REGULATORY PERSPECTIVE ON MANAGING RISKS AT WOOD TREATING SITES

EPA Science Inventory

Over 700 sites in the United States have been identified where wood preserving operations have been conducted. The most common types of wood preservatives found at these sites are creosote, pentachlorophenol (PCP), and copper chromated arsenate (CCA). When properly used and dis...

Soil and sediment concentrations of chromium, copper, and arsenic adjacent to a chromated copper arsenate-treated wetland boardwalk

Treesearch

Stan Lebow; Daniel Foster

2010-01-01

Environmental accumulation of preservative adjacent to a chromated copper arsenate (type C)–treated wetland boardwalk was evaluated. The site is considered a realistic ‘‘worst case’’ because of the large volume of treated wood, low current speeds, high annual rainfall, and environmental sensitivity. Soil and sediment samples were collected before construction and 0.5,...

Structural and functional characterisation of multi-copper oxidase CueO from lignin-degrading bacterium Ochrobactrum sp. reveal its activity towards lignin model compounds and lignosulfonate.

PubMed

Granja-Travez, Rommel Santiago; Wilkinson, Rachael C; Persinoti, Gabriela Felix; Squina, Fabio M; Fülöp, Vilmos; Bugg, Timothy D H

2018-05-01

The identification of enzymes responsible for oxidation of lignin in lignin-degrading bacteria is of interest for biotechnological valorization of lignin to renewable chemical products. The genome sequences of two lignin-degrading bacteria, Ochrobactrum sp., and Paenibacillus sp., contain no B-type DyP peroxidases implicated in lignin degradation in other bacteria, but contain putative multicopper oxidase genes. Multi-copper oxidase CueO from Ochrobactrum sp. was expressed and reconstituted as a recombinant laccase-like enzyme, and kinetically characterized. Ochrobactrum CueO shows activity for oxidation of β-aryl ether and biphenyl lignin dimer model compounds, generating oxidized dimeric products, and shows activity for oxidation of Ca-lignosulfonate, generating vanillic acid as a low molecular weight product. The crystal structure of Ochrobactrum CueO (OcCueO) has been determined at 1.1 Å resolution (PDB: 6EVG), showing a four-coordinate mononuclear type I copper center with ligands His495, His434 and Cys490 with Met500 as an axial ligand, similar to that of Escherichia coli CueO and bacterial azurin proteins, whereas fungal laccase enzymes contain a three-coordinate type I copper metal center. A trinuclear type 2/3 copper cluster was modeled into the active site, showing similar structure to E. coli CueO and fungal laccases, and three solvent channels leading to the active site. Site-directed mutagenesis was carried out on amino acid residues found in the solvent channels, indicating the importance for residues Asp102, Gly103, Arg221, Arg223, and Asp462 for catalytic activity. The work identifies a new bacterial multicopper enzyme with activity for lignin oxidation, and implicates a role for bacterial laccase-like multicopper oxidases in some lignin-degrading bacteria. Structural data are available in the PDB under the accession number 6EVG. © 2018 Federation of European Biochemical Societies.

X-ray structure of a two-domain type laccase: a missing link in the evolution of multi-copper proteins.

PubMed

Komori, Hirofumi; Miyazaki, Kentaro; Higuchi, Yoshiki

2009-04-02

A multi-copper protein with two cupredoxin-like domains was identified from our in-house metagenomic database. The recombinant protein, mgLAC, contained four copper ions/subunits, oxidized various phenolic and non-phenolic substrates, and had spectroscopic properties similar to common laccases. X-ray structure analysis revealed a homotrimeric architecture for this enzyme, which resembles nitrite reductase (NIR). However, a difference in copper coordination was found at the domain interface. mgLAC contains a T2/T3 tri-nuclear copper cluster at this site, whereas a mononuclear T2 copper occupies this position in NIR. The trimer is thus an essential part of the architecture of two-domain multi-copper proteins, and mgLAC may be an evolutionary precursor of NIR.

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

Crystal structures of E. coli laccase CueO at different copper concentrations

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

Li Xu; Wei Zhiyi; National Laboratory of Biomacromolecules, Institute of Biophysics, Chinese Academy of Sciences, Beijing 100101

2007-03-02

CueO protein is a hypothetical bacterial laccase and a good laccase candidate for large scale industrial application. Four CueO crystal structures were determined at different copper concentrations. Low copper occupancy in apo-CueO and slow copper reconstitution process in CueO with exogenous copper were demonstrated. These observations well explain the copper dependence of CueO oxidase activity. Structural comparison between CueO and other three fungal laccase proteins indicates that Glu106 in CueO constitutes the primary counter-work for reconstitution of the trinuclear copper site. Mutation of Glu106 to a Phe enhanced CueO oxidation activity and supported this hypothesis. In addition, an extra {alpha}-helixmore » from Leu351 to Gly378 covers substrate biding pocket of CueO and might compromises the electron transfer from substrate to type I copper.« less

Inactivation of Laccase by the Attack of As (III) Reaction in Water.

