper(II) by using the Schiff base 4-(4‧-chlorobenzylideneimino)-3-methyl-5-mercapto-1, 2, 4-triazole [CBIMMT]. This chromogenic reagent forms a yellow coloured complex with copper(II) in acetate buffer at pH 4.2. The copper(II) complex with ligand is instantly extracted into chloroform and shows a maximum absorbance at 414 nm which remains stable for > 48 h. The composition of extracted complex is found to be 1:2 [copper(II): reagent] which was ascertained using Job's method of continuous variation, mole ratio method and slope ratio method. Under optimal conditions, the copper(II) complex in chloroform adheres to Beer's law up to 17.5 μg mL- 1 of copper(II). The optimum concentration range obtained from Ringbom's plot is from 5 μg mL- 1 to 17.5 μg mL- 1. The molar absorptivity, Sandell's sensitivity and enrichment factor of the extracted copper(II) chelate are 0.33813 × 104 L mol- 1 cm- 1, 0.01996 μg cm- 2 and 2.49 respectively. In the extraction of copper(II), several affecting factors including the solution pH, ligand concentration, equilibrium time, effect of foreign ions are optimized. The interfering effects of various cations and anions were also studied and use of masking agents enhances the selectivity of the method. The chromogenic sulphur containing reagent, 4-(4‧-chlorobenzylideneimino)-3-methyl-5-mercapto-1, 2, 4-triazole has been synthesized in a single step with high purity and yield. The synthesized reagent has been successfully applied first time for determination of copper(II). The reagent forms stable chelate with copper(II) in buffer medium instantly and quantitatively extracted in chloroform within a minute. The method is successfully applied for the determination of copper(II) in various synthetic mixtures, complexes, fertilizers, environmental samples such as food samples, leafy vegetables, and water samples. The results are compared with those obtained with a reference procedure. Good agreement was attained. All the obtained results are indicative of a convenient, fast method for the extraction and quantification of micro levels of copper(II) from various environmental matrices without use of sophisticated instrumentation and procedure. The method showed a relative standard deviation of 0.42%.

An efficient, cost effective, sensing behaviour liquid-liquid extraction and spectrophotometric determination of copper(II) incorporated with 4-(4'-chlorobenzylideneimino)-3-methyl-5-mercapto-1, 2, 4-triazole: Analysis of food samples, leafy vegetables, fertilizers and environmental samples.

PubMed

Barache, Umesh B; Shaikh, Abdul B; Lokhande, Tukaram N; Kamble, Ganesh S; Anuse, Mansing A; Gaikwad, Shashikant H

2018-01-15

The aim of the present work is to develop an efficient, simple and selective moreover cost-effective method for the extractive spectrophotometric determination of copper(II) by using the Schiff base 4-(4'-chlorobenzylideneimino)-3-methyl-5-mercapto-1, 2, 4-triazole [CBIMMT]. This chromogenic reagent forms a yellow coloured complex with copper(II) in acetate buffer at pH4.2. The copper(II) complex with ligand is instantly extracted into chloroform and shows a maximum absorbance at 414nm which remains stable for >48h. The composition of extracted complex is found to be 1:2 [copper(II): reagent] which was ascertained using Job's method of continuous variation, mole ratio method and slope ratio method. Under optimal conditions, the copper(II) complex in chloroform adheres to Beer's law up to 17.5μgmL -1 of copper(II). The optimum concentration range obtained from Ringbom's plot is from 5μgmL -1 to 17.5μgmL -1 . The molar absorptivity, Sandell's sensitivity and enrichment factor of the extracted copper(II) chelate are 0.33813×10 4 Lmol -1 cm -1 , 0.01996μgcm -2 and 2.49 respectively. In the extraction of copper(II), several affecting factors including the solution pH, ligand concentration, equilibrium time, effect of foreign ions are optimized. The interfering effects of various cations and anions were also studied and use of masking agents enhances the selectivity of the method. The chromogenic sulphur containing reagent, 4-(4'-chlorobenzylideneimino)-3-methyl-5-mercapto-1, 2, 4-triazole has been synthesized in a single step with high purity and yield. The synthesized reagent has been successfully applied first time for determination of copper(II). The reagent forms stable chelate with copper(II) in buffer medium instantly and quantitatively extracted in chloroform within a minute. The method is successfully applied for the determination of copper(II) in various synthetic mixtures, complexes, fertilizers, environmental samples such as food samples, leafy vegetables, and water samples. The results are compared with those obtained with a reference procedure. Good agreement was attained. All the obtained results are indicative of a convenient, fast method for the extraction and quantification of micro levels of copper(II) from various environmental matrices without use of sophisticated instrumentation and procedure. The method showed a relative standard deviation of 0.42%. Copyright © 2017 Elsevier B.V. All rights reserved.

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

PubMed

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

2012-12-01

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

A ruthenium(II) complex as turn-on Cu(II) luminescent sensor based on oxidative cyclization mechanism and its application in vivo

NASA Astrophysics Data System (ADS)

Zhang, Yunfei; Liu, Zonglun; Yang, Kui; Zhang, Yi; Xu, Yongqian; Li, Hongjuan; Wang, Chaoxia; Lu, Aiping; Sun, Shiguo

2015-02-01

Copper ions play a vital role in a variety of fundamental physiological processes not only in human beings and plants, but also for extensive insects and microorganisms. In this paper, a novel water-soluble ruthenium(II) complex as a turn-on copper(II) ions luminescent sensor based on o-(phenylazo)aniline was designed and synthesized. The azo group would undergo a specific oxidative cyclization reaction with copper(II) ions and turn into high luminescent benzotriazole, triggering significant luminescent increasements which were linear to the concentrations of copper(II) ions. The sensor distinguished by its high sensitivity (over 80-fold luminescent switch-on response), good selectivity (the changes of the emission intensity in the presence of other metal ions or amino acids were negligible) and low detection limit (4.42 nM) in water. Moreover, the copper(II) luminescent sensor exhibited good photostability under light irradiation. Furthermore, the applicability of the proposed sensor in biological samples assay was also studied and imaged copper(II) ions in living pea aphids successfully.

Kinetics of the Reaction Between Alcohols and Isocyanates Catalyzed by Ferric Acetylacetonate

NASA Technical Reports Server (NTRS)

Schieler, Leroy

1961-01-01

The rate and temperature dependence of reaction for the ferric acetylacetonate catalyzed reaction between a-naphthyl, ortho-tolyl, and para-tolyl isocyanates and n-butyl alcohol are investigated. The effect of substituents on the reactivity of isocyanate and hydroxyl group are reported and for substituted isocyanates are correlated by means of the Hammett equation. Several metal chelates were studied and their catalytic activity was compared to that of ferric acetylacetonate. All rate data are interpreted in terms of a mechanism involving simultaneous second-order uncatalyzed and catalyzed reactions between alcohol and isocyanate.

Synthetic bioactive novel ether based Schiff bases and their copper(II) complexes

NASA Astrophysics Data System (ADS)

Shabbir, Muhammad; Akhter, Zareen; Ismail, Hammad; Mirza, Bushra

2017-10-01

Novel ether based Schiff bases (HL1- HL4) were synthesized from 5-chloro-2-hydroxy benzaldehyde and primary amines (1-amino-4-phenoxybenzene, 4-(4-aminophenyloxy) biphenyl, 1-(4-aminophenoxy) naphthalene and 2-(4-aminophenoxy) naphthalene). From these Schiff bases copper(II) complexes (Cu(L1)2-Cu(L4)2)) were synthesized and characterized by elemental analysis and spectroscopic (FTIR, NMR) techniques. The synthesized Schiff bases and copper(II) complexes were further assessed for various biological studies. In brine shrimp assay the copper(II) complexes revealed 4-fold higher activity (LD50 3.8 μg/ml) as compared with simple ligands (LD50 12.4 μg/ml). Similar findings were observed in potato disc antitumor assay with higher activities for copper(II) complexes (IC50 range 20.4-24.1 μg/ml) than ligands (IC50 range 40.5-48.3 μg/ml). DPPH assay was performed to determine the antioxidant potential of the compounds. Significant antioxidant activity was shown by the copper(II) complexes whereas simple ligands have shown no activity. In DNA protection assay significant protection behavior was exhibited by simple ligand molecules while copper(II) complexes showed neutral behavior (neither protective nor damaging).

Determination of formal redox potentials in aqueous solution of copper(II) complexes with ligands having nitrogen and oxygen donor atoms and comparison with their EPR and UV-Vis spectral features.

PubMed

Tabbì, Giovanni; Giuffrida, Alessandro; Bonomo, Raffaele P

2013-11-01

Formal redox potentials in aqueous solution were determined for copper(II) complexes with ligands having oxygen and nitrogen as donor atoms. All the chosen copper(II) complexes have well-known stereochemistries (pseudo-octahedral, square planar, square-based pyramidal, trigonal bipyramidal or tetrahedral) as witnessed by their reported spectroscopic, EPR and UV-visible (UV-Vis) features, so that a rough correlation between the measured redox potential and the typical geometrical arrangement of the copper(II) complex could be established. Negative values have been obtained for copper(II) complexes in tetragonally elongated pseudo-octahedral geometries, when measured against Ag/AgCl reference electrode. Copper(II) complexes in tetrahedral environments (or flattened tetrahedral geometries) show positive redox potential values. There is a region, always in the field of negative redox potentials which groups the copper(II) complexes exhibiting square-based pyramidal arrangements. Therefore, it is suggested that a measurement of the formal redox potential could be of great help, when some ambiguities might appear in the interpretation of spectroscopic (EPR and UV-Vis) data. Unfortunately, when the comparison is made between copper(II) complexes in square-based pyramidal geometries and those in square planar environments (or a pseudo-octahedral) a little perturbed by an equatorial tetrahedral distortion, their redox potentials could fall in the same intermediate region. In this case spectroscopic data have to be handled with great care in order to have an answer about a copper complex geometrical characteristics. © 2013.

Disulfiram and Copper Ions Kill Mycobacterium tuberculosis in a Synergistic Manner

PubMed Central

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

2015-01-01

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 (CuII/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 CuII/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 CuII/I and exerted its bactericidal activity well below the active concentration of CuII/I or disulfiram alone. No other physiologically relevant bivalent transition metals (e.g., FeII, NiII, MnII, and CoII) 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 CuII/I alone. Our data suggest that by complexing with disulfiram, CuII/I is likely allowed unfettered access to vulnerable intracellular components, bypassing the normally sufficient copper homeostatic machinery. Overall, the synergistic antibacterial activity of CuII/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. PMID:26033731

Copper-containing zeolite catalysts

DOEpatents

Price, G.L.; Kanazirev, V.

1996-12-10

A catalyst useful in the conversion of nitrogen oxides or in the synthesis of nitriles or imines from amines, is formed by preparing an intimate mechanical mixture of a copper (II)-containing species, such as CuO or CuCl{sub 2}, or elemental copper, with a zeolite having a pore mouth comprising 10 oxygen atoms, such as ZSM-5, converting the elemental copper or copper (II) to copper (I), and driving the copper (I) into the zeolite.

Copper-containing zeolite catalysts

DOEpatents

Price, Geoffrey L.; Kanazirev, Vladislav

1996-01-01

A catalyst useful in the conversion of nitrogen oxides or in the synthesis of nitriles or imines from amines, formed by preparing an intimate mechanical mixture of a copper (II)-containing species, such as CuO or CuCl.sub.2, or elemental copper, with a zeolite having a pore mouth comprising 10 oxygen atoms, such as ZSM-5, converting the elemental copper or copper (II) to copper (I), and driving the copper (I) into the zeolite.

Predicting the potentials, solubilities and stabilities of metal-acetylacetonates for non-aqueous redox flow batteries using density functional theory calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kucharyson, J. F.; Cheng, L.; Tung, S. O.

New active materials are needed to improve the performance and reduce the cost of non-aqueous redox flow batteries (RFBs) for grid-scale energy storage applications. Efforts to develop better performing materials, which have largely been empirical, would benefit from a better understanding of relationships between structural, electronic and RFB-relevant functional properties. This paper focuses on metal-acetylacetonates, a class of metal coordination complexes that has shown promise for use in RFBs, and describes correlations between their experimentally measured standard potentials, solubilities, and stabilities (cycle lifes), and selected chemical, structural and electronic properties determined from Density Functional Theory (DFT) calculations. The training setmore » consisted of 16 complexes including 5 different metals and 11 different substituents on the acetylacetonate ligand. Standard potentials for those compounds were calculated and are in good agreement with experimentally measured results. A predictive equation based on the solvation energies and dipole moments, two easily computed properties, reasonably modeled the experimentally determined solubilities. Importantly, we were able to identify a descriptor for the stability of acetylacetonates. The experimentally determined stability, quantified as the cycle life to a given degree of degradation, correlated with the percentage of the highest occupied (HOMO) or lowest unoccupied molecular orbital (LUMO) on the metal of the complex. This percentage is influenced by the degree of ligand innocence (irreducibility), and complexes with the most innocent ligands yielded the most stable redox reactions. To this end, VO(acetylacetonate)(2) and Fe(acetylacetonate)(3), with nearly 80% of the HOMO and LUMO on the metal, possessed the most stable oxidation and reduction half-reactions, respectively. The structure-function relationships and correlations presented in this paper could be used to predict new, highly soluble and stable complexes for RFB applications.« less

DNA/RNA binding and anticancer/antimicrobial activities of polymer-copper(II) complexes

NASA Astrophysics Data System (ADS)

Lakshmipraba, Jagadeesan; Arunachalam, Sankaralingam; Riyasdeen, Anvarbatcha; Dhivya, Rajakumar; Vignesh, Sivanandham; Akbarsha, Mohammad Abdulkader; James, Rathinam Arthur

2013-05-01

Water soluble polymer-copper(II) complexes with various degrees of coordination in the polymer chain were synthesized and characterized by elemental analysis, IR, UV-visible and EPR spectra. The DNA/RNA binding behavior of these polymer-copper(II) complexes was examined by UV-visible absorption, emission and circular dichroism spectroscopic methods, and cyclic voltammetry techniques. The binding of the polymer-copper(II) complexes with DNA/RNA was mainly through intercalation but some amount of electrostatic interaction was also observed. This binding capacity increased with the degree of coordination of the complexes. The polymer-copper(II) complex having the highest degree of coordination was subjected to analysis of cytotoxic and antimicrobial properties. The cytotoxicity study indicated that the polymer-copper(II) complexes affected the viability of MCF-7 mammary carcinoma cells, and the cells responded to the treatment with mostly through apoptosis although a few cells succumbed to necrosis. The antimicrobial screening showed activity against some human pathogens.

Equilibrium and kinetic studies of copper biosorption by dead Ceriporia lacerata biomass isolated from the litter of an invasive plant in China.

PubMed

Li, Xiaona; Li, Airong; Long, Mingzhong; Tian, Xingjun

2015-01-01

Ceriporia lacerata, a strain of white-rot fungus isolated from the litter of an invasive plant (Solidago canadensis) in China, was little known about its properties and utilization. In this work, the copper(II) biosorption characteristics of formaldehyde inactivated C. lacerata biomass were examined as a function of initial pH, initial copper(II) concentration and contact time, and the adsorptive equilibrium and kinetics were simulated, too. The optimum pH was found to be 6.0 at experimental conditions of initial copper(II) concentration 100 mg/L, biomass dose 2 g/L, contact time 12 h, shaking rate 150 r/min and temperature 25°C. Biosorption equilibrium cost about 1 hour at experimental conditions of pH 6.0, initial copper(II) concentration 100 mg/L, C. lacerata dose 2 g/L, shaking rate 150 r/min and temperature 25°C. At optimum pH 6.0, highest copper(II) biosorption amounts were 6.79 and 7.76 mg/g for initial copper(II) concentration of 100 and 200 mg/L, respectively (with other experimental parameters of C. lacerata dose 2 g/L, shaking rate 150 r/min and temperature 25°C). The pseudo second-order adsorptive model gave the best adjustment for copper(II) biosorption kinetics. The equilibrium data fitted very well to both Langmuir and Freundlich adsorptive isotherm models. Without further acid or alkali treatment for improving adsorption properties, formaldehyde inactivated C. lacerata biomass possesses good biosorption characteristics on copper(II) removal from aqueous solutions.

Characterization and mechanism of copper biosorption by a highly copper-resistant fungal strain isolated from copper-polluted acidic orchard soil.

PubMed

Tu, Chen; Liu, Ying; Wei, Jing; Li, Lianzhen; Scheckel, Kirk G; Luo, Yongming

2018-06-22

In this paper, a highly copper-resistant fungal strain NT-1 was characterized by morphological, physiological, biochemical, and molecular biological techniques. Physiological response to Cu(II) stress, effects of environmental factors on Cu(II) biosorption, as well as mechanisms of Cu(II) biosorption by strain NT-1 were also investigated in this study. The results showed that NT-1 belonged to the genus Gibberella, which exhibited high tolerance to both acidic conditions and Cu(II) contamination in the environment. High concentrations of copper stress inhibited the growth of NT-1 to various degrees, leading to the decreases in mycelial biomass and colony diameter, as well as changes in morphology. Under optimal conditions (initial copper concentration: 200 mg L -1 , temperature 28 °C, pH 5.0, and inoculum dose 10%), the maximum copper removal percentage from solution through culture of strain NT-1 within 5 days reached up to 45.5%. The biosorption of Cu(II) by NT-1 conformed to quasi-second-order kinetics and Langmuir isothermal adsorption model and was confirmed to be a monolayer adsorption process dominated by surface adsorption. The binding of NT-1 to Cu(II) was mainly achieved by forming polydentate complexes with carboxylate and amide group through covalent interactions and forming Cu-nitrogen-containing heterocyclic complexes via Cu(II)-π interaction. The results of this study provide a new fungal resource and key parameters influencing growth and copper removal capacity of the strain for developing an effective bioremediation strategy for copper-contaminated acidic orchard soils.

Copper complexes as a source of redox active MRI contrast agents.

PubMed

Dunbar, Lynsey; Sowden, Rebecca J; Trotter, Katherine D; Taylor, Michelle K; Smith, David; Kennedy, Alan R; Reglinski, John; Spickett, Corinne M

2015-10-01

The study reports an advance in designing copper-based redox sensing MRI contrast agents. Although the data demonstrate that copper(II) complexes are not able to compete with lanthanoids species in terms of contrast, the redox-dependent switch between diamagnetic copper(I) and paramagnetic copper(II) yields a novel redox-sensitive contrast moiety with potential for reversibility.

Role of copper transport protein Antioxidant-1 in Angiotensin II-induced hypertension: A key regulator of Extracellular SOD

PubMed Central

Ozumi, Kiyoshi; Sudhahar, Varadarajan; Kim, Ha Won; Chen, Gin-Fu; Kohno, Takashi; Finney, Lydia; Vogt, Stefan; McKinney, Ronald D.; Ushio-Fukai, Masuko; Fukai, Tohru

2012-01-01

Extracellular superoxide dismutase (SOD3) is a secretory copper enzyme involved in protecting angiotensin II (Ang II)-induced hypertension. We previously found that Ang II upregulates SOD3 expression and activity as a counter-regulatory mechanism; however, underlying mechanisms are unclear. Antioxidant-1 (Atox1) is shown to act as a copper-dependent transcription factor as well as copper chaperone for SOD3 in vitro, but its role in Ang II-induced hypertension in vivo is unknown. Here we show that Ang II infusion increases Atox1 expression as well as SOD3 expression and activity in aortas of wild-type mice, which are inhibited in mice lacking Atox1. Accordingly, Ang II increases vascular O2•− production, reduces endothelium-dependent vasodilation and increases vasoconstriction in mesenteric arterioles to a greater extent in Atox1−/− than in wild-type mice. This contributes to augmented hypertensive response to Ang II in Atox1−/− mice. In cultured vascular smooth muscle cells, Ang II promotes translocation of Atox1 to the nucleus, thereby increasing SOD3 transcription by binding to Atox1 responsive element in the SOD3 promoter. Furthermore, Ang II increases Atox1 binding to the copper exporter ATP7A which obtains copper from Atox1 as well as translocation of ATP7A to plasma membranes where it colocalizes with SOD3. As its consequence, Ang II decreases vascular copper levels, which is inhibited in Atox1−/− mice. In summary, Atox1 functions to prevent Ang II-induced endothelial dysfunction and hyper-contraction in resistant vessels as well as hypertension in vivo by reducing extracellular O2•− levels via increasing vascular SOD3 expression and activity. PMID:22753205

Fe(II)/Cu(II) interaction on goethite stimulated by an iron-reducing bacteria Aeromonas Hydrophila HS01 under anaerobic conditions.

PubMed

Tao, Liang; Zhu, Zhen-Ke; Li, Fang-Bai; Wang, Shan-Li

2017-11-01

Copper is a trace element essential for living creatures, but copper content in soil should be controlled, as it is toxic. The physical-chemical-biological features of Cu in soil have a significant correlation with the Fe(II)/Cu(II) interaction in soil. Of significant interest to the current study is the effect of Fe(II)/Cu(II) interaction conducted on goethite under anaerobic conditions stimulated by HS01 (a dissimilatory iron reduction (DIR) microbial). The following four treatments were designed: HS01 with α-FeOOH and Cu(II) (T1), HS01 with α-FeOOH (T2), HS01 with Cu(II) (T3), and α-FeOOH with Cu(II) (T4). HS01 presents a negligible impact on copper species transformation (T3), whereas the presence of α-FeOOH significantly enhanced copper aging contributing to the DIR effect (T1). Moreover, the violent reaction between adsorbed Fe(II) and Cu(II) leads to the decreased concentration of the active Fe(II) species (T1), further inhibiting reactions between Fe(II) and iron (hydr)oxides and decelerating the phase transformation of iron (hydr)oxides (T1). From this study, the effects of the Fe(II)/Cu(II) interaction on goethite under anaerobic conditions by HS01 are presented in three aspects: (1) the accelerating effect of copper aging, (2) the reductive transformation of copper, and (3) the inhibition effect of the phase transformation of iron (hydr)oxides. Copyright © 2017 Elsevier Ltd. All rights reserved.

The coordination structure of the extracted copper(II) complex with a synergistic mixture containing dinonylnaphthalene sulfonic acid and n-hexyl 3-pyridinecarboxylate ester

NASA Astrophysics Data System (ADS)

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

2017-09-01

In continuation of our interest in the coordination structure of the nickel(II) complex with dinonylnaphthalene sulfonic acid (HDNNS) and 2-ethylhexyl 4-pyridinecarboxylate ester (4PC), it was observed that the coordination sphere was completed by the coordination of two N atoms of pyridine rings in ligands 4PC and four water molecules while no direct interaction between Ni(II) and deprotonated HDNNS was observed. To investigate whether the coordination structure of nickel(II) with the synergistic mixture containing HDNNS and 4PC predominates or not in the copper(II) complex with the synergistic mixtures containing HDNNS and pyridinecarboxylate esters, a copper(II) synergist complex with n-hexyl 3-pyridinecarboxylate ester (L) and naphthalene-2-sulfonic acid (HNS, the short chain analogue of HDNNS), was prepared and studied by X-ray single crystal diffraction, elemental analyses and thermo gravimetric analysis (TGA), respectively. It was shown that the composition of the copper(II) synergist complex was [Cu(H2O)2(L)2(NS)2] and formed a trans-form distorted octahedral coordination structure. Two oxygen atoms of the two coordinated water molecules and two N atoms of the pyridine rings in the ligands L defined the basal plane while two O atoms from two sulfonate anions of the deprotonated HNS ligands occupied the apical positions by direct coordination with Cu(II), which was distinguished from the coordination structure of the nickel(II) synergist complex as reported in our previous work. In the crystal lattice, neighboring molecules [Cu(H2O)2L2(NS)2] were linked through the intermolecular hydrogen bonds between the hydrogen atoms of the coordinated water molecules and the oxygen atoms of the sulfonate anions in the copper(II) synergist complex to form a 2D plane. In order to bridge the gap between the solid state structure of the copper(II) synergist complex and the solution structure of the extracted copper(II) complex with the actual synergistic mixture containing L and HDNNS in the non-polar organic phase, the structures of the two copper(II) complexes were further investigated by Fourier transform infrared spectroscopy (FT-IR) and electrospray ionization mass spectrometry (ESI-MS), and the results indicated that the extracted copper(II) complex in the non-polar organic phase might possess a similar coordination structure as the copper(II) synergist complex.

The structures of the crystalline phase and columnar mesophase of rhodium (II) heptanoate and of its binary mixture with copper (II) heptanoate probed by EXAFS

NASA Astrophysics Data System (ADS)

Inb-Elhaj, M.; Guillon, D.; Skoulios, A.; Maldivi, P.; Giroud-Godquin, A. M.; Marchon, J.-C.

1992-12-01

EXAFS was used to investigate the local structure of the polar spines of rhodium (II) soaps in the columnar liquid crystalline state. It was also used to ascertain the degree of blending of the cores in binary mixtures of rhodium (II) and copper (II) soaps. For the pure rhodium soaps, the columns are shown to result from the stacking of binuclear metal-metal bonded dirhodium tetracarboxylate units bonded to one another by apical ligation of the metal atom of each complex with one of the oxygen atoms of the adjacent molecule. Mixtures of rhodium (II) and copper (II) soaps give a hexagonal columnar mesophase in which pure rhodium and pure copper columns are randomly distributed.

Microporous Materials of Metal Carboxylates

NASA Astrophysics Data System (ADS)

Mori, Wasuke; Takamizawa, Satoshi

2000-06-01

Copper(II) terephthalate absorbs a large amount of gases such as N2, Ar, O2, and Xe. The maximum amounts of absorption of gases were 1.8, 1.9, 2.2, and 0.9 mole per mole of the copper(II) salt for N2, Ar, O2, and Xe, respectively, indicating that the gases were not adsorbed on the surface but occluded within the solid. Other microporous copper(II) dicarboxylates are also reviewed. The porous structure of copper(II) terephthalate, in which the gas is occluded, is deduced from the temperature dependence of magnetic susceptibilities and the linear structure of terephthalate. Microporous molybdenum(II) and ruthenium(II, III) dicarboxylates are discussed. We describe that rhodium(II) monocarboxylate bridged by pyrazine form stable micropores by self-assembly of infinite linear chain complexes.

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

PubMed Central

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

2011-01-01

A mechanistic model is formulated to account for the high reactivity of chelating azides (organic azides capable of chelation-assisted metal coordination at the alkylated azido nitrogen position) and copper(II) acetate (Cu(OAc)2) in copper(II)-mediated azide-alkyne cycloaddition (AAC) reactions. Fluorescence and 1H NMR assays are developed for monitoring the reaction progress in two different solvents – methanol and acetonitrile. Solvent kinetic isotopic effect and pre-mixing experiments give credence to the proposed different induction reactions for converting copper(II) to catalytic copper(I) species in methanol (methanol oxidation) and acetonitrile (alkyne oxidative homocoupling), respectively. The kinetic orders of individual components in a chelation-assisted, copper(II)-accelerated AAC reaction are determined in both methanol and acetonitrile. Key conclusions resulting from the kinetic studies include (1) the interaction between copper ion (either in +1 or +2 oxidation state) and a chelating azide occurs in a fast, pre-equilibrium step prior to the formation of the in-cycle copper(I)-acetylide, (2) alkyne deprotonation is involved in several kinetically significant steps, and (3) consistent with prior experimental and computational results by other groups, two copper centers are involved in the catalysis. The X-ray crystal structures of chelating azides with Cu(OAc)2 suggest a mechanistic synergy between alkyne oxidative homocoupling and copper(II)-accelerated AAC reactions, in which both a bimetallic catalytic pathway and a base are involved. The different roles of the two copper centers (a Lewis acid to enhance the electrophilicity of the azido group and a two-electron reducing agent in oxidative metallacycle formation, respectively) in the proposed catalytic cycle suggest that a mixed valency (+2 and +1) dinuclear copper species be a highly efficient catalyst. This proposition is supported by the higher activity of the partially reduced Cu(OAc)2 in mediating a 2-picolylazide-involved AAC reaction than the fully reduced Cu(OAc)2. Finally, the discontinuous kinetic behavior that has been observed by us and others in copper(I/II)-mediated AAC reactions is explained by the likely catalyst disintegration during the course of a relatively slow reaction. Complementing the prior mechanistic conclusions drawn by other investigators which primarily focus on the copper(I)/alkyne interactions, we emphasize the kinetic significance of copper(I/II)/azide interaction. This work not only provides a mechanism accounting for the fast Cu(OAc)2-mediated AAC reactions involving chelating azides, which has apparent practical implications, but suggests the significance of mixed-valency dinuclear copper species in catalytic reactions where two copper centers carry different functions. PMID:21809811

π-Stacking between Casiopeinas® and DNA bases.

PubMed

Galindo-Murillo, Rodrigo; Hernandez-Lima, Joseelyne; González-Rendón, Mayra; Cortés-Guzmán, Fernando; Ruíz-Azuara, Lena; Moreno-Esparza, Rafael

2011-08-28

Casiopeínas® are copper complexes with the general formula [Cu(N-N)(N-O)]NO(3) and [Cu(N-N)(O-O)]NO(3) where N-N denotes a substituted bipyridine or phenanthroline, N-O indicates α-aminoacidate or peptide and O-O represents acetylacetonate or salicylaldehyde. This family of compounds has been evaluated in vitro and in vivo showing cytotoxic, genotoxic, and antineoplastic activity. The action mechanism is still not completely elucidated, but the possibility exists that these compounds interact with DNA by intercalation due to the aromatic moiety. In this work we found, using the properties of the electron density of a π-complex model base-Casiopeína®-base, that the stacking mechanism between Casiopeínas® and DNA bases is due to an electron density deficiency of the ligand of the Casiopeína® which is compensated for by an electron transfer from adenines by a π-π interaction.

Rapid assessment of human amylin aggregation and its inhibition by copper(II) ions by laser ablation electrospray ionization mass spectrometry with ion mobility separation

DOE PAGES

Li, Hang; Ha, Emmeline; Donaldson, Robert P.; ...

2015-09-09

Native electrospray ionization (ESI) mass spectrometry (MS) is often used to monitor noncovalent complex formation between peptides and ligands. The relatively low throughput of this technique, however, is not compatible with extensive screening. Laser ablation electrospray ionization (LAESI) MS combined with ion mobility separation (IMS) can analyze complex formation and provide conformation information within a matter of seconds. Islet amyloid polypeptide (IAPP) or amylin, a 37-amino acid residue peptide, is produced in pancreatic beta-cells through proteolytic cleavage of its prohormone. Both amylin and its precursor can aggregate and produce toxic oligomers and fibrils leading to cell death in the pancreasmore » that can eventually contribute to the development of type 2 diabetes mellitus. The inhibitory effect of the copper(II) ion on amylin aggregation has been recently discovered, but details of the interaction remain unknown. Finding other more physiologically tolerated approaches requires large scale screening of potential inhibitors. In this paper, we demonstrate that LAESI-IMS-MS can reveal the binding stoichiometry, copper oxidation state, and the dissociation constant of human amylin–copper(II) complex. The conformations of hIAPP in the presence of copper(II) ions were also analyzed by IMS, and preferential association between the β-hairpin amylin monomer and the metal ion was found. The copper(II) ion exhibited strong association with the —HSSNN– residues of the amylin. In the absence of copper(II), amylin dimers were detected with collision cross sections consistent with monomers of β-hairpin conformation. When copper(II) was present in the solution, no dimers were detected. Thus, the copper(II) ions disrupt the association pathway to the formation of β-sheet rich amylin fibrils. Using LAESI-IMS-MS for the assessment of amylin–copper(II) interactions demonstrates the utility of this technique for the high-throughput screening of potential inhibitors of amylin oligomerization and fibril formation. Finally and more generally, this rapid technique opens the door for high-throughput screening of potential inhibitors of amyloid protein aggregation.« less

Structural and magnetic characterization of a tetranuclear copper(II) cubane stabilized by intramolecular metal cation-π interactions.

PubMed

Papadakis, Raffaello; Rivière, Eric; Giorgi, Michel; Jamet, Hélène; Rousselot-Pailley, Pierre; Réglier, Marius; Simaan, A Jalila; Tron, Thierry

2013-05-20

A novel tetranuclear copper(II) complex (1) was synthesized from the self-assembly of copper(II) perchlorate and the ligand N-benzyl-1-(2-pyridyl)methaneimine (L(1)). Single-crystal X-ray diffraction studies revealed that complex 1 consists of a Cu4(OH)4 cubane core, where the four copper(II) centers are linked by μ3-hydroxo bridges. Each copper(II) ion is in a distorted square-pyramidal geometry. X-ray analysis also evidenced an unusual metal cation-π interaction between the copper ions and phenyl substituents of the ligand. Calculations based on the density functional theory method were used to quantify the strength of this metal-π interaction, which appears as an important stabilizing parameter of the cubane core, possibly acting as a driving parameter in the self-aggregation process. In contrast, using the ligand N-phenethyl-1-(2-pyridyl)methaneimine (L(2)), which only differs from L(1) by one methylene group, the same synthetic procedure led to a binuclear bis(μ-hydroxo)copper(II) complex (2) displaying intermolecular π-π interactions or, by a slight variation of the experimental conditions, to a mononuclear complex (3). These complexes were studied by X-ray diffraction techniques. The magnetic properties of complexes 1 and 2 are reported and discussed.

DNA binding and biological studies of some novel water-soluble polymer-copper(II)-phenanthroline complexes.

PubMed

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.

The Electrochemical Synthesis of Transition-Metal Acetylacetonates

ERIC Educational Resources Information Center

Long, S. R.; Browning, S. R.; Lagowski, J. J.

2008-01-01

The electrochemical synthesis of transition-metal acetylacetonates described here can form the basis of assisting in the transformation of an entry-level laboratory course into a research-like environment where all members of a class are working on the same problem, but where each member has a personal responsibility for the synthesis and…

Effect of Dioxygen on Copper(II) Binding to α-Synuclein

PubMed Central

Lucas, Heather R.; Lee, Jennifer C.

2010-01-01

Using the fluorescent amino acid tryptophan (Trp), we have characterized the copper(II) binding of F4W α-synuclein in the presence and absence of dioxygen at neutral pH. Variations in Trp fluorescence indicate that copper(II) binding is enhanced by the presence of dioxygen, with the apparent dissociation constant (Kd(app)) changing from 100 nM (anaerobic) to 10 nM (aerobic). To investigate the possible role of methionine oxidation, complementary work focused on synthetic peptide models of the N-terminal Cu(II)-α-syn site, MDV(F/W) and M*DV(F/W), where M*= methionine sulfoxide. Furthermore, we employed circular dichroism (CD) spectroscopy to demonstrate that the phenyl-to-indole (F→W) substitution does not alter copper(II) binding properties and to confirm the 1:1 metal-peptide binding stoichiometry. CD comparisons also revealed that Met1 oxidation does not affect the copper-peptide conformation and further suggested the possible existence of a CuII-Trp/Phe (cation-π) interaction. PMID:20064662

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

PubMed Central

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

2013-01-01

Zinc and copper are trace elements essential for proper folding, stabilization and catalytic activity of many metalloenzymes in living organisms. However, disturbed zinc and copper homeostasis is reported in many types of cancer. We have previously demonstrated that copper complexes induced proteasome inhibition and apoptosis in cultured human cancer cells. In the current study we hypothesized that zinc complexes could also inhibit the proteasomal chymotrypsin-like activity responsible for subsequent apoptosis induction. We first showed that zinc(II) chloride was able to inhibit the chymotrypsin-like activity of a purified 20S proteasome with an IC50 value of 13.8 μM, which was less potent than copper(II) chloride (IC50 5.3 μM). We then compared the potencies of a pyrrolidine dithiocarbamate (PyDT)-zinc(II) complex and a PyDT-copper(II) complex to inhibit cellular proteasomal activity, suppress proliferation and induce apoptosis in various human breast and prostate cancer cell lines. Consistently, zinc complex was less potent than copper complex in inhibiting the proteasome and inducing apoptosis. Additionally, zinc and copper complexes appear to use somewhat different mechanisms to kill tumor cells. Zinc complexes were able to activate calpain-, but not caspase-3-dependent pathway, while copper complexes were able to induce activation of both proteases. Furthermore, the potencies of these PyDT-metal complexes depend on the nature of metals and also on the ratio of PyDT to the metal ion within the complex, which probably affects their stability and availability for interacting with and inhibiting the proteasome in tumor cells. PMID:18501397

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

PubMed Central

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. PMID:25045338

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Hang; Ha, Emmeline; Donaldson, Robert P.

Native electrospray ionization (ESI) mass spectrometry (MS) is often used to monitor noncovalent complex formation between peptides and ligands. The relatively low throughput of this technique, however, is not compatible with extensive screening. Laser ablation electrospray ionization (LAESI) MS combined with ion mobility separation (IMS) can analyze complex formation and provide conformation information within a matter of seconds. Islet amyloid polypeptide (IAPP) or amylin, a 37-amino acid residue peptide, is produced in pancreatic beta-cells through proteolytic cleavage of its prohormone. Both amylin and its precursor can aggregate and produce toxic oligomers and fibrils leading to cell death in the pancreasmore » that can eventually contribute to the development of type 2 diabetes mellitus. The inhibitory effect of the copper(II) ion on amylin aggregation has been recently discovered, but details of the interaction remain unknown. Finding other more physiologically tolerated approaches requires large scale screening of potential inhibitors. In this paper, we demonstrate that LAESI-IMS-MS can reveal the binding stoichiometry, copper oxidation state, and the dissociation constant of human amylin–copper(II) complex. The conformations of hIAPP in the presence of copper(II) ions were also analyzed by IMS, and preferential association between the β-hairpin amylin monomer and the metal ion was found. The copper(II) ion exhibited strong association with the —HSSNN– residues of the amylin. In the absence of copper(II), amylin dimers were detected with collision cross sections consistent with monomers of β-hairpin conformation. When copper(II) was present in the solution, no dimers were detected. Thus, the copper(II) ions disrupt the association pathway to the formation of β-sheet rich amylin fibrils. Using LAESI-IMS-MS for the assessment of amylin–copper(II) interactions demonstrates the utility of this technique for the high-throughput screening of potential inhibitors of amylin oligomerization and fibril formation. Finally and more generally, this rapid technique opens the door for high-throughput screening of potential inhibitors of amyloid protein aggregation.« less

Determination of copper (II) in foodstuffs based on its quenching effect on the fluorescence of N,N'-bis(pyridoxal phosphate)-o-phenylenediamine.

PubMed

Xu, Canhui; Liao, Lifu; He, Yunfei; Wu, Rurong; Li, Shijun; Yang, Yanyan

2015-01-01

A Schiff base-type fluorescence probe was prepared for the detection of copper (II) in foodstuffs. The probe is N,N'-bis(pyridoxal phosphate)-o-phenylenediamine (BPPP). It was synthesized by utilizing the Schiff base condensation reaction of pyridoxal 5-phosphate with 1,2-phenylenediamine. BPPP has the properties of high fluorescence stability, good water solubility and low toxicity. Its maximum excitation wavelength and maximum fluorescence emission wavelength are at 389 and 448 nm, respectively. When BPPP coexists with copper (II), its fluorescence is dramatically quenched. Under a certain condition, the fluorescence intensity decreased proportionally to the concentration of copper (II) by the quenching effect. Based on this fact, we established a fluorescence quenching method for the determination of copper (II). Under optimal conditions a linear range was found to be 0.5-50 ng/mL with a detection limit of 0.2 ng/mL. The method has been applied to determine copper (II) in foodstuff samples and the analytical results show good agreement with that obtained from atomic absorption spectrometry method. Copyright © 2015 Elsevier B.V. All rights reserved.

Spectroscopic and molecular docking studies on the interaction of human serum albumin with copper(II) complexes

NASA Astrophysics Data System (ADS)

Guhathakurta, Bhargab; Pradhan, Ankur Bikash; Das, Suman; Bandyopadhyay, Nirmalya; Lu, Liping; Zhu, Miaoli; Naskar, Jnan Prakash

2017-02-01

Two osazone based ligands, butane-2,3-dione bis(2‧-pyridylhydrazone) (BDBPH) and hexane-3,4-dione bis(2‧-pyridylhydrazone) (HDBPH), were synthesized out of the 2:1 M Schiff base condensation of 2-hydrazino pyridine respectively with 2,3-butanedione and 3,4-hexanedione. The X-ray crystal structures of both the ligands have been determined. The copper(II) complex of HDBPH has also been synthesized and structurally characterized. HDBPH and its copper(II) complex have thoroughly been characterized through various spectroscopic and analytical techniques. The X-ray crystal structure of the copper complex of HDBPH shows that it is a monomeric Cu(II) complex having 'N4O2' co-ordination chromophore. Interaction of human serum albumin (HSA) with these ligands and their monomeric copper(II) complexes have been studied by various spectroscopic means. The experimental findings show that the ligands as well as their copper complexes are good HSA binders. Molecular docking investigations have also been done to unravel the mode of binding of the species with HSA.

Characterization of Cu(II)-reconstituted ACC Oxidase using experimental and theoretical approaches.

PubMed

El Bakkali-Tahéri, Nadia; Tachon, Sybille; Orio, Maylis; Bertaina, Sylvain; Martinho, Marlène; Robert, Viviane; Réglier, Marius; Tron, Thierry; Dorlet, Pierre; Simaan, A Jalila

2017-06-01

1-Aminocyclopropane-1-carboxylic acid oxidase (ACCO) is a non heme iron(II) containing enzyme that catalyzes the final step of the ethylene biosynthesis in plants. The iron(II) ion is bound in a facial triad composed of two histidines and one aspartate (H177, D179 and H234). Several active site variants were generated to provide alternate binding motifs and the enzymes were reconstituted with copper(II). Continuous wave (cw) and pulsed Electron Paramagnetic Resonance (EPR) spectroscopies as well as Density Functional Theory (DFT) calculations were performed and models for the copper(II) binding sites were deduced. In all investigated enzymes, the copper ion is equatorially coordinated by the two histidine residues (H177 and H234) and probably two water molecules. The copper-containing enzymes are inactive, even when hydrogen peroxide is used in peroxide shunt approach. EPR experiments and DFT calculations were undertaken to investigate substrate's (ACC) binding on the copper ion and the results were used to rationalize the lack of copper-mediated activity. Copyright © 2017 Elsevier Inc. All rights reserved.

Nanomolar Copper Enhances Mercury Methylation by Desulfovibrio desulfuricans ND132

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Xia; Johs, Alexander; Zhao, Linduo

Methylmercury (MeHg) is produced by certain anaerobic microorganisms, such as the sulfate-reducing bacterium Desulfovibrio desulfuricans ND132, but environmental factors affecting inorganic mercury [Hg(II)] uptake and methylation remain unclear. We report that the presence of a small amount of copper ions [Cu(II), <100 nM] enhances Hg(II) uptake and methylation by washed cells of ND132, while Hg(II) methylation is inhibited at higher Cu(II) concentrations because of the toxicity of copper to the microorganism. The enhancement or inhibitory effect of Cu(II) is dependent on both time and concentration. The presence of nanomolar concentrations of Cu(II) facilitates rapid uptake of Hg(II) (within minutes) andmore » doubles MeHg production within a 24 h period, but micromolar concentrations of Cu(II) completely inhibit Hg(II) methylation. Metal ions such as zinc [Zn(II)] and nickel [Ni(II)] also inhibit but do not enhance Hg(II) methylation under the same experimental conditions. Furthermore, these observations suggest a synergistic effect of Cu(II) on Hg(II) uptake and methylation, possibly facilitated by copper transporters or metallochaperones in this organism, and highlight the fact that complex environmental factors affect MeHg production in the environment.« less

Nanomolar Copper Enhances Mercury Methylation by Desulfovibrio desulfuricans ND132

DOE PAGES

Lu, Xia; Johs, Alexander; Zhao, Linduo; ...

2018-05-29

Methylmercury (MeHg) is produced by certain anaerobic microorganisms, such as the sulfate-reducing bacterium Desulfovibrio desulfuricans ND132, but environmental factors affecting inorganic mercury [Hg(II)] uptake and methylation remain unclear. We report that the presence of a small amount of copper ions [Cu(II), <100 nM] enhances Hg(II) uptake and methylation by washed cells of ND132, while Hg(II) methylation is inhibited at higher Cu(II) concentrations because of the toxicity of copper to the microorganism. The enhancement or inhibitory effect of Cu(II) is dependent on both time and concentration. The presence of nanomolar concentrations of Cu(II) facilitates rapid uptake of Hg(II) (within minutes) andmore » doubles MeHg production within a 24 h period, but micromolar concentrations of Cu(II) completely inhibit Hg(II) methylation. Metal ions such as zinc [Zn(II)] and nickel [Ni(II)] also inhibit but do not enhance Hg(II) methylation under the same experimental conditions. Furthermore, these observations suggest a synergistic effect of Cu(II) on Hg(II) uptake and methylation, possibly facilitated by copper transporters or metallochaperones in this organism, and highlight the fact that complex environmental factors affect MeHg production in the environment.« less

The lumenal loop M672-P707 of the Menkes protein (ATP7A) transfers copper to peptidylglycine monooxygenase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Otoikhian, Adenike; Barry, Amanda N.; Mayfield, Mary

2012-05-14

Copper transfer to cuproproteins located in vesicular compartments of the secretory pathway depends on activity of the copper translocating ATPase (ATP7A or ATP7B) but the mechanism of transfer is largely unexplored. Copper-ATPase ATP7A is unique in having a sequence rich in histidine and methionine residues located on the lumenal side of the membrane. The corresponding fragment binds Cu(I) when expressed as a chimera with a scaffold protein, and mutations or deletions of His and/or Met residues in its sequence inhibit dephosphorylation of the ATPase, a catalytic step associated with copper release. Here we present evidence for a potential role ofmore » this lumenal region of ATP7A in copper transfer to cuproenzymes. Both Cu(II) and Cu(I) forms were investigated since the form in which copper is transferred to acceptor proteins is currently unknown. Analysis of Cu(II) using EPR demonstrated that at Cu:P ratios below 1:1, 15N-substituted protein had Cu(II) bound by 4 His residues, but this coordination changed as the Cu(II) to protein ratio increased towards 2:1. XAS confirmed this coordination via analysis of the intensity of outer-shell scattering from imidazole residues. The Cu(II) complexes could be reduced to their Cu(I) counterparts by ascorbate, but here again, as shown by EXAFS and XANES spectroscopy, the coordination was dependent on copper loading. At low copper Cu(I) was bound by a mixed ligand set of His + Met while at higher ratios His coordination predominated. The copper-loaded loop was able to transfer either Cu(II) or Cu(I) to peptidylglycine monooxygenase in the presence of chelating resin, generating catalytically active enzyme in a process that appeared to involve direct interaction between the two partners. The variation of coordination with copper loading suggests copper-dependent conformational change which in turn could act as a signal for regulating copper release by the ATPase pump.« less

The Lumenal Loop M672-P707 of the Menkes Protein (ATP7A) Transfers Copper to Peptidylglycine Monooxygenase

PubMed Central

Otoikhian, Adenike; Barry, Amanda N.; Mayfield, Mary; Nilges, Mark; Huang, Yiping; Lutsenko, Svetlana; Blackburn, Ninian J.

2012-01-01

Copper transfer to cuproproteins located in vesicular compartments of the secretory pathway depends on activity of the copper translocating ATPase (ATP7A or ATP7B) but the mechanism of transfer is largely unexplored. Copper-ATPase ATP7A is unique in having a sequence rich in histidine and methionine residues located on the lumenal side of the membrane. The corresponding fragment binds Cu(I) when expressed as a chimera with a scaffold protein, and mutations or deletions of His and/or Met residues in its sequence inhibit dephosphorylation of the ATPase, a catalytic step associated with copper release. Here we present evidence for a potential role of this lumenal region of ATP7A in copper transfer to cuproenzymes. Both Cu(II) and Cu(I) forms were investigated since the form in which copper is transferred to acceptor proteins is currently unknown. Analysis of Cu(II) using EPR demonstrated that at Cu:P ratios below 1:1, 15N-substituted protein had Cu(II) bound by 4 His residues, but this coordination changed as the Cu(II) to protein ratio increased towards 2:1. XAS confirmed this coordination via analysis of the intensity of outer-shell scattering from imidazole residues. The Cu(II) complexes could be reduced to their Cu(I) counterparts by ascorbate, but here again, as shown by EXAFS and XANES spectroscopy, the coordination was dependent on copper loading. At low copper Cu(I) was bound by a mixed ligand set of His + Met while at higher ratios His coordination predominated. The copper-loaded loop was able to transfer either Cu(II) or Cu(I) to peptidylglycine monooxygenase in the presence of chelating resin, generating catalytically active enzyme in a process that appeared to involve direct interaction between the two partners. The variation of coordination with copper loading suggests copper-dependent conformational change which in turn could act as a signal for regulating copper release by the ATPase pump. PMID:22577880

Spectroscopy of Cu(II)-PcoC and the multicopper oxidase function of PcoA, two essential components of Escherichia coli pco copper resistance operon.

PubMed

Huffman, David L; Huyett, Jennifer; Outten, F Wayne; Doan, Peter E; Finney, Lydia A; Hoffman, Brian M; O'Halloran, Thomas V

2002-08-06

The plasmid-encoded pco copper resistance operon in Escherichia coli consists of seven genes that are expressed from two pco promoters in response to elevated copper; however, little is known about how they mediate resistance to excess environmental copper. Two of the genes encode the soluble periplasmic proteins PcoA and PcoC. We show here that inactivation of PcoC, and PcoA to a lesser extent, causes cells to become more sensitive to copper than wild-type nonresistant strains, consistent with a tightly coupled detoxification pathway. Periplasmic extracts show copper-inducible oxidase activity, attributed to the multicopper oxidase function of PcoA. PcoC, a much smaller protein than PcoA, binds one Cu(II) and exhibits a weak electronic transition characteristic of a type II copper center. ENDOR and ESEEM spectroscopy of Cu(II)-PcoC and the (15)N- and Met-CD(3)-labeled samples are consistent with a tetragonal ligand environment of three nitrogens and one aqua ligand "in the plane". A weakly associated S-Met and aqua are likely axial ligands. At least one N is a histidine and is likely trans to the in-plane aqua ligand. The copper chemistry of PcoC and the oxidase function of PcoA are consistent with the emerging picture of the chromosomally encoded copper homeostasis apparatus in the E. coli cell envelope [Outten, F. W., Huffman, D. L., Hale, J. A., and O'Halloran, T. V. (2001) J. Biol. Chem. 276, 30670-30677]. We propose a model for the plasmid system in which Cu(I)-PcoC functions in this copper efflux pathway as a periplasmic copper binding protein that docks with the multiple repeats of Met-rich domains in PcoA to effect oxidation of Cu(I) to the less toxic Cu(II) form. The solvent accessibility of the Cu(II) in PcoC may allow for metal transfer to other plasmid and chromosomal factors and thus facilitate removal of Cu(II) from the cell envelope.

Characterization and copper binding properties of human COMMD1 (MURR1).

PubMed

Narindrasorasak, Suree; Kulkarni, Prasad; Deschamps, Patrick; She, Yi-Min; Sarkar, Bibudhendra

2007-03-20

COMMD1 (copper metabolism gene MURR1 (mouse U2af1-rs1 region1) domain) belongs to a family of multifunctional proteins that inhibit nuclear factor NF-kappaB. COMMD1 was implicated as a regulator of copper metabolism by the discovery that a deletion of exon 2 of COMMD1 causes copper toxicosis in Bedlington terriers. Here, we report the detailed characterization and specific copper binding properties of purified recombinant human COMMD1 as well as that of the exon 2 product, COMMD(61-154). By using various techniques including native-PAGE, EPR, UV-visible electronic absorption, intrinsic fluorescence spectroscopies as well as DEPC modification of histidines, we demonstrate that COMMD1 specifically binds copper as Cu(II) in 1:1 stoichiometry and does not bind other divalent metals. Moreover, the exon 2 product, COMMD(61-154), alone was able to bind Cu(II) as well as the wild type protein, with a stoichiometry of 1 mol of Cu(II) per protein monomer. The protection of DEPC modification of COMMD1 by Cu(II) implied that Cu(II) binding involves His residues. Further investigation by DEPC modification of COMMD(61-154) and subsequent MALDI MS mapping and MS/MS sequencing identified the protection of His101 and His134 residues in the presence of Cu(II). Fluorescence studies of single point mutants of the full-length protein revealed the involvement of M110 in addition to H134 in direct Cu(II) binding. Taken together, the data provide insight into the function of COMMD1 and especially COMMD(61-154), a product of exon 2 that is deleted in terriers affected by copper toxicosis, as a regulator of copper homeostasis.

Fluorescence Lifetime Imaging of Physiological Free Cu(II) Levels in Live Cells with a Cu(II)-Selective Carbonic Anhydrase-Based Biosensor

PubMed Central

McCranor, Bryan J.; Szmacinski, Henryk; Zeng, Hui Hui; Stoddard, A.K.; Hurst, Tamiika; Fierke, Carol A.; Lakowicz, J.R.

2014-01-01

Copper is a required trace element that plays key roles in a number of human enzymes, such that copper deficiency or genetic defects in copper transport lead to serious or fatal disease. Rae, et al., had famously predicted that free copper ion levels in the cell cytoplasm were extremely low, typically too low to be observable. We recently developed a variant of human apocarbonic anhydrase II for sensing metal ions that exhibits 25-fold better selectivity for Cu(II) over Zn(II) than the wild type protein, enabling us to accurately measure Cu(II) in the presence of ordinary cellular (picomolar) concentrations of free zinc. We inserted a fluorescent labeled Cu(II)-specific variant of human apocarbonic anhydrase into PC-12 cells and found that the levels are indeed extremely low (in the femtomolar range). We imaged the free Cu(II) levels in living cells by means of frequency-domain fluorescence lifetime microscopy. Implications of this finding are discussed. PMID:24671220

Cu(II) and Cu(I) complexes with 1,2-dithiosquarate as a ligand; from molecular compounds to supramolecular network structures

NASA Astrophysics Data System (ADS)

Calatayud, M. Luisa; Castro, Isabel; Julve, Miguel; Sletten, Jorunn

2008-03-01

Four new complexes of copper(II) and/or copper(I) with 1,2-dtsq as a ligand have been synthesized and characterized by single crystal X-ray diffraction methods, [Cu II(terpy)(1,2-dtsq)] ( 1), [Cu II(dmen)(1,2-dtsq)] n ( 2), {[Cu II(dmen) 2][Cu I(1,2-dtsq)] 2} n·2nH 2O( 3) and {[Cu II(men) 2][Cu I (1,2-dtsq)] 2} n·nH 2O ( 4) (1,2-dtsq = 1,2-dithiosquarate, dianion of 3,4-dimercapto-1-cyclobutene-1,2-dione; dmen = N, N-dimethylethylenediamine; men = N-methylethylenediamine, terpy = 2,2':6,2″-terpyridine). Compound 1 consists of neutral [Cu II(terpy)(1,2-dtsq)] mononuclear units which are held together by O⋯H-C and van der Waals interactions. Compound 2 is built of neutral [Cu II(dmen)(1,2-dtsq)] entities which are connected through weak Cu-S (pairs) and Cu-O (single) interactions into a layer structure. The structures of 3 and 4 feature polynuclear [Cu(1,2-dtsq)]nn- chains, in which dtsq groups are linking copper(I) ions in the μ-1,1, μ-1,1,1 and μ-1,2 bridging modes. The dtsq groups in these chains connect to the copper(II) ions of the [Cu IIL 2] 2+ cations [L being the bidentate dmen ( 3) and men ( 4) ligands], but in different manners in the two structures. The connections in compound 3 are unsymmetrical, so that columns of {[Cu II(dmen) 2][Cu I(1,2-dtsq)] 2} n where the copper(II) ions bind to 1,2-dtsq oxygen atoms with relatively strong axial bonds may be identified. These columns are further connected to each other through weak axial Cu II⋯S interactions, creating a three-dimensional (3D) network with channels containing the solvent water. In compound 4, on the other hand, the two crystallographically independent cations each forms a symmetrical link between the anionic chains through, respectively, O-Cu II-O and S-Cu II-S axial bonds, again creating a 3D structure with channels running parallel to the chain axis. The reduction of copper(II) to copper(I) by 1,2-dtsq is precluded when the coordination sphere of the copper(II) ion is partially blocked with the tridentate terpy ligand whereas this process occurs when the blocking ligands are the bidentate dmen and men groups.

Copper(II) complexes of methimazole, an anti Grave's disease drug. Synthesis, characterization and its potential biological behavior as alkaline phosphatase inhibitor.

PubMed

Urquiza, Nora M; Manca, Silvia G; Moyano, María A; Dellmans, Raquel Arrieta; Lezama, Luis; Rojo, Teófilo; Naso, Luciana G; Williams, Patricia A M; Ferrer, Evelina G

2010-04-01

Methimazole (MeimzH) is an anti-thyroid drug and the first choice for patients with Grave's disease. Two new copper(II) complexes of this drug: [Cu(MeimzH)(2)(NO(3))(2)]*0.5H(2)O and [Cu(MeimzH)(2)(H(2)O)(2)](NO(3))(2)*H(2)O were synthesized and characterized by elemental analysis, dissolution behavior, thermogravimetric analysis and UV-vis, diffuse reflectance, FTIR and EPR spectroscopies. As it is known that copper(II) cation can act as an inhibitor of alkaline phosphatase (ALP), the inhibitory effect of methimazole and its copper(II) complexes on ALP activity has also been investigated.

New Mechanism for the Reduction of Vanadyl Acetylacetonate to Vanadium Acetylacetonate for Room Temperature Flow Batteries.

PubMed

Shamie, Jack S; Liu, Caihong; Shaw, Leon L; Sprenkle, Vincent L

2017-02-08

In this study, a new mechanism for the reduction of vanadyl acetylacetonate, VO(acac) 2 , to vanadium acetylacetonate, V(acac) 3 , is introduced. V(acac) 3 has been studied for use in redox flow batteries (RFBs) for some time; however, contamination by moisture leads to the formation of VO(acac) 2 . In previous work, once this transformation occurs, it is no longer reversible because there is a requirement for extreme low potentials for the reduction to occur. Here, we propose that, in the presence of excess acetylacetone (Hacac) and free protons (H + ), the reduction can take place between 2.25 and 1.5 V versus Na/Na + via a one-electron-transfer reduction. This reduction can take place in situ during discharge in a novel hybrid Na-based flow battery (HNFB) with a molten Na-Cs alloy as the anode. The in situ recovery of V(acac) 3 during discharge is shown to allow the Coulombic efficiency of the HNFB to be ≈100 % with little or no capacity decay over cycles. In addition, utilizing two-electron-transfer redox reactions (i.e., V 3+ /V 4+ and V 2+ /V 3+ redox couples) per V ion to increase the energy density of RFBs becomes possible owing to the in situ recovery of V(acac) 3 during discharge. The concept of in situ recovery of material can lead to more advances in maintaining the cycle life of RFBs in the future. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Colloidal chemical synthesis and formation kinetics of uniformly sized nanocrystals of metals, oxides, and chalcogenides.

PubMed

Kwon, Soon Gu; Hyeon, Taeghwan

2008-12-01

Nanocrystals exhibit interesting electrical, optical, magnetic, and chemical properties not achieved by their bulk counterparts. Consequently, to fully exploit the potential of nanocrystals, the synthesis of nanocrystals must focus on producing materials with uniform size and shape. Top-down physical processes can produce large quantities of nanocrystals, but controlling the size is difficult with these methods. On the other hand, colloidal chemical synthetic methods can produce uniform nanocrystals with a controlled particle size. In this Account, we present our synthesis of uniform nanocrystals of various shapes and materials, and we discuss the kinetics of nanocrystal formation. We employed four different synthetic approaches including thermal decomposition, nonhydrolytic sol-gel reactions, thermal reduction, and use of reactive chalcogen reagents. We synthesized uniform oxide nanocrystals via heat-up methods. This method involved slowly heat-up reaction mixtures composed of metal precursors, surfactants, and solvents from room temperature to high temperature. We then held reaction mixtures at an aging temperature for a few minutes to a few hours. Kinetics studies revealed a three-step mechanism for the synthesis of nanocrystals through the heat-up method with size distribution control. First, as metal precursors thermally decompose, monomers accumulate. At the aging temperature, burst nucleation occurs rapidly; at the end of this second phase, nucleation stops, but continued diffusion-controlled growth leads to size focusing to produce uniform nanocrystals. We used nonhydrolytic sol-gel reactions to synthesize various transition metal oxide nanocrystals. We employed ester elimination reactions for the synthesis of ZnO and TiO(2) nanocrystals. Uniform Pd nanoparticles were synthesized via a thermal reduction reaction induced by heating up a mixture of Pd(acac)(2), tri-n-octylphosphine, and oleylamine to the aging temperature. Similarly, we synthesized nanoparticles of copper and nickel using metal(II) acetylacetonates. Ni/Pd core/shell nanoparticles were synthesized by simply heating the reaction mixture composed of acetylacetonates of nickel and palladium. Using alternative chalcogen reagents, we synthesized uniform nanocrystals of various metal chalcogenides. Uniform nanocrystals of PbS, ZnS, CdS, and MnS were obtained by heating reaction mixtures composed of metal chlorides and sulfur dissolved in oleylamine. In the future, a detailed understanding of nanocrystal formation kinetics and synthetic chemistry will lead to the synthesis of uniform nanocrystals with controlled size, shape, and composition. In particular, the synthesis of uniform nanocrystals of doped materials, core/shell materials, and multicomponent materials is still a challenge. We expect that these uniformly sized nanocrystals will find important applications in areas including information technology, biomedicine, and energy/environmental technology.

Magnetic separation of heavy metal ions and evaluation based on surface-enhanced Raman spectroscopy: copper(II) ions as a case study.

PubMed

Yan, Xue; Zhang, Xue-Jiao; Yuan, Ya-Xian; Han, San-Yang; Xu, Min-Min; Gu, Ren'ao; Yao, Jian-Lin

2013-11-01

A new approach was developed for the magnetic separation of copper(II) ions with easy operation and high efficiency. p-Mercaptobenzoic acid served as the modified tag of Fe2O3@Au nanoparticles both for the chelation ligand and Raman reporter. Through the chelation between the copper(II) ions and carboxyl groups on the gold shell, the Fe2O3@Au nanoparticles aggregated to form networks that were enriched and separated from the solution by a magnet. A significant decrease in the concentration of copper(II) ions in the supernatant solution was observed. An extremely sensitive method based on surface-enhanced Raman spectroscopy was employed to detect free copper(II) ions that remained after the magnetic separation, and thus to evaluate the separation efficiency. The results indicated the intensities of the surface-enhanced Raman spectroscopy bands from p-mercaptobenzoic acid were dependent on the concentration of copper(II) ions, and the concentration was decreased by several orders of magnitude after the magnetic separation. The present protocol effectively decreased the total amount of heavy metal ions in the solution. This approach opens a potential application in the magnetic separation and highly sensitive detection of heavy metal ions. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Antibacterial, antibiofilm and antioxidant screening of copper(II)-complexes with some S-alkyl derivatives of thiosalicylic acid. Crystal structure of the binuclear copper(II)-complex with S-propyl derivative of thiosalicylic acid

NASA Astrophysics Data System (ADS)

Bukonjić, Andriana M.; Tomović, Dušan Lj.; Nikolić, Miloš V.; Mijajlović, Marina Ž.; Jevtić, Verica V.; Ratković, Zoran R.; Novaković, Slađana B.; Bogdanović, Goran A.; Radojević, Ivana D.; Maksimović, Jovana Z.; Vasić, Sava M.; Čomić, Ljiljana R.; Trifunović, Srećko R.; Radić, Gordana P.

2017-01-01

The spectroscopically predicted structure of the obtained copper(II)-complex with S-propyl derivative of thiosalicylic acid was confirmed by X-ray structural study. The binuclear copper(II)-complex with S-propyl derivative of thiosalicylic acid crystallized in two polymorphic forms with main structural difference in the orientation of phenyl rings relative to corresponding carboxylate groups. The antibacterial activity was tested determining the minimum inhibitory concentration (MIC) and the minimum bactericidal concentration (MBC) by using microdilution method. The influence on bacterial biofilm formation was determined by tissue culture plate method. In general, the copper(II)-complexes manifested a selective and moderate activity. The most sensitive bacteria to the effects of Cu(II)-complexes was a clinical isolate of Pseudomonas aeruginosa. For this bacteria MIC and biofilm inhibitory concentration (BIC) values for all tested complexes were in the range or better than the positive control, doxycycline. Also, for the established biofilm of clinical isolate Staphylococcus aureus, BIC values for the copper(II)-complex with S-ethyl derivative of thiosalicylic acid,[Cu2(S-et-thiosal)4(H2O)2] (C3) and copper(II)-complex with S-butyl derivative of thiosalicylic acid, [Cu2(S-bu-thiosal)4(H2O)2] (C5) were in range or better than the positive control. All the complexes acted better against Gram-positive bacteria (Staphylococcus aureus and Staphylococcus aureus ATCC 25923) than Gram-negative bacteria (Proteus mirabilis ATCC 12453, Pseudomonas aeruginosa, and P. aeruginosa ATCC 27855). The complexes showed weak antioxidative properties tested by two methods (1,1-diphenyl-2-picrylhydrazyl (DPPH) and reducing power assay).

Copper-mercury film electrode for cathodic stripping voltammetric determination of Se(IV).

PubMed

Sladkov, Vladimir; David, François; Fourest, Blandine

2003-01-01

The copper-mercury film electrode has been suggested for the determination of Se(IV) in a wide range of concentration from 1x10(-9) to 1x10(-6) mol L(-1)by square-wave cathodic stripping voltammetry. Insufficient reproducibility and sensitivity of the mercury film electrode have been overcome by using copper(II) ions during the plating procedure. Copper(II) has been found to be reduced and form a reproducible copper-mercury film on a glassy carbon electrode surface. The plating potential and time, the concentration of copper(II) and the concentration of the supporting electrolyte have been optimised. Microscopy has been used for a study of the morphology of the copper-mercury film. It has been found that it is the same as for the mercury one. The preconcentration step consists in electrodeposition of copper selenide on the copper-mercury film. The relative standard deviation is 4.3% for 1x10(-6) mol L(-1) of Se(IV). The limit of detection is 8x10(-10) mol L(-1) for 5 min of accumulation.

Long-Range Intramolecular Electronic Communication in a Trinuclear Ruthenium Tropolonate Complex.

PubMed

Yoshida, Jun; Kuwahara, Kyohei; Suzuki, Kota; Yuge, Hidetaka

2017-02-20

Dinuclear and trinuclear ruthenium complexes, [Ru(trop) 2 (C 2 trop)Ru(dppe)Cp] [2b; trop = tropolonato, C 2 trop = ethynyltropolonato, dppe = 1,2-bis(diphenylphosphino)ethane] and [Ru(trop){(C 2 trop)Ru(dppe)Cp} 2 ] (3), were synthesized, and their electronic and electrochemical properties were investigated in comparison with our previously reported complex [Ru(acac) 2 (C 2 trop)Ru(dppe)Cp] (2a). The electron-donating Ru II (dppe)Cp unit and electron-accepting Ru III O 6 unit are connected by C 2 trop in these complexes. 2a incorporates acetylacetonate as an ancillary ligand, while 2b and 3 incorporate tropolonate as an ancillary ligand. Every complex, 2a, 2b, and 3, exhibits similar UV-vis-near-IR (NIR) absorption spectra, demonstrating the lack of explicit intramolecular electronic communication between the units at least in the neutral state. The weak NIR absorption in 2a further diminished upon electrochemical oxidation, indicating almost no electronic communication between the units. In contrast, 2b and 3 exhibit broad NIR absorptions upon oxidation. Additionally, 3 exhibits four stepwise redox couples in the electrochemical study, which are formally attributed to [Ru II (trop) 3 ] - /[Ru III (trop) 3 ], two [Ru II (dppe)Cp]/[Ru III (dppe)Cp] + , and [Ru III (trop) 3 ]/[Ru IV (trop) 3 ] + couples. Clear separation of the redox couples attributed to the two terminal [Ru(dppe)Cp] units demonstrates the thermodynamic stability of the intermediate oxidation states with respect to disproportionation. Further electrochemical studies using an electrolyte including perfluorinated weakly coordinating anions and density functional theory/time-dependent density functional theory calculations confirmed the effect of ancillary ligands, acetylacetonate and tropolonate. In the case of 2a, electronic delocalization over the whole complex, especially over the [Ru(acac) 2 (trop)] unit, appears to be small. In contrast, the electronic communication between [Ru(dppe)Cp] and [Ru(trop) 3 ] units in 3 seems to be enhanced upon oxidation, resulting in the long-range intramolecular electronic communication.

Interactions between copper(II) and DOM in the urban stormwater runoff: modeling and characterizations.

PubMed

Zhao, Chen; Wang, Chong-Chen; Li, Jun-Qi; Wang, Peng; Ou, Jia-Qi; Cui, Jing-Rui

2018-01-01

Dissolved organic matter (DOM) can strongly interact with both organic and inorganic contaminants to influence their transportation, transformation, bioavailability, toxicity and even their ultimate fate. Within this work, DOM was extracted from urban stormwater runoff samples collected from a regular sampling site of a typical residential area in Beijing, China. Copper(II) ions were selected as model to investigate the interactions between DOM and typical heavy metals. Both ultraviolet (UV) absorbance and fluorescence titration methods were introduced to determine the complex capacities (C L ) and conditional stability constants (log K M ) of bonding between DOM and copper (II) ions, which revealed that the values of C L were 85.62 and 87.23 μmol mg -1 and the log K M values were 5.37 and 5.48, respectively. The results suggested the successful complexation between DOM and copper(II) ions. Furthermore, morphology of the DOM binding to copper(II) ions was confirmed by both energy-dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS), which can facilitate to clarify the corresponding mechanism. The Cu 2p 3/2 peak at 933.7 eV and the characteristic shake-up peaks of Cu-O were found in the XPS spectra, implying that copper(II) ions might coordinate with hydroxyl (aliphatic or phenolic) or carboxyl groups. With these profitable results, it can be concluded that DOM in urban stormwater runoff has a strong binding affinity with copper(II) ions, which may further lead to potentially significant influence on their migration and transformation.

1T1R Nonvolatile Memory with Al/TiO₂/Au and Sol-Gel-Processed Insulator for Barium Zirconate Nickelate Gate in Pentacene Thin Film Transistor.

PubMed

Lee, Ke-Jing; Chang, Yu-Chi; Lee, Cheng-Jung; Wang, Li-Wen; Wang, Yeong-Her

2017-12-09

A one-transistor and one-resistor (1T1R) architecture with a resistive random access memory (RRAM) cell connected to an organic thin-film transistor (OTFT) device is successfully demonstrated to avoid the cross-talk issues of only one RRAM cell. The OTFT device, which uses barium zirconate nickelate (BZN) as a dielectric layer, exhibits favorable electrical properties, such as a high field-effect mobility of 5 cm²/Vs, low threshold voltage of -1.1 V, and low leakage current of 10 -12 A, for a driver in the 1T1R operation scheme. The 1T1R architecture with a TiO₂-based RRAM cell connected with a BZN OTFT device indicates a low operation current (10 μA) and reliable data retention (over ten years). This favorable performance of the 1T1R device can be attributed to the additional barrier heights introduced by using Ni (II) acetylacetone as a substitute for acetylacetone, and the relatively low leakage current of a BZN dielectric layer. The proposed 1T1R device with low leakage current OTFT and excellent uniform resistance distribution of RRAM exhibits a good potential for use in practical low-power electronic applications.

Graphene oxide/manganese ferrite nanohybrids for magnetic resonance imaging, photothermal therapy and drug delivery.

PubMed

Yang, Yan; Shi, Haili; Wang, Yapei; Shi, Benzhao; Guo, Linlin; Wu, Dongmei; Yang, Shiping; Wu, Huixia

2016-01-01

Superparamagnetic manganese ferrite (MnFe2O4) nanoparticles have been deposited on graphene oxide (GO) by the thermal decomposition of manganese (II) acetylacetonate and iron (III) acetylacetonate precursors in triethylene glycol. The resulting GO/MnFe2O4 nanohybrids show very low cytotoxicity, negligible hemolytic activity, and imperceptible in vivo toxicity. In vitro and in vivo magnetic resonance imaging experiments demonstrate that GO/MnFe2O4 nanohybrids could be used as an effective T2 contrast agent. The strong optical absorbance in the near-infrared (NIR) region and good photothermal stability of GO/MnFe2O4 nanohybrids result in the highly efficient photothermal ablation of cancer cells. GO/MnFe2O4 nanohybrids can be further loaded with doxorubicin (DOX) by π-π conjugate effect for chemotherapy. DOX release from GO/MnFe2O4 is significantly influenced by pH and can be triggered by NIR laser. The enhanced cancer cell killing by GO/MnFe2O4/DOX composites has been achieved when irradiated with near-infrared light, suggesting that the nanohybrids could deliver both DOX chemotherapy and photothermal therapy with a synergistic effect. © The Author(s) 2015.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Simonen, F.A.; Khaleel, M.A.

This paper describes a statistical evaluation of the through-thickness copper variation for welds in reactor pressure vessels, and reviews the historical basis for the static and arrest fracture toughness (K{sub Ic} and K{sub Ia}) equations used in the VISA-II code. Copper variability in welds is due to fabrication procedures with copper contents being randomly distributed, variable from one location to another through the thickness of the vessel. The VISA-II procedure of sampling the copper content from a statistical distribution for every 6.35- to 12.7-mm (1/4- to 1/2-in.) layer through the thickness was found to be consistent with the statistical observations.more » However, the parameters of the VISA-II distribution and statistical limits required further investigation. Copper contents at few locations through the thickness were found to exceed the 0.4% upper limit of the VISA-II code. The data also suggest that the mean copper content varies systematically through the thickness. While, the assumption of normality is not clearly supported by the available data, a statistical evaluation based on all the available data results in mean and standard deviations within the VISA-II code limits.« less

Binding Selectivity of Methanobactin from Methylosinus trichosporium OB3b for Copper(I), Silver(I), Zinc(II), Nickel(II), Cobalt(II), Manganese(II), Lead(II), and Iron(II)

NASA Astrophysics Data System (ADS)

McCabe, Jacob W.; Vangala, Rajpal; Angel, Laurence A.