PubMed

Hu, Jinyuan; Lu, Kun; Dong, Shipeng; Huang, Qingguo; Mao, Liang

2018-03-06

Laccase is a multicopper oxidase containing four coppers as reaction sites, including one type 1, one type 2, and two type 3. We here provide the first experimental data showing that As (III) can be effectively removed from water and transformed to As (V) through reactions mediated by laccase with the presence of oxygen. To this end, the As (III) removal, As (V) yields, total protein, active laccase, and copper concentrations in the aqueous phase were determined, respectively. Additionally, electron paramagnetic resonance spectra and UV-vis spectra were applied to probe possible structural changes of the laccase during the reaction. The data offer the first evidence that laccase can be inactivated by As (III) attack thus leading to the release of type 2 copper. The released copper has no reactivity with the As (III). These findings provide new ideas into a significant pathway likely to master the environmental transformation of arsenite, and advance the understanding of laccase inactivation mechanisms, thus providing a foundation for optimization of enzyme-based processes and potential development for removal and remediation of arsenite contamination in the environment.

Resolving distinct molecular origins for copper effects on PAI-1.

PubMed

Bucci, Joel C; McClintock, Carlee S; Chu, Yuzhuo; Ware, Gregory L; McConnell, Kayla D; Emerson, Joseph P; Peterson, Cynthia B

2017-10-01

Components of the fibrinolytic system are subjected to stringent control to maintain proper hemostasis. Central to this regulation is the serpin plasminogen activator inhibitor-1 (PAI-1), which is responsible for specific and rapid inhibition of fibrinolytic proteases. Active PAI-1 is inherently unstable and readily converts to a latent, inactive form. The binding of vitronectin and other ligands influences stability of active PAI-1. Our laboratory recently observed reciprocal effects on the stability of active PAI-1 in the presence of transition metals, such as copper, depending on the whether vitronectin was also present (Thompson et al. Protein Sci 20:353-365, 2011). To better understand the molecular basis for these copper effects on PAI-1, we have developed a gel-based copper sensitivity assay that can be used to assess the copper concentrations that accelerate the conversion of active PAI-1 to a latent form. The copper sensitivity of wild-type PAI-1 was compared with variants lacking N-terminal histidine residues hypothesized to be involved in copper binding. In these PAI-1 variants, we observed significant differences in copper sensitivity, and these data were corroborated by latency conversion kinetics and thermodynamics of copper binding by isothermal titration calorimetry. These studies identified a copper-binding site involving histidines at positions 2 and 3 that confers a remarkable stabilization of PAI-1 beyond what is observed with vitronectin alone. A second site, independent from the two histidines, binds metal and increases the rate of the latency conversion.

Techno-Economic Analysis of Solar Water Heating Systems inTurkey.

PubMed

Ertekin, Can; Kulcu, Recep; Evrendilek, Fatih

2008-02-25

In this study, solar water heater was investigated using meteorological and geographical data of 129 sites over Turkey. Three different collector types were compared in terms of absorber material (copper, galvanized sheet and selective absorber). Energy requirement for water heating, collector performances, and economical indicators were calculated with formulations using observed data. Results showed that selective absorbers were most appropriate in terms of coverage rate of energy requirement for water-heating all over Turkey. The prices of selective, copper and galvanized absorber type's heating systems in Turkey were 740.49, 615.69 and 490.89 USD, respectively. While payback periods (PBPs) of the galvanized absorber were lower, net present values (NPVs) of the selective absorber were higher than the rest. Copper absorber type collectors did not appear to be appropriate based on economical indicators.

Techno-Economic Analysis of Solar Water Heating Systems in Turkey

PubMed Central

Ertekin, Can; Kulcu, Recep; Evrendilek, Fatih

2008-01-01

In this study, solar water heater was investigated using meteorological and geographical data of 129 sites over Turkey. Three different collector types were compared in terms of absorber material (copper, galvanized sheet and selective absorber). Energy requirement for water heating, collector performances, and economical indicators were calculated with formulations using observed data. Results showed that selective absorbers were most appropriate in terms of coverage rate of energy requirement for water-heating all over Turkey. The prices of selective, copper and galvanized absorber type's heating systems in Turkey were 740.49, 615.69 and 490.89 USD, respectively. While payback periods (PBPs) of the galvanized absorber were lower, net present values (NPVs) of the selective absorber were higher than the rest. Copper absorber type collectors did not appear to be appropriate based on economical indicators. PMID:27879764

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.

Copper-transporting P-type ATPases use a unique ion-release pathway

PubMed Central

Andersson, Magnus; Mattle, Daniel; Sitsel, Oleg; Nielsen, Anna Marie; White, Stephen H.; Nissen, Poul; Gourdon, Pontus

2014-01-01

Heavy metals in cells are typically regulated by PIB-type ATPases such as the copper transporting Cu+-ATPases. The first crystal structure of a Cu+-ATPase (LpCopA) was trapped in a transition state of dephosphorylation (E2.Pi) and inferred to be occluded. The structure revealed a PIB-specific topology and suggested a copper transport pathway across the membrane. Here we show by molecular dynamics (MD) simulations that extracellular water solvates the transmembrane (TM) domain, indicative of a pathway for Cu+ release. Furthermore, a new LpCopA crystal structure determined at 2.8 Å resolution, trapped in the E2P state (which is associated with extracellular exchange in PII-type ATPases), delineates the same conduit as also further supported by site-directed mutagenesis. The E2P and E2.Pi states therefore appear equivalent and open to the extracellular side, in contrast to PII-type ATPases where the E2.Pi state is occluded. This indicates that Cu+-ATPases couple dephosphorylation differently to the conformational changes associated with ion extrusion. The ion pathway may explain why Menkes’ and Wilson’s disease mutations at the extracellular side impair protein function, and points to an accessible site for novel inhibitors targeting Cu+-ATPases of pathogens. PMID:24317491