2017-12-01

Methanobactin (Mb) from Methylosinus trichosporium OB3b is a member of a class of metal binding peptides identified in methanotrophic bacteria. Mb will selectively bind and reduce Cu(II) to Cu(I), and is thought to mediate the acquisition of the copper cofactor for the enzyme methane monooxygenase. These copper chelating properties of Mb make it potentially useful as a chelating agent for treatment of diseases where copper plays a role including Wilson's disease, cancers, and neurodegenerative diseases. Utilizing traveling wave ion mobility-mass spectrometry (TWIMS), the competition for the Mb copper binding site from Ag(I), Pb(II), Co(II), Fe(II), Mn(II), Ni(II), and Zn(II) has been determined by a series of metal ion titrations, pH titrations, and metal ion displacement titrations. The TWIMS analyses allowed for the explicit identification and quantification of all the individual Mb species present during the titrations and measured their collision cross-sections and collision-induced dissociation patterns. The results showed Ag(I) and Ni(II) could irreversibly bind to Mb and not be effectively displaced by Cu(I), whereas Ag(I) could also partially displace Cu(I) from the Mb complex. At pH ≈ 6.5, the Mb binding selectivity follows the order Ag(I)≈Cu(I)>Ni(II)≈Zn(II)>Co(II)>>Mn(II)≈Pb(II)>Fe(II), and at pH 7.5 to 10.4 the order is Ag(I)>Cu(I)>Ni(II)>Co(II)>Zn(II)>Mn(II)≈Pb(II)>Fe(II). Breakdown curves of the disulfide reduced Cu(I) and Ag(I) complexes showed a correlation existed between their relative stability and their compact folded structure indicated by their CCS. Fluorescence spectroscopy, which allowed the determination of the binding constant, compared well with the TWIMS analyses, with the exception of the Ni(II) complex. [Figure not available: see fulltext.

Binding Selectivity of Methanobactin from Methylosinus trichosporium OB3b for Copper(I), Silver(I), Zinc(II), Nickel(II), Cobalt(II), Manganese(II), Lead(II), and Iron(II).

PubMed

McCabe, Jacob W; Vangala, Rajpal; Angel, Laurence A

2017-12-01

Methanobactin (Mb) from Methylosinus trichosporium OB3b is a member of a class of metal binding peptides identified in methanotrophic bacteria. Mb will selectively bind and reduce Cu(II) to Cu(I), and is thought to mediate the acquisition of the copper cofactor for the enzyme methane monooxygenase. These copper chelating properties of Mb make it potentially useful as a chelating agent for treatment of diseases where copper plays a role including Wilson's disease, cancers, and neurodegenerative diseases. Utilizing traveling wave ion mobility-mass spectrometry (TWIMS), the competition for the Mb copper binding site from Ag(I), Pb(II), Co(II), Fe(II), Mn(II), Ni(II), and Zn(II) has been determined by a series of metal ion titrations, pH titrations, and metal ion displacement titrations. The TWIMS analyses allowed for the explicit identification and quantification of all the individual Mb species present during the titrations and measured their collision cross-sections and collision-induced dissociation patterns. The results showed Ag(I) and Ni(II) could irreversibly bind to Mb and not be effectively displaced by Cu(I), whereas Ag(I) could also partially displace Cu(I) from the Mb complex. At pH ≈ 6.5, the Mb binding selectivity follows the order Ag(I)≈Cu(I)>Ni(II)≈Zn(II)>Co(II)>Mn(II)≈Pb(II)>Fe(II), and at pH 7.5 to 10.4 the order is Ag(I)>Cu(I)>Ni(II)>Co(II)>Zn(II)>Mn(II)≈Pb(II)>Fe(II). Breakdown curves of the disulfide reduced Cu(I) and Ag(I) complexes showed a correlation existed between their relative stability and their compact folded structure indicated by their CCS. Fluorescence spectroscopy, which allowed the determination of the binding constant, compared well with the TWIMS analyses, with the exception of the Ni(II) complex. Graphical abstract ᅟ.

Copper import in Escherichia coli by the yersiniabactin metallophore system

PubMed Central

Koh, Eun-Ik; Robinson, Anne E.; Bandara, Nilantha; Rogers, Buck E.; Henderson, Jeffrey P.

2017-01-01

Copper plays a dual role as nutrient and toxin during bacterial infections. While uropathogenic Escherichia coli (UPEC) strains can use the copper-binding metallophore yersiniabactin (Ybt) to resist copper toxicity, Ybt also converts bioavailable copper to Cu(II)-Ybt in low copper conditions. Although E. coli have long been considered to lack a copper import pathway, we observed Ybt-mediated copper import in UPEC using canonical Fe(III)-Ybt transport proteins. UPEC removed copper from Cu(II)-Ybt with subsequent re-export of metal-free Ybt to the extracellular space. Copper released through this process became available to an E. coli cuproenzyme (the amine oxidase TynA), linking this import pathway to a nutrient acquisition function. Ybt-expressing E. coli thus engage in nutritional passivation, a strategy of minimizing a metal ion's toxicity while preserving its nutritional availability. Copper acquisition through this process may contribute to the marked virulence defect of Ybt transport-deficient UPEC. PMID:28759019

Towards a selective adsorbent for arsenate and selenite in the presence of phosphate: Assessment of adsorption efficiency, mechanism, and binary separation factors of the chitosan-copper complex.

PubMed

Yamani, Jamila S; Lounsbury, Amanda W; Zimmerman, Julie B

2016-01-01

The potential for a chitosan-copper polymer complex to select for the target contaminants in the presence of their respective competitive ions was evaluated by synthesizing chitosan-copper beads (CCB) for the treatment of (arsenate:phosphate), (selenite:phosphate), and (selenate:sulfate). Based on work by Rhazi et al., copper (II) binds to the amine moiety on the chitosan backbone as a monodentate complex (Type I) and as a bidentate complex crosslinking two polymer chains (Type II), depending on pH and copper loading. In general, the Type I complex exists alone; however, beyond threshold conditions of pH 5.5 during synthesis and a copper loading of 0.25 mol Cu(II)/mol chitosan monomer, the Type I and Type II complexes coexist. Subsequent chelation of this chitosan-copper ligand to oxyanions results in enhanced and selective adsorption of the target contaminants in complex matrices with high background ion concentrations. With differing affinities for arsenate, selenite, and phosphate, the Type I complex favors phosphate chelation while the Type II complex favors arsenate chelation due to electrostatic considerations and selenite chelation due to steric effects. No trend was exhibited for the selenate:sulfate system possibly due to the high Ksp of the corresponding copper salts. Binary separation factors, α12, were calculated for the arsenate-phosphate and selenite-phosphate systems, supporting the mechanistic hypothesis. While, further research is needed to develop a synthesis method for the independent formation of the Type II complexes to select for target contaminants in complex matrices, this work can provide initial steps in the development of a selective adsorbent. Copyright © 2015 Elsevier Ltd. All rights reserved.

Removal of Copper(II) Ions in Aqueous Solutions Using Tannin-Rich Plants as Natural Bio-Adsorbents

NASA Astrophysics Data System (ADS)

Paksamut, J.; Boonsong, P.

2018-03-01

In this study, the purpose of our interest is to investigatethe adsorption behavior of copper (II) ions in aqueous solution using some tannin-rich plants as natural bio-adsorbents such as mangosteen peels (Garciniamangostana L.), cassava leaves (Manihotesculenta Crantz) and Thai copper pod leaves (Sennasiamea (Lam.)) as powder form in different dosage of adsorbent plant materials.The adsorption capacities at different pH of solution and contact time were performed.All the experiments in this studywere chosen at room temperature by batch technique. From the experimental results showed that cassava leaves gave better adsorbent properties than mangosteen peels and Thai copper pod leaves. The increasing dosage of all adsorbents and contact time have been found to increase adsorption capacities. In this respect, the adsorption capacities depend crucially on the adsorbents and contact time. The optimum pH of copper (II) ions adsorption was pH4. According to this work, it was observed that bioadsorbent materials from tannin-rich plants could be used to remove copper (II) ions from aqueous solutions.

Evidence for Alkene cis-Aminocupration, an Aminooxygenation Case Study: Kinetics, EPR Spectroscopy, and DFT Calculations

PubMed Central

Paderes, Monissa C.; Belding, Lee; Fanovic, Branden; Dudding, Travis; Keister, Jerome B.

2012-01-01

Alkene difunctionalization reactions are important in organic synthesis. We have recently shown that copper(II) complexes can promote and catalyze intramolecular alkene aminooxygenation, carboamination, and diamination reactions. In this contribution, we report a combined experimental and theoretical examination of the mechanism of the copper(II)-promoted olefin aminooxygenation reaction. Kinetics experiments revealed a mechanistic pathway involving an equilibrium reaction between a copper(II) carboxylate complex and the γ-alkenyl sulfonamide substrate and a rate-limiting intramolecular cis-addition of N–Cu across the olefin. Kinetic isotope effect studies support that the cis-aminocupration is the rate-determining step. UV/Vis spectra support a role for the base in the break-up of copper(II) carboxylate dimer to monomeric species. Electron paramagnetic resonance (EPR) spectra provide evidence for a kinetically competent N–Cu intermediate with a CuII oxidation state. Due to the highly similar stereochemical and reactivity trends among the CuII-promoted and catalyzed alkene difunctionalization reactions we have developed, the cis-aminocupration mechanism can reasonably be generalized across the reaction class. The methods and findings disclosed in this report should also prove valuable to the mechanism analysis and optimization of other copper(-II) carboxylate promoted reactions, especially those that take place in aprotic organic solvents. PMID:22237868

N-benzoylated 1,4,8,11-tetraazacyclotetradecane and their copper(II) and nickel(II) complexes: Spectral, magnetic, electrochemical, crystal structure, catalytic and antimicrobial studies

NASA Astrophysics Data System (ADS)

Nirmala, G.; Rahiman, A. Kalilur; Sreedaran, S.; Jegadeesh, R.; Raaman, N.; Narayanan, V.

2010-09-01

A series of N-benzoylated cyclam ligands incorporating three different benzoyl groups 1,4,8,11-tetra-(benzoyl)-1,4,8,11-tetraazacyclotetradecane (L 1), 1,4,8,11-tetra-(2-nitrobenzoyl)-1,4,8,11-tetraazacyclotetradecane (L 2) and 1,4,8,11-tetra-(4-nitrobenzoyl)-1,4,8,11-tetraazacyclotetradecane (L 3) and their nickel(II) and copper(II) complexes are described. Crystal structure of L 1 is also reported. The ligands and complexes were characterized by elemental analysis, electronic, IR, 1H NMR and 13C NMR spectral studies. N-benzoylation causes red shift in the λmax values of the complexes. The cyclic voltammogram of the complexes of ligand L 1 show one-electron, quasi-reversible reduction wave in the region -1.00 to -1.04 V, whereas that of L 2 and L 3 show two quasi-reversible reduction peaks. Nickel complexes show one-electron quasi-reversible oxidation wave at a positive potential in the range +1.05 to +1.15 V. The ESR spectra of the mononuclear copper(II) complexes show four lines, characteristic of square-planar geometry with nuclear hyperfine spin 3/2. All copper(II) complexes show a normal room temperature magnetic moment values μeff 1.70-1.73 BM which is close to the spin-only value of 1.73 BM. Kinetic studies on the oxidation of pyrocatechol to o-quinone using the copper(II) complexes as catalysts and hydrolysis of 4-nitrophenylphosphate using the copper(II) and nickel(II) complexes as catalysts were carried out. All the ligands and their complexes were also screened for antimicrobial activity against Gram-positive, Gram-negative bacteria and human pathogenic fungi.

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

NASA Astrophysics Data System (ADS)

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

2002-08-01

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

Yb3+ can be much better than Dy3+: SMM properties and controllable self-assembly of novel lanthanide 3,5-dinitrobenzoate-acetylacetonate complexes.

PubMed

Gavrikov, Andrey V; Efimov, Nikolay N; Ilyukhin, Andrey B; Dobrokhotova, Zhanna V; Novotortsev, Vladimir M

2018-05-01

The first representatives of the binuclear lanthanide 3,5-dinitrobenzoate-acetylacetonate complexes, namely isostructural compounds [Ln(dnbz)(acac)2(H2O)(EtOH)]2 (Ln = Eu (1), Gd (2), Tb (3), Dy (4), Ho (5), Er (6), Tm (7), and Yb (8); dnbz - 3,5-dinitrobenzoate anion; acac - acetylacetonate (pentane-2,4-dionate) anion) were prepared and characterized. The SMM behavior of the Yb compound 8 was shown to be surprisingly less sensitive to the composition of the Yb3+ coordination environment in comparison with that of the Dy derivative. For Yb compound 8, the anisotropy barrier is Δeff/kB = 26 K under the dc field of 2000 Oe. This value is the highest one currently known for binuclear Yb complexes.

Iodometric determination of peroxydiphosphate in the presence of copper(II) or iron(II) as catalyst.

PubMed

Kapoor, S; Sharma, P D; Gupta, Y K

1975-09-01

Peroxydiphosphate can be determined iodometrically in the presence of a large excess of potassium iodide with copper(II) or iron(II) as catalyst through the operation of the Cu(II)/Cu(I) or Fe(II)/Fe(III) cycle. The method is applicable in HClO(4), H(2)SO(4), HCl and CH(3)COOH acid media in the range 0.1-1.0M studied. Nickel, manganese(II), cobalt(II), silver, chloride and phosphate are without effect.

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

NASA Astrophysics Data System (ADS)

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

2015-01-01

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

Copper(II) carboxylate promoted intramolecular diamination of terminal alkenes: improved reaction conditions and expanded substrate scope.

PubMed

Zabawa, Thomas P; Chemler, Sherry R

2007-05-10

The copper(II) carboxylate promoted diamination reaction has been improved by the use of the organic soluble copper(II) neodecanoate [Cu(ND)2]. Cu(ND)2 allowed the less-polar solvent dichloroethane (DCE) to be used, and as a consequence, decomposition of less-reactive substrates could be avoided. High diastereoselectivity was observed in the synthesis of 2,5-disubstituted pyrrolidines. Ureas, bis(anilines), and alpha-amido pyrroles derived from 2-allylaniline could also participate in the diamination reaction.

C-H oxidation and chelation of a dipyrromethane mediated rapid colorimetric naked-eye Cu(ii) chemosensor.

PubMed

Rajmohan, Rajamani; Ayaz Ahmed, Khan Behlol; Sangeetha, Sampathkumar; Anbazhagan, Veerappan; Vairaprakash, Pothiappan

2017-09-08

Copper(ii) ion mediated C-H oxidation of dipyrromethanes (DPMs) to the corresponding dipyrrins followed by complexation invoked the selective sensing of copper(ii) ions in aqueous solutions. On the addition of copper, the colour of the DPM solution instantaneously changes from yellow to pink with the detection limit of 0.104 μM measured by absorption spectroscopy, whereas visible colour changes could be observed by the naked eye for concentrations as low as 3 μM.

Heptacopper(II) and dicopper(II)-adenine complexes: synthesis, structural characterization, and magnetic properties

DOE PAGES

Leite Ferreira, B. J. M.; Brandão, Paula; Dos Santos, A. M.; ...

2015-07-13

The syntheses, crystal structures, and magnetic properties of two new copper(II) complexes with molecular formulas [Cu 7(μ 2-OH 2) 6(μ 3-O) 6(adenine) 6(NO 3) 26H 2O (1) and [Cu 2(μ 2-H 2O) 2(adenine) 2(H 2O) 4](NO 3) 42H 2O (2) are reported. We composed the heptanuclear compound of a central octahedral CuO 6 core sharing edges with six adjacent copper octahedra. In 2, the copper octahedra shares one equatorial edge. In both compounds, these basic copper cluster units are further linked by water bridges and bridging adenine ligands through N3 and N9 donors. All copper(II) centers exhibit Jahn-Teller distorted octahedralmore » coordination characteristic of a d 9 center. Our study of the magnetic properties of the heptacopper complex revealed a dominant ferromagnetic intra-cluster interaction, while the dicopper complex exhibits antiferromagnetic intra-dimer interactions with weakly ferromagnetic inter-dimer interaction.« less

The electronic spectra and the structures of the individual copper(II) chloride and bromide complexes in acetonitrile according to steady-state absorption spectroscopy and DFT/TD-DFT calculations

NASA Astrophysics Data System (ADS)

Olshin, Pavel K.; Myasnikova, Olesya S.; Kashina, Maria V.; Gorbunov, Artem O.; Bogachev, Nikita A.; Kompanets, Viktor O.; Chekalin, Sergey V.; Pulkin, Sergey A.; Kochemirovsky, Vladimir A.; Skripkin, Mikhail Yu.; Mereshchenko, Andrey S.

2018-03-01

The results of spectrophotometric study and quantum chemical calculations for copper(II) chloro- and bromocomplexes in acetonitrile are reported. Electronic spectra of the individual copper(II) halide complexes were obtained in a wide spectral range 200-2200 nm. Stability constants of the individual copper(II) halide complexes in acetonitrile were calculated: log β1 = 8.5, log β2 = 15.6, log β3 = 22.5, log β4 = 25.7 for [CuCln]2-n and log β1 = 17.0, log β2 = 24.6, log β3 = 28.1, log β4 = 30.4 for [CuBrn]2-n. Structures of the studied complexes were optimized and electronic spectra were simulated using DFT and TD-DFT methodologies, respectively. According to the calculations, the more is the number of halide ligands the less is coordination number of copper ion.

77 FR 1679 - Notice of Receipt of Requests To Voluntarily Cancel Certain Pesticide Registrations

Federal Register 2010, 2011, 2012, 2013, 2014

2012-01-11

.... II. 075341-00012 Hollow Heart CF.. Copper naphthenate; Sodium fluoride. 075341-00013 COP-R-Plastic II Copper naphthenate; Wood Preserving Sodium fluoride. Compound. CA110009 Ethylene......... Ethylene...

Importance of acetylacetone and 2,2'-bipyridyl ligands in radiation-chemical processes of complex compounds

NASA Astrophysics Data System (ADS)

Kalecińska, E.; Kaleciński, J.

The study of radiation response of free ligands: acetylacetone and 2,2'-bipyridyl in frozen chloride-alcohol-water glasses allows us to identify the intermediates playing the significant role in radiation decomposition of the complexes. On the basis of absorption spectra of the intermediates it has been shown that both examined ligands are effective scavengers of electrons. In the case of acetylacetone the intermediate most probably acacOH (exhibiting absorption band with λ max at ca. 580 nm) is not sensitive for bleaching light and its concentration increases during the warming up (from 77 to 160 K) of the sample. In the case of 2,2'-bipyridyl two intermediates (high intensity narrow bands with λ max at ca. 385 and 370 nm) are formed depending on pH of the system. Their formation and interconversion have also been studied.

Water-Soluble Ruthenium (II) Chiral Heteroleptic Complexes with Amoebicidal in Vitro and in Vivo Activity.

PubMed

Toledano-Magaña, Yanis; García-Ramos, Juan C; Torres-Gutiérrez, Carolina; Vázquez-Gasser, Cristina; Esquivel-Sánchez, José M; Flores-Alamo, Marcos; Ortiz-Frade, Luis; Galindo-Murillo, Rodrigo; Nequiz, Mario; Gudiño-Zayas, Marco; Laclette, Juan P; Carrero, Julio C; Ruiz-Azuara, Lena

2017-02-09

Three water-soluble Ru(II) chiral heteroleptic coordination compounds [Ru(en)(pdto)]Cl 2 (1), [Ru(gly)(pdto)]Cl (2), and [Ru(acac)(pdto)]Cl (3), where pdto = 2,2'-[1,2-ethanediylbis-(sulfanediyl-2,1-ethanediyl)]dipyridine, en = ethylendiamine, gly = glycinate, and acac = acetylacetonate, have been synthezised and fully characterized. The crystal structures of compounds 1-3 are described. The IC 50 values for compounds 1-3 are within nanomolar range (14, 12, and 6 nM, respectively). The cytotoxicity for human peripheral blood lymphocytes is extremely low (>100 μM). Selectivity indexes for Ru(II) compounds are in the range 700-1300. Trophozoites exposed to Ru(II) compounds die through an apoptotic pathway triggered by ROS production. The orally administration to infected mice induces a total elimination of the parasite charge in mice faeces 1-2-fold faster than metronidazole. Besides, all compounds inhibit the trophozoite proliferation in amoebic liver abscess induced in hamster. All our results lead us to propose these compounds as promising candidates as antiparasitic agents.

Catalysis of copper corrosion products on chlorine decay and HAA formation in simulated distribution systems.

PubMed

Zhang, Hong; Andrews, Susan A

2012-05-15

This study investigated the effect of copper corrosion products, including Cu(II), Cu(2)O, CuO and Cu(2)(OH)(2)CO(3), on chlorine degradation, HAA formation, and HAA speciation under controlled experimental conditions. Chlorine decay and HAA formation were significantly enhanced in the presence of copper with the extent of copper catalysis being affected by the solution pH and the concentration of copper corrosion products. Accelerated chlorine decay and increased HAA formation were observed at pH 8.6 in the presence of 1.0 mg/L Cu(II) compared with that observed at pH 6.6 and pH 7.6. Further investigation of chlorine decay in the presence of both Suwannee River NOM and Cu(II) indicated that an increased reactivity of NOM with dissolved and/or solid surface-associated Cu(II), rather than chlorine auto-decomposition, was a primary reason for the observed rapid chlorine decay. Copper corrosion solids [Cu(2)O, CuO, Cu(2)(OH)(2)CO(3)] exhibited catalytic effects on both chlorine decay and HAA formation. Contrary to the results observed when in the absence of copper corrosion products, DCAA formation was consistently predominant over other HAA species in the presence of copper corrosion products, especially at neutral and high pH. This study improves the understanding for water utilities and households regarding chlorine residuals and HAA concentrations in distribution systems, in particular once the water reaches domestic plumbing where copper is widely used. Copyright © 2012 Elsevier Ltd. All rights reserved.

Copper(II) Carboxylate Promoted Intramolecular Diamination of Terminal Alkenes: Improved Reaction Conditions and Expanded Substrate Scope

PubMed Central

Zabawa, Thomas P.

2008-01-01

The copper(II) carboxylate promoted diamination reaction has been improved by the use of the organic soluble copper(II) neodecanoate [Cu(ND)2]. Cu(ND)2 allowed the less polar solvent, dichloroethane (DCE) to be used, and as a consequence, decomposition of less reactive substrates could be avoided. High diastereoselectivity was observed in the synthesis of 2,5-disubstituted pyrrolidines. Ureas, bis(anilines) and α-amido pyrroles derived from 2-allylaniline could also participate in the diamination reaction. PMID:17447781

C-H functionalization of 1,4-naphthoquinone by oxidative coupling with anilines in the presence of a catalytic quantity of copper(II) acetate.

PubMed

Lisboa, Cinthia da S; Santos, Vanessa G; Vaz, Boniek G; de Lucas, Nanci C; Eberlin, Marcos N; Garden, Simon J

2011-07-01

The oxidative addition of anilines (2) with 1,4-naphthoquinone (3) to give N-aryl-2-amino-1,4-naphthoquinones (1) was found to be catalyzed by copper(II) acetate. In the absence of the catalyst, the reactions are slower and give lower yields with the formation of many colateral products. In the presence of 10 mol % hydrated copper(II) acetate, the reactions are generally more efficient in that they are cleaner, higher yielding, and faster.

1T1R Nonvolatile Memory with Al/TiO2/Au and Sol-Gel-Processed Insulator for Barium Zirconate Nickelate Gate in Pentacene Thin Film Transistor

PubMed Central

Lee, Ke-Jing; Chang, Yu-Chi; Lee, Cheng-Jung; Wang, Li-Wen; Wang, Yeong-Her

2017-01-01

A one-transistor and one-resistor (1T1R) architecture with a resistive random access memory (RRAM) cell connected to an organic thin-film transistor (OTFT) device is successfully demonstrated to avoid the cross-talk issues of only one RRAM cell. The OTFT device, which uses barium zirconate nickelate (BZN) as a dielectric layer, exhibits favorable electrical properties, such as a high field-effect mobility of 2.5 cm2/Vs, low threshold voltage of −2.8 V, and low leakage current of 10−12 A, for a driver in the 1T1R operation scheme. The 1T1R architecture with a TiO2-based RRAM cell connected with a BZN OTFT device indicates a low operation current (10 μA) and reliable data retention (over ten years). This favorable performance of the 1T1R device can be attributed to the additional barrier heights introduced by using Ni (II) acetylacetone as a substitute for acetylacetone, and the relatively low leakage current of a BZN dielectric layer. The proposed 1T1R device with low leakage current OTFT and excellent uniform resistance distribution of RRAM exhibits a good potential for use in practical low-power electronic applications. PMID:29232828

Recent advances in heterobimetallic palladium(II)/copper(II) catalyzed domino difunctionalization of carbon-carbon multiple bonds.

PubMed

Beccalli, Egle M; Broggini, Gianluigi; Gazzola, Silvia; Mazza, Alberto

2014-09-21

The double functionalization of carbon-carbon multiple bonds in one-pot processes has emerged in recent years as a fruitful tool for the rapid synthesis of complex molecular scaffolds. This review covers the advances in domino reactions promoted by the couple palladium(ii)/copper(ii), which was proven to be an excellent catalytic system for the functionalization of substrates.

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

PubMed

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.

A peroxynitrite complex of copper: formation from a copper-nitrosyl complex, transformation to nitrite and exogenous phenol oxidative coupling or nitration.

PubMed

Park, Ga Young; Deepalatha, Subramanian; Puiu, Simona C; Lee, Dong-Heon; Mondal, Biplab; Narducci Sarjeant, Amy A; del Rio, Diego; Pau, Monita Y M; Solomon, Edward I; Karlin, Kenneth D

2009-11-01

Reaction of nitrogen monoxide with a copper(I) complex possessing a tridentate alkylamine ligand gives a Cu(I)-(*NO) adduct, which when exposed to dioxygen generates a peroxynitrite (O=NOO(-))-Cu(II) species. This undergoes thermal transformation to produce a copper(II) nitrito (NO(2) (-)) complex and 0.5 mol equiv O(2). In the presence of a substituted phenol, the peroxynitrite complex effects oxidative coupling, whereas addition of chloride ion to dissociate the peroxynitrite moiety instead leads to phenol ortho nitration. Discussions include the structures (including electronic description) of the copper-nitrosyl and copper-peroxynitrite complexes and the formation of the latter, based on density functional theory calculations and accompanying spectroscopic data.

Bismesitoylphosphinic Acid (BAPO-OH): A Ligand for Copper Complexes and Four-Electron Photoreductant for the Preparation of Copper Nanomaterials.

PubMed

Beil, Andreas; Müller, Georgina; Käser, Debora; Hattendorf, Bodo; Li, Zhongshu; Krumeich, Frank; Rosenthal, Amos; Rana, Vijay Kumar; Schönberg, Hartmut; Benkő, Zoltán; Grützmacher, Hansjörg

2018-05-16

Bismesitoylphosphinic acid, (HO)PO(COMes) 2 (BAPO-OH), is an efficient photoinitiator for free-radical polymerizations of olefins in aqueous phase. Described here are the structures of various copper(II) and copper(I) complexes with BAPO-OH as the ligand. The complex Cu II (BAPO-O) 2 (H 2 O) 2 is photoactive, and under irradiation with UV light in aqueous phase, it serves as a source of metallic copper in high purity and yield (>80 %). Simultaneously, the radical polymerization of acrylates can be initiated and allows the preparation of nanoparticle/polymer nanocomposites in which the metallic Cu nanoparticles are protected against oxidation. The determination of the stoichiometry of the photoreductions suggests an almost quantitative conversion from Cu II into Cu 0 with half an equivalent of BAPO-OH, which serves as a four-electron photoreductant. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Distinctive EPR signals provide an understanding of the affinity of bis-(3-hydroxy-4-pyridinonato) copper(II) complexes for hydrophobic environments.

PubMed

Rangel, Maria; Leite, Andreia; Silva, André M N; Moniz, Tânia; Nunes, Ana; Amorim, M João; Queirós, Carla; Cunha-Silva, Luís; Gameiro, Paula; Burgess, John

2014-07-07

In this work we report the synthesis and characterization of a set of 3-hydroxy-4-pyridinone copper(ii) complexes with variable lipophilicity. EPR spectroscopy was used to characterize the structure of copper(ii) complexes in solution, and as a tool to gain insight into solvent interactions. EPR spectra of solutions of the [CuL2] complexes recorded in different solvents reveal the presence of two copper species whose ratio depends on the nature of the solvent. Investigation of EPR spectra in the pure solvents methanol, dimethylsulfoxide, dichloromethane and their 50% (v/v) mixtures with toluene allowed the characterization of two types of copper signals (gzz = 2.30 and gzz = 2.26) whose spin-Hamiltonian parameters are consistent with solvated and non-solvated square-planar copper(ii) complexes. Regarding the potential biological application of ligands and complexes and to get insight into the partition properties in water-membrane interfaces, EPR spectra were also obtained in water-saturated octanol, an aqueous solution buffered at pH = 7.4 and liposome suspensions, for three compounds representative of different hydro-lipophilic balances. Analysis of the EPR spectra obtained in liposomes allowed establishment of the location of the complexes in the water and lipid phases. In view of the results of this work we put forward the use of EPR spectroscopy to assess the affinity of copper(ii) complexes for a hydrophobic environment and also to obtain indirect information about the lipophilicity of the ligands and similar EPR silent complexes.

BSA binding and antimicrobial studies of branched polyethyleneimine-copper(II)bipyridine/phenanthroline complexes

NASA Astrophysics Data System (ADS)

Vignesh, Gopalaswamy; Arunachalam, Sankaralingam; Vignesh, Sivanandham; James, Rathinam Arthur

2012-10-01

The interaction of two water soluble branched polyethyleneimine-copper(II) complexes containing bipyridine/phenanthroline with bovine serum albumin (BSA) was studied by, UV-Visible absorption, fluorescence, lifetime measurements and circular dichroism spectroscopic techniques. The polymer-copper(II) complexes strongly quench the intrinsic fluorescence of BSA is the static quenching mechanism through hydrogen bonds and van der Waal's attraction. The distance r, between the BSA and the complexes seems to be less than 2 nm indicating that the energy transfer between the donor and acceptor occurs with high probability. Synchronous fluorescence studies indicate the binding of polymer-copper(II) complexes with BSA mostly changes the polarity around tryptophan residues rather than tyrosine residues. The circular dichroism studies indicate that the binding has induced considerable amount of conformational changes in the protein. The complexes also show some antibacterial and antifungal properties.

High sensitive detection of copper II ions using D-penicillamine-coated gold nanorods based on localized surface plasmon resonance

NASA Astrophysics Data System (ADS)

Hong, Yoochan; Jo, Seongjae; Park, Joohyung; Park, Jinsung; Yang, Jaemoon

2018-05-01

In this paper, we describe the development of a nanoplasmonic biosensor based on the localized surface plasmon resonance (LSPR) effect that enables a sensitive and selective recognition of copper II ions. First, we fabricated the nanoplasmonics as LSPR substrates using gold nanorods (GNR) and the nano-adsorption method. The LSPR sensitivity of the nanoplasmonics was evaluated using various solvents with different refractive indexes. Subsequently, D-penicillamine (DPA)—a chelating agent of copper II ions—was conjugated to the surface of the GNR. The limit of detection (LOD) for the DPA-conjugated nanoplasmonics was 100 pM. Furthermore, selectivity tests were conducted using various divalent cations, and sensitivity tests were conducted on the nanoplasmonics under blood-like environments. Finally, the developed nanoplasmonic biosensor based on GNR shows great potential for the effective recognition of copper II ions, even in human blood conditions.

High sensitive detection of copper II ions using D-penicillamine-coated gold nanorods based on localized surface plasmon resonance.

PubMed

Hong, Yoochan; Jo, Seongjae; Park, Joohyung; Park, Jinsung; Yang, Jaemoon

2018-05-25

In this paper, we describe the development of a nanoplasmonic biosensor based on the localized surface plasmon resonance (LSPR) effect that enables a sensitive and selective recognition of copper II ions. First, we fabricated the nanoplasmonics as LSPR substrates using gold nanorods (GNR) and the nano-adsorption method. The LSPR sensitivity of the nanoplasmonics was evaluated using various solvents with different refractive indexes. Subsequently, D-penicillamine (DPA)-a chelating agent of copper II ions-was conjugated to the surface of the GNR. The limit of detection (LOD) for the DPA-conjugated nanoplasmonics was 100 pM. Furthermore, selectivity tests were conducted using various divalent cations, and sensitivity tests were conducted on the nanoplasmonics under blood-like environments. Finally, the developed nanoplasmonic biosensor based on GNR shows great potential for the effective recognition of copper II ions, even in human blood conditions.

Assessing the Release of Copper from Nanocopper-treated and Conventional Copper-treated Lumber into Marine Waters II: Forms and Bioavailability

EPA Science Inventory

One application of nanocopper is as a wood‐preserving pesticide in pressure‐treated lumber. Recent research has shown that pressure‐treated lumber amended with micronized copper azole (MCA), which contains nanosized copper, releases copper under estuarine and ma...

Synergistic extraction and spectrophotometric determination of copper(II) using 1-(2',4'-dinitro aminophenyl)-4,4,6-trimethyl-1,4-dihydropyrimidine-2-thiol: Analysis of alloys, pharmaceuticals and biological samples

NASA Astrophysics Data System (ADS)

Kamble, Ganesh S.; Kolekar, Sanjay S.; Anuse, Mansing A.

2011-05-01

A simple and selective spectrophotometric method was developed for the determination of copper(II) with 1-(2',4'-dinitro aminophenyl)-4,4,6-trimethyl-1,4-dihydropyrimidine-2-thiol [2',4'-dinitro APTPT] as a chromogenic reagent. The procedure was based on the synergistic extraction of copper(II) with 2',4'-dinitro APTPT in the presence of 0.5 mol L -1 pyridine to give green colored ternary complex of a molar ratio 1:2:2 (M:L:Py) in the pH range 8.7-10.5. It exhibits a maximum absorption of colored complex at 445 nm and 645 nm in chloroform against the reagent blank. Beer's law was followed in the concentration range 10-80 μg mL -1 of copper(II) and optimum range of 20-70 μg mL -1 the metal as evaluated from Ringbom's plot. The molar absorptivity and Sandell's sensitivity of copper(II)-2',4'-dinitro APTPT-pyridine complex in chloroform are 0.87 × 10 3 L mol -1 cm -1 and 0.072 μg cm -2, respectively. The interfering effects of various cations and anions were also studied, and use of suitable masking agents enhances the selectivity of the method. The proposed method is rapid, reproducible and successfully applied for the determination of copper(II) in binary and synthetic mixtures, alloys, pharmaceutical formulations, environmental and fertilizer samples. Comparison of the results with those obtained using an atomic absorption spectrophotometer also tested the validity of the method.

XAFS Study of the Ferro- and Antiferromagnetic Binuclear Copper(II) Complexes of Azomethine Based Tridentate Ligands

NASA Astrophysics Data System (ADS)

Vlasenko, Valery G.; Vasilchenko, Igor S.; Pirog, Irina V.; Shestakova, Tatiana E.; Uraev, Ali I.; Burlov, Anatolii S.; Garnovskii, Alexander D.

2007-02-01

Binuclear copper complexes are known to be models for metalloenzymes containing copper active sites, and some of them are of considerable interest due to their magnetic and charge transfer properties. The reactions of the complex formation of bibasic tridentate heterocyclic imines with copper acetate leads to two types of chelates with mono deprotonated ligands and with totally deprotonated ligands. Cu K-edge EXAFS has been applied to determine the local structure around the metal center in copper(II) azomethine complexes with five tridentate ligands: 1-(salycilideneimino)- or 1-(2-tosylaminobenzilideneimino)-2-amino(oxo, thio)benzimidazoles. It has been found that some of the chelates studied are bridged binuclear copper complexes, and others are mononuclear complexes. The copper-copper interatomic distances in the bridged binuclear copper complexes were found to be 2.85-3.01 Å. Variable temperature magnetic susceptibility data indicate the presence of both ferromagnetic and antiferromagnetic interactions within the dimer, the former is dominating at low temperatures and the latter at high temperatures.

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

PubMed

Pasán, Jorge; Sanchiz, Joaquín; Ruiz-Pérez, Catalina; Lloret, Francesc; Julve, Miguel

2005-10-31

Two new phenylmalonate-bridged copper(II) complexes with the formulas [Cu(4,4'-bpy)(Phmal)](n).2nH(2)O (1) and [Cu(2,4'-bpy)(Phmal)(H(2)O)](n)() (2) (Phmal = phenylmalonate dianion, 4,4'-bpy = 4,4'-bipyridine, 2,4'-bpy = 2,4'-bipyridine) have been synthesized and characterized by X-ray diffraction. Complex 1 crystallizes in monoclinic space group P2(1), Z = 4, with unit cell parameters of a = 9.0837(6) Angstroms, b = 9.3514(4) Angstroms, c = 11.0831(8) Angstroms, and beta = 107.807(6) degrees , whereas complex 2 crystallizes in orthorhombic space group C2cb, Z = 8, with unit cell parameters of a = 10.1579(7) Angstroms, b = 10.3640(8) Angstroms, and c = 33.313(4) Angstroms. The structures of 1 and 2 consist of layers of copper(II) ions with bridging bis-monodentate phenylmalonate (1 and 2) and 4,4'-bpy (1) ligands and terminal monodentate 2,4'-bpy (2) groups. Each layer in 1 contains rectangles with dimensions of 11.08 x 4.99 Angstroms(2), the edges being defined by the Phmal and 4,4'-bpy ligands. The intralayer copper-copper separations in 1 through the anti-syn equatorial-apical carboxylate-bridge and the 4,4'-bpy molecule are 4.9922(4) and 11.083(1) Angstroms, respectively. The anti-syn equatorial-equatorial carboxylate bridge links the copper(II) atoms in complex 2 within each layer with a mean copper-copper separation of 5.3709(8) Angstroms. The presence of 2,4'-bpy as a terminal ligand accounts for the large interlayer separation of 15.22 Angstroms. The copper(II) environment presents a static pseudo-Jahn-Teller disorder which has been studied by EPR and low-temperature X-ray diffraction. Magnetic susceptibility measurements of both compounds in the temperature range 2-290 K show the occurrence of weak antiferromagnetic [J = -0.59(1) cm(-1) (1)] and ferromagnetic [J = +0.77(1) cm(-1) (2)] interactions between the copper(II) ions. The conformation of the phenylmalonate-carboxylate bridge and other structural factors, such as the planarity of the exchange pathway in 1, account for the different nature of the magnetic interaction.

Manganese(II), iron(II), cobalt(II), and copper(II) complexes of an extended inherently chiral tris-bipyridyl cage.

PubMed

Perkins, David F; Lindoy, Leonard F; McAuley, Alexander; Meehan, George V; Turner, Peter

2006-01-17

Manganese(II), iron(II), cobalt(II), and copper(II) derivatives of two inherently chiral, Tris(bipyridyl) cages (L and L') of type [ML]-(PF(6))(2)(solvent)(n) and [FeL'](ClO(4))(2) are reported, where L is the hexa-tertiary butyl-substituted derivative of L'. These products were obtained by using the free cage and metal template procedures; the latter involved the reductive amination of the respective Tris-dialdehyde precursor complexes of iron(II), cobalt(II), or nickel(II). Electrochemical, EPR, and NMR studies have been used to probe the nature of the individual complexes. X-ray structures of the manganese(II), iron(II), and copper(II) complexes of L and the iron(II) complex of L' are presented; these are compared with the previously reported structures of the corresponding nickel(II) complex and metal-free cage (L). In each complex the metal cation occupies the cage's central cavity and is coordinated to six nitrogens from the three bipyridyl groups. The cations [MnL](2+) and [FeL](2+) are isostructural but both exhibit a different arrangement of the bound cage to that observed in the corresponding nickel(II) and copper(II) complexes. The latter have an exo-exo arrangement of the bridgehead nitrogen lone pairs, with the metal inducing a triple helical twist that extends approximately 22 A along the axial length of each complex. In contrast, [MnL](2+) and [FeL](2+) have their terminal nitrogen lone pairs directed endo, causing a significant change in the configuration of the bound ligand. In [FeL'](2+), the cage has both bridgehead nitrogen lone pairs orientated exo. Semiempirical calculations indicate that the observed endo-endo and exo-exo arrangements are of comparable energy.

Liquid-crystalline dendrimer Cu(II) complexes and Cu(0) nanoclusters based on the Cu(II) complexes: An electron paramagnetic resonance investigation

NASA Astrophysics Data System (ADS)

Domracheva, N. E.; Mirea, A.; Schwoerer, M.; Torre-Lorente, L.; Lattermann, G.

2007-07-01

New nanostructured materials, namely, the liquid-crystalline copper(II) complexes that contain poly(propylene imine) dendrimer ligands of the first (ligand 1) and second (ligand 2) generations and which have a columnar mesophase and different copper contents (x = Cu/L), are investigated by EPR spectroscopy. The influence of water molecules and nitrate counterions on the magnetic properties of complex 2 (x = 7.3) is studied. It is demonstrated that water molecules can extract some of the copper ions from dendrimer complexes and form hexaaqua copper complexes with free ions. The dimer spectra of fully hydrated complex 2 (x = 7.3) are observed at temperatures T < 10 K. For this complex, the structure is identified and the distance between the copper ions is determined. It is shown that the nitrate counterion plays the role of a bridge between the hexaaqua copper(II) complex and the dendrimer copper(II) complex. The temperature-induced valence tautomerism attended by electron transport is revealed for the first time in blue dendrimer complexes 1 (x = 1.9) with a dimer structure. The activation energy for electron transport is estimated to be 0.35 meV. The coordination of the copper ion site (NO4) and the structural arrangement of green complexes 1 (x = 1.9) in the columnar mesophase are determined. Complexes of this type form linear chains in which nitrate counterions serve as bridges between copper centers. It is revealed that green complexes 1 (x = 1.9) dissolved in isotropic inert solvents can be oriented in the magnetic field (B 0 = 8000 G). The degree of orientation of these complexes is rather high (S z = 0.76) and close to that of systems with a complete ordering (S z = 1) in the magnetic field. Copper(0) nanoclusters prepared by reduction of complex 2 (x = 7.3) in two reducing agents (NaBH4, N2H4 · H2O) are examined. A model is proposed for a possible location of Cu(0) nanoclusters in a dendrimer matrix.

A novel dumbbell-like polyoxometalate assembled of copper(II)-disubstituted monovacant keggin polyoxoanions with a tetranuclear copper cluster.

PubMed

Miao, Hao; Xu, Xiao; Ju, Wei-Wei; Wan, Hong-Xiang; Zhang, Yu; Zhu, Dun-Ru; Xu, Yan

2014-03-17

A dimeric Keggin polyoxometalate, [Cu(bpy)(μ2-OH)]4[(H2O)(bpy)2HPW11Cu2O39]2·2CH3CH2OH·10H2O (1), constructed from two dicopper(II)-substituted monovacant Keggin polyoxoanions bridged by a Cu4 cluster, has been hydrothermally synthesized. Magnetic analysis indicates predominantly an antiferromagnetic interaction between copper(II) centers. Compound 1 also shows very high catalytic activity for the esterification of phosphoric acid with equimolar lauryl alcohol to monoalkyl phosphate ester.

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

PubMed Central

Honda, Akinori; Noda, Keisuke; Tamaki, Yoshinori; Miyamura, Kazuo

2016-01-01

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. PMID:28773957

Copper (II) addition to accelerate lactic acid production from co-fermentation of food waste and waste activated sludge: Understanding of the corresponding metabolisms, microbial community and predictive functional profiling.

PubMed

Ye, Tingting; Li, Xiang; Zhang, Ting; Su, Yinglong; Zhang, Wenjuan; Li, Jun; Gan, Yanfei; Zhang, Ai; Liu, Yanan; Xue, Gang

2018-06-01

Bio-refinery of food waste and waste activated sludge to high value-added chemicals, such as lactic acid, has attracted particular interest in recent years. In this paper, the effect of copper (II) dosing to the organic waste fermentation system on lactic acid production was evaluated, which proved to be a promising method to stimulate high yield of lactic acid (77.0% higher than blank) at dosage of 15 μM-Cu 2+ /g VSS. As mechanism study suggested, copper addition enhanced the activity of α-glycosidase and glycolysis, which increased the substrate for subsequent acidification; whereas, the high dosage (70 μM-Cu 2+ /g VSS) inhibited the conversion of lactic acid to VFA, thus stabilized lactic acid concentration. Microbial community study revealed that small amount of copper (II) at 15 μM/g VSS resulted in the proliferation of Lactobacillus to 82.6%, which mainly produced lactic acid. Finally, the variation of functional capabilities implied that the proposed homeostatic system II was activated at relatively low concentration of copper. Meanwhile, membrane transport function and carbohydrate metabolism were also strengthened. This study provides insights into the effect of copper (II) on the enhancement of lactic acid production from co-fermentation of food waste and waste activated sludge. Copyright © 2018 Elsevier Ltd. All rights reserved.

Flotation-separation and ICP-AES determination of ultra trace amounts of copper, cadmium, nickel and cobalt using 2-aminocyclopentene-1-dithiocarboxylic acid.

PubMed

Shamsipur, Mojtaba; Hashemi, Omid Reza; Safavi, Afsaneh

2005-09-01

A rapid flotation method for separation and enrichment of ultra trace amounts of copper(II), cadmium(II), nickel(II) and cobalt(II) ions from water samples is established. At pH 6.5 and with sodium dodecylsulfate used as a foaming reagent, Cu2+, Cd2+, Ni2+ and Co2+ were separated simultaneously with 2-aminocyclopentene-1-dithiocarboxylic acid (ACDA) added to 1 l of aqueous solution. The proposed procedure of preconcentration is applied prior to the determination of these four analytes using inductivity coupled plasma-atomic emission spectrometry (ICP-AES). The effects of pH, concentration of ACDA, applicability of different surfactants and foreign ions on the separation efficiency were investigated. The preconcentration factor of the method is 1000 and the detection limits of copper(II), cadmium(II), nickel(II) and cobalt(II) ions are 0.078, 0.075, 0.072 and 0.080 ng ml(-1), respectively.

Precursor Ion Scan Mode-Based Strategy for Fast Screening of Polyether Ionophores by Copper-Induced Gas-Phase Radical Fragmentation Reactions.

PubMed

Crevelin, Eduardo J; Possato, Bruna; Lopes, João L C; Lopes, Norberto P; Crotti, Antônio E M

2017-04-04

The potential of copper(II) to induce gas-phase fragmentation reactions in macrotetrolides, a class of polyether ionophores produced by Streptomyces species, was investigated by accurate-mass electrospray tandem mass spectrometry (ESI-MS/MS). Copper(II)/copper(I) transition directly induced production of diagnostic acylium ions with m/z 199, 185, 181, and 167 from α-cleavages of [macrotetrolides + Cu] 2+ . A UPLC-ESI-MS/MS methodology based on the precursor ion scan of these acylium ions was developed and successfully used to identify isodinactin (1), trinactin (2), and tetranactin (3) in a crude extract of Streptomyces sp. AMC 23 in the precursor ion scan mode. In addition, copper(II) was also used to induce radical fragmentation reactions in the carboxylic acid polyether ionophore nigericin. The resulting product ions with m/z 755 and 585 helped to identify nigericin in a crude extract of Streptomyces sp. Eucal-26 by means of precursor ion scan experiments, demonstrating that copper-induced fragmentation reactions can potentially identify different classes of polyether ionophores rapidly and selectively.

Long-Term Effects of Soldering By-Products on Nickel-Coated Copper Wire

NASA Technical Reports Server (NTRS)

Rolin, T. D.; Hodge, R. E.

2008-01-01

An analysis of thirty-year-old, down graded flight cables was conducted to determine the makeup of a green material on the surface of the shielded wire near soldered areas and to ascertain if the green material had corroded the nickel-coated copper wire. Two likely candidates were possible due to the handling and environments to which these cables were exposed. The flux used to solder the cables is known to contain abietic acid, a carboxylic acid found in many pine rosins used for the soldering process. The resulting material copper abietate is green in color and is formed during the application of heat during soldering operations. Copper (II) chloride, which is also green in color is known to contaminate flight parts and is corrosive. Data is presented that shows the material is copper abietate, not copper (II) chloride, and more importantly that the abietate does not aggressively attack nickel-plated copper wire.

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

PubMed

Varzatskii, Oleg A; Shul'ga, Sergey V; Belov, Alexander S; Novikov, Valentin V; Dolganov, Alexander V; Vologzhanina, Anna V; Voloshin, Yan Z

2014-12-28

Iron(II) dibromo- and diiodoclathrochelates undergo copper(I)-promoted reductive homocoupling in HMPA at 70-80 °C leading to C-C conjugated dibromo- and diiodo-bis-clathrochelates in high yields. Under the same conditions, their dichloroclathrochelate analog does not undergo the same homocoupling reaction, so the target dichloro-bis-cage product was obtained in high yield via dimerization of its heterodihalogenide iodochloromonomacrobicyclic precursor. The use of NMP as a solvent at 120-140 °C gave the mixture of bis-clathrochelates resulting from a tandem homocoupling-hydrodehalogenation reaction: the initial acetonitrile copper(I) solvato-complex at a high temperature underwent re-solvatation and disproportionation leading to Cu(II) ions and nano-copper, which promoted the hydrodehalogenation process even at room temperature. The most probable pathway of this reaction in situ includes hydrodehalogenation of the already formed dihalogeno-bis-clathrochelate via the formation of reduced anion radical intermediates. As a result, chemical transformations of the iron(II) dihalogenoclathrochelates in the presence of an acetonitrile copper(I) solvato-complex were found to depend both on the nature of halogen atoms in their ribbed chelate fragments and on reaction conditions (i.e. solvent and temperature). The C-C conjugated iron(II) dihalogeno-bis-clathrochelates easily undergo nucleophilic substitution with various N,S-nucleophiles giving ribbed-functionalized bis-cage species. These iron(II) complexes were characterized by elemental analysis, MALDI-TOF mass spectrometry, IR, UV-Vis, (1)H and (13)C NMR spectroscopy, and by X-ray diffraction; their electrochemical properties were studied by cyclic voltammetry. The isomeric shift values in (57)Fe Mössbauer spectra of such cage compounds allowed identifying them as low-spin iron(II) complexes, while those of the quadrupole splitting are the evidence for a significant TP distortion of their FeN6-coordination polyhedra. As follows from CV data, the C-C conjugated iron(II) bis-clathrochelates undergo stepwise electrochemical reduction and oxidation giving mixed-valence Fe(II)Fe(I) and Fe(II)Fe(III) bis-cage intermediates.

Indole synthesis by conjugate addition of anilines to activated acetylenes and an unusual ligand-free copper(II)-mediated intramolecular cross-coupling.

PubMed

Gao, Detian; Back, Thomas G

2012-11-12

A versatile new synthesis of indoles was achieved by the conjugate addition of N-formyl-2-haloanilines to acetylenic sulfones, ketones, and esters followed by a copper-catalyzed intramolecular C-arylation. The conjugate addition step was conducted under exceptionally mild conditions at room temperature in basic, aqueous DMF. Surprisingly, the C-arylation was performed most effectively by employing copper(II) acetate as the catalyst in the absence of external ligands, without the need for protection from air or water. An unusual feature of this process, for the case of acetylenic ketones, is the ability of the initial conjugate-addition product to serve as a ligand for the catalyst, which enables it to participate in the catalysis of its further transformation to the final indole product. Mechanistic studies, including EPR experiments, indicated that copper(II) is reduced to the active copper(I) species by the formate ion that is produced by the base-catalyzed hydrolysis of DMF. This process also served to recycle any copper(II) that was produced by the adventitious oxidation of copper(I), thereby preventing deactivation of the catalyst. Several examples of reactions involving acetylenic sulfones attached to a modified Merrifield resin demonstrated the feasibility of solid-phase synthesis of indoles by using this protocol, and tricyclic products were obtained in one pot by employing acetylenic sulfones that contain chloroalkyl substituents. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development and characterisation of polymeric microparticle of poly(d,l-lactic acid) loaded with holmium acetylacetonate.

PubMed

de Azevedo, Mariangela de Burgos M; de Melo, Vitor H S; Soares, Carlos Roberto J; Miyamoto, Douglas M; Katayama, Ricardo A; Squair, Peterson L; Barros, Caio H N; Tasic, Ljubica

2018-06-14

Biodegradable polymers containing radioactive isotopes such as Holmium 166 ( 166 Ho) have potential applications as beta particle emitters in tumour tissues. It is also a gamma ray emitter, allowing nuclear imaging of any tissue to be acquired. It is frequently used in the form of complexes such as holmium acetylacetonate (HoAcAc), which may cause damages in tissues next to the targets cancer cells, as it is difficult to control its linkage or healthy tissues radiotherapy effects. Poly(d,l-lactic acid), PDLLA, was used to encapsulate holmium acetylacetonate (HoAcAc) using an emulsion solvent extraction/evaporation technique. Microspheres with sizes between 20-53 µm were extensively characterised. HoAcAc release from the microspheres was assessed through studies using Inductively Coupled Plasma - Optical Emission Spectroscopy, and the microspheres showed no holmium leakage after a period of 10 half-lives and following gamma irradiation. Thus, HoAcAc loaded microspheres are here presented as a potential system for brachytherapy and imaging purposes.

Synthesis, spectroscopy, magnetic and redox behaviors of copper(II) complexes with tert-butylated salen type ligands bearing bis(4-aminophenyl)ethane and bis(4-aminophenyl)amide backbones.

PubMed

Kasumov, Veli T; Yerli, Yusuf; Kutluay, Aysegul; Aslanoglu, Mehmet

2013-03-01

New salen type ligands, N,N'-bis(X-3-tert-butylsalicylidene)-4,4'-ethylenedianiline [(X=H (1), 5-tert-butyl (2)] and N,N'-bis(X-3-tert-butylsalicylidene)-4,4'-amidedianiline [X=H (3), 5-tert (4)] and their copper(II) complexes 5-8, have been synthesized. Their spectroscopic (IR, (1)H NMR, UV/vis, ESR) properties, as well as magnetic and redox-reactivity behavior are reported. IR spectra of 7 and 8 indicate the coordination of amide oxygen atoms of 3 and 4 ligands to Cu(II). The solid state ESR spectra of 5-8 exhibits less informative exchange narrowed isotropic or anisotropic signals with weak unresolved low field patterns. The magnetic moments of 5 (2.92 μ(B) per Cu(II)) and 6 (2.79 μ(B) per Cu(II)) are unusual for copper(II) complexes and considerably higher than those for complexes 7 and 8. Cryogenic measurements (300-10 K) show weak antiferromagnetic exchange interactions between the copper(II) centers in complexes 6 and 8. The results of electrochemical and chemical redox-reactivity studies are discussed. Copyright © 2012 Elsevier B.V. All rights reserved.

A copper(II) paddle-wheel structure of tranexamic acid: di-chloro-tetra-kis-[μ-4-(ammonio-meth-yl)cyclo-hexane-1-carboxyl-ato-O,O']dicopper(II) dichloride hexa-hydrate.

PubMed

Altaf, Muhammad; Stoeckli-Evans, Helen

2017-10-01

Tranexamic acid [systematic name: trans -4-(amino-meth-yl)cyclo-hexane-1-carb-oxy-lic acid], is an anti-fibrinolytic amino acid that exists as a zwitterion [ trans -4-(ammonio-meth-yl)cyclo-hexane-1-carboxyl-ate] in the solid state. Its reaction with copper chloride leads to the formation of a compound with a copper(II) paddle-wheel structure that crystallizes as a hexa-hydrate, [Cu 2 Cl 2 (C 8 H 15 NO 2 ) 4 ] 2+ ·2Cl - ·6H 2 O. The asymmetric unit is composed of a copper(II) cation, two zwitterionic tranexamic acid units, a coordinating Cl - anion and a free Cl - anion, together with three water mol-ecules of crystallization. The whole structure is generated by inversion symmetry, with the Cu⋯Cu axle of the paddle-wheel dication being located about a center of symmetry. The cyclo-hexane rings of the zwitterionic tranexamic acid units have chair conformations. The carboxyl-ate groups that bridge the two copper(II) cations are inclined to one another by 88.4 (8)°. The copper(II) cation is ligated by four carboxyl-ate O atoms in the equatorial plane and by a Cl - ion in the axial position. Hence, it has a fivefold O 4 Cl coordination sphere with a perfect square-pyramidal geometry and a τ 5 index of zero. In the crystal, the paddle-wheel dications are linked by a series of N-H⋯Cl hydrogen bonds, involving the coordinating and free Cl - ions, forming a three-dimensional network. This network is strengthened by a series of N-H⋯O water , O water -H⋯Cl and O water -H⋯O hydrogen bonds.

Isolation, Characterization and Antitumour Propirties of the 1,2-Popylenediaminetetraacetate trans-Diaqua-Copper (II)

PubMed Central

Kamah, S.; Vilaplana, R.; Moreno, J.; Akdi, K.; García-Herdugo, G.

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 (ID50 = 2.29 μM 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. PMID:18475948

Targeting copper(II)-induced oxidative stress and the acetylcholinesterase system in Alzheimer's disease using multifunctional tacrine-coumarin hybrid molecules.

PubMed

Hamulakova, Slavka; Poprac, Patrik; Jomova, Klaudia; Brezova, Vlasta; Lauro, Peter; Drostinova, Lenka; Jun, Daniel; Sepsova, Vendula; Hrabinova, Martina; Soukup, Ondrej; Kristian, Pavol; Gazova, Zuzana; Bednarikova, Zuzana; Kuca, Kamil; Valko, Marian

2016-08-01

Alzheimer's disease is a multifactorial disease that is characterized mainly by Amyloid-β (A-β) deposits, cholinergic deficit and extensive metal (copper, iron)-induced oxidative stress. In this work we present details of the synthesis, antioxidant and copper-chelating properties, DNA protection study, cholinergic activity and amyloid-antiaggregation properties of new multifunctional tacrine-7-hydroxycoumarin hybrids. The mode of interaction between copper(II) and hybrids and interestingly, the reduction of Cu(II) to Cu(I) species (for complexes Cu-5e-g) were confirmed by EPR measurements. EPR spin trapping on the model Fenton reaction, using 5,5-dimethyl-1-pyrroline N-oxide (DMPO) as a spin trap, demonstrated a significantly suppressed formation of hydroxyl radicals for the Cu-5e complex in comparison with free copper(II). This suggests that compound 5e upon coordination to free copper ion prevents the Cu(II)-catalyzed decomposition of hydrogen peroxide, which in turn may alleviate oxidative stress-induced damage. Protective activity of hybrids 5c and 5e against DNA damage in a Fenton system (copper catalyzed) was found to be in excellent agreement with the EPR spin trapping study. Compound 5g was the most effective in the inhibition of acetylcholinesterase (hAChE, IC50=38nM) and compound 5b was the most potent inhibitor of butyrylcholinesterase (hBuChE, IC50=63nM). Compound 5c was the strongest inhibitor of A-β1-40 aggregation, although a significant inhibition (>50%) was detected for compounds 5b, 5d, 5e and 5g. Collectively, these results suggest that the design and investigation of multifunctional agents containing along with the acetylcholinesterase inhibitory segment also an antioxidant moiety capable of alleviating metal (copper)-induced oxidative stress, may be of importance in the treatment of Alzheimer's disease. Copyright © 2016 Elsevier Inc. All rights reserved.

Biosorption of lead and copper by heavy-metal tolerant Micrococcus luteus DE2008.

PubMed

Puyen, Zully M; Villagrasa, Eduard; Maldonado, Juan; Diestra, Elia; Esteve, Isabel; Solé, Antoni

2012-12-01

Micrococcus luteus DE2008 has the ability to absorb lead and copper. The effect of these metals on biomass and viability of this microorganism were investigated and removal of the metals from culture media was determined. Lead had no effect on the biomass expressed as mg Carbon/cm(3) of M. Iuteus DE2008, but in the case of copper, the minimum metal concentration that affected the biomass was 0.1 mM Cu(II). According to these results this microorganism shows a greater tolerance for lead. The minimum metal concentration that affected viability (expressed as the percentage of live cells) was 0.5 mM for both metals. M. luteus DE2008 exhibited a specific removal capacity of 408 mg/g for copper and 1965 mg/g for lead. This microorganism has a greater ability to absorb Pb(II) than Cu(II). M. luteus DE2008 could be seen as a microorganism capable of restoring environments polluted by lead and copper. Copyright © 2012 Elsevier Ltd. All rights reserved.

Interaction of polyethyleneimine-anchored copper(II) complexes with tRNA studied by spectroscopy methods and biological activities.

PubMed

Lakshmipraba, Jagadeesan; Arunachalam, Sankaralingam; Gandi, Devadas A; Thirunalasundari, Thyagarajan; Vignesh, Sivanandham; James, Rathinam A

2017-05-01

Ultraviolet-visible, emission and circular dichroism spectroscopic methods were used in transfer RNA (tRNA) interaction studies performed for polyethyleneimine-copper(II) complexes [Cu(phen)(l-Tyr)BPEI]ClO 4 (where phen =1,10-phenanthroline, l-Tyr = l-tyrosine and BPEI = branched polyethyleneimine) with various degrees of coordination (x = 0.059, 0.149, 0.182) in the polymer chain. The results indicated that polyethyleneimine-copper(II) complexes bind with tRNA mostly through surface binding, although other binding modes, such as hydrogen bonding and van der Waals interactions, might also be present. Dye-exclusion, sulforhodamine B and 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assays of a polyethyleneimine-copper(II) complex with a higher degree of coordination against different cancer cell lines proved that the complex exhibited cytotoxic specificity and a significant cancer cell inhibition rate. Antimicrobial screening showed activity against some human pathogens. Copyright © 2016 John Wiley & Sons, Ltd.

CFD simulation of copper(II) extraction with TFA in non-dispersive hollow fiber membrane contactors.

PubMed

Muhammad, Amir; Younas, Mohammad; Rezakazemi, Mashallah

2018-04-01

This study presents computational fluid dynamics (CFD) simulation of dispersion-free liquid-liquid extraction of copper(II) with trifluoroacetylacetone (TFA) in hollow fiber membrane contactor (HFMC). Mass and momentum balance Navier-Stokes equations were coupled to address the transport of copper(II) solute across membrane contactor. Model equations were simulated using COMSOL Multiphysics™. The simulation was run to study the detailed concentration distribution of copper(II) and to investigate the effects of various parameters like membrane characteristics, partition coefficient, and flow configuration on extraction efficiency. Once-through extraction was found to be increased from 10 to 100% when partition coefficient was raised from 1 to 10. Similarly, the extraction efficiency was almost doubled when porosity to tortuosity ratio of membrane was increased from 0.05 to 0.81. Furthermore, the study revealed that CFD can be used as an effective optimization tool for the development of economical membrane-based dispersion-free extraction processes.

Cytotoxicity of copper(II)-complexes with some S-alkyl derivatives of thiosalicylic acid. Crystal structure of the binuclear copper(II)-complex with S-ethyl derivative of thiosalicylic acid

NASA Astrophysics Data System (ADS)

Nikolić, Miloš V.; Mijajlović, Marina Ž.; Jevtić, Verica V.; Ratković, Zoran R.; Novaković, Slađana B.; Bogdanović, Goran A.; Milovanović, Jelena; Arsenijević, Aleksandar; Stojanović, Bojana; Trifunović, Srećko R.; Radić, Gordana P.

2016-07-01

The spectroscopically predicted structure of the obtained copper(II)-complex with S-ethyl derivative of thiosalicylic acid was confirmed by X-ray structural study and compared to previously reported crystal structure of the Cu complex with S-methyl derivative. Single crystals suitable for X-ray measurements were obtained by slow crystallization from a water solution. Cytotoxic effects of S-alkyl (R = benzyl (L1), methyl (L2), ethyl (L3), propyl (L4) and butyl (L5)) derivatives of thiosalicylic acid and the corresponding binuclear copper(II)-complexes on murine colon carcinoma cell lines, CT26 and CT26.CL25 and human colon carcinoma cell line HCT-116 were reported here. The analysis of cancer cell viability showed that all the tested complexes had low cytotoxic effect on murine colon carcinoma cell lines, but several times higher cytotoxicity on normal human colon carcinoma cells.

Synthesis, characterization, electrical conductivity and luminescence properties of two copper(II) complexes with tridentate N2O chelating ligands containing imine bond

NASA Astrophysics Data System (ADS)

Gönül, İlyas; Ay, Burak; Karaca, Serkan; Şahin, Onur; Serin, Selahattin

2018-03-01

In the present study, we describe the synthesis and characterization of two tridentate N2O donor ligands, namely, (E)-2-(((2-(diethylamino)ethyl)imino)methyl)-6-methoxyphenol (HL1) and (E)-2-(((2-(diethylamino)ethyl)imino)methyl)-6-ethoxyphenol (HL2), and their copper(II) complexes, [Cu(L1)(CH3COO)] (1), [Cu(L2)(CH3COO)] (2). They have been synthesized under conventional methods and characterized by elemental analysis, FTIR, 1H and 13C NMR, ICP-OES, TGA and GC/MS analysis. For the morphological analysis field emission scanning electron microscopy (FESEM) was used. The geometry of the copper(II) complexes was determined by single crystal X-ray diffraction analysis. The copper(II) ions are in distorted square-pyramidal coordination environments. Complexes crystallize in monoclinic space group, P21/c. The electrical conductivity and luminescence properties of 1-2 have been investigated.

Characterization of copper oxides, iron oxides, and zinc copper ferrite desulfurization sorbents by X-ray photoelectron spectroscopy and scanning electron microscopy

NASA Astrophysics Data System (ADS)

Siriwardane, Ranjani V.; Poston, James A.

1993-05-01

Characterization of copper oxides, iron oxides, and zinc copper ferrite desulfurization sorbents was performed by X-ray photoelectron spectroscopy and scanning electron microscopy/energy-dispersive spectroscopy at temperatures of 298 to 823 K. Analysis of copper oxides indicated that the satellite structure of the Cu22p region was absent in the Cu(I) state but was present in the Cu(II) state. Reduction of CuO at room temperature was observed when the ion gauge was placed close to the sample. The satellite structure was absent in all the copper oxides at 823 K in vacuum. Differentiation of the oxidation state of copper utilizing both Cu(L 3M 4,5M 4,5) X-ray-induced Auger lines and Cu2p satellite structure, indicated that the copper in zinc copper ferrite was in the + 1 oxidation state at 823 K. This + 1 state of copper was not significantly changed after exposure to H 2, CO, and H 2O. There was an increase in Cu/Zn ratio and a decrease in Fe/Zn ratio on the surface of zinc copper ferrite at 823 K compared to that at room temperature. These conditions of copper offered the best sulfidation equilibrium for the zinc copper ferrite desulfurization sorbent. Analysis of iron oxides indicated that there was some reduction of both Fe 2O 3 and FeO at 823K. The iron in zinc copper ferrite was similar to that of Fe 2O 3 at room temperature but there was some reduction of this Fe(III) state to Fe(II) at 823 K. This reduction was more enhanced in the presence of H 2 and CO. Reduction to Fe(II) may not be desirable for the lifetime of the sorbent.

Spontaneous resolution of binary copper(II) complexes with racemic dipeptides: crystal structures of glycyl-L-alpha-amino-n-butyrato copper(II) monohydrate, glycyl-D-valinato copper(II) hemihydrate, and glycyl-L-valinato copper(II) hemihydrate.

PubMed

Inomata, Yoshie; Yamaguchi, Takeshi; Tomita, Airi; Yamada, Dai; Howell, F Scott

2005-08-01

Copper(II) complexes with glycyl-DL-alpha-amino-n-butyric acid (H2gly-DL-but), glycyl-DL-valine (H2gly-DL-val), glycyl-DL-norleucine (H2gly-DL-norleu), glycyl-DL-threonine (H2gly-DL-thr), glycyl-DL-serine (H2gly-DL-ser), glycyl-DL-phenylalanine (H2gly-DL-phe), and glycyl-L-valine (H2gly-L-val), have been prepared and characterized by IR, powder diffuse reflection, CD and ORD spectra, and magnetic susceptibility measurements, and by single-crystal X-ray diffraction. The crystal structures of the copper complex with H2gly-DL-but, the copper complex with H2gly-DL-val, and [Cu(gly-L-val)]n.0.5nH2O have been determined by a single-crystal X-ray diffraction method. As for the structure of the copper complex with H2gly-DL-but, the configuration around the asymmetric carbon atom is similar to that of [Cu(gly-L-val)]n.0.5nH2O. Therefore it is concluded that the copper complex with H2gly-DL-but is [Cu(gly-L-but)]n.nH2O. On the contrary, as for the structure of the copper complex with H2gly-DL-val, the configuration around the asymmetric carbon atom is different from that of [Cu(gly-L-val)]n.0.5nH2O. Therefore it is concluded that the copper complex with H2gly-dl-val is [Cu(gly-D-val)]n.0.5nH2O. So during the crystallization of the copper(II) complexes with H2gly-DL-but and H2gly-DL-val, spontaneous resolution has been observed; the four complexes have separated as [Cu(gly-D-but)]n.nH2O, [Cu(gly-L-but)]n.nH2O, [Cu(gly-D-val)]n.0.5nH2O, and [Cu(gly-L-val)]n.0.5nH2O, respectively. [Cu(gly-L-but)]n.nH2O is orthorhombic with the space group P2(1)2(1)2(1). [Cu(gly-D-val)]n.0.5nH2O and [Cu(gly-L-val)]n.0.5nH2O are monoclinic with the space group C2. In these complexes, the copper atom is in a square-pyramidal geometry, ligated by a peptide nitrogen atom, an amino nitrogen atom, a carboxyl oxygen atom, and a carboxyl oxygen atom and a peptide oxygen atom from neighboring molecules. So these complexes consist of a two-dimensional polymer chain bridged by a carboxyl oxygen atom and a peptide oxygen atom from neighboring molecules. The axial oxygen atom is located above the basal plane and the side chain of an amino acid is located below it. These polymer chains consist of only one or the other type of optical isomers; no racemic dipeptides are found. Therefore, spontaneous resolution has been observed in the crystallization of copper(II) complexes with H2gly-DL-but and H2gly-DL-val. The crystal structure of [Cu(gly-D-val)]n.0.5nH2O agrees almost completely with that of [Cu(gly-L-val)]n.0.5nH2O, except for the configuration around the asymmetric carbon atom.

The impact of ionic liquids on the coordination of anions with solvatochromic copper complexes.

PubMed

Kuzmina, O; Hassan, N H; Patel, L; Ashworth, C; Bakis, E; White, A J P; Hunt, P A; Welton, T

2017-09-28

Solvatochromic transition metal (TM)-complexes with weakly associating counter-anions are often used to evaluate traditional neutral solvent and anion coordination ability. However, when employed in ionic liquids (IL) many of the common assumptions made are no longer reliable. This study investigates the coordinating ability of weakly coordinating IL anions in traditional solvents and within IL solvents employing a range of solvatochromic copper complexes. Complexes of the form [Cu(acac)(tmen)][X] (acac = acetylacetonate, tmen = tetramethylethylenediamine) where [X] - = [ClO 4 ] - , Cl - , [NO 3 ] - , [SCN] - , [OTf] - , [NTf 2 ] - and [PF 6 ] - have been synthesised and characterised both experimentally and computationally. ILs based on these anions and imidazolium and pyrrolidinium cations, some of which are functionalised with hydroxyl and nitrile groups, have been examined. IL-anion coordination has been investigated and compared to typical weakly coordinating anions. We have found there is potential for competition at the Cu-centre and cases of anions traditionally assigned as weakly associating that demonstrate a stronger than expected level of coordinating ability within ILs. [Cu(acac)(tmen)][PF 6 ] is shown to contain the least coordinating anion and is established as the most sensitive probe studied here. Using this probe, the donor numbers (DNs) of ILs have been determined. Relative donor ability is further confirmed based on the UV-Vis of a neutral complex, [Cu(sacsac) 2 ] (sacsac = dithioacetylacetone), and DNs evaluated via 23 Na NMR spectroscopy. We demonstrate that ILs can span a wide donor range, similar in breadth to conventional solvents.

Indirect Redox Transformations of Iron, Copper, and Chromium Catalyzed by Extremely Acidophilic Bacteria

PubMed Central

Johnson, D. Barrie; Hedrich, Sabrina; Pakostova, Eva

2017-01-01

Experiments were carried out to examine redox transformations of copper and chromium by acidophilic bacteria (Acidithiobacillus, Leptospirillum, and Acidiphilium), and also of iron (III) reduction by Acidithiobacillus spp. under aerobic conditions. Reduction of iron (III) was found with all five species of Acidithiobacillus tested, grown aerobically on elemental sulfur. Cultures maintained at pH 1.0 for protracted periods displayed increasing propensity for aerobic iron (III) reduction, which was observed with cell-free culture liquors as well as those containing bacteria. At. caldus grown on hydrogen also reduced iron (III) under aerobic conditions, confirming that the unknown metabolite(s) responsible for iron (III) reduction were not (exclusively) sulfur intermediates. Reduction of copper (II) by aerobic cultures of sulfur-grown Acidithiobacillus spp. showed similar trends to iron (III) reduction in being more pronounced as culture pH declined, and occurring in both the presence and absence of cells. Cultures of Acidithiobacillus grown anaerobically on hydrogen only reduced copper (II) when iron (III) (which was also reduced) was also included; identical results were found with Acidiphilium cryptum grown micro-aerobically on glucose. Harvested biomass of hydrogen-grown At. ferridurans oxidized iron (II) but not copper (I), and copper (I) was only oxidized by growing cultures of Acidithiobacillus spp. when iron (II) was also included. The data confirmed that oxidation and reduction of copper were both mediated by acidophilic bacteria indirectly, via iron (II) and iron (III). No oxidation of chromium (III) by acidophilic bacteria was observed even when, in the case of Leptospirillum spp., the redox potential of oxidized cultures exceeded +900 mV. Cultures of At. ferridurans and A. cryptum reduced chromium (VI), though only when iron (III) was also present, confirming an indirect mechanism and contradicting an earlier report of direct chromium reduction by A. cryptum. Measurements of redox potentials of iron, copper and chromium couples in acidic, sulfate-containing liquors showed that these differed from situations where metals are not complexed by inorganic ligands, and supported the current observations of indirect copper oxido-reduction and chromium reduction mediated by acidophilic bacteria. The implications of these results for both industrial applications of acidophiles and for exobiology are discussed. PMID:28239375

Physicochemical, antioxidant, DNA cleaving properties and antimicrobial activity of fisetin-copper chelates.