The non-octarepeat copper binding site of the prion protein is a key regulator of prion conversion

NASA Astrophysics Data System (ADS)

Giachin, Gabriele; Mai, Phuong Thao; Tran, Thanh Hoa; Salzano, Giulia; Benetti, Federico; Migliorati, Valentina; Arcovito, Alessandro; Longa, Stefano Della; Mancini, Giordano; D'Angelo, Paola; Legname, Giuseppe

2015-10-01

The conversion of the prion protein (PrPC) into prions plays a key role in transmissible spongiform encephalopathies. Despite the importance for pathogenesis, the mechanism of prion formation has escaped detailed characterization due to the insoluble nature of prions. PrPC interacts with copper through octarepeat and non-octarepeat binding sites. Copper coordination to the non-octarepeat region has garnered interest due to the possibility that this interaction may impact prion conversion. We used X-ray absorption spectroscopy to study copper coordination at pH 5.5 and 7.0 in human PrPC constructs, either wild-type (WT) or carrying pathological mutations. We show that mutations and pH cause modifications of copper coordination in the non-octarepeat region. In the WT at pH 5.5, copper is anchored to His96 and His111, while at pH 7 it is coordinated by His111. Pathological point mutations alter the copper coordination at acidic conditions where the metal is anchored to His111. By using in vitro approaches, cell-based and computational techniques, we propose a model whereby PrPC coordinating copper with one His in the non-octarepeat region converts to prions at acidic condition. Thus, the non-octarepeat region may act as the long-sought-after prion switch, critical for disease onset and propagation.

Sites of electron transfer to membrane-bound copper and hydroperoxide-induced damage in the respiratory chain of Escherichia coli.

PubMed

Rodríguez-Montelongo, L; Farías, R N; Massa, E M

1995-10-20

Previous studies in Escherichia coli as a model system for peroxide toxicity (L. Rodríguez-Montelongo, L. C. De la Cruz-Rodríguez, R. N. Farías, and E. M. Massa, 1993, Biochim. Biophys. Acta 1144, 77-84) have shown that electron flow through the respiratory chain supports a membrane-associated Cu(II)/Cu(I) redox cycle involved in irreversible impairment of the respiratory system by tert-butyl hydroperoxide (t-BOOH). In this paper, E. coli mutants deficient in specific respiratory chain components have been used to determine the sites of copper reduction and the targets inactivated by t-BOOH. Two sites of electron transfer to membrane-bound copper were identified: one in the region between NADH and ubiquinone supported by NADH as electron donor and another localized between ubiquinone and the cytochromes supported by electrons coming from NADH, succinate, or D-lactate. Electron flow through the former site in the presence of t-BOOH led to inactivation of NADH dehydrogenase II, whereas electron flow through the latter site in the presence of the hydroperoxide led to damage of ubiquinone. In agreement with the above in vitro results with isolated membranes, copper-dependent inactivation of NADH dehydrogenase and ubiquinone was demonstrated in E. coli cells exposed to t-BOOH. It is proposed that the t-BOOH-induced damage is a consequence of t-butylalkoxy radical generation through a Fenton-type reaction mediated by redox cycling of membrane-bound copper at those two loci of the respiratory chain.

Proton and metal ion binding to natural organic polyelectrolytes-II. Preliminary investigation with a peat and a humic acid

USGS Publications Warehouse

Marinsky, J.A.; Reddy, M.M.

1984-01-01

We summarize here experimental studies of proton and metal ion binding to a peat and a humic acid. Data analysis is based on a unified physico-chemical model for reaction of simple ions with polyelectrolytes employing a modified Henderson-Hasselbalch equation. Peat exhibited an apparent intrinsic acid dissociation constant of 10-4.05, and an apparent intrinsic metal ion binding constant of: 400 for cadmium ion; 600 for zinc ion; 4000 for copper ion; 20000 for lead ion. A humic acid was found to have an apparent intrinsic proton binding constant of 10-2.6. Copper ion binding to this humic acid sample occurred at two types of sites. The first site exhibited reaction characteristics which were independent of solution pH and required the interaction of two ligands on the humic acid matrix to simultaneously complex with each copper ion. The second complex species is assumed to be a simple monodentate copper ion-carboxylate species with a stability constant of 18. ?? 1984.

X-ray structural studies of the fungal laccase from Cerrena maxima.

PubMed

Lyashenko, Andrey V; Bento, Isabel; Zaitsev, Viatcheslav N; Zhukhlistova, Nadezhda E; Zhukova, Yuliya N; Gabdoulkhakov, Azat G; Morgunova, Ekaterina Y; Voelter, Wolfgang; Kachalova, Galina S; Stepanova, Elena V; Koroleva, Ol'ga V; Lamzin, Victor S; Tishkov, Vladimir I; Betzel, Christian; Lindley, Peter F; Mikhailov, Al'bert M

2006-11-01

Laccases are members of the blue multi-copper oxidase family. These enzymes oxidize substrate molecules by accepting electrons at a mononuclear copper centre and transferring them to a trinuclear centre. Dioxygen binds to the trinuclear centre and following the transfer of four electrons is reduced to two molecules of water. The X-ray structure of a laccase from Cerrena maxima has been elucidated at 1.9 A resolution using synchrotron data and the molecular replacement technique. The final refinement coefficients are Rcryst = 16.8% and Rfree = 23.0%, with root mean square deviations on bond lengths and bond angles of 0.015 A and 1.51 degrees , respectively. The type 1 copper centre has an isoleucine residue at the axial position and the "resting" state of the trinuclear centre comprises a single oxygen (OH) moiety asymmetrically disposed between the two type 3 copper ions and a water molecule attached to the type 2 ion. Several carbohydrate binding sites have been identified and the glycan chains appear to promote the formation of well-ordered crystals. Two tyrosine residues near the protein surface have been found in a nitrated state.