PubMed

Łodyga-Chruscińska, Elżbieta; Pilo, Maria; Zucca, Antonio; Garribba, Eugenio; Klewicka, Elżbieta; Rowińska-Żyrek, Magdalena; Symonowicz, Marzena; Chrusciński, Longin; Cheshchevik, Vitalij T

2018-03-01

Fisetin (3,3',4',7-tetrahydroxyflavone) metal chelates are of interest as this plant polyphenol has revealed broad prospects for its use as natural medicine in the treatment of various diseases. Metal interactions may change or enhance fisetin biological properties so understanding fisetin metal chelation is important for its application not only in medicine but also as a food additive in nutritional supplements. This work was aimed to determine and characterize copper complexes formed in different pH range at applying various metal/ligand ratios. Fisetin and Cu(II)-fisetin complexes were characterized by potentiometric titrations, UV-Vis (Ultraviolet-visible spectroscopy), EPR, ESI-MS, FTIR and cyclic voltammetry. Their effects on DNA were investigated by using circular dichroism, spectrofluorimetry and gel electrophoresis methods. The copper complex with the ratio of Cu(II)/fisetin 1/2 exhibited significant DNA cleavage activity, followed by complete degradation of DNA. The influence of copper(II) ions on antioxidant activity of fisetin in vitro has been studied using DPPH, ABTS and mitochondrial assays. The results have pointed out that fisetin or copper complexes can behave both as antioxidants or pro-oxidants. Antimicrobial activity of the compounds has been investigated towards several bacteria and fungi. The copper complex of Cu(II)/fisetin 1/2 ratio showed higher antagonistic activity against bacteria comparing to the ligand and it revealed a promising antifungal activity. Copyright © 2017 Elsevier Inc. All rights reserved.

Protective role of quercetin against copper(II)-induced oxidative stress: A spectroscopic, theoretical and DNA damage study.

PubMed

Jomova, Klaudia; Lawson, Michael; Drostinova, Lenka; Lauro, Peter; Poprac, Patrik; Brezova, Vlasta; Michalik, Martin; Lukes, Vladimir; Valko, Marian

2017-12-01

The radical scavenging and metal chelating properties of flavonoids indicate that they may play a protective role in diseases with perturbed metal homeostasis such as Alzheimer's disease. In this work we investigated the effect of the coordination of quercetin to copper(II) in view of the formation of ROS in Cu-catalyzed Fenton reaction. ABTS and DPPH assays confirmed that the copper(II)-quercetin complex exhibits a stronger radical scavenging activity than does quercetin alone. EPR spin trapping experiments have shown that chelation of quercetin to copper significantly suppressed the formation of hydroxyl radicals in the Cu(II)-Fenton reaction. DNA damage experiments revealed a protective effect for quercetin, but only at higher stoichiometric ratios of quercetin relative to copper. DNA protective effect of quercetin against ROS attack was described by two mechanisms. The first mechanism lies in suppressed formation of ROS due to the decreased catalytic action of copper in the Fenton reaction, as a consequence of its chelation and direct scavenging of ROS by free quercetin. Since the Cu-quercetin complex intercalates into DNA, the second mechanism was attributed to a suppressed intercalating ability of the Cu-quercetin complex due to the mildly intercalating free quercetin into DNA, thus creating a protective wall against stronger intercalators. Copyright © 2017 Elsevier Ltd. All rights reserved.

Photochemistry of copper(II) complexes with macrocyclic amine ligands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muralidharan, S.; Ferraudi, G.

1981-07-01

The photochemical properties of Cu(dl-Me/sub 6/(14)aneN/sub 4/)/sup 2 +/ and Cu(rac-Me/sub 6/(14)aneN/sub 4/)/sup 2 +/ in the presence and absence of axially coordinated ligands have been investigated by continuous and flash irradiations. Flash photolysis of the complexes in deaerated aqueous solutions revealed the presence of copper-ligand radical complexes with closed- and open-cycle ligands. Flash photolysis of methanolic solutions of the complexes, in the presence of halides and pseudohalides, shows Cu(III) macrocyclic intermediates. The experimental observations can be explained in terms of two primary photoprocesses with origins in distinctive charge transfer to metal states. These states have been assigned as aminomore » to copper(II) charge-transfer state and acido to copper(II) charge-transfer state.« less

Copper(II)-bis(thiosemicarbazonato) complexes as anti-chlamydial agents.

PubMed

Marsh, James W; Djoko, Karrera Y; McEwan, Alastair G; Huston, Wilhelmina M

2017-09-29

Lipophilic copper (Cu)-containing complexes have shown promising antibacterial activity against a range of bacterial pathogens. To examine the susceptibility of the intracellular human pathogen Chlamydia trachomatis to copper complexes containing bis(thiosemicarbazone) ligands [Cu(btsc)], we tested the in vitro effect of CuII-diacetyl- and CuII-glyoxal-bis[N(4)-methylthiosemicarbazonato] (Cu(atsm) and Cu(gtsm), respectively) on C. trachomatis. Cu(atsm) and to a greater extent, Cu(gtsm), prevented the formation of infectious chlamydial progeny. Impacts on host cell viability and respiration were also observed in addition to the Chlamydia impacts. This work suggests that copper-based complexes may represent a new lead approach for future development of new therapeutics against chlamydial infections, although host cell impacts need to be fully explored. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Permanganate-assisted removal of PCR inhibitors during the DNA Chelex extraction from stained denim samples.

PubMed

Pîrlea, Sorina; Puiu, Mihaela; Răducan, Adina; Oancea, Dumitru

2017-03-01

In this study, it was demonstrated that the DNA Chelex extraction combined with the permanganate assisted-oxidation is highly efficient in removing the PCR inhibitors often found in clothing materials, such as phthalocyanine. The extraction assays were conducted in saliva, blood and epithelial cells samples mixed with three oxidation-resistant dye copper(II) α-phthalocyanine, copper(II) β-phthalocyanine and tetrasulfonated copper(II) β-phthalocyanine. After DNA amplification, all samples were able to provide full DNA profiles. The permanganate/Chelex system was tested further on denim-stained samples and displayed the same ability to remove the PCR inhibitors from the commercial textile materials.

Copper(II)-catalyzed trifluoromethylation of N-aryl imines.

PubMed

Zhang, Yong-Qiang; Liu, Ji-Dan; Xu, Hao

2013-10-07

Methods for imine trifluoromethylation are of great importance because amines with trifluoromethylated stereogenic centers are useful building blocks for synthetic chemistry and drug discovery. Herein, we describe a new copper(II)-catalyzed imine trifluoromethylation method without the use of Lewis base activators, presumably through cooperative activation.

The Cu(II) affinity of the N-terminus of human copper transporter CTR1: Comparison of human and mouse sequences.

PubMed

Bossak, Karolina; Drew, Simon C; Stefaniak, Ewelina; Płonka, Dawid; Bonna, Arkadiusz; Bal, Wojciech

2018-05-01

Copper Transporter 1 (CTR1) is a homotrimeric membrane protein providing the main route of copper transport into eukaryotic cells from the extracellular milieu. Its N-terminal extracellular domain, rich in His and Met residues, is considered responsible for directing copper into the transmembrane channel. Most of vertebrate CTR1 proteins contain the His residue in position three from N-terminus, creating a well-known Amino Terminal Cu(II)- and Ni(II)-Binding (ATCUN) site. CTR1 from humans, primates and many other species contains the Met-Asp-His (MDH) sequence, while some rodents including mouse have the Met-Asn-His (MNH) N-terminal sequence. CTR1 is thought to collect Cu(II) ions from blood copper transport proteins, including albumin, but previous reports indicated that the affinity of N-terminal peptide/domain of CTR1 is significantly lower than that of albumin, casting serious doubt on this aspect of CTR1 function. Using potentiometry and spectroscopic techniques we demonstrated that MDH-amide, a tripeptide model of human CTR1 N-terminus, binds Cu(II) with K of 1.3 × 10 13  M -1 at pH 7.4, ~13 times stronger than Human Serum Albumin (HSA), and MNH-amide is even stronger, K of 3.2 × 10 14  M -1 at pH 7.4. These results indicate that the N-terminus of CTR1 may serve as intermediate binding site during Cu(II) transfer from blood copper carriers to the transporter. MDH-amide, but not MNH-amide also forms a low abundance complex with non-ATCUN coordination involving the Met amine, His imidazole and Asp carboxylate. This species might assist Cu(II) relay down the peptide chain or its reduction to Cu(I), both steps necessary for the CTR1 function. Copyright © 2018 Elsevier Inc. All rights reserved.

Mechanistic Study on Cu(II)-Catalyzed Oxidative Cross-Coupling Reaction between Arenes and Boronic Acids under Aerobic Conditions.

PubMed

Zhang, Qian; Liu, Yang; Wang, Ting; Zhang, Xinhao; Long, Chao; Wu, Yun-Dong; Wang, Mei-Xiang

2018-04-25

Substantial attention has been given to modern organocopper chemistry in recent years since copper salts are naturally abundant, cheap, and less toxic in comparison to precious metals. Copper salts also exhibit versatility in catalyzing and mediating carbon-carbon and carbon-heteroatom bond forming reactions. Despite the wide applications of copper salts in catalysis, reaction mechanisms have remained elusive. Using azacalix[1]arene[3]pyridine, an arene-embedded macrocycle, and its isolated and structurally well-defined ArCu(II) and ArCu(III) compounds as molecular tools, we now report an in-depth experimental and computational study on the mechanism of a Cu(II)-catalyzed oxidative cross-coupling reaction between arenes and boronic acids with air as the oxidant. Stoichiometric reaction of organocopper compounds with p-tolylboronic acid validated arylcopper(II) rather than arylcopper(III) as a reactive organometallic intermediate. XPS, EPR, 1 H NMR, HRMS, and UV-vis spectroscopic evidence along with the isolation and quantification of all products and copper speciation, combined with computational analysis of the electronic structure and energetics of the transient intermediates, suggested a reaction sequence involving electrophilic metalation of arene by Cu(II), transmetalation of arylboronate to ArCu(II), the redox reaction between the resulting ArCu(II)Ar' and ArCu(II) to form respectively ArCu(III)Ar' and ArCu(I), and finally reductive elimination of ArCu(III)Ar'. Under aerobic catalytic conditions, all Cu(I) ions released from reductive elimination of ArCu(III)Ar' and from protolysis of ArCu(I) were oxidized by oxygen to regenerate Cu(II) species that enters into the next catalytic cycle. The unraveled reactivity of arylcopper(II) compounds and the catalytic cycle would enrich our knowledge of modern organocopper chemistry and provide useful information in the design of copper-catalyzed reactions.

Metals in Metal Salts: A Copper Mirror Demonstration

ERIC Educational Resources Information Center

Pike, Robert D.

2010-01-01

A simple lecture demonstration is described to show the latent presence of metal atoms in a metal salt. Copper(II) formate tetrahydrate is heated in a round-bottom flask forming a high-quality copper mirror.

Copper-Hydroperoxo Mediated N-Debenzylation Chemistry Mimicking Aspects of Copper Monoxygenases

PubMed Central

Maiti, Debabrata; Narducci Sarjeant, Amy A.; Karlin, Kenneth D.

2008-01-01

Substantial oxidative N-debenzylation reaction along with PhCH=O formation occurs from a hydroperoxo copper(II) complex which has a dibenzylamino substrate (-N(CH2Ph)2 appended as a substituent on one pyridyl group of its tripodal tetradentate TMPA {≡ TPA ≡ tris(2-pyridylmethyl)amine)} ligand framework. During the course of the (LN(CH2Ph)2)CuII(−OOH) reactivity, formation of a substrate and −OOH (an oxygen atom) derived alkoxo CuII(−OR) complex occurs. The observation that the same CuII(−OR) species occurs from CuI/PhIO chemistry suggests the possibility that a copper-oxo (cupryl) reactive intermediate forms during alkoxo species formation, and new ESI-MS data obtained provides some further support for this high-valent intermediate. Net H-atom abstraction chemistry is proposed, based on kinetic isotope effect studies provided here and that previously published for a closely related CuII(−OOH) species incorporating dimethylamine (-N(CH3)2) as the internal substrate (J. Am. Chem. Soc. 2007, 129, 6720-6721); the CuI/PhIO reactivity, with similar isotope effect results, provides further support. The reactivity of these chemical systems closely resembles proposed oxidative N-dealkylation mechanisms effected by the copper-monooxygenases dopamine β-monooxygenase (DβM) or peptidylglycine-α-hydroxylating monooxygenase (PHM). PMID:18783212

Particulate representation of a chemical reaction mechanism

NASA Astrophysics Data System (ADS)

Lee, Kam-Wah Lucille

1999-09-01

A growing area of interest in chemical education has been the research associated with conceptual understanding at the particulate level. This study investigated the views of 10 university chemistry lecturers, 85 pre-service chemistry teachers and 23 Secondary 3 (equivalent to Year 9) chemistry students about the particulate level of a chemical reaction, namely the heating of copper (II) carbonate. Four characteristic views were identified on the basis of their diagrammatic representations of particles. These were: (a) formation of intermediates; (b) formation of free particles (e. g., atoms or ions); (c) combination of a and b: formation of free particles (e. g., atoms or ions) first, and then intermediates; (d) no mechanism. Both the majority of the lecturers and the pre-service teachers held an identical view about the reaction mechanism, namely that the decomposition of copper (II) carbonate goes through a transition stage by forming intermediates. In contrast, even though the students were familiar with this reaction, about half of them naïvely believed that copper (II) carbonate broke up on heating and the particles recombined directly to form copper (II) oxide and carbon dioxide, the two observed products. About one-third of the students had neither any notion of how the atoms in the copper (II) carbonate lattice interacted and were rearranged in the reaction nor any concept of bond-breaking and reformation in a chemical reaction.

Stereochemical investigations of a novel class of chiral phosphapalladacycle complexes derived from 1-[(2,5-dimethyl)phenyl]ethyldiphenylphosphine.

PubMed

Ng, Joseph Kok-Peng; Li, Yongxin; Tan, Geok-Kheng; Koh, Lip-Lin; Vittal, Jagadese J; Leung, Pak-Hing

2005-12-26

The phosphapalladacycle derived from 1-(2',5'-dimethylphenyl)ethyldiphenylphosphine has been prepared in the optically active and racemic forms. The phosphine was synthesized as a racemate by the treatment of 1-chloro-1-(2',5'-dimethylphenyl)ethane with sodium diphenylphosphide in THF. The racemic phosphapalladacycle was subsequently obtained as the chloro-bridged dimer by the treatment of the phosphine with palladium(II) acetate followed by anion metathesis with lithium chloride. Alternatively, the phosphine could be optically resolved via metal complexation using (R,R)-bis(mu-chloro)bis{1-[1-(N,N-dimethylamino)ethyl]naphthyl-C(2),N}dipalladium(II) as the resolving agent. An efficient separation of the resulting diastereomeric complexes was achieved by silica gel chromatography. The obtained optically resolved diastereomers were next subject to chemoselective removal of the (R)-N,N-(dimethylamino)-1-(1-naphthyl)ethylaminate auxiliary by treatment with concentrated hydrochloric acid. This process yielded the binuclear dimer complexes containing the resolved eta(1)-P ligand. Cyclopalladation of the coordinated phosphine could next be performed by treatment of its eta(1)-P binuclear dimer with silver(I) hexafluorophosphate(V) in a dichloromethane/water mixture followed by treatment with lithium chloride, giving rise to a pair of optically pure enantiomeric dimers with [alpha](D) -322 and +319 degrees in CH(2)Cl(2). Despite the possibilities of the phosphine to attain a five- membered structure by ortho-palladation or a six-membered ring formation by aliphatic C-H bond activation, only the former was observed. X-ray crystallographic data of the meso dimer and an acetylacetonate derivative indicated that the phosphapalladacycle alpha-C methyl substituent was axially located. The 2-D (1)H-(1)H ROESY spectrum of the acetylacetonate derivative further revealed that the phosphapalladacycle was conformationally rigid in CDCl(3).

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

PubMed

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.

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

ERIC Educational Resources Information Center

Harris, Arlo D.; Kalbus, Lee H.

1979-01-01

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

The Synthesis of Copper(II) Carboxylates Revisited

ERIC Educational Resources Information Center

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

2006-01-01

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

Lead-Free Initiator Materials for Small Electro-Explosive Devices for Medium Caliber Munitions: Final Report 04 June 2003

DTIC Science & Technology

2004-05-01

dissolution of copper (II) sulfate pentahydrate (25 g) in 100 ml water) in a 1L jacketed vessel containing a thermometer and magnetic stirrer at a...solution containing copper (II) sulfate pentahydrate (2.37 g) and ethylenediamine (3.98 g) in water (6 ml). The dark purple mixture was stirred until all...ethylenedinitramine (as its sodium salt) with copper sulfate , although no details were available owing to the inaccessibility of the report (see Scheme 1). Scheme 1

Concise and diversity-oriented synthesis of ligand arm-functionalized azoamides.

PubMed

Urankar, Damijana; Kosmrlj, Janez

2008-01-01

Azoamides, previously established as bioactive intracellular GSH-depleting agents, were decorated with a terminal alkyne moiety to 4 and then were transformed, by copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC), into different ligand-arm functionalized azoamides 6. Azides 5 having ligand-arms amenable for binding to platinum(II) were selected for this study. Because, for the fragile azoamides 4, the typically employed reaction conditions for CuAAC failed, several alternative solvents and copper catalysts were tested. Excellent results were obtained with copper(II) sulfate pentahydrate/metallic copper and especially with heterogeneous catalysts, such as copper-in-charcoal, cupric oxide, and cuprous oxide. The heterogeneous catalysts were employed to obtain the desired products in almost quantitative yields by a simple three-step "stir-filter-evaporate" protocol with no or negligible contamination with copper impurities. This is of particular importance because compounds 6 have been designed for coordination.

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

NASA Astrophysics Data System (ADS)

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.

Neutral Red versus MTT assay of cell viability in the presence of copper compounds.

PubMed

Gomez Perez, Mariela; Fourcade, Lyvia; Mateescu, Mircea Alexandru; Paquin, Joanne

2017-10-15

Copper is essential for numerous physiological functions, and copper compounds may display therapeutic as well as cytotoxic effects. The MTT (3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide) assay is a standard test largely used in cytotoxicity studies. This report shows that low micromolar levels of copper compounds such as Cu(II)Urea 2 , Cu(II)Ser 2 and CuCl 2 can interfere with the MTT assay making improper the detection of formazan product of MTT reduction. Comparatively, the Neutral Red assay appears to be sensitive and showing no interference with these compounds. The lactate dehydrogenase alternative assay cannot be used because of inhibitory effect of these copper compounds on the enzyme activity. Copyright © 2017 Elsevier Inc. All rights reserved.

Copper(II)-Catalyzed Conversion of Aryl/Heteroaryl Boronic Acids, Boronates, and Trifluoroborates into the Corresponding Azides: Substrate Scope and Limitations.

PubMed

Grimes, Kimberly D; Gupte, Amol; Aldrich, Courtney C

2010-05-01

We report the copper(II)-catalyzed conversion of organoboron compounds into the corresponding azide derivatives. A systematic series of phenylboronic acid derivatives is evaluated to examine the importance of steric and electronic effects of the substituents on reaction yield as well as functional group compatibility. Heterocyclic substrates are also shown to participate in this mild reaction while compounds incorporating B-C(sp(3)) bonds are unreactive under the reaction conditions. The copper(II)-catalyzed boronic acid-azide coupling reaction is further extended to both boronate esters and potassium organotrifluoroborate salts. The method described herein complements existing procedures for the preparation of aryl azides from the respective amino, triazene, and halide derivatives and we expect that it will greatly facilitate copper- and ruthenium-catalyzed azide-alkyne cycloaddition reactions for the preparation of diversely functionalized 1-aryl- or 1-heteroaryl-1,2,3-triazoles derivatives.

Copper and the oxidation of hemoglobin: a comparison of horse and human hemoglobins.

PubMed

Rifkind, J M; Lauer, L D; Chiang, S C; Li, N C

1976-11-30

Oxidation studies of hemoglobin by Cu(II) indicate that for horse hemoglobin, up to a Cu(II)/heme molar ratio of 0.5, all of the Cu(II) added is used to rapidly oxidize the heme. On the other hand, most of the Cu(II) added to human hemoglobin at low Cu(II)/heme molar ratios is unable to oxidize the heme. Only at Cu(II)/heme molar ratios greater than 0.5 does the amount of oxidation per added Cu(II) approach that of horse hemoglobin. At the same time, binding studies indicate that human hemoglobin has an additional binding site involving one copper for every two hemes, which has a higher copper affinity than the single horse hemoglobin binding site. The Cu(II) oxidation of human hemoglobin is explained utilizing this additional binding site by a mechanism where a transfer of electrons cannot occur between the heme and the Cu(II) bound to the high affinity human binding site. The electron transfer must involve the Cu(II) bound to the lower affinity human hemoglobin binding site, which is similar to the only horse hemoglobin site. The involvement of beta-2 histidine in the binding of this additional copper is indicated by a comparison of the amino acid sequences of various hemoglobins which possess the additional site, with the amino acid sequences of hemoglobins which do not possess the additional site. Zn(II), Hg(II), and N-ethylmaleimide (NEM) are found to decrease the Cu(II) oxidation of hemoglobin. The sulfhydryl reagents, Hg(II) and NEM, produce a very dramatic decrease in the rate of oxidation, which can only be explained by an effect on the rate for the actual transfer of electrons between the Cu(II) and the Fe(II). The effect of Zn(II) is much smaller and can, for the most part, be explained by the increased oxygen affinity, which affects the ligand dissociation process that must precede the electron transfer process.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shardin, Rosidah; Pui, Law Kung; Yamin, Bohari M.

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 C{sub benzoyl}N 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 complexmore » 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 (ε = 116 dm{sup 3} mol{sup −1} cm{sup −1}) supports the presence of Cu(II) centres.« less

The Copper-nicotinamide complex: sustainable applications in coupling and cycloaddition reactions

EPA Science Inventory

Crystalline copper (II)-nicotinamide complex, synthesized via simple mixing of copper chloride and nicotinamide solution at room temperature, catalyzes the C-S, C-N bond forming and cycloaddition reactions under a variety of sustainable reaction conditions.

Synthesis and Cytotoxic Evaluation of Steroidal Copper (Cu (II)) Complexes

PubMed Central

Huang, Yanmin; Kong, Erbin; Zhan, Junyan; Chen, Shuang; Gan, Chunfang; Liu, Zhiping; Pang, Liping

2017-01-01

Using estrone and pregnenolone as starting materials, some steroidal copper complexes were synthesized by the condensation of steroidal ketones with thiosemicarbazide or diazanyl pyridine and then complexation of steroidal thiosemicarbazones or steroidal diazanyl pyridines with Cu (II). The complexes were characterized by IR, NMR, and HRMS. The synthesized compounds were screened for their cytotoxicity against HeLa, Bel-7404, and 293T cell lines in vitro. The results show that all steroidal copper (II) complexes display obvious antiproliferative activity against the tested cancer cells. The IC50 values of complexes 5 and 12 against Bel-7404 (human liver carcinoma) are 5.0 and 7.0 μM. PMID:29180937

Antimicrobial Activity and Urease Inhibition of Schiff Bases Derived from Isoniazid and Fluorinated Benzaldehydes and of Their Copper(II) Complexes.

PubMed

Habala, Ladislav; Varényi, Samuel; Bilková, Andrea; Herich, Peter; Valentová, Jindra; Kožíšek, Jozef; Devínsky, Ferdinand

2016-12-17

In order to evaluate the influence of substitution on biological properties of Schiff bases and their metal complexes, a series of differently substituted fluorine-containing Schiff bases starting from the drug isoniazid (isonicotinylhydrazide) were prepared and their structures were established by single-crystal X-ray diffraction. Also, four copper(II) complexes of these Schiff bases were synthesized. The prepared compounds were evaluated for their antimicrobial activity and urease inhibition. Two of the Schiff bases exerted activity against C. albicans . All copper(II) complexes showed excellent inhibitory properties against jack bean urease, considerably better than that of the standard inhibitor acetohydroxamic acid.

Synthesis, structure, spectroscopic and electrochemical properties of (2-amino-4-methylpyrimidine)-(pyridine-2,6-dicarboxylato)copper(II) monohydrate

NASA Astrophysics Data System (ADS)

Uçar, İbrahim; Karabulut, Bünyamin; Bulut, Ahmet; Büyükgüngör, Orhan

2007-05-01

The (2-amino-4-methylpyrimidine)-(pyridine-2,6-dicarboxylato)copper(II) monohydrate complex was synthesized and characterized by spectroscopic (IR, UV/Vis, EPR), thermal (TG/DTA) and electrochemical methods. X-ray structural analysis of the title complex revealed that the copper ion can be considered to have two coordination spheres. In the first coordination sphere the copper ion forms distorted square-planar geometry with trans-N 2O 2 donor set, and also the metal ion is weakly bonded to the amino-nitrogen in the layer over and to the carboxylic oxygen in the layer underneath in the second coordination sphere. The second coordination environment on the copper ion is attributed to pseudo octahedron. The powder EPR spectra of Cu(II) complex at room and liquid nitrogen temperature were recorded. The calculated g and A parameters have indicated that the paramagnetic centre is axially symmetric. The molecular orbital bond coefficients of the Cu(II) ion in d 9 state is also calculated by using EPR and optical absorption parameters. The cyclic voltammogram of the title complex investigated in DMSO (dimethylsulfoxide) solution exhibits only metal centered electroactivity in the potential range -1.25 to 1.5 V versus Ag/AgCl reference electrode.

Restrained management of copper level enhances the antineoplastic activity of imatinib in vitro and in vivo.

PubMed

Hassan, Iftekhar; Khan, Azmat Ali; Aman, Shazia; Qamar, Wajhul; Ebaid, Hossam; Al-Tamimi, Jameel; Alhazza, Ibrahim M; Rady, Ahmed M

2018-01-26

The present study was designed to investigate if elevated copper level can be targeted to enhance the efficacy of a significant anticancer drug, imatinib (ITB). The antineoplastic activity of this drug was assessed in the HepG2, HEK-293, MCF-7 and MDA-MD-231 cells targeting elevated copper level as their common drug target. The cell lines were treated with the different doses of copper chloride (Cu II) and disulfiram (DSF) alone as well as in their combinations with the drug for 24 h in standard culture medium and conditions. The treated cells were subjected to various assays including MTT, PARP, p-53, caspase-7, caspase-3, LDH and single cell electrophoresis. The study shows that DSF and Cu (II) synergizes the anticancer activity of ITB to a significant extent in a dose-specific way as evidenced by the combinations treated groups. Furthermore, the same treatment strategy was employed in cancer-induced rats in which the combinations of ITB-DSF and ITB-Cu II showed enhanced antineoplastic activity as compared to ITB alone. However, DSF was more effective than Cu (II) as an adjuvant to the drug. Hence, restrained manipulation of copper level in tumor cells can orchestrate the redox and molecular dispositions inside the cells favoring the induction of apoptosis.

Binary adsorption of copper(II) and cadmium(II) from aqueous solutions by biomass of marine alga Durvillaea potatorum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Q.; Kaewsarn, P.

1999-06-01

Much work on the biosorption of heavy metals by low-cost, natural biomass has been on the uptake of single metals. In practice, wastewaters often contain multiple heavy metal ions. In this paper the binary adsorption of copper(II) and cadmium(II) by a pretreated biomass of the marine alga Durvillaea potatorum from aqueous solutions was studied. The results showed that the uptake capacities for each heavy metal of the binary system were lower when compared with the single metal biosorption for copper and cadmium, respectively, but the total capacities for the binary system were similar to those obtained for single metal biosorption.more » The uptake capacities for copper and cadmium increased as the equilibrium pH increased and reached a plateau at a pH around 5.0. The uptake process was relatively fast, with 90% of the adsorption completed within 10 minutes for copper and 30 minutes for cadmium, and equilibrium reached after about 60 minutes of stirring. The biosorption isotherms of binary systems were not significantly affected by equilibrium temperature. The presence of light metal ions in solution also did not affect adsorption significantly. The binary adsorption was successfully predicted by the extended Langmuir model, using parameters and capacities obtained from single component systems.« less

Cu(II) potentiation of Alzheimer Abeta1-40 cytotoxicity and transition on its secondary structure.

PubMed

Dai, Xue-Ling; Sun, Ya-Xuan; Jiang, Zhao-Feng

2006-11-01

Mounting evidence has shown that dyshomeostasis of the redox-active biometals such as Cu and Fe can lead to oxidative stress, which plays a key role in the neuropathology of Alzheimer' disease (AD). Here we demonstrate that with the formation of Cu(II).beta1-40 complexes, copper markedly potentiates the neurotoxicity exhibited by beta-amyloid peptide (Ab). A greater amount of hydrogen peroxide was released when Cu(II).beta1-40 complexes was added to the xanthine oxidase/xanthine system detected by potassium iodide spectrophotometry. Copper bound to Abeta1-40 was observed by electron paramagnetic resonance (EPR) spectroscopy. Circular dichroism (CD) studies indicated that copper chelation could cause a structural transition of Abeta. The addition of copper to Ab introduced an increase on beta-sheet as well as alpha-helix, which may be responsible for the aggregation of Abeta. We hypothesized that Abeta aggregation induced by copper may be responsible for local injury in AD. The interaction between Cu(2+) and Ab also provides a possible mechanism for the enrichment of metal ions in amyloid plaques in the AD brain.

Copper-Catalyzed Oxidative Dehydrogenative Carboxylation of Unactivated Alkanes to Allylic Esters via Alkenes

PubMed Central

2015-01-01

We report copper-catalyzed oxidative dehydrogenative carboxylation (ODC) of unactivated alkanes with various substituted benzoic acids to produce the corresponding allylic esters. Spectroscopic studies (EPR, UV–vis) revealed that the resting state of the catalyst is [(BPI)Cu(O2CPh)] (1-O2CPh), formed from [(BPI)Cu(PPh3)2], oxidant, and benzoic acid. Catalytic and stoichiometric reactions of 1-O2CPh with alkyl radicals and radical probes imply that C–H bond cleavage occurs by a tert-butoxy radical. In addition, the deuterium kinetic isotope effect from reactions of cyclohexane and d12-cyclohexane in separate vessels showed that the turnover-limiting step for the ODC of cyclohexane is C–H bond cleavage. To understand the origin of the difference in products formed from copper-catalyzed amidation and copper-catalyzed ODC, reactions of an alkyl radical with a series of copper–carboxylate, copper–amidate, and copper–imidate complexes were performed. The results of competition experiments revealed that the relative rate of reaction of alkyl radicals with the copper complexes follows the trend Cu(II)–amidate > Cu(II)–imidate > Cu(II)–benzoate. Consistent with this trend, Cu(II)–amidates and Cu(II)–benzoates containing more electron-rich aryl groups on the benzamidate and benzoate react faster with the alkyl radical than do those with more electron-poor aryl groups on these ligands to produce the corresponding products. These data on the ODC of cyclohexane led to preliminary investigation of copper-catalyzed oxidative dehydrogenative amination of cyclohexane to generate a mixture of N-alkyl and N-allylic products. PMID:25389772

Ternary copper(II) complexes with amino acid chains and heterocyclic bases: DNA binding, cytotoxic and cell apoptosis induction properties.

PubMed

Ma, Tieliang; Xu, Jun; Wang, Yuan; Yu, Hao; Yang, Yong; Liu, Yang; Ding, Weiliang; Zhu, Wenjiao; Chen, Ruhua; Ge, Zhijun; Tan, Yongfei; Jia, Lei; Zhu, Taofeng

2015-03-01

Nowadays, chemotherapy is a common means of oncology. However, it is difficult to find excellent chemotherapy drugs. Here we reported three new ternary copper(II) complexes which have potential chemotherapy characteristics with reduced Schiff base ligand and heterocyclic bases (TBHP), [Cu(phen)(TBHP)]H2O (1), [Cu(dpz)(TBHP)]H2O (2) and [Cu(dppz)(TBHP)]H2O (3) (phen=1,10-phenanthroline, dpz=dipyrido [3,2:2',3'-f]quinoxaline, dppz=dipyrido [3,2-a:2',3'-c]phenazine, H2TBHP=2-(3,5-di-tert-butyl-2-hydroxybenzylamino)-2-benzyl-acetic acid). The DNA-binding properties of the complexes were investigated by spectrometric titrations, ethidium bromide displacement experiments and viscosity measurements. The results indicated that the three complexes, especially the complex 13, can strongly bind to calf-thymus DNA (CT-DNA). The intrinsic binding constants Kb of the ternary copper(II) complexes with CT-DNA were 1.37×10(5), 1.81×10(5) and 3.21×10(5) for 1, 2 and 3 respectively. Comparative cytotoxic activities of the copper(II) complexes were also determined by 3-(4,5-dimethylthiazol-2yl)-2,5-diphenyltetrazolium bromide (MTT) assay. The results showed that the ternary copper(II) complexes had significant cytotoxic activity against the human lung cancer (A549), human esophageal cancer (Eca109) and human gastric cancer (SGC7901) cell lines. Cell apoptosis were detected by AnnexinV/PI flow cytometry and by Western blotting with the protein expression of p53, Bax and Bcl-2. All the three copper complexes can effectively induce apoptosis of the three human tumor cells. Copyright © 2014 Elsevier Inc. All rights reserved.

Degradation reaction of Diazo reactive black 5 dye with copper (II) sulfate catalyst in thermolysis treatment.

PubMed

Lau, Yen-Yie; Wong, Yee-Shian; Ang, Tze-Zhang; Ong, Soon-An; Lutpi, Nabilah Aminah; Ho, Li-Ngee

2018-03-01

The theme of present research demonstrates performance of copper (II) sulfate (CuSO 4 ) as catalyst in thermolysis process to treat reactive black 5 (RB 5) dye. During thermolysis without presence of catalyst, heat was converted to thermal energy to break the enthalpy of chemical structure bonding and only 31.62% of color removal. With CuSO 4 support as auxiliary agent, the thermally cleaved molecular structure was further destabilized and reacted with CuSO 4 . Copper ions functioned to delocalize the coordination of π of the lone paired electron in azo bond, C=C bond of the sp 2 carbon to form C-C of the sp 3 amorphous carbon in benzene and naphthalene. Further, the radicals of unpaired electrons were stabilized and RB 5 was thermally decomposed to methyl group. Zeta potential measurement was carried out to analyze the mechanism of RB 5 degradation and measurement at 0 mV verified the critical chemical concentration (CCC) (0.7 g/L copper (II) sulfate), as the maximum 92.30% color removal. The presence of copper (II) sulfate catalyst has remarkably increase the RB 5 dye degradation as the degradation rate constant without catalyst, k 1 is 6.5224 whereas the degradation rate constant with catalyst, k 2 is 25.6810. This revealed the correlation of conversion of thermal energy from heat to break the chemical bond strength, subsequent fragmentation of RB 5 dye molecular mediated by copper (II) sulfate catalyst. The novel framework on thermolysis degradation of molecular structure of RB 5 with respect to the bond enthalpy and interfacial intermediates decomposition with catalyst reaction were determined.

Structures of nitrato-(2-hydroxybenzaldehydo) (2,2 Prime -bipyridyl)copper and nitrato-(2-hydroxy-5-nitrobenzaldehydo)(2,2 Prime -bipyridyl)copper

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chumakov, Yu. M.; Paladi, L. G.; Antosyak, B. Ya.

2011-03-15

Nitrato-(2-hydroxy-5-nitrobenzaldehydo)(2,2 Prime -bipyridyl)copper (I) and nitrato-(2-hydroxybenzaldehydo)(2,2 Prime -bipyridyl)copper (II) were synthesized and characterized by X-ray diffraction. The coordination polyhedron of the central copper atom in complex I can be described as a distorted tetragonal pyramid whose base is formed by the phenol and carbonyl oxygen atoms of the monodeprotonated 2-hydroxy-5nitrobenzaldehyde molecule and the nitrogen atoms of the 2,2 Prime -bipyridyl ligand and whose apex is occupied by the oxygen atom of the nitrato group. In the crystal structure, complexes I are linked by the acido ligands and the NO{sub 2} groups of the aldehyde molecule into infinite chains. In complexmore » II, the central copper atom is coordinated by 2-hydroxybenzaldehyde, 2,2 Prime -bipyridyl, and the nitrato group, resulting in the formation of centrosymmetric dimers. The coordination polyhedron of the central copper atom can be described as a bipyramid (4 + 1 + 1) with the same base as in complex I. The axial vertices of the bipyramid are occupied by the oxygen atom of the nitrato group and the bridging phenol oxygen atom of the adjacent complex related to the initial complex by a center of symmetry. In the crystal structure, complexes II are hydrogen bonded into infinite chains.« less

Preparation and Analysis of Libethenite: A Project for the First-Year Laboratory

ERIC Educational Resources Information Center

Ginion, Kelly E.; Yoder, Claude H.

2004-01-01

The preparation of libethenite, a double salt of copper(II) phosphate and copper(II) hydroxide presents the opportunity to discuss the prevalence of double salts in the environment, the relationship between solubility and stability in aqueous solution, the origin of the color of transition metal compounds and gravimetric analyses. Typical results…

Ligand effects on the structure and magnetic properties of alternating copper(II) chains with 2,2'-bipyrimidine- and polymethyl-substituted pyrazolates as bridging ligands.

PubMed

Castro, Isabel; Calatayud, M Luisa; Barros, Wdeson P; Carranza, José; Julve, Miguel; Lloret, Francesc; Marino, Nadia; De Munno, Giovanni

2014-06-02

A novel series of heteroleptic copper(II) compounds of formulas {[Cu2(μ-H2O)(μ-pz)2(μ-bpm)(ClO4)(H2O)]ClO4·2H2O}n (1), {[Cu2(μ-H2O)(μ-3-Mepz)2(μ-bpm)](ClO4)2·2H2O}n (2), and {[Cu2(μ-OH)(μ-3,5-Me2pz)(μ-bpm)(H-3,5-Me2pz)2](ClO4)2}n (3) [bpm = 2,2'-bipyrimidine, Hpz = pyrazole, H-3-Mepz = 3-methylpyrazole, and H-3,5-Me2pz = 3,5-dimethylpyrazole] have been synthesized and structurally characterized by X-ray diffraction methods. The crystal structures of 1 and 2 consist of copper(II) chains with regular alternating bpm and bis(pyrazolate)(aqua) bridges, whereas that of 3 is made up of copper(II) chains with regular alternating bpm and (pyrazolate)(hydroxo) bridges. The copper centers are six- (1) or five-coordinate (2) in axially elongated, octahedral (1) or square-pyramidal (2) environments in 1 and 2, whereas they are five-coordinate in distorted trigonal-bipyramidal surroundings in 3. The values of the copper-copper separations across the bpm/pyrazolate bridges are 5.5442(7)/3.3131(6) (1), 5.538(1)/3.235(1) (2), and 5.7673(7)/3.3220(6) Å (3). The magnetic properties of 1-3 have been investigated in the temperature range of 25-300 K. The analysis of their magnetic susceptibility data through the isotropic Hamiltonian for an alternating antiferromagnetic copper(II) chain model [H = -J∑i=1-n/2 (S2i·S2i-1 + αS2i·S2i+1), with α = J'/J and Si = SCu = 1/2] reveals the presence of a strong to moderate antiferromagnetic coupling through the bis(pyrazolate)(aqua) [-J = 217 (1) and 215 cm(-1) (2)] and (pyrazolate)(hydroxo) bridges [-J = 153 cm(-1) (3)], respectively, whereas a strong to weak antiferromagnetic coupling occurs through the bis-bidentate bpm [-J' = 211 (1), 213 (2), and 44 cm(-1) (3)]. A simple orbital analysis of the magnetic exchange interaction within the bpm- and pyrazolate-bridged dicopper(II) fragments of 1-3 visualizes the σ-type pathways involving the (dx(2)-y(2)) (1 and 2) or d(z(2)) (3) magnetic orbitals on each metal ion, which account for the variation of the magnetic properties in these three novel examples of one-dimensional copper(II) compounds with regular alternating intrachain antiferromagnetic interactions.

The Application of Orthophosphate to Reduce Elevated Copper Levels in a New Building with High DIC Water

EPA Science Inventory

Public water utilities in the United States are required to meet the 1991 Lead and Copper Rule action level of 1.3 mg/L for copper I drinking water. The effect of water chemistry on Cu(II) solubility has been studied, and drawing upon conclusions from this research , new copper ...

catena-Poly[copper(II)-mu-L-tyrosyl-L-leucinato].

PubMed

Baggio, Ricardo; Casado, Nieves M C; Calvo, Rafael; Rapp, Raul E; Garland, María Teresa

2005-05-01

In the title compound, [Cu(C15H20N2O4)]n, the copper(II) coordination is square planar. The anionic L-tyrosyl-L-leucinate ligand binds in an N,N',O-tridentate mode to one Cu(II) cation on one side and in an O-monodentate mode to a second Cu(II) cation on the other side, thus defining -Cu-O-C-O-Cu'- chains which run along the a axis. These chains are held together by a strong hydrogen bond involving the hydroxy H atom.

Kinetic studies of adsorption of Cu (II) from aqueous solution by coriander seeds (Coriandrum Sativum)

NASA Astrophysics Data System (ADS)

Kadiri, L.; Lebkiri, A.; Rifi, E. H.; Ouass, A.; Essaadaoui, Y.; Lebkiri, I.; Hamad, H.

2018-05-01

The adsorption of copper ions Cu2+ by Coriandrum Sativum seeds (CSS) from aqueous solution was studied in order to highlight the importance of coriander seeds as a potential tool in the treatment of wastewaters containing heavy metals. The kinetic studies of adsorption of Cu (II) were discussed using the spectroscopic technique "Inducting Coupled Plasma" (ICP). The effects of initial copper ion concentration and contact time were determined. All results show that coriander seeds have, over their culinary and medicinal benefits, a significant adsorbent power of copper ions.

An extended X-Ray absorption fine structure (exafs) study of copper (II) sulphate pentahydrate

NASA Astrophysics Data System (ADS)

Joyner, Richard W.

1980-05-01

The EXAFS spectrum of copper (II) sulphate pentahydrate has been measured using synchrotron radiation. Comparison with the results of ab initio calculation gives a mean copper-oxygen distance of 1.95 Å, in reasonable agreement with the known value of 1.97 Å. The relation between the EXAFS Debye-Waller factor and thermal parameters measured by neutron diffraction is discussed. Absence in the EXAFS spectrum of evidence for the second-nearest neighbour oxygen atoms, at Cu-O ≈ 2.4 Å, is discussed.

Crystal structures of two mixed-valence copper cyanide complexes with N-methyl­ethylenedi­amine

PubMed Central

Sabatino, Alexander

2017-01-01

The crystal structures of two mixed-valence copper cyanide compounds involving N-methyl­ethylenedi­amine (meen), are described. In compound (I), poly[bis(μ3-cyanido-κ3 C:C:N)tris(μ2-cyanido-κ2 C:N)bis(N-methylethane-1,2-di­amine-κ2 N,N′)tricopper(I)copper(II)], [Cu4(CN)5(C3H10N2)2] or Cu4(CN)5meen2, cyanide groups link CuI atoms into a three-dimensional network containing open channels parallel to the b axis. In the network, two tetra­hedrally bound CuI atoms are bonded by the C atoms of two end-on bridging CN groups to form Cu2(CN)6 moieties with the Cu atoms in close contact at 2.560 (1) Å. Other trigonally bound CuI atoms link these units together to form the network. The CuII atoms, coordinated by two meen units, are covalently linked to the network via a cyanide bridge, and project into the open network channels. In the mol­ecular compound (II), [(N-methylethylenediamine-κ2 N,N′)copper(II)]-μ2-cyanido-κ2 C:N-[bis(cyanido-κC)copper(I)] monohydrate, [Cu2(CN)3(C3H10N2)2]·H2O or Cu2(CN)3meen2·H2O, a CN group connects a CuII atom coordinated by two meen groups with a trigonal–planar CuI atom coordinated by CN groups. The mol­ecules are linked into centrosymmetric dimers via hydrogen bonds to two water mol­ecules. In both compounds, the bridging cyanide between the CuII and CuI atoms has the N atom bonded to CuII and the C atom bonded to CuI, and the CuII atoms are in a square-pyramidal coordination. PMID:28217329

Blue phosphorescent nitrile containing C^C* cyclometalated NHC platinum(II) complexes.

PubMed

Tronnier, Alexander; Metz, Stefan; Wagenblast, Gerhard; Muenster, Ingo; Strassner, Thomas

2014-02-28

Since C^C* cyclometalated Pt(II) complexes with N-heterocyclic carbene (NHC) ligands have been identified as potential emitter materials in organic light-emitting devices (OLEDs), very promising results regarding quantum yields, colour and stability have been presented. Herein, we report on four nitrile substituted complexes with a chelating NHC ligand (1-(4-cyanophenyl)-3-isopropyl-1H-benzo[d]imidazole or 4-(tert-butyl)-1-(4-cyanophenyl)-3-methyl-1H-imidazole) and a bidentate monoanionic auxiliary ligand (acetylacetone or dimesitoylmethane). The complexes have been fully characterized including extensive 2D NMR studies (COSY, HSQC, HMBC, NOESY, (195)Pt NMR), three of them also by solid-state structures. Photophysical measurements in amorphous PMMA films and pure emitter films at room temperature reveal the impact of the mesityl groups in the auxiliary ligand, which led to a significant increase of the quantum yield, while the decay lifetimes decreased. The electron withdrawing nitrile groups shift the emission towards blue colour coordinates.

Spectator Ions ARE Important! A Kinetic Study of the Copper-Aluminum Displacement Reaction

ERIC Educational Resources Information Center

Sobel, Sabrina G.; Cohen, Skyler

2010-01-01

Surprisingly, spectator ions are responsible for unexpected kinetics in the biphasic copper(II)-aluminum displacement reaction, with the rate of reaction dependent on the identity of the otherwise ignored spectator ions. Application of a published kinetic analysis developed for a reaction between a rotating Al disk and a Cu(II) ion solution to the…

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

NASA Astrophysics Data System (ADS)

Mekahlia, S.; Bouzid, B.

2009-11-01

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

Antimalarial evaluation of copper(II) nanohybrid solids: inhibition of plasmepsin II, a hemoglobin-degrading malarial aspartic protease from Plasmodium falciparum.

PubMed

Mohapatra, Subash Chandra; Tiwari, Hemandra Kumar; Singla, Manisha; Rathi, Brijesh; Sharma, Arun; Mahiya, Kuldeep; Kumar, Mukesh; Sinha, Saket; Chauhan, Shyam Singh

2010-03-01

A new class of copper(II) nanohybrid solids, LCu(CH(3)COO)(2) and LCuCl(2), have been synthesized and characterized by transmission electron microscopy, dynamic light scattering, and IR spectroscopy, and have been found to be capped by a bis(benzimidazole) diamide ligand (L). The particle sizes of these nanohybrid solids were found to be in the ranges 5-10 and 60-70 nm, respectively. These nanohybrid solids were evaluated for their in vitro antimalarial activity against a chloroquine-sensitive isolate of Plasmodium falciparum (MRC 2). The interactions between these nanohybrid solids and plasmepsin II (an aspartic protease and a plausible novel target for antimalarial drug development), which is believed to be essential for hemoglobin degradation by the parasite, have been assayed by UV-vis spectroscopy and inhibition kinetics using Lineweaver-Burk plots. Our results suggest that these two compounds have antimalarial activities, and the IC(50) values (0.025-0.032 microg/ml) are similar to the IC(50) value of the standard drug chloroquine used in the bioassay. Lineweaver-Burk plots for inhibition of plasmepsin II by LCu(CH(3)COO)(2) and LCuCl(2) show that the inhibition is competitive with respect to the substrate. The inhibition constants of LCu(CH(3)COO)(2) and LCuCl(2) were found to be 10 and 13 microM, respectively. The IC(50) values for inhibition of plasmepsin II by LCu(CH(3)COO)(2) and LCuCl(2) were found to be 14 and 17 microM, respectively. Copper(II) metal capped by a benzimidazole group, which resembles the histidine group of copper proteins (galactose oxidase, beta-hydroxylase), could provide a suitable anchoring site on the nanosurface and thus could be useful for inhibition of target enzymes via binding to the S1/S3 pocket of the enzyme hydrophobically. Both copper(II) nanohybrid solids were found to be nontoxic against human hepatocellular carcinoma cells and were highly selective for plasmepsin II versus human cathepsin D. The pivotal mechanism of antimalarial activity of these compounds via plasmepsin II inhibition in the P. falciparum malaria parasite is demonstrated.

Coordination of different ligands to copper(II) and cobalt(III) metal centers enhances Zika virus and dengue virus loads in both arthropod cells and human keratinocytes.

PubMed

Dutta, Shovan; Celestine, Michael J; Khanal, Supreet; Huddleston, Alexis; Simms, Colin; Arca, Jessa Faye; Mitra, Amlan; Heller, Loree; Kraj, Piotr J; Ledizet, Michel; Anderson, John F; Neelakanta, Girish; Holder, Alvin A; Sultana, Hameeda

2018-01-01

Trace elements such as copper and cobalt have been associated with virus-host interactions. However, studies to show the effect of conjugation of copper(II) or cobalt(III) metal centers to thiosemicarbazone ligand(s) derived from either food additives or mosquito repellent such as 2-acetylethiazole or citral, respectively, on Zika virus (ZIKV) or dengue virus (serotype 2; DENV2) infections have not been explored. In this study, we show that four compounds comprising of thiosemicarbazone ligand derived from 2-acetylethiazole viz., (E)-N-ethyl-2-[1-(thiazol-2-yl)ethylidene]hydrazinecarbothioamide (acetylethTSC) (compound 1), a copper(II) complex with acetylethTSC as a ligand (compound 2), a thiosemicarbazone ligand-derived from citral (compound 3) and a cobalt(III) complex with a citral-thiosemicarbazone ligand (compound 4) increased DENV2 and ZIKV replication in both mosquito C6/36 cells and human keratinocytes (HaCaT cells). Treatment of both cell lines with compounds 2 or 4 showed increased dengue viral titers at all three tested doses. Enhanced dengue viral plaque formation was also noted at the tested dose of 100μM, suggesting higher production of infectious viral particles. Treatment with the compounds 2 or 4 enhanced ZIKV and DENV2 RNA levels in HeLa cell line and primary cultures of mouse bone marrow derived dendritic cells. Also, pre- or post treatments with conjugated compounds 2 or 4 showed higher loads of ZIKV or DENV2 envelope (E) protein in HaCaT cells. No changes in loads of E-protein were found in ZIKV-infected C6/36 cells, when compounds were treated after infection. In addition, we tested bis(1,10-phenanthroline)copper(II) chloride ([Cu(phen) 2 ]Cl 2 , (compound 5) and tris(1,10-phenanthroline)cobalt(III) chloride ([Co(phen) 3 ]Cl 3 , (compound 6) that also showed enhanced DENV2 loads. Also, we found that copper(II) chloride dehydrate (CuCl 2 ·2H 2 O) or cobalt(II) chloride hexahydrate (CoCl 2 ·6H 2 O) alone had no effects as "free" cations. Taken together, these findings suggest that use of Cu(II) or Co(III) conjugation to organic compounds, in insect repellents and/or food additives could enhance DENV2/ZIKV loads in human cells and perhaps induce pathogenesis in infected individuals or individuals pre-exposed to such conjugated complexes. Mosquito-borne diseases are of great concern to the mankind. Use of chemicals/repellents against mosquito bites and transmission of microbes has been the topic of interest for many years. Here, we show that thiosemicarbazone ligand(s) derived from 2-acetylethiazole or citral or 1,10-phenanthroline upon conjugation with copper(II) or cobalt(III) metal centers enhances dengue virus (serotype 2; DENV2) and/or Zika virus (ZIKV) infections in mosquito, mouse and human cells. Enhanced ZIKV/DENV2 capsid mRNA or envelope protein loads were evident in mosquito cells and human keratinocytes, when treated with compounds before/after infections. Also, treatment with copper(II) or cobalt(III) conjugated compounds increased viral titers and number of plaque formations. These studies suggest that conjugation of compounds in repellents/essential oils/natural products/food additives with copper(II) or cobalt(III) metal centers may not be safe, especially in tropical and subtropical places, where several dengue infection cases and deaths are reported annually or in places with increased ZIKV caused microcephaly. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis, X-ray crystal structures, and phosphate ester cleavage properties of bis(2-pyridylmethyl)amine copper(II) complexes with guanidinium pendant groups.

PubMed

Belousoff, Matthew J; Tjioe, Linda; Graham, Bim; Spiccia, Leone

2008-10-06

Three new derivatives of bis(2-pyridylmethyl)amine (DPA) featuring ethylguanidinium (L (1)), propylguanidinium (L (2)), or butylguanidinium (L (3)) pendant groups have been prepared by the reaction of N, N- bis(2-pyridylmethyl)alkane-alpha,omega-diamines with 1 H-pyrazole-1-carboxamidine hydrochloride. The corresponding mononuclear copper(II) complexes were prepared by reacting the ligands with copper(II) nitrate and were isolated as [Cu(LH (+))(OH 2)](ClO 4) 3. xNaClO 4. yH 2O ( C1: L = L (1), x = 2, y = 3; C2: L = L (2), x = 2, y = 4; C3: L = L (3), x = 1, y = 0) following cation exchange purification. Recrystallization yielded crystals of composition [Cu(LH (+))(X)](ClO 4) 3.X ( C1': L = L (1), X = MeOH; C2': L = L (2), X = H 2O; C3': L = L (3), X = H 2O), which were suitable for X-ray crystallography. The crystal structures of C1', C2', and C3' indicate that the DPA moieties of the ligands coordinate to the copper(II) centers in a meridional fashion, with a water or methanol molecule occupying the fourth basal position. Weakly bound perchlorate anions located in the axial positions complete the distorted octahedral coordination spheres. The noncoordinating, monoprotonated guanidinium groups project away from the Cu(II)-DPA units and are involved in extensive charge-assisted hydrogen-bonding interactions with cocrystallized water/methanol molecules and perchlorate anions within the crystal lattices. The copper(II) complexes were tested for their ability to promote the cleavage of two model phosphodiesters, bis( p-nitrophenyl)phosphate (BNPP) and uridine-3'- p-nitrophenylphosphate (UpNP), as well as supercoiled plasmid DNA (pBR 322). While the presence of the guanidine pendants was found to be detrimental to BNPP cleavage efficiency, the functionalized complexes were found to cleave plasmid DNA and, in some cases, the model ribose phosphate diester, UpNP, at a faster rate than the parent copper(II) complex of DPA.

Photocatalytic oxidation of organic dyes with visible-light-driven codoped TiO2 photocatalysts

NASA Astrophysics Data System (ADS)

Zhang, Dongfang; Zeng, Fanbin

2011-06-01

A novel copper (II) and zinc (II) codoped TiO2 photocatalyst was synthesized by a modified sol-gel method using titanium (IV) isopropoxide, Zn(NO3)2 · 6H2O and copper(Il) nitrate as precursors. The samples were characterized by X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS) and photo-luminescence spectra (PL). The XRD results showed undoped and Zn, Cu-codoped TiO2 nanoparticles mainly including anatase phase and a tiny amount of Zn- and Cu-oxides exist in the mixed system, which is attributed to the decomposition of copper and zinc nitrates in the TiO2 gel to form CuO and ZnO and randomly dispersed on the TiO2 surface. On the basis of the optical characterization results, we found that the codoping of copper (II) and zinc (II) resulted a red shift of adsorption and lower recombination probability between electrons and holes, which were the reasons for high photocatalytic activity of Zn, Cu-codoped TiO2 nanoparticles under visible light (λ > 400 nm). The photocatalytic activity of samples was tested for degradation of methyl orange (MO) in solutions. The results indicated that the visible-light driven capability of the codoped catalyst were much higher than that of the pure TiO2 catalyst under visible irradiation. Because of the synergetic effect of copper (II) and zinc (II) element, the Zn, Cu-codoped TiO2 catalyst will show higher quantum yield and enhance absorption of visible light. In the end, a key mechanism was proposed in order to account for the enhanced activity.

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

PubMed

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

2016-12-01

Herein, the design and syntheses of two new mononuclear oxindolimine-copper(II) (1 and 2) and corresponding heterobinuclear oxindolimine Cu(II)Pt(II) complexes (3 and 4), are described. All the isolated complexes were characterized by spectroscopic techniques (UV/Vis, IR, EPR), in addition to elemental analysis and mass spectrometry. Cyclic voltammetry (CV) measurements showed that in all cases, one-electron quasi-reversible waves were observed, and ascribed to the formation of corresponding copper(I) complexes. Additionally, waves related to oxindolimine ligand reduction was verified, and confirmed using analogous oxindolimine-Zn(II) complexes. The Pt(IV/II) reduction, and corresponding oxidation, for complexes 3 and 4 occurred at very close values to those observed for cisplatin. By complementary fluorescence studies, it was shown that glutathione (GSH) cannot reduce any of these complexes, under the experimental conditions (room temperature, phosphate buffer 50mM, pH7.4), using an excess of 20-fold [GSH]. All these complexes showed characteristic EPR spectral profile, with parameters values g ǁ >g ⊥ suggesting an axially distorted environment around the copper(II) center. Interactions with calf thymus-DNA, monitored by circular dichroism (CD), indicated different effects modulated by the ligands. Finally, the cytotoxicity of each complex was tested toward different tumor cells, in comparison to cisplatin, and low values of IC 50 in the range 0.6 to 4.0μM were obtained, after 24 or 48h incubation at 37°C. The obtained results indicate that such complexes can be promising alternative antitumor agents. Copyright © 2016 Elsevier Inc. All rights reserved.

Halo-substituted thiosemicarbazones and their copper(II), nickel(II) complexes: Detailed spectroscopic characterization and study of antitumour activity against HepG2 human hepatoblastoma cells

NASA Astrophysics Data System (ADS)

Jagadeesh, M.; Kalangi, Suresh K.; Sivarama Krishna, L.; Reddy, A. Varada

2014-01-01

Copper(II) and nickel(II) complexes of two different halogen substituted thiosemicarbazone ligands were synthesized. The ligands 3,4-difluoroacetophenone thiosemicarbazone (1) and 2-bromo-4'-chloroacetophenone thiosemicarbazone (2) were characterized and confirmed spectroscopically by FT-IR, FT-Raman, UV-vis and fluorescence spectral analysis, while the respective copper(II) complexes [Cu(C9H9N3F2S)2Cl2] (1a), [Cu(C9H9N3ClBrS)2Cl2] (2a) and nickel(II) complexes [Ni(C9H9N3F2S)2] (1b), [Ni(C9H9N3ClBrS)2] (2b) were characterized by FT-IR, UV-vis and electron paramagnetic spectroscopy (EPR). The EPR spectra of the Cu(II) complexes provided the rhombic octahedral and axial symmetry of the complexes 1a and 2a respectively. For the complex 1a, the g values calculated as g1 = 2.1228, g2 = 2.0706 and g3 = 2.001 between 2900 and 3300 G. While for the complex 2a, a set of two resonance absorptions were observed. The synthesized compounds were tested for antitumor activity and showed that the ability to kill liver cancer cells significantly. Out of all the synthesized compounds, copper(II) complexes 1a and 2a showed high cytotoxic effect on liver cancer cells with 67.51% and 42.77% of cytotoxicity respectively at 100 μM.

Supramolecular architectures in Co(II) and Cu(II) complexes with thiophene-2-carboxylate and 2-amino-4,6-dimethoxypyrimidine ligands.

PubMed

Karthikeyan, Ammasai; Thomas Muthiah, Packianathan; Perdih, Franc

2016-05-01

The coordination chemistry of mixed-ligand complexes continues to be an active area of research since these compounds have a wide range of applications. Many coordination polymers and metal-organic framworks are emerging as novel functional materials. Aminopyrimidine and its derivatives are flexible ligands with versatile binding and coordination modes which have been proven to be useful in the construction of organic-inorganic hybrid materials and coordination polymers. Thiophenecarboxylic acid, its derivatives and their complexes exhibit pharmacological properties. Cobalt(II) and copper(II) complexes of thiophenecarboxylate have many biological applications, for example, as antifungal and antitumor agents. Two new cobalt(II) and copper(II) complexes incorporating thiophene-2-carboxylate (2-TPC) and 2-amino-4,6-dimethoxypyrimidine (OMP) ligands have been synthesized and characterized by X-ray diffraction studies, namely (2-amino-4,6-dimethoxypyrimidine-κN)aquachlorido(thiophene-2-carboxylato-κO)cobalt(II) monohydrate, [Co(C5H3O2S)Cl(C6H9N3O2)(H2O)]·H2O, (I), and catena-poly[copper(II)-tetrakis(μ-thiophene-2-carboxylato-κ(2)O:O')-copper(II)-(μ-2-amino-4,6-dimethoxypyrimidine-κ(2)N(1):N(3))], [Cu2(C5H3O2S)4(C6H9N3O2)]n, (II). In (I), the Co(II) ion has a distorted tetrahedral coordination environment involving one O atom from a monodentate 2-TPC ligand, one N atom from an OMP ligand, one chloride ligand and one O atom of a water molecule. An additional water molecule is present in the asymmetric unit. The amino group of the coordinated OMP molecule and the coordinated carboxylate O atom of the 2-TPC ligand form an interligand N-H...O hydrogen bond, generating an S(6) ring motif. The pyrimidine molecules also form a base pair [R2(2)(8) motif] via a pair of N-H...N hydrogen bonds. These interactions, together with O-H...O and O-H...Cl hydrogen bonds and π-π stacking interactions, generate a three-dimensional supramolecular architecture. The one-dimensional coordination polymer (II) contains the classical paddle-wheel [Cu2(CH3COO)4(H2O)2] unit, where each carboxylate group of four 2-TPC ligands bridges two square-pyramidally coordinated Cu(II) ions and the apically coordinated OMP ligands bridge the dinuclear copper units. Each dinuclear copper unit has a crystallographic inversion centre, whereas the bridging OMP ligand has crystallographic twofold symmetry. The one-dimensional polymeric chains self-assemble via N-H...O, π-π and C-H...π interactions, generating a three-dimensional supramolecular architecture.

Evidence of CuI/CuII Redox Process by X-ray Absorption and EPR Spectroscopy: Direct Synthesis of Dihydrofurans from b-Ketocarbonyl Derivatives and Olefins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yi, Hong; Liao, Zhixiong; Zhang, Guanghui

Abstract: The CuI/CuII and CuI/CuIII catalytic cycles have been subject to intense debate in the field of copper-catalyzed oxidative coupling reactions. A mechanistic study on the CuI/CuII redox process, by X-ray absorption (XAS) and electron paramagnetic resonance (EPR) spectroscopies, has elucidated the reduction mechanism of CuII to CuI by 1,3-diketone and detailed investigation revealed that the halide ion is important for the reduction process. The oxidative nature of the thereby-formed CuI has also been studied by XAS and EPR spectroscopy. This mechanistic information is applicable to the copper-catalyzed oxidative cyclization of b-ketocarbonyl derivatives to dihydrofurans. This protocol provides an idealmore » route to highly substituted dihydrofuran rings from easily available 1,3-dicarbonyls and olefins. Copper« less

Synthesis, characterization and catalytic oxidation properties of multi-wall carbon nanotubes with a covalently attached copper(II) salen complex

NASA Astrophysics Data System (ADS)

Salavati-Niasari, Masoud; Bazarganipour, Mehdi

2009-06-01

Hydroxyl functionalized copper(II) Schiff-base, N,N'-bis(4-hydroxysalicylidene)-ethylene-1,2-diaminecopper(II), [Cu((OH) 2-salen)], has been covalently anchored on modified MWCNTs. The new modified MWCNTs ([Cu((OH) 2-salen)]-MWCNTs) have been characterized by TEM, thermal analysis, XRD, XPS, UV-vis, DRS, FT-IR spectroscopy and elemental analysis. The modified copper(II) MWCNTs solid was used to affect the catalytic oxidation of ethylbenzene with tert-butylhydroperoxide as the oxidant at 333 K. The system is truly heterogeneous (no leaching observed) and reusable (no decrease in activity) in three consecutive runs. Acetophenone was the major product though small amounts of o- and p-hydroxyacetophenones were also formed revealing that C-H bond activation takes place both at benzylic and aromatic ring carbon atoms. Ring hydroxylation was more over the "neat" complexes than over the encapsulated complexes.

Synthesis, structure, and magnetic properties of two 1-D helical coordination polymeric Cu(II) complexes

NASA Astrophysics Data System (ADS)

Bian, He-Dong; Yang, Xiao-E.; Yu, Qing; Chen, Zi-Lu; Liang, Hong; Yan, Shi-Ping; Liao, Dai-Zheng

2008-01-01

Two helical coordination polymeric copper(II) complexes bearing amino acid Schiff bases HL or HL', which are condensed from 2-hydroxy-1-naphthaldehyde with 2-aminobenzoic acid or L-valine, respectively, have been prepared and characterised by X-ray crystallography. In [CuL] n ( 1) the copper(II) atoms are bridged by syn- anti carboxylate groups giving infinite 1-D right-handed helical chains which are further connected by weak C-H⋯Cu interactions to build a 2-D network. While in [CuL'] n ( 2) the carboxylate group acts as a rare monatomic bridge to connect the adjacent copper(II) atoms leading to the formation of a left-handed helical chain. Magnetic susceptibility measurements indicate that 1 exhibits weak ferromagnetic interactions whereas an antiferromagnetic coupling is established for 2. The magnetic behavior can be satisfactorily explained on the basis of the structural data.

The CULTEX RFS: A Comprehensive Technical Approach for the In Vitro Exposure of Airway Epithelial Cells to the Particulate Matter at the Air-Liquid Interface

PubMed Central

Aufderheide, Michaela; Hochrainer, Dieter

2013-01-01

The EU Regulation on Registration, Evaluation, Authorization and Restriction of Chemicals (REACH) demands the implementation of alternative methods for analyzing the hazardous effects of chemicals including particulate formulations. In the field of inhalation toxicology, a variety of in vitro models have been developed for such studies. To simulate the in vivo situation, an adequate exposure device is necessary for the direct exposure of cultivated lung cells at the air-liquid interface (ALI). The CULTEX RFS fulfills these requirements and has been optimized for the exposure of cells to atomized suspensions, gases, and volatile compounds as well as micro- and nanosized particles. This study provides information on the construction and functional aspects of the exposure device. By using the Computational Fluid Dynamics (CFD) analysis, the technical design was optimized to realize a stable, reproducible, and homogeneous deposition of particles. The efficiency of the exposure procedure is demonstrated by exposing A549 cells dose dependently to lactose monohydrate, copper(II) sulfate, copper(II) oxide, and micro- and nanoparticles. All copper compounds induced cytotoxic effects, most pronounced for soluble copper(II) sulfate. Micro- and nanosized copper(II) oxide also showed a dose-dependent decrease in the cell viability, whereby the nanosized particles decreased the metabolic activity of the cells more severely. PMID:23509768

Investigation of copper(II) binding to the protein precursor of Non-Amyloid-Beta Component of Alzheimer Disease Amyloid Plaque

NASA Astrophysics Data System (ADS)

Rose, Francis; Hodak, Miroslav; Bernholc, Jerry

2007-03-01

The Non-Amyloid-Beta Component Precursor (NACP) is a natively unfolded synaptic protein that is implicated in Alzheimers and Parkinsons diseases. Its aggregation into fibrillar structures is accelerated by the binding of copper(II). Experimental studies suggest that the dominant copper binding site is located at the histidine residue in NACP. Based on this evidence we assembled a model fragment of the binding site and used DFT to analyze the conformational details of the most probable binding motifs. We investigated the overall conformational effects with classical MD by constraining the copper binding site to the most energetically favorable geometry obtained from the DFT calculations. These results are compared and contrasted with those of the unbound NACP.

Low frequency vibrational spectra and the nature of metal-oxygen bond of alkaline earth metal acetylacetonates

NASA Astrophysics Data System (ADS)

Fakheri, Hamideh; Tayyari, Sayyed Faramarz; Heravi, Mohammad Momen; Morsali, Ali

2017-12-01

Theoretical quantum chemistry calculations were used to assign the observed vibrational band frequencies of Be, Mg, Ca, Sr, and Ba acetylacetonates complexes. Density functional theory (DFT) calculations have been carried out at the B3LYP level, using LanL2DZ, def2SVP, and mixed, GenECP, (def2SVP for metal ions and 6-311++G** for all other atoms) basis sets. The B3LYP level, with mixed basis sets, was utilized for calculations of vibrational frequencies, IR intensity, and Raman activity. Analysis of the vibrational spectra indicates that there are several bands which could almost be assigned mainly to the metal-oxygen vibrations. The strongest Raman band in this region could be used as a measure of the stability of the complex. The effects of central metal on the bond orders and charge distributions in alkaline earth metal acetylacetonates were studied by the Natural Bond Orbital (NBO) method for fully optimized compounds. Optimization were performed at the B3LYP/6-311++G** level for the lighter alkaline earth metal complexes (Be, Mg, and Ca acetylacetonates) while the B3LYP level, using LanL2DZ (extrabasis, d and f on oxygen and metal atoms), def2SVP and mixed (def2SVP on metal ions and 6-311++G** for all other atoms) basis sets for all understudy complexes. Calculations indicate that the covalence nature of metal-oxygen bonds considerably decreases from Be to Ba complexes. The nature of metal-oxygen bond was further studied by using Atoms In Molecules (AIM) analysis. The topological parameters, Wiberg bond orders, natural charges of O and metal ions, and also some vibrational band frequencies were correlated with the stability constants of understudy complexes.

Dynamics of the sorption of copper(II) and silver(I) by materials based on sulfoethylchitosan with various degrees of crosslinking

NASA Astrophysics Data System (ADS)

Petrova, Yu. S.; Pestov, A. V.; Alifkhanova, L. M. k.; Neudachina, L. K.

2017-04-01

Optimum conditions of the dynamic concentration of copper(II) and silver(I) ions simultaneously present in a solution with N-(2-sulfoethyl)chitosan with a degree of modification equal to 0.5 and different degrees of crosslinking by glutaraldehyde are determined. The values of coefficients of selectivity K Ag/Cu are determined under dynamic conditions. It is shown that the selectivity of the sorption of silver(I) increases (compared to copper(II)) as the degree of crosslinking of sorbents based on N-(2-sulfoethyl)chitosan is raised. Mathematical treatment of the obtained dynamic curves is performed according to the Thomas, Adams-Bohart, and Yoon and Nelson models. As a result, the values of dynamic capacity of sorbents, the rate constant of the reaction, and the release time of 50% of the sorbate are determined. The quantitative desorption of copper and silver from the surface of sorbents is achieved by using 1 mol/dm3 solution of nitric acid.

[Co(NH3)6]3[Cu4(OH)(CO3)8].2H2O--a new carbonato-copper(II) anion stabilized by extensive hydrogen bonding.

PubMed

Abrahams, Brendan F; Haywood, Marissa G; Robson, Richard

2004-04-21

Addition of Co(NH3)6(3+) to aqueous solutions of Cu(II) in excess carbonate promotes the assembly of a new highly charged carbonato-copper(II) anion, [Cu4(OH)(CO3)8](9-), which contains an unusual mu4 hydroxo-bridged square Cu4 arrangement, stabilised in the crystal by no less than forty hydrogen bonds (< 3 Angstrom) to hexammine cations.

A combination of experimental and computational studies on a new oxamido bridged dinuclear copper(II) complex

NASA Astrophysics Data System (ADS)

Bhattacharya, Arnab; Saha, Pinki; Saha, Baptu; Maiti, Debasish; Mitra, Partha; Naskar, Jnan Prakash; Chowdhury, Shubhamoy

2017-10-01

Reaction of N,N‧-bis(2-pyridylmethyl)oxamide (H2L), and copper(II)nitrate trihydrate in 1:2 M proportion in methanol generates oxamido bridged dimeric copper(II) compound, [Cu2L(H2O)2(NO3)2]H2O (1a.H2O) in good yield. 1a.H2O has been characterized by C, H and N microanalyses, copper estimation, FT-IR, UV-Vis and room temperature magnetic susceptibility measurements. The X-ray crystal structure of 1a.H2O has been determined. Bond Valence Sum (BVS) analysis was undertaken to assign the oxidation state of each copper center in 1a. Thermal behavior of 1a.H2O has been studied by TGA. Electrochemical studies on 1a.H2O shows single electron two step sequential reductions of Cu(II) to Cu(I) in dimethyl sulphoxide. Our optimized geometry of 1a as obtained through conceptual Density Functional Theory (DFT) corroborates well with that obtained from single crystal X-ray diffraction. TD-DFT method was also adopted to delve into the electronic properties of 1a. We have taken recourse to employ our optimized structure of 1a to investigate systematically the relative stabilities of various dimeric Cu(II) complexes obtained through variation of ligands bearing uni-donor anion through substitution of nitrate in 1a. The in vitro antibacterial potentiality of 1a.H2O was also tested against some bacterial cell lines, pathogenic to mankind.

Genistein Binding to Copper(II)-Solvent Dependence and Effects on Radical Scavenging.

PubMed

Yang, Jing; Xu, Yi; Liu, Hao-Yu; Han, Rui-Min; Zhang, Jian-Ping; Skibsted, Leif H

2017-10-18

Genistein, but not daidzein, binds to copper(II) with a 1:2 stoichiometry in ethanol and with a 1:1 stoichiometry in methanol, indicating chelation by the 5-phenol and the 4-keto group of the isoflavonoid as demonstrated by the Jobs method and UV-visible absorption spectroscopy. In ethanol, the stability constants had the value 1.12 × 10 11 L²∙mol -2 for the 1:2 complex and in methanol 6.0 × 10⁵ L∙mol -1 for the 1:1 complex at 25 °C. Binding was not detected in water, as confirmed by an upper limit for the 1:1 stability constant of K = 5 mol -1 L as calculated from the difference in solvation free energy of copper(II) between methanol and the more polar water. Solvent molecules compete with genistein as demonstrated in methanol where binding stoichiometry changes from 1:2 to 1:1 compared to ethanol and methanol/chloroform (7/3, v / v ). Genistein binding to copper(II) increases the scavenging rate of the stable, neutral 2,2-diphenyl-1-picrylhydrazyl radical by more than a factor of four, while only small effects were seen for the short-lived but more oxidizing β -carotene radical cation using laser flash photolysis. The increased efficiency of coordinated genistein is concluded to depend on kinetic rather than on thermodynamic factors, as confirmed by the small change in reduction potential of -0.016 V detected by cyclic voltammetry upon binding of genistein to copper(II) in methanol/chloroform solutions.

Extraction of copper from an oxidized (lateritic) ore using bacterially catalysed reductive dissolution.

PubMed

Nancucheo, Ivan; Grail, Barry M; Hilario, Felipe; du Plessis, Chris; Johnson, D Barrie

2014-01-01

An oxidized lateritic ore which contained 0.8 % (by weight) copper was bioleached in pH- and temperature-controlled stirred reactors under acidic reducing conditions using pure and mixed cultures of the acidophilic chemolithotrophic bacterium Acidithiobacillus ferrooxidans. Sulfur was provided as the electron donor for the bacteria, and ferric iron present in goethite (the major ferric iron mineral present in the ore) acted as electron acceptor. Significantly more copper was leached by bacterially catalysed reductive dissolution of the laterite than in aerobic cultures or in sterile anoxic reactors, with up to 78 % of the copper present in the ore being extracted. This included copper that was leached from acid-labile minerals (chiefly copper silicates) and that which was associated with ferric iron minerals in the lateritic ore. In the anaerobic bioreactors, soluble iron in the leach liquors was present as iron (II) and copper as copper (I), but both metals were rapidly oxidized (to iron (III) and copper (II)) when the reactors were aerated. The number of bacteria added to the reactors had a critical role in dictating the rate and yield of copper solubilised from the ore. This work has provided further evidence that reductive bioprocessing, a recently described approach for extracting base metals from oxidized deposits, has the potential to greatly extend the range of metal ores that can be biomined.

Synthesis of Copper-Chelates Derived from Amino Acids and Evaluation of Their Efficacy as Copper Source and Growth Stimulator for Lactuca sativa in Nutrient Solution Culture.

PubMed

Kaewchangwat, Narongpol; Dueansawang, Sattawat; Tumcharern, Gamolwan; Suttisintong, Khomson

2017-11-15

Five tetradentate ligands were synthesized from l-amino acids and utilized for the synthesis of Cu(II)-chelates 1-5. The efficacy of Cu(II)-chelates as copper (Cu) source and growth stimulator in hydroponic cultivation was evaluated with Lactuca sativa. Their stability test was performed at pH 4-10. The results suggested that Cu(II)-chelate 3 is the most pH tolerant complex. Levels of Cu, Zn, and Fe accumulated in plants supplied with Cu(II)-chelates were compared with those supplied with CuSO 4 at the same Cu concentration of 8.0 μM. The results showed that Cu(II)-chelate 3 significantly enhanced Cu, Zn, and Fe content in shoot by 35, 15, and 48%, respectively. Application of Cu(II)-chelate 3 also improved plant dry matter yield by 54%. According to the results, Cu(II)-chelate 3 demonstrated the highest stimulating effect on plant growth and plant mineral accumulation so that it can be used as an alternative to CuSO 4 for supplying Cu in nutrient solutions and enhancing the plant growth.

The Preparation and Characterization of the Geometric Isomers of a Coordination Complex: cis- and trans-bis Glycinato Copper (II) Monohydrates.

ERIC Educational Resources Information Center

O'Brien, Paul

1982-01-01

Preparation of cis and trans isomers of the kinetically labile bis glycinato copper (II) has a number of advantages including its facility, economy, ready theoretical interpretation, and biological relevance. Background information, laboratory procedures, results/discussion are provided for this experiment which can be completed in a single,…

Strong copper(II) species in estuarine and sea waters investigated by a method with high detection window.

PubMed

Alberti, Giancarla; Biesuz, Raffaela; D'Agostino, Girolamo; Scarponi, Giuseppe; Pesavento, Maria

2007-02-15

The distribution of copper(II) in species of different stability in some estuarine and sea water samples (Adriatic Sea) was investigated by a method based on the sorption of the metal ion on a strongly sorbing resin, Chelex 100, whose sorbing properties have been previously characterized. From them, it is possible to predict very high values of detection windows at the considered conditions, for example side reaction coefficient as high as 10(10) at pH 7.5. Strong copper(II) species in equilibrium with Chelex 100 were detected, at concentration 2-20nM, with a reaction coefficient approximately 10(10.6) at pH 7.45 in sea water, strictly depending on the acidity. They represent 50-70% of the total metal ion and are the strongest copper(II) complexes found in sea water. Weak complexes too were detected in all the samples, with reaction coefficient lower than ca. 10(9) at the same pH. The method applied, named resin titration (RT), was described in a previous investigation, and is here modified in order to be carried out on oceanographic boat during a cruise in the Adriatic Sea.

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

ERIC Educational Resources Information Center

Petrusevski, Vladimir M.; Stojanovska, Marina

2010-01-01

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

PROMETHEE II: A knowledge-driven method for copper exploration

NASA Astrophysics Data System (ADS)

Abedi, Maysam; Ali Torabi, S.; Norouzi, Gholam-Hossain; Hamzeh, Mohammad; Elyasi, Gholam-Reza

2012-09-01

This paper describes the application of a well-known Multi Criteria Decision Making (MCDM) technique called Preference Ranking Organization METHod for Enrichment Evaluation (PROMETHEE II) to explore porphyry copper deposits. Various raster-based evidential layers involving geological, geophysical, and geochemical geo-datasets are integrated to prepare a mineral prospectivity mapping (MPM). In a case study, thirteen layers of the Now Chun copper deposit located in the Kerman province of Iran are used to explore the region of interest. The PROMETHEE II technique is applied to produce the desired MPM, and the outputs are validated using twenty-one boreholes that have been classified into five classes. This proposed method shows a high performance when providing the MPM while reducing the cost of exploratory drilling in the study area.

Electronic structure of binuclear acetylacetonates of boron difluoride

NASA Astrophysics Data System (ADS)

Tikhonov, Sergey A.; Svistunova, Irina V.; Samoilov, Ilya S.; Osmushko, Ivan S.; Borisenko, Aleksandr V.; Vovna, Vitaliy I.

2018-05-01

The electronic structure of boron difluoride acetylacetonate and its three derivatives was studied using photoelectron and absorption spectroscopy, as well as the density functional theory. In a series of binuclear acetylacetonate complexes containing bridge-moieties of sulfur and selenium atoms, it was found an appreciable mixing of the π3-orbital of the chelate cycle with atomic orbitals S 3p and Se 4p resulting in destabilization of the HOMO levels by 0.4-0.6 eV, in comparison with the monomer. The positively charged fragment C(CH3)-CX-C(CH3) causes the field effect, which leads to stabilization of the LUMO levels by 0.3-0.4 eV and C 1s-levels by 0.5-1.2 eV. An analysis of the research results on the electronic structure made it possible to determine the effect of substituents in the γ position on the absorption spectra, which is mainly determined by the electron density transfer from the chalcogen atoms to the chelate cycles. It is shown that the calculated energy intervals between electron levels correlate well with the structure of the photoelectron spectra of valence and core electrons.

Preparation and Biodistribution Studies of a Radiogallium-Acetylacetonate Bis (Thiosemicarbazone) Complex in Tumor-Bearing Rodents

PubMed Central

Jalilian, Amir Reza; Yousefnia, Hassan; Shafaii, Kamaleddin; Novinrouz, Aytak; Rajamand, Amir Abbas

2012-01-01

Various radiometal complexes have been developed for tumor imaging, especially Ga-68 tracer. In the present study, the development of a radiogallium bis-thiosemicarbazone complex has been reported. [67Ga] acetylacetonate bis(thiosemicarbazone) complex ([67Ga] AATS) was prepared starting [67Ga]Gallium acetate and freshly prepared acetylacetonate bis (thiosemicarbazone) (AATS) in 30 min at 90°C. The partition co-efficient and the stability of the tracer were determined in final solution (25°C) and the presence of human serum (37°C) up to 24 h. The biodistribution of the labeled compound in wild-type and fibrosarcoma-bearing rodents were determined up to 72 h. The radiolabled Ga complex was prepared in high radiochemical purity (> 97%, HPLC) followed by initial biodistribution data with the significant tumor accumulation of the tracer in 2 h which is far higher than free Ga-67 cation while the compound wash-out is significantly faster. Above-mentioned pharmacokinetic properties suggest an interesting radiogallium complex while prepared by the PET Ga radioisotope, 68Ga, in accordance with the physical half life, for use in fibrosarcoma tumors, and possibly other malignancies. PMID:24250475

Determination of Zinc, Cadmium, Lead, Copper and Silver Using a Carbon Paste Electrode and a Screen Printed Electrode Modified with Chromium(III) Oxide

PubMed Central

Koudelkova, Zuzana; Syrovy, Tomas; Ambrozova, Pavlina; Moravec, Zdenek; Kubac, Lubomir; Hynek, David; Adam, Vojtech

2017-01-01

In this study, the preparation and electrochemical application of a chromium(III) oxide modified carbon paste electrode (Cr-CPE) and a screen printed electrode (SPE), made from the same material and optimized for the simple, cheap and sensitive simultaneous determination of zinc, cadmium, lead, copper and the detection of silver ions, is described. The limits of detection and quantification were 25 and 80 µg·L−1 for Zn(II), 3 and 10 µg·L−1 for Cd(II), 3 and 10 µg·L−1 for Pb(II), 3 and 10 µg·L−1 for Cu(II), and 3 and 10 µg·L−1 for Ag(I), respectively. Furthermore, this promising modification was transferred to the screen-printed electrode. The limits of detection for the simultaneous determination of zinc, cadmium, copper and lead on the screen printed electrodes were found to be 350 µg·L−1 for Zn(II), 25 µg·L−1 for Cd(II), 3 µg·L−1 for Pb(II) and 3 µg·L−1 for Cu(II). Practical usability for the simultaneous detection of these heavy metal ions by the Cr-CPE was also demonstrated in the analyses of wastewaters. PMID:28792450

Determination of Zinc, Cadmium, Lead, Copper and Silver Using a Carbon Paste Electrode and a Screen Printed Electrode Modified with Chromium(III) Oxide.

PubMed

Koudelkova, Zuzana; Syrovy, Tomas; Ambrozova, Pavlina; Moravec, Zdenek; Kubac, Lubomir; Hynek, David; Richtera, Lukas; Adam, Vojtech

2017-08-09

In this study, the preparation and electrochemical application of a chromium(III) oxide modified carbon paste electrode (Cr-CPE) and a screen printed electrode (SPE), made from the same material and optimized for the simple, cheap and sensitive simultaneous determination of zinc, cadmium, lead, copper and the detection of silver ions, is described. The limits of detection and quantification were 25 and 80 µg·L -1 for Zn(II), 3 and 10 µg·L -1 for Cd(II), 3 and 10 µg·L -1 for Pb(II), 3 and 10 µg·L -1 for Cu(II), and 3 and 10 µg·L -1 for Ag(I), respectively. Furthermore, this promising modification was transferred to the screen-printed electrode. The limits of detection for the simultaneous determination of zinc, cadmium, copper and lead on the screen printed electrodes were found to be 350 µg·L -1 for Zn(II), 25 µg·L -1 for Cd(II), 3 µg·L -1 for Pb(II) and 3 µg·L -1 for Cu(II). Practical usability for the simultaneous detection of these heavy metal ions by the Cr-CPE was also demonstrated in the analyses of wastewaters.

Speciation study in the sulfamethoxazole-copper-pH-soil system: implications for retention prediction.

PubMed

Morel, Marie-Christine; Spadini, Lorenzo; Brimo, Khaled; Martins, Jean M F

2014-05-15

Sulfamethoxazole (SMX) is a persistent sulfonamide antibiotic drug used in the veterinary and human medical sectors and is widely detected in natural waters. To better understand the reactive transport of this antibiotic in soil, the speciation of the SMX-Cu(II)-H(+) system in solution and the combined sorption of these components in a natural vineyard soil were investigated by acid-base titrimetry and infrared spectroscopy. Cu(II) is considered to represent a strongly complexing trace element cation (such as Cd(2+), Zn(2+), Pb(2+), Ni(2+), etc.) in comparison to more prevalent but more weakly binding cations (such as Ca(2+) and Mg(2+)). Titrimetric studies showed that, relative to other antibiotics, such as tetracycline, SMX is a weak copper chelating agent and a weak soil sorbent at the soil pH (pH6). However, the sorption of SMX in soil increases strongly (by a factor of 6) in the presence of copper. This finding strongly supports the hypothetical formation of ternary SMX-Cu-soil complexes, especially considering that copper is dominantly sorbed in a state at pH6. The data were successfully modelled with PhreeqC assuming the existence of binary and ternary surface complexes in equilibrium with aqueous Cu, SMX and Cu-SMX complexes. It is thought that other strongly complexing cations present on the surface of reactive organic and mineral soil phases, such as Cd(II), Ni(II), Zn(II), Pb(II), Fe(II/III), Mn(II/IV) and Al(III), affect the solid/solution partitioning of SMX. This study thus suggests that surface-adsorbed cations significantly increase the sorption of SMX. Copyright © 2014 Elsevier B.V. All rights reserved.

Mechanisms of iron and copper-frataxin interactions.

PubMed

Han, T H L; Camadro, J M; Santos, R; Lesuisse, E; El Hage Chahine, J M; Ha-Duong, N T

2017-08-16

Frataxin is a mitochondrial protein whose deficiency is the cause of Friedreich's ataxia, a hereditary neurodegenerative disease. This protein plays a role in iron-sulfur cluster biosynthesis, protection against oxidative stress and iron metabolism. In an attempt to provide a better understanding of the role played by metals in its metabolic functions, the mechanisms of mitochondrial metal binding to frataxin in vitro have been investigated. A purified recombinant yeast frataxin homolog Yfh1 binds two Cu(ii) ions with a K d1 (Cu II ) of 1.3 × 10 -7 M and a K d2 (Cu II ) of 3.1 × 10 -4 M and a single Cu(i) ion with a higher affinity than for Cu(ii) (K d (Cu I ) = 3.2 × 10 -8 M). Mn(ii) forms two complexes with Yfh1 (K d1 (Mn II ) = 4.0 × 10 -8 M; K d2 (Mn II ) = 4.0 × 10 -7 M). Cu and Mn bind Yfh1 with higher affinities than Fe(ii). It is established for the first time that the mechanisms of the interaction of iron and copper with frataxin are comparable and involve three kinetic steps. The first step occurs in the 50-500 ms range and corresponds to a first metal uptake. This is followed by two other kinetic processes that are related to a second metal uptake and/or to a change in the conformation leading to thermodynamic equilibrium. Frataxin deficient Δyfh1 yeast cells exhibited a marked growth defect in the presence of exogenous Cu or Mn. Mitochondria from Δyfh1 strains also accumulated higher amounts of copper, suggesting a functional role of frataxin in vivo in copper homeostasis.

Structural diversity in binuclear complexes of alkaline earth metal ions with 4,6-diacetylresorcinol

NASA Astrophysics Data System (ADS)

Shebl, Magdy; Khalil, Saied M. E.; Taha, A.; Mahdi, M. A. N.

2012-11-01

A new series of binuclear and mixed-ligand complexes with the general formula: [M 2(LO)yClz]; where M = Mg(II), Ca(II), Sr(II) and Ba(II); H2L = 4,6-diacetylresorcinol, the secondary ligand L' = acetylacetone (acac), 8-hydroxyquinoline (8-HQ) or 2,2'-bipyridyl (Bipy), n = 0-2, m = 1, 2, x = 0, 1, 2, 4, y = 0, 2, 4, 5 and z = 0-2; have been synthesized. They have been characterized by the analytical and spectral methods (IR, 1H NMR and mass) as well as TGA and molar conductivity measurements. The spectroscopic and conductance data suggested that the H2L ligand behaves as a neutral, monobasic or dibasic tetradentate ligand, depending on the basicity of the secondary ligand, through the two phenolic and two carbonyl groups. Binuclear octahedral geometry has been assigned to all of the prepared complexes in various molar ratios 2:2; 2:2:2; 1:2:1 and 1:2:4 (L:M:L'). Molecular orbital calculations were performed for the ligands and their complexes using Hyperchem 7.52 program on the bases of PM3 level and the results were correlated with the experimental data. The ligand and some of its alkaline metal(II) complexes showed antibacterial activity towards some of Gram-positive and Gram-negative bacteria, yeast (Candida albicans) and fungus (Aspergillus fumigatus).

Effect of substituent of terpyridines on the in vitro antioxidant, antitubercular, biocidal and fluorescence studies of copper(II) complexes with clioquinol

NASA Astrophysics Data System (ADS)

Kharadi, G. J.

2014-01-01

An octahedral complexes of copper with clioquinol(CQ) and substituted terpyridine have been synthesized. The Cu(II) complexes have been characterized by elemental analyses, thermogravimetric analyses, magnetic moment measurements, FT-IR, electronic, 1H NMR and FAB mass spectra. Antimycobacterial screening of ligand and its copper compound against Mycobacterium tuberculosis shows clear enhancement in the antitubercular activity upon copper complexation. Ferric-reducing anti-oxidant power of all complexes were measured. 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. The antimicrobial efficiency of the complexes were tested on five different microorganisms and showed good biological activity.

Preparation and adsorption characteristics for heavy metals of active silicon adsorbent from leaching residue of lead-zinc tailings.

PubMed

Lei, Chang; Yan, Bo; Chen, Tao; Xiao, Xian-Ming

2018-05-19

To comprehensively reuse the leaching residue obtained from lead-zinc tailings, an active silicon adsorbent (ASA) was prepared from leaching residue and studied as an adsorbent for copper(II), lead(II), zinc(II), and cadmium(II) in this paper. The ASA was prepared by roasting the leaching residue with either a Na 2 CO 3 /residue ratio of 0.6:1 at 700 °C for 1 h or a CaCO 3 /residue ratio of 0.8:1 at 800 °C for 1 h. Under these conditions, the available SiO 2 content of the ASA was more than 20%. The adsorption behaviors of the metal ions onto the ASA were investigated and the Langmuir, Freundlich, and Dubinin-Radushkevich isotherm models were used to analyze the adsorption isotherm. The result showed that the maximum adsorption capacities of copper(II), lead(II), cadmium(II), and zinc(II) calculated by the Langmuir model were 3.40, 2.83, 0.66, and 0.62 mmol g -1 , respectively. The FT-IR spectra of the ASA and the mean free adsorption energies indicated that ion exchange was the mechanism of copper(II), lead(II), and cadmium(II) adsorption and that chemical reaction was the mechanism of zinc(II) adsorption. These results provide a method for reusing the leaching residue obtained from lead-zinc tailings and show that the ASA is an effective adsorbent for heavy metal pollution remediation.

Distinct oxidative cleavage and modification of bovine [Cu-Zn]-SOD by an ascorbic acid/Cu(II) system: Identification of novel copper binding site on SOD molecule

PubMed Central

Uehara, Hiroshi; Luo, Shen; Aryal, Baikuntha; Levine, Rodney L.; Rao, V. Ashutosh

2016-01-01

We investigated the combined effect of ascorbate and copper [Asc/Cu(II)] on the integrity of bovine [Cu-Zn]-superoxide dismutase (bSOD1) as a model system to study the metal catalyzed oxidation (MCO) and fragmentation of proteins. We found Asc/Cu(II) mediates specific cleavage of bSOD1 and generates 12.5 and 3.2 kDa fragments in addition to oxidation/carbonylation of the protein. The effect of other tested transition metals, a metal chelator, and hydrogen peroxide on the cleavage and oxidation indicated that binding of copper to a previously unknown site on SOD1 is responsible for the Asc/Cu(II) specific cleavage and oxidation. We utilized tandem mass spectrometry to identify the specific cleavage sites of Asc/Cu(II)-treated bSOD1. Analyses of tryptic- and AspN-peptides have demonstrated the cleavage to occur at Gly31 with peptide bond breakage with Thr30 and Ser32 through diamide and α-amidation pathways, respectively. The three-dimensional structure of bSOD1 reveals the imidazole ring of His19 localized within 5 Angstrom from the α-carbon of Gly31 providing a structural basis that copper ion, most likely coordinated by His19, catalyzes the specific cleavage reaction. PMID:26872685

Distinct oxidative cleavage and modification of bovine [Cu- Zn]-SOD by an ascorbic acid/Cu(II) system: Identification of novel copper binding site on SOD molecule.

PubMed

Uehara, Hiroshi; Luo, Shen; Aryal, Baikuntha; Levine, Rodney L; Rao, V Ashutosh

2016-05-01

We investigated the combined effect of ascorbate and copper [Asc/Cu(II)] on the integrity of bovine [Cu-Zn]-superoxide dismutase (bSOD1) as a model system to study the metal catalyzed oxidation (MCO) and fragmentation of proteins. We found Asc/Cu(II) mediates specific cleavage of bSOD1 and generates 12.5 and 3.2kDa fragments in addition to oxidation/carbonylation of the protein. The effect of other tested transition metals, a metal chelator, and hydrogen peroxide on the cleavage and oxidation indicated that binding of copper to a previously unknown site on SOD1 is responsible for the Asc/Cu(II) specific cleavage and oxidation. We utilized tandem mass spectrometry to identify the specific cleavage sites of Asc/Cu(II)-treated bSOD1. Analyses of tryptic- and AspN-peptides have demonstrated the cleavage to occur at Gly31 with peptide bond breakage with Thr30 and Ser32 through diamide and α-amidation pathways, respectively. The three-dimensional structure of bSOD1 reveals the imidazole ring of His19 localized within 5Å from the α-carbon of Gly31 providing a structural basis that copper ion, most likely coordinated by His19, catalyzes the specific cleavage reaction. Published by Elsevier Inc.

All-vapor processing of p-type tellurium-containing II-VI semiconductor and ohmic contacts thereof

DOEpatents

McCandless, Brian E.

2001-06-26

An all dry method for producing solar cells is provided comprising first heat-annealing a II-VI semiconductor; enhancing the conductivity and grain size of the annealed layer; modifying the surface and depositing a tellurium layer onto the enhanced layer; and then depositing copper onto the tellurium layer so as to produce a copper tellurium compound on the layer.

Copper(II) sulfamate: an efficient catalyst for the one-pot synthesis of 3,4-dihydropyrimidine-2(1H)-ones and thiones.

PubMed

Liu, Chen-Jiang; Wang, Ji-De

2009-02-13

A simple, efficient procedure for the one-pot Biginelli condensation reaction of aldehydes, beta-ketoesters and urea or thiourea employing copper(II) sulfamate as a novel catalyst is described. Compared to the classical Biginelli reaction conditions, the present method has the advantages of good yields, short reaction times and experimental simplicity.

Pyrazolate-based copper(II) and nickel(II) [2 x 2] grid complexes: protonation-dependent self-assembly, structures and properties.

PubMed

Klingele, Julia; Prikhod'ko, Alexander I; Leibeling, Guido; Demeshko, Serhiy; Dechert, Sebastian; Meyer, Franc

2007-05-28

The pyrazole-based diamide ligand N,N'-bis(2-pyridylmethyl)pyrazole-3,5-dicarboxamide (H(3)L) has been structurally characterised and successfully employed in the preparation of [2 x 2] grid-type complexes. Thus, the reaction of H(3)L with Cu(ClO(4))2.6H(2)O or Ni(ClO(4))2.6H(2)O in the presence of added base (NaOH) affords the tetranuclear complexes [M(4)(HL(4))].8H(2)O (1: M = Cu, 2: M = Ni). Employment of a mixture of the two metal salts under otherwise identical reaction conditions leads to the formation of the mixed-metal species [Cu(x)Ni(4-x)(HL)(4)].8H(2)O (x

A Study on the Copper Effect on gold leaching in copper-ethanediamine-thiosulphate solutions

NASA Astrophysics Data System (ADS)

Liu, Qiong; Xiang, Pengzhi; Huang, Yao

2018-01-01

A simple, fast and sensitive square-wave voltammetry (SWV), cyclic voltammetry(CV) and tafel method for the determination of various factors of gold in thiosulphate solution in this paper. We present our study on the effect of copper(II) on the leaching of gold in thiosulphate solutions. The current study aims to establish the interaction of copper in the leaching process by electrochemical method.

Synthesis, crystal structures and antitumor activities of copper(II) complexes with a 2-acetylpyrazine isonicotinoyl hydrazone ligand

NASA Astrophysics Data System (ADS)

Xu, Jun; Zhou, Tao; Xu, Zhou-Qing; Gu, Xin-Nan; Wu, Wei-Na; Chen, Hong; Wang, Yuan; Jia, Lei; Zhu, Tao-Feng; Chen, Ru-Hua

2017-01-01

Five complexes, [Cu(L)2]·4.5H2O (1), [Cu(HL)2](NO3)2·CH3OH (2) {[Cu2(L)2(NO3)(H2O)2]·(NO3)}n (3), [Cu2(HL)2(SO4)2]·2CH3OH (4) and [Cu4(L)4Cl4]·5H2O (5) based on HL (where HL = 2-acetylpyrazine isonicotinoyl hydrazone) have been synthesized and characterized by X-ray diffraction analyses. The counter anion and organic base during the synthesis procedure influence the structures of the complexes efficiently, which generate five complexes as mono-, bi-, tetra-nuclear and one-dimensional structures. The antitumor activities of the complexes 1-5 (except for complex 3 with the poor solubility) against the Patu8988 human pancreatic cancer, ECA109 human esophagus cancer and SGC7901 human gastric cancer cell lines are screened by MTT assay. The results indicate that the chelation of Cu(II) with the ligand is responsible for the observed high cytotoxicity of the copper(II) complexes and the 1:2 copper species 1 and 2 demonstrate lower antitumor activities than that of the 1:1 copper species 4 and 5. In addition, the in vitro apoptosis inducing activity of the copper(II) complex 5 against SGC7901 cell line is determined. And the results show that the complex can bring about apoptosis of the cancerous cells in vitro.

Differential affinity of BsSCO for Cu(II) and Cu(I) suggests a redox role in copper transfer to the Cu(A) center of cytochrome c oxidase.

PubMed

Hill, Bruce C; Andrews, Diann

2012-06-01

SCO (synthesis of cytochrome c oxidase) proteins are involved in the assembly of the respiratory chain enzyme cytochrome c oxidase acting to assist in the assembly of the Cu(A) center contained within subunit II of the oxidase complex. The Cu(A) center receives electrons from the reductive substrate ferrocytochrome c, and passes them on to the cytochrome a center. Cytochrome a feeds electrons to the oxygen reaction site composed of cytochrome a(3) and Cu(B). Cu(A) consists of two copper ions positioned within bonding distance and ligated by two histidine side chains, one methionine, a backbone carbonyl and two bridging cysteine residues. The complex structure and redox capacity of Cu(A) present a potential assembly challenge. SCO proteins are members of the thioredoxin family which led to the early suggestion of a disulfide exchange function for SCO in Cu(A) assembly, whereas the copper binding capacity of the Bacillus subtilis version of SCO (i.e., BsSCO) suggests a direct role for SCO proteins in copper transfer. We have characterized redox and copper exchange properties of apo- and metalated-BsSCO. The release of copper (II) from its complex with BsSCO is best achieved by reducing it to Cu(I). We propose a mechanism involving both disulfide and copper exchange between BsSCO and the apo-Cu(A) site. This article is part of a Special Issue entitled: Biogenesis/Assembly of Respiratory Enzyme Complexes. Copyright © 2011 Elsevier B.V. All rights reserved.

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

ERIC Educational Resources Information Center

Ochiai, Ei-Ichiro

1986-01-01

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

Redox cycling of Cu(II) by 6-mercaptopurine leads to ROS generation and DNA breakage: possible mechanism of anticancer activity.

PubMed

Rehman, Sayeed Ur; Zubair, Haseeb; Sarwar, Tarique; Husain, Mohammed Amir; Ishqi, Hassan Mubarak; Nehar, Shamshun; Tabish, Mohammad

2015-02-01

6-Mercaptopurine (6MP) is a well-known purine antimetabolite used to treat childhood acute lymphoblastic leukemia and other diseases. Cancer cells as compared to normal cells are under increased oxidative stress and show high copper level. These differences between cancer cells and normal cells can be targeted to develop effective cancer therapy. Pro-oxidant property of 6MP in the presence of metal ions is not well documented. Redox cycling of Cu(II) to Cu(I) was found to be efficiently mediated by 6MP. We have performed a series of in vitro experiments to demonstrate the pro-oxidant property of 6MP in the presence of Cu(II). Studies on human lymphocytes confirmed the DNA damaging ability of 6MP in the presence of Cu(II). Since 6MP possesses DNA damaging ability by producing reactive oxygen species (ROS) in the presence of Cu(II), it may also possess apoptosis-inducing activity by involving endogenous copper ions. Essentially, this would be an alternative and copper-dependent pathway for anticancer activity of 6MP.

Copper(II) catalysis in cyanide conversion into ethyl carbamate in spirits and relevant reactions.

PubMed

Aresta, M; Boscolo, M; Franco, D W

2001-06-01

The role of copper(II) species in the oxidation of inorganic cyanide to cyanate and in the conversion of cyanate or urea into ethyl carbamate was investigated. The oxidation process has been shown to be independent from the dissolved oxygen. Elemental analysis and infrared spectroscopy have shown the formation of a mixed copper carbonate/hydroxide in the process of oxidation of cyanide to cyanate in water/ethanol. The complexation to Cu(II) of cyanate formed upon cyanide oxidation makes the former more susceptible to nucleophilic attack from ethanol, with conversion into ethyl carbamate. Comparatively, urea has a minor role with respect to cyanide in the formation of ethyl carbamate. Therefore, the urea present in some samples of Brazilian sugar cane spirit (cachaça) has been shown to have almost no influence on the ethyl carbamate content of cachaças, which comes essentially from cyanide. Fe(II,III) affords results similar to those found with Cu(II). Some suggestions are presented to avoid ethyl carbamate formation in spirits during distillation.

Cu(I)/Cu(II) mixed-valence surface complexes of S-[(2-hydroxyamino)-2-oxoethyl]-N,N-dibutyldithiocarbamate: Hydrophobic mechanism to malachite flotation.

PubMed

Liu, Sheng; Zhong, Hong; Liu, Guangyi; Xu, Zhenghe

2018-02-15

Hydroxamate and sulfhydryl surfactants are effective collectors for flotation of copper minerals. The combination application of hydroxamate and sulfhydryl collectors has been proved to be an effective approach for improving the flotation recovery of non-sulfide copper minerals. A surfactant owing both hydroxamate and dithiocarbamate groups might exhibit strong affinity to non-sulfide copper minerals through double sites adsorption, rendering an enhanced hydrophobization to non-sulfide copper minerals flotation. The flotation performance of S-[(2-hydroxyamino)-2-oxoethyl]- N,N-dibutyldithiocarbamate (HABTC) to malachite, calcite and quartz were first evaluated through systematic micro-flotation experiments. HABTC's hydrophobic mechanism to malachite was further investigated and analyzed by zeta potential, Fourier transform infrared spectroscopy (FTIR), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS). The micro-flotation results demonstrated HABTC was an excellent collector for malachite flotation and exhibited favorable selectivity for flotation separation of malachite from quartz or calcite under pH 8.5-10.3. Zeta potential and FTIR implied that HABTC might bond with the surface copper atoms of malachite, with releasing the H + ions of its hydroxamate group into pulp. ToF-SIMS provided clear evidences that the Cu-hydroxamate and Cu-dithiocarbamate groups were formed on malachite surfaces after HABTC adsorption. XPS revealed that Cu(I)/Cu(II) mixed-valence surface complexes of HABTC anchored on malachite through formation of Cu(I)S and Cu(II)O bonds, accompanying with reduction of partial surface Cu(II) to Cu(I). The Cu(I)/Cu(II) mixed-valence double chelating character and "chair"-shape N,N-dibutyldithiocarbamate hydrophobic group, resulting in an enhanced affinity and hydrophobization of HABTC to malachite flotation. Copyright © 2017 Elsevier Inc. All rights reserved.

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

PubMed

Gardberg, A S; Ibers, J A

2001-05-01

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

Forms of adsorption and transition states of oxidation of carbon monoxide by molecular oxygen and dissociation of nitrogen monooxide, catalyzed by monovalent copper

NASA Astrophysics Data System (ADS)

Ermakov, A. I.; Mashutin, V. Y.; Vishnjakov, A. V.

With the help of the results of semiempirical (parametric method 3) and ab initio (second-order Møller-Plesset [MP2] unrestricted Hartree-Fock [UHF] 6-31G**, unrestricted density functional theory [UDFT] 6-31G** Becke's three-parameter exchange functional and the gradient-corrected functional of Lee, Yang, and Paar [B3LYP] and UDFT LANL2DZ B3LYP) quantum-chemical calculations has been studied the complexation CO and NO with molecular hydroxide of copper(I). The influence of charge defects has been simulated by the calculations of anionic, neutral, and cationic systems. It is shown that CO and NO are mainly coordinated by nonoxygen atom on an atom of copper(I) hydroxide as one- and two-center forms. These forms are suitable for appearance of prereactionary complexes of catalytic oxidation CO by molecular oxygen and decomposition NO into atoms of nitrogen and oxygen. The corresponding prereactionary complexes for systems with participation of copper(II) hydroxide and copper(III) hydroxide are not revealed. The calculations predict inhibiting impact of copper(II) and copper(III) of the observed reactions. Computed stability of complexes CO and NO with copper(I) hydroxide and activation energy of catalytic conversion of monooxides essentially depend on an excessive charge of the system. Introduction of electron-donating additives into copper(I) hydroxide promotes rise of catalytic activity of copper(I) compound.

Functionalized mesoporous silica supported copper(II) and nickel(II) catalysts for liquid phase oxidation of olefins.

PubMed

Nandi, Mahasweta; Roy, Partha; Uyama, Hiroshi; Bhaumik, Asim

2011-12-14

Highly ordered 2D-hexagonal mesoporous silica has been functionalized with 3-aminopropyltriethoxysilane (3-APTES). This is followed by its condensation with a dialdehyde, 4-methyl-2,6-diformylphenol to produce an immobilized Schiff-base ligand (I). This material is separately treated with methanolic solution of copper(II) chloride and nickel(II) chloride to obtain copper and nickel anchored mesoporous materials, designated as Cu-AMM and Ni-AMM, respectively. The materials have been characterized by Fourier transform infrared (FT-IR) and UV-vis diffuse reflectance (DRS) spectroscopy, powder X-ray diffraction (XRD), transmission electron microscopy (TEM), N(2) adsorption-desorption studies and (13)C CP MAS NMR spectroscopy. The metal-grafted mesoporous materials have been used as catalysts for the efficient and selective epoxidation of alkenes, viz. cyclohexene, trans-stilbene, styrene, α-methyl styrene, cyclooctene and norbornene to their corresponding epoxides in the presence of tert-butyl hydroperoxide (TBHP) as the oxidant under mild liquid phase conditions.

A novel asymmetric chair-like hydroxyl-bridged tetra-copper compound: Synthesis, supramolecular structure and magnetic property

NASA Astrophysics Data System (ADS)

Wang, Xiao-Feng; Du, Ke-Jie; Wang, Hong-Qing; Zhang, Xue-Li; Nie, Chang-Ming

2017-06-01

A new polynuclear Cu(II) compound, [Cu4(bpy)4(OH)4(H2O)(BTC)]NO3·8H2O (1), was prepared by self-assembly from the solution of copper(II) nitrate and two kinds of ligands, 2,2‧-bipyridine (bpy) and benzene-tricarboxylic acid (H3BTC). Single crystal structure analysis reveals that 1 features a rare asymmetric chair-like hydroxyl-bridged tetra-copper cluster: [Cu4(OH)4] core along with one H2O and one BTC3- occupied each terminal coordinated site. In addition, the magnetic property has been investigated.

Pharmacological Role of Anions (Sulphate, Nitrate, Oxalate and Acetate) on the Antibacterial Activity of Cobalt(II), Copper(II) and Nickel(II) Complexes With Nicotinoylhydrazine-Derived ONO, NNO and SNO Ligands

PubMed Central

Rauf, Abdur

1996-01-01

Mixed ligands biologically active complexes of cobalt(II), copper(II) and nickel(II) with nicotinoylhydrazine-derived ONO, NNO and SNO donor schiff-base ligands having the same metal ion but different anions such as sulphate, nitrate, oxalate and acetate have been synthesised and characterised on the basis of their physical, analytical and spectral data. In order to evaluate the role of anions on their bioability, these ligands and their synthesised metal complexes with various anions have been screened against bacterial species such as Escherichia coli, Pseudomonas aeruginosa and Staphylococcus aureus and the title studies have proved a definative role of anions in increasing the biological activity PMID:18472896

Copper(II)-rubeanic acid coprecipitation system for separation-preconcentration of trace metal ions in environmental samples for their flame atomic absorption spectrometric determinations.

PubMed

Soylak, Mustafa; Erdogan, Nilgun D

2006-09-21

A simple and facile preconcentration procedure based on the coprecipitation of trace heavy metal ions with copper(II)-rubeanic acid complex has been developed. The analytical parameters including pH, amounts of rubeanic acid, sample volume, etc. was investigated for the quantitative recoveries of Pb(II), Fe(III), Cd(II), Au(III), Pd(II) and Ni(II). No interferic effects were observed from the concomitant ions. The detection limits for analyte ions by 3 sigma were in the range of 0.14 microg/l for iron-3.4 microg/l for lead. The proposed coprecipitation method was successfully applied to water samples from Palas Lake-Kayseri, soil and sediment samples from Kayseri and Yozgat-Turkey.

Copper(II) Thiosemicarbazone Complexes and Their Proligands upon UVA Irradiation: An EPR and Spectrophotometric Steady-State Study.

PubMed

Hricovíni, Michal; Mazúr, Milan; Sîrbu, Angela; Palamarciuc, Oleg; Arion, Vladimir B; Brezová, Vlasta

2018-03-21

X- and Q-band electron paramagnetic resonance (EPR) spectroscopy was used to characterize polycrystalline Cu(II) complexes that contained sodium 5-sulfonate salicylaldehyde thiosemicarbazones possessing a hydrogen, methyl, ethyl, or phenyl substituent at the terminal nitrogen. The ability of thiosemicarbazone proligands to generate superoxide radical anions and hydroxyl radicals upon their exposure to UVA irradiation in aerated aqueous solutions was evidenced by the EPR spin trapping technique. The UVA irradiation of proligands in neutral or alkaline solutions and dimethylsulfoxide (DMSO) caused a significant decrease in the absorption bands of aldimine and phenolic chromophores. Mixing of proligand solutions with the equimolar amount of copper(II) ions resulted in the formation of 1:1 Cu(II)-to-ligand complex, with the EPR and UV-Vis spectra fully compatible with those obtained for the dissolved Cu(II) thiosemicarbazone complexes. The formation of the complexes fully inhibited the photoinduced generation of reactive oxygen species, and only subtle changes were found in the electronic absorption spectra of the complexes in aqueous and DMSO solutions upon UVA steady-state irradiation. The dark redox activity of copper(II) complexes and proligand/Cu(II) aqueous solutions towards hydrogen peroxide which resulted in the generation of hydroxyl radicals, was confirmed by spin trapping experiments.

Aqueous aerobic oxidation of alkyl arenes and alcohols catalyzed by copper(II) phthalocyanine supported on three-dimensional nitrogen-doped graphene at room temperature.

PubMed

Mahyari, Mojtaba; Laeini, Mohammad Sadegh; Shaabani, Ahmad

2014-07-25

Copper(ii) tetrasulfophthalocyanine supported on three-dimensional nitrogen-doped graphene-based frameworks was synthesized and introduced as a bifunctional catalyst for selective aerobic oxidation of alkyl arenes and alcohols to the corresponding carbonyl compounds. The ease of catalyst separation, high turnover, low catalyst loading and recyclability could potentially render it applicable in industrial setting.

Potentiometric and DFT studies of Cu(II) complexes with glycylglycine and methionine of interest for the brain chemistry

NASA Astrophysics Data System (ADS)

Vilhena, Felipe S.; Felcman, Judith; Szpoganicz, Bruno; Miranda, Fabio S.

2017-01-01

A large number of copper (II) complexes have been used as mimetic models for metalloproteins and metalloenzymes. Due to the lack of structural information about copper (II) complexes in aqueous solution, the coordination environment of this metal is not well established. In this work, pKa values of the complexes in the Cu:GlyGly, Cu:Met and Cu:GlyGly:Met systems were calculated by potentiometric titration at 25 °C and ionic strength of 0.1 mol L-1. The coordination modes of the ligands were explored for the main hydrolytic species throught RI-PBE/def2-SVP/COSMO level. In the Cu:GlyGly system, DFT results indicated that the NamineNpept coordination of dipeptide is 2.1 kcal mol-1 more stable than the tridentate NamineNpeptOcarboxy coordination moiety. The deprotonation of the peptide nitrogen is 13.7 kcal mol-1 more favorable than the hydrolysis of the water molecule coordinated to the metal. In the Cu:GlyGly:Met system, the sulfur atom does not belong to the copper (II) coordination sphere. Once the copper ion is incorporated into peptides, another ligand as methionine could bind to this system and carry an antioxidant site to different brain regions.

LC-MS based metabolomics and chemometrics study of the toxic effects of copper on Saccharomyces cerevisiae.

PubMed

Farrés, Mireia; Piña, Benjamí; Tauler, Romà

2016-08-01

Copper containing fungicides are used to protect vineyards from fungal infections. Higher residues of copper in grapes at toxic concentrations are potentially toxic and affect the microorganisms living in vineyards, such as Saccharomyces cerevisiae. In this study, the response of the metabolic profiles of S. cerevisiae at different concentrations of copper sulphate (control, 1 mM, 3 mM and 6 mM) was analysed by liquid chromatography coupled to mass spectrometry (LC-MS) and multivariate curve resolution-alternating least squares (MCR-ALS) using an untargeted metabolomics approach. Peak areas of the MCR-ALS resolved elution profiles in control and in Cu(ii)-treated samples were compared using partial least squares regression (PLSR) and PLS-discriminant analysis (PLS-DA), and the intracellular metabolites best contributing to sample discrimination were selected and identified. Fourteen metabolites showed significant concentration changes upon Cu(ii) exposure, following a dose-response effect. The observed changes were consistent with the expected effects of Cu(ii) toxicity, including oxidative stress and DNA damage. This research confirmed that LC-MS based metabolomics coupled to chemometric methods are a powerful approach for discerning metabolomics changes in S. cerevisiae and for elucidating modes of toxicity of environmental stressors, including heavy metals like Cu(ii).

Pyrrolidine and Piperidine Formation Via Copper(II) Carboxylate Promoted Intramolecular Carboamination of Unactivated Olefins: Diastereoselectivity and Mechanism

PubMed Central

Sherman, Eric S.; Fuller, Peter H.; Kasi, Dhanalakshmi; Chemler, Sherry R.

2008-01-01

An expanded substrate scope and in depth analysis of the reaction mechanism of the copper(II) carboxylate promoted intramolecular carboamination of unactivated alkenes is described. This method provides access to N-functionalized pyrrolidines and piperidines. Both aromatic and aliphatic γ- and δ-alkenyl N-arylsulfonamides undergo the oxidative cyclization reaction efficiently. N-Benzoyl-2-allylaniline also underwent the oxidative cyclization. The terminal olefin substrates examined were more reactive than those with internal olefins, and the latter terminated in elimination rather than carbon-carbon bond formation. The efficiency of the reaction was enhanced by the use of more organic soluble copper(II) carboxylate salts, copper(II) neodecanoate in particular. The reaction times were reduced by the use of microwave heating. High levels of diastereoselectivity were observed in the synthesis of 2,5-disubstituted pyrrolidines, wherein the cis substitution pattern predominates. The mechanism of the reaction is discussed in the context of the observed reactivity and in comparison to analogous reactions promoted by other reagents and conditions. Our evidence supports a mechanism wherein the N-C bond is formed via intramolecular syn aminocupration and the C-C bond is formed via intramolecular addition of a primary carbon radical to an aromatic ring. PMID:17428100

5-Nitroimidazole-derived Schiff bases and their copper(II) complexes exhibit potent antimicrobial activity against pathogenic anaerobic bacteria.

PubMed

Oliveira, Alexandre A; Oliveira, Ana P A; Franco, Lucas L; Ferencs, Micael O; Ferreira, João F G; Bachi, Sofia M P S; Speziali, Nivaldo L; Farias, Luiz M; Magalhães, Paula P; Beraldo, Heloisa

2018-05-07

In the present work a family of novel secnidazole-derived Schiff base compounds and their copper(II) complexes were synthesized. The antimicrobial activities of the compounds were evaluated against clinically important anaerobic bacterial strains. The compounds exhibited in vitro antibacterial activity against Bacteroides fragilis, Bacteroides thetaiotaomicron, Bacteroides vulgatus, Bacteroides ovatus, Parabacteroides distasonis and Fusubacterium nucleatum pathogenic anaerobic bacteria. Upon coordination to copper(II) the antibacterial activity significantly increased in several cases. Some derivatives were even more active than the antimicrobial drugs secnidazole and metronidazole. Therefore, the compounds under study are suitable for in vivo evaluation and the microorganisms should be classified as susceptible to them. Electrochemical studies on the reduction of the nitro group revealed that the compounds show comparable reduction potentials, which are in the same range of the bio-reducible drugs secnidazole and benznidazole. The nitro group reduction potential is more favorable for the copper(II) complexes than for the starting ligands. Hence, the antimicrobial activities of the compounds under study might in part be related to intracellular bio-reduction activation. Considering the increasing resistance rates of anaerobic bacteria against a wide range of antimicrobial drugs, the present work constitutes an important contribution to the development of new antibacterial drug candidates.

Adsorption kinetic and desorption studies of Cu2+ on Multi-Carboxylic-Functionalized Silica Gel

NASA Astrophysics Data System (ADS)

Li, Min; Meng, Xiaojing; Liu, Yushuang; Hu, Xinju; Liang, Xiuke

2018-01-01

In the present study, the adsorption behavior of copper (II) ion from aqueous solution onto multi-carboxylic-functionalized silica gel (SG-MCF) has been investigated in detail by means of batch and column experiments. Batch experiments were performed to evaluate the effects of contact time on adsorption capacity of copper (II) ion. The kinetic data were analyzed on the basis of the pseudo-first-order kinetic and the pseudo-second-order kinetic models and consequently, the pseudo-second-order kinetic can better describe the adsorption process than the pseudo-first-order kinetic model. And the adsorption mechanism of the process was studied by intra-particle and film diffusion, it was found out that the adsorption rate was governed primarily by film diffusion to the adsorption onto the SG-MCF. In addition, column experiments were conducted to assess the effects initial inlet concentration and the flow rate on breakthrough time and adsorption capacity ascertaining the practical applicability of the adsorbent. The results suggest that the total amount of adsorbed copper (II) ion increased with declined flow rate and increased the inlet concentration. The adsorption-desorption experiment confirmed that adsorption capacity of copper (II) ion didn’t present an obvious decrease after five cycles.

Structural characterization of two solvates of a luminescent copper(II) bis­(pyridine)-substituted benzimidazole complex

PubMed Central

DeStefano, Matthew R.; Lewis, Robert A.

2017-01-01

Copper(II) complexes of benzimidazole are known to exhibit biological activity that makes them of inter­est for chemotherapeutic and other pharmaceutical uses. The complex bis­(acetato-κO){5,6-dimethyl-2-(pyridin-2-yl)-1-[(pyridin-2-yl)meth­yl]-1H-benzimidazole-κ2 N 2,N 3}copper(II), has been prepared. The absorption spectrum has features attributed to intra­ligand and ligand-field transitions and the complex exhibits ligand-centered room-temperature luminescence in solution. The aceto­nitrile monosolvate, [Cu(C2H3O2)2(C20H18N4)]·C2H3N (1), and the ethanol hemisolvate, [Cu(C2H3O2)2(C20H18N4)]·0.5C2H6O (2), have been structurally characterized. Compound 2 has two copper(II) complexes in the asymmetric unit. In both 1 and 2, distorted square-planar N2O2 coordination geometries are observed and the Cu—N(Im) bond distance is slightly shorter than the Cu—N(py) bond distance. Inter­molecular π–π inter­actions are found in 1 and 2. A weak C—H⋯π inter­action is observed in 1. PMID:29152336

Synthesis of novel coumarin nucleus-based DPA drug-like molecular entity: In vitro DNA/Cu(II) binding, DNA cleavage and pro-oxidant mechanism for anticancer action

PubMed Central

Khan, Saman; Malla, Ali Mohammed; Zafar, Atif

2017-01-01

Despite substantial research on cancer therapeutics, systemic toxicity and drug-resistance limits the clinical application of many drugs like cisplatin. Therefore, new chemotherapeutic strategies against different malignancies are needed. Targeted cancer therapy is a new paradigm for cancer therapeutics which targets pathways or chemical entities specific to cancer cells than normal ones. Unlike normal cells, cancer cells contain elevated copper which plays an integral role in angiogenesis. Copper is an important metal ion associated with chromatin DNA, particularly with guanine. Thus, targeting copper via copper-specific chelators in cancer cells can serve as an effective anticancer strategy. New pharmacophore di(2-picolyl)amine (DPA)-3(bromoacetyl) coumarin (ligand-L) was synthesized and characterized by IR, ESI-MS, 1H- and 13C-NMR. Binding ability of ligand-L to DNA/Cu(II) was evaluated using a plethora of biophysical techniques which revealed ligand-L-DNA and ligand-L-Cu(II) interaction. Competitive displacement assay and docking confirmed non-intercalative binding mode of ligand-L with ctDNA. Cyclic voltammetry confirmed ligand-L causes quasi reversible Cu(II)/Cu(I) conversion. Further, acute toxicity studies revealed no toxic effects of ligand-L on mice. To evaluate the chemotherapeutic potential and anticancer mechanism of ligand-L, DNA damage via pBR322 cleavage assay and reactive oxygen species (ROS) generation were studied. Results demonstrate that ligand-L causes DNA cleavage involving ROS generation in the presence of Cu(II). In conclusion, ligand-L causes redox cycling of Cu(II) to generate ROS which leads to oxidative DNA damage and pro-oxidant cancer cell death. These findings will establish ligand-L as a lead molecule to synthesize new molecules with better copper chelating and pro-oxidant properties against different malignancies. PMID:28763458

Neutron and Atomic Resolution X-ray Structures of a Lytic Polysaccharide Monooxygenase Reveal Copper-Mediated Dioxygen Binding and Evidence for N-Terminal Deprotonation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bacik, John-Paul; Mekasha, Sophanit; Forsberg, Zarah

A 1.1 Å resolution, room-temperature X-ray structure and a 2.1 Å resolution neutron structure of a chitin-degrading lytic polysaccharide monooxygenase domain from the bacterium Jonesia denitrificans (JdLPMO10A) show a putative dioxygen species equatorially bound to the active site copper. We found that both structures show an elongated density for the dioxygen, most consistent with a Cu(II)-bound peroxide. The coordination environment is consistent with Cu(II). Furthermore, in the neutron and X-ray structures, difference maps reveal the N-terminal amino group, involved in copper coordination, is present as a mixed ND 2 and ND –, suggesting a role for the copper ion inmore » shifting the pK a of the amino terminus.« less

Toxicities of triclosan, phenol, and copper sulfate in activated sludge.

PubMed

Neumegen, Rosalind A; Fernández-Alba, Amadeo R; Chisti, Yusuf

2005-04-01

The effect of toxicants on the BOD degradation rate constant was used to quantitatively establish the toxicity of triclosan, phenol, and copper (II) against activated sludge microorganisms. Toxicities were tested over the following ranges of concentrations: 0-450 mg/L for phenol, 0-2 mg/L for triclosan, and 0-35 mg/L for copper sulfate (pentahydrate). According to the EC(50) values, triclosan was the most toxic compound tested (EC(50) = 1.82 +/- 0.1 mg/L), copper (II) had intermediate toxicity (EC(50) = 18.3 +/- 0.37 mg/L), and phenol was the least toxic (EC(50) = 270 +/- 0.26 mg/L). The presence of 0.2% DMSO had no toxic effect on the activated sludge. The toxicity evaluation method used was simple, reproducible, and directly relevant to activated sludge wastewater treatment processes.

Neutron and Atomic Resolution X-ray Structures of a Lytic Polysaccharide Monooxygenase Reveal Copper-Mediated Dioxygen Binding and Evidence for N-Terminal Deprotonation

DOE PAGES

Bacik, John-Paul; Mekasha, Sophanit; Forsberg, Zarah; ...

2017-05-08

A 1.1 Å resolution, room-temperature X-ray structure and a 2.1 Å resolution neutron structure of a chitin-degrading lytic polysaccharide monooxygenase domain from the bacterium Jonesia denitrificans (JdLPMO10A) show a putative dioxygen species equatorially bound to the active site copper. We found that both structures show an elongated density for the dioxygen, most consistent with a Cu(II)-bound peroxide. The coordination environment is consistent with Cu(II). Furthermore, in the neutron and X-ray structures, difference maps reveal the N-terminal amino group, involved in copper coordination, is present as a mixed ND 2 and ND –, suggesting a role for the copper ion inmore » shifting the pK a of the amino terminus.« less

Cyclam Derivatives with a Bis(phosphinate) or a Phosphinato-Phosphonate Pendant Arm: Ligands for Fast and Efficient Copper(II) Complexation for Nuclear Medical Applications.

PubMed

David, Tomáš; Kubíček, Vojtěch; Gutten, Ondrej; Lubal, Přemysl; Kotek, Jan; Pietzsch, Hans-Jürgen; Rulíšek, Lubomír; Hermann, Petr

2015-12-21

Cyclam derivatives bearing one geminal bis(phosphinic acid), -CH2PO2HCH2PO2H2 (H2L(1)), or phosphinic-phosphonic acid, -CH2PO2HCH2PO3H2 (H3L(2)), pendant arm were synthesized and studied as potential copper(II) chelators for nuclear medical applications. The ligands showed good selectivity for copper(II) over zinc(II) and nickel(II) ions (log KCuL = 25.8 and 27.7 for H2L(1) and H3L(2), respectively). Kinetic study revealed an unusual three-step complex formation mechanism. The initial equilibrium step leads to out-of-cage complexes with Cu(2+) bound by the phosphorus-containing pendant arm. These species quickly rearrange to an in-cage complex with cyclam conformation II, which isomerizes to another in-cage complex with cyclam conformation I. The first in-cage complex is quantitatively formed in seconds (pH ≈5, 25 °C, Cu:L = 1:1, cM ≈ 1 mM). At pH >12, I isomers undergo nitrogen atom inversion, leading to III isomers; the structure of the III-[Cu(HL(2))] complex in the solid state was confirmed by X-ray diffraction analysis. In an alkaline solution, interconversion of the I and III isomers is mutual, leading to the same equilibrium isomeric mixture; such behavior has been observed here for the first time for copper(II) complexes of cyclam derivatives. Quantum-chemical calculations showed small energetic differences between the isomeric complexes of H3L(2) compared with analogous data for isomeric complexes of cyclam derivatives with one or two methylphosphonic acid pendant arm(s). Acid-assisted dissociation proved the kinetic inertness of the complexes. Preliminary radiolabeling of H2L(1) and H3L(2) with (64)Cu was fast and efficient, even at room temperature, giving specific activities of around 70 GBq of (64)Cu per 1 μmol of the ligand (pH 6.2, 10 min, ca. 90 equiv of the ligand). These specific activities were much higher than those of H3nota and H4dota complexes prepared under identical conditions. The rare combination of simple ligand synthesis, very fast copper(II) complex formation, high thermodynamic stability, kinetic inertness, efficient radiolabeling, and expected low bone tissue affinity makes such ligands suitably predisposed to serve as chelators of copper radioisotopes in nuclear medicine.

Synthesis, spectral, thermal and antimicrobial studies on cobalt(II), nickel(II), copper(II), zinc(II) and palladium(II) complexes containing thiosemicarbazone ligand

NASA Astrophysics Data System (ADS)

El-Sawaf, Ayman K.; El-Essawy, Farag; Nassar, Amal A.; El-Samanody, El-Sayed A.

2018-04-01

The coordination characteristic of new N4-morpholinyl isatin-3-thiosemicarbazone (HL) towards Co(II), Ni(II), Cu(II), Zn(II) and Pd(II) has been studies. The structures of the complexes were described by elemental analyses, molar conductivity, magnetic, thermal and spectral (IR, UV-Vis, 1H and 13C NMR and ESR) studies. On the basis of analytical and spectral studies the ligand behaves as monobasic tridentate ONS donor forming two five membered rings towards cobalt, copper and palladium and afforded complexes of the kind [M(L)X], (Mdbnd Co, Cu or Pd; Xdbnd Cl, Br or OAc). Whereas the ligand bound to NiCl2 as neutral tridentate ONS donor and with ZnCl2 as neutral bidentate NS donor. The newly synthesized thiosemicarbazone ligand and some of its complexes were examined for antimicrobial activity against 2 gram negative bacterial strains (Escherichia coli Pseudomonas and aeruginosa), 2 gram positive bacterial strains (Streptococcus pneumoniae and Staphylococcus aureus)} and two Pathogenic fungi (Aspergillus fumigatus and Candida albicans). All metal complexes possess higher antimicrobial activity comparing with the free thiosemicarbazone ligand. The high potent activities of the complexes may arise from the coordination and chelation, which tends to make metal complexes act as more controlling and potent antimicrobial agents, thus hindering the growing of the microorganisms. The antimicrobial results also show that copper bromide complex is better antimicrobial agent as compared to the Schiff base and its metal complexes.

Copper-promoted sulfenylation of sp2 C-H bonds.

PubMed

Tran, Ly Dieu; Popov, Ilya; Daugulis, Olafs

2012-11-07

An auxiliary-assisted, copper catalyzed or promoted sulfenylation of benzoic acid derivative β-C-H bonds and benzylamine derivative γ-C-H bonds has been developed. The method employs disulfide reagents, copper(II) acetate, and DMSO solvent at 90-130 °C. Application of this methodology to the direct trifluoromethylsulfenylation of C-H bonds was demonstrated.

Theoretical study on ultrafast intersystem crossing of chromium(III) acetylacetonate

NASA Astrophysics Data System (ADS)

Ando, Hideo; Iuchi, Satoru; Sato, Hirofumi

2012-05-01

In the relaxation process from the 4T2g state of chromium(III) acetylacetonate, CrIII(acac)3, ultrafast intersystem crossing (ISC) competes with vibrational relaxation (VR). This contradicts the conventional cascade model, where ISC rates are slower than VR ones. We hence investigate the relaxation process with quantum chemical calculations and excited-state wavepacket simulations to obtain clues about the origins of the ultrafast ISC. It is found that a potential energy curve of the 4T2g state crosses those of the 2T1g states near the Franck-Condon region and their spin-orbit couplings are strong. Consequently, ultrafast ISC between these states is observed in the wavepacket simulation.

Steric Effects on the Binding of Phosphate and Polyphosphate Anions by Zinc(II) and Copper(II) Dinuclear Complexes of m-Xylyl-bis-cyclen.

PubMed

Esteves, Catarina V; Esteban-Gómez, David; Platas-Iglesias, Carlos; Tripier, Raphaël; Delgado, Rita

2018-05-11

The triethylbenzene-bis-cyclen (cyclen = 1,4,7,10-tetraazacyclododecane) compound (tbmce) was designed with an imposed structural rigidity at the m-xylyl spacer to be compared to a less restrained and known parent compound (bmce). The framework of both compounds differs only in the substituents of the m-xylyl spacer. The study was centered in the differences observed in the acid-base reactions of both compounds, their copper(II) and zinc(II) complexation behaviors, as well as in the uptake of phosphate and polyphosphate anions (HPPi 3- , ATP 4- , ADP 3- , AMP 2- , PhPO 4 2- , and HPO 4 2- ). On the one hand, the acid-base reactions showed lower values for the third and fourth protonation constants of tbmce than for bmce, suggesting that the ethyl groups of the spacer in tbmce force the two cyclen units to more conformational restricted positions. On the other hand, the stability constant values for copper(II) and zinc(II) complexes revealed that bmce is a better chelator than tbmce pointing out to additional conformational restraints imposed by the triethylbenzene spacer. The binding studies of phosphates by the dinuclear copper(II) and zinc(II) complexes showed much smaller effective association constants for the dicopper complexes. Single-crystal X-ray and computational (density functional theory) studies suggest that anion binding promotes the formation of tetranuclear entities in which anions are bridging the metal centers. Our studies also revealed the dinuclear zinc(II) complex of bmce as a promising receptor for phosphate anions, with the largest effective association constant of 5.94 log units being observed for the formation of [Zn 2 bmce(HPPi)] + . Accordingly, a colorimetric study via an indicator displacement assay to detect phosphates in aqueous solution found that the [Zn 2 bmce] 4+ complex acts as the best receptor for pyrophosphate displaying a detection limit of 2.5 nM by changes visible to naked eye.

Effects of copper-oxide nanoparticles, dissolved copper and ultraviolet radiation on copper bioaccumulation, photosynthesis and oxidative stress in the aquatic macrophyte Elodea nuttallii.

PubMed

Regier, Nicole; Cosio, Claudia; von Moos, Nadia; Slaveykova, Vera I

2015-06-01

In this study, the uptake and sub-toxic effects of CuO nanoparticles (CuO-NPs), dissolved Cu(II) alone or in combination with UV radiation on the aquatic macrophyte Elodea nuttallii were studied. Emphasis was on Cu accumulation, growth, photosynthesis and the oxidative stress related enzymes peroxidase (POD) and superoxide dismutase (SOD). The results showed stronger Cu accumulation in plants exposed to 10 mg L(-1) CuO-NPs, corresponding to 1.4-2 mg L(-1) dissolved Cu(II), than to 256 μg L(-1) Cu(II). However, the ratio between the accumulated Cu and dissolved Cu in CuO treatments was lower than in Cu(II) treatments. Additional UV exposure increased accumulation in both treatments, with the effect being stronger for Cu accumulation from CuO-NPs than for dissolved Cu(II). Photosynthetic capacity was strongly reduced by UV treatment, whereas remained unaffected by Cu(II) or CuO-NP treatments. Similarly, the increase of SOD activity was more pronounced in the UV treatments. On the other hand, POD activity enhancement was strongest in the plants exposed to CuO-NPs for 24 h. Expression of the copper transporter COPT1 as revealed by RT-qPCR was inhibited by Cu(II) and CuO-NP treatment, limiting the uptake of excess Cu into the cells. Overall, the combined exposure of E. nuttallii to UV radiation with CuO-NPs or Cu(II) has a higher impact than exposure to CuO-NPs or Cu(II) alone. The results imply that heavy pollution of natural water with CuO-NPs or dissolved Cu might have stronger effects in combination with natural UV irradiation on organisms in situ. Copyright © 2015 Elsevier Ltd. All rights reserved.

Synthesis and spectral characterization of mono- and binuclear copper(II) complexes derived from 2-benzoylpyridine-N4-methyl-3-thiosemicarbazone: Crystal structure of a novel sulfur bridged copper(II) box-dimer

NASA Astrophysics Data System (ADS)

Jayakumar, K.; Sithambaresan, M.; Aiswarya, N.; Kurup, M. R. Prathapachandra

2015-03-01

Mononuclear and binuclear copper(II) complexes of 2-benzoylpyridine-N4-methyl thiosemicarbazone (HL) were prepared and characterized by a variety of spectroscopic techniques. Structural evidence for the novel sulfur bridged copper(II) iodo binuclear complex is obtained by single crystal X-ray diffraction analysis. The complex [Cu2L2I2], a non-centrosymmetric box dimer, crystallizes in monoclinic C2/c space group and it was found to have distorted square pyramidal geometry (Addison parameter, τ = 0.238) with the square basal plane occupied by the thiosemicarbazone moiety and iodine atom whereas the sulfur atom from the other coordinated thiosemicarbazone moiety occupies the apical position. This is the first crystallographically studied system having non-centrosymmetrical entities bridged via thiolate S atoms with Cu(II)sbnd I bond. The tridentate thiosemicarbazone coordinates in mono deprotonated thionic tautomeric form in all complexes except in sulfato complex, [Cu(HL)(SO4)]·H2O (1) where it binds to the metal centre in neutral form. The magnetic moment values and the EPR spectral studies reflect the binuclearity of some of the complexes. The spin Hamiltonian and bonding parameters are calculated based on EPR studies. In all the complexes g|| > g⊥ > 2.0023 and the g values in frozen DMF are consistent with the dx2-y2 ground state. The thermal stabilities of some of the complexes were also determined.

Biosorption of Copper (II) from Aqueous Solution Using Non-Living Mesorhizobium amorphae Strain CCNWGS0123

PubMed Central

Mohamad, Osama Abdalla; Hao, Xiuli; Xie, Pin; Hatab, Shaimaa; Lin, Yanbing; Wei, Gehong

2012-01-01

The mining industry generates huge amounts of wastewater, containing toxic heavy metals. Treatment to remove heavy metals is necessary and recent work has been focused on finding more environmentally friendly materials for removing heavy metals from wastewater. Biosorption can be an effective process for heavy metal removal from aqueous solutions. Our objectives were to investigate the removal of copper (II) from aqueous solutions using dead cells of Mesorhizobium amorphae CCNWGS0123 under differing levels of pH, agitation speed, temperature, initial copper concentration, biosorbent dose and contact time using flame atomic absorption spectroscopy for metal estimation. The maximum copper removal rate was achieved at pH 5.0, agitation speed 150×g, temperature 28°C and initial Cu (II) concentration of 100 mg L−1. Maximum biosorption capacity was at 0.5 g L−1 and equilibrium was attained within 30 min. Langmuir and Freundlich isotherms showed correlation coefficients of 0.958 and 0.934, respectively. Fourier transform-infrared spectroscopy (FT-IR) analysis indicated that many functional groups, such as O-H, N-H, C-H, C=O, -NH, -CN, C-N, C-O, amide -I, -II, -III and unsaturated alkenes, alkyls and aromatic groups on the cell surface were involved in the interaction between CCNWGS0123 and Cu. Scanning electron microscope and energy dispersive X-ray scanning results showed deformation, aggregation, and cell-surface damage due to the precipitation of copper on the cell surface. Dead cells of CCNWGS0123 showed potential as an efficient biosorbent for the removal of Cu2+ from aqueous solutions. PMID:22353770

Fabrication of flower-like micro/nano dual scale structured copper oxide surfaces: Optimization of self-cleaning properties via Taguchi design

NASA Astrophysics Data System (ADS)

Moosavi, Saeideh Sadat; Norouzbeigi, Reza; Velayi, Elmira

2017-11-01

In the present work, copper oxide superhydrophobic surface is fabricated on a copper foil via the chemical bath deposition (CBD) method. The effects of some influential factors such as initial concentrations of Cu (II) ions and the surface energy modifier, solution pH, reaction and modification steps time on the wettability property of copper oxide surface were evaluated using Taguchi L16 experimental design. Results showed that the initial concentration of Cu (II) has the most significant impact on the water contact angle and wettability characteristics. The XRD, SEM, AFM and FTIR analyses were used to characterize the copper oxide surfaces. The Water contact angle (WCA) and contact angle hysteresis (CAH) were also measured. The SEM results indicated the formation of a flower-like micro/nano dual-scale structure of copper oxide on the substrate. This structure composed of numerous nano-petals with a thickness of about 50 nm. As a result, a copper oxide hierarchical surface with WCA of 168.4°± 3.5° and CAH of 2.73° exhibited the best superhydrophobicity under proposed optimum condition. This result has been obtained just by 10 min hydrolysis reaction. Besides, this surface showed a good stability under acidic and saline conditions.

Drastic Effect of the Peptide Sequence on the Copper-Binding Properties of Tripeptides and the Electrochemical Behaviour of Their Copper(II) Complexes.

PubMed

Mena, Silvia; Mirats, Andrea; Caballero, Ana B; Guirado, Gonzalo; Barrios, Leoní A; Teat, Simon J; Rodriguez-Santiago, Luis; Sodupe, Mariona; Gamez, Patrick

2018-04-06

The binding and electrochemical properties of the complexes Cu II -HAH, Cu II -HWH, Cu II -Ac-HWH, Cu II -HHW, and Cu II -WHH have been studied by using NMR and UV/Vis spectroscopies, CV, and density functional calculations. The results obtained highlight the importance of the peptidic sequence on the coordination properties and, consequently, on the redox properties of their Cu II complexes. For Cu II -HAH and Cu II -HWH, no cathodic processes are observed up to -1.2 V; that is, the complexes exhibit very high stability towards copper reduction. This behaviour is associated with the formation of very stable square-planar (5,5,6)-membered chelate rings (ATCUN motif), which enclose two deprotonated amides. In contrast, for non-ATCUN Cu II -Ac-HWH, Cu II -HHW complexes, simulations seem to indicate that only one deprotonated amide is enclosed in the coordination sphere. In these cases, the main electrochemical feature is a reductive irreversible one electron-transfer process from Cu II to Cu I , accompanied with structural changes of the metal coordination sphere and reprotonation of the amide. Finally, for Cu II -WHH, two major species have been detected: one at low pH (<5), with no deprotonated amides, and another one at high pH (>10) with an ATCUN motif, both species coexisting at intermediate pH. The present study shows that the use of CV, using glassy carbon as a working electrode, is an ideal and rapid tool for the determination of the redox properties of Cu II metallopeptides. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modeling ultrasonic compression wave absorption during the seeded crystallization of copper (II) sulphate pentahydrate from aqueous solution.

PubMed

Marshall, Thomas; Challis, Richard E; Holmes, Andrew K; Tebbutt, John S

2002-11-01

Ultrasonic compression wave absorption is investigated as a means to monitor the seeded crystallization of copper (II) sulphate pentahydrate from aqueous solution. Simple models are applied to predict crystal yield, crystal size distribution, and the changing nature of the continuous phase. The Allegra-Hawley scattering formulation is used to simulate ultrasonic absorption as crystallization proceeds. Experiments confirm that simulated attenuation is in agreement with measured results.

Removal of Cu(II) from leachate using natural zeolite as a landfill liner material.

PubMed

Turan, N Gamze; Ergun, Osman Nuri

2009-08-15

All hazardous waste disposal facilities require composite liner systems to act as a barrier against migration of contaminated leachate into the subsurface environment. Removal of copper(II) from leachate was studied using natural zeolite. A serial of laboratory systems on bentonite added natural zeolite was conducted and copper flotation waste was used as hazardous waste. The adsorption capacities and sorption efficiencies were determined. The sorption efficiencies increased with increasing natural zeolite ratio. The pseudo-first-order, the pseudo-second-order, Elovich and the intra-particle diffusion kinetic models were used to describe the kinetic data to estimate the rate constants. The second-order model best described adsorption kinetic data. The results indicated that natural zeolite showed excellent adsorptive characteristics for the removal of copper(II) from leachate and could be used as very good liner materials due to its high uptake capacity and the abundance in availability.

A nanocomplex of Cu(II) with theophylline drug; synthesis, characterization, and anticancer activity against K562 cell line

NASA Astrophysics Data System (ADS)

Sahlabadi, Maryam; Daryanavard, Marzieh; Hadadzadeh, Hassan; Amirghofran, Zahra

2018-03-01

A new mononuclear of copper (II), [Cu(theophylline)2(H2O)3]·2H2O, has been synthesized by reaction of theophylline (1,3-dimethyl-7H-purine-2,6-dione) with copper (II) nitrate in water. Further, its nanocomplex has been prepared through the three different methods including sonication, grinding, and a combination thereof, sonication-grinding. The prepared nanocomplex was characterized using different techniques including FT-IR, UV-Vis, X-ray diffraction (XRD) analysis, and field-emission scanning electron microscopy (FE-SEM). Moreover, the anticancer activity of the precursor complex, nanocomplex, free theophylline ligand, and the starting copper salt (Cu(NO3)2·3H2O) was investigated against the K562 cell line. The results show that the nanocomplex is an effective nano metal-based anticancer agent with IC50 = 11.7 μM.