Mechanical tearing of graphene on an oxidizing metal surface.

PubMed

George, Lijin; Gupta, Aparna; Shaina, P R; Das Gupta, Nandita; Jaiswal, Manu

2015-12-11

Graphene, the thinnest possible anticorrosion and gas-permeation barrier, is poised to transform the protective coatings industry for a variety of surface applications. In this work, we have studied the structural changes of graphene when the underlying copper surface undergoes oxidation upon heating. Single-layer graphene directly grown on a copper surface by chemical vapour deposition was annealed under ambient atmosphere conditions up to 400 °C. The onset temperature of the surface oxidation of copper is found to be higher for graphene-coated foils. Parallel arrays of graphene nanoripples are a ubiquitous feature of pristine graphene on copper, and we demonstrate that these form crucial sites for the onset of the oxidation of copper, particularly for ∼0.3-0.4 μm ripple widths. In these regions, the oxidation proceeds along the length of the nanoripples, resulting in the formation of parallel stripes of oxidized copper regions. We demonstrate from temperature-dependent Raman spectroscopy that the primary defect formation process in graphene involves boundary-type defects rather than vacancy or sp(3)-type defects. This observation is consistent with a mechanical tearing process that splits graphene into small polycrystalline domains. The size of these is estimated to be sub-50 nm.

Pseudomonas stutzeri N2O reductase contains CuA-type sites.

PubMed Central

Scott, R A; Zumft, W G; Coyle, C L; Dooley, D M

1989-01-01

N2O reductase (N2O----N2) is the terminal enzyme in the energy-conserving denitrification pathway of soil and marine denitrifying bacteria. The protein is composed of two identical subunits and contains eight copper ions per enzyme molecule. The magnetic circular dichroism spectrum of resting (oxidized) N2O reductase is strikingly similar to the magnetic circular dichroism spectrum of the CuA site in mammalian cytochrome c oxidase [Greenwood, C., Hull, B. C., Barber, D., Eglinton, D. G. & Thomson, A. J. (1983) Biochem. J. 215, 303-316] and is unlike the magnetic circular dichroism spectra of all other biological copper chromophores obtained to date. Sulfur (or chlorine) scatterers are required to fit the copper extended x-ray absorption fine structure data of both the oxidized and reduced forms of N2O reductase. Satisfactory fits require a Cu-N or Cu-O [denoted Cu-(N, O)] interaction at 2.0 A, a Cu-(S, Cl) interaction at 2.3 A and an additional Cu(S, Cl) interaction at approximately 2.6 A (oxidized) or approximately 2.7 A (reduced). Approximately eight sulfur ions (per eight copper ions) at approximately 2.3 A are required to fit the extended x-ray absorption fine structure data for both the oxidized and reduced N2O reductase. The 2.3-A Cu-(S, Cl) distance is nearly identical to that previously determined for the CuA site in cytochrome c oxidase. A 2.6-2.7 A Cu-(S, Cl) interaction is also present in resting and fully reduced cytochrome c oxidase. Comparison of the N2O reductase sequence, determined by translating the structural NosZ gene, with cytochrome c oxidase subunit II sequences from several sources indicates that a Gly-Xaa-Xaa-Xaa-Xaa-Xaa-Cys-Ser-Xaa-Xaa-Cys-Xaa-Xaa-Xaa-His stretch is highly conserved. This sequence contains three of the probable ligands (two cysteines and one histidine) in a CuA-type site. Collectively these data establish that Pseudomonas stutzeri N2O reductase contains CuA-type sites. PMID:2542963

Modeling dioxygen reduction at multicopper oxidase cathodes.

PubMed

Agbo, Peter; Heath, James R; Gray, Harry B

2014-10-01

We report a general kinetics model for catalytic dioxygen reduction on multicopper oxidase (MCO) cathodes. Our rate equation combines Butler-Volmer (BV) electrode kinetics and the Michaelis-Menten (MM) formalism for enzymatic catalysis, with the BV model accounting for interfacial electron transfer (ET) between the electrode surface and the MCO type 1 copper site. Extending the principles of MM kinetics to this system produced an analytical expression incorporating the effects of subsequent intramolecular ET and dioxygen binding to the trinuclear copper cluster into the cumulative model. We employed experimental electrochemical data on Thermus thermophilus laccase as benchmarks to validate our model, which we suggest will aid in the design of more efficient MCO cathodes. In addition, we demonstrate the model's utility in determining estimates for both the electronic coupling and average distance between the laccase type-1 active site and the cathode substrate.