Synthesis and characterization of a multifunctional inorganic-organic hybrid mixed-valence copper(I/II) coordination polymer: {[CuCN][Cu(isonic)2]}n

NASA Astrophysics Data System (ADS)

Liu, Dong-Sheng; Chen, Wen-Tong; Ye, Guang-Ming; Zhang, Jing; Sui, Yan

2017-12-01

A new multifunctional mixed-valence copper(I/II) coordination polymer, {[CuCN][Cu(isonic)2]}n(1) (Hisonic = isonicotinic acid), was synthesized by treating isonicotinic acid and 5-amino-tetrazolate (Hatz = 5-amino-tetrazolate) with copper(II) salts under hydrothermal conditions, and characterized by elemental analysis, infrared spectroscopy, and single crystal X-ray diffraction, respectively. The X-ray diffraction analysis reveals that compound exhibit noncentrosymmetric polar packing arrangement. It is three-dimensional (3D) framework with (3,5)-connected 'seh-3' topological network constructed from metal organic framework {[Cu(isonic)2]}n and the inorganic linear chain{Cu(CN)}n subunits. A remarkable feature of 1 is the rhombic open channels that are occupied by a linear chain of {Cu(CN)}n. Impressively compound 1 displays not only a second harmonic generation (SHG) response, but also a ferroelectric behavior and magnetic properties.

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

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

Synthesis, characterization, antibacterial activity, SOD mimic and interaction with DNA of drug based copper(II) complexes

NASA Astrophysics Data System (ADS)

Patel, Mohan N.; Dosi, Promise A.; Bhatt, Bhupesh S.; Thakkar, Vasudev R.

2011-02-01

Novel metal complexes of the second-generation quinolone antibacterial agent enrofloxacin with copper(II) and neutral bidentate ligands have been prepared and characterized with elemental analysis reflectance, IR and mass spectroscopy. Complexes have been screened for their in-vitro antibacterial activity against two Gram (+ve)Staphylococcus aureus, Bacillus subtilis, and three Gram (-ve)Serratia marcescens, Escherichia coli and Pseudomonas aeruginosa organisms using the double dilution technique. The binding of this complex with CT-DNA has been investigated by absorption titration, salt effect and viscosity measurements. Binding constant is ranging from 1.3 × 10 4-3.7 × 10 4. The cleavage ability of complexes has been assessed by gel electrophoresis using pUC19 DNA. The catalytic activity of the copper(II) complexes towards the superoxide anion (O 2rad -) dismutation was assayed by their ability to inhibit the reduction of nitroblue tetrazolium (NBT).

Synthesis, characterization and investigation of electrochemical and spectroelectrochemical properties of peripherally tetra 4-phenylthiazole-2-thiol substituted metal-free, zinc(II), copper(II) and cobalt(II) phthalocyanines

NASA Astrophysics Data System (ADS)

Demirbaş, Ümit; Akçay, Hakkı Türker; Koca, Atıf; Kantekin, Halit

2017-08-01

In this study novel peripherally tetra 4-phenylthiazole-2-thiol substituted metal-free phthalocyanine (4) and its zinc(II) (5), copper(II) (6) and cobalt(II) (7) derivatives were synthesized and characterized by a combination of various spectroscopic techniques such as FT-IR, 1H-NMR, UV-vis and MALDI-TOF mass. Electrochemical characterizations of metallo-phthalocyanine complexes were conducted by voltammetric and in situ spectroelectrochemical measurements. CoIIPc went [CoIIPc-2]/[CoIPc-2]1-, [CoIPc-2]1-/[CoIPc-3]2-, [CoIPc-3]2-/[CoIPc-4]3- and [CoIIPc-2]/[CoIIPc-2]1+ reduction and oxidation processes respectively. Differently ZnIIPc only showed four ligand-based reductions and two ligand based oxidation processes.

Dinuclear metallacycles with single M-O(H)-M bridges [M = Fe(II), Co(II), Ni(II), Cu(II)]: effects of large bridging angles on structure and antiferromagnetic superexchange interactions.

PubMed

Reger, Daniel L; Pascui, Andrea E; Foley, Elizabeth A; Smith, Mark D; Jezierska, Julia; Ozarowski, Andrew

2014-02-17

The reactions of M(ClO4)2·xH2O and the ditopic ligands m-bis[bis(1-pyrazolyl)methyl]benzene (Lm) or m-bis[bis(3,5-dimethyl-1-pyrazolyl)methyl]benzene (Lm*) in the presence of triethylamine lead to the formation of monohydroxide-bridged, dinuclear metallacycles of the formula [M2(μ-OH)(μ-Lm)2](ClO4)3 (M = Fe(II), Co(II), Cu(II)) or [M2(μ-OH)(μ-Lm*)2](ClO4)3 (M = Co(II), Ni(II), Cu(II)). With the exception of the complexes where the ligand is Lm and the metal is copper(II), all of these complexes have distorted trigonal bipyramidal geometry around the metal centers and unusual linear (Lm*) or nearly linear (Lm) M-O-M angles. For the two solvates of [Cu2(μ-OH)(μ-Lm)2](ClO4)3, the Cu-O-Cu angles are significantly bent and the geometry about the metal is distorted square pyramidal. All of the copper(II) complexes have structural distortions expected for the pseudo-Jahn-Teller effect. The two cobalt(II) complexes show moderate antiferromagnetic coupling, -J = 48-56 cm(-1), whereas the copper(II) complexes show very strong antiferromagnetic coupling, -J = 555-808 cm(-1). The largest coupling is observed for [Cu2(μ-OH)(μ-Lm*)2](ClO4)3, the complex with a Cu-O-Cu angle of 180°, such that the exchange interaction is transmitted through the dz(2) and the oxygen s and px orbitals. The interaction decreases, but it is still significant, as the Cu-O-Cu angle decreases and the character of the metal orbital becomes increasingly d(x(2)-y(2)). These intermediate geometries and magnetic interactions lead to spin Hamiltonian parameters for the copper(II) complexes in the EPR spectra that have large E/D ratios and one g matrix component very close to 2. Density functional theory calculations were performed using the hybrid B3LYP functional in association with the TZVPP basis set, resulting in reasonable agreement with the experiments.

The influence of salinity on copper accumulation and its toxic effects in estuarine animals with differing osmoregulatory strategies.

PubMed

Lee, Jacqueline A; Marsden, Islay D; Glover, Chris N

2010-08-01

Copper is an important ionoregulatory toxicant in freshwater, but its effects in marine and brackish water systems are less well characterised. The effect of salinity on short-term copper accumulation and sublethal toxicity in two estuarine animals was investigated. The osmoregulating crab Hemigrapsus crenulatus accumulated copper in a concentration-dependent, but salinity-independent manner. Branchial copper accumulation correlated positively with branchial sodium accumulation. Sublethal effects of copper were most prevalent in 125% seawater, with a significant increase in haemolymph chloride noted after 96h at exposure levels of 510 microg Cu(II) L(-1). The osmoconforming gastropod, Scutus breviculus, was highly sensitive to copper exposure, a characteristic recognised previously in related species. Toxicity, as determined by a behavioural index, was present at all salinities and was positively correlated with branchial copper accumulation. At 100% seawater, increased branchial sodium accumulation, decreased haemolymph chloride and decreased haemolymph osmolarity were observed after 48h exposure to 221 microg Cu(II) L(-1), suggesting a mechanism of toxicity related to ionoregulation. However, these effects were likely secondary to a general effect on gill barrier function, and possibly mediated by mucus secretion. Significant impacts of copper on haemocyanin were also noted in both animals, highlighting a potentially novel mechanism of copper toxicity to animals utilising this respiratory pigment. Overall these findings indicate that physiology, as opposed to water chemistry, exerts the greatest influence over copper toxicity. An understanding of the physiological limits of marine and estuarine organisms may be critical for calibration of predictive models of metal toxicity in waters of high and fluctuating salinities. Copyright 2010 Elsevier B.V. All rights reserved.

Effect of the substituents on the photophysical, electrochemical and electroluminescence properties of OLED dopant Iridium bis(2-phenylbenzothiozolato- N,C2')(acetylacetonate)

NASA Astrophysics Data System (ADS)

Ivanov, P.; Tomova, R.; Petrova, P.

2014-12-01

The effect of two substituents: clorine and 1,3-diphenylpropane-1,3-dionate, placed on different position in the molecule of Iridium (III) bis(2-phenylbenzothiozolato-N,C2')- (acetylacetonate) (bt)2Ir(acac), on its electrochemical behaviour, photophysical and electroluminescence properties were investigated. Three complexes (bt)2Ir(acac), Iridium (III) bis[2-(4-chlorophenyl)benzothiazolato-N,C2']-acetylacetonate (Clbt)2Ir(acac), in which the Cl atom was introduced on the 4-position in the benzothiazole ring, and the new Iridium (Ill) bis[2 -phenylbenzothiazolato -N,C2'] -(1,3 -diphenylpropane-1,3 -dionate) (bt)2Ir(dbm), where ancillary acetylacetonate ligand was replaced by 1,3-diphenylpropane-1,3-dionate, were synthesized and characterised by 1H-NMR and elemental analysis. The HOMO/LUMO energy levels of the complexes were determined by cyclic voltammetry (CV) and their properties were established by UV-Visible and fluorescence spectroscopy. The application of (Clbt)2Ir(acac), (bt)2Ir(bsm) and (bt)2Ir(acac) as dopants in hole transporting layer (HTL) of Organic light- emitting diodes(OLEDs). It was found that with respect to the reference (bt)2Ir(acac): both LUMO and HOMO of the substituted complexes were shifted to more positive values accordingly with 0.23 and 0.19 eV for (Clbt)2Ir(acac) and 0.14 and 0.12 eV for (bt)2Ir(dbm). OLEDs doped with 1 w% of the complexes irradiated the warm white light with Commission internationale de l'eclairage (CIE) coordinates: 0.24;0.38 for (Clbt)2Ir(acac), 0.30;0.44 for (bt)2Ir(acac) and 0.28;0.46 for (bt)2Ir(dbm). Devices doped with 10 w% of all complexes irradiated in the yellow orange region of the spectrum.

Structural study of Ni- or Mg-based complexes incorporated within UiO-66-NH{sub 2} framework and their impact on hydrogen sorption properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Žunkovič, E.; Mazaj, M.; Mali, G.

2015-05-15

Nickel and magnesium acetylacetonate molecular complexes were post-synthetically incorporated into microporous zirconium-based MOF (UiO-66-NH{sub 2}) in order to introduce active open-metal sites for hydrogen sorption. Elemental analysis, nitrogen physisorption and DFT calculations revealed that 5 molecules of Ni(acac){sub 2} or 2 molecules of Mg(acac){sub 2} were incorporated into one unit cell of UiO-66-NH{sub 2}. {sup 1}H–{sup 13}C CPMAS and {sup 1}H MAS NMR spectroscopy showed that, although embedded within the pores, both Ni- and Mg-complexes interacted with the UiO-66-NH{sub 2} framework only through weak van der Waals bonds. Inclusion of metal complexes led to the decrease of hydrogen sorption capacitiesmore » in Ni-modified as well as in Mg-modified samples in comparison with the parent UiO-66-NH{sub 2}. The isosteric hydrogen adsorption enthalpy slightly increased in the case of Ni-modified material, but not in the case of Mg-modified analogue. - Graphical abstract: A post-synthesis impregnation of Mg- and Ni-acetylacetonate complexes performed on zirconium-based MOF UiO-66-NH{sub 2} does influence the hydrogen sorption performance with respect to the parent matrix. The structural study revealed that Mg- and Ni-acetylacetonate molecules interact with zirconium-terephthalate framework only by weak interactions and they are not covalently bonded to aminoterephthalate ligand. Still, they remain confined into the pores even after hydrogen sorption experiments. - Highlights: • Mg- and Ni-acetylacetonate molecules embedded in the pores of UiO-66-NH{sub 2} by PSM. • Molecules of complexes interact with framework only by van der Waals interactions. • Type/structure of deposited metal-complex impact hydrogen enthalpy of adsorption.« less

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

NASA Astrophysics Data System (ADS)

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

2014-10-01

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

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

NASA Astrophysics Data System (ADS)

Mamyrbekova, Aigul K.; Mamitova, A. D.; Mamyrbekova, Aizhan K.

2016-06-01

Conductometry is used to investigate the electric conductivity of Cu(NO3)2 ṡ 3H2O solutions in dimethyl sulfoxide in the 0.01-2.82 M range of concentrations and at temperatures of 288-318 K. The limiting molar conductivity of the electrolyte and the mobility of Cu2+ and NO 3 - ions, the effective coefficients of diffusion of copper(II) ions and nitrate ions, and the degree and constant of electrolytic dissociation are calculated for different temperatures from the experimental results. It is established that solutions containing 0.1-0.6 M copper nitrate trihydrate in DMSO having low viscosity and high electrical conductivity can be used in electrochemical deposition.

Crystal and electronic structures of magnesium(II), copper(II), and mixed magnesium(II)-copper(II) complexes of the quinoline half of styrylquinoline-type HIV-1 integrase inhibitors.

PubMed

Courcot, B; Firley, D; Fraisse, B; Becker, P; Gillet, J-M; Pattison, P; Chernyshov, D; Sghaier, M; Zouhiri, F; Desmaële, D; d'Angelo, J; Bonhomme, F; Geiger, S; Ghermani, N E

2007-05-31

A new target in AIDS therapy development is HIV-1 integrase (IN). It was proven that HIV-1 IN required divalent metal cations to achieve phosphodiester bond cleavage of DNA. Accordingly, all newly investigated potent IN inhibitors contain chemical fragments possessing a high ability to chelate metal cations. One of the promising leads in the polyhydroxylated styrylquinolines (SQLs) series is (E)-8-hydroxy-2-[2-(4,5-dihydroxy-3-methoxyphenyl)-ethenyl]-7-quinoline carboxylic acid (1). The present study focuses on the quinoline-based progenitor (2), which is actually the most probable chelating part of SQLs. Conventional and synchrotron low-temperature X-ray crystallographic studies were used to investigate the chelating power of progenitor 2. Mg2+ and Cu2+ cations were selected for this purpose, and three types of metal complexes of 2 were obtained: Mg(II) complex (4), Cu(II) complex (5) and mixed Mg(II)-Cu(II) complexes (6 and 7). The analysis of the crystal structure of complex 4 indicates that two tridentate ligands coordinate two Mg2+ cations, both in octahedral geometry. The Mg-Mg distance was found equal to 3.221(1) A, in agreement with the metal-metal distance of 3.9 A encountered in the crystal structure of Escherichia coli DNA polymerase I. In 5, the complex is formed by two bidentate ligands coordinating one copper ion in tetrahedral geometry. Both mixed Mg(II)-Cu(II) complexes, 6 and 7 exhibit an original arrangement of four ligands linked to a central heterometallic cluster consisting of three octahedrally coordinated magnesium ions and one tetrahedrally coordinated copper ion. Quantum mechanics calculations were also carried out in order to display the electrostatic potential generated by the dianionic ligand 2 and complex 4 and to quantify the binding energy (BE) during the formation of the magnesium complex of progenitor 2. A comparison of the binding energies of two hypothetical monometallic Mg(II) complexes with that found in the bimetallic magnesium complex 4 was made.

Rapid Copper Metallization of Textile Materials: a Controlled Two-Step Route to Achieve User-Defined Patterns under Ambient Conditions.

PubMed

Zhang, Shuang-Yuan; Guan, Guijian; Jiang, Shan; Guo, Hongchen; Xia, Jing; Regulacio, Michelle D; Wu, Mingda; Shah, Kwok Wei; Dong, Zhili; Zhang, Jie; Han, Ming-Yong

2015-09-30

Throughout history earth-abundant copper has been incorporated into textiles and it still caters to various needs in modern society. In this paper, we present a two-step copper metallization strategy to realize sequentially nondiffusive copper(II) patterning and rapid copper deposition on various textile materials, including cotton, polyester, nylon, and their mixtures. A new, cost-effective formulation is designed to minimize the copper pattern migration on textiles and to achieve user-defined copper patterns. The metallized copper is found to be very adhesive and stable against washing and oxidation. Furthermore, the copper-metallized textile exhibits excellent electrical conductivity that is ~3 times better than that of stainless steel and also inhibits the growth of bacteria effectively. This new copper metallization approach holds great promise as a commercially viable method to metallize an insulating textile, opening up research avenues for wearable electronics and functional garments.

Comparative study of copper(II)-curcumin complexes as superoxide dismutase mimics and free radical scavengers.

PubMed

Barik, Atanu; Mishra, Beena; Kunwar, Amit; Kadam, Ramakant M; Shen, Liang; Dutta, Sabari; Padhye, Subhash; Satpati, Ashis K; Zhang, Hong-Yu; Indira Priyadarsini, K

2007-04-01

Two stoichiometrically different copper(II) complexes of curcumin (stoichiometry, 1:1 and 1:2 for copper:curcumin), were examined for their superoxide dismutase (SOD) activity, free radical-scavenging ability and antioxidant potential. Both the complexes are soluble in lipids and DMSO. The formation constants of the complexes were determined by voltammetry. EPR spectra of the complexes in DMSO at 77K showed that the 1:2 Cu(II)-curcumin complex is square planar and the 1:1 Cu(II)-curcumin complex is distorted orthorhombic. Cu(II)-curcumin complex (1:1) with larger distortion from square planar structure shows higher SOD activity. These complexes inhibit gamma-radiation induced lipid peroxidation in liposomes and react with DPPH acting as free radical scavengers. One-electron oxidation of the two complexes by radiolytically generated azide radicals in Tx-100 micellar solutions produced phenoxyl radicals, indicating that the phenolic moiety of curcumin in the complexes participates in free radical reactions. Depending on the structure, these two complexes possess different SOD activities, free radical neutralizing abilities and antioxidant potentials. In addition, quantum chemical calculations with density functional theory have been performed to support the experimental observations.

Composition and particle size of electrolytic copper powders prepared in water-containing dimethyl sulfoxide electrolytes

NASA Astrophysics Data System (ADS)

Mamyrbekova, Aigul'; Abzhalov, B. S.; Mamyrbekova, Aizhan

2017-07-01

The possibility of the electroprecipitation of copper powder via the cathodic reduction of an electrolyte solution containing copper(II) nitrate trihydrate and dimethyl sulfoxide (DMSO) is shown. The effect electrolysis conditions (current density, concentration and temperature of electrolyte) have on the dimensional characteristics of copper powder is studied. The size and shape of the particles of the powders were determined by means of electron microscopy; the qualitative composition of the powders, with X-ray diffraction.

Composition distributions in FePt(Au) nanoparticles

NASA Astrophysics Data System (ADS)

Srivastava, C.; Nikles, D. E.; Harrell, J. W.; Thompson, G. B.

2010-08-01

Ternary alloy FePt(Au) nanoparticles were prepared by the co-reduction of platinum(II) acetylacetonate and gold(III) acetate and the thermal decomposition of iron pentacarbonyl in hot phenyl ether in the presence of oleic acid and oleylamine ligands. This gave spherical particles with an average diameter of 4.4 nm with a range of diameters from approximately 1.6-9 nm. The as-synthesized particles had a solid solution, face-centered-cubic structure. Though the average composition of the particles was Fe44Pt45Au11, individual particle analysis by Scanning Transmission Electron Microscopy-X-ray Energy Dispersive Spectroscopy showed a broad distribution in composition. In general, smaller-sized particles tended to have a lower amount of Au as compared to larger-sized particles. As the Au content increased, the ratio of Fe/Pt widened.

Synthesis, structural characterization, superoxide dismutase and antimicrobial activities studies of copper (II) complexes with 2-(E)-(2-(2-aminoethylamino) methyl)-4-bromophenol and (19E, 27E)-N1, N2-bis (phenyl (pyridine-2-yl)-methylene)-ethane-1, 2-diamine as ligands

NASA Astrophysics Data System (ADS)

Choudhary, Mukesh; Patel, R. N.; Rawat, S. P.

2014-07-01

Three new copper (II) complexes, [Cu(L)(H2O)]ClO4 (1), [Cu(L1)(ClO4)]+ (2) and [Cu(L1)]2+ (3), where HL = 2-(E)-(2-(2-aminoethylamino)methyl)-4-bromophenol, L1 =(19E, 27E)-N1,N2-bis(phenyl(pyridine-2-yl)-methylene)-ethane-1, 2-diamine, have been synthesized and characterized by using various physic-chemical and spectroscopic methods. The solid-state structures of 1 and 2 were determined by single crystal X-ray crystallography. Infrared spectra, ligand field spectra and magnetic susceptibility measurements agree with the observed crystal structures. The molecular structure of copper complexes showed that the ligands occupies the basal plane of square pyramidal geometry with the H2O of 1 or the ClO4 of 2 occupying the remaining apical position. Complexes 1 and 2 crystallize in the monoclinic system of the space group P21/c, a = 10.5948(6)Å, b = 19.6164(11)Å, c = 8.6517(5)Å, α = 90°, β = 108.213(2)°, γ = 90° and Z = 4 for 1, a = 9.5019(3)Å, b = 11.3 801(3)Å, c = 25.3168(14)Å, α = 90°, β = 100.583(4)°, γ = 90°, and Z = 4 for 2. The synthesized Schiff base (HL/L1) was behaves as tetradentate ON3/N4 ligands with donor groups suitable placed for forming 2 or 3 five membered chelate rings. Copper (II) complexes display X-band EPR spectra in 100% DMSO at 77 K giving g|| > g⊥ > 2.0023 indicating dx2-y2 ground state. The half-wave potential values for Cu (II)/Cu (I) redox couple obtained in the reaction of the copper (II) complexes with molecular oxygen and superoxide radical (O2-) electronegated in DMSO are in agreement with the SOD-like activity of the copper (II) complexes. In vitro antimicrobial activities of the complexes against the two bacteria (Escherichia coli, Salmonella typhi) and the two fungi (Penicillium, Aspergillus sp.) have been investigated comparing with the Schiff base ligands.

Supramolecular architecture of metal-organic frameworks involving dinuclear copper paddle-wheel complexes.

PubMed

Gomathi, Sundaramoorthy; Muthiah, Packianathan Thomas

2013-12-15

The two centrosymmetric dinuclear copper paddle-wheel complexes tetrakis(μ-4-hydroxybenzoato-κ(2)O:O')bis[aquacopper(II)] dimethylformamide disolvate dihydrate, [Cu2(C7H5O3)4(H2O)2]·2C3H7NO·2H2O, (I), and tetrakis(μ-4-methoxybenzoato-κ(2)O:O')bis[(dimethylformamide-κO)copper(II)], [Cu2(C8H7O3)4(C3H7NO)2], (II), crystallize with half of the dinuclear paddle-wheel cage unit in the asymmetric unit and, in addition, complex (I) has one dimethylformamide (DMF) and one water solvent molecule in the asymmetric unit. In both (I) and (II), two Cu(II) ions are bridged by four syn,syn-η(1):η(1):μ carboxylate groups, showing a paddle-wheel cage-type structure with a square-pyramidal coordination geometry. The equatorial positions of (I) and (II) are occupied by the carboxylate groups of 4-hydroxy- and 4-methoxybenzoate ligands, and the axial positions are occupied by aqua and DMF ligands, respectively. The three-dimensional supramolecular metal-organic framework of (I) consists of three different R2(2)(20) and an R4(4)(36) ring motif formed via O-H···O and OW-HW···O hydrogen bonds. Complex (II) simply packs as molecular species.

Study of Copper and Purine-Copper Complexes on Modified Carbon Electrodes by Cyclic and Elimination Voltammetry

PubMed Central

Trnkova, Libuse; Zerzankova, Lenka; Dycka, Filip; Mikelova, Radka; Jelen, Frantisek

2008-01-01

Using a paraffin impregnated graphite electrode (PIGE) and mercury-modified pyrolytic graphite electrode with basal orientation (Hg-PGEb) copper(II) and Cu(II)-DNA purine base solutions have been studied by cyclic (CV) and linear sweep voltammetry (LSV) in connection with elimination voltammetry with linear scan (EVLS). In chloride and bromide solutions (pH 6), the redox process of Cu(II) proceeded on PIGE with two cathodic and two anodic potentially separated signals. According to the elimination function E4, the first cathodic peak corresponds to the reduction Cu(II) + e- → Cu(I) with the possibility of fast disproportionation 2Cu(I) → Cu(II)+ Cu(0). The E4 of the second cathodic peak signalized an electrode process controlled by a surface reaction. The electrode system of Cu(II) on Hg-PGEb in borate buffer (pH 9.2) was characterized by one cathodic and one anodic peak. Anodic stripping voltammetry (ASV) on PIGE and cathodic stripping voltammetry (CSV) on Hg-PGEb were carried out at potentials where the reduction of copper ions took place and Cu(I)-purine complexes were formed. By using ASV and CSV in combination with EVLS, the sensitivity of Cu(I)-purine complex detection was enhanced relative to either ASV or CSV alone, resulting in higher peak currents of more than one order of magnitude. The statistical treatment of CE data was used to determine the reproducibility of measurements. Our results show that EVLS in connection with the stripping procedure is useful for both qualitative and quantitative microanalysis of purine derivatives and can also reveal details of studied electrode processes. PMID:27879715

High stability and biological activity of the copper(II) complexes of alloferon 1 analogues containing tryptophan.

PubMed

Kadej, Agnieszka; Kuczer, Mariola; Czarniewska, Elżbieta; Urbański, Arkadiusz; Rosiński, Grzegorz; Kowalik-Jankowska, Teresa

2016-10-01

Copper(II) complex formation processes between the alloferon 1 (Allo1) (HGVSGHGQHGVHG) analogues where the tryptophan residue is introducing in the place His residue H1W, H6W, H9W and H12W have been studied by potentiometric, UV-visible, CD and EPR spectroscopic, and MS methods. For all analogues of alloferon 1 complex speciation have been obtained for a 1:1 metal-to-ligand molar ratio and 2:1 of H1W because of precipitation at higher (2:1, 3:1 and 4:1) ratios. At physiological pH7.4 and a 1:1 metal-to-ligand molar ratio the tryptophan analogues of alloferon 1 form the CuH -1 L and/or CuH -2 L complexes with the 4N binding mode. The introduction of tryptophan in place of histidine residues changes the distribution diagram of the complexes formed with the change of pH and their stability constants compared to the respective substituted alanine analogues of alloferon 1. The CuH -1 L, CuH -2 L and CuH -3 L complexes of the tryptophan analogues are more stable from 1 to 5 log units in comparison to those of the alanine analogues. This stabilization of the complexes may result from cation(Cu(II))-π and indole/imidazole ring interactions. The induction of apoptosis in vivo, in Tenebrio molitor cells by the ligands and their copper(II) complexes at pH7.4 was studied. The biological results show that copper(II) ions in vivo did not cause any apparent apoptotic features. The most active were the H12W peptide and Cu(II)-H12W complex formed at pH7.4. Copyright © 2016 Elsevier Inc. All rights reserved.

Flocculation of copper(II) and tetracycline from water using a novel pH- and temperature-responsive flocculants.

PubMed

Yang, Zhen; Jia, Shuying; Zhuo, Ning; Yang, Weiben; Wang, Yuping

2015-12-01

Insufficient research is available on flocculation of combined pollutants of heavy metals and antibiotics, which widely exist in livestock wastewaters. Aiming at solving difficulties in flocculation of this sort of combined pollution, a novel pH- and temperature-responsive biomass-based flocculant, carboxymethyl chitosan-graft-poly(N-isoproyl acrylamide-co-diallyl dimethyl ammonium chloride) (denoted as CND) with two responsive switches [lower critical solution temperature (LCST) and isoelectric point (IEP)], was designed and synthesized. Its flocculation performance at different temperatures and pHs was evaluated using copper(II) and tetracycline (TC) as model contaminants. CND exhibited high efficiency for coremoval of both contaminants, whereas two commercial flocculants (polyaluminum chloride and polyacrylamide) did not. Especially, flocculation performance of the dual-responsive flocculant under conditions of temperature>LCST and IEP(contaminants)

Activation of persulfate/copper by hydroxylamine via accelerating the cupric/cuprous redox couple.

PubMed

Zhou, Peng; Zhang, Jing; Liang, Juan; Zhang, Yongli; Liu, Ya; Liu, Bei

2016-01-01

Cuprous copper [Cu(I)] reacts with sodium persulfate (PDS) to generate sulfate radical SO4(-)•, but it has been seldom investigated owing to its instability and difficulty in dissolving it. This study proposes a new method to regenerate Cu(I) from cupric copper [Cu(II)] by addition of hydroxylamine (HA) to induce the continuous production of radicals through active PDS, and investigates the resulting enhanced methyl orange (MO) degradation efficiency and mechanism in the new system. HA accelerated the degradation of MO markedly in the pH range from 6.0 to 8.0 in the HA/Cu(II)/PDS process. Both SO4(-)• and hydroxyl radicals (•OH) were considered as the primary reactive radicals in the process. The MO degradation in the HA/Cu(II)/PDS process can be divided into three stages: the fast stage, the transitory stage, and the low stage. MO degradation was enhanced with increased dosage of PDS. Although high dosage of HA could accelerate the transformation of the Cu(II)/Cu(I) cycle to produce more reactive radicals, excess HA can quench the reactive radicals. This study indicates that through a copper-redox cycling mechanism by HA, the production of SO4(-)• and •OH can be strongly enhanced, and the effective pH range can be expanded to neutral conditions.

Reactions of the melatonin metabolite N(1)-acetyl-5-methoxykynuramine with carbamoyl phosphate and related compounds.

PubMed

Kuesel, Jana T; Hardeland, Rüdiger; Pfoertner, Henrike; Aeckerle, Nelia

2010-01-01

N-[2-(6-methoxyquinazolin-4-yl)-ethyl] acetamide (MQA) is a compound formed from the melatonin metabolite N(1)-acetyl-5-methoxykynuramine (AMK). We followed MQA production in reaction systems containing various putative reaction partners, in the absence and presence of hydrogen peroxide and/or copper(II). Although MQA may be formally described as a condensation product of either N(1)-acetyl-N(2)-formyl-5-methoxykynuramine (AFMK) with ammonia, or AMK with formamide, none of these combinations led to substantial quantities of MQA. However, MQA formation was observed in mixtures containing AMK, hydrogen peroxide, hydrogen carbonate and ammonia, or AMK, hydrogen peroxide, copper(II) and potentially carbamoylating agents, such as potassium cyanate or, more efficiently, carbamoyl phosphate. In the presence of hydrogen peroxide, copper(II) and carbamoyl phosphate, MQA was the major product obtained from AMK, but the omission of copper(II) mainly led to another metabolite, 3-acetamidomethyl-6-methoxycinnolinone (AMMC). This was caused by nitric oxide (NO) generated under oxidative conditions from carbamoyl phosphate, as shown by an NO spin trap. MQA formation with carbamoyl phosphate was not due to the possible decomposition product, formamide. The reaction of AMK with carbamoyl phosphate under oxidative conditions, in which inorganic phosphate and water are released and which differs from the typical process of carbamoylation via isocyanate, may be considered as a new physiological route of MQA formation.

Repurposing of Copper(II)-chelating Drugs for the Treatment of Neurodegenerative Diseases.

PubMed

Lanza, Valeria; Milardi, Danilo; Di Natale, Giuseppe; Pappalardo, Giuseppe

2018-02-12

There is mounting urgency to find new drugs for the treatment of neurodegenerative disorders. A large number of reviews have exhaustively described either the molecular or clinical aspects of neurodegenerative diseases such as Alzheimer's (AD) and Parkinson's (PD). Conversely, reports outlining how known drugs in use for other diseases can also be effective as therapeutic agents in neurodegenerative diseases are less reported. This review focuses on the current uses of some copper(II) chelating molecules as potential drug candidates in neurodegeneration. Starting from the well-known harmful relationships existing between the dyshomeostasis and mis-management of metals and AD onset, we surveyed the experimental work reported in the literature, which deals with the repositioning of metal-chelating drugs in the field of neurodegenerative diseases. The reviewed papers were retrieved from common literature and their selection was limited to those describing the biomolecular aspects associated with neuroprotection. In particular, we emphasized the copper(II) coordination abilities of the selected drugs. Copper, together with zinc and iron, are known to play a key role in regulating neuronal functions. Changes in copper homeostasis are crucial for several neurodegenerative disorders. The studies included in this review may provide an overview on the current strategies aimed at repurposing copper (II) chelating drugs for the treatment of neurodegenerative disorders. Starting from the exemplary case of clioquinol repurposing, we discuss the challenge and the opportunities that repurposing of other metal-chelating drugs may provide (e.g. PBT-2, metformin and cyclodipeptides) in the treatment of neurodegenerative disease. In order to improve the success rate of drug repositioning, comprehensive studies on the molecular mechanism and therapeutic efficacy are still required. The present review upholds that drug repurposing makes significant advantages over drug discovery since repositioned drugs had already passed the safety and toxicity tests. Promising drug candidates in neurodegenerative diseases may be represented by copper chelating classes of drugs, provided that sufficient details on their mechanism of action are available to encourage further investigations and clinical trials. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Selective flotation-spectrophotometric determination of trace copper(II) in natural waters, human blood and drug samples using phenanthraquinone monophenylthiosemicarbazone.

PubMed

Khalifa, M E; Akl, M A; Ghazy, S E

2001-06-01

Copper(II) forms 1:1 and 1:2 intense red complexes with phenanthraquinone monophenylthiosemicarbazone (PPT) at pH 3-3.5 and > or =6.5, respectively. These complexes exhibit maximal absorbance at 545 and 517 nm, the molar absorptivity being 2.3 x 10(4) and 4.8 x 10(4) l mol(-1) cm(-1), respectively. However, the 1:1 complex was quantitatively floated with oleic acid (HOL) surfactant in the pH range 4.5-5.5, providing a highly selective and sensitive procedure for the spectrophotometric determination of CuII. The molar absorptivity of the floated Cu-PPT complex was 1.5 x 10(5) l mol)(-1) cm(-1). Beer's law was obeyed over the range 3-400 ppb at 545 nm. The analytical parameters affecting the flotation process and hence the determination of copper traces were reported. Also, the structure of the isolated solid complex and the mechanism of flotation were suggested. Moreover, the procedure was successfully applied to the analysis of CuII in natural waters, serum blood and some drug samples.

Computational study of the binding of CuII to Alzheimer's amyloid-beta peptide: do Abeta42 and Abeta40 bind copper in identical fashion?

PubMed

Mantri, Yogita; Fioroni, Marco; Baik, Mu-Hyun

2008-11-01

One of the many hypotheses on the pathogenesis of Alzheimer's disease is that the amyloid-beta peptide (Abeta) binds CuII and can catalytically generate H2O2, leading to oxidative damage in brain tissues. For a molecular level understanding of such catalysis it is critical to know the structure of the Abeta-CuII complex precisely. Unfortunately, no high-resolution structure is available to date and there is considerable debate over the copper coordination environment with no clear consensus on which residues are directly bound to CuII. Considering all plausible isomers of the copper-bound Abeta42 and Abeta40 using a combination of density functional theory and classical molecular dynamics methods, we report an atomic resolution structure for each possible complex. We evaluated the relative energies of these isomeric structures and surprisingly found that Abeta42 and Abeta40 display very different binding modes, suggesting that shorter peptides that are truncated at the C-terminus may not be realistic models for understanding the chemistry of the most neurotoxic peptide, Abeta42.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chumakov, Yu. M.; Paholnitcaia, A. Yu.; Petrenko, P. A.

Two crystal modifications of nitrato-(2-[2-(1-pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazolo) aquacopper (I and II) and two modifications of chloro-(2-[2-phenyl(pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazolo) copper (III and IV) have been synthesized and studied by X-ray diffraction. In structures I and II, the copper atoms coordinate a monodeprotonated molecule of the organic ligand, nitrate ions, and a water molecule. In crystals of I, the complexes are monomeric, whereas complexes II are linked via nitrate ions to form polymeric chains. In both structures the coordination polyhedron of the copper atom can be described as a distorted tetragonal bipyramid—(4 + 1 + 1) in I and (4 + 2) in II. These coordinationmore » polyherdra have different compositions. In structures III and IV, the metal atoms coordinate a monodeprotonated (2-[2-phenyl(pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazole molecule and chloride ions. In III the complex-forming ion has square-planar coordination geometry, whereas structure IV consists of centrosymmetric dimers with two bridging chlorine atoms. It was found that nitrato-(2-[2-(1-pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazolo) aquacopper possesses antitumor activity.« less

Metamagnetism in hydrophobically induced carboxylate (phenylmalonate)-bridged copper(II) layers.

PubMed

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.

Theoretical study of hydrated copper(II) interactions with guanine: a computational density functional theory study.

PubMed

Pavelka, Matej; Shukla, Manoj K; Leszczynski, Jerzy; Burda, Jaroslav V

2008-01-17

Optimization of the hydrated Cu(II)(N7-guanine) structures revealed a number of minima on the potential energy surface. For selected structures, energy decompositions together with the determination of electronic properties (partial charges and electron spin densities) were performed. In the complexes of guanine with the bare copper cation and that with the monoaqua ligated cation, an electron transfer from guanine to Cu(II) was observed, resulting in a Cu(I)-guanine(+) type of complex. Conformers with two aqua ligands are borderline systems characterized by a Cu partial charge of +0.7e and a similar value of the spin density (0.6e) localized on guanine. When tetracoordination of copper was achieved, only then the prevailing electron spin density is unambiguously localized on copper. The energetic preference of diaqua-Cu-(N7,O6-guanine) over triaqua-Cu-(N7-guanine) was found for the four-coordinate structures. However, the energy difference between these two conformations decreases with the number of water molecules present in the systems, and in complexes with five water molecules this preference is preserved only at DeltaG level where thermal and entropy terms are included.

Therapeutic potential of copper chelation with triethylenetetramine in managing diabetes mellitus and Alzheimer's disease.

PubMed

Cooper, Garth J S

2011-07-09

This article reviews recent evidence, much of which has been generated by my group's research programme, which has identified for the first time a previously unknown copper-overload state that is central to the pathogenesis of diabetic organ damage. This state causes tissue damage in the blood vessels, heart, kidneys, retina and nerves through copper-mediated oxidative stress. This author now considers this copper-overload state to provide an important new target for therapeutic intervention, the objective of which is to prevent or reverse the diabetic complications. Triethylenetetramine (TETA) has recently been identified as the first in a new class of anti-diabetic molecules through the original work reviewed here, thus providing a new use for this molecule, which was previously approved by the US FDA in 1985 as a second-line treatment for Wilson's disease. TETA acts as a highly selective divalent copper (Cu(II)) chelator that prevents or reverses diabetic copper overload, thereby suppressing oxidative stress. TETA treatment of diabetic animals and patients has identified and quantified the interlinked defects in copper metabolism that characterize this systemic copper overload state. Copper overload in diabetes mellitus differs from that in Wilson's disease through differences in their respective causative molecular mechanisms, and resulting differences in tissue localization and behaviour of the excess copper. Elevated pathogenetic tissue binding of copper occurs in diabetes. It may well be mediated by advanced-glycation endproduct (AGE) modification of susceptible amino-acid residues in long-lived fibrous proteins, for example, connective tissue collagens in locations such as blood vessel walls. These AGE modifications can act as localized, fixed endogenous chelators that increase the chelatable-copper content of organs such as the heart and kidneys by binding excessive amounts of catalytically active Cu(II) in specific vascular beds, thereby focusing the related copper-mediated oxidative stress in susceptible tissues. In this review, summarized evidence from our clinical studies in healthy volunteers and diabetic patients with left-ventricular hypertrophy, and from nonclinical models of diabetic cardiac, arterial, renal and neural disease is used to construct descriptions of the mechanisms by which TETA treatment prevents injury and regenerates damaged organs. Our recent phase II proof-of-principle studies in patients with type 2 diabetes and in nonclinical models of diabetes have helped to define the pathogenetic defects in copper regulation, and have shown that they are reversible by TETA. The drug tightly binds and extracts excess systemic Cu(II) into the urine whilst neutralizing its catalytic activity, but does not cause systemic copper deficiency, even after prolonged use. Its physicochemical properties, which are pivotal for its safety and efficacy, clearly differentiate it from all other clinically available transition metal chelators, including D-penicillamine, ammonium tetrathiomolybdate and clioquinol. The studies reviewed here show that TETA treatment is generally effective in preventing or reversing diabetic organ damage, and support its ongoing development as a new medicine for diabetes. Trientine (TETA dihydrochloride) has been used since the mid-1980s as a second-line treatment for Wilson's disease, and our recent clinical studies have reinforced the impression that it is likely to be safe for long-term use in patients with diabetes and related metabolic disorders. There is substantive evidence to support the view that diabetes shares many pathogenetic mechanisms with Alzheimer's disease and vascular dementia. Indeed, the close epidemiological and molecular linkages between them point to Alzheimer's disease/vascular dementia as a further therapeutic target where experimental pharmacotherapy with TETA could well find further clinical application.

Structure and Stability of Carboxylate Complexes. 20. Diaqua Bis(methoxyacetato) Complexes of Nickel(II), Copper(II), and Zinc(II): A Structural Study of the Dynamic Pseudo-Jahn-Teller Effect.

PubMed

Prout, Keith; Edwards, Alison; Mtetwa, Victor; Murray, Jon; Saunders, John F.; Rossotti, Francis J. C.

1997-06-18

The crystal structure of trans-diaquabis(methoxyacetato)copper(II), C(6)H(14)O(8)Cu, has been determined by neutron diffraction at 4.2 K (monoclinic, P2(1)/n, a = 6.88(1), b = 7.19(1), c = 9.77(2) Å, gamma = 95.7(1) degrees, (Z = 2)) and by X-ray diffraction at 125, 165, 205, 240, 265, 295, and 325 K. These measurements show that there is no phase change in the temperature range 4.2-325 K. The copper(II) coordination at 4.2 K is a tetragonally distorted elongated rhombic octahedron (Cu-OOC 1.955(1), Cu-OMe 2.209(1), and Cu-OH(2) 2.031(2) Å). As the temperature increases to 325 K, the Cu-OOC bonds shorten slightly to 1.934(5) Å, the Cu-OMe bonds shorten more markedly to 2.137(4) Å, and Cu-OH(2) lengthens to 2.155(6) Å to give a tetragonally distorted compressed rhombic octahedron. For comparison the structure of the isomorphous nickel(II) complex (monoclinic, P2(1)/n, a = 6.633(1), b = 7.192(1), c = 10.016(2) Å, gamma = 98.30(2) degrees, (Z = 2)) has been redetermined at 295 K and the structure of the analogous zinc(II) complex (orthorhombic, F2dd, a = 7.530(1), b = 13.212(1), c = 21.876(2) Å (Z = 8)) has also been determined. The nickel(II) complex has an almost regular trans (centrosymmetric) octahedral coordination (Ni-OOC 2.022(1), Ni-OMe 2.043(1), and Ni-OH(2) 2.077(2) Å). However, zinc(II) has a very distorted octahedral coordination with the zinc atom on a 2-fold axis with the water molecules and the methoxy ligators cis and the carboxylate ligators trans (Zn-OOC 1.985(1), Zn-OMe 2.304(2), and Zn-OH(2) 2.038(2) Å). The variation in the dimensions of the copper(II) coordination sphere is discussed in terms of static (low temperature) and planar dynamic (high temperature) pseudo-Jahn-Teller effects.

Evaluation of some heavy metals residues in batteries and deep litter rearing systems in Japanese quail meat and offal in Egypt

PubMed Central

Ahmed, Ali M.; Hamed, Dalia M.; Elsharawy, Nagwa T.

2017-01-01

Aim: The main objectives of this study were for comparing the effect of batteries and deep litter rearing systems of domesticated Japanese quail, Coturnix coturnix japonica, on the concentration levels of cadmium, copper, lead, and zinc from the quail meat and offal in Ismailia, Egypt. Materials and Methods: A total of 40 quail meat and their offal samples were randomly collected from two main quail rearing systems: Battery (Group I) and deep litter system (Group II) for determination of concentration levels of cadmium, copper, lead, and zinc. In addition, 80 water and feed samples were randomly collected from water and feeders of both systems in the Food Hygiene Laboratory, Faculty of Veterinary Medicine, Suez Canal University for heavy metals determination. Results: The mean concentration levels of cadmium, copper, lead, and zinc in Group I were 0.010, 0.027, 1.137, and 0.516 ppm and for Group II were 0.093, 0.832, 0.601, and 1.651 ppm, respectively. The mean concentration levels of cadmium, copper, lead, and zinc in quail feed in Group I were 1.114, 1.606, 5.822, and 35.11 ppm and for Group II were 3.010, 2.576, 5.852, and 23.616 ppm, respectively. The mean concentration levels of cadmium, copper, lead, and zinc in quail meat for Group I were 0.058, 5.902, 10.244, and 290 ppm and for Group II were 0.086, 6.092, 0.136, and 1.280 ppm, respectively. The mean concentration levels of cadmium, copper, lead, and zinc for liver samples in Group I were 0.15, 8.32, 1.05, and 3.41 ppm and for Group II were 0.13, 8.88, 0.95, and 4.21 ppm, respectively. The mean concentration levels of cadmium, copper, lead, and zinc in kidney samples for the Group I were 0.24, 4.21, 1.96, and 4.03 ppm and for Group II were 0.20, 5.00, 1.56, and 3.78 ppm, respectively. Kidney had the highest concentration levels of heavy metals followed by liver then muscles. The highest concentration levels of copper were observed in liver samples. The order of the levels of these trace elements obtained from the four different quail organs is Ca > Pb > Zn > Cu. Lead and cadmium concentration levels in quail meat samples were exceeded the Egyptian standardization limits and suggesting a health threat from lead and cadmium to the quail consumers. Conclusion: Battery rearing system is more hygienic than deep litter system from the point of heavy metals pollution of water and feeds of quail. Feed samples from battery system had means concentration levels of lead not significantly higher (p>0.05) than those samples from deep litter system. Meanwhile, water samples from battery system had means concentration levels of cadmium, copper, and zinc significantly higher (p>0.05) than those samples from deep litter system. Quail may carry health risks to consumers. PMID:28344413

Evaluation of some heavy metals residues in batteries and deep litter rearing systems in Japanese quail meat and offal in Egypt.

PubMed

Ahmed, Ali M; Hamed, Dalia M; Elsharawy, Nagwa T

2017-02-01

The main objectives of this study were for comparing the effect of batteries and deep litter rearing systems of domesticated Japanese quail, Coturnix coturnix japonica , on the concentration levels of cadmium, copper, lead, and zinc from the quail meat and offal in Ismailia, Egypt. A total of 40 quail meat and their offal samples were randomly collected from two main quail rearing systems: Battery (Group I) and deep litter system (Group II) for determination of concentration levels of cadmium, copper, lead, and zinc. In addition, 80 water and feed samples were randomly collected from water and feeders of both systems in the Food Hygiene Laboratory, Faculty of Veterinary Medicine, Suez Canal University for heavy metals determination. The mean concentration levels of cadmium, copper, lead, and zinc in Group I were 0.010, 0.027, 1.137, and 0.516 ppm and for Group II were 0.093, 0.832, 0.601, and 1.651 ppm, respectively. The mean concentration levels of cadmium, copper, lead, and zinc in quail feed in Group I were 1.114, 1.606, 5.822, and 35.11 ppm and for Group II were 3.010, 2.576, 5.852, and 23.616 ppm, respectively. The mean concentration levels of cadmium, copper, lead, and zinc in quail meat for Group I were 0.058, 5.902, 10.244, and 290 ppm and for Group II were 0.086, 6.092, 0.136, and 1.280 ppm, respectively. The mean concentration levels of cadmium, copper, lead, and zinc for liver samples in Group I were 0.15, 8.32, 1.05, and 3.41 ppm and for Group II were 0.13, 8.88, 0.95, and 4.21 ppm, respectively. The mean concentration levels of cadmium, copper, lead, and zinc in kidney samples for the Group I were 0.24, 4.21, 1.96, and 4.03 ppm and for Group II were 0.20, 5.00, 1.56, and 3.78 ppm, respectively. Kidney had the highest concentration levels of heavy metals followed by liver then muscles. The highest concentration levels of copper were observed in liver samples. The order of the levels of these trace elements obtained from the four different quail organs is Ca > Pb > Zn > Cu. Lead and cadmium concentration levels in quail meat samples were exceeded the Egyptian standardization limits and suggesting a health threat from lead and cadmium to the quail consumers. Battery rearing system is more hygienic than deep litter system from the point of heavy metals pollution of water and feeds of quail. Feed samples from battery system had means concentration levels of lead not significantly higher (p>0.05) than those samples from deep litter system. Meanwhile, water samples from battery system had means concentration levels of cadmium, copper, and zinc significantly higher (p>0.05) than those samples from deep litter system. Quail may carry health risks to consumers.

Copper tolerance and virulence in bacteria

PubMed Central

Ladomersky, Erik; Petris, Michael J.

2015-01-01

Copper (Cu) is an essential trace element for all aerobic organisms. It functions as a cofactor in enzymes that catalyze a wide variety of redox reactions due to its ability to cycle between two oxidation states, Cu(I) and Cu(II). This same redox property of copper has the potential to cause toxicity if copper homeostasis is not maintained. Studies suggest that the toxic properties of copper are harnessed by the innate immune system of the host to kill bacteria. To counter such defenses, bacteria rely on copper tolerance genes for virulence within the host. These discoveries suggest bacterial copper intoxication is a component of host nutritional immunity, thus expanding our knowledge of the roles of copper in biology. This review summarizes our current understanding of copper tolerance in bacteria, and the extent to which these pathways contribute to bacterial virulence within the host. PMID:25652326

Copper Metallochaperones

PubMed Central

Robinson, Nigel J.; Winge, Dennis R.

2014-01-01

The current state of knowledge on how copper metallochaperones support the maturation of cuproproteins is reviewed. Copper is needed within mitochondria to supply the CuA and intramembrane CuB sites of cytochrome oxidase, within the trans-Golgi network to supply secreted cuproproteins and within the cytosol to supply superoxide dismutase 1 (Sod1). Subpopulations of copper-zinc superoxide dismutase also localize to mitochondria, the secretory system, the nucleus and, in plants, the chloroplast, which also requires copper for plastocyanin. Prokaryotic cuproproteins are found in the cell membrane and in the periplasm of gram-negative bacteria. Cu(I) and Cu(II) form tight complexes with organic molecules and drive redox chemistry, which unrestrained would be destructive. Copper metallochaperones assist copper in reaching vital destinations without inflicting damage or becoming trapped in adventitious binding sites. Copper ions are specifically released from copper metallochaperones upon contact with their cognate cuproproteins and metal transfer is thought to proceed by ligand substitution. PMID:20205585

Pathogenic adaptations to host-derived antibacterial copper

PubMed Central

Chaturvedi, Kaveri S.; Henderson, Jeffrey P.

2014-01-01

Recent findings suggest that both host and pathogen manipulate copper content in infected host niches during infections. In this review, we summarize recent developments that implicate copper resistance as an important determinant of bacterial fitness at the host-pathogen interface. An essential mammalian nutrient, copper cycles between copper (I) (Cu+) in its reduced form and copper (II) (Cu2+) in its oxidized form under physiologic conditions. Cu+ is significantly more bactericidal than Cu2+ due to its ability to freely penetrate bacterial membranes and inactivate intracellular iron-sulfur clusters. Copper ions can also catalyze reactive oxygen species (ROS) generation, which may further contribute to their toxicity. Transporters, chaperones, redox proteins, receptors and transcription factors and even siderophores affect copper accumulation and distribution in both pathogenic microbes and their human hosts. This review will briefly cover evidence for copper as a mammalian antibacterial effector, the possible reasons for this toxicity, and pathogenic resistance mechanisms directed against it. PMID:24551598

Blue copper model complexes with distorted tetragonal geometry acting as effective electron-transfer mediators in dye-sensitized solar cells.

PubMed

Hattori, Shigeki; Wada, Yuji; Yanagida, Shozo; Fukuzumi, Shunichi

2005-07-06

The electron self-exchange rate constants of blue copper model complexes, [(-)-sparteine-N,N'](maleonitriledithiolato-S,S')copper ([Cu(SP)(mmt)])(0/)(-), bis(2,9-dimethy-1,10-phenanthroline)copper ([Cu(dmp)(2)](2+/+)), and bis(1,10-phenanthroline)copper ([Cu(phen)(2)](2+/+)) have been determined from the rate constants of electron transfer from a homologous series of ferrocene derivatives to the copper(II) complexes in light of the Marcus theory of electron transfer. The resulting electron self-exchange rate constant increases in the order: [Cu(phen)(2)](2+/+) < [Cu(SP)(mmt)](0/)(-) < [Cu(dmp)(2)](2+/+), in agreement with the order of the smaller structural change between the copper(II) and copper(I) complexes due to the distorted tetragonal geometry. The dye-sensitized solar cells (DSSC) were constructed using the copper complexes as redox couples to compare the photoelectrochemical responses with those using the conventional I(3)(-)/I(-) couple. The light energy conversion efficiency (eta) values under illumination of simulated solar light irradiation (100 mW/cm(2)) of DSSCs using [Cu(phen)(2)](2+/+), [Cu(dmp)(2)](2+/+), and [Cu(SP)(mmt)](0/)(-) were recorded as 0.1%, 1.4%, and 1.3%, respectively. The maximum eta value (2.2%) was obtained for a DSSC using the [Cu(dmp)(2)](2+/+) redox couple under the light irradiation of 20 mW/cm(2) intensity, where a higher open-circuit voltage of the cell was attained as compared to that of the conventional I(3)(-)/I(-) couple.

Theoretical (in B3LYP/6-3111++G** level), spectroscopic (FT-IR, FT-Raman) and thermogravimetric studies of gentisic acid and sodium, copper(II) and cadmium(II) gentisates.

PubMed

Regulska, E; Kalinowska, M; Wojtulewski, S; Korczak, A; Sienkiewicz-Gromiuk, J; Rzączyńska, Z; Swisłocka, R; Lewandowski, W

2014-11-11

The DFT calculations (B3LYP method with 6-311++G(d,p) mixed with LanL2DZ for transition metals basis sets) for different conformers of 2,5-dihydroxybenzoic acid (gentisic acid), sodium 2,5-dihydroxybenzoate (gentisate) and copper(II) and cadmium(II) gentisates were done. The proposed hydrated structures of transition metal complexes were based on the results of experimental findings. The theoretical geometrical parameters and atomic charge distribution were discussed. Moreover Na, Cu(II) and Cd(II) gentisates were synthesized and the composition of obtained compounds was revealed by means of elemental and thermogravimetric analyses. The FT-IR and FT-Raman spectra of gentisic acid and gentisates were registered and the effect of metals on the electronic charge distribution of ligand was discussed. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis, electrochemical, structural, spectroscopic and biological activities of mixed ligand copper (II) complexes with 2-{[(Z)-(5-bromo-2-hydroxyphenyl)methylidene]amino}benzoic acid and nitrogenous bases

NASA Astrophysics Data System (ADS)

Choudhary, Mukesh; Patel, R. N.; Rawat, S. P.

2014-02-01

Three new copper (II) complexes viz. [Cu(L1)(bipy)]ṡ2H2O 1, [Cu(L1)(dmp)]ṡCH3CN 2, [Cu(L1)(phen)] 3 where L1H2 = 2-{[(Z)-(5-bromo-2-hydroxyphenyl)methylidene]amino}benzoic acid, bipy = 2,2‧-bipyridine; dmp = 2,9-dimethyl 1,10-phenanthroline, phen = 1,10-phenanthroline have been synthesized and characterized by physic-chemical and spectroscopic methods. The solid-state structures of 1 and 2 were determined by single crystal X-ray crystallography, which revealed distorted square pyramidal geometry. In solid-state structure, 1 is self-assembled via intermolecular π…π stacking and the distances between centroids of aromatic ring is 3.525 Å. L1H2 is a diprotic tridentate Schiff base ligand having ONO donor site. Infrared spectra, ligand field spectra and magnetic susceptibility measurements agree with the observed crystal structures. The EPR spectra of these complexes in frozen DMSO solutions showed a single at g ca. 2. The trend in g-value (g|| > g⊥ > 2.0023) suggests that the unpaired electron on copper (II) has d character. Copper (II) complexes 1-3 yielded an irreversible couple corresponding to the Cu (II)/Cu (I) redox process. Superoxide dismutase activity of all these complexes has been revealed to catalyze the dismutation of superoxide (O2-) and IC50 values were evaluated and discussed. Antimicrobial and antifungal activities of these complexes were also investigated.

Ferromagnetic coupling by spin polarization in a trinuclear copper(II) metallacyclophane with a triangular cage-like structure.

PubMed

Dul, Marie-Claire; Ottenwaelder, Xavier; Pardo, Emilio; Lescouëzec, Rodrigue; Journaux, Yves; Chamoreau, Lise-Marie; Ruiz-García, Rafael; Cano, Joan; Julve, Miguel; Lloret, Francesc

2009-06-15

A series of trinuclear copper(II) complexes of general formula A(6)[Cu(3)L(2)] x nH(2)O [L = benzene-1,3,5-tris(oxamate); A = Li(+) (n = 8), 1a; Na(+) (n = 11.5), 1b; and K(+) (n = 8.5), 1c] have been synthesized, and they have been structurally and magnetically characterized. X-ray diffraction on single crystals of 1c shows the presence of three square-planar copper(II)-bis(oxamato) moieties which are connected by a double benzene-1,3,5-triyl skeleton to give a unique metallacyclophane-type triangular cage. The copper basal planes are virtually orthogonal to the two benzene rings, which adopt an almost perfect face-to-face alignment. Complexes 1a-c exhibit a quartet (S = 3/2) ground spin state resulting from the moderate ferromagnetic coupling (J values in the range of +7.3 to +16.5 cm(-1)) between the three Cu(II) ions across the two benzene-1,3,5-tris(amidate) bridges [H = -J(S(1) x S(2) + S(2) x S(3) + S(3) x S(1)) with S(1) = S(2) = S(3) = S(Cu) = 1/2]. Density functional theory calculations on the S = 3/2 Cu(II)(3) ground spin state of 1c support the occurrence of a spin polarization mechanism for the propagation of the exchange interaction, as evidenced by the sign alternation of the spin density in the 1,3,5-substituted benzene spacers.

Synthesis and spectral characterization of mono- and binuclear copper(II) complexes derived from 2-benzoylpyridine-N⁴-methyl-3-thiosemicarbazone: crystal structure of a novel sulfur bridged copper(II) box-dimer.

PubMed

Jayakumar, K; Sithambaresan, M; Aiswarya, N; Kurup, M R Prathapachandra

2015-03-15

Mononuclear and binuclear copper(II) complexes of 2-benzoylpyridine-N(4)-methyl thiosemicarbazone (HL) were prepared and characterized by a variety of spectroscopic techniques. Structural evidence for the novel sulfur bridged copper(II) iodo binuclear complex is obtained by single crystal X-ray diffraction analysis. The complex [Cu2L2I2], a non-centrosymmetric box dimer, crystallizes in monoclinic C2/c space group and it was found to have distorted square pyramidal geometry (Addison parameter, τ=0.238) with the square basal plane occupied by the thiosemicarbazone moiety and iodine atom whereas the sulfur atom from the other coordinated thiosemicarbazone moiety occupies the apical position. This is the first crystallographically studied system having non-centrosymmetrical entities bridged via thiolate S atoms with Cu(II)I bond. The tridentate thiosemicarbazone coordinates in mono deprotonated thionic tautomeric form in all complexes except in sulfato complex, [Cu(HL)(SO4)]·H2O (1) where it binds to the metal centre in neutral form. The magnetic moment values and the EPR spectral studies reflect the binuclearity of some of the complexes. The spin Hamiltonian and bonding parameters are calculated based on EPR studies. In all the complexes g||>g⊥>2.0023 and the g values in frozen DMF are consistent with the d(x2-y2) ground state. The thermal stabilities of some of the complexes were also determined. Copyright © 2014 Elsevier B.V. All rights reserved.

[1,1′-Diphenyl-3,3′-(propane-1,3-diyldinitrilo)dibut-1-enolato]copper(II)

PubMed Central

Salehi, Mehdi; Meghdadi, Soraia; Amirnasr, Mehdi; Mereiter, Kurt

2009-01-01

The title compound, [Cu(C23H24N2O2)] or [Cu{(BA)2pn}], where (BA)2pn is 1,1′-diphenyl-3,3′-(propane-1,3-diyldinitrilo)dibut-1-enolate, is a mononuclear copper(II) complex, located on a twofold axis. The four-coordinate CuII atom is in a tetra­hedrally distorted square plane defined by the N and O atoms of the Schiff base ligand. In the tetra­dentate ligand, the two chelate rings are twisted relative to each other, making a dihedral angle of 36.57 (3)°. PMID:21581795

The second Cu(II)-binding site in a proton-rich environment interferes with the aggregation of amyloid-beta(1-40) into amyloid fibrils.

PubMed

Jun, Sangmi; Gillespie, Joel R; Shin, Byong-kyu; Saxena, Sunil

2009-11-17

The overall morphology and Cu(II) ion coordination for the aggregated amyloid-beta(1-40) [Abeta(1-40)] in N-ethylmorpholine (NEM) buffer are affected by Cu(II) ion concentration. This effect is investigated by transmission electron microscopy (TEM), atomic force microscopy (AFM), and electron spin echo envelope modulation (ESEEM) spectroscopy. At lower than equimolar concentrations of Cu(II) ions, fibrillar aggregates of Abeta(1-40) are observed. At these concentrations of Cu(II), the monomeric and fibrillar Abeta(1-40) ESEEM data indicate that the Cu(II) ion is coordinated by histidine residues. For aggregated Abeta(1-40) at a Cu(II):Abeta molar ratio of 2:1, TEM and AFM images show both linear fibrils and granular amorphous aggregates. The ESEEM spectra show that the multi-histidine coordination for Cu(II) ion partially breaks up and becomes exposed to water or exchangeable protons of the peptide at a higher Cu(II) concentration. Since the continuous-wave electron spin resonance results also suggest two copper-binding sites in Abeta(1-40), the proton ESEEM peak may arise from the second copper-binding site, which may be significantly involved in the formation of granular amorphous aggregates. Thioflavin T fluorescence and circular dichroism experiments also show that Cu(II) inhibits the formation of fibrils and induces a nonfibrillar beta-sheet conformation. Therefore, we propose that Abeta(1-40) has a second copper-binding site in a proton-rich environment and the second binding Cu(II) ion interferes with a conformational transition into amyloid fibrils, inducing the formation of granular amorphous aggregates.

Colossal internal barrier layer capacitance effect in polycrystalline copper (II) oxide

NASA Astrophysics Data System (ADS)

Sarkar, Sudipta; Jana, Pradip Kumar; Chaudhuri, B. K.

2008-01-01

Dielectric spectroscopy analysis of the high permittivity (κ˜104) copper (II) oxide (CuO) ceramic shows that the grain contribution plays a major role for the giant-κ value at low temperature, whereas grain boundary (GB) contribution dominates around room temperature and above. Moreover, impedance spectroscopy analysis reveals electrically heterogeneous microstructure in CuO consisting of semiconducting grains and insulating GBs. Finally, the giant dielectric phenomenon exhibited by CuO is attributed to the internal barrier layer (due to GB) capacitance mechanism.

Ligand- and base-free copper(II)-catalyzed C-N bond formation: cross-coupling reactions of organoboron compounds with aliphatic amines and anilines.

PubMed

Quach, Tan D; Batey, Robert A

2003-11-13

[reaction: see text] A ligandless and base-free Cu-catalyzed protocol for the cross-coupling of arylboronic acids and potassium aryltrifluoroborate salts with primary and secondary aliphatic amines and anilines is described. The process utilizes catalytic copper(II) acetate monohydrate and 4 A molecular sieves in dichloromethane at slightly elevated temperatures under an atmosphere of oxygen. A broad range of functional groups are tolerated on both of the cross-coupling partners.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eilert, André; Roberts, F. Sloan; Friebel, Daniel

Nanostructured copper cathodes are among the most efficient and selective catalysts to date for making multicarbon products from the electrochemical carbon dioxide reduction reaction (CO 2RR). We report an in situ X-ray absorption spectroscopy investigation of the formation of a copper nanocube CO 2RR catalyst with high activity that highly favors ethylene over methane production. The results show that the precursor for the copper nanocube formation is copper(I)-oxide, not copper(I)-chloride as previously assumed. A second route to an electrochemically similar material via a copper(II)–carbonate/hydroxide is also reported. In conclusion, this study highlights the importance of using oxidized copper precursors formore » constructing selective CO 2 reduction catalysts and shows the precursor oxidation state does not affect the electrocatalyst selectivity toward ethylene formation.« less

High catalytic activity of oriented 2.0.0 copper(I) oxide grown on graphene film

PubMed Central

Primo, Ana; Esteve-Adell, Ivan; Blandez, Juan F.; Dhakshinamoorthy, Amarajothi; Álvaro, Mercedes; Candu, Natalia; Coman, Simona M.; Parvulescu, Vasile I.; García, Hermenegildo

2015-01-01

Metal oxide nanoparticles supported on graphene exhibit high catalytic activity for oxidation, reduction and coupling reactions. Here we show that pyrolysis at 900 °C under inert atmosphere of copper(II) nitrate embedded in chitosan films affords 1.1.1 facet-oriented copper nanoplatelets supported on few-layered graphene. Oriented (1.1.1) copper nanoplatelets on graphene undergo spontaneous oxidation to render oriented (2.0.0) copper(I) oxide nanoplatelets on few-layered graphene. These films containing oriented copper(I) oxide exhibit as catalyst turnover numbers that can be three orders of magnitude higher for the Ullmann-type coupling, dehydrogenative coupling of dimethylphenylsilane with n-butanol and C–N cross-coupling than those of analogous unoriented graphene-supported copper(I) oxide nanoplatelets. PMID:26509224

Syntheses, crystal structures, magnetic properties, and EPR spectra of tetranuclear copper(II) complexes featuring pairs of "roof-shaped" Cu2X2 dimers with hydroxide, methoxide, and azide bridges.

PubMed

Graham, B; Hearn, M T; Junk, P C; Kepert, C M; Mabbs, F E; Moubaraki, B; Murray, K S; Spiccia, L

2001-03-26

Hydroxo- and methoxo-bridged tetranuclear copper(II) complexes of the tetramacrocyclic ligand 1,2,4,5-tetrakis(1,4,7-triazacyclonon-1-ylmethyl)benzene (Ldur), have been prepared from [Cu4Ldur(H2O)8](ClO4)8.9H2O (1). Addition of base to an aqueous solution of 1 gave [Cu4Ldur(mu2-OH)4](ClO4)4 (2). Diffusion of MeOH into a DMF solution of 2 produces [Cu4Ldur(mu2-OMe)4](ClO4)4.HClO4.2/3MeOH (3), a complex which hydrolyzes on exposure to moisture regenerating 2. The structurally related azido-bridged complex, [Cu4Ldur(mu2-N3)4](PF6)4.4H2O.6CH3CN (4), was produced by reaction of Ldur with 4 molar equiv of Cu(OAc)2.H2O and NaN3 in the presence of excess KPF6. Compounds 2-4 crystallize in the triclinic space group P1 (No. 2) with a = 10.248(1) A, b = 12.130(2) A, c = 14.353(2) A, alpha = 82.23(1) degrees, beta = 80.79(1) degrees, gamma = 65.71(1) degrees, and Z = 1 for 2, a = 10.2985(4) A, b = 12.1182(4) A, c = 13.9705(3) A, alpha = 89.978(2) degrees, beta = 82.038(2) degrees, gamma = 65.095(2) degrees, and Z = 1 for 3, and a = 12.059(2) A, b = 12.554(2) A, c = 14.051(2) A, alpha = 91.85(1) degrees, beta = 98.22(1) degrees, gamma = 105.62(1) degrees, and Z = 1 for 4. The complexes feature pairs of isolated dibridged copper(II) dimers with "roof-shaped" Cu2(mu2-X)2 cores (X = OH-, OMe-, N3-), as indicated by the dihedral angle between the two CuX2 planes (159 degrees for 2, 161 degrees for 3, and 153 degrees for 4). This leads to Cu.Cu distances of 2.940(4) A for 2, 2.962(1) A for 3, and 3.006(5) A for 4. Variable-temperature magnetic susceptibility measurements indicate weak antiferromagnetic coupling (J = -27 cm(-1)) for the hydroxo-bridged copper(II) centers in 2 and very strong antiferromagnetic coupling (J = -269 cm(-1)) for the methoxo-bridged copper(II) centers in 3. Pairs of copper(II) centers in 4 display the strongest ferromagnetic interaction (J = 94 cm(-1)) reported thus far for bis(mu2-1,1-azido)-bridged dicopper units. Spectral measurements on a neat powdered sample of 4 at 33.9 GHz or 90 Ghz confirm the spin-triplet ground state for the azido-bridged copper(II) pairs.

Applications of RIGAKU Dmax Rapid II micro-X-ray diffractometer in the analysis of archaeological metal objects

NASA Astrophysics Data System (ADS)

Mozgai, Viktória; Szabó, Máté; Bajnóczi, Bernadett; Weiszburg, Tamás G.; Fórizs, István; Mráv, Zsolt; Tóth, Mária

2017-04-01

During material analysis of archaeological metal objects, especially their inlays or corrosion products, not only microstructure and chemical composition, but mineralogical composition is necessary to be determined. X-ray powder diffraction (XRD) is a widely-used method to specify the mineralogical composition. However, when sampling is not or limitedly allowed due to e.g. the high value of the object, the conventional XRD analysis can hardly be used. Laboratory micro-XRD instruments provide good alternatives, like the RIGAKU Dmax Rapid II micro-X-ray diffractometer, which is a unique combination of a MicroMax-003 third generation microfocus, sealed tube X-ray generator and a curved 'image plate' detector. With this instrument it is possible to measure as small as 10 µm area in diameter on the object. Here we present case studies for the application of the micro-XRD technique in the study of archaeological metal objects. In the first case niello inlay of a Late Roman silver augur staff was analysed. Due to the high value of the object, since it is the only piece known from the Roman Empire, only non-destructive analyses were allowed. To reconstruct the preparation of the niello, SEM-EDX analysis was performed on the niello inlays to characterise their chemical composition and microstructure. Two types of niello are present: a homogeneous, silver sulphide niello (acanthite) and an inhomogeneous silver-copper sulphide niello (exsolution of acanthite and jalpaite or jalpaite and stromeyerite). The micro-X-ray diffractometer was used to verify the mineralogical composition of the niello, supposed on the base of SEM results. In the second case corrosion products of a Late Roman copper cauldron with uncertain provenance were examined, since they may hold clues about the burial conditions (pH, Eh, etc.) of the object. A layer by layer analysis was performed in cross sections of small metal samples by using electron microprobe and micro-X-ray diffractometer. The results show two corrosion zones: 1) the original (internal) surface zone of the metallic copper object was replaced by copper(I) oxide (cuprite), while 2) basic copper(II) carbonate (malachite) was deposited (externally) on the original surface. In our view these two minerals were formed during long-time burial, and protected the cauldron from further corrosion. Rarely copper(I) chloride (nantokite), basic copper(II) trihydroxychloride (atacamite/paratacamite) and basic copper(II) sulphate (brochantite) were also identified in the two corrosion zones. Their uneven distribution on the cauldron and their known formation conditions indicate, that these latter mineral phases may be the results of active corrosion, started possibly after excavation.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shamie, Jack S.; Liu, Caihong; Shaw, Leon L.

In this study, a new mechanism for the reduction of vanadyl acetylacetonate, VO(acac)2, to vanadium acetylacetonate, V(acac)3, is introduced. V(acac)3 has been studied for use in redox flow batteries (RFBs) for some time; however, contamination by moisture leads to the formation of VO(acac)2. In previous work, once this transformation occurs, it is no longer reversible because there is a requirement for extreme low potentials for the reduction to occur. Here, we propose that, in the presence of excess acetylacetone (Hacac) and free protons (H+), the reduction can take place between 2.25 and 1.5 V versus Na/Na+ via a one-electron-transfer reduction.more » This reduction can take place in situ during discharge in a novel hybrid Na-based flow battery (HNFB) with a molten Na–Cs alloy as the anode. The in situ recovery of V(acac)3 during discharge is shown to allow the Coulombic efficiency of the HNFB to be ≈100 % with little or no capacity decay over cycles. In addition, utilizing two-electron-transfer redox reactions (i.e., V3+/V4+ and V2+/V3+ redox couples) per V ion to increase the energy density of RFBs becomes possible owing to the in situ recovery of V(acac)3 during discharge. The concept of in situ recovery of material can lead to more advances in maintaining the cycle life of RFBs in the future.« less

Adsorption properties of Silochrom chemically modified with nickel acetylacetonate

NASA Astrophysics Data System (ADS)

Pakhnutova, Evgeniya; Slizhov, Yuriy

2017-11-01

One of the areas of development of gas chromatography is the creation of new chromatographic materials that have improved sorption and analytical characteristics. In this work, for the first time, a new sorbent based on Silochrom C-120 modified with nickel acetylacetonate was studied using a complex of physico-chemical methods. It has been established that due to chemical modification of silica gel surface with nickel acetylacetonate the surface area of the specific surface decreases from 112 to 98 m2/g and surface acidity diminishes by 1.2 pH units. Using the thermogravimetric analysis it has been revealed that the obtained sorbent can be used in gas chromatography up to 290°C. Gas chromatography method was used to investigate the adsorption properties of the modified materials. According to the retention data of adsorbates: n-alkanes (C6-C9), benzene, ethanol, nitropropane and butanone-2 the differential molar adsorption energy q¯dif, 1, Henry adsorption constants K1,C, the differential molar entropy ΔS¯S1 and Δ q¯dif, 1 (special) of adsorbates in dispersion and specific interactions were calculated. The influence of the modifying additive on the changings in the thermodynamic retention characteristics of all sorbates because of the manifestation of specific sorbate-sorbent interactions has been shown. The highest values of the thermodynamic parameters were indicative for sorbates forming hydrogen bonds and capable of donor-acceptor interaction.

Optimization of the Yield of Lingzhi or Reishi Medicinal Mushroom, Ganoderma lucidum (Higher Basidiomycetes), Cultivated on a Sunflower Seed Hull Substrate Produced in Argentina: Effect of Olive Oil and Copper.