DFT study of ethyl xanthate interaction with sphalerite (1 1 0) surface in the absence and presence of copper

NASA Astrophysics Data System (ADS)

Liu, Jian; Wen, Shuming; Deng, Jiushuai; Chen, Xiumin; Feng, Qicheng

2014-08-01

The interaction among sphalerite (1 1 0) surface, copper and ethyl xanthate (EX) was simulated using the density functional theory (DFT). The results of DFT indicate that four types of stable interaction models exist among sphalerite surface, copper and EX, i.e., EX interacts with the Cu substituted for Zn, Cu adsorbed on the top site of S, Cu adsorbed on the bridge site of S and Cu(OH)2 adsorbed on the sphalerite surface. The four interaction models can result in the activation flotation of sphalerite. Density of states (DOS) analysis shows that the energy level discrepancy of the Zn 3d orbital in ZnS and the bonding S 3p orbital in EX results in the weak adsorption of EX on un-activated sphalerite surface. However, after copper activation, the Cu 3d orbital peak and bonding S 3p orbital peak are just maximally overlapped nearby the Fermi level. This study provides an insight into the nature that sphalerite responds not well to EX and also a comprehensive understanding on the possible interaction cases existing among sphalerite surface, copper and EX.

Inheritable copper tolerance in the chlorophyte macroalga Enteromorpha intestinalis

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

Lewis, S.; Williams, P.; Donkin, M.

1995-12-31

A study was carried out to determine if a population of Enteromorpha intestinalis, from a metal polluted site, exhibited copper tolerance. This work was in preparation for investigating stress protein patterns in copper tolerant and sensitive populations. The effects of copper on growth of E. intestinalis from three clean and one metal polluted site were compared. Growth was assessed by incubating thallus sections in a range of copper solutions and measuring increase in length. Offspring were cultured from clean and polluted sites and the effects of copper on their growth assessed, to determine if any tolerance was inheritable. Concentrations ofmore » the trace metals; copper, zinc and manganese in the populations were also determined. Over the range of copper concentrations tested (0--150 {micro}g/i), growth of the polluted site populations was not significantly affected (P > 0.05). However growth of the clean site populations was significantly depressed by exposure to 50 {micro}g/l. This pattern of response was also exhibited by the offspring. Trace metal concentrations in the clean site populations were very similar, however the polluted site population contained {sup {minus}}10 times the control site values of manganese and {approximately}35 times the values of zinc and copper. The results suggest that the polluted site population of E. intestinalis has developed a degree of copper tolerance which appears to have a genetic basis. This investigation is consistent with previous work into copper tolerance in ship-fouling populations of E. intestinalis var. compressa. A commercially available HSP70 antibody with a high degree of cross-reactivity to E. intestinalis has been identified and used to screen samples of the seaweed from the aforementioned populations.« less

Effect of the L499M mutation of the ascomycetous Botrytis aclada laccase on redox potential and catalytic properties

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

Osipov, Evgeny; Polyakov, Konstantin; Engelhardt Institute of Molecular Biology, Vavilova Str. 32, Moscow 119991

2014-11-01

The structures of the ascomycetous B. aclada laccase and its L499M T1-site mutant have been solved at 1.7 Å resolution. The mutant enzyme shows a 140 mV lower redox potential of the type 1 copper and altered kinetic behaviour. The wild type and the mutant have very similar structures, which makes it possible to relate the changes in the redox potential to the L499M mutation Laccases are members of a large family of multicopper oxidases that catalyze the oxidation of a wide range of organic and inorganic substrates accompanied by the reduction of dioxygen to water. These enzymes contain fourmore » Cu atoms per molecule organized into three sites: T1, T2 and T3. In all laccases, the T1 copper ion is coordinated by two histidines and one cysteine in the equatorial plane and is covered by the side chains of hydrophobic residues in the axial positions. The redox potential of the T1 copper ion influences the enzymatic reaction and is determined by the nature of the axial ligands and the structure of the second coordination sphere. In this work, the laccase from the ascomycete Botrytis aclada was studied, which contains conserved Ile491 and nonconserved Leu499 residues in the axial positions. The three-dimensional structures of the wild-type enzyme and the L499M mutant were determined by X-ray crystallography at 1.7 Å resolution. Crystals suitable for X-ray analysis could only be grown after deglycosylation. Both structures did not contain the T2 copper ion. The catalytic properties of the enzyme were characterized and the redox potentials of both enzyme forms were determined: E{sub 0} = 720 and 580 mV for the wild-type enzyme and the mutant, respectively. Since the structures of the wild-type and mutant forms are very similar, the change in the redox potential can be related to the L499M mutation in the T1 site of the enzyme.« less

A Purple Cupredoxin from Nitrosopumilus maritimus Containing a Mononuclear Type 1 Copper Center with an Open Binding Site

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

Hosseinzadeh, Parisa; Tian, Shiliang; Marshall, Nicholas M.

2016-05-25

Mononuclear cupredoxin proteins usually contain a coordinately saturated type 1 copper (T1Cu) center and function exclusively as electron carriers. Here we report a cupredoxin isolated from the nitrifying archaeon Nitrosopumilus maritimus SCM1, called Nmar1307, that contains a T1Cu center with an open binding site containing water. It displays a deep purple color due to strong absorptions around 413 nm (1880 M –1 cm –1) and 558 nm (2290 M –1 cm –1) in the UV–vis electronic spectrum. EPR studies suggest the protein contains two Cu(II) species of nearly equal population, one nearly axial, with hyperfine constant A∥ = 98 ×more » 10 –4 cm –1, and another more rhombic, with a smaller A∥ value of 69 × 10 –4 cm –1. The X-ray crystal structure at 1.6 Å resolution confirms that it contains a Cu atom coordinated by two His and one Cys in a trigonal plane, with an axial H2O at 2.25 Å. Both UV–vis absorption and EPR spectroscopic studies suggest that the Nmar1307 can oxidize NO to nitrite, an activity that is attributable to the high reduction potential (354 mV vs SHE) of the copper site. These results suggest that mononuclear cupredoxins can have a wide range of structural features, including an open binding site containing water, making this class of proteins even more versatile.« less

Intrinsic point defects in off-stoichiometric Cu2ZnSnSe4: A neutron diffraction study

NASA Astrophysics Data System (ADS)

Gurieva, Galina; Valle Rios, Laura Elisa; Franz, Alexandra; Whitfield, Pamela; Schorr, Susan

2018-04-01

This work is an experimental study of intrinsic point defects in off-stoichiometric kesterite type CZTSe by means of neutron powder diffraction. We revealed the existence of copper vacancies (VCu), various cation anti site defects (CuZn, ZnCu, ZnSn, SnZn, and CuZn), as well as interstitials (Cui, Zni) in a wide range of off-stoichiometric polycrystalline powder samples synthesized by the solid state reaction. The results show that the point defects present in off-stoichiometric CZTSe agree with the off-stoichiometry type model, assuming certain cation substitutions accounting for charge balance. In addition to the known off-stoichiometry types A-H, new types (I-L) have been introduced. For the very first time, a correlation between the chemical composition of the CZTSe kesterite type phase and the occurring intrinsic point defects is presented. In addition to the off-stoichiometry type specific defects, the Cu/Zn disorder is always present in the CZTSe phase. In Cu-poor/Zn-rich CZTSe, a composition considered as the one that delivers the best photovoltaic performance, mainly copper vacancies, ZnCu and ZnSn anti sites are present. Also, this compositional region shows the lowest degree of Cu/Zn disorder.

Probability-based estimates of site-specific copper water quality criteria for the Chesapeake Bay, USA.

PubMed

Arnold, W Ray; Warren-Hicks, William J

2007-01-01

The object of this study was to estimate site- and region-specific dissolved copper criteria for a large embayment, the Chesapeake Bay, USA. The intent is to show the utility of 2 copper saltwater quality site-specific criteria estimation models and associated region-specific criteria selection methods. The criteria estimation models and selection methods are simple, efficient, and cost-effective tools for resource managers. The methods are proposed as potential substitutes for the US Environmental Protection Agency's water effect ratio methods. Dissolved organic carbon data and the copper criteria models were used to produce probability-based estimates of site-specific copper saltwater quality criteria. Site- and date-specific criteria estimations were made for 88 sites (n = 5,296) in the Chesapeake Bay. The average and range of estimated site-specific chronic dissolved copper criteria for the Chesapeake Bay were 7.5 and 5.3 to 16.9 microg Cu/L. The average and range of estimated site-specific acute dissolved copper criteria for the Chesapeake Bay were 11.7 and 8.3 to 26.4 microg Cu/L. The results suggest that applicable national and state copper criteria can increase in much of the Chesapeake Bay and remain protective. Virginia Department of Environmental Quality copper criteria near the mouth of the Chesapeake Bay, however, need to decrease to protect species of equal or greater sensitivity to that of the marine mussel, Mytilus sp.

Copper tolerance and copper accumulation of herbaceous plants colonizing inactive California copper mines

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

Kruckeberg, A.L.; Wu, L.

1992-06-01

Herbaceous plant species colonizing four copper mine waste sites in northern California were investigated for copper tolerance and copper accumulation. Copper tolerance was found in plant species colonizing soils with high concentrations of soil copper. Seven of the eight plant species tested were found at more than one copper mine. The mines are geographically isolated, which makes dispersal of seeds from one mine to another unlikely. Tolerance has probably evolved independently at each site. The nontolerant field control population of Vulpia microstachya displays significantly higher tolerance to copper at all copper concentration levels tested than the nontolerant Vulpia myrous population,more » and the degree of copper tolerance attained by V. microstachya at the two copper mines was much greater than that found in V. myrous. It suggests that even in these two closely related species, the innate tolerance in their nontolerant populations may reflect their potential for evolution of copper tolerance and their ability to initially colonize copper mine waste sites. The shoot tissue of the copper mine plants of Arenaria douglasii, Bromous mollis, and V. microstachya accumulated less copper than those plants of the same species from the field control sites when the two were grown in identical conditions in nutrient solution containing copper. The root tissue of these mine plants contain more copper than the roots of the nonmine plants. This result suggests that exclusion of copper from the shoots, in part by immobilization in the roots, may be a feature of copper tolerance. No difference in the tissue copper concentration was detected between tolerant and nontolerant plants of Lotus purshianus, Lupinus bicolor, and Trifolium pratense even though the root tissue had more copper than the leaves.« less

Engineering Klebsiella sp. 601 multicopper oxidase enhances the catalytic efficiency towards phenolic substrates.