PubMed

Bidegain, Maximiliano A; Cubitto, Maria Amelia; Curvetto, Nestor Raul

2015-01-01

Sunflower seed hulls were used as the main component of a solid substrate for the cultivation of the lingzhi or reishi medicinal mushroom Ganoderma lucidum. This study evaluated the effects of supplementing the substrate with olive oil and copper (II) on the mushroom production (MP) parameters and fruiting body total triterpenoid content. The addition of 1.5% olive oil increased total MP by 21.7% (dry basis) in 3 flushes. Copper (60 ppm) increased the daily productivity of the first flush (MP per day) by both reducing the time needed to harvest the crop and increasing the MP. However, the MP at the second and third flushes was reduced. When both supplements were combined, the MP at the first flush was 43% higher than with control treatment. No significant change in mushroom total triterpenoid content was observed by the addition of supplements to the substrate. An increase of 145-155% in the mushroom copper content was obtained by the addition of 60 ppm copper to the substrate. It is thus recommended to use substrate formulations containing both olive oil and copper (II) and harvest just the first flush.

INORGANIC COORDINATION POLYMERS. IV. THE ATTEMPTED REPLACEMENT OF ACETYLACETONATE LIGANDS WITH PICOLINATE LIGANDS,

DTIC Science & Technology

HETEROCYCLIC COMPOUNDS, PHOSPHENE OXIDES, BENZENE, CHROMIUM COMPOUNDS, CHEMICAL REAC, SYNTHESIS (CHEMISTRY), CHEMICAL ANALY, SPECTRA (INFRARED), ABSORPTION, DISPLACE, POLYMERIZATION, ORGANIC NITROGEN, AROMATIC COMPOUNDS.

Two intriguing hydroxy-copper(II) coordination polymers with bis(triazole) and bicarboxylate ligands: Syntheses, structures and photocatalytic degradation of organic dyes

NASA Astrophysics Data System (ADS)

Zhao, Shan; Zheng, Tian-Rui; Shi, Lu-Lu; Li, Ke; Li, Bao-Long; Li, Hai-Yan

2017-09-01

Two intriguing coordination polymers [Cu2(OH)(mbtx)(sip)(H2O)2]n (1) and {[Cu3(OH)2(mbtx)(nip)2]·H2O}n (2) were synthesized by the hydrothermal method and characterized by elementary analysis, IR, PXRD, diffuse reflectance spectra and single-crystal X-ray diffraction (mbtx = 1,3-bis(1,2,4-triazol-4-yl)benzene, sip = sulfoisophthalate, nip = 5-nitroisophthalate). 1 shows an unusual 3-connected 2D network based on the dimeric hydroxy-copper(II) cluster [Cu2(μ-OH)] with the point symbol of 63. 2 exhibits an unusual 3D network based on 1D hydroxyl-copper(II) chains [Cu3(OH)2]n. 1 and 2 are highly efficient and universal photocatalysts for the degradation of the organic dyes such as methyl orange (MO), methylene blue (MB) and rhodamine B (RhB) under UV irradiation. The photocatalytic mechanism was supposed.

Interchange reaction of disulfides and denaturation of oxytocin by copper(II)/ascorbic acid/O2 system.

PubMed

Inoue, H; Hirobe, M

1987-05-29

The interchange reaction of disulfides was caused by the copper(II)/ascorbic acid/O2 system. The incubation of two symmetric disulfides, L-cystinyl-bis-L-phenylalanine (PP) and L-cystinyl-bis-L-tyrosine (TT), with L-ascorbic acid and CuSO4 in potassium phosphate buffer (pH 7.2, 50 mM) resulted in the formation of an asymmetric disulfide, L-cystinyl-L-phenylalanine-L-tyrosine (PT), and the final ratio of PP:PT:TT was 1:2:1. As the reaction was inhibited by catalase and DMSO only at the initial time, hydroxyl radical generated by the copper(II)/ascorbic acid/O2 system seemed to be responsible for the initiation of the reaction. Oxytocin and insulin were denatured by this system, and catalase and DMSO similarly inhibited these denaturations. As the composition of amino acids was unchanged after the reaction, hydroxyl radical was thought to cause the cleavage and/or interchange reaction of disulfides to denature the peptides.

ATR-FTIR spectroscopic investigation of the cis- and trans-bis-(α-amino acids) copper(II) complexes

NASA Astrophysics Data System (ADS)

Berestova, Tatyana V.; Kuzina, Lyudmila G.; Amineva, Natalya A.; Faizrakhmanov, Ilshat S.; Massalimov, Ismail A.; Mustafin, Akhat G.

2017-06-01

The crystalline phases of the trans-(a) and cis-(b)-isomers of bis-(α-amino acids) copper(II) complexes [Cu(bL)2] 1-5 (bL - bidentate ligand: gly (1), S-ala (2), R,S-val (3), (±)-thr (4), R,S-phe (5)) were studied by ATR-FTIR spectroscopy in the mid region IR spectrum. It was established that asymmetric νas(COO) and symmetric νs(COO) stretching vibrations of carboxylic groups of 1-5 are sensitive to change of the geometric structure and have a different maxima for the trans(a)- and cis(b)-isomers. It found that νas(COO) and νs(COO) stretching vibrations of cis-isomers are broadened and shifted to longer wavelengths (b) as compared with trans-isomers (a). Shown that peculiarities of crystal packing molecules of geometric isomers may affect on carboxylate stretching vibration bis-α-amino acids complexes copper(II) 1-5 a,b.

How copper corrosion can be retarded--New ways investigating a chronic problem for cellulose in paper.

PubMed

Ahn, Kyujin; Hofmann, Christa; Horsky, Monika; Potthast, Antje

2015-12-10

To better assess the stabilization effects of chemical treatments on Cu(II)-catalyzed cellulose degradation, we developed Cu(II)-containing model rag paper with typical copper corrosion characteristics using e-beam radiation. The paper can be prepared homogeneously and quickly compared to tedious pre-aging methods. Using the Cu(II)-containing model rag paper, the stabilization effects of various chemicals on Cu(II)-catalyzed degradation of cellulose were tested. Benzotriazol was highly effective in retarding the degradation of the Cu(II)-containing model rag paper under hot and humid aging condition, as well as under photo-oxidative stress. Tetrabutylammonium bromide reduced Cu(II)-catalyzed degradation of cellulose, but its efficacy was dependent on the accelerated aging conditions. The results with the alkaline treatments and gelatin treatment suggested that their roles in the degradation mechanisms of cellulose in the presence of Cu(II) differ from those of benzotriazol and tetrabutylammonium bromide. Copyright © 2015 Elsevier Ltd. All rights reserved.

Reaction Mechanisms of Metals with Hydrogen Sulfide and Thiols in Model Wine. Part 1: Copper-Catalyzed Oxidation.

PubMed

Kreitman, Gal Y; Danilewicz, John C; Jeffery, David W; Elias, Ryan J

2016-05-25

Sulfidic off-odors as a result of hydrogen sulfide (H2S) and low-molecular-weight thiols are commonly encountered in wine production. These odors are usually removed by the process of Cu(II) fining, a process that remains poorly understood. The present study aims to elucidate the underlying mechanisms by which Cu(II) interacts with H2S and thiol compounds (RSH) under wine-like conditions. Copper complex formation was monitored along with H2S, thiol, oxygen, and acetaldehyde concentrations after the addition of Cu(II) (50 or 100 μM) to air-saturated model wine solutions containing H2S, cysteine, 6-sulfanylhexan-1-ol, or 3-sulfanylhexan-1-ol (300 μM each). The presence of H2S and thiols in excess to Cu(II) led to the rapid formation of ∼1.4:1 H2S/Cu and ∼2:1 thiol/Cu complexes, resulting in the oxidation of H2S and thiols and reduction of Cu(II) to Cu(I), which reacted with oxygen. H2S was observed to initially oxidize rather than form insoluble copper sulfide. The proposed reaction mechanisms provide insight into the extent to which H2S can be selectively removed in the presence of thiols in wine.

Interpretation of the Electron Paramagnetic Resonance Spectra of Copper(II)-Tyrosine Complex

NASA Astrophysics Data System (ADS)

Xu, Xiao-Hui; Kuang, Min-Quan

2017-12-01

The electron paramagnetic resonance (EPR) spectra of [Cu(l-tyrosine)2]n (CuA) were interpreted based on the fourth-order perturbation treatments where the contributions due to the local distortion, ligand orbit and spin-orbit coupling were included. The calculated band transitions d_{x^2} - y^2 to dxy (≈16412 cm-1) and d_{z^2} (≈14845 cm-1) agree well with the band analysis results (d_{x^2} - y^2 \\to d_{xy} ≈16410 and d_{x^2} - y^2 \\to d_{z^2} ≈14850 cm-1). The unresolved separations d_{x^2} - y^2 \\to d_{xz} and d_{x^2} - y^2 \\to d_{yz} in the absorption spectra were evaluated as 26283 and 26262 cm-1, respectively. For CuA, copper chromophores in 1,3-diaminorpropane isophtalate copper(II) complex (CuB) and N-methyl-1,2-diaminoetaane-bis copper(II) polymer (CuC), the transition d_{x^2} - y^2 \\to d_{xy} (=E1≈10Dq) suffered an increase with a decrease in R̅L which was evaluated as the mean value of the copper-ligand bond lengths. The correlations between the tetragonal elongation ratio ρ (=(Rz-R̅L)/R̅L) (or the ratio G=(gz-ge)/((gx+gy)/2-ge)) and the g isotropy gav (=(gx+gy+gz)/3) (or the covalency factor N) for CuA, CuB and CuC were acquired and all the results were discussed.

Two Silene vulgaris copper transporters residing in different cellular compartments confer copper hypertolerance by distinct mechanisms when expressed in Arabidopsis thaliana.

PubMed

Li, Yanbang; Iqbal, Mazhar; Zhang, Qianqian; Spelt, Cornelis; Bliek, Mattijs; Hakvoort, Henk W J; Quattrocchio, Francesca M; Koes, Ronald; Schat, Henk

2017-08-01

Silene vulgaris is a metallophyte of calamine, cupriferous and serpentine soils all over Europe. Its metallicolous populations are hypertolerant to zinc (Zn), cadmium (Cd), copper (Cu) or nickel (Ni), compared with conspecific nonmetallicolous populations. These hypertolerances are metal-specific, but the underlying mechanisms are poorly understood. We investigated the role of HMA5 copper transporters in Cu-hypertolerance of a S. vulgaris copper mine population. Cu-hypertolerance in Silene is correlated and genetically linked with enhanced expression of two HMA5 paralogs, SvHMA5I and SvHMA5II, each of which increases Cu tolerance when expressed in Arabidopsis thaliana. Most Spermatophytes, except Brassicaceae, possess homologs of SvHMA5I and SvHMA5II, which originate from an ancient duplication predating the appearance of spermatophytes. SvHMA5II and the A. thaliana homolog AtHMA5 localize in the endoplasmic reticulum and upon Cu exposure move to the plasma membrane, from where they are internalized and degraded in the vacuole. This resembles trafficking of mammalian homologs and is apparently an extremely ancient mechanism. SvHMA5I, instead, neofunctionalized and always resides on the tonoplast, likely sequestering Cu in the vacuole. Adaption of Silene to a Cu-polluted soil is at least in part due to upregulation of two distinct HMA5 transporters, which contribute to Cu hypertolerance by distinct mechanisms. © 2017 The Authors. New Phytologist © 2017 New Phytologist Trust.

Formation of Copper Catalysts for CO 2 Reduction with High Ethylene/Methane Product Ratio Investigated with In Situ X-ray Absorption Spectroscopy

DOE PAGES

Eilert, André; Roberts, F. Sloan; Friebel, Daniel; ...

2016-04-04

Nanostructured copper cathodes are among the most efficient and selective catalysts to date for making multicarbon products from the electrochemical carbon dioxide reduction reaction (CO 2RR). We report an in situ X-ray absorption spectroscopy investigation of the formation of a copper nanocube CO 2RR catalyst with high activity that highly favors ethylene over methane production. The results show that the precursor for the copper nanocube formation is copper(I)-oxide, not copper(I)-chloride as previously assumed. A second route to an electrochemically similar material via a copper(II)–carbonate/hydroxide is also reported. In conclusion, this study highlights the importance of using oxidized copper precursors formore » constructing selective CO 2 reduction catalysts and shows the precursor oxidation state does not affect the electrocatalyst selectivity toward ethylene formation.« less

Developing Anticancer Copper(II) Pro-drugs Based on the Nature of Cancer Cells and the Human Serum Albumin Carrier IIA Subdomain.

PubMed

Gou, Yi; Qi, Jinxu; Ajayi, Joshua-Paul; Zhang, Yao; Zhou, Zuping; Wu, Xiaoyang; Yang, Feng; Liang, Hong

2015-10-05

To synergistically enhance the selectivity and efficiency of anticancer copper drugs, we proposed and built a model to develop anticancer copper pro-drugs based on the nature of human serum albumin (HSA) IIA subdomain and cancer cells. Three copper(II) compounds of a 2-hydroxy-1-naphthaldehyde benzoyl hydrazone Schiff-base ligand in the presence pyridine, imidazole, or indazole ligands were synthesized (C1-C3). The structures of three HSA complexes revealed that the Cu compounds bind to the hydrophobic cavity in the HSA IIA subdomain. Among them, the pyridine and imidazole ligands of C1 and C2 are replaced by Lys199, and His242 directly coordinates with Cu(II). The indazole and Br ligands of C3 are replaced by Lys199 and His242, respectively. Compared with the Cu(II) compounds alone, the HSA complexes enhance cytotoxicity in MCF-7 cells approximately 3-5-fold, but do not raise cytotoxicity levels in normal cells in vitro through selectively accumulating in cancer cells to some extent. We find that the HSA complex has a stronger capacity for cell cycle arrest in the G2/M phase of MCF-7 by targeting cyclin-dependent kinase 1 (CDK1) and down-regulating the expression of CDK1 and cyclin B1. Moreover, the HSA complex promotes MCF-7 cell apoptosis possibly through the intrinsic reactive oxygen species (ROS) mediated mitochondrial pathway, accompanied by the regulation of Bcl-2 family proteins.

Theoretical, biological and in silico studies of pendant-armed heteroleptic copper(II) phenolate complexes

NASA Astrophysics Data System (ADS)

Arthi, P.; Mahendiran, D.; Shobana, S.; Srinivasan, P.; Rahiman, A. Kalilur

2018-06-01

A new series of pendant-armed heteroleptic copper(II) phenolate complexes of the type [CuL1-3(diimine)] (1-6) have been synthesized by the reaction of pendant-armed ligands 2,2'-(benzoyliminodiethylene)bissalicylidene (H2L1), 2,2'-(4-nitrobenzoyliminodiethylene)bissalicylidene (H2L2) or 2,2'-(3,5-dinitrobenzoyliminodiethylene)bissalicylidene (H2L3) with coligands (diimine; 2,2‧-bipyridyl (bpy) or 1,10-phenanthroline (phen)) in the presence of copper(II) chloride, and characterized by spectroscopic techniques. The seven coordinated pentagonal-bipyramidal geometry around the copper(II) center was inferred from the electronic spectra of the complexes. The bond length, bond angle and HOMO-LUMO energy gap calculations were carried out by DFT studies, using Gaussian 03 program. Electrochemical studies of the mononuclear complexes evidenced one-electron irreversible reduction wave in the cathodic region (Epc = -0.61 to -0.65 V). Experimental and in silico molecular docking studies support groove mode of binding with DNA. Further, the molecular docking studies of complexes with B-DNA indicate the binding of the guanine-cytosine residues in the minor groove of the DNA. Molecular docking studies also revealed the interaction of complexes with protein ERK2 kinase and significant topoisomerase (Topo-I) inhibitory activity. All the complexes display pronounced cleavage activity against supercoiled pBR322 DNA in the presence of H2O2. In vitro cytotoxicity of the complexes was tested against liver cancer cell line (HepG2) by MTT reduction assay.

Investigation of simultaneous biosorption of copper(II) and chromium(VI) on dried Chlorella vulgaris from binary metal mixtures: Application of multicomponent adsorption isotherms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aksu, Z.; Acikel, U.; Kutsal, T.

1999-02-01

Although the biosorption of single metal ions to various kinds of microorganisms has been extensively studied and the adsorption isotherms have been developed for only the single metal ion situation, very little attention has been given to the bioremoval and expression of adsorption isotherms of multimetal ions systems. In this study the simultaneous biosorption of copper(II) and chromium(VI) to Chlorella vulgaris from a binary metal mixture was studied and compared with the single metal ion situation in a batch stirred system. The effects of pH and single- and dual-metal ion concentrations on the equilibrium uptakes were investigated. In previous studiesmore » the optimum biosorption pH had been determined as 4.0 for copper(II) and as 2.0 for chromium(VI). Multimetal ion biosorption studies were performed at these two pH values. It was observed that the equilibrium uptakes of copper(II) or chromium(VI) ions were changed due to the biosorption pH and the presence of other metal ions. Adsorption isotherms were developed for both single- and dual-metal ions systems at these two pH values, and expressed by the mono- and multicomponent Langmuir and Freundlich adsorption models. Model parameters were estimated by nonlinear regression. It was seen that the adsorption equilibrium data fitted very well to the competitive Freundlich model in the concentration ranges studied.« less

Electrochemical Water Oxidation and Stereoselective Oxygen Atom Transfer Mediated by a Copper Complex.

PubMed

Kafentzi, Maria-Chrysanthi; Papadakis, Raffaello; Gennarini, Federica; Kochem, Amélie; Iranzo, Olga; Le Mest, Yves; Le Poul, Nicolas; Tron, Thierry; Faure, Bruno; Simaan, A Jalila; Réglier, Marius

2018-04-06

Water oxidation by copper-based complexes to form dioxygen has attracted attention in recent years, with the aim of developing efficient and cheap catalysts for chemical energy storage. In addition, high-valent metal-oxo species produced by the oxidation of metal complexes in the presence of water can be used to achieve substrate oxygenation with the use of H 2 O as an oxygen source. To date, this strategy has not been reported for copper complexes. Herein, a copper(II) complex, [(RPY2)Cu(OTf) 2 ] (RPY2=N-substituted bis[2-pyridyl(ethylamine)] ligands; R=indane; OTf=triflate), is used. This complex, which contains an oxidizable substrate moiety (indane), is used as a tool to monitor an intramolecular oxygen atom transfer reaction. Electrochemical properties were investigated and, upon electrolysis at 1.30 V versus a normal hydrogen electrode (NHE), both dioxygen production and oxygenation of the indane moiety were observed. The ligand was oxidized in a highly diastereoselective manner, which indicated that the observed reactivity was mediated by metal-centered reactive species. The pH dependence of the reactivity was monitored and correlated with speciation deduced from different techniques, ranging from potentiometric titrations to spectroscopic studies and DFT calculations. Water oxidation for dioxygen production occurs at neutral pH and is probably mediated by the oxidation of a mononuclear copper(II) precursor. It is achieved with a rather low overpotential (280 mV at pH 7), although with limited efficiency. On the other hand, oxygenation is maximum at pH 8-8.5 and is probably mediated by the electrochemical oxidation of an antiferromagnetically coupled dinuclear bis(μ-hydroxo) copper(II) precursor. This constitutes the first example of copper-centered oxidative water activation for a selective oxygenation reaction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A universal approach to the synthesis of nanodendrites of noble metals.

PubMed

Feng, Yan; Ma, Xiaohong; Han, Lin; Peng, Zhijian; Yang, Jun

2014-06-07

Nanomaterials usually exhibit structure-dependent catalytic activity, selectivity, and stability. Herein, we report a universal approach for the synthesis of noble metal nanoparticles with a dendritic structure, which is based on the reduction of metal acetylacetonate precursors in oleylamine at a temperature of 160 °C. In this strategy, the metal acetylacetonate precursors are reduced into metal atoms by oleylamine and grow into metal nanoparticles, while oleylamine is simultaneously converted into oleylamide to protect the nanoparticles. The competition between particle aggregation and oleylamide passivation is essential to the formation of a large number of particle aggregates, which eventually grow into nanodendrites via Ostwald ripening process. In particular, in comparison with commercial PtRu/C catalysts, the alloy PtRuOs nanodendrites exhibited superior catalytic activity toward methanol oxidation.

Resonance Raman spectra of the copper-sulfur chromophores in Achromobacter cycloclastes nitrite reductase.

PubMed

Dooley, D M; Moog, R S; Liu, M Y; Payne, W J; LeGall, J

1988-10-15

Resonance Raman spectroscopy at ambient temperature and 77 K has been used to probe the structures of the copper sites in Achromobacter cycloclastes nitrite reductase. This enzyme contains three copper ions per protein molecule and has two principal electronic absorption bands with lambda max values of 458 and 585 nm. Comparisons between the resonance Raman spectra of nitrite reductase and blue copper proteins establish that both the 458 and 585 nm bands are associated with Cu(II)-S(Cys) chromophores. A histidine ligand probably is also present. Different sets of vibrational frequencies are observed with 457.9 nm (ambient) or 476.1 nm (77 K) excitation as compared with 590 nm (ambient) or 593 nm (77 K) excitation. Excitation profiles indicate that the 458 and 585 nm absorption bands are associated with separate [Cu(II)-S(Cys)N(His)] sites or with inequivalent and uncoupled cysteine ligands in the same site. The former possibility is considered to be more likely.

Effects of ultrasound and temperature on copper electro reduction in Deep Eutectic Solvents (DES).

PubMed

Mandroyan, Audrey; Mourad-Mahmoud, Mahmoud; Doche, Marie-Laure; Hihn, Jean-Yves

2014-11-01

This paper concerns a preliminary study for a new copper recovery process from ionic solvent. The aim of this work is to study the reduction of copper in Deep Eutectic Solvent (choline chloride-ethylene glycol) and to compare the influence of temperature and the ultrasound effects on kinetic parameters. Solutions were prepared by dissolution of chloride copper salt CuCl2 (to obtain Copper in oxidation degree II) or CuCl (to obtain Copper in oxidation degree I) and by leaching metallic copper directly in DES. The spectrophotometry UV-visible analysis of the leached solution showed that the copper soluble form obtained is at oxidation degree I (Copper I). Both cyclic voltammetry and linear voltammetry were performed in the three solutions at three temperatures (25, 50 and 80°C) and under ultrasonic conditions (F=20kHz, PT=5.8W) to calculate the mass transfer diffusion coefficient kD and the standard rate coefficient k°. These parameters are used to determine that copper reduction is carried out via a mixed kinetic-diffusion control process. Temperature and ultrasound have the same effect on mass transfer for reduction of Cu(II)/Cu(I). On the other hand, temperature is more beneficial than ultrasound for mass transfer of Cu(I)/Cu. Standard rate constant improvement due to temperature increase is of the same order as that obtained with ultrasound. But, by combining higher temperature and ultrasound (F=20kHz, PT=5.6W at 50°C), reduction limiting current is increased by a factor of 10 compared to initial conditions (T=25°C, silent), because ultrasonic stirring is more efficient in lower viscosity fluid. These values can be considered as key-parameters in the design of copper recovery in global processes using ultrasound. Copyright © 2014 Elsevier B.V. All rights reserved.

Copper(II) imidazolate frameworks as highly efficient photocatalysts for reduction of CO{sub 2} into methanol under visible light irradiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Jingtian; Luo, Deliang; Yang, Chengju

2013-07-15

Three copper(II) imidazolate frameworks were synthesized by a hydrothermal (or precipitation) reaction. The catalysts were characterized by X-ray diffraction (XRD), nitrogen adsorption, transmission electron microscopy (TEM), ultraviolet–visible spectroscopy (UV–vis), Fourier transform infrared spectra (FTIR), thermogravimetry (TG). Meanwhile, the photocatalytic activities of the samples for reduction of CO{sub 2} into methanol and degradation of methylene blue (MB) under visible light irradiation were also investigated. The results show that the as-prepared samples exhibit better photocatalytic activities for the reduction of carbon dioxide into methanol with water and degradation of MB under visible light irradiation. The orthorhombic copper(II) imidazolate frameworks with a bandmore » gap of 2.49 eV and green (G) color has the best photocatalytic activity for reduction of CO{sub 2} into methanol, 1712.7 μmol/g over 5 h, which is about three times as large as that of monoclinic copper(II) imidazolate frameworks with a band gap 2.70 eV and blue (J) color. The degradation kinetics of MB over three photocatalysts fitted well to the apparent first-order rate equation and the apparent rate constants for the degradation of MB over G, J and P (with pink color) are 0.0038, 0.0013 and 0.0016 min{sup −1}, respectively. The synergistic effects of smallest band gap and orthorhombic crystal phase structure are the critical factors for the better photocatalytic activities of G. Moreover, three frameworks can also be stable up to 250 °C. The investigation of Cu-based zeolitic imidazolate frameworks maybe provide a design strategy for a new class of photocatalysts applied in degradation of contaminations, reduction of CO{sub 2}, and even water splitting into hydrogen and oxygen under visible light. - Graphical abstract: Carbon dioxide was reduced into methanol with water over copper(II) imidazolate frameworks under visible light irradiation. - Highlights: • Three copper(II) imidazolate frameworks were first applied in the photo-reduction of CO{sub 2}. • The photocatalytic activities of the frameworks depend on their band gap and phase structures. • The photocatalytic activity of orthorhombic frameworks is 3 times that of monoclinic frameworks. • The degradation kinetics of MB over three photocatalysts followed the first-order rate equation. • The largest yield for reduction of CO{sub 2} into methanol on green framworks was 1712.7 μmol/g over 5 h.« less

Synthesis, crystal structure and spectroscopic and electrochemical properties of bridged trisbenzoato copper-zinc heterobinuclear complex of 2,2‧-bipyridine

NASA Astrophysics Data System (ADS)

Koch, Angira; Kumar, Arvind; Singh, Suryabhan; Borthakur, Rosmita; Basumatary, Debajani; Lal, Ram A.; Shangpung, Sankey

2015-03-01

The synthesis of the heterobinuclear copper-zinc complex [CuZn(bz)3(bpy)2]ClO4 (bz = benzoate) from benzoic acid and bipyridine is described. Single crystal X-ray diffraction studies of the heterobinuclear complex reveals the geometry of the benzoato bridged Cu(II)-Zn(II) centre. The copper or zinc atom is pentacoordinate, with two oxygen atoms from bridging benzoato groups and two nitrogen atoms from one bipyridine forming an approximate plane and a bridging oxygen atom from a monodentate benzoate group. The Cu-Zn distance is 3.345 Å. The complex is normal paramagnetic having μeff value equal to 1.75 BM, ruling out the possibility of Cu-Cu interaction in the structural unit. The ESR spectrum of the complex in CH3CN at RT exhibit an isotropic four line spectrum centred at g = 2.142 and hyperfine coupling constants Aav = 63 × 10-4 cm-1, characteristic of a mononuclear square-pyramidal copper(II) complexes. At LNT, the complex shows an isotropic spectrum with g|| = 2.254 and g⊥ = 2.071 and A|| = 160 × 10-4 cm-1. The Hamiltonian parameters are characteristic of distorted square pyramidal geometry. Cyclic voltammetric studies of the complex have indicated quasi-reversible behaviour in acetonitrile solution.

Preparation and testing of a tetra-amine copper(II) chitosan bead system for enhanced phosphate remediation.

PubMed

Kumar, Ilango Aswin; Viswanathan, Natrayasamy

2018-03-01

A tetra-amine copper(II) chitosan bead system (TAC@CS composite beads) was developed by grafting tetra-amine copper(II) (TAC) with chitosan (CS) and utilized for phosphate removal. The prepared TAC@CS composite beads possess enhanced phosphate sorption capacity (SC) of 41.42 ± 0.071 mg/g than copper grafted chitosan (Cu@CS) composite, TAC and chitosan which were found to be 37.01 ± 0.803, 33.20 ± 0.650 and 7.24 ± 0.059 mg/g respectively. In batch mode, various adsorption influencing parameters like contact time, initial phosphate concentration, solution pH, co-anions and temperature were optimized for maximum phosphate sorption. The prepared adsorbents were characterized by FTIR, XRD, UV-Visible, SEM and EDAX analysis. The adsorption isotherms and thermodynamic parameters of the adsorbent were studied. The feasible phosphate uptake mechanism of TAC@CS biocomposite beads was reported. The reusability studies of TAC@CS composite beads were carried out using NaOH as elutant. The suitability of TAC@CS composite beads at field conditions was tested with phosphate contaminated field water samples collected from nearby areas of Dindigul district. Copyright © 2017 Elsevier Ltd. All rights reserved.

Preparation of Pt Nanocatalyst on Carbon Materials via a Reduction Reaction of a Pt Precursor in a Drying Process.

PubMed

Lee, Jae-Young; Lee, Woo-Kum; Rim, Hyung-Ryul; Joung, Gyu-Bum; Weidner, John W; Lee, Hong-Ki

2016-06-01

Platinum (Pt) nanocatalyst for a proton-exchange membrane fuel cell (PEMFC) was prepared on a carbon black particle or a graphite particle coated with a nafion polymer via a reduction of platinum(II) bis(acetylacetonate) denoted as Pt(acac)2 as a Pt precursor in a drying process. Sublimed Pt(acac)2 adsorbed on the nafion-coated carbon materials was reduced to Pt nanoparticles in a glass reactor at 180 degrees C of N2 atmosphere. The morphology of Pt nanoparticles on carbon materials was observed by scanning electron microscopy (SEM) and the distribution of Pt nanoparticles was done by transmission electron microscopy (TEM). The particle size was estimated by analyzing the TEM image using an image analyzer. It was found that nano-sized Pt particles were deposited on the surface of carbon materials, and the number density and the average particle size increased with increasing reduction time.

Operando X-ray absorption and EPR evidence for a single electron redox process in copper catalysis

DOE PAGES

Lu, Qingquan; Zhang, Jian; Peng, Pan; ...

2015-05-26

An unprecedented single electron redox process in copper catalysis is confirmed using operando X-ray absorption and EPR spectroscopies. The oxidation state of the copper species in the interaction between Cu(II) and a sulfinic acid at room temperature, and the accurate characterization of the formed Cu(I) are clearly shown using operando X-ray absorption and EPR evidence. Further investigation of anion effects on Cu(II) discloses that bromine ions can dramatically increase the rate of the redox process. Moreover, it is proven that the sulfinic acids are converted into sulfonyl radicals, which can be trapped by 2-arylacrylic acids and various valuable β-keto sulfonesmore » are synthesized with good to excellent yields under mild conditions.« less

Cu(II)-catalyzed oxidation of dopamine in aqueous solutions: mechanism and kinetics.

PubMed

Pham, A Ninh; Waite, T David

2014-08-01

Spontaneous oxidation of dopamine (DA) and the resultant formation of free radical species within dopamine neurons of the substantia nigra (SN) is thought to bestow a considerable oxidative load upon these neurons and may contribute to their vulnerability to degeneration in Parkinson's disease (PD). An understanding of DA oxidation under physiological conditions is thus critical to understanding the relatively selective vulnerability of these dopaminergic neurons in PD and may support the development of novel neuro-protective approaches for this disorder. In this study, the oxidation of dopamine (0.2-10μM) was investigated both in the absence and the presence of copper (0.01-0.4μM), a redox active metal that is present at considerable concentrations in the SN, over a range of background chloride concentrations (0.01-0.7M), different oxygen concentrations and at physiological pH7.4. DA was observed to oxidize extremely slowly in the absence of copper and at moderate rates only in the presence of copper but without chloride. The oxidation of DA however was significantly enhanced in the presence of both copper and chloride with the rate of DA oxidation greatest at intermediate chloride concentrations (0.05-0.2M). The variability of the catalytic effect of Cu(II) on DA oxidation at different chloride concentrations can be explained and successfully modeled by appropriate consideration of the reaction of Cu(II) species with DA and the conversion of Cu(I) to Cu(II) through oxygenation. This model suggests that the speciation of Cu(II) and Cu(I) is critically important to the kinetics of DA oxidation and thus the vulnerability to degradation of dopaminergic neuron in the brain milieu. Copyright © 2014 Elsevier Inc. All rights reserved.

Flavonoids and urate antioxidant interplay in plasma oxidative stress.

PubMed

Filipe, P; Lança, V; Silva, J N; Morlière, P; Santus, R; Fernandes, A

2001-05-01

Flavonoids are naturally occurring plant compounds with antioxidant properties. Their consumption has been associated with the protective effects of certain diets against some of the complications of atherosclerosis. Low-density lipoprotein (LDL) oxidative modification is currently thought to be a significant event in the atherogenic process. Most of the experiments concerning the inhibition of LDL oxidation used isolated LDL. We used diluted human whole plasma to study the influence of flavonoids on lipid peroxidation (LPO) promoted by copper, and their interaction with uric acid, one of the most important plasma antioxidants. Lipid peroxidation was evaluated by the formation of thiobarbituric acid reactive substances (TBARS) and of free malondialdehyde (MDA). The comparative capability of the assayed flavonoids on copper (II) reduction was tested using the neocuproine colorimetric test. In our assay system, urate disappears and free MDA and TBARS formation increase during the incubation of plasma with copper. Most of the tested flavonoids inhibited copper-induced LPO. The inhibition of LPO by flavonoids correlated positively with their capability to reduce copper (II). The urate consumption during the incubation of plasma with copper was inhibited by myricetin, quercetin and kaempferol. The inhibition of urate degradation by flavonoids correlated positively with the inhibition of LPO. Urate inhibited the copper-induced LPO in a concentration-dependent mode. Luteolin, rutin, catechin and quercetin had an antioxidant synergy with urate. Our results show that some flavonoids could protect endogenous urate from oxidative degradation, and demonstrate an antioxidant synergy between urate and some of the flavonoids.

Selective separation of copper over solder alloy from waste printed circuit boards leach solution.

PubMed

Kavousi, Maryam; Sattari, Anahita; Alamdari, Eskandar Keshavarz; Firozi, Sadegh

2017-02-01

The printed circuit boards (PCBs) from electronic waste are important resource, since the PCBs contain precious metals such as gold, copper, tin, silver, platinum and so forth. In addition to the economic point of view, the presence of lead turns this scrap into dangerous to environment. This study was conducted as part of the development of a novel process for selective recovery of copper over tin and lead from printed circuit boards by HBF 4 leaching. In previous study, Copper with solder alloy was associated, simultaneously were leached in HBF 4 solution using hydrogen peroxide as an oxidant at room temperature. The objective of this study is the separation of copper from tin and lead from Fluoroborate media using CP-150 as an extractant. The influence of organic solvent's concentration, pH, temperature and A/O phase ratio was investigated. The possible extraction mechanism and the composition of the extracted species have been determined. The separation factors for these metals using this agent are reported, while efficient methods for separation of Cu (II) from other metal ions are proposed. The treatment of leach liquor for solvent extraction of copper with CP-150 revealed that 20% CP-150 in kerosene, a 30min period of contact time, and a pH of 3 were sufficient for the extraction of Cu(II) and 99.99% copper was recovered from the leached solution. Copyright © 2016. Published by Elsevier Ltd.

The serum concentration of copper in bipolar disorder.

PubMed

Siwek, Marcin; Styczeń, Krzysztof; Sowa-Kućma, Magdalena; Dudek, Dominika; Reczyński, Witold; Szewczyk, Bernadeta; Misztak, Paulina; Opoka, Włodzimierz; Topór-Mądry, Roman; Nowak, Gabriel; Rybakowski, Janusz K

2017-06-18

Some scientific reports indicate the changes in the concentration of serum copper in patients with bipolar disorder (BD), however the data are inconclusive. The aim of this study was to assess the concentration of copper in the blood serum of patients in various phases of BD compared to healthy volunteers, taking into consideration the specific clinical features, and the stage of illness. The study enrolled 133 patients with a diagnosis of BD (type I, II and NOS), including 61 people in depressive episode, 23 in mania or hypomania and 49 in remission. The control group consisted of 50 people. Atomic absorption spectrometry was used to measure the concentration of copper. There were no statistically significant differences in the serum copper concentration between patients in various phases of BD (mania/hypomania, depression, remission), sub-types (Type I, Type II + NOS) or stages and healthy volunteers. However, serum copper concentrations in patients in stage 1 was significantly higher than in advanced stages (2+3+4), (ß = 0.22; p = 0.02). Serum copper concentration was also the higher, the later the age of onset was (ß = 0.33; p < 0.001), and the lower, the greater the number of illness episodes (ß = - 0.23; p = 0.02) (multiple regression model, adj R2 = 0.19, p = 0.0001). The dependencies demonstrated above may reflect pathophysiological processes that occur in the course of BD (e.g., inflammatory response and oxidative stress) with a different intensity depending on its stage.

Copper phthalocyanine films deposited by liquid-liquid interface recrystallization technique (LLIRCT).

PubMed

Patil, K R; Sathaye, S D; Hawaldar, R; Sathe, B R; Mandale, A B; Mitra, A

2007-11-15

The simple recrystallization process is innovatively used to obtain the nanoparticles of copper phthalocyanine by a simple method. Liquid-liquid interface recrystallization technique (LLIRCT) has been employed successfully to produce small sized copper phthalocyanine nanoparticles with diameter between 3-5 nm. The TEM-SAED studies revealed the formation of 3-5 nm sized with beta-phase dominated mixture of alpha and beta copper phthalocyanine nanoparticles. The XRD, SEM, and the UV-vis studies were further carried out to confirm the formation of copper phthalocyanine thin films. The cyclic voltametry (CV) studies conclude that redox reaction is totally reversible one electron transfer process. The process is attributed to Cu(II)/Cu(I) redox reaction.

Photochemical studies and nanomolar photodynamic activities of phthalocyanines functionalized with 1,4,7-trioxanonyl moieties at their non-peripheral positions.

PubMed

Sobotta, Lukasz; Wierzchowski, Marcin; Mierzwicki, Michal; Gdaniec, Zofia; Mielcarek, Jadwiga; Persoons, Leentje; Goslinski, Tomasz; Balzarini, Jan

2016-02-01

Manganese(III), cobalt(II), copper(II), magnesium(II), zinc(II) and metal-free phthalocyanines, possessing 1,4,7-trioxanonyl substituents, at their non-peripheral positions, were subjected to photochemical, photodynamic and biological activity studies. Demetallated phthalocyanine and its metallated d-block analogues, with copper(II), cobalt(II), manganese(III) chloride, were found to be less efficient singlet oxygen generators in comparison to the zinc(II) analogue and zinc(II) phthalocyanine reference. Irradiation of several phthalocyanines for short time periods resulted in a substantially increased cytostatic activity against both suspension (leukemic/lymphoma at 85nM) and solid (cervix carcinoma at 72nM and melanoma at 81nM) tumour cell lines (up to 200-fold). Noteworthy is that enveloped viruses, such as for herpesvirus and influenza A virus, but not, non-enveloped virus strains, such as Coxsackie B4 virus and reovirus-1, exposed to irradiation in the presence of the phthalocyanines, markedly lost their infectivity potential. Copyright © 2015 Elsevier Inc. All rights reserved.

Synthesis, structure, and magnetic properties of regular alternating μ-bpm/di-μ-X copper(II) chains (bpm = 2,2'-bipyrimidine; X = OH, F).

PubMed

Marino, Nadia; Armentano, Donatella; De Munno, Giovanni; Cano, Joan; Lloret, Francesc; Julve, Miguel

2012-04-02

The preparation and X-ray crystal structure of four 2,2'-bipyrimidine (bpm)-containing copper(II) complexes of formula {[Cu(2)(μ-bpm)(H(2)O)(4)(μ-OH)(2)][Mn(H(2)O)(6)](SO(4))(2)}(n) (1), {[Cu(2)(μ-bpm)(H(2)O)(4)(μ-OH)(2)]SiF(6)}(n) (2), {Cu(2)(μ-bpm)(H(2)O)(2)(μ-F)(2)F(2)}(n) (3), and [Cu(bpm)(H(2)O)(2)F(NO(3))][Cu(bpm)(H(2)O)(3)F]NO(3)·2H(2)O (4) are reported. The structures of 1-3 consist of chains of copper(II) ions with regular alternation of bis-bidentate bpm and di-μ-hydroxo (1 and 2) or di-μ-fluoro (3) groups, the electroneutrality being achieved by either hexaaqua manganese(II) cations plus uncoordinated sulfate anions (1), uncoordinated hexafluorosilicate anions (2), or terminally bound fluoride ligands (3). Each copper(II) ion in 1-4 is six-coordinated in elongated octahedral surroundings. 1 and 2 show identical, linear chain motifs with two bpm-nitrogen atoms and two hydroxo groups building the equatorial plane at each copper(II) ion and the axial position being filled by water molecules. In the case of 3, the axial sites at the copper atom are occupied by a bpm-nitrogen atom and a bis-monodentate fluoride anion, producing a "step-like" chain motif. The values of the angle at the hydroxo and fluoro bridges are 94.11(6) (1), 94.75(4) (2), and 101.43(4)° (3). In each case, the copper-copper separation through the bis-bidentate bpm [5.428(1) (1), 5.449(1) (2), and 5.9250(4) Å (3)] is considerably longer than that through the di-μ-hydroxo [2.8320(4) (1) and 2.824(1) Å (2)] or di-μ-fluoro [3.3027(4) Å (3)] bridges. Compound 4 is a mononuclear species whose structure is made up of neutral [Cu(bpm)(H(2)O)(2)F(NO(3))] units, [Cu(bpm)(H(2)O)(3)F](+) cations, uncoordinated nitrate anions, and crystallization water molecules, giving rise to a pseudo-helical, one-dimensional (1D) supramolecular motif. The magnetic properties of 1-3 have been investigated in the temperature range 1.9-300 K. Relatively large, alternating antiferro- [J = -149 (1) and -141 cm(-1) (2) across bis-bidentate bpm] and ferromagnetic [αJ = +194 (1) and +176 cm(-1) (2) through the dihydroxo bridges] interactions occur in 1 and 2 [the Hamiltonian being defined as H = -J∑(i=1)(n/2) (S(2i)·S(2i-1) - αS(2i)·S(2i+1))]. These values compare well with those previously reported for parent examples. Two weak intrachain antiferromagnetic interactions [J = -0.30 and αJ = -8.1 cm(-1) across bpm and the di-μ-fluoro bridges, respectively] whose values were substantiated by density functional theory (DFT)-type calculations occur in 3.

Copper(II)-catalyzed hydroxylation of aryl halides using glycolic acid as a ligand.

PubMed

Xiao, Yan; Xu, Yongnan; Cheon, Hwan-Sung; Chae, Junghyun

2013-06-07

Copper(II)-catalyzed hydroxylation of aryl halides has been developed to afford functionalized phenols. The protocol utilizes the reagent combination of Cu(OH)2, glycolic acid, and NaOH in aqueous DMSO, all of which are cheap, readily available, and easily removable after the reaction. A broad range of aryl iodides and activated aryl bromides were transformed into the corresponding phenols in excellent yields. Moreover, it has been shown that C-O(alkyl)-coupled product, instead of phenol, can be predominantly formed under similar reaction conditions.

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

PubMed

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.

Scalable room-temperature conversion of copper(II) hydroxide into HKUST-1 (Cu3 (btc)2).

PubMed

Majano, Gerardo; Pérez-Ramírez, Javier

2013-02-20

Copper(II) hydroxide is converted directly to HKUST-1 (Cu(3) (btc)(2) ) after only 5 min at room-temperature in aqueous ethanolic solution without the need of additional solvents. Scale up to the kilogram scale does not influence porous properties yielding pure-phase product with a remarkable total surface area exceeding 1700 m(2) g(-1) featuring aggregates of nanometer-sized crystals (<600 nm) and extremely high space-time yields. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetics of Electrocatalysis of Dibromoalkyl Reductions Using Electrodes with Covalently Immobilized Metallotetraphenylporphyrins.

DTIC Science & Technology

1981-01-29

Technical Report Using Electrodes with Covalently Immobilized Metal l otetraphenyl porphyri ns G. PERFORMING ORG. REPORT NUMBER 7. AU𔄁IOR(’.) 0...and CH2BrCHBrCH 3 at the surfaces of electrodes to which cobalt(II) or copper (II) tetra(p-aminophenyl)porphyrin has been covalently attached is strongly...27514 ABSTRACT The reduction of PhCHBrCH 2 Br, PhCHBrCHBrPh, and CH2BrCHBrCH3 at the surfaces of electrodes to which cobalt(lI) or copper (If) tetra(p

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

NASA Astrophysics Data System (ADS)

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.

Using Nazarov Electrocyclization to Stage Chemoselective [1,2]-Migrations: Stereoselective Synthesis of Functionalized Cyclopentenones

PubMed Central

Lebœuf, David; Huang, Jie; Gandon, Vincent

2012-01-01

Highly functionalized cyclopentenones are prepared stereospecifically based on a chemoselective copper(II)-mediated Nazarov/Wagner-Meerwein rearrangement sequence. After the initial 4π electrocyclization, this reaction involves two sequential [1,2]-migrations depending upon both migratory ability and steric bulk of the substituents at C1 and C5. This sequence can be achieved by using a catalytic quantity of copper(II) in combination with a weak Lewis acid. The mechanism of the reaction is also supported by DFT computations. PMID:21953873

Isolation of a new two-dimensional honeycomb carbonato-bridged copper(II) complex exhibiting long-range ferromagnetic ordering.

PubMed

Majumder, Arpi; Choudhury, Chirantan Roy; Mitra, Samiran; Rosair, Georgina M; El Fallah, M Salah; Ribas, Joan

2005-04-28

Atmospheric CO2 fixation by an aqueous solution containing Cu(ClO4)2.6H2O and 4-aminopyridine (4-apy) yields a novel example of a two-dimensional mu3-CO3 bridged copper(II) complex {[Cu(4-apy)2]3(mu3-CO3)2(ClO4)2.(1/2)CH3OH}n that has been characterized by IR, UV and X-ray crystallography; preliminary magnetic measurements show that complex exhibits long-range ordered ferromagnetic coupling.

Acute toxicities of copper, cadmium and Cu: Cd mixture to larvae of the shrimp Penaeus Penicillatus

NASA Astrophysics Data System (ADS)

Munshi, A. B.; Su, Yong-Quan; Li, Shao-Jing

1996-06-01

This study showed lethal concentrations (LC) of copper for Peneaus penicillatus at various stages of its life cycle were 1000 μg/L for nauplii, 1000 μg/L for Zoea I, 2000 vg/L for Zoea II, 2500 μg/L for Zoea III, 3000 μg/L for Mysis I, II and III and that for almost 100% mortality for postlarvae was 3000 μg/L. For cadmium LC were 100 μg/L for nauplii, 500 μg/L for Zoea I, 1000 μg/L for Zoea II, 2000 μg/L for Zoea III, 2500 μg/L for Mysis I and 3500 μg/L for Mysis II, III and postlarvae. For mixture of both metals, LC were 400 μg/L for nauplii, 1000 μg/L for Zoea I, 2000 μg/L for Zoea II and 3000 μg/L for Mysis I, II, III and post larvae.

Improvement of ion chromatography with ultraviolet photometric detection and comparison with conductivity detection for the determination of serum cations.

PubMed

Shintani, H

1985-05-31

Studies were made of the analytical conditions required for indirect photometric ion chromatography using ultraviolet photometric detection (UV method) for the determination of serum cations following a previously developed serum pre-treatment. The sensitivities of the conductivity detection (CD) and UV methods and the amounts of serum cations determined by both methods were compared. Attempts to improve the sensitivity of the conventional UV method are reported. It was found that the mobile phase previously reported by Small and Miller showed no quantitative response when more than 4 mM copper(II) sulphate pentahydrate was used. As a result, there was no significant difference in the amounts of serum cations shown by the CD and UV methods. However, by adding 0.5-5 mM cobalt(II) sulphate heptahydrate, nickel(II) sulphate hexahydrate, zinc(II) sulphate heptahydrate or cobalt(II) diammonium sulphate hexahydrate to 0.5-1.5 mM copper(II) sulphate pentahydrate, higher sensitivity and a quantitative response were attained.

Exploration of a Variety of Copper Molybdate Coordination Hybrids Based on a Flexible Bis(1,2,4-triazole) Ligand: A Look through the Composition-Space Diagram.

PubMed

Senchyk, Ganna A; Lysenko, Andrey B; Domasevitch, Konstantin V; Erhart, Oliver; Henfling, Stefan; Krautscheid, Harald; Rusanov, Eduard B; Krämer, Karl W; Decurtins, Silvio; Liu, Shi-Xia

2017-11-06

We investigated the coordination ability of the bis(1,2,4-triazolyl) module, tr 2 pr = 1,3-bis(1,2,4-triazol-4-yl)propane, toward the engineering of solid-state structures of copper polyoxomolybdates utilizing a composition space diagram approach. Different binding modes of the ligand including [N-N]-bridging and N-terminal coordination and the existence of favorable conformation forms (anti/anti, gauche/anti, and gauche/gauche) resulted in varieties of mixed metal Cu I /Mo VI and Cu II /Mo VI coordination polymers prepared under hydrothermal conditions. The composition space analysis employed was aimed at both the development of new coordination solids and their crystallization fields through systematic changes of the reagent ratios [copper(II) and molybdenum(VI) oxide precursors and the tr 2 pr ligand]. Nine coordination compounds were synthesized and structurally characterized. The diverse coordination architectures of the compounds are composed of cationic fragments such as [Cu II 3 (μ 2 -OH) 2 (μ 2 -tr) 2 ] 4+ , [Cu II 3 (μ 2 -tr) 6 ] 6+ , [Cu II 2 (μ 2 -tr) 3 ] 4+ , etc., connected to polymeric arrays by anionic species (molybdate MoO 4 2- , isomeric α-, δ-, and β-octamolybdates {Mo 8 O 26 } 4- or {Mo 8 O 28 H 2 } 6- ). The inorganic copper(I,II)/molybdenum(VI) oxide matrix itself forms discrete or low-dimensional subtopological motifs (0D, 1D, or 2D), while the organic spacers interconnect them into higher-dimensional networks. The 3D coordination hybrids show moderate thermal stability up to 230-250 °C, while for the 2D compounds, the stability of the framework is distinctly lower (∼190 °C). The magnetic properties of the most representative samples were investigated. The magnetic interactions were rationalized in terms of analyzing the planes of the magnetic orbitals.

Copper(II)-catalyzed electrophilic amination of quinoline N-oxides with O-benzoyl hydroxylamines.

PubMed

Li, Gang; Jia, Chunqi; Sun, Kai; Lv, Yunhe; Zhao, Feng; Zhou, Kexiao; Wu, Hankui

2015-03-21

Copper acetate-catalyzed C-H bond functionalization amination of quinoline N-oxides was achieved using O-benzoyl hydroxylamine as an electrophilic amination reagent, thereby affording the desired products in moderate to excellent yields. Electrophilic amination can also be performed in good yield on a gram scale.

Stereoselective Synthesis of Morpholines Via Copper-Promoted Oxyamination of Alkenes

PubMed Central

Sequeira, Fatima C.

2012-01-01

A new copper(II) 2-ethylhexanoate promoted addition of an alcohol and an amine across an alkene (oxyamination) is reported. The alcohol addition is intramolecular while coupling with the amine occurs intermolecularly. Several 2-aminomethyl morpholines were synthesized in good to excellent yields and diastereoselectivities. PMID:22894680

Optimization of chemical displacement deposition of copper on porous silicon.

PubMed

Bandarenka, Hanna; Redko, Sergey; Nenzi, Paolo; Balucani, Marco; Bondarenko, Vitaly

2012-11-01

Copper (II) sulfate was used as a source of copper to achieve uniform distribution of Cu particles deposited on porous silicon. Layers of the porous silicon were formed by electrochemical anodization of Si wafers in a mixture of HF, C3H7OH and deionized water. The well-known chemical displacement technique was modified to grow the copper particles of specific sizes. SEM and XRD analysis revealed that the outer surface of the porous silicon was covered with copper particles of the crystal orientation inherited from the planes of porous silicon skeleton. The copper crystals were found to have the cubic face centering elementary cell. In addition, the traces of Cu2O cubic primitive crystalline phases were identified. The dimensions of Cu particles were determined by the Feret's analysis of the SEM images. The sizes of the particles varied widely from a few to hundreds of nanometers. A phenomenological model of copper deposition was proposed.

Macrocyclic bifunctional chelating agents

DOEpatents

Meares, Claude F.; DeNardo, Sally J.; Cole, William C.; Mol, Min K.

1987-01-01

A copper chelate conjugate which is stable in human serum. The conjugate includes the copper chelate of a cyclic tetraaza di-, tri-, or tetra-acetic acid, a linker attached at one linker end to a ring carbon of the chelate, and a biomolecule joined at the other end of the linker. The conjugate, or the linker-copper chelate compound used in forming the conjugate, are designed for use in diagnostic and therapeutic applications which involve Cu(II) localization via the systemic route.

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

Mixed-ligand cobalt(II) complexes of bioinorganic and medicinal relevance, involving dehydroacetic acid and β-diketones: Their synthesis, hyphenated experimental-DFT, thermal and bactericidal facets

NASA Astrophysics Data System (ADS)

Maurya, R. C.; Malik, B. A.; Mir, J. M.; Vishwakarma, P. K.; Rajak, D. K.; Jain, N.

2015-11-01

The present report pertains to synthesis and combined experimental-DFT studies of a series of four novel mixed-ligand complexes of cobalt(II) of the general composition [Co(dha)(L)(H2O)2], where dhaH = dehydroacetic acid, LH = β-ketoenolates viz., o-acetoacetotoluidide (o-aatdH), o-acetoacetanisidide (o-aansH), acetylacetone (acacH) or 1-benzoylacetone (1-bac). The resulting complexes were formulated based on elemental analysis, molar conductance, magnetic measurements, mass spectrometric, IR, electronic, electron spin resonance and cyclic voltammetric studies. The TGA based thermal behavior of one representative complex was evaluated. Molecular geometry optimizations and vibrational frequency calculations have been performed with Gaussian 09 software package by using density functional theory (DFT) methods with B3LYP/LANL2MB combination for dhaH and one of its complexes, [Co(dha)(1-bac)(H2O)2]. Theoretical data has been found in an excellent agreement with the experimental results. Based on experimental and theoretical data, suitable trans-octahedral structure has been proposed for the present class of complexes. Moreover, the complexes also showed a satisfactory antibacterial activity.

Fluorescence and electron paramagnetic resonance studies of norfloxacin and N-donor mixed-ligand ternary copper(II) complexes: Stability and interaction with SDS micelles

NASA Astrophysics Data System (ADS)

Vignoli Muniz, Gabriel S.; Incio, Jimmy Llontop; Alves, Odivaldo C.; Krambrock, Klaus; Teixeira, Letícia R.; Louro, Sonia R. W.

2018-01-01

The stability of ternary copper(II) complexes of a heterocyclic ligand, L (L being 2,2‧-bipyridine (bipy) or 1,10-phenanthroline (phen)) and the fluorescent antibacterial agent norfloxacin (NFX) as the second ligand was studied at pH 7.4 and different ionic strengths. Fluorescence quenching upon titration of NFX with the binary complexes allowed to obtain stability constants for NFX binding, Kb, as a function of ionic strength. The Kb values vary by more than two orders of magnitude when buffer concentration varies from 0.5 to 100 mM. It was observed that previously synthesized ternary complexes dissociate in buffer according with the obtained stability constants. This shows that equimolar solutions of NFX and binary complexes are equivalent to solutions of synthesized ternary complexes. The interaction of the ternary copper complexes with anionic SDS (sodium dodecyl sulfate) micelles was studied by fluorescence and electron paramagnetic resonance (EPR). Titration of NFX-loaded SDS micelles with the complexes Cu:L allowed to determine the stability constants inside the micelles. Fluorescence quenching demonstrated that SDS micelles increase the stability constants by factors around 50. EPR spectra gave details of the copper(II) local environment, and demonstrated that the structure of the ternary complexes inside SDS micelles is different from that in buffer. Mononuclear ternary complexes formed inside the micelles, while in buffer most ternary complexes are binuclear. The results show that anionic membrane interfaces increase formation of copper fluoroquinolone complexes, which can influence bioavailability, membrane diffusion, and mechanism of action of the antibiotics.

The DFT Calculations of Structures and EPR Parameters for the Dinuclear Paddle-Wheel Copper(II) Complex {Cu2(μ2-O2CCH3)4}(OCNH2CH3) as Powder or Single Crystal

NASA Astrophysics Data System (ADS)

Ding, Chang-Chun; Wu, Shao-Yi; Xu, Yong-Qiang; Zhang, Li-Juan; Zhang, Zhi-Hong; Zhu, Qin-Sheng; Wu, Ming-He; Teng, Bao-Hua

2017-10-01

Density functional theory (DFT) calculations of the structures and the Cu2+ g factors (gx, gy and gz ) and hyperfine coupling tensor A (Ax , Ay and Az ) were performed for the paddle-wheel (PW)-type binuclear copper(II) complex {Cu2(μ2-O2CCH3)4}(OCNH2CH3) powder and single crystal. Calculations were carried out with the ORCA software using the functionals BHandHlyp, B3P86 and B3LYP with five different basis sets: 6-311g, 6-311g(d,p), VTZ, def-2 and def2-TZVP. Results were tested by the MPAD analysis to find the most suitable functional and basis sets. The electronic structure and covalency between copper and oxygen were investigated by the electron localisation function and the localised orbital locator as well as the Mayer bond order for the [CuO5] group. The optical spectra were theoretically calculated by the time-dependent DFT module and plotted by the Multiwfn program for the [CuO5] group and reasonably associated with the local structure in the vicinity of the central ion copper. In addition, the interactions between the OCNH2CH3, NH3 and H2O molecules and the uncoordinated PW copper(II) complex were studied, and the corresponding adsorption energies, the frequency shifts with respect to the free molecules and the changes of the Cu-Cu distances were calculated and compared with the relevant systems.

Four-electron Reduction of Dioxygen by a Multicopper Oxidase, CueO, and Roles of Asp112 and Glu506 Located Adjacent to the Trinuclear Copper Center*S⃞

PubMed Central

Kataoka, Kunishige; Sugiyama, Ryosuke; Hirota, Shun; Inoue, Megumi; Urata, Kanae; Minagawa, Yoichi; Seo, Daisuke; Sakurai, Takeshi

2009-01-01

The mechanism of the four-electron reduction of dioxygen by a multicopper oxidase, CueO, was studied based on reactions of single and double mutants with Cys500, a type I copper ligand, and the noncoordinating Asp112 and Glu506, which form hydrogen bonds with the trinuclear copper center directly and indirectly via a water molecule. The reaction of C500S containing a vacant type I copper center produced intermediate I in an EPR-silent peroxide-bound form. The formation of intermediate I from C500S/D112N was restricted due to a reduction in the affinity of the trinuclear copper center for dioxygen. The state of intermediate I was realized to be the resting form of C500S/E506Q and C500S of the truncated mutant Δα5–7CueO, in which the 50 amino acids covering the substrate-binding site were removed. Reactions of the recombinant CueO and E506Q afforded intermediate II, a fully oxidized form different from the resting one, with a very broad EPR signal, g < 2, detectable only at cryogenic temperatures and unsaturated with high power microwaves. The lifetime of intermediate II was prolonged by the mutation at Glu506 involved in the donation of protons. The structure of intermediates I and II and the mechanism of the four-electron reduction of dioxygen driven by Asp112 and Glu506 are discussed. PMID:19297322

Copper-redox cycling by coumarin-di(2-picolyl)amine hybrid molecule leads to ROS-mediated DNA damage and apoptosis: A mechanism for cancer chemoprevention.

PubMed

Khan, Saman; Zafar, Atif; Naseem, Imrana

2018-06-25

Coumarin is an important bioactive pharmacophore. It is found in plants as a secondary metabolite and exhibits diverse pharmacological properties including anticancer effects against different malignancies. Therapeutic efficacy of coumarin derivatives depends on the pattern of substitution and conjugation with different moieties. Cancer cells contain elevated copper as compared to normal cells that plays a role in angiogenesis. Thus, targeting copper in malignant cells via copper chelators can serve as an attractive targeted anticancer strategy. Our previous efforts led to the synthesis of di(2-picolyl)amine-3(bromoacetyl)coumarin hybrid molecule (ligand-L) endowed with DNA/Cu(II) binding properties, and ROS generation ability in the presence of copper ions. In the present study, we aimed to validate copper-dependent cytotoxic action of ligand-L against malignant cells. For this, we used a cellular model system of copper (Cu) overloaded lymphocytes (CuOLs) to simulate malignancy-like condition. In CuOLs, lipid peroxidation/protein carbonylation, ROS generation, DNA fragmentation and apoptosis were investigated in the presence of ligand-L. Results showed that ligand-L-Cu(II) interaction leads to ROS generation, lipid peroxidation/protein carbonylation (oxidative stress parameters), DNA damage, up-regulation of p53 and mitochondrial-mediated apoptosis in treated lymphocytes. Further, pre-incubation with neocuproine (membrane permeable copper chelator) and ROS scavengers attenuated the DNA damage and apoptosis. These results suggest that cellular copper acts as molecular target for ligand-L to propagate redox cycling and generation of ROS via Fenton-like reaction leading to DNA damage and apoptosis. Further, we showed that ligand-L targets elevated copper in breast cancer MCF-7 and colon cancer HCT116 cells leading to a pro-oxidant inhibition of proliferation of cancer cells. In conclusion, we propose copper-dependent ROS-mediated mechanism for the cytotoxic action of ligand-L in malignant cells. Thus, targeting elevated copper represents an effective therapeutic strategy for selective cytotoxicity against malignant cells. Copyright © 2018 Elsevier B.V. All rights reserved.

Luminescent zinc(ii) and copper(i) complexes for high-performance solution-processed monochromic and white organic light-emitting devices.

PubMed

Cheng, Gang; So, Gary Kwok-Ming; To, Wai-Pong; Chen, Yong; Kwok, Chi-Chung; Ma, Chensheng; Guan, Xiangguo; Chang, Xiaoyong; Kwok, Wai-Ming; Che, Chi-Ming

2015-08-01

The synthesis and spectroscopic properties of luminescent tetranuclear zinc(ii) complexes of substituted 7-azaindoles and a series of luminescent copper(i) complexes containing 7,8-bis(diphenylphosphino)-7,8-dicarba- nido -undecaborate ligand are described. These complexes are stable towards air and moisture. Thin film samples of the luminescent copper(i) complexes in 2,6-dicarbazolo-1,5-pyridine and zinc(ii) complexes in poly(methyl methacrylate) showed emission quantum yields of up to 0.60 (for Cu-3 ) and 0.96 (for Zn-1 ), respectively. Their photophysical properties were examined by ultrafast time-resolved emission spectroscopy, temperature dependent emission lifetime measurements and density functional theory calculations. Monochromic blue and orange solution-processed OLEDs with these Zn(ii) and Cu(i) complexes as light-emitting dopants have been fabricated, respectively. Maximum external quantum efficiency (EQE) of 5.55% and Commission Internationale de l'Eclairage (CIE) coordinates of (0.16, 0.19) were accomplished with the optimized Zn-1 -OLED while these values were, respectively 15.64% and (0.48, 0.51) for the optimized Cu-3 -OLED. Solution-processed white OLEDs having maximum EQE of 6.88%, CIE coordinates of (0.42, 0.44), and colour rendering index of 81 were fabricated by using these luminescent Zn(ii) and Cu(i) complexes as blue and orange light-emitting dopant materials, respectively.

Synthesis, characterization, crystal structure and antimicrobial studies of a novel Cu(II) complex based on itaconic acid and nicotinamide

NASA Astrophysics Data System (ADS)

Tella, Adedibu C.; Owalude, Samson O.; Ajibade, Peter A.; Simon, Nzikahyel; Olatunji, Sunday J.; Abdelbaky, Mohammed S. M.; Garcia-Granda, Santiago

2016-12-01

A novel complex was synthesized from Cu(II), nicotinamide and itaconic acid and is formulated as [Cu(C5H4O4)2(C6H6N2O)2(H2O)2·2(H2O)] (1). The compound was characterized by elemental analysis, FTIR spectroscopy, UV-Vis and single crystal X-ray diffraction. The complex crystallizes in the triclinic P-1 space group, with a = 7.5111(2) Å, b = 9.8529(3) Å, c = 10.5118(4) Å, α = 116.244(3)°, β = 90.291(3)°, γ = 103.335(3)°, V = 673.81(4) Å3, Z = 1.The octahedral geometry around the copper(II) ion is of the form CuN2O4 consisting of two molecules of nicotinamide acting as monodentate ligand through the nitrogen atoms, two molecules itaconate ligand and two coordinated water molecules each coordinating through the oxygen atoms. The structure of 1 showed infinite chains build up linking the molecules together via strong Osbnd H⋯O and Nsbnd H⋯O intermolecular hydrogen bonds generating a two dimensional network sheet along c axis. The antimicrobial study of the synthesized complex 1 was investigated and showed higher antibacterial activity against all the organisms comparing with Copper(II) nicotinamide 2 and Copper(II) itaconate 3.

Raman, IR, UV-vis and EPR characterization of two copper dioxolene complexes derived from L-dopa and dopamine

NASA Astrophysics Data System (ADS)

Barreto, Wagner J.; Barreto, Sônia R. G.; Ando, Rômulo A.; Santos, Paulo S.; DiMauro, Eduardo; Jorge, Thiago

2008-12-01

The anionic complexes [Cu(L 1-) 3] 1-, L - = dopasemiquinone or L-dopasemiquinone, were prepared and characterized. The complexes are stable in aqueous solution showing intense absorption bands at ca. 605 nm for Cu(II)-L-dopasemiquinone and at ca. 595 nm for Cu(II)-dopasemiquinone in the UV-vis spectra, that can be assigned to intraligand transitions. Noradrenaline and adrenaline, under the same reaction conditions, did not yield Cu-complexes, despite the bands in the UV region showing that noradrenaline and adrenaline were oxidized during the process. The complexes display a resonance Raman effect, and the most enhanced bands involve ring modes and particularly the νCC + νCO stretching mode at ca. 1384 cm -1. The free radical nature of the ligands and the oxidation state of the Cu(II) were confirmed by the EPR spectra that display absorptions assigned to organic radicals with g = 2.0005 and g = 2.0923, and for Cu(II) with g = 2.008 and g = 2.0897 for L-dopasemiquinone and dopasemiquinone, respectively. The possibility that dopamine and L-dopa can form stable and aqueous-soluble copper complexes at neutral pH, whereas noradrenaline and adrenaline cannot, may be important in understanding how Cu(II)-dopamine crosses the cellular membrane as proposed in the literature to explain the role of copper in Wilson disease.

Nano/microstructure and optical properties of ZnO particles precipitated from zinc acetylacetonate

NASA Astrophysics Data System (ADS)

Petrović, Željka; Ristić, Mira; Musić, Svetozar; Fabián, Martin

2015-06-01

The influence of experimental conditions on the nano/microstructure and optical properties of ZnO particles produced by rapid hydrolysis of zinc acetylacetonate, followed by aging of the precipitation system at 160 °C, was investigated. Samples were characterized by XRD, FE scanning electron microscopy (FE-SEM), FT-IR, UV/Vis/NIR and photoluminescence (PL) spectroscopies. XRD patterns of all samples were assigned to the hexagonal ZnO phase (wurtzite-type), as well as the corresponding FT-IR spectra. FE-SEM inspection showed a high dependence of the ZnO nano/microstructure on the chemical composition of the reaction mixture and autoclaving time after the rapid hydrolysis of zinc acetylacetonate. Microstructural differences were noticed between C2H5OH/H2O and H2O media, as well as under the influence of NH4OH addition. Measurements of nanocrystallite sizes showed no significant preferential orientation in the (1 0 0) and (0 0 2) directions relative to the (1 0 1) and (1 1 0) directions. Somewhat smaller crystallite sizes were noticed for ZnO samples synthesized by adding the NH4OH solution. Dissolution/recrystallization of ZnO particles played an important role in the formation of different ZnO nano/microstructures. The band gap values for prepared ZnO samples were calculated on the basis of recorded UV/Vis spectra. PL spectra were recorded for ZnO samples in powder form and their suspensions in pure ethanol. Noticed differences are discussed.

Synthesis of oxide and spinel nanocrystals for use in solid state lighting

NASA Astrophysics Data System (ADS)

Foley, Megan Elizabeth

In this dissertation, microwave chemistry is employed to synthesize a variety of different crystalline nanoparticles (NPs). This introduction will describe the structures, properties and applications of the NPs studied within the dissertation, with a main focus being on ligand sensitization for the goal of enhanced luminescence. The use of metal acetylacetonate complexes to make Europium (III) doped Ytrrium (Y2O3) NPs is explored, where the acetylacetonate acts both as a source of oxygen for the synthesis of Y2O3, as well as an organic chromophore acting as an "antenna" for the absorption of light and subsequent excitation transfer to the incorporated Europium (III) (Chapter 2). Other host materials are investigated by method of metal acetylacetonate decomposition to synthesize a variety of different nanospinels, having the general formula AB2X4, with sulfide variants made by decomposition of diethyldithiocarbamate, (Chapter 3). The antenna ligand thenoyltrifluoroacetone (tta), which is known to undergo a Dexter energy transfer (DET) mechanism to efficiently sensitize Europium (III) emission, is used to determine the distance of energy transfer in Europium (III) doped nanospinels by passivating the surface of the nanospinel with a tta (Chapter 4). A variety of ligands are explored in order to optimize the sensitization efficiency in relation to the difference in energy between the singlet and triplet levels of the ligands versus the 5D0 and 5D4 energy levels of Europium (III) and Terbium (III) respectively (Chapter 5).

Synthesis, characterization, and antimicrobial activity of silver(I) and copper(II) complexes of phosphate derivatives of pyridine and benzimidazole.

PubMed

Kalinowska-Lis, Urszula; Szewczyk, Eligia M; Chęcińska, Lilianna; Wojciechowski, Jakub M; Wolf, Wojciech M; Ochocki, Justyn

2014-01-01

Two silver(I) complexes--[Ag(4-pmOpe)]NO₃}(n) and [Ag(2-bimOpe)₂]NO₃--and three copper(II) complexes--[Cu₄Cl₆O(2-bimOpe)₄], [CuCl₂(4-pmOpe)₂], and [CuCl₂(2-bis(pm)Ope]--were synthesized by reaction of silver(I) nitrate or copper(II) chloride with phosphate derivatives of pyridine and benzimidazole, namely diethyl (pyridin-4-ylmethyl)phosphate (4-pmOpe), 1H-benzimidazol-2-ylmethyl diethyl phosphate (2-bimOpe), and ethyl bis(pyridin-2-ylmethyl)phosphate (2-bis(pm)Ope). These compounds were characterized by ¹H, ¹³C, and ³¹P NMR as well as IR spectroscopy, elemental analysis, and ESIMS spectrometry. Additionally, molecular and crystal structures of {[Ag(4-pmOpe)]NO₃}n and [Cu₄Cl₆O(2-bimOpe)₄] were determined by single-crystal X-ray diffraction analysis. The antimicrobial profiles of synthesized complexes and free ligands against test organisms from the ATCC and clinical sources were determined. Silver(I) complexes showed good antimicrobial activities against Candida albicans strains (MIC values of ∼19 μM). [Ag(2-bimOpe)₂]NO₃ was particularly active against Pseudomonas aeruginosa and methicillin-resistant Staphylococcus epidermidis, with MIC values of ∼5 and ∼10 μM, respectively. Neither copper(II) complexes nor the free ligands inhibited the growth of test organisms at concentrations below 500 μg mL⁻¹. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, structure and catechol-oxidase activity of copper(II) complexes of 17-hydroxy-16-(N-3-oxo-prop-1-enyl)amino steroids.

PubMed

Wegner, Rainer; Dubs, Manuela; Görls, Helmar; Robl, Christian; Schönecker, Bruno; Jäger, Ernst-G

2002-09-01

Copper is next to iron the most important element in the biological transport, storage and in redox reactions of dioxygen. A bioanalogous activation of dioxygen with copper complexes is used for catalytical epoxidation, allylic hydroxylation and oxidative coupling of aromatic substrates, for example. With stereochemical information in form of chiral ligands, enantioselective reactions may be possible. Another aspect of interest on copper catalyzed reactions with dioxygen is that the exact mechanism and biological function of some enzymes (especially catechol oxidase) is yet not fully clear. For studies mimicking the copper-containing catechol oxidase appropriate chiral steroid ligands with defined stereochemistry and conformation have been synthesized. The four diastereomeric 16,17-aminoalcohols of the 3-methoxy-estra-1,3,5(10)-triene series have been condensed with salicylic aldehyde and different beta-ketoenols to the chiral ligand types 1-5. These compounds with different steric and electronic properties and different arrangements of the neighboring hydroxy and nitrogen functions were reacted with copper(II) acetate to copper complexes. The structure of these complexes will be discussed. The bioanalogous oxidation of 3,5-di-tbutyl-catechol (dtbc) to the corresponding quinone was catalyzed by most of the complexes, indicating their ability to activate dioxygen. The trans configurations c and d showed an activity one magnitude higher than the cis configurations a and b. Comparing compounds with the same diastereomeric configuration, the main influence was that of the peripheral R(1-3) substituents at the beta-ketoenaminic group which are useful for the fine-tuning of the properties of the copper atoms like redox potential and Lewis acidity.