PubMed

Li, Yadong; Gong, Zijun; Li, Xin; Li, Yang; Wang, Xing-Guo

2011-05-31

Structural comparison between bacterial CueO and fungal laccases has suggested that a charged residue Glu (E106) in CueO replaces the corresponding residue Phe in fungal laccases at the gate of the tunnel connecting type II copper to the protein surface and an extra α-helix (L351-G378) near the type I copper site covers the substrate binding pocket and might compromise the electron transfer from substrate to type I copper. To test this hypothesis, several mutants were made in Klebsiella sp. 601 multicopper oxidase, which is highly homologous to E. coli CueO with a similarity of 90% and an identity of 78%. The E106F mutant gave smaller K(m) (2.4-7 fold) and k(cat) (1-4.4 fold) values for all three substrates DMP, ABTS and SGZ as compared with those for the wild-type enzyme. Its slightly larger k(cat)/K(m) values for three substrates mainly come from the decreased K(m). Deleting α-helix (L351-G378) resulted in the formation of inactive inclusion body when the mutant (Δ)α351-378 was expressed in E. coli. Another mutant α351-380M was then made via substitution of seven amino acid residues in the α-helix (L351-G378) region. The α351-380M mutant was active, and displayed a far-UV CD spectrum markedly different from that for wild-type enzyme. Kinetic studies showed the α351-380M mutant gave very low K(m) values for DMP, ABTS and SGZ, 4.5-, 1.9- and 7-fold less than those for the wild type. In addition, k(cat)/K(m) values were increased, 9.4-fold for DMP, similar for ABTS and 3-fold for SGZ. The Glu residue at position 106 appears not to be the only factor affecting the copper binding, and it may also play a role in maintaining enzyme conformation. The α-helix (L351-G378) may not only block access to the type I copper site but also play a role in substrate specificities of bacterial MCOs. The α351-380M mutant catalyzing oxidation of the phenolic substrate DMP effectively would be very useful in green chemistry.

77 FR 46091 - Notice of Proposed Administrative Settlement Pursuant to the Comprehensive Environmental Response...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-08-02

... Copper Mine Site AGENCY: Environmental Protection Agency. ACTION: Notice, request for public comments... concerning the ANACONDA COPPER MINE SITE (the ``Site''), located in Yerington, Lyon County, Nevada. The... Peak Services Agreement for the Anaconda Copper Mine Site, and Region IX Docket No. 9-2012-07. FOR...

Selected Water- and Sediment-Quality, Aquatic Biology, and Mine-Waste Data from the Ely Copper Mine Superfund Site, Vershire, VT, 1998-2007

USGS Publications Warehouse

Argue, Denise M.; Kiah, Richard G.; Piatak, Nadine M.; Seal, Robert R.; Hammarstrom, Jane M.; Hathaway, Edward; Coles, James F.

2008-01-01

The data contained in this report are a compilation of selected water- and sediment-quality, aquatic biology, and mine-waste data collected at the Ely Copper Mine Superfund site in Vershire, VT, from August 1998 through May 2007. The Ely Copper Mine Superfund site is in eastern, central Vermont (fig. 1) within the Vermont Copper Belt (Hammarstrom and others, 2001). The Ely Copper Mine site was placed on the U.S. Environmental Protection Agency (USEPA) National Priorities List in 2001. Previous investigations conducted at the site documented that the mine is contributing metals and highly acidic waters to local streams (Hammarstrom and others, 2001; Holmes and others, 2002; Piatak and others, 2003, 2004, and 2006). The U.S. Geological Survey (USGS), in cooperation with the USEPA, compiled selected data from previous investigations into uniform datasets that will be used to help characterize the extent of contamination at the mine. The data may be used to determine the magnitude of biological impacts from the contamination and in the development of remediation activities. This report contains analytical data for samples collected from 98 stream locations, 6 pond locations, 21 surface-water seeps, and 29 mine-waste locations. The 98 stream locations are within 3 streams and their tributaries. Ely Brook flows directly through the Ely Copper Mine then into Schoolhouse Brook (fig. 2), which joins the Ompompanoosuc River (fig. 1). The six pond locations are along Ely Brook Tributary 2 (fig. 2). The surface-water seeps and mine-waste locations are near the headwaters of Ely Brook (fig. 2 and fig. 3). The datasets 'Site_Directory' and 'Coordinates' contain specific information about each of the sample locations including stream name, number of meters from the mouth of stream, geographic coordinates, types of samples collected (matrix of sample), and the figure on which the sample location is depicted. Data have been collected at the Ely Copper Mine Superfund site by the USEPA, the Vermont Department of Environmental Conservation (VTDEC), and the USGS. Data also have been collected on behalf of USEPA by the following agencies: Arthur D. Little Incorporated (ADL), U.S. Army Cold Region Research and Engineering Laboratory (CRREL), URS Corporation (URS), USEPA, and USGS. These data provide information about the aquatic communities and their habitats, including chemical analyses of surface water, pore water, sediments, and fish tissue; assessments of macroinvertebrate and fish assemblages; physical characteristics of sediments; and chemical analyses of soil and soil leachate collected in and around the piles of mine waste.

A purple cupredoxin from Nitrosopumilus maritimus containing a mononuclear type 1 copper center with an open binding site

DOE PAGES

Hosseinzadeh, Parisa; Tian, Shiliang; Marshall, Nicholas M.; ...