Synthesis, molecular docking and DNA binding studies of phthalimide-based copper(II) complex: In vitro antibacterial, hemolytic and antioxidant assessment

NASA Astrophysics Data System (ADS)

Arif, Rizwan; Nayab, Pattan Sirajuddin; Ansari, Istikhar A.; Shahid, M.; Irfan, Mohammad; Alam, Shadab; Abid, Mohammad; Rahisuddin

2018-05-01

In the present research work, we prepared N-substituted phthalimide, 2-(-(2-(2-(2-(1,3-dioxoisoindoline-2-yl-ethylamino)ethylamino)ethyl)isoindoline-1,3-dione (DEEI) and its copper(II) complex. The ligand (DEEI) and its Cu(II) complex were structurally identified using absorption, FTIR, NMR, electron spin resonance, X-ray diffraction spectral studies, thermogravimetric and elemental analyses. The electronic spectrum and magnetic moment value proposed that Cu(II) complex has square planar geometry. The DNA interaction ability of the ligand (DEEI) and Cu(II) complex was studied by means of absorption and fluorescence spectrophotometer, viscosity measurements, cyclic voltammetery, and circular dichroism methods. The extent of DNA binding (Kb) with Calf thymus (Ct-DNA) follows the order of Cu(II) complex (1.11 × 106 M-1) > DEEI (1.0 × 105 M-1), indicating that Cu(II) complex interact with Ct-DNA through groove binding mode and more sturdily than ligand (DEEI). Interestingly, in silico predictions were corroborated with in vitro DNA binding studies. The antibacterial evaluation of these compounds was screened against a panel of bacterial strains Pseudomonas aeruginosa (MTCC 2453), Salmonella enterica (MTCC 3224), Streptococcus pneumoniae (MTCC 655), Enterococcus faecalis (MTCC 439), Klebsiella pneumonia and Escherichia coli (ATCC 25922). The results showed that the copper(II) complex has significant antibacterial potential (IC50 = 0.0019 μg/mL) against Salmonella enteric comparable with ligand (DEEI) and standard drug ciprofloxacin. Growth curve study of Cu(II) complex against only three bacterial strains S. enterica, E. faecalis and S. pneumoniae showed its bactericidal nature. Cu(II) complex showed less than 2% hemolysis on human RBCs indicating its non toxic nature. The results of antioxidant assay demonstrated that scavenging activity of Cu(II) complex is higher as compared to ligand and ascorbic acid as standard.

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

PubMed

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

2017-10-04

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 n i ), 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. Q b /Q s ) 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.

Iron, copper, and manganese complexes with in vitro superoxide dismutase and/or catalase activities that keep Saccharomyces cerevisiae cells alive under severe oxidative stress.

PubMed

Ribeiro, Thales P; Fernandes, Christiane; Melo, Karen V; Ferreira, Sarah S; Lessa, Josane A; Franco, Roberto W A; Schenk, Gerhard; Pereira, Marcos D; Horn, Adolfo

2015-03-01

Due to their aerobic lifestyle, eukaryotic organisms have evolved different strategies to overcome oxidative stress. The recruitment of some specific metalloenzymes such as superoxide dismutases (SODs) and catalases (CATs) is of great importance for eliminating harmful reactive oxygen species (hydrogen peroxide and superoxide anion). Using the ligand HPClNOL {1-[bis(pyridin-2-ylmethyl)amino]-3-chloropropan-2-ol}, we have synthesized three coordination compounds containing iron(III), copper(II), and manganese(II) ions, which are also present in the active site of the above-noted metalloenzymes. These compounds were evaluated as SOD and CAT mimetics. The manganese and iron compounds showed both SOD and CAT activities, while copper showed only SOD activity. The copper and manganese in vitro SOD activities are very similar (IC50~0.4 μmol dm(-3)) and about 70-fold higher than those of iron. The manganese compound showed CAT activity higher than that of the iron species. Analyzing their capacity to protect Saccharomyces cerevisiae cells against oxidative stress (H2O2 and the O2(•-) radical), we observed that all compounds act as antioxidants, increasing the resistance of yeast cells mainly due to a reduction of lipid oxidation. Especially for the iron compound, the data indicate complete protection when wild-type cells were exposed to H2O2 or O2(•-) species. Interestingly, these compounds also compensate for both superoxide dismutase and catalase deficiencies; their antioxidant activity is metal ion dependent, in the order iron(III)>copper(II)>manganese(II). The protection mechanism employed by the complexes proved to be independent of the activation of transcription factors (such as Yap1, Hsf1, Msn2/Msn4) and protein synthesis. There is no direct relation between the in vitro and the in vivo antioxidant activities. Copyright © 2014 Elsevier Inc. All rights reserved.

Antimicrobial and mutagenic activity of some carbono- and thiocarbonohydrazone ligands and their copper(II), iron(II) and zinc(II) complexes.

PubMed

Bacchi, A; Carcelli, M; Pelagatti, P; Pelizzi, C; Pelizzi, G; Zani, F

1999-06-15

Several mono- and bis- carbono- and thiocarbonohydrazone ligands have been synthesised and characterised; the X-ray diffraction analysis of bis(phenyl 2-pyridyl ketone) thiocarbonohydrazone is reported. The coordinating properties of the ligands have been studied towards Cu(II), Fe(II), and Zn(II) salts. The ligands and the metal complexes were tested in vitro against Gram positive and Gram negative bacteria, yeasts and moulds. In general, the bisthiocarbonohydrazones possess the best antimicrobial properties and Gram positive bacteria are the most sensitive microorganisms. Bis(ethyl 2-pyridyl ketone) thiocarbonohydrazone, bis(butyl 2-pyridyl ketone)thiocarbonohydrazone and Cu(H2nft)Cl2 (H2nft, bis(5-nitrofuraldehyde)thiocarbonohydrazone) reveal a strong activity with minimum inhibitory concentrations of 0.7 microgram ml-1 against Bacillus subtilis and of 3 micrograms ml-1 against Staphylococcus aureus. Cu(II) complexes are more effective than Fe(II) and Zn(II) ones. All bisthiocarbono- and carbonohydrazones are devoid of mutagenic properties, with the exception of the compounds derived from 5-nitrofuraldehyde. On the contrary a weak mutagenicity, that disappears in the copper complexes, is exhibited by monosubstituted thiocarbonohydrazones.

Ferrate(VI)-Prompted Removal of Metals in Aqueous Media: Mechanistic Delineation of Enhanced Efficiency via Metal Entrenchment in Magnetic Oxides

EPA Science Inventory

The removal efficiency of heavy metal ions (cadmium(II) – Cd(II), cobalt(II) – Co(II), nickel(II) – Ni(II), and copper(II) – Cu(II)) by potassium ferrate(VI) (K2FeO4, Fe(VI)), was studied as a function of added amount of Fe(VI) (or Fe) and varying pH. At pH = 6.6, the effective r...

Production of Copper-Plated Beamline Bellows and Spools for LCLS-II

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilson, Katherine M.; Carpenter, Brian C.; Daly, Ed

The SLAC National Accelerator Laboratory is currently constructing a major upgrade to its accelerator, the Linac Coherent Light Source II (LCLS-II). Several Department of Energy national laboratories, including the Thomas Jefferson National Accelerator Facility (JLab) and Fermi National Accelerator Laboratory (FNAL), are participating in this project. The 1.3-GHz cryomodules for this project consist of eight cavities separated by bellows (expansion joints) and spools (tube sections), which are copper plated for RF conduction. JLab is responsible for procurement of these bellows and spools, which are delivered to JLab and FNAL for assembly into cryomodules. Achieving accelerator-grade copper plating is always amore » challenge and requires careful specification of requirements and application of quality control processes. Due to the demanding technical requirements of this part, JLab implemented procurement strategies to make the process more efficient as well as provide process redundancy. This paper discusses the manufacturing challenges that were encountered and resolved, as well as the strategies that were employed to minimize the impact of any technical issues.« less

Nitrogen enriched mesoporous organic polymer anchored copper(II) material: an efficient and reusable catalyst for the synthesis of esters and amides from aromatic systems.

PubMed

Molla, Rostam Ali; Iqubal, Md Asif; Ghosh, Kajari; Kamaluddin; Islam, Sk Manirul

2015-04-14

A new copper-grafted mesoporous poly-melamine-formaldehyde (Cu-mPMF) has been synthesized from melamine and paraformaldehyde in DMSO medium, followed by grafting of Cu(ii) at its surface. Cu-mPMF has been characterized by elemental analysis, powder XRD, HR TEM, FE-SEM, N2 adsorption study, FT-IR, UV-vis DRS, TGA-DTA, EPR spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). The Cu-grafted mesoporous material showed very good catalytic activity in methyl esterification of benzylic alcohols and amidation of nitriles. Moreover, the catalyst is easily recoverable and can be reused seven times without appreciable loss of catalytic activity in the above reactions. The highly dispersed and strongly bound Cu(ii) sites in the Cu-grafted mesoporous polymer could be responsible for the observed high activities of the Cu-mPMF catalyst. Due to strong binding with the functional groups of the polymer, no evidence of leached copper from the catalyst during the course of reaction emerged, suggesting true heterogeneity in the catalytic process.

Synthesis and Characterization of Tetrakis(2-amino-3-methylpyridine)copper(II) Sulfate Tetrahydrate

NASA Astrophysics Data System (ADS)

Rahardjo, S. B.; Saraswati, T. E.; Masykur, A.; Finantrena, N. N. F.; Syaima, H.

2018-04-01

The complex of Tetrakis(2-amino-3-methylpyridine)copper(II) sulfate tetrahydrate has been synthesized in a ratio of 1: 6 metal to ligand in methanol. The percentage of copper in the complex measured by Atomic Absorption Spectrometer (AAS) showed the complex formula was Cu(2-amino-3-metilpyridine)4SO4(H2O)n (n = 3, 4, or 5). The analysis of TG/DTA showed that 1 mole of complex contains 4 moles of H2O. The conductivity measurement indicated that the complex is in 1 to 1 electrolyte. The formula of the complex was estimated as [Cu(2-amino-3-metilpyridine)4]SO4·4H2O. The complex was paramagnetic with µeff of 1.85 BM. The UV-Vis spectra showed a band peak at 730 nm with an electronic transition Eg→T2g. IR spectral data indicated that the functional groups of N-pyridine 2-amino-3-metilpyridine coordinated to ion Cu(II). The geometry of the complex was probably square planar.

Evidence of desulfurization in the oxidative cyclization of thiosemicarbazones. Conversion to 1,3,4-oxadiazole derivatives.

PubMed

Gómez-Saiz, Patricia; García-Tojal, Javier; Maestro, Miguel A; Arnaiz, Francisco J; Rojo, Teófilo

2002-03-25

The addition of pyridine-2-carbaldehyde 4N-methylthiosemicarbazone (C8H10N4S) to an aqueous solution of copper(II) nitrate yields [[Cu(C8H9N4S)(NO3)]2] (1). This complex consists of centrosymmetric dinuclear entities containing square-pyramidal copper(II) ions bridged through the sulfur thioamide atoms. The oxidation of 1 with KBrO3 or KIO3 gives rise to a compound with formula [[Cu(C8H8N4O)(H2O)2(SO4)]2]*2H2O (2) (C8H8N4O = 2-methylamino-5-pyridin-2-yl-1,3,4-oxadiazole). The structure of 2 is made up of centrosymmetric dimers where the copper(II) ions exhibit a distorted octahedral coordination and are connected by the oxadiazole moiety. The metal ions in 2 can be removed by addition of K4[Fe(CN)6], and then the oxadiazole ligand can be isolated and recrystallized as (C8H8N4O)*3H2O (3).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jin, Xin; Zhou, Pei; Zheng, Chunying

A copper complex ([Cu(py){sub 2}(L){sub 2}]·2CH{sub 3}OH){sub n} (HL=(E)-3-(3-hydroxyl-phenyl)-acrylic acid) (1) with acrylic acid ligand was synthesized and structurally analyzed by IR, elemental analysis, TGA and the single-crystal X-ray diffraction methods. It is the first time to find that phenolic hydroxyl of L coordinates to Cu(II). Complex 1 exhibits 1D chain by a double-bridge of ligands, and the 3D supramolecular framework in complex 1 is constructed by π–π stacking interactions and van der Waals Contacts among the 1D chains. The magnetic properties of complex 1 have been studied. - Graphical abstract: A copper complex based on (E)-3-(3-hydroxyl-phenyl)-acrylic acid in amore » novel coordinated way was synthesized and a ferromagnetic exchange interactions between neighboring Cu(II) ions has be achieved. - Highlights: • A new copper complex with acrylic acid ligand was synthesized and analyzed. • We find the phenolic hydroxyl of MCA ligand coordinates to metal ion firstly. • A ferromagnetic exchange interactions between Cu(II) ions has been achieved.« less

Biosorption of Cu(II) by powdered anaerobic granular sludge from aqueous medium.

PubMed

Zhou, Xu; Chen, Chuan; Wang, Aijie; Jiang, Guangming; Liu, Lihong; Xu, Xijun; Yuan, Ye; Lee, Duu-Jung; Ren, Nanqi

2013-01-01

Copper(II) biosorption processes by two pre-treated powdered anaerobic granular sludges (PAGS) (original sludges were methanogenic anaerobic granules and denitrifying sulfide removal (DSR) anaerobic granules) were investigated through batch tests. Factors affecting the biosorption process, such as pH, temperature and initial copper concentrations, were examined. Also, the physico-chemical characteristics of the anaerobic sludge were analyzed by Fourier transform infrared spectroscopy, scanning electron microscopy image, surface area and elemental analysis. A second-order kinetic model was applied to describe the biosorption process, and the model could fit the biosorption process. The Freundlich model was used for describing the adsorption equilibrium data and could fit the equilibrium data well. It was found that the methanogenic PAGS was more effective in Copper(II) biosorption process than the DSR PAGS, whose maximum biosorption capacity was 39.6% lower. The mechanisms of the biosorption capacities for different PAGS were discussed, and the conclusion suggested that the environment and biochemical reactions during the growth of biomass may have affected the structure of the PAGS. The methanogenic PAGS had larger specific surface area and more biosorption capacity than the DSR PAGS.

Toxicity and deficiency of copper in Elsholtzia splendens affect photosynthesis biophysics, pigments and metal accumulation.

PubMed

Peng, Hongyun; Kroneck, Peter M H; Küpper, Hendrik

2013-06-18

Elsholtzia splendens is a copper-tolerant plant species growing on copper deposits in China. Spatially and spectrally resolved kinetics of in vivo absorbance and chlorophyll fluorescence in mesophyll of E. splendens were used to investigate the copper-induced stress from deficiency and toxicity as well as the acclimation to excess copper stress. The plants were cultivated in nutrient solutions containing either Fe(III)-EDTA or Fe(III)-EDDHA. Copper toxicity affected light-acclimated electron flow much stronger than nonphotochemical quenching (NPQ) or dark-acclimated photochemical efficiency of PSIIRC (Fv/Fm). It also changed spectrally resolved Chl fluorescence kinetics, in particular by strengthening the short-wavelength (<700 nm) part of NPQ altering light harvesting complex II (LHCII) aggregation. Copper toxicity reduced iron accumulation, decreased Chls and carotenoids in leaves. During acclimation to copper toxicity, leaf copper decreased but leaf iron increased, with photosynthetic activity and pigments recovering to normal levels. Copper tolerance in E. splendens was inducible; acclimation seems be related to homeostasis of copper and iron in E. splendens. Copper deficiency appeared at 10 mg copper per kg leaf DW, leading to reduced growth and decreased photosynthetic parameters (F0, Fv/Fm, ΦPSII). The importance of these results for evaluating responses of phytoremediation plants to stress in their environment is discussed.

Application of cotton as a solid phase extraction sorbent for on-line preconcentration of copper in water samples prior to inductively coupled plasma optical emission spectrometry determination.

PubMed

Faraji, Mohammad; Yamini, Yadollah; Shariati, Shahab

2009-07-30

Copper, as a heavy metal, is toxic for many biological systems. Thus, the determination of trace amounts of copper in environmental samples is of great importance. In the present work, a new method was developed for the determination of trace amounts of copper in water samples. The method is based on the formation of ternary Cu(II)-CAS-CTAB ion-pair and adsorption of it into a mini-column packed with cotton prior applying inductively coupled plasma optical emission spectrometry (ICP-OES). The experimental parameters that affected the extraction efficiency of the method such as pH, flow rate and volume of the sample solution, concentration of chromazurol S (CAS) and cethyltrimethylammonium bromide (CTAB) as well as type and concentration of eluent were investigated and optimized. The ion-pair (Cu(II)-CAS-CTAB) was quantitatively retained on the cotton under the optimum conditions, then eluted completely using a solution of 25% (v/v) 1-propanol in 0.5 mol L(-1) HNO(3) and directly introduced into the nebulizer of the ICP-OES. The detection limit (DL) of the method for copper was 40 ng L(-1) (V(sample)=100mL) and the relative standard deviation (R.S.D.) for the determination of copper at 10 microg L(-1) level was found to be 1.3%. The method was successfully applied to determine the trace amounts of copper in tap water, deep well water, seawater and two different mineral waters, and suitable recoveries were obtained (92-106%).

Treatment of model and galvanic waste solutions of copper(II) ions using a lignin/inorganic oxide hybrid as an effective sorbent.

PubMed

Ciesielczyk, Filip; Bartczak, Przemysław; Klapiszewski, Łukasz; Jesionowski, Teofil

2017-04-15

A study was made concerning the removal of copper(II) ions from model and galvanic waste solutions using a new sorption material consisting of lignin in combination with an inorganic oxide system. Specific physicochemical properties of the material resulted from combining the activity of the functional groups present in the structure of lignin with the high surface area of the synthesized oxide system (585m 2 /g). Analysis of the porous structure parameters, particle size and morphology, elemental composition and characteristic functional groups confirmed the effective synthesis of the new type of sorbent. A key element of the study was a series of tests of adsorption of copper(II) ions from model solutions. It was determined how the efficiency of the adsorption process was affected by the process time, mass of sorbent, concentration of adsorbate, pH and temperature. Potential regeneration of adsorbent, which provides the possibility of its reusing and recovering the adsorbed copper, was also analyzed. The sorption capacity of the material was measured (83.98mg/g), and the entire process was described using appropriate kinetic models. The results were applied to the design of a further series of adsorption tests, carried out on solutions of real sewage from a galvanizing plant. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of Acid and Alcohol Network Forces within Functionalized Multiwall Carbon Nanotubes Bundles on Adsorption of Copper (II) Species

EPA Science Inventory

Adsorption of metals on carbon nanotubes (CNTs) has important applications in sensors, membranes, and water treatment. The adsorptive capacity of multiwall CNTs for copper species in water depends on the type of functional group present on their surface. The alcohol (COOH) and ac...

Simple Potentiometric Determination of Reducing Sugars

ERIC Educational Resources Information Center

Moresco, Henry; Sanson, Pedro; Seoane, Gustavo

2008-01-01

In this article a potentiometric method for reducing sugar quantification is described. Copper(II) ion reacts with the reducing sugar (glucose, fructose, and others), and the excess is quantified using a copper wire indicator electrode. In order to accelerate the kinetics of the reaction, working conditions such as pH and temperature must be…

Some More Microscale Gas Experiments

ERIC Educational Resources Information Center

Worley, Bob

2011-01-01

In 1984, a teacher was successfully prosecuted by the Health and Safety Executive. The case centred around chemically prepared hydrogen that was dried by bubbling it through concentrated sulfuric(VI) acid and then passed over hot copper(II) oxide. The procedure was often carried out quantitatively to find the mass of copper in a sample of…

The Use of Stimulable Bioluminescence From Dinoflagellates as a Means of Detecting Toxicity in the Marine Environment

DTIC Science & Technology

1993-03-01

tributyltin chloride (TFITCI), Copper (11) Sulfate (CuSO 4 I. zinc sulfate (ZnSO4 ), or storm drain effluent. Stimulable bioluminescence was measured at...to several metals and storm drain effluent. Dinoflagellate cells were exposed to various concentrations of tributyltin chloride (TBI1C), copper (II

Hand-held optical sensor using denatured antibody coated electro-active polymer for ultra-trace detection of copper in blood serum and environmental samples.

PubMed

Chandra, Sutapa; Dhawangale, Arvind; Mukherji, Soumyo

2018-07-01

An optimum copper concentration in environment is highly desired for all forms of life. We have developed an ultrasensitive copper sensor which functions from femto to micro molar concentration accurately (R 2 = 0.98). The sensor is based on denatured antibody immunoglobulin G (IgG), immobilized on polyaniline (PAni) which in turn is the coating on the core of an optical fiber. The sensing relies on changes in evanescent wave absorbance in the presence of the analyte. The sensor showed excellent selectivity towards Cu (II) ions over all other metal ions. The sensor was tested with lake and marine water samples to determine unknown concentrations of copper ions and the recovery results were within 90-115%, indicating reasonable accuracy. We further integrated the fiber-optic sensor with a miniaturized hand-held instrumentation platform to develop an accurate and field deployable device which can broadly be applicable to determine Cu (II) concentration in a wide range of systems - natural water bodies, soil as well as blood serum. Copyright © 2018 Elsevier B.V. All rights reserved.

Biogeochemical spatio-temporal transformation of copper in Aspergillus niger colonies grown on malachite with different inorganic nitrogen sources.

PubMed

Fomina, Marina; Bowen, Andrew D; Charnock, John M; Podgorsky, Valentin S; Gadd, Geoffrey M

2017-03-01

This work elucidates spatio-temporal aspects of the biogeochemical transformation of copper mobilized from malachite (Cu 2 (CO 3 )(OH) 2 ) and bioaccumulated within Aspergillus niger colonies when grown on different inorganic nitrogen sources. It was shown that the use of either ammonium or nitrate determined how copper was distributed within the colony and its microenvironment and the copper oxidation state and succession of copper coordinating ligands within the biomass. Nitrate-grown colonies yielded ∼1.7× more biomass, bioaccumulated ∼7× less copper, excreted ∼1.9× more oxalate and produced ∼1.75× less water-soluble copper in the medium in contrast to ammonium-grown colonies. Microfocus X-ray absorption spectroscopy revealed that as the mycelium matured, bioaccumulated copper was transformed from less stable and more toxic Cu(I) into less toxic Cu(II) which was coordinated predominantly by phosphate/malate ligands. With time, a shift to oxalate coordination of bioaccumulated copper occurred in the central older region of ammonium-grown colonies. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.

Copper-doped waveguides in glass substrates

NASA Astrophysics Data System (ADS)

Spirkova-Hradilova, Jarmila; Tresnakova-Nebolova, Pavlina; Jirka, Ivan; Mach, Karel; Perina, Vratislav; Mackova, Anna; Kuncova, Gabriela

2001-05-01

We have studied fabrication and properties of copper ion- exchanged waveguides fabricated in various types of special soda-lime silicate glass as well as commercial optical glass substrates. The ion exchange was performed in melts containing either CuI or CuII at temperatures from 350 degrees C to 500 degrees C for times ranging from 5 minutes to 21 hrs. Optical properties of the fabricated waveguides were studied using mode spectroscopy and photoluminescence spectroscopy and composition of the waveguides was determined by SEM, RBS, EPR and ESCA. After the ion exchange the refractive index increased, according to fabrication conditions, up to (Delta) n equals +0.0693 and the guides supported up to 16 TE and TM modes. The CuI $ARLR CuII redox reaction during the fabrication depended strongly on the composition as well as the temperature of the reaction melts. In the Cu2Cl2ZnCl2 melts the oxidation of CuI to CuII was strongly hampered, so that CuI prevailed in the waveguiding region. These samples exhibited the most intensive blue-green luminescence, in spite of those fabricated using the CuII-based reaction melts, where practically no blue-green luminescence was observed. ESCA measurement revealed an easy charge transfer between the both oxidation states of copper in the very surface regions of the samples.

Structural measurements and cell line studies of the copper-PEG-Rifampicin complex against Mycobacterium tuberculosis.

PubMed

Manning, Thomas; Mikula, Rachel; Wylie, Greg; Phillips, Dennis; Jarvis, Jackie; Zhang, Fengli

2015-02-01

The bacterium responsible for tuberculosis is increasing its resistance to antibiotics resulting in new multidrug-resistant Mycobacterium tuberculosis (MDR-TB) and extensively drug-resistant tuberculosis (XDR-TB). In this study, several analytical techniques including NMR, FT-ICR, MALDI-MS, LC-MS and UV/Vis are used to study the copper-Rifampicin-Polyethylene glycol (PEG-3350) complex. The copper (II) cation is a carrier for the antibiotic Rifampicin as well as nutrients for the bacterium. The NIH-NIAID cell line containing several Tb strains (including antibiotic resistant strains) is tested against seven copper-PEG-RIF complex variations. Copyright © 2014 Elsevier Ltd. All rights reserved.

Direct-writing of copper-based micropatterns on polymer substrates using femtosecond laser reduction of copper (II) oxide nanoparticles

NASA Astrophysics Data System (ADS)

Mizoshiri, Mizue; Ito, Yasuaki; Sakurai, Junpei; Hata, Seiichi

2017-04-01

Copper (Cu)-based micropatterns were fabricated on polymer substrates using femtosecond laser reduction of copper (II) oxide (CuO) nanoparticles. CuO nanoparticle solution, which consisted of CuO nanoparticles, ethylene glycol as a reductant agent, and polyvinylpyrrolidone as a dispersant, was spin-coated on poly(dimethylsiloxane) (PDMS) substrates and was irradiated by focused femtosecond laser pulses to fabricate Cu-based micropatterns. When the laser pulses were raster-scanned onto the solution, CuO nanoparticles were reduced and sintered. Cu-rich and copper (I)-oxide (Cu2O)-rich micropatterns were formed at laser scanning speeds of 15 mm/s and 0.5 mm/s, respectively, and at a pulse energy of 0.54 nJ. Cu-rich electrically conductive micropatterns were obtained without significant damages on the substrates. On the other hand, Cu2O-rich micropatterns exhibited no electrical conductivity, indicating that microcracks were generated on the micropatterns by thermal expansion and shrinking of the substrates. We demonstrated a direct-writing of Cu-rich micro-temperature sensors on PDMS substrates using the foregoing laser irradiation condition. The resistance of the fabricated sensors increased with increasing temperature, which is consistent with that of Cu. This direct-writing technique is useful for fabricating Cu-polymer composite microstructures.

Paintings on copper by the Flemish artist Frans Francken II: PIXE characterization by external microbeam

NASA Astrophysics Data System (ADS)

Corregidor, V.; Oliveira, A. R.; Rodrigues, P. A.; Alves, L. C.

2015-04-01

Resorting to an external proton microbeam, PIXE analyses of three oil paintings on copper support dated from the XVII century and attributed to the Flemish artist Frans Francken II, were undertaken. The present work aims to contribute to the compositional study of the painting materials employed by XVII century artists that exploited copper as a support for oil painting, and specifically the materials used by Francken's workshop, particularly copper plates. Because of the low thickness of the pictorial layers of this type of paintings and its non-destructive character, PIXE is the ideal technique to study the elemental composition of the paintings. Several spots in each painting were chosen for analysis in order to cover almost all the pigments used in the colour palette. Lead and calcium were detected in practically every analysed regions, probably related to the presence of lead white and chalk, usually used as ground layer on copper paintings. Small quantities of gold were also detected, which is present in many of this artist's works to embellish some details of the representations. Also this work reports the first application of the external proton microbeam set-up available at CTN/IST in Portugal for the characterization of oil paintings.

Copper(II)-catalyzed amidations of alkynyl bromides as a general synthesis of ynamides and Z-enamides. An intramolecular amidation for the synthesis of macrocyclic ynamides.

PubMed

Zhang, Xuejun; Zhang, Yanshi; Huang, Jian; Hsung, Richard P; Kurtz, Kimberly C M; Oppenheimer, Jossian; Petersen, Matthew E; Sagamanova, Irina K; Shen, Lichun; Tracey, Michael R

2006-05-26

A general and efficient method for the coupling of a wide range of amides with alkynyl bromides is described here. This novel amidation reaction involves a catalytic protocol using copper(II) sulfate-pentahydrate and 1,10-phenanthroline to direct the sp-C-N bond formation, leading to a structurally diverse array of ynamides including macrocyclic ynamides via an intramolecular amidation. Given the surging interest in ynamide chemistry, this atom economical synthesis of ynamides should invoke further attention from the synthetic organic community.

Synthesis and Spectral Evaluation of Some Unsymmetrical Mesoporphyrinic Complexes

PubMed Central

Boscencu, Rica; Oliveira, Anabela Sousa; Ferreira, Diana P.; Ferreira, Luís Filipe Vieira

2012-01-01

Synthesis and spectral evaluation of new zinc and copper unsymmetrical mesoporphyrinic complexes are reported. Zn(II)-5-(4-acetoxy-3-methoxyphenyl)-10,15,20- tris-(4-carboxymethylphenyl)porphyrin, Zn(II)-5-[(3,4-methylenedioxy)phenyl]-10,15,20- tris-(4-carboxymethylphenyl)porphyrin, Cu(II)-5-(4-acetoxy-3-methoxyphenyl)-10,15,20- tris-(4-carboxymethylphenyl)porphyrin and Cu(II)-5-[(3,4-methylenedioxy)phenyl]-10,15,20- tris-(4-carboxymethylphenyl)porphyrin were synthesized using microwave-assisted synthesis. The complexes were characterized by elemental analysis, FT-IR, UV-Vis, EPR and NMR spectroscopy, which fully confirmed their structure. The spectral absorption properties of the porphyrinic complexes were studied in solvents with different polarities. Fluorescence emission and singlet oxygen formation quantum yields were evaluated for the compounds under study, revealing high yields for the zinc derivatives. The copper complexes are not emissive and only display residual capacity for singlet oxygen formation. PMID:22942693

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

PubMed

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

2017-03-01

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

Spectrophotometric Determination of Metoprolol Tartrate in Pharmaceutical Dosage Forms on Complex Formation with Cu(II)

PubMed Central

Cesme, Mustafa; Tarinc, Derya; Golcu, Aysegul

2011-01-01

A new, simple, sensitive and accurate spectrophotometric method has been developed for the assay of metoprolol tartrate (MPT), which is based on the complexation of drug with copper(II) [Cu(II)] at pH 6.0, using Britton-Robinson buffer solution, to produce a blue adduct. The latter has a maximum absorbance at 675 nm and obeys Beer's law within the concentration range 8.5-70 μg/mL. Regression analysis of the calibration data showed a good correlation coefficient (r = 0.998) with a limit of detection of 5.56 μg/mL. The proposed procedure has been successfully applied to the determination of this drug in its tablets. In addition, the spectral data and stability constant for the binuclear copper(II) complex of MPT (Cu2MPT2Cl2) have been reported.

Spectral, biological screening of metal chelates of chalcone based Schiff bases of N-(3-aminopropyl) imidazole.

PubMed

Kalanithi, M; Rajarajan, M; Tharmaraj, P; Sheela, C D

2012-02-15

Tridentate chelate complexes of Co(II), Ni(II), Cu(II) and Zn(II) have been synthesized from the chalcone based ligands 2-[1-(3-(1H-imidazol-1-yl)propylimino)-3-(phenylallyl)]phenol(HL(1)), 2-[1-(3-(1H-imidazol-1-yl)propylimino)-3-p-tolylallyl]phenol(HL(2)), 2-[1-(3-(1H-imidazol-1-yl)propylimino)-3-4-nitrophenylallyl]phenol(HL(3)). Microanalytical data, UV-vis spectrophotometric method, magnetic susceptibility measurements, IR, 1H NMR, Mass, and EPR techniques were used to characterize the structure of chelates. The electronic absorption spectra and magnetic susceptibility measurements suggest a distorted square planar geometry for the copper(II) ion. The other metal complexes show distorted tetrahedral geometry. The coordination of the ligands with metal(II) ions was further confirmed by solution fluorescence spectrum. The antimicrobial activity of the ligands and metal(II) complexes against the species Pseudomonas aeruginosa, Escherichia coli, Staphylococcus aureus, Bacillus subtilis, Candida albigans and Aspergillus niger has been carried out and compared. The electrochemical behavior of copper(II) complex is studied by cyclic voltammetry. Copyright © 2011 Elsevier B.V. All rights reserved.

In situ study of binding of copper by fulvic acid: comparison of differential absorbance data and model predictions.

PubMed

Yan, Mingquan; Dryer, Deborah; Korshin, Gregory V; Benedetti, Marc F

2013-02-01

This study examined the binding of copper(II) by Suwannee River fulvic acid (SRFA) using the method of differential absorbance that was used at environmentally-relevant concentrations of copper and SRFA. The pH- and metal-differential spectra were processed via numeric deconvolution to establish commonalities seen in the changes of absorbance caused by deprotonation of SRFA and its interactions with copper(II) ions. Six Gaussian bands were determined to be present in both the pH- and Cu-differential spectra. Their maxima were located, in the order of increasing wavelengths at 208 nm, 242 nm, 276 nm, 314 nm, 378 nm and 551 nm. The bands with these maxima were denoted as A0, A1, A2, A3, A4 and A5, respectively. Properties of these bands were compared with those existing in the spectra of model compounds such as sulfosalicylic acid (SSA), tannic acid (TA), and polystyrenesulfonic acid-co-maleic acid (PSMA). While none of the features observed in differential spectra of the model compound were identical to those present in the case of SRFA, Gaussian bands A1, A3 and possibly A2 were concluded to be largely attributable to a combination of responses of salicylic- and polyhydroxyphenolic groups. In contrast, bands A4 and A5 were detected in the differential spectra of SRFA only. Their nature remains to be elucidated. To examine correlations between the amount of copper(II) bound by SRFA and changes of its absorbance, differential absorbances measured at indicative wavelengths 250 nm and 400 nm were compared with the total amount of SRFA-bound copper estimated based on Visual MINTEQ calculations. This examination showed that the differential absorbances of SRFA in a wide range of pH values and copper concentrations were strongly correlated with the concentration of SRFA-bound copper. The approach presented in this study can be used to generate in situ information concerning the nature of functional groups in humic substances engaged in interactions with metals ions. This information can be useful for further elaboration and development of detailed theoretic models that describe the complexation of metals in the environment. Copyright © 2012 Elsevier Ltd. All rights reserved.

Influence of oxygen, albumin and pH on copper dissolution in a simulated uterine fluid.

PubMed

Bastidas, D M; Cano, E; Mora, E M

2005-06-01

The aim of this paper is to study the influence of albumin content, from 5 to 45 g/L, on copper dissolution and compounds composition in a simulated uterine solution. Experiments were performed in atmospheric pressure conditions and with an additional oxygen pressure of 0.2 atmospheres, at 6.3 and 8.0 pH values, and at a temperature of 37 +/- 0.1 degrees C for 1, 3, 7, and 30 days experimentation time. The copper dissolution rate has been determined using absorbance measurements, finding the highest value for pH 8.0, 35 g/L albumin, and with an additional oxygen pressure of 0.2 atmospheres: 674 microg/day for 1 day, and 301 microg/day for 30 days. X-ray photoelectron spectroscopy (XPS) results show copper(II) as the main copper oxidation state at pH 8.0; and copper(I) and metallic copper at pH 6.3. The presence of albumin up to 35 g/L, accelerates copper dissolution. For high albumin content a stabilisation on the copper dissolution takes place. Corrosion product layer morphology is poorly protective, showing paths through which copper ions can release.

Design of a microfluidic sensor for high-sensitivity Copper (II) sensing applications

NASA Astrophysics Data System (ADS)

Gibson, Ceri; Byrne, Patrick; Gray, David; MacCraith, Brian D.; Paull, Brett; Tyrrell, Eadaoin

2003-03-01

An all-plastic micro-sensor system for remote measurement of copper (II) ions in the aqueous environment has been developed. The sensing structure was designed for ease of milling and fabricated in poly (methyl methacrylate) (PMMA) using a hot-embossing technique. Issues of sealing the structure were studied extensively and an efficient protocol has been established. The detection system comprises a compact photo-multiplier tube and integrated photon counting system. This method has advantages of low sample volume, (creating a minimal volume of waste), low exposure to contaminants due to the closed system, no moving parts and employs a robust polymer material which is resistant to the environment of intended use. The sensor operates on the principle of flow injection analysis and has been tested using a chemiluminescence (FIA-CL) reaction arising from the complexation of copper with 1,10-phenanthroline and subsequent oxidation by hydrogen peroxide.

Redox chemistry of a binary transition metal oxide (AB 2 O 4 ): a study of the Cu 2+ /Cu 0 and Fe 3+ /Fe 0 interconversions observed upon lithiation in a CuFe 2 O 4 battery using X-ray absorption spectroscopy

DOE PAGES

Cama, Christina A.; Pelliccione, Christopher J.; Brady, Alexander B.; ...

2016-06-06

Copper ferrite, CuFe 2 O 4, is a promising candidate for application as a high energy electrode material in lithium based batteries. Mechanistic insight on the electrochemical reduction and oxidation processes was gained through the first X-ray absorption spectroscopic study of lithiation and delithiation of CuFe 2 O 4. A phase pure tetragonal CuFe 2 O 4 material was prepared and characterized using laboratory and synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. We used ex situ X-ray absorption spectroscopy (XAS) measurements to study the battery redox processes at the Fe and Cu K-edges, using X-ray absorption near-edge structuremore » (XANES), extended X-ray absorption fine structure (EXAFS), and transmission X-ray microscopy (TXM) spectroscopies. EXAFS analysis showed upon discharge, an initial conversion of 50% of the copper(II) to copper metal positioned outside of the spinel structure, followed by a migration of tetrahedral iron(III) cations to octahedral positions previously occupied by copper(II). Then, upon charging to 3.5 V, the copper metal remained in the metallic state, while iron metal oxidation to iron(III) was achieved. Our results provide new mechanistic insight regarding the evolution of the local coordination environments at the iron and copper centers upon discharging and charging.« less

Redox chemistry of a binary transition metal oxide (AB2O4): a study of the Cu(2+)/Cu(0) and Fe(3+)/Fe(0) interconversions observed upon lithiation in a CuFe2O4 battery using X-ray absorption spectroscopy.

PubMed

Cama, Christina A; Pelliccione, Christopher J; Brady, Alexander B; Li, Jing; Stach, Eric A; Wang, Jiajun; Wang, Jun; Takeuchi, Esther S; Takeuchi, Kenneth J; Marschilok, Amy C

2016-06-22

Copper ferrite, CuFe2O4, is a promising candidate for application as a high energy electrode material in lithium based batteries. Mechanistic insight on the electrochemical reduction and oxidation processes was gained through the first X-ray absorption spectroscopic study of lithiation and delithiation of CuFe2O4. A phase pure tetragonal CuFe2O4 material was prepared and characterized using laboratory and synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. Ex situ X-ray absorption spectroscopy (XAS) measurements were used to study the battery redox processes at the Fe and Cu K-edges, using X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and transmission X-ray microscopy (TXM) spectroscopies. EXAFS analysis showed upon discharge, an initial conversion of 50% of the copper(ii) to copper metal positioned outside of the spinel structure, followed by a migration of tetrahedral iron(iii) cations to octahedral positions previously occupied by copper(ii). Upon charging to 3.5 V, the copper metal remained in the metallic state, while iron metal oxidation to iron(iii) was achieved. The results provide new mechanistic insight regarding the evolution of the local coordination environments at the iron and copper centers upon discharging and charging.

Irreversible insertion of benzonitrile into platinum(II)-nitrogen bonds of nucleobase complexes. Synthesis and structural characterization of stable azametallacycle compounds.

PubMed

Montagner, Diego; Venzo, Alfonso; Zangrando, Ennio; Longato, Bruno

2010-03-01

Deprotonation of 1-methylcytosine (1-MeCy) and 9-methyladenine (9-MeAd) promoted by cis-[L(2)Pt(mu-OH)](2)(NO(3))(2) (L = PPh(3), PMePh(2), (1)/(2)dppe) in PhCN causes the irreversible insertion of a nitrile molecule into the Pt-N4 and Pt-N6 bonds of the cytosinate and adeninate ligands, respectively, to form the stable azametallacycle complexes cis-[L(2)PtNH=C(Ph){1-MeCy(-2H)}]NO(3) (L = PPh(3), 1; PMePh(2), 2; (1)/(2)dppe, 3) and cis-[L(2)PtNH=C(Ph){9-MeAd(-2H)}]NO(3) (L = PPh(3), 4; PMePh(2), 5) containing the deprotonated form of the molecules (Z)-9-N-(1-methyl-2-oxo-2,3-dihydropyrimidin-4(1H)-ylidene)benzimidamide and (Z)-N-(9-methyl-1H-purin-6(9H)-ylidene)benzimidamide. Single-crystal X-ray analyses of 2 and 4 show the metal coordinated to the N3 cytosine site [Pt-N3 = 2.112(7) A] and to the N1 site of adenine [Pt-N1 = 2.116(6) A] and to the nitrogen atom of the inserted benzonitrile [Pt-N2 = 2.043(6) and 2.010(6) A in 2 and 4, respectively], with the exocyclic nucleobase amino nitrogen bound to the carbon atom of the CN group. Complex 2, in solution, undergoes a dynamic process related to a partially restricted rotation around Pt-P bonds, arising from a steric interaction of the oxygen atom of the cytosine with one ring of the phosphine ligands. The reaction of 4 with acetylacetone (Hacac) causes the quantitative protonation of the anionic ligand, affording the acetylacetonate complex cis-[(PPh(3))(2)Pt(acac)]NO(3) and the free benzimidamide NH=C(Ph){9-MeAd(-H)}. In the same experimental conditions, complex 3 reacts with Hacac only partially.

Concentration-dependent Cu(II) binding to prion protein

NASA Astrophysics Data System (ADS)

Hodak, Miroslav; Lu, Wenchang; Bernholc, Jerry

2008-03-01

The prion protein plays a causative role in several neurodegenerative diseases, including mad cow disease in cattle and Creutzfeldt-Jakob disease in humans. The normal function of the prion protein is unknown, but it has been linked to its ability to bind copper ions. Experimental evidence suggests that copper can be bound in three distinct modes depending on its concentration, but only one of those binding modes has been fully characterized experimentally. Using a newly developed hybrid DFT/DFT method [1], which combines Kohn-Sham DFT with orbital-free DFT, we have examined all the binding modes and obtained their detailed binding geometries and copper ion binding energies. Our results also provide explanation for experiments, which have found that when the copper concentration increases the copper binding mode changes, surprisingly, from a stronger to a weaker one. Overall, our results indicate that prion protein can function as a copper buffer. 1. Hodak, Lu, Bernholc, JCP, in press.

Low cost disposal of MMH

NASA Technical Reports Server (NTRS)

Thomas, J. J.; French, T.

1980-01-01

Concentration of gaseous toxic monomethylhydrazine (MMH) can be removed at 99.9% efficiency using scrubbers containing acetylacetone solutions as scrubbing liquors. Resulting product is easily disposable and expensive liners for protecting scrubber from strong oxidizing agents are not needed.

Use of Eichhornia crassipes modified Nano-chitosan as a biosorbent for lead (II), cadmium (II), and copper (II) ion removal from aqueous solutions

NASA Astrophysics Data System (ADS)

Alkaff, A. H.; Hendri, H.; Farozy, I. H.; Annisa, M.; Aritonang, R. P.

2018-01-01

Industrial waste in a major city poses a considerable threat to water environment from the accumulation of heavy metals. Additionally, uncontrolled growth of Eichhornia crassipes will also damage the water environment by lowering the levels of dissolved oxygen. Therefore, we conduct research to not only treat industrial waste in water but also reduce the population of E. crassipes in water. We made this biosorbent by mixing E. crassipes with nano-chitosan in various compositions. Its absorptivity was tested against single metal solutions of lead (II), cadmium (II), and copper (II) to get the best biosorbent composition. The chosen biosorbent then went through an adsorptivity test against a mixture of three solutions, with each test was carried at various pH. The best biosorbent composition is the mixture of 1 g of E. crassipes with 30 mL of nano-chitosan 0.01%, while adsorption tests in single or three metals solution show that the biosorbent performs better in neutral pH.

Vibrational assignment of aluminum(III) Tris-acetylacetone

NASA Astrophysics Data System (ADS)

Tayyari, Sayyed Faramarz; Raissi, Haydar; Ahmadabadi, Zahra

2002-10-01

The geometry, frequency and intensity of the vibrational bands of aluminum(III) Tris-acetylacetone Al(AA) 3 and its 1, 3, 5- 13C derivative were obtained by the Hartree-Fock (HF) and Density Functional Theory (DFT) with the B3LYP, B1LYP, and G96LYP functionals and using the 6-31G* basis set. The calculated frequencies are compared with the solid IR and Raman spectra. All of the measured IR and Raman bands were interpreted in terms of the calculated vibrational modes. Most computed bands are predicted to be at higher wavenumbers than the experimental bands. The calculated bond lengths and bond angles are in good agreement with the experimental results. Analysis of the vibrational spectra indicates a strong coupling between the chelated ring modes. Four bands in the 500-390 cm -1 frequency range are assigned to the vibrations of metalligand bonds.

An improved soft-chemistry approach to the preparation of spinel powders

NASA Astrophysics Data System (ADS)

Cook, Ronald

2007-04-01

Spinel powders for the production of transparent polycrystalline ceramic windows have been produced using a number of traditional ceramic and sol-gel methods. We have demonstrated that magnesium aluminate spinel powders produced from the reaction of organo-magnesium compounds with surface modified boehmite precursors can be used to produce high quality transparent spinel parts. In previous work, the spinel powders were prepared by the reaction of surface-modified boehmite nanoparticles with magnesium acetylacetonate. While the magnesium acetylacetonate can produce small quantities of high quality spinel powders, it use for large scale production of spinel powders is problematic. Through a thermodynamic analysis we have identified a new high-purity, low-cost, low-toxicity organomagnesium compound that reacts the with surface modified boehmite nanoparticles to produce a spinel precursor. The magnesium doped precursor readily transforms into pure phase spinel at temperature between 900°C and 1200°C.

Spectroscopic studies on some fluorescent mixed-ligand titanium(IV) complexes.

PubMed

Baranwal, Balram Prasad; Singh, Alok Kumar; Varma, Anand

2011-12-15

A novel route to synthesize some titanium(IV) complexes containing acetylacetone, straight chain carboxylic acid and hydroxycarboxylic acid ligands has been investigated. Complexes with the general formula [Ti(acac)Cl(2-n)(OOCR*)(n)(OOCC(15)H(31))] (where Hacac=acetylacetone, R*COOH=hydroxycarboxylic acids and n=1 or 2) have been isolated and characterized. Molecular weight determinations indicated mononuclear nature of the complexes. LMCT bands were observed in the electronic spectra. Infrared spectra suggested bidentate nature of the ligands. Fluorescent behaviour of the complexes was noticed on the basis of fluorescence spectra. Powder XRD indicated them to be semi-crystalline having the crystallite size in 136-185 nm range. Transmission electron microscopy (TEM) indicated spherical particles of ~ 200 nm diameter. On the basis of physico-chemical studies, it is suggested that titanium is having coordination number 7 or 8 in these complexes. Copyright © 2011 Elsevier B.V. All rights reserved.

Economically attractive route for the preparation of high quality magnetic nanoparticles by the thermal decomposition of iron(III) acetylacetonate.

PubMed

Effenberger, Fernando B; Couto, Ricardo A; Kiyohara, Pedro K; Machado, Giovanna; Masunaga, Sueli H; Jardim, Renato F; Rossi, Liane M

2017-03-17

The thermal decomposition (TD) methods are among the most successful in obtaining magnetic nanoparticles with a high degree of control of size and narrow particle size distribution. Here we investigated the TD of iron(III) acetylacetonate in the presence of oleic acid, oleylamine, and a series of alcohols in order to disclose their role and also investigate economically attractive alternatives for the synthesis of iron oxide nanoparticles without compromising their size and shape control. We have found that some affordable and reasonably less priced alcohols, such as 1,2-octanediol and cyclohexanol, may replace the commonly used and expensive 1,2-hexadecanediol, providing an economically attractive route for the synthesis of high quality magnetic nanoparticles. The relative cost for the preparation of Fe 3 O 4 NPs is reduced to only 21% and 9% of the original cost when using 1,2-octanediol and cyclohexanol, respectively.

Efficient alkene epoxidation catalyzed by molybdenyl acetylacetonate supported on aminated UiO-66 metal-organic framework

NASA Astrophysics Data System (ADS)

Kardanpour, Reihaneh; Tangestaninejad, Shahram; Mirkhani, Valiollah; Moghadam, Majid; Mohammadpoor-Baltork, Iraj; Zadehahmadi, Farnaz

2015-03-01

Metal-organic frameworks (MOFs) containing Mo Schiff base complexes were prepared by post-synthesis method and applied as efficient catalysts in the epoxidation of alkenes with tert-BuOOH. In this manner, UiO-66-NH2 (UiO=University of Oslo) MOF was reacted with salicylaldehyde and thiophene-2-carbaldehyde to produce bidentate Schiff bases. Then, the Schiff base ligands were used for immobilization of molybdenyl acetylacetonate. These new catalysts were characterized by FT-IR, UV-vis spectroscopic techniques, X-ray diffraction (XRD), BET, inductively coupled plasma atomic emission spectroscopy (ICP-AES) and field emission scanning electron microscopy (FE-SEM). These catalytic systems showed excellent activity in the epoxidation of alkenes such as cyclic and linear ones with tert-butyl hydroperoxide (TBHP) in 1,2-dichloroethane, and reused several times without any appreciable loss of their activity.

Preparation of Copper (II) Containing Phosphomolybdic Acid Salt as Catalyst for the Synthesis of Biodiesel by Esterification.

PubMed

Cai, Jie; Zhang, Qiu-Yun; Wei, Fang-Fang; Huang, Jin-Shu; Feng, Yun-Mei; Ma, Hai-Tao; Zhang, Yutao-

2018-04-01

Copper (II) containing phosphomolybdic acid (PMA) catalysts were synthesized by ion exchange method and characterization using various physico-chemical techniques such as X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), thermogravimetric (TG) and scanning electron microscopy (SEM). The characterization results showed that the Keggin ions were retained in the catalysts and possessed well thermal stability. The catalytic esterification of lauric acid with methanol could be easily achieved about 78.7% conversion under optimum condition, the catalyst also contributed to the stability of the catalyst in which it can be reused for a certain time. This study demonstrated an alternative approach to biodiesel production with high efficiency by Cu (II) ion exchanged phosphomolybdic acid catalyst in the esterification catalytic.

Use of Copper to Selectively Inhibit Brachionus calyciflorus (Predator) Growth in Chlorella kessleri (Prey) Mass Cultures for Algae Biodiesel Production

PubMed Central

Pradeep, Vishnupriya; Van Ginkel, Steven W.; Park, Sichoon; Igou, Thomas; Yi, Christine; Fu, Hao; Johnston, Rachel; Snell, Terry; Chen, Yongsheng

2015-01-01

A single Brachionus rotifer can consume thousands of algae cells per hour causing an algae pond to crash within days of infection. Thus, there is a great need to reduce rotifers in order for algal biofuel production to become reality. Copper can selectively inhibit rotifers in algae ponds, thereby protecting the algae crop. Differential toxicity tests were conducted to compare the copper sensitivity of a model rotifer—B. calyciflorus and an alga, C. kessleri. The rotifer LC50 was <0.1 ppm while the alga was not affected up to 5 ppm Cu(II). The low pH of the rotifer stomach may make it more sensitive to copper. However, when these cultures were combined, a copper concentration of 1.5 ppm was needed to inhibit the rotifer as the alga bound the copper, decreasing its bioavailability. Copper (X ppm) had no effect on downstream fatty acid methyl ester extraction. PMID:26404247

Speciation of copper diffused in a bi-porous molecular sieve

NASA Astrophysics Data System (ADS)

Huang, C.-H.; Paul Wang, H.; Wei, Y.-L.; Chang, J.-E.

2010-07-01

To better understand diffusion of copper in the micro- and mesopores, speciation of copper in a bi-porous molecular sieve (BPMS) possessing inter-connecting 3-D micropores (0.50-0.55 nm) and 2-D mesopores (4.1 nm) has been studied by X-ray absorption near edge structure (XANES) spectroscopy. It is found that about 77% (16% of CuO nanoparticles and 61% of CuO clusters) and 23% (CuO ads) of copper can be diffused into the meso- and micropores, respectively, in the BPMS. At least two diffusion steps in the BPMS may be involved: (i) free diffusion of copper in the mesopores and (ii) diffusion-controlled copper migrating into the micropores of the BPMS. The XANES data also indicate that diffusion rate of copper in the BPMS (4.68×10 -5 g/s) is greater than that in the ZSM-5 (1.11×10 -6 g/s) or MCM-41 (1.17×10 -5 g/s).

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

PubMed

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. Copyright © 2013 Elsevier B.V. All rights reserved.

Biologically active Schiff bases containing thiophene/furan ring and their copper(II) complexes: Synthesis, spectral, nonlinear optical and density functional studies

NASA Astrophysics Data System (ADS)

Gündüzalp, Ayla Balaban; Özsen, İffet; Alyar, Hamit; Alyar, Saliha; Özbek, Neslihan

2016-09-01

Schiff bases; 1,8-bis(thiophene-2-carboxaldimine)-p-menthane (L1) and 1,8-bis(furan-2-carboxaldimine)-p-menthane (L2) have been synthesized and characterized by elemental analysis, 1Hsbnd 13C NMR, UV-vis, FT-IR and LC-MS methods. 1H and 13C shielding tensors for L1 and L2 were calculated with GIAO/DFT/B3LYP/6-311++G(d,p) methods in CDCl3. The vibrational band assignments, nonlinear optical (NLO) activities, frontier molecular orbitals (FMOs) and absorption spectrum have been investigated by the same basis set. Schiff base-copper(II) complexes have been synthesized and structurally characterized with spectroscopic methods, magnetic and conductivity measurements. The spectroscopic data suggest that Schiff base ligands coordinate through azomethine-N and thiophene-S/furan-O donors (as SNNS and ONNO chelating systems) to give a tetragonal geometry around the copper(II) ions. Schiff bases and Cu(II) complexes have been screened for their biological activities on different species of pathogenic bacteria, those are, Gram positive bacteria: Bacillus subtitilus, Yersinia enterotica, Bacillus cereus, Listeria monocytogenes, Micrococcus luteus and Gram negative bacteria: Escherichia coli, Pseudomonas aeroginosa, Shigella dysenteriae, Salmonella typhi, Klebsiella pseudomonas by using microdilution technique (MIC values in mM). Biological activity results show that Cu(II) complexes have higher activities than parent ligands and metal chelation may affect significantly the antibacterial behavior of the organic ligands.

76 FR 76153 - Notice of Effectiveness of Exempt Wholesale Generator Status; Caney River Wind Project, LLC...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-12-06

...] Notice of Effectiveness of Exempt Wholesale Generator Status; Caney River Wind Project, LLC, Mesquite Solar 1, LLC, Copper Crossing Solar LLC, Copper Mountain Solar 1, LLC, Pinnacle Wind, LLC, Bellevue Solar, LLC, Yamhill Solar, LLC, Osage Wind, LLC, Minco Wind II, LLC Take notice that during the month of...

The Chemical Vapor Deposition of Thin Metal Oxide Films

NASA Astrophysics Data System (ADS)

Laurie, Angus Buchanan

1990-01-01

Chemical vapor deposition (CVD) is an important method of preparing thin films of materials. Copper (II) oxide is an important p-type semiconductor and a major component of high T_{rm c} superconducting oxides. By using a volatile copper (II) chelate precursor, copper (II) bishexafluoroacetylacetonate, it has been possible to prepare thin films of copper (II) oxide by low temperature normal pressure metalorganic chemical vapor deposition. In the metalorganic CVD (MOCVD) production of oxide thin films, oxygen gas saturated with water vapor has been used mainly to reduce residual carbon and fluorine content. This research has investigated the influence of water-saturated oxygen on the morphology of thin films of CuO produced by low temperature chemical vapor deposition onto quartz, magnesium oxide and cubic zirconia substrates. ZnO is a useful n-type semiconductor material and is commonly prepared by the MOCVD method using organometallic precursors such as dimethyl or diethylzinc. These compounds are difficult to handle under atmospheric conditions. In this research, thin polycrystalline films of zinc oxide were grown on a variety of substrates by normal pressure CVD using a zinc chelate complex with zinc(II) bishexafluoroacetylacetonate dihydrate (Zn(hfa)_2.2H _2O) as the zinc source. Zn(hfa) _2.2H_2O is not moisture - or air-sensitive and is thus more easily handled. By operating under reduced-pressure conditions (20-500 torr) it is possible to substantially reduce deposition times and improve film quality. This research has investigated the reduced-pressure CVD of thin films of CuO and ZnO. Sub-micron films of tin(IV) oxide (SnO _2) have been grown by normal pressure CVD on quartz substrates by using tetraphenyltin (TPT) as the source of tin. All CVD films were characterized by X-ray powder diffraction (XRPD), scanning electron microscopy (SEM) and electron probe microanalysis (EPMA).

Mononuclear late first row transition metal complexes of ONO donor hydrazone ligand: Synthesis, characterization, crystallographic insight, in vivo and in vitro anti-inflammatory activity

NASA Astrophysics Data System (ADS)

Kendur, Umashri; Chimmalagi, Geeta H.; Patil, Sunil M.; Gudasi, Kalagouda B.; Frampton, Christopher S.; Mangannavar, Chandrashekhar V.; Muchchandi, Iranna S.

2018-02-01

Air and moisture stable coordination compounds of late first row transition metal ions, viz., Co(II), Ni(II), Cu(II) and Zn(II) with a newly designed ligand, (E)-2-amino-N'-(1-(2-hydroxy-6-methyl-4-oxo-4H-pyran-3-yl)ethylidene)benzohydrazide (H2L) were prepared and extensively characterized using various spectro-analytical techniques. The ligand acts both in mono as well as doubly deprotonated manner. The ligand to metal stoichiometry was found to be 1:2 in case of complexes using chloride salts, whereas 1:1 in case of copper (II) complex using its acetate salt. The molecular structures of H2L, nickel and copper complexes were unambiguously determined by single-crystal X-ray diffraction studies reveal that H2L exists in a zwitterionic form while copper complex has copper centre in a distorted square planar environment. On the other hand, cobalt, nickel and zinc complexes display distorted octahedral coordination around the metal ion. In case of [Ni(HL)2].H2O, intramolecular Csbnd H⋯π stacking interaction were observed between the centroid of five membered chelate ring and phenyl proton C5sbnd H5 and intermolecular Csbnd H⋯π stacking interaction between the centroid of phenyl ring, dehydroacetic acid (DHA) ring and phenyl protons. The [Cu(L)DMF] complex is stabilized by intramolecular hydrogen bonding N1H⋯N2 and by intermolecular hydrogen bonding N1H⋯O4. Intermolecular interactions were investigated by Hirshfeld surfaces. Further, H2L and its metal complexes were screened for their in vivo and in vitro anti-inflammatory activities. The activity of the ligand has enhanced on coordination with transition metals. The tested compounds have shown excellent activity, which is almost equipotent to the standard used in the study.

Synthesis and application of surface-imprinted activated carbon sorbent for solid-phase extraction and determination of copper (II)

NASA Astrophysics Data System (ADS)

Li, Zhenhua; Li, Jingwen; Wang, Yanbin; Wei, Yajun

2014-01-01

A new Cu(II)-imprinted amino-functionalized activated carbon sorbent was prepared by a surface imprinting technique for selective solid-phase extraction (SPE) of Cu(II) prior to its determination by inductively coupled plasma atomic emission spectrometry (ICP-AES). Experimental conditions for effective adsorption of Cu(II) were optimized with respect to different experimental parameters using static and dynamic procedures in detail. Compared with non-imprinted sorbent, the ion-imprinted sorbent had higher selectivity and adsorption capacity for Cu(II). The maximum static adsorption capacity of the ion-imprinted and non-imprinted sorbent for Cu(II) was 26.71 and 6.86 mg g-1, respectively. The relatively selectivity factor values (αr) of Cu(II)/Zn(II), Cu(II)/Ni(II), Cu(II)/Co(II) and Cu(II)/Pb(II) were 166.16, 50.77, 72.26 and 175.77, respectively, which were greater than 1. Complete elution of the adsorbed Cu(II) from Cu(II)-imprinted sorbent was carried out using 2 mL of 0.1 mol L-1 EDTA solution. The relative standard deviation of the method was 2.4% for eleven replicate determinations. The method was validated for the analysis by two certified reference materials (GBW 08301, GBW 08303), the results obtained is in good agreement with standard values. The developed method was also successfully applied to the determination of trace copper in natural water samples with satisfactory results.

Synthesis and application of surface-imprinted activated carbon sorbent for solid-phase extraction and determination of copper (II).

PubMed

Li, Zhenhua; Li, Jingwen; Wang, Yanbin; Wei, Yajun

2014-01-03

A new Cu(II)-imprinted amino-functionalized activated carbon sorbent was prepared by a surface imprinting technique for selective solid-phase extraction (SPE) of Cu(II) prior to its determination by inductively coupled plasma atomic emission spectrometry (ICP-AES). Experimental conditions for effective adsorption of Cu(II) were optimized with respect to different experimental parameters using static and dynamic procedures in detail. Compared with non-imprinted sorbent, the ion-imprinted sorbent had higher selectivity and adsorption capacity for Cu(II). The maximum static adsorption capacity of the ion-imprinted and non-imprinted sorbent for Cu(II) was 26.71 and 6.86 mg g(-1), respectively. The relatively selectivity factor values (αr) of Cu(II)/Zn(II), Cu(II)/Ni(II), Cu(II)/Co(II) and Cu(II)/Pb(II) were 166.16, 50.77, 72.26 and 175.77, respectively, which were greater than 1. Complete elution of the adsorbed Cu(II) from Cu(II)-imprinted sorbent was carried out using 2 mL of 0.1 mol L(-1) EDTA solution. The relative standard deviation of the method was 2.4% for eleven replicate determinations. The method was validated for the analysis by two certified reference materials (GBW 08301, GBW 08303), the results obtained is in good agreement with standard values. The developed method was also successfully applied to the determination of trace copper in natural water samples with satisfactory results. Copyright © 2013 Elsevier B.V. All rights reserved.

X-Ray absorption spectroscopy quantitative analysis of biomimetic copper(II) complexes with tridentate nitrogen ligands mimicking the tris(imidazole) array of protein centres.

PubMed

Borghi, Elena; Casella, Luigi

2010-02-21

In this study copper(ii) complexes with the tridentate nitrogen ligand bis[2-(1-methylbenzimidazol-2-yl)ethyl]amine (2-BB) are considered as model compounds for the Cu-tris(imidazole) array found in several copper proteins. 2-BB chelates copper(ii) forming two six-membered rings and the complexes contain methanol, nitrite, azide and water as ancillary ligands; both the coordination numbers and stereochemistries differ in these complexes. Their key structural features were investigated by using full multiple-scattering theoretical analysis of the copper K-edge X-ray absorption spectrum with the MXAN code. We showed that using cluster sizes large enough to include all atoms of the ligand, the analysis of the XANES region can give both a structural model of the metal centre and map the structure of the 2-BB complexes. Complex [Cu(2-BB)(N(3))](+) provided a critical test through the comparison of the XANES simulation results with crystallographic data, thus permitting the extension of the method to the complex [Cu(2-BB)(H(2)O)(n)](+) (n = 1 or 2), for which crystallographic data are not available but is expected to bear a five-coordinated Cu(3N)(2O) core (n = 2). The structural data of [Cu(2-BB)(MeOH)(ClO(4))](+) and [Cu(2-BB)(NO(2))](+), both with a Cu(3N)(2O) core but with a different stereochemistry, were used as the starting parameters for two independent simulations of the XANES region of the [Cu(2-BB)(H(2)O)(2)](+) cation. The two structural models generated by simulation converge towards a structure for the aqua-cation with a lower coordination number. New calculations, where four-coordinated Cu(3N)(O) cores were considered as the starting structures, validated that the structure of the aqua-complex in the powder state has a copper(ii) centre with a four-coordinated Cu(3N)(O) core and a molecular formula [Cu(2-BB)(H(2)O)](ClO(4)).(H(2)O). A water solvation molecule, presumed to be disordered from the simulations with the two Cu(3N)(2O) cores, is present. The successful treatment of this Cu-2-BB complex system allows the extension of the method to other biomimetic compounds when a structural characterization is lacking.

Homogeneity of Pb(Zr ,Ti)O3 thin films by chemical solution deposition: Extended x-ray absorption fine structure spectroscopy study of zirconium local environment

NASA Astrophysics Data System (ADS)

Malic, Barbara; Arcon, Iztok; Kodre, Alojz; Kosec, Marija

2006-09-01

Sols for Pb(Zr0.53Ti0.47)O3 (PZT) thin films were prepared by 2-methoxyethanol route from lead acetate, titanium n-propoxide, and zirconium n-propoxide, the latter either unmodified or modified with acetylacetone or acetic acid in a 2/1 molar ratio and deposited on sapphire (0001). By Zr K-edge extended x-ray absorption fine structure (EXAFS) spectroscopy, the structural changes in the Zr local environment, induced by the addition of the two modifiers, were followed from the synthesis of the PZT sol to the transition to the amorphous film. In the unmodified PZT sol segregation of Zr species occurs from the original dimers present in the Zr propoxide solution in 2-methoxyethanol. The immediate neighborhood of Zr atoms changes markedly at the transition from the sol to the amorphous film: the local structure around Zr atoms is similar to the one found in tetragonal zirconia particles. The modification of Zr propoxide with acetylacetone in 2-methoxyethanol results in Zr monomers. In PZT sol, clustering of Zr species is observed continuing into the amorphous film. By modification with acetic acid the original dimeric structure of the Zr precursor is retained in the PZT sol and further in the amorphous film. Selective modification of Zr propoxide with acetic acid therefore results in a more homogeneous distribution of Zr atoms in the PZT sol and amorphous film than in both as-received and acetylacetone-modified Zr propoxide.

Synthesis and Properties of Homonuclear, Dimetallic Nickel(II), Copper(II) and Zinc(II) Complexes of p-Xylenediyl and 2-Butynediyl-Bridged Dicyclens

DTIC Science & Technology

1993-05-01

urease which contains two nickel ions in the active site. Catalytic hydrolysis studies are in progress. 20 DISTRIBUTION /AVAILABILITY OF ABSTRACT 21...for hydrolytic metalloenzymes. In contrast, the enzyme urease has becti show’n tU coftifl two nickel(II) ions in the active site," but as yet the

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

PubMed

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

2017-04-01

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

Copper(II) complexes of alloferon 1 with point mutations (H1A) and (H9A) stability structure and biological activity.

PubMed

Matusiak, Agnieszka; Kuczer, Mariola; Czarniewska, Elżbieta; Rosiński, Grzegorz; Kowalik-Jankowska, Teresa

2014-09-01

Mono- and polynuclear copper(II) complexes of the alloferon 1 with point mutations (H1A) A(1)GVSGH(6)GQH(9)GVH(12)G (Allo1A) and (H9A) H(1)GVSGH(6)GQA(9)GVH(12)G (Allo9A) have been studied by potentiometric, UV-visible, CD, EPR spectroscopic and mass spectrometry (MS) methods. To obtain a complete complex speciation different metal-to-ligand molar ratios ranging from 1:1 to 4:1 for Allo1A and to 3:1 for Allo9A were studied. The presence of the His residue in first position of the peptide chain changes the coordination abilities of the Allo9A peptide in comparison to that of the Allo1A. Imidazole-N3 atom of N-terminal His residue of the Allo9A peptide forms stable 6-membered chelate with the terminal amino group. Furthermore, the presence of two additional histidine residues in the Allo9A peptide (H(6),H(12)) leads to the formation of the CuL complex with 4N {NH2,NIm-H(1),NIm-H(6),NIm-H(12)} binding site in wide pH range (5-8). For the Cu(II)-Allo1A system, the results demonstrated that at physiological pH7.4 the predominant complex the CuH-1L consists of the 3N {NH2,N(-),CO,NIm} coordination mode. The inductions of phenoloxidase activity and apoptosis in vivo in Tenebrio molitor cells by the ligands and their copper(II) complexes at pH7.4 were studied. The Allo1A, Allo1K peptides and their copper(II) complexes displayed the lowest hemocytotoxic activity while the most active was the Cu(II)-Allo9A complex formed at pH7.4. The results may suggest that the N-terminal-His(1) and His(6) residues may be more important for their proapoptotic properties in insects than those at positions 9 and 12 in the peptide chain. Copyright © 2014 Elsevier Inc. All rights reserved.

Discovery and development of microporous metal carboxylates.

PubMed

Mori, Wasuke; Sato, Tomohiko; Kato, Chika Nozaki; Takei, Tohru; Ohmura, Tetsushi

2005-01-01

We have found a form of copper(II) terephthalate that occluded an enormous amount of gases such as N2, Ar, O2, and Xe. Copper(II) terephthalate is the first metal complex found capable of adsorbing gases. This complex has opened a new field of adsorbent chemistry and is recognized as a leader in the construction of microporous metal complexes. In extending the route for the synthesis of microporous complexes, we obtained many new porous materials that are widely recognized as useful materials for applications in areas such as gas storage, molecular sieves, catalysis, inclusion complexes, and surface science. 2005 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.

Impact of substituents and nonplanarity on nickel and copper porphyrin electrochemistry: first observation of a Cu(II)/Cu(III) reaction in nonaqueous media.

PubMed

Fang, Yuanyuan; Senge, Mathias O; Van Caemelbecke, Eric; Smith, Kevin M; Medforth, Craig J; Zhang, Min; Kadish, Karl M

2014-10-06

Electrochemical studies of the oxidation of dodecasubstituted and highly nonplanar nickel porphyrins in a noncoordinating solvent have previously revealed the first nickel(III) porphyrin dication. Herein, we investigate if these nonplanar porphyrins can also be used to detect the so far unobserved copper(III) porphyrin dication. Electrochemical studies of the oxidation of (DPP)Cu and (OETPP)Cu show three processes, the first two of which are macrocycle-centered to give the porphyrin dication followed by a Cu(II)/Cu(III) process at more positive potential. Support for the assignment of the Cu(II)/Cu(III) process comes from the linear relationships observed between E1/2 and the third ionization potential of the central metal ions for iron, cobalt, nickel, and copper complexes of (DPP)M and (OETPP)M. In addition, the oxidation behavior of additional nonplanar nickel porphyrins is investigated in a noncoordinating solvent, with nickel meso-tetraalkylporphyrins also being found to form nickel(III) porphyrin dications. Finally, examination of the nickel meso-tetraalkylporphyrins in a coordinating solvent (pyridine) reveals that the first oxidation becomes metal-centered under these conditions, as was previously noted for a range of nominally planar porphyrins.

Synthesis of mononuclear copper(II) complexes of N3O2 and N4O2 donors containing Schiff base ligands: Theoretical and biological observations

NASA Astrophysics Data System (ADS)

Mancha Madha, K.; Gurumoorthy, P.; Arul Antony, S.; Ramalakshmi, N.

2017-09-01

A new series of six mononuclear copper(II) complexes were synthesized from N3O2 and N4O2 donors containing Schiff base ligands, and characterized by various spectral methods. The geometry of the complexes was determined using UV-Vis, EPR and DFT calculations. The complexes of N3O2 donors (1-3) adopted square pyramidal geometry and the remaining complexes of N4O2 donors (4-6) show distorted octahedral geometry around copper(II) nuclei. Redox properties of the complexes show a one-electron irreversible reduction process in the cathodic potential (Epc) region from -0.74 to -0.98 V. The complexes show potent antioxidant activity against DPPH radicals. Molecular docking studies of complexes showed σ-π interaction, hydrogen bonding, electrostatic and van der Waals interactions with VEGFR2 kinase receptor. In vitro cytotoxicity of the complexes was tested against human breast cancer (MDA-MB-231) cell lines and one normal human dermal fibroblasts (NHDF) cell line through MTT assay. The morphological assessment data obtained by Hoechst 33258 and AO/EB staining revealed that the complexes induce apoptosis pathway of cell death.

Carboxylate-assisted C–H activation of phenylpyridines with copper, palladium and ruthenium: a mass spectrometry and DFT study† †Electronic supplementary information (ESI) available: Details on the mass-spectrometry experiments and theoretical calculations, Hammett studies, potential energy surfaces, energies, optimized Gaussian geometries and laser-power dependence during the IRMPD spectra measurements. See DOI: 10.1039/c5sc01729g

PubMed Central

Gray, A.; Tsybizova, A.

2015-01-01

The C–H activation of 2-phenylpyridine, catalyzed by copper(ii), palladium(ii) and ruthenium(ii) carboxylates, was studied in the gas phase. ESI-MS, infrared multiphoton dissociation spectroscopy and quantum chemical calculations were combined to investigate the intermediate species in the reaction. Collision induced dissociation (CID) experiments and DFT calculations allowed estimation of the energy required for this C–H activation step and the subsequent acetic acid loss. Hammett plots constructed from the CID experiments using different copper carboxylates as catalysts revealed that the use of stronger acids accelerates the C–H activation step. The reasoning can be traced from the associated transition structures that suggest a concerted mechanism and the key effect of the carbon–metal bond pre-formation. Carboxylates derived from stronger acids make the metal atom more electrophilic and therefore shift the reaction towards the formation of C–H activated products. PMID:29861892

A novel high performance nano chemosensor for copper (II) ion based on an ultrasound-assisted synthesized diphenylamine-based Schiff base: Design, fabrication and density functional theory calculations.

PubMed

Parsaee, Zohreh; Haratipour, Pouya; Lariche, Milad Janghorban; Vojood, Arash

2018-03-01

A novel high selective colorimetric chemosensor was introduced based on a nano diphenyl-based Schiff base (H 2 L), 2,2'-((1E,1'E)-(((hexylazanediyl)bis(4,1-phenylene))bis(methanylylidene))bis(azanylylidene))bis(4-methylphenol) that synthesized using sonochemical method. H 2 L was characterized by FT-IR, MS, TGA, 1 H NMR, 13 C NMR, SEM and elemental analysis techniques, then fabricated as the portable strips for sensing copper (II) ions in aqueous media. The binding interaction between H 2 L and various metal ions was investigated by UV-Vis spectroscopic that showed favorable coordination toward Cu 2+ ion. H 2 L exhibited binding-induced color changes from yellow to pink and practically no interference in the presence of other metal ions, i.e., Cr 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Zn 2+ , Cd 2+ , Hg 2+ , Pb 2+ , Mg 2+ and Ca 2+ . The chemsensor showd the color change from yellow to pink in presence of copper (II) ion in aqueous media due to binging of H 2 L and Cu (II). This sensor can determine the copper (II) at in the rang of 7.5 × 10 -8 -1.8 × 10 -5  mol L -1 with a correlation equation: Absorbance = 0.0450[Cu 2+ ] × 10 -6  + 0.71 and R 2  = 0.975 and low detection limit of 1.89 × 10 -8  mol L -1 . Density functional theory (DFT) calculations were carried out at the B3LYP levels of theory with B3LYP/6-311+G(d,p) and LANL2DZ/6-311+G(d,p) basis sets for chemosensor and its copper complex respectively. The optimized geometry, harmonic vibrational frequencies, 1 H NMR and 13 C NMR chemical, Molecular orbital (M.O.), Mulliken population analysis (MPA), contour of Electrostatic Potential (ESP) and Molecular Electrostatic Potential (MEP) map of H 2 L were calculated which show good agreement with behavior of sensor for detection of Cu 2+ ion. Copyright © 2017 Elsevier B.V. All rights reserved.

Mononuclear Copper Complex Catalyzed Four-Electron Reduction of Oxygen

PubMed Central

Fukuzumi, Shunichi; Kotani, Hiroaki; Lucas, Heather R.; Doi, Kaoru; Suenobu, Tomoyoshi; Peterson, Ryan L.; Karlin, Kenneth D.

2010-01-01

A mononuclear CuII complex acts as an efficient catalyst for four-electron reduction of O2 to H2O by a ferrocene derivative via formation of the dinuclear CuII peroxo complex that is further reduced in the presence of protons by a ferrocene derivative to regenerate the CuII complex. PMID:20443560

Indirect spectrophotometric determination of sodium ceftriaxone with n-propyl alcohol-ammonium sulfate-water system by extraction flotation of copper(II).

PubMed

Zhao, Wei; Zhang, Yan; Li, Quanmin

2008-05-01

Although the determination methods of sodium ceftriaxone has been increasingly reported, these methods have their inherent limits preventing them from being broadly applied in common laboratories. In order to circumvent this problem, a rapid and simple method for the indirect spectrophotometric determination of sodium ceftriaxone is reported. Sodium ceftriaxone was degraded completely in the presence of 0.20 mol/l sodium hydroxide in boiling water bath for 20 min. The thiol group (-SH) of the degradation product (I) of sodium ceftriaxone could reduce cupric to cuprous ions, and the resulting which was precipitated with the thiol group (-SH) of the degradation product (II) at pH 4.0. By determining the residual amount of copper (II), the indirect determination of sodium ceftriaxone can be achieved. Standard curve of sodium ceftriaxone versus the flotation yield of copper(II) showed that sodium ceftriaxone could be determined in low concentrations. The linear range of sodium ceftriaxone was 0.70-32 microg/ml and the detection limit evaluated by calibration curve (3sigma/k) was found to be 0.60 microg/ml. A simple and efficient method was developed and it has been successfully applied to the determination of sodium ceftriaxone in human serum and urine samples, respectively. It is expected that this method will find broad applications in the detection of cephalosporin derivatives with similar structure.

Distribution and potential sources and sinks of copper chelators in the Sargasso Sea

NASA Astrophysics Data System (ADS)

Moffett, J. W.; Zika, R. G.; Brand, L. E.

1990-01-01

Copper speciation has been studied at an oligotrophic station in the southwestern Sargasso Sea to determine the distribution of Cu binding ligands and evaluate their potential sources and sinks. Speciation was studied using a ligand exchange/liquid-liquid partition procedure used in a previous study in Florida coastal waters [ MOFFET and ZIKA (1987a) Marine Chemistry, 21, 301-313]. Copper speciation was dominated by organic complexation at all depths studied (16-950 m). Complexation was greatest in the region of the chlorophyll maximum. In this region, speciation was dominated by two ligands or ligand classes; L 1, with K cond. = 10 13.2, concentration = 2 nM, and a weaker but more abundant ligand class, L 2 with Kincond. = 10 9.7, concentration = 80 nM. From 140 to 16 m, [Cu(II)] free/[Cu(II)] total increases by a factor of 20, due to a decrease in [L 1] to a value below the ambient Cu concentration. Exposure of water from 140 m to sunlight indicated that photochemical decomposition of L 1 may account for the decrease. Below the chlorophyll maximum there is a gradual increase in [Cu(II)] free/[Cu(II)] total suggesting that the ligands are of recent biological origin rather than derived from refractory materials. Cultures of a ubiquitous marine cyanobacterium, Synechococcus sp. produced a ligand with K cond. comparable to L 1, indicating that a biological source is plausible.

Newer mixed ligand Schiff base complexes from aquo-N-(2‧-hydroxy acetophenone) glycinatocopper(II) as synthon: DFT, antimicrobial activity and molecular docking study

NASA Astrophysics Data System (ADS)

Pramanik, Harun A. R.; Das, Dharitri; Paul, Pradip C.; Mondal, Paritosh; Bhattacharjee, Chira R.

2014-02-01

Synthesis of a series of newer mixed ligand copper(II) complexes of aminoacid Schiff base of the type [CuL(X)] (L = N-(2‧-hydroxy acetophenone) glycinate, X = imidazole (im) 2, benzimidazole (benz) 3, pyridine (py) 4, hydrazine (hz) 5,8-hydroxyquinoline (8-hq) 6, pyrrolidine (pyrr) 7, piperidine (pip) 8, and nicotinamide (nic) 9) have been accomplished from the interaction of an aquated Schiff base complex, [CuL(H2O)]·H2O, 1 with some selected neutral nitrogen-donor ligands. The copper(II) Schiff base complex, [CuL(H2O)]·H2O, L = N-(2‧-hydroxy acetophenone) glycinate was synthesized from the reaction of glycine and 2‧ hydroxy acetophenone and copper(II) acetate. The compounds were characterised by elemental analysis, spectral, magnetic and thermal studies. The density functional theory calculations were performed using LANL2DZ and 6-311 G(d, p) basis sets with B3LYP correlation functional to ascertain the stable electronic structure, HOMO-LUMO energy gap, chemical hardness and dipole moment of the mixed ligand complexes. A distorted square planar geometry has been conjectured for the complexes. Antibacterial activities of the ligand and its metal complexes have been tested against selected gram-positive and gram-negative strains and correlated with computational docking scores.

Assessing change in diet and biological affinity between the 4th and 3rd millennia cal BCE in the Portuguese Estremadura: a preliminary dental comparison of Feteira II and Bolores.

PubMed

Horwath, B C; Waterman, A J; Lillios, K T; Irish, J D

2014-04-01

Although the social and political changes accompanying the transition from the Neolithic through Copper Age, between the 4th and 3rd millennia cal BCE, in southwestern Iberia are reasonably well understood, much less is known about whether population movements and dietary changes accompanied these transformations. To address this question, human dental remains from the Middle through Late Neolithic site of Feteira II (3600-2900 cal BCE) and the Late Neolithic site of Bolores (2800-2600 cal BCE) in the Portuguese Estremadura were used to examine diet (microwear) and affinity (dental non-metrics). Microwear features were not found to be significantly different between Feteira II and Bolores, suggesting that the emergence of social complexity during this period did not result in large-scale changes in subsistence practices during the period of use at these sites. Using the Arizona State University Dental Anthropology System and supporting statistics, no significant difference between the samples from Feteira II and Bolores was observed, suggesting that no population replacement occurred between the Middle Neolithic and Late Neolithic/Copper Age. However, at Bolores there is some indication that there may have been demographic exchanges between southern Iberian and North African populations during the Late Neolithic/Copper Age. Copyright © 2013 Elsevier GmbH. All rights reserved.

Synthesis and Characterization of Chlorpyrifos/Copper(II) Schiff Base Mesoporous Silica with pH Sensitivity for Pesticide Sustained Release.

PubMed

Chen, Huayao; Lin, Yueshun; Zhou, Hongjun; Zhou, Xinhua; Gong, Sheng; Xu, Hua

2016-11-02

The salicylaldehyde-modified mesoporous silica (SA-MCM-41) was prepared through a co-condensation method. Through the bridge effect from the copper ion, which also acts as the nutrition of the plant, the model drug chlorpyrifos (CH) was supported on the copper(II) Schiff base mesoporous silica (Cu-MCM-41) to form a highly efficient sustained-release system (CH-Cu-MCM-41) for pesticide delivery. The experimental results showed that the larger the concentration of the copper ion, the more adsorption capacity (AC) of Cu-MCM-41 for chlorpyrifos and the smaller its release rate. The results confirmed the existence of a coordination bond between SA-MCM-41 and copper ions as well as a coordination bond between Cu-MCM-41 and chlorpyrifos. The AC of SA-MCM-41 is 106 mg/g, while that of Cu-MCM-41 is 295 mg/g. The as-synthesized system showed significant pH sensitivity. Under the condition of pH ≤ 7, the release rate of chlorpyrifos decreased with increasing pH, whereas its release rate in weak base conditions was slightly larger than that in weak acid conditions. Meanwhile, the drug release rate of the as-synthesized system was also affected by the temperature. Their sustained-release curves can be described by the Korsmeyer-Peppas equation.

Mineral potential for sediment-hosted copper deposits in the Islamic Republic of Mauritania (phase V, deliverable 75): Chapter K in Second projet de renforcement institutionnel du secteur minier de la République Islamique de Mauritanie (PRISM-II)

USGS Publications Warehouse

Taylor, Cliff D.; Giles, Stuart A.

2015-01-01

Although mineral occurrence data and descriptive geological information are adequate to delineate areas favorable for sediment-hosted copper deposits, this review indicates that potential for this type of deposit in Mauritania is low.

Copper(II) mediated facile and ultra fast peptide synthesis in methanol.

PubMed

Mali, Sachitanand M; Jadhav, Sandip V; Gopi, Hosahudya N

2012-07-18

A novel, ultrafast, mild and scalable amide bond formation strategy in methanol using simple thioacids and amines is described. The mechanism suggests that the coupling reactions are initially mediated by CuSO(4)·5H(2)O and subsequently catalyzed by in situ generated copper sulfide. The pure peptides were isolated in satisfactory yields in less than 5 minutes.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Osiry, H.; Cano, A.; Lemus-Santana, A.A.

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 wasmore » 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.« less

Removal of copper by oxygenated pyrolytic tire char: kinetics and mechanistic insights.

PubMed

Quek, Augustine; Balasubramanian, Rajashekhar

2011-04-01

The kinetics of copper ion (Cu(II)) removal from aqueous solution by pyrolytic tire char was modeled using five different conventional models. A modification to these models was also developed through a modified equation that accounts for precipitation. Conventional first- and second-order reaction models did not fit the copper sorption kinetics well, indicating a lack of simple rate-order dependency on solute concentration. Instead, a reversible first-order rate reaction showed the best fit to the data, indicating a dependence on surface functional groups. Due to the varying solution pH during the sorption process, modified external and internal mass transfer models were employed. Results showed that the sorption of copper onto oxygenated chars was limited by external mass transfer and internal resistance with and without the modification. However, the modification of the sorption process produced very different results for unoxygenated chars, which showed neither internal nor external limitation to sorption. Instead, its slow sorption rate indicates a lack of surface functional groups. The sorption of Cu(II) by oxygenated and unoxygenated chars was also found to occur via three and two distinct stages, respectively. Copyright © 2010 Elsevier Inc. All rights reserved.

Synthesis, characterization and toxicity studies of pyridinecarboxaldehydes and L-tryptophan derived Schiff bases and corresponding copper (II) complexes.

PubMed

Malakyan, Margarita; Babayan, Nelly; Grigoryan, Ruzanna; Sarkisyan, Natalya; Tonoyan, Vahan; Tadevosyan, Davit; Matosyan, Vladimir; Aroutiounian, Rouben; Arakelyan, Arsen

2016-01-01

Schiff bases and their metal-complexes are versatile compounds exhibiting a broad range of biological activities and thus actively used in the drug development process. The aim of the present study was the synthesis and characterization of new Schiff bases and their copper (II) complexes, derived from L-tryptophan and isomeric (2-; 3-; 4-) pyridinecarboxaldehydes, as well as the assessment of their toxicity in vitro . The optimal conditions of the Schiff base synthesis resulting in up to 75-85% yield of target products were identified. The structure-activity relationship analysis indicated that the location of the carboxaldehyde group at 2-, 3- or 4-position with regard to nitrogen of the pyridine ring in aldehyde component of the L-tryptophan derivative Schiff bases and corresponding copper complexes essentially change the biological activity of the compounds. The carboxaldehyde group at 2- and 4-positions leads to the higher cytotoxic activity, than that of at 3-position, and the presence of the copper in the complexes increases the cytotoxicity. Based on toxicity classification data, the compounds with non-toxic profile were identified, which can be used as new entities in the drug development process using Schiff base scaffold.

Synthesis, characterization and toxicity studies of pyridinecarboxaldehydes and L-tryptophan derived Schiff bases and corresponding copper (II) complexes

PubMed Central

Malakyan, Margarita; Babayan, Nelly; Grigoryan, Ruzanna; Sarkisyan, Natalya; Tonoyan, Vahan; Tadevosyan, Davit; Matosyan, Vladimir; Aroutiounian, Rouben; Arakelyan, Arsen

2016-01-01

Schiff bases and their metal-complexes are versatile compounds exhibiting a broad range of biological activities and thus actively used in the drug development process. The aim of the present study was the synthesis and characterization of new Schiff bases and their copper (II) complexes, derived from L-tryptophan and isomeric (2-; 3-; 4-) pyridinecarboxaldehydes, as well as the assessment of their toxicity in vitro. The optimal conditions of the Schiff base synthesis resulting in up to 75-85% yield of target products were identified. The structure-activity relationship analysis indicated that the location of the carboxaldehyde group at 2-, 3- or 4-position with regard to nitrogen of the pyridine ring in aldehyde component of the L-tryptophan derivative Schiff bases and corresponding copper complexes essentially change the biological activity of the compounds. The carboxaldehyde group at 2- and 4-positions leads to the higher cytotoxic activity, than that of at 3-position, and the presence of the copper in the complexes increases the cytotoxicity. Based on toxicity classification data, the compounds with non-toxic profile were identified, which can be used as new entities in the drug development process using Schiff base scaffold. PMID:28344771

Fabrication of visible light-triggered photocatalytic materials from the coupling of n-type zinc oxide and p-type copper oxide

NASA Astrophysics Data System (ADS)

Gorospe, A. B.; Herrera, M. U.

2017-04-01

Coupling of copper oxide (CuO) and zinc oxide (ZnO) was done by chemical precipitation method. In this method, copper sulfate pentahydrate and zinc sulfate heptahydrate salt precursors were separately dissolved in distilled water; then were mixed together. The copper sulfate-zinc sulfate solution was then combined with a sodium hydroxide solution. The precipitates were collected and washed in distilled water and ethanol several times, then filtered and dried. The dried sample was grounded, and then undergone heat treatment. After heating, the sample was grounded again. Zinc oxide powder and copper oxide powder were also fabricated using chemical precipitation method. X-Ray Diffraction measurements of the coupled CuO/ZnO powder showed the presence of CuO and ZnO in the fabricated sample. Furthermore, other peaks shown by XRD were also identified corresponding to copper, copper (II) oxide, copper sulfate and zinc sulfate. Results of the photocatalytic activity investigation show that the sample exhibited superior photocatalytic degradation of methyl orange under visible light illumination compared to copper oxide powder and zinc oxide powder. This may be attributed to the lower energy gap at the copper oxide-zinc oxide interface, compared to zinc oxide, allowing visible light to trigger its photocatalytic activity.

Aqua[bis(pyrimidin-2-yl-kappa N)amine](carbonato-kappa 2O,O')copper(II) dihydrate.

PubMed

van Albada, Gerard A; Mutikainen, Ilpo; Turpeinen, Urho; Reedijk, Jan

2002-03-01

The title mononuclear complex, [Cu(CO(3))(C(8)H(7)N(5))(H(2)O)] x 2H(2)O, was obtained by fixation of CO(2) by a mixture of copper(II) tetrafluoroborate and the ligand bis(pyrimidin-2-yl)amine in ethanol/water. The Cu(II) ion of the complex has a distorted square-pyramidal environment, with a basal plane formed by two N atoms of the ligand and two chelating O atoms of the carbonate group, while the apical position is occupied by the O atom of the coordinating water molecule. In the solid state, hydrogen-bonding interactions are dominant, the most unusual being the Watson-Crick-type coplanar ligand pairing through two N--H...N bonds. Lattice water molecules also participate in hydrogen bonding.

Identification of a copper(I) intermediate in the conversion of 1-aminocyclopropane carboxylic acid (ACC) into ethylene by Cu(II)-ACC complexes and hydrogen peroxide.

PubMed

Ghattas, Wadih; Giorgi, Michel; Mekmouche, Yasmina; Tanaka, Tsunehiro; Rockenbauer, Antal; Réglier, Marius; Hitomi, Yutaka; Simaan, A Jalila

2008-06-02

Several Cu(II) complexes with ACC (=1-aminocyclopropane carboxylic acid) or AIB (=aminoisobutyric acid) were prepared using 2,2'-bipyridine, 1,10-phenanthroline, and 2-picolylamine ligands: [Cu(2,2'-bipyridine)(ACC)(H2O)](ClO4) (1a), [Cu(1,10-phenanthroline)(ACC)](ClO4) (2a), [Cu(2-picolylamine)(ACC)](ClO4) (3a), and [Cu(2,2'-bipyridine)(AIB)(H2O)](ClO4) (1b). All of the complexes were characterized by X-ray diffraction analysis. The Cu(II)-ACC complexes are able to convert the bound ACC moiety into ethylene in the presence of hydrogen peroxide, in an "ACC-oxidase-like" activity. A few equivalents of base are necessary to deprotonate H2O2 for optimum activity. The presence of dioxygen lowers the yield of ACC conversion into ethylene by the copper(II) complexes. During the course of the reaction of Cu(II)-ACC complexes with H2O2, brown species (EPR silent and lambda max approximately 435 nm) were detected and characterized as being the Cu(I)-ACC complexes that are obtained upon reduction of the corresponding Cu(II) complexes by the deprotonated form of hydrogen peroxide. The geometry of the Cu(I) species was optimized by DFT calculations that reveal a change from square-planar to tetrahedral geometry upon reduction of the copper ion, in accordance with the observed nonreversibility of the redox process. In situ prepared Cu(I)-ACC complexes were also reacted with hydrogen peroxide, and a high level of ethylene formation was obtained. We propose Cu(I)-OOH as a possible active species for the conversion of ACC into ethylene, the structure of which was examined by DFT calculation.

Removal of copper and iron by polyurethane foam column in FIA system for the determination of nickel in pierced ring.

PubMed

Vongboot, Monnapat; Suesoonthon, Monrudee

2015-01-01

Polyurethane foam (PUF) mini-column was used to eliminate copper and iron for the determination of nickel in pierced rings. The PUF mini-column was connected to FIA system for on-line sorption of copper and iron in complexes form of CuSCN(+) and FeSCN(2+). For this season, the acid solution containing a mixture of Ni(II), Fe(III), Cu(II) and SCN(-) ions was firstly flew into the PUF column. Then, the percolated solution which Fe(III) and Cu(II) ions is separated from analysis was injected into FIA system to react with 4-(2-pyridylazo) resorcinol (PAR) reagent in basic condition which this method is called pH gradient technique. The Ni-PAR complexes obtained were measured theirs absorbance at 500 nm by UV visible spectrophotometer. In this study, it was found that Cu(II) and Fe(III) were completely to form complexes with 400 mmol/L KSCN and entirely to eliminate in acidic condition at pH 3.0. In the optimum condition of these experiments, the method provided the linear relationship between absorbance and the concentration of Ni(II) in the range from 5.00 to 30.00 mg/L. Linear equation is y=0.0134x+0.0033 (R(2)=0.9948). Precision, assessed in the term of the relative standard deviation, RSD, and accuracy for multiple determinations obtained in values of 0.77-1.73% and 97.4%, respectively. The level of an average amount of Ni(II) in six piercing rings was evaluated to be 14.78 mg/g. Copyright © 2014 Elsevier B.V. All rights reserved.

Increase in the Quantum Yield of Photoinhibition Contributes to Copper Toxicity in Vivo1

PubMed Central

Pätsikkä, Eija; Aro, Eva-Mari; Tyystjärvi, Esa

1998-01-01

The effect of copper on photoinhibition of photosystem II in vivo was studied in bean (Phaseolus vulgaris L. cv Dufrix). The plants were grown hydroponically in the presence of various concentrations of Cu2+ ranging from the optimum 0.3 μm (control) to 15 μm. The copper concentration of leaves varied according to the nutrient medium from a control value of 13 mg kg−1 dry weight to 76 mg kg−1 dry weight. Leaf samples were illuminated in the presence and absence of lincomycin at different light intensities (500–1500 μmol photons m−2 s−1). Lincomycin prevents the concurrent repair of photoinhibitory damage by blocking chloroplast protein synthesis. The photoinhibitory decrease in the light-saturated rate of O2 evolution measured from thylakoids isolated from treated leaves correlated well with the decrease in the ratio of variable to maximum fluorescence measured from the leaf discs; therefore, the fluorescence ratio was used as a routine measurement of photoinhibition in vivo. Excess copper was found to affect the equilibrium between photoinhibition and repair, resulting in a decrease in the steady-state concentration of active photosystem II centers of illuminated leaves. This shift in equilibrium apparently resulted from an increase in the quantum yield of photoinhibition (ΦPI) induced by excess copper. The kinetic pattern of photoinhibition and the independence of ΦPI on photon flux density were not affected by excess copper. An increase in ΦPI may contribute substantially to Cu2+ toxicity in certain plant species. PMID:9625715

Influence of electron donors and copper concentration on geochemical and mineralogical processes under conditions of biological sulphate reduction

NASA Astrophysics Data System (ADS)

Wolicka, Dorota; Borkowski, Andrzej

2014-03-01

Sulphidogenous microorganism communities were isolated from soil polluted by crude oil. The study was focused on determining the influence of 1) copper (II) concentration on the activity of selected microorganism communities and 2) the applied electron donor on the course and evolution of mineral-forming processes under conditions favouring growth of sulphate-reducing bacteria (SRB). The influence of copper concentration on the activity of selected microorganism communities and the type of mineral phases formed was determined during experiments in which copper (II) chloride at concentrations of 0.1, 0.2, 0.5 and 0.7 g/L was added to SRB cultures. The experiments were performed in two variants: with ethanol (4 g/L) or lactate (4 g/L) as the sole carbon source. In order to determine the taxonomic composition of the selected microorganism communities, the 16S rRNA method was used. Results of this analysis confirmed the presence of Desulfovibrio, Desulfohalobium, Desulfotalea, Thermotoga, Solibacter, Gramella, Anaeromyxobacter and Myxococcus sp. in the stationary cultures. The post-culture sediments contained covelline (CuS) and digenite (Cu9S5 ). Based on the results, it can be stated that the type of carbon source applied during incubation plays a crucial role in determining the mineral composition of the post-culture sediments. Thus, regardless of the amount of copper ion introduced to a culture with lactate as the sole carbon source, no copper sulphide was observed in the post-culture sediments. Cultures with ethanol as the sole carbon source, on the other hand, yielded covelline or digenite in all post-culture sediments.

Matrix effects on copper(II)phthalocyanine complexes. A combined continuous wave and pulse EPR and DFT study.

PubMed

Finazzo, Cinzia; Calle, Carlos; Stoll, Stefan; Van Doorslaer, Sabine; Schweiger, Arthur

2006-04-28

The effect of the electron withdrawing or donating character of groups located at the periphery of the phthalocyanine ligand, as well as the influence of polar and nonpolar solvents are of importance for the redox chemistry of metal phthalocyanines. Continuous wave and pulse electron paramagnetic resonance and pulse electron nuclear double resonance spectroscopy at X- and Q-band are applied to investigate the electronic structure of the complexes Cu(II)phthalocyanine (CuPc), copper(II) 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine (CuPc(t)), and copper(II) 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecafluoro-29H,31H-phthalocyanine (CuPc(F)) in various matrices. Isotope substitutions are used to determine the g values, the copper hyperfine couplings and the hyperfine interactions with the 14N, 1H and 19F nuclei of the macrocycle and the surrounding matrix molecules. Simulations and interpretations of the spectra are shown and discussed, and a qualitative analysis of the data using previous theoretical models is given. Density functional computations facilitate the interpretation of the EPR parameters. The experimental g, copper and nitrogen hyperfine and nuclear quadrupole values are found to be sensitive to changes of the solvent and the structure of the macrocycle. To elucidate the electronic, structural and bonding properties the changes in the g principal values are related to data from UV/Vis spectroscopy and to density functional theory (DFT) computations. The analysis of the EPR data indicates that the in-plane metal-ligand sigma bonding is more covalent for CuPc(t) in toluene than in sulfuric acid. Furthermore, the out-of-plane pi bonding is found to be less covalent in the case of a polar sulfuric acid environment than with nonpolar toluene or H2Pc environment, whereby the covalency of this bonding is increased upon addition of tert-butyl groups. No contribution from in-plane pi bonding is found.

Copper as a target for prostate cancer therapeutics: copper-ionophore pharmacology and altering systemic copper distribution.

PubMed

Denoyer, Delphine; Pearson, Helen B; Clatworthy, Sharnel A S; Smith, Zoe M; Francis, Paul S; Llanos, Roxana M; Volitakis, Irene; Phillips, Wayne A; Meggyesy, Peter M; Masaldan, Shashank; Cater, Michael A

2016-06-14

Copper-ionophores that elevate intracellular bioavailable copper display significant therapeutic utility against prostate cancer cells in vitro and in TRAMP (Transgenic Adenocarcinoma of Mouse Prostate) mice. However, the pharmacological basis for their anticancer activity remains unclear, despite impending clinical trails. Herein we show that intracellular copper levels in prostate cancer, evaluated in vitro and across disease progression in TRAMP mice, were not correlative with copper-ionophore activity and mirrored the normal levels observed in patient prostatectomy tissues (Gleason Score 7 & 9). TRAMP adenocarcinoma cells harbored markedly elevated oxidative stress and diminished glutathione (GSH)-mediated antioxidant capacity, which together conferred selective sensitivity to prooxidant ionophoric copper. Copper-ionophore treatments [CuII(gtsm), disulfiram & clioquinol] generated toxic levels of reactive oxygen species (ROS) in TRAMP adenocarcinoma cells, but not in normal mouse prostate epithelial cells (PrECs). Our results provide a basis for the pharmacological activity of copper-ionophores and suggest they are amendable for treatment of patients with prostate cancer. Additionally, recent in vitro and mouse xenograft studies have suggested an increased copper requirement by prostate cancer cells. We demonstrated that prostate adenocarcinoma development in TRAMP mice requires a functional supply of copper and is significantly impeded by altered systemic copper distribution. The presence of a mutant copper-transporting Atp7b protein (tx mutation: A4066G/Met1356Val) in TRAMP mice changed copper-integration into serum and caused a remarkable reduction in prostate cancer burden (64% reduction) and disease severity (grade), abrogating adenocarcinoma development. Implications for current clinical trials are discussed.

Copper as a target for prostate cancer therapeutics: copper-ionophore pharmacology and altering systemic copper distribution

PubMed Central

Denoyer, Delphine; Pearson, Helen B.; Clatworthy, Sharnel A.S.; Smith, Zoe M.; Francis, Paul S.; Llanos, Roxana M.; Volitakis, Irene; Phillips, Wayne A.; Meggyesy, Peter M.; Masaldan, Shashank; Cater, Michael A.

2016-01-01

Copper-ionophores that elevate intracellular bioavailable copper display significant therapeutic utility against prostate cancer cells in vitro and in TRAMP (Transgenic Adenocarcinoma of Mouse Prostate) mice. However, the pharmacological basis for their anticancer activity remains unclear, despite impending clinical trails. Herein we show that intracellular copper levels in prostate cancer, evaluated in vitro and across disease progression in TRAMP mice, were not correlative with copper-ionophore activity and mirrored the normal levels observed in patient prostatectomy tissues (Gleason Score 7 & 9). TRAMP adenocarcinoma cells harbored markedly elevated oxidative stress and diminished glutathione (GSH)-mediated antioxidant capacity, which together conferred selective sensitivity to prooxidant ionophoric copper. Copper-ionophore treatments [CuII(gtsm), disulfiram & clioquinol] generated toxic levels of reactive oxygen species (ROS) in TRAMP adenocarcinoma cells, but not in normal mouse prostate epithelial cells (PrECs). Our results provide a basis for the pharmacological activity of copper-ionophores and suggest they are amendable for treatment of patients with prostate cancer. Additionally, recent in vitro and mouse xenograft studies have suggested an increased copper requirement by prostate cancer cells. We demonstrated that prostate adenocarcinoma development in TRAMP mice requires a functional supply of copper and is significantly impeded by altered systemic copper distribution. The presence of a mutant copper-transporting Atp7b protein (tx mutation: A4066G/Met1356Val) in TRAMP mice changed copper-integration into serum and caused a remarkable reduction in prostate cancer burden (64% reduction) and disease severity (grade), abrogating adenocarcinoma development. Implications for current clinical trials are discussed. PMID:27175597

Copper-complexing ligands produced by an intact estuarine microbial community in response to copper stress.

NASA Astrophysics Data System (ADS)

Bingham, J.; Dryden, C.; Gordon, A.

2002-12-01

Copper is both an important nutrient and a pollutant in the marine environment. By studying the interactions between microorganisms and copper in the Elizabeth River (VA), home to a major Naval Base, we field tested the hypothesis that picoplankton and/or bacterioplankton produce strong, copper-complexing ligands in response to elevated copper concentrations. A simple light/ dark test was used to distinguish between heterotrophic and phototrophic ligand production. Samples were bottled and moored, submerged one meter, for a week. Direct counts using DAPI stain and epiflourescence were conducted to find concentrations of picoplankton and bacterioplankton. Using cathodic stripping voltammetry, we found the total copper concentrations, and then from a titration of the ligands by copper, the ligand concentrations and conditional stability constants were obtained. The Elizabeth River naturally had between 10-20 nM total dissolved copper concentrations. However when copper complexation was considered we found that the levels of bio-available Cu(II) ions were much lower. In fact in the natural samples the levels were not high enough to affect the relative reproductive rates of several microorganisms. Naturally there was a 50 nM "buffer zone" of ligand to total dissolved copper concentration. Furthermore, when stressed with excess copper, healthy picoplankton produced enough ligand to alleviate toxicity, and rebuild the buffer zone. However bacterioplankton only produced enough ligand so that they were no longer affected. Therefore, intact estuarine communities regulate copper bioavailability and toxicity with ligand production.

Preparation and characterization of Fe3O4-Pt nanoparticles

NASA Astrophysics Data System (ADS)

Andrade, Ângela Leão; Cavalcante, Luis Carlos Duarte; Fabris, José Domingos; Pereira, Márcio César; Ardisson, José Domingos; Domingues, Rosana Zacarias

2017-11-01

Pt and Pt-based nanomaterials are active anticancer drugs for their ability to inhibit the division of living cells. Nanoparticles of magnetite containing variable proportions of platinum were prepared in the laboratory. The magnetite nanoparticles with platinum (Pt-Fe3O4) were obtained by reducing the Fe3+ of the maghemite ( γ Fe2O3) mixed with platinum (II) acetylacetonate and sucrose in two inversely coupled ceramic crucibles and heated in a furnace at 400 °C for 20 min. The formed carbon during this preparation acts to chemically reduce the ferric iron in maghemite. Moreover, its residual layer on the particle surface prevents the forming magnetite from oxidizing in air and helps retain the platinum in the solid mixture. The produced Pt-magnetite samples were characterized by 57Fe-Mössbauer spectroscopy, powder X-ray diffraction, scanning electron microscopy, and magnetization measurements. Measurements of AC magnetic-field-induced heating properties of the obtained nanocomposites, in aqueous solution, showed that they are suitable as a hyperthermia agent for biological applications.

Isolation of the Copper Redox Steps in the Standard Selective Catalytic Reduction on Cu-SSZ-13

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paolucci, Christopher; Verma, Anuj A.; Bates, Shane A.

2014-10-27

Operando X-ray absorption experiments and density functional theory (DFT) calculations are reported that elucidate the role of copper redox chemistry in the selective catalytic reduction (SCR) of NO over Cu-exchanged SSZ-13. Catalysts prepared to contain only isolated, exchanged CuII ions evidence both CuII and CuI ions under standard SCR conditions at 473 K. Reactant cutoff experiments show that NO and NH3 together are necessary for CuII reduction to CuI. DFT calculations show that NO-assisted NH3 dissociation is both energetically favorable and accounts for the observed CuII reduction. The calculations predict in situ generation of Brønsted sites proximal to CuI uponmore » reduction, which we quantify in separate titration experiments. Both NO and O2 are necessary for oxidation of CuI to CuII, which DFT suggests to occur by a NO2 intermediate. Reaction of Cu-bound NO2 with proximal NH4 + completes the catalytic cycle. N2 is produced in both reduction and oxidation half-cycles.« less

Isolation of the Copper Redox Steps in the Standard Selective Catalytic Reduction on Cu-SSZ-13

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paolucci, Christopher; Verma, Anuj A.; Bates, Shane A.

2014-09-12

Operando X-ray absorption experiments and density functional theory (DFT) calculations are reported that elucidate the role of copper redox chemistry in the selective catalytic reduction (SCR) of NO over Cu-exchanged SSZ-13. Catalysts prepared to contain only isolated, exchanged CuII ions evidence both CuII and CuI ions under standard SCR conditions at 473 K. Reactant cutoff experiments show that NO and NH3 together are necessary for CuII reduction to CuI. DFT calculations show that NO-assisted NH3 dissociation is both energetically favorable and accounts for the observed CuII reduction. The calculations predict in situ generation of Brønsted sites proximal to CuI uponmore » reduction, which we quantify in separate titration experiments. Both NO and O2 are necessary for oxidation of CuI to CuII, which DFT suggests to occur by a NO2 intermediate. Reaction of Cu-bound NO2 with proximal NH4 + completes the catalytic cycle. N2 is produced in both reduction and oxidation half-cycles.« less

Reactivity of food phenols with iron and copper ions: binding, dioxygen activation and oxidation mechanisms.

PubMed

Nkhili, Ezzohra; Loonis, Michèle; Mihai, Simona; El Hajji, Hakima; Dangles, Olivier

2014-06-01

In this work, the affinity of common dietary phenols (gallic acid, caffeic acid, catechin, and rutin) for iron and copper ions was quantitatively investigated in neutral phosphate buffer as well as the reactivity of the complexes toward dioxygen. Contrasting behaviors were observed: because of the competing phosphate ions, Fe(III) binding is much slower than Fe(II) binding, which is rapidly followed by autoxidation of Fe(II) into Fe(III). With both ions, O2 consumption and H2O2 production are modest and the phenolic ligands are only slowly oxidized. By contrast, metal-phenol binding is fast with both Cu(I) and Cu(II). With Cu(I), O2 consumption and H2O2 production are very significant and the phenolic ligands are rapidly oxidized into a complex mixture of oligomers. The corresponding mechanism with Cu(II) is hampered by the preliminary rate-determining step of Cu(II) reduction by the phenols. The consequences of these findings for the stability and antioxidant activity of plant phenols are discussed.

Two novel two-dimensional copper(II) coordination polymers with 1-(4-aminobenzyl)-1,2,4-triazole: Synthesis, crystal structure, magnetic characterization and absorption of anion pollutants

NASA Astrophysics Data System (ADS)

Zhang, Xin; Wu, Xiang Xia; Guo, Jian-Hua; Huo, Jian-Zhong; Ding, Bin

2017-01-01

In this work a flexible multi-dentate 1-(4-aminobenzyl)-1,2,4-triazole (abtz) ligand has been employed, two novel triazole-Cu(II) coordination polymers {[Cu(abtz)2(Br)2]·(H2O)2}n (1) and {[Cu(abtz)2]·(SiF6)·(H2O)2}n (2) have been isolated under solvo-thermal conditions. 1 is a 2D neutral CuII coordination polymer while 2 is 2D cation micro-porous CuII coordination polymer with the channel dimensionalities of 11.852(1) Å × 11.852(1) Å (metal-metal distances). Variable-temperature magnetic susceptibility data of 1 and 2 have been recorded in the 2-300 K temperature range indicating weak anti-ferromagnetic interactions. Further absorption properties of anion pollutants for 2 also have been investigated. 2 presents the novel example of cationic triazole-copper(II) coordination framework for effectively capturing anion pollutants Cr2O72- in the water solutions and selectively capturing Congo Red in the methanol solutions.

Assessment of copper removal from highway stormwater runoff using Apatite II(TM) and compost : laboratory and field testing.

DOT National Transportation Integrated Search

2015-03-01

-Stormwater runoff introduces heavy metals to surface waters that are harmful to aquatic organisms, : including endangered salmon. This work evaluates Apatite II, a biogenic fish bone based adsorbent, for removing metal : from stormwater. The meta...

Ternary copper(II) complex: NCI60 screening, toxicity studies, and evaluation of efficacy in xenograft models of nasopharyngeal carcinoma.

PubMed

Ahmad, Munirah; Suhaimi, Shazlan-Noor; Chu, Tai-Lin; Abdul Aziz, Norazlin; Mohd Kornain, Noor-Kaslina; Samiulla, D S; Lo, Kwok-Wai; Ng, Chew-Hee; Khoo, Alan Soo-Beng

2018-01-01

Copper(II) ternary complex, [Cu(phen)(C-dmg)(H2O)]NO3 was evaluated against a panel of cell lines, tested for in vivo efficacy in nasopharyngeal carcinoma xenograft models as well as for toxicity in NOD scid gamma mice. The Cu(II) complex displayed broad spectrum cytotoxicity against multiple cancer types, including lung, colon, central nervous system, melanoma, ovarian, and prostate cancer cell lines in the NCI-60 panel. The Cu(II) complex did not cause significant induction of cytochrome P450 (CYP) 3A and 1A enzymes but moderately inhibited CYP isoforms 1A2, 2C9, 2C19, 2D6, 2B6, 2C8 and 3A4. The complex significantly inhibited tumor growth in nasopharyngeal carcinoma xenograft bearing mice models at doses which were well tolerated without causing significant or permanent toxic side effects. However, higher doses which resulted in better inhibition of tumor growth also resulted in toxicity.

Synthesis, characterization and investigation of electrochemical and spectroelectrochemical properties of non-peripherally tetra-5-methyl-1,3,4-thiadiazole substituted copper(II) iron(II) and oxo-titanium (IV) phthalocyanines

NASA Astrophysics Data System (ADS)

Demirbaş, Ümit; Akyüz, Duygu; Akçay, Hakkı Türker; Barut, Burak; Koca, Atıf; Kantekin, Halit

2017-09-01

In this study novel substituted phthalonitrile (3) and non-peripherally tetra 5-Methyl-1,3,4-thiadiazole substituted copper(II) (4), iron(II) (5) and oxo-titanium (IV) (6) phthalocyanines were synthesized. These novel compounds were fully characterized by FT-IR, 1H NMR, UV-vis and MALDI-TOF mass spectroscopic techniques. Voltammetric and in situ spectroelectrochemical measurements were performed for metallo-phthalocyanines (4-6). TiIVOPc and FeIIPc showed metal-based and ligand-based electron transfer reactions while CuIIPc shows only ligand-based electron transfer reaction. Voltammetric measurements indicated that the complexes have reversible, diffusion controlled and one-electron redox reactions. The assignments of the redox processes and color of the electrogenerated species of the complexes were determined with in-situ spectroelectrochemical and electrocolorimetric measurements. These measurements showed that the complexes can be used as the electrochromic materials for various display technologies.

Copper and the Prion Protein: Methods, Structures, Function, and Disease

NASA Astrophysics Data System (ADS)

Millhauser, Glenn L.

2007-05-01

The transmissible spongiform encephalopathies (TSEs) arise from conversion of the membrane-bound prion protein from PrPC to PrPSc. Examples of the TSEs include mad cow disease, chronic wasting disease in deer and elk, scrapie in goats and sheep, and kuru and Creutzfeldt-Jakob disease in humans. Although the precise function of PrPC in healthy tissues is not known, recent research demonstrates that it binds Cu(II) in an unusual and highly conserved region of the protein termed the octarepeat domain. This review describes recent connections between copper and PrPC, with an emphasis on the electron paramagnetic resonance elucidation of the specific copper-binding sites, insights into PrPC function, and emerging connections between copper and prion disease.

Ultrasonic-assisted chemical reduction synthesis and structural characterization of copper nanoparticles

NASA Astrophysics Data System (ADS)

Anh-Nga, Nguyen T.; Tuan-Anh, Nguyen; Thanh-Quoc, Nguyen; Ha, Do Tuong

2018-04-01

Copper nanoparticles, due to their special properties, small dimensions and low-cost preparation, have many potential applications such as in optical, electronics, catalysis, sensors, antibacterial agents. In this study, copper nanoparticles were synthesized by chemical reduction method with different conditions in order to investigate the optimum conditions which gave the smallest (particle diameter) dimensions. The synthesis step used copper (II) acetate salt as precursor, ascorbic acid as reducing agent, glycerin and polyvinylpyrrolidone (PVP) as protector and stabilizer. The assistance of ultrasonic was were considered as the significant factor affecting the size of the synthesized particles. The results showed that the copper nanoparticles have been successfully synthesized with the diameter as small as 20-40 nm and the conditions of ultrasonic waves were 48 kHz of frequency, 20 minutes of treated time and 65-70 °C of temperature. The synthesized copper nanoparticles were characterized by optical absorption spectrum, scanning electron microscopy (SEM), and Fourier Transform Infrared Spectrometry.

Removal of copper and nickel from water using nanocomposite of magnetic hydroxyapatite nanorods

NASA Astrophysics Data System (ADS)

Thanh, Dong Nguyen; Novák, Pavel; Vejpravova, Jana; Vu, Hong Nguyen; Lederer, Jaromír; Munshi, Tasnim

2018-06-01

A nanocomposite of magnetic hydroxyapatite was synthesized and tested as an adsorbent for the removal of copper (Cu (II)) and nickel (Ni(II)) from aqueous solution. The adsorbent was investigated using Transmission Electron Microscopy (TEM), Scanning Electron Microscopy equipped with an Energy Dispersive Spectrometer (SEM/EDS), X-ray powder diffraction (XRD) and the Brunauer-Elmet-Teller nitrogen adsorption technique (BET-N2 adsorption). Batch experiments were carried out to determine and compare the adsorption parameters of Fe3O4 and its composite with hydroxyapatite. It was found that the adsorbent is nanostructured and has a specific surface area of 101.2 m2 g-1. The Langmuir adsorption isotherm was found to be an appropriate model to describe the adsorption processes, showing the adsorption capacities of Cu(II) and Ni(II) of 48.78 mg g-1 and 29.07 mg g-1, respectively. In addition to the high adsorption capacity, the fully-adsorbed material could be easily separated from aqueous media using an external magnetic field. These results suggested that the utilization of new hydroxyapatite - Fe3O4 nanocomposite for the removal of Cu(II) and Ni(II) is a promising method in water technology.

β-Ketoiminato-based copper(ii) complexes as CVD precursors for copper and copper oxide layer formation.

PubMed

Pousaneh, Elaheh; Korb, Marcus; Dzhagan, Volodymyr; Weber, Marcus; Noll, Julian; Mehring, Michael; Zahn, Dietrich R T; Schulz, Stefan E; Lang, Heinrich

2018-06-19

The synthesis of ketoiminato copper(ii) complexes [Cu(OCRCHC(CH3)NCH2CH2X)(μ-OAc)]2 (X = NMe2: 4a, R = Me; 4b, R = Ph. X = OMe: 5, R = Me) and [Cu(OCRCHCMeNCH2CH2NEt2)(OAc)] (6, R = Me) from RC(O)CHC(CH3)N(H)CH2CH2X (X = NMe2: 1a, R = Me; 1b, R = Ph. X = NEt2: 1c, R = Me. X = OMe: 2, R = Me) and [Cu(OAc)2·H2O] (3) is reported. The molecular solid-state structures of 4-6 were determined by single crystal X-ray diffraction studies, showing that 4a,b and 5 are dimers which are set up by two [{Cu(μ-OAc)L}] (L = ketoiminato ligand) units featuring a square-planar Cu2O2 core with a distorted square-pyramidal geometry at Cu(ii). In contrast, 6 is monomeric with a tridentate-coordinated OCMeCHCMeNCH2CH2NEt2 ligand and a σ-bonded acetate group, thus inducing a square-planar environment around Cu(ii). The thermal behavior of all complexes was studied by TG (Thermogravimetry) and DSC (Differential Scanning Calorimetry) under an atmosphere of Ar and O2. Complex 4b shows the highest first onset temperature at 213 °C (under O2) and 239 °C (Ar). PXRD studies confirmed the formation of CuO under an atmosphere of O2 and Cu/Cu2O under Ar. TG-MS studies, exemplarily carried out with 4a, indicate the elimination of the ketoiminato ligands with detectable fragments such as m/z = 15, 28, 43, 44, 45, and 60 at a temperature above 250 °C. Vapor pressure measurements displayed that 5 shows the highest volatility of 3.6 mbar at 70 °C (for comparison, 4a, 1.4; 4b, 1.3; 6, 0.4 mbar) and hence 4a and 5 were used as MOCVD precursors for Cu/Cu2O deposition on Si/SiO2 at substrate temperatures of 450 °C and 510 °C. The deposition experiments were carried out under an atmosphere of nitrogen as well as oxygen. The as-obtained layers were characterized by SEM, EDX, XPS, and PXRD, showing that with oxygen as the reactive gas a mixture of metallic copper and copper(i) oxide without carbon impurities was formed, while under N2 Cu films with 53-68 mol% C contamination were produced. In a deposition experiment using precursor 5 at 510 °C under N2 a pure copper film was obtained.

Sulfonato-imino copper(ii) complexes: fast and general Chan-Evans-Lam coupling of amines and anilines.

PubMed

Hardouin Duparc, V; Schaper, F

2017-10-14

Sulfonato-imine copper complexes with either chloride or triflate counteranions were prepared in a one-step reaction followed by anion-exchange. They are highly active in Chan-Evans-Lam couplings under mild conditions with a variety of amines or anilines, in particular with sterically hindered substrates. No optimization of reaction conditions other than time and/or temperature is required.

Improving the two-step remediation process for CCA-treated wood. Part II, Evaluating bacterial nutrient sources

Treesearch

Carol A. Clausen

2004-01-01

Remediation processes for recovery and reuse of chromated-copper-arsenate-(CCA) treated wood are not gaining wide acceptance because they are more expensive than landfill disposal. One reason is the high cost of the nutrient medium used to culture the metal tolerant bacterium, Bacillus licheniformis, which removes 70-100% of the copper, chromium, and arsenic from CCA-...

Copper-promoted methylene C-H oxidation to a ketone derivative by O2.

PubMed

Deville, Claire; McKee, Vickie; McKenzie, Christine J

2017-01-17

The methylene group of the ligand 1,2-di(pyridin-2-yl)-ethanone oxime (dpeo) is slowly oxygenated by the O 2 in air under ambient conditions when [Cu(dpeo) 2 ](ClO 4 ) 2 is dissolved in ethanol or acetonitrile. An initial transient ketone product, 2-(hydroxyimino)-1,2-di(pyridine-2-yl)ethanone, (hidpe) was characterized in the heteroleptic copper(ii) complex [Cu(bpca)(hidpe)](ClO 4 ). The co-ligand in this complex, N-(2'-pyridylcarbonyl)pyridine-2-carboximidate (bpca - ), is derived from a copper-promoted Beckmann rearrangement of hidpe. In the presence of bromide only [Cu(bpca)Br] is isolated. When significant water is present in reaction mixtures copper complexes of dpeo, hidpe and bpca - are not recovered and [Cu(pic) 2 H 2 O] is isolated. This occurs since two equivalents of picolinate are ultimately generated from one equivalent of oxidized and hydrolysed dpeo. The copper-dependent O 2 activation and consequent stoichiometric dpeo C-H oxidation is reminiscent of the previously observed catalysis of dpeo oxidation by Mn(ii) [C. Deville, S. K. Padamati, J. Sundberg, V. McKee, W. R. Browne, C. J. McKenzie, Angew. Chem., Int. Ed., 2016, 55, 545-549]. By contrast dpeo oxidation is not observed during complexation reactions with other late transition metal(ii) ions (M = Fe, Co, Ni, Zn) under aerobic conditions. In these cases bis and tris complexes of bidentate dpeo are isolated in good yields. It is interesting to note that dpeo is not oxidised by H 2 O 2 in the absence of Cu or Mn, suggesting that metal-based oxidants capable of C-H activation are produced from the dpeo-Cu/Mn systems and specifically O 2 . The metastable copper complexes [Cu(dpeo) 2 ](ClO 4 ) 2 and [Cu(bpca)(hidpe)](ClO 4 ), along with [NiX 2 (dpeo) 2 ] (X = Cl, Br), [Ni(dpeo) 3 ](ClO 4 ) 2 , [Co(dpeo) 3 ](ClO 4 ) 3 and the mixed valence complex [Fe III Fe(dpeo-H) 3 (dpeo) 3 ](PF 6 ) 4 , have been structurally characterized.

Comparative acute toxicity of gallium(III), antimony(III), indium(III), cadmium(II), and copper(II) on freshwater swamp shrimp (Macrobrachium nipponense).

PubMed

Yang, Jen-Lee

2014-04-01

Acute toxicity testing were carried out the freshwater swamp shrimp, Macrobrachium nipponense, as the model animal for the semiconductor applied metals (gallium, antimony, indium, cadmium, and copper) to evaluate if the species is an suitable experimental animal of pollution in aquatic ecosystem. The static renewal test method of acute lethal concentrations determination was used, and water temperature was maintained at 24.0 ± 0.5°C. Data of individual metal obtained from acute toxicity tests were determined using probit analysis method. The median lethal concentration (96-h LC50) of gallium, antimony, indium, cadmium, and copper for M. nipponense were estimated as 2.7742, 1.9626, 6.8938, 0.0539, and 0.0313 mg/L, respectively. Comparing the toxicity tolerance of M. nipponense with other species which exposed to these metals, it is obviously that the M. nipponense is more sensitive than that of various other aquatic animals.

Towards a more ecologically relevant assessment of the impact of heavy metals on the photosynthesis of the seagrass, Zostera capricorni.

PubMed

Macinnis-Ng, Catriona M O; Ralph, Peter J

2002-01-01

This in situ study used photosynthetic activity (measured as chlorophyll a fluorescence) and photosynthetic pigment concentrations to assess the effect of copper, cadmium, lead and zinc on the seagrass Zostera capricorni. Custom-made portable in situ exposure (PIE) chambers were developed so seagrasses could be dosed within the meadow. Z capricorni was exposed to 0.1 and I mg l(-1) of metal solutions for 10 h. During this time and for the subsequent four-day recovery period, the effective quantum yield of photosystem II (PS II) (deltaF/Fm') was measured. While the results were variable, copper and zinc exposed samples had a depressed deltaF/Fm' during the exposure period. Samples exposed to zinc recovered to pre-exposure levels but those exposed to copper did not. Cadmium and lead did not impact on the chlorophyll a fluorescence and the chlorophyll pigment data supported these findings. This study presents an innovative new application of chlorophyll a fluorescence stress assessment.

Developing of a magnetite film of carboxymethyl cellulose grafted carboxymethyl polyvinyl alcohol (CMC-g-CMPVA) for copper removal.

PubMed

Dahlan, Nuraina Anisa; Veeramachineni, Anand Kumar; Langford, Steven James; Pushpamalar, Janarthanan

2017-10-01

Crosslinked carboxymethyl cellulose grafted carboxymethyl polyvinyl alcohol (CMC-g-CMPVA) was loaded with modified magnetite iron oxide (Fe 3 O 4 ) nanoparticles to synthesise a new and easily separable adsorbent for the removal of copper (II) ions from water. The novel adsorbents were characterised by the presence of the functional group, surface morphology, crystallinity and magnetic property. The equilibrium time from the adsorption studies was found to be less than 240min for both film and bead forms while the rate of Cu 2+ removal decreased as the initial Cu 2+ concentration increased. In addition, CMC-g-CMPVA film loaded with Fe 3 O 4 /SiO 2 nanoparticles was the best adsorbent with maximum adsorption capacity of 35.34mg/g and exhibited a reusable potential. The properties exhibited by the new heterogeneous material is a promising adsorbent for the removal and recovery of copper (II) from wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

Polyhydroxybutyrate-b-polyethyleneglycol block copolymer for the solid phase extraction of lead and copper in water, baby foods, tea and coffee samples.

PubMed

Wadhwa, Sham Kumar; Tuzen, Mustafa; Kazi, Tasneem Gul; Soylak, Mustafa; Hazer, Baki

2014-01-01

A new adsorbent, polyhydroxybutyrate-b-polyethyleneglycol, was used for the separation and preconcentration of copper(II) and lead(II) ions prior to their flame atomic absorption spectrometric detections. The influences of parameters such as pH, amount of adsorbent, flow rates and sample volumes were investigated. The polymer does not interact with alkaline, alkaline-earth metals and transition metals. The enrichment factor was 50. The detection limits were 0.32 μg L(-1) and 1.82 μg L(-1) for copper and lead, respectively. The recovery values were found >95%. The relative standard deviations were found to be less than 6%. The validation of the procedure was performed by analysing certified reference materials; NIST SRM 1515 Apple leaves, IAEA-336 Lichen and GBW-07605 Tea. The method was successfully applied for the analysis of analytes in water and food samples. Copyright © 2013 Elsevier Ltd. All rights reserved.

CotA, a Multicopper Oxidase from Bacillus pumilus WH4, Exhibits Manganese-Oxidase Activity

PubMed Central

Su, Jianmei; Bao, Peng; Bai, Tenglong; Deng, Lin; Wu, Hui; Liu, Fan; He, Jin

2013-01-01

Multicopper oxidases (MCOs) are a family of enzymes that use copper ions as cofactors to oxidize various substrates. Previous research has demonstrated that several MCOs such as MnxG, MofA and MoxA can act as putative Mn(II) oxidases. Meanwhile, the endospore coat protein CotA from Bacillus species has been confirmed as a typical MCO. To study the relationship between CotA and the Mn(II) oxidation, the cotA gene from a highly active Mn(II)-oxidizing strain Bacillus pumilus WH4 was cloned and overexpressed in Escherichia coli strain M15. The purified CotA contained approximately four copper atoms per molecule and showed spectroscopic properties typical of blue copper oxidases. Importantly, apart from the laccase activities, the CotA also displayed substantial Mn(II)-oxidase activities both in liquid culture system and native polyacrylamide gel electrophoresis. The optimum Mn(II) oxidase activity was obtained at 53°C in HEPES buffer (pH 8.0) supplemented with 0.8 mM CuCl2. Besides, the addition of o-phenanthroline and EDTA both led to a complete suppression of Mn(II)-oxidizing activity. The specific activity of purified CotA towards Mn(II) was 0.27 U/mg. The Km, Vmax and kcat values towards Mn(II) were 14.85±1.17 mM, 3.01×10−6±0.21 M·min−1 and 0.32±0.02 s−1, respectively. Moreover, the Mn(II)-oxidizing activity of the recombinant E. coli strain M15-pQE-cotA was significantly increased when cultured both in Mn-containing K liquid medium and on agar plates. After 7-day liquid cultivation, M15-pQE-cotA resulted in 18.2% removal of Mn(II) from the medium. Furthermore, the biogenic Mn oxides were clearly observed on the cell surfaces of M15-pQE-cotA by scanning electron microscopy. To our knowledge, this is the first report that provides the direct observation of Mn(II) oxidation with the heterologously expressed protein CotA, Therefore, this novel finding not only establishes the foundation for in-depth study of Mn(II) oxidation mechanisms, but also offers a potential biocatalyst for Mn(II) removal. PMID:23577125

Cooperative binding modes of Cu(II) in prion protein

NASA Astrophysics Data System (ADS)

Hodak, Miroslav; Chisnell, Robin; Lu, Wenchang; Bernholc, Jerry

2007-03-01

The misfolding of the prion protein, PrP, is responsible for a group of neurodegenerative diseases including mad cow disease and Creutzfeldt-Jakob disease. It is known that the PrP can efficiently bind copper ions; four high-affinity binding sites located in the octarepeat region of PrP are now well known. Recent experiments suggest that at low copper concentrations new binding modes, in which one copper ion is shared between two or more binding sites, are possible. Using our hybrid Thomas-Fermi/DFT computational scheme, which is well suited for simulations of biomolecules in solution, we investigate the geometries and energetics of two, three and four binding sites cooperatively binding one copper ion. These geometries are then used as inputs for classical molecular dynamics simulations. We find that copper binding affects the secondary structure of the PrP and that it stabilizes the unstructured (unfolded) part of the protein.

Discrete Cu(i) complexes for azide-alkyne annulations of small molecules inside mammalian cells.

PubMed

Miguel-Ávila, Joan; Tomás-Gamasa, María; Olmos, Andrea; Pérez, Pedro J; Mascareñas, José L

2018-02-21

The archetype reaction of "click" chemistry, namely, the copper-promoted azide-alkyne cycloaddition (CuAAC), has found an impressive number of applications in biological chemistry. However, methods for promoting intermolecular annulations of exogenous, small azides and alkynes in the complex interior of mammalian cells, are essentially unknown. Herein we demonstrate that isolated, well-defined copper(i)-tris(triazolyl) complexes featuring designed ligands can readily enter mammalian cells and promote intracellular CuAAC annulations of small, freely diffusible molecules. In addition to simplifying protocols and avoiding the addition of "non-innocent" reductants, the use of these premade copper complexes leads to more efficient processes than with the alternative, in situ made copper species prepared from Cu(ii) sources, tris(triazole) ligands and sodium ascorbate. Under the reaction conditions, the well-defined copper complexes exhibit very good cell penetration properties, and do not present significant toxicities.

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

EPA Science Inventory

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Peigong; Fan, Caimei, E-mail: fancm@163.com; Wang, Yawen

Graphical abstract: The cubic phase BaTiO{sub 3} nanoparticles can be obtained at 600 °C and changed into tetragonal phase at 900 °C by a dual chelating sol–gel method, and the photocatalytic activities of the photocatalysts calcined at different temperatures were investigated by the removal of humic acid (HA) from water under UV light irradiation. Highlights: ► The humic acid in water was firstly degradated by BaTiO{sub 3} photocatalyst. ► The cubic BaTiO{sub 3} was obtained and changed into tetragonal phase at lower temperature. ► The chelating agents had an important influence on the phase formation of BaTiO{sub 3}. ► Themore » tetragonal phase BaTiO{sub 3} calcined at 900 °C exhibited higher photocatalytic activity under UV irradiation. -- Abstract: In this paper, a dual chelating sol–gel method was used to synthesize BaTiO{sub 3} nanoparticles by using acetylacetone and citric acid as chelating agents. The samples calcined at different temperatures were analyzed by thermogravimetric and differential thermal analysis (TG-DTA), X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), scanning electron microscope (SEM) and UV–vis diffuse reflectance spectra (UV–vis). The results indicated that cubic phase BaTiO{sub 3} nanoparticles about 19.6 nm can be obtained at 600 °C and changed into tetragonal phase at 900 °C about 97.1 nm. All the BaTiO{sub 3} nanoparticles showed effective photocatalytic activities on the removal of humic acid (HA) under UV light irradiation. A comparison of single (acetylacetone or citric acid) and dual chelating (acetylacetone and citric acid) synthetic processes was also studied and the results demonstrated that the dual chelating agents indeed reduced phase transformation temperature from cubic to tetragonal BaTiO{sub 3}.« less

The importance of surface functional groups in the adsorption of copper onto walnut shell derived activated carbon.

PubMed

Xie, Ruzhen; Jin, Yan; Chen, Yao; Jiang, Wenju

2017-12-01

In this study, activated carbon (AC) was prepared from walnut shell using chemical activation. The surface chemistry of the prepared AC was modified by introducing or blocking certain functional groups, and the role of the different functional groups involved in the copper uptake was investigated. The structural and chemical heterogeneity of the produced carbons are characterized by Fourier transform infrared spectrometry, X-ray photoelectron spectroscopy, Boehm titration method and N 2 /77 K adsorption isotherm analysis. The equilibrium and the kinetics of copper adsorption onto AC were studied. The results demonstrated that the functional groups on AC played an important role in copper uptake. Among various surface functional groups, the oxygen-containing group was found to play a critical role in the copper uptake, and oxidation is the most effective way to improve Cu (II) adsorption onto AC. Ion-exchange was identified to be the dominant mechanism in the copper uptake by AC. Some other types of interactions, like complexation, were also proven to be involved in the adsorption process, while physical force was found to play a small role in the copper uptake. The regeneration of copper-loaded AC and the recovery of copper were also studied to evaluate the reusability of the oxidized AC.

Room Temperature ppb Level Chlorine Gas Sensor Based on Copper (II) 1, 4, 8, 11, 15, 18, 22, 25-octabutoxy-29 H, 31 H-phthalocyanine Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bedi, R. K.; Saini, Rajan; Mahajan, Aman

2010-12-01

Spin coating technique has been used to fabricate room temperature chlorine gas sensor based on copper (II) 1, 4, 8, 11, 15, 18, 22, 25-octabutoxy-29 H, 31 H-phthalocyanine (CuPc(OBu){sub 8}) films. Gas sensor shows a response of 185% to few parts per billion level of Cl{sub 2} gas with response time of 9.5 minutes at room temperature. The interactions between sensor and analytes followed first order kinetics with rate constant 0.01{<=}k{<=}0.02. The chemiresistive sensor showed very good stability at room temperature over a long period of time.

Catalytic and inhibiting effect of amino acids on the porphyrin metallation reactions

NASA Astrophysics Data System (ADS)

Mamardashvili, Galina M.; Zhdanova, Daria Yu.; Mamardashvili, Nugzar Zh.; Koifman, Oskar I.; Dehaen, Wim

In the present work, using the interaction of tetra-(4-sulfophenyl)porphyrin with copper(II) chloride as an example, it has been shown how different amino acid additives (glycine, valine, leucine and tryptophan) catalyze or inhibit the formation of Cu-porphyrin as a function of the chemical environment (borate buffer (pH7.4), DMSO) and the concentration of the additive. It has been demonstrated that the type of amino acid affects the complexation reaction rate. Possible mechanisms of metalloporphyrin formation and the ways of their acceleration are discussed. Ways in which different amino acid additives catalyze or inhibit the interaction of tetra-(4-sulfophenyl)porphyrin with copper(II) chloride are examined.

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

NASA Astrophysics Data System (ADS)

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

2015-02-01

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, 1H NMR, 13C 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+, Al3+, Ni2+, Co2+, Fe3+, Zn2+, Pb2+) 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 Cu2+ ions were also investigated using quantum chemical computations.

Evaluation of a reconfigurable portable instrument for copper determination based on luminescent carbon dots.

PubMed

Salinas-Castillo, Alfonso; Morales, Diego P; Lapresta-Fernández, Alejandro; Ariza-Avidad, María; Castillo, Encarnación; Martínez-Olmos, Antonio; Palma, Alberto J; Capitan-Vallvey, Luis Fermin

2016-04-01

A portable reconfigurable platform for copper (Cu(II)) determination based on luminescent carbon dot (Cdots) quenching is described. The electronic setup consists of a light-emitting diode (LED) as the carbon dot optical exciter and a photodiode as a light-to-current converter integrated in the same instrument. Moreover, the overall analog conditioning is simply performed with one integrated solution, a field-programmable analog array (FPAA), which makes it possible to reconfigure the filter and gain stages in real time. This feature provides adaptability to use the platform as an analytical probe for carbon dots coming from different batches with some variations in luminescence characteristics. The calibration functions obtained that fit a modified Stern-Volmer equation were obtained using luminescence signals from Cdots quenching by Cu(II). The analytical applicability of the reconfigurable portable instrument for Cu(II) using Cdots has been successfully demonstrated in tap water analysis.

Non-rigid molecule of copper(II) diiminate Cu[CF3C(NH)C(F)C(NH)CF3]2, its conformational polymorphism in crystal and structure in solutions (Raman, UV-vis and quantum chemistry study)

NASA Astrophysics Data System (ADS)

Bukalov, Sergey S.; Aysin, Rinat R.; Leites, Larissa A.; Kurykin, Mikhail A.; Khrustalev, Victor N.

2015-10-01

Calculation of potential energy surface (PES) of isolated molecule of copper(II) diiminate Cu[CF3С(NH)C(F)C(NH)CF3]2 (1) resulted a double-well curve with the minima corresponding to equivalent screwed conformations. The low barrier leads to molecular non-rigidity which seems to be the reason of conformational polymorphism in crystals, reported in [1]. For one of newly found polymorphs, the X-ray structure was determined. The differences in the Raman and UV-vis spectra between differently colored species and their solutions were revealed, they are determined by different geometries of Cu(II) coordination polyhedron and different systems of intermolecular interactions in crystals. Transformations of the polymorphs under thermal, mechanical and photo exposures were studied.

Copper(II) complexes of tridentate N, N, N', N″, N″-pentamethyldiethylenetriamine: Superoxide dismutase and inhibitory activity against bacteria and fungi

NASA Astrophysics Data System (ADS)

Patel, R. N.; Singh, Nripendra; Gundla, V. L. N.; Chauhan, U. K.

2007-03-01

A series of ternary copper(II) complexes containing same coordination sphere but difference in the counter ions, viz., [Cu(PMDT)(OAc)]PF 6(1); [Cu(PMDT)(OAc)]ClO 4(2); [Cu(PMDT)(OAc)]BF 4(3) and [Cu(PMDT)(OAc)]BPh 4(4) where PMDT = N, N, N', N″, N″-pentamethyldiethylenetriamine, OAc = Acetate ion were synthesized and characterized by means of spectroscopic, magnetic and cyclic voltammetric measurements. In frozen solution e.p.r. spectra, an interesting relation g|| > g⊥ has been observed which is a typical of the axially symmetric d 9 Cu II ( SCu = 1/2) having an unpaired electron in a d orbital. Single crystal X-ray analysis of (1) has revealed the presence of distorted square planar geometry. The influence of the counter ion on the complexes has been examined by performing some biological experiments like superoxide dismutase and anti-microbial activity.

Binding of Copper and Silver to Single-Site Variants of Peptidylglycine Monooxygenase Reveals the Structure and Chemistry of the Individual Metal Centers

PubMed Central

2015-01-01

Peptidylglycine monooxygenase (PHM) catalyzes the final step in the biosynthesis of amidated peptides that serve as important signaling molecules in numerous endocrine pathways. The catalytic mechanism has attracted much attention because of a number of unique attributes, including the presence of a pair of uncoupled copper centers separated by 11 Å (termed CuH and CuM), an unusual Cu(I)SMet interaction at the oxygen binding M-site, and the postulated Cu(II)–superoxo intermediate. Understanding the mechanism requires determining the catalytic roles of the individual copper centers and how they change during catalysis, a task made more difficult by the overlapping spectral signals from each copper center in the wild-type (WT) protein. To aid in this effort, we constructed and characterized two PHM variants that bound metal at only one site. The H242A variant bound copper at the H-center, while the H107AH108A double mutant bound copper at the M-center; both mutants were devoid of catalytic activity. Oxidized Cu(II) forms showed electron paramagnetic resonance and extended X-ray absorption fine structure (EXAFS) spectra consistent with their previously determined Cu(II)His3O and Cu(II)His2O2 ligand sets for the H- and M-centers, respectively. Cu(I) forms, on the other hand, showed unique chemistry. The M-center bound two histidines and a methionine at all pHs, while the H-center was two-coordinate at neutral pH but coordinated a new methionine S ligand at low pH. Fourier transform infrared studies confirmed and extended previous assignments of CO binding and showed unambiguously that the 2092 cm–1 absorbing species observed in the WT and many variant forms is an M-site Cu(I)–CO adduct. Silver binding was also investigated. When H107AH108A and M109I (a WT analogue with both sites intact) were incubated with excess AgNO3, each variant bound a single Ag(I) ion, from which it was inferred that Ag(I) binds selectively at the M-center with little or no affinity for the H-center. EXAFS at the Ag K-edge established a strong degree of similarity between the ligand sets of Cu and Ag bound at the M-center. These studies validate previous spectral assignments and provide new insights into the detailed chemistry of each metal site. PMID:24471980

Non-hydroxyl radical mediated photochemical processes for dye degradation.

PubMed

Liu, Xitong; Song, Xiaojie; Zhang, Shujuan; Wang, Mengshu; Pan, Bingcai

2014-04-28

Using solar energy for the decontamination of wastewater is a promising solution to the water-energy nexus. Current advanced oxidation processes have an unsatisfactory efficiency in the treatment of dye wastewater due to the non-selectivity of hydroxyl radicals. More efficient photochemical approaches for dye degradation are highly needed. Three diketones, biacetyl, acetylacetone, and acetonylacetone, were proven to be potent activators for the photodecoloration of azo, triarylmethane and anthraquinone dyes. The photodegradation kinetics of Acid Orange 7 in the UV/diketone processes was much faster than that in the UV/H2O2 system. Photo-induced energy and electron transfer were possible mechanisms for dye degradation in the diketone systems. Adducts of dye and acetylacetone were identified, indicating a unique dye degradation route through adduct formation and decomposition. Unlike acting only as the target substrate of ˙OH in advanced oxidation processes, the dyes played vital roles in the UV/diketone processes. The findings here provide new insights for designing more efficient technologies for environmental remediation, based on diketone photochemistry.

L-Lactide Ring-Opening Polymerization with Tris(acetylacetonate)Titanium(IV) for Renewable Material.

PubMed

Kim, Da Hee; Yoo, Ji Yun; Ko, Young Soo

2016-05-01

A new Ti-type of catalyst for L-lactide polymerization was synthesized by reaction of titanium(IV) isopropoxide (TTIP) with acetylacetone (AA). Moreover, PLA was prepared by the bulk ring-opening polymerization using synthesized Ti catalyst. Polymerization behaviors were examined depending on monomer/catalyst molar ratio, polymerization temperature and time. The structure of synthesized catalysts was verified with FT-IR and 1H NMR and the properties of poly(L-lactide) (PLLA) were examined by GPC, DSC and FT-IR. There existed about 30 minutes of induction time at the monomer/catalyst molar ratio of 300. The molecular weight (MW) increased as monomer/catalyst molar ratio increased. The MW increased almost linearly as polymerization progressed. Increasing polymerization temperature increased the molecular weight of PLLA as well as monomer/catalyst molar ratio. The melting point (T(m)) of polymers was in the range of 142 to 167 degrees C. Lower T(m) was expected to be resulted from relatively lower molecular weight.

Biotin Decorated Gold Nanoparticles for Targeted Delivery of a Smart-Linked Anticancer Active Copper Complex: In Vitro and In Vivo Studies.

PubMed

Pramanik, Anup K; Siddikuzzaman; Palanimuthu, Duraippandi; Somasundaram, Kumaravel; Samuelson, Ashoka G

2016-12-21

The synthesis and anticancer activity of a copper(II) diacetyl-bis(N4-methylthiosemicarbazone) complex and its nanoconjugates are reported. The copper(II) complex is connected to a carboxylic acid group through a cleavable disulfide link to enable smart delivery. The copper complex is tethered to highly water-soluble 20 nm gold nanoparticles (AuNPs), stabilized by amine terminated lipoic acid-polyethylene glycol (PEG). The gold nanoparticle carrier was further decorated with biotin to achieve targeted action. The copper complex and the conjugates with and without biotin, were tested against HeLa and HaCaT cells. They show very good anticancer activity against HeLa cells, a cell line derived from cervical cancer and are less active against HaCaT cells. Slow and sustained release of the complex from conjugates is demonstrated through cleavage of disulfide linker in the presence of glutathione (GSH), a reducing agent intrinsically present in high concentrations within cancer cells. Biotin appended conjugates do not show greater activity than conjugates without biotin against HeLa cells. This is consistent with drug uptake studies, which suggests similar uptake profiles for both conjugates in vitro. However, in vivo studies using a HeLa cell xenograft tumor model shows 3.8-fold reduction in tumor volume for the biotin conjugated nanoparticle compared to the control whereas the conjugate without biotin shows only 2.3-fold reduction in the tumor volume suggesting significant targeting.

Reduction of paraquat-induced renal cytotoxicity by manganese and copper complexes of EGTA and EHPG.

PubMed

Samai, Mohamed; Hague, Theresa; Naughton, Declan P; Gard, Paul R; Chatterjee, Prabal K

2008-02-15

Superoxide anion generation plays an important role in the development of paraquat toxicity. Although superoxide dismutase mimetics (SODm) have provided protection against organ injury involving generation of superoxide anions, they often suffer problems, e.g., regarding their bioavailability or potential pro-oxidant activity. The aim here was to investigate and compare the therapeutic potential of two novel SODm, manganese(II) and copper(II) complexes of the calcium chelator ethylenebis(oxyethylenenitrilo)tetraacetic acid (EGTA) and of the contrast agent ethylenebis(hydroxyphenylglycine) (EHPG), against paraquat-induced renal toxicity in vitro. Incubation of renal NRK-52E cells with paraquat (1 mM) for 24 h produced submaximal, yet significant, reduction in cellular viability and cell death and produced significant increases in superoxide anion and hydroxyl radical generation. Manganese and copper complexes of EGTA (10-100 microM) and EHPG (30-100 microM) reduced paraquat-induced renal cell toxicity and reduced superoxide anion and hydroxyl radical generation significantly. Manganese complexes displayed greater efficacy than copper complexes and, at equivalent concentrations, manganese complexed with EHPG provided the greatest protection. Furthermore, these metal complexes did not interfere with the uptake of [methyl-(14)C]paraquat into NRK-52E cells, suggesting that they provided protection against paraquat cytotoxicity via intracellular mechanisms. These complexes did not display cytotoxicity at the concentrations examined. Together, these results suggest that manganese and copper complexes of EGTA and EHPG, and especially the manganese-EHPG complex, could provide benefit against paraquat nephrotoxicity.