2016-04-27

Mononuclear cupredoxin proteins usually contain a coordinately saturated type 1 copper (T1Cu) center and function exclusively as electron carriers. Here we report a cupredoxin isolated from the nitrifying archaeon Nitrosopumilus maritimus SCM1, called Nmar1307, that contains a T1Cu center with an open binding site containing water. It displays a deep purple color due to strong absorptions around 413 nm (1880 M –1 cm –1) and 558 nm (2290 M –1 cm –1) in the UV–vis electronic spectrum. EPR studies suggest the protein contains two Cu(II) species of nearly equal population, one nearly axial, with hyperfine constant A ∥ = 98more » × 10 –4 cm –1, and another more rhombic, with a smaller A ∥ value of 69 × 10 –4 cm –1. The X-ray crystal structure at 1.6 Å resolution confirms that it contains a Cu atom coordinated by two His and one Cys in a trigonal plane, with an axial H 2O at 2.25 Å. Both UV–vis absorption and EPR spectroscopic studies suggest that the Nmar1307 can oxidize NO to nitrite, an activity that is attributable to the high reduction potential (354 mV vs SHE) of the copper site. Lastly, these results suggest that mononuclear cupredoxins can have a wide range of structural features, including an open binding site containing water, making this class of proteins even more versatile.« less

The Lumenal Loop Met672–Pro707 of Copper-transporting ATPase ATP7A Binds Metals and Facilitates Copper Release from the Intramembrane Sites*

PubMed Central

Barry, Amanda N.; Otoikhian, Adenike; Bhatt, Sujata; Shinde, Ujwal; Tsivkovskii, Ruslan; Blackburn, Ninian J.; Lutsenko, Svetlana

2011-01-01

The copper-transporting ATPase ATP7A has an essential role in human physiology. ATP7A transfers the copper cofactor to metalloenzymes within the secretory pathway; inactivation of ATP7A results in an untreatable neurodegenerative disorder, Menkes disease. Presently, the mechanism of ATP7A-mediated copper release into the secretory pathway is not understood. We demonstrate that the characteristic His/Met-rich segment Met672–Pro707 (HM-loop) that connects the first two transmembrane segments of ATP7A is important for copper release. Mutations within this loop do not prevent the ability of ATP7A to form a phosphorylated intermediate during ATP hydrolysis but inhibit subsequent dephosphorylation, a step associated with copper release. The HM-loop inserted into a scaffold protein forms two structurally distinct binding sites and coordinates copper in a mixed His-Met environment with an ∼2:1 stoichiometry. Binding of either copper or silver, a Cu(I) analog, induces structural changes in the loop. Mutations of 4 Met residues to Ile or two His-His pairs to Ala-Gly decrease affinity for copper. Altogether, the data suggest a two-step process, where copper released from the transport sites binds to the first His(Met)2 site, triggering a structural change and binding to a second 2-coordinate His-His or His-Met site. We also show that copper binding within the HM-loop stabilizes Cu(I) and protects it from oxidation, which may further aid the transfer of copper from ATP7A to acceptor proteins. The mechanism of copper entry into the secretory pathway is discussed. PMID:21646353

The evaluation and validation of copper (II) force field parameters of the Auxiliary Activity family 9 enzymes

NASA Astrophysics Data System (ADS)

Moses, Vuyani; Tastan Bishop, Özlem; Lobb, Kevin A.

2017-06-01

The Auxiliary Activity family 9 (AA9) proteins are Cu2+ coordinating enzymes which are crucial for the early stages of cellulose degradation. In this study, the force field parameters for copper-containing bonds in the Type 1 AA9 protein active site were established and used in a molecular dynamics simulation on a solvated, neutralized system containing an AA9 protein, Cu2+ and a β-cellulose surface. The copper to cellulose interaction was evident during the dynamics, which could also be accelerated by the use of high Cusbnd O van der Waals parameters. The interaction of AA9, Cu2+ and cellulose is described in detail.

Copper-zinc superoxide dismutase is activated through a sulfenic acid intermediate at a copper ion entry site.

PubMed

Fetherolf, Morgan M; Boyd, Stefanie D; Taylor, Alexander B; Kim, Hee Jong; Wohlschlegel, James A; Blackburn, Ninian J; Hart, P John; Winge, Dennis R; Winkler, Duane D

2017-07-21

Metallochaperones are a diverse family of trafficking molecules that provide metal ions to protein targets for use as cofactors. The copper chaperone for superoxide dismutase (Ccs1) activates immature copper-zinc superoxide dismutase (Sod1) by delivering copper and facilitating the oxidation of the Sod1 intramolecular disulfide bond. Here, we present structural, spectroscopic, and cell-based data supporting a novel copper-induced mechanism for Sod1 activation. Ccs1 binding exposes an electropositive cavity and proposed "entry site" for copper ion delivery on immature Sod1. Copper-mediated sulfenylation leads to a sulfenic acid intermediate that eventually resolves to form the Sod1 disulfide bond with concomitant release of copper into the Sod1 active site. Sod1 is the predominant disulfide bond-requiring enzyme in the cytoplasm, and this copper-induced mechanism of disulfide bond formation obviates the need for a thiol/disulfide oxidoreductase in that compartment. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

Spectroscopic and DFT Studies of Second Sphere Variants of the Type 1 Copper Site in Azurin: Covalent and Non-Local Electrostatic Contributions to Reduction Potentials

PubMed Central

Hadt, Ryan G.; Sun, Ning; Marshall, Nicholas M.; Hodgson, Keith O.; Hedman, Britt; Lu, Yi; Solomon, Edward I.

2012-01-01

The reduction potentials (E0) of type 1 (T1) or blue copper (BC) sites in proteins and enzymes with identical first coordination spheres around the redox active copper ion can vary by ~400 mV. Here, we use a combination of low temperature electronic absorption and magnetic circular dichroism, electron paramagnetic resonance, resonance Raman, and S K-edge X-ray absorption spectroscopies to investigate a series of second sphere variants—F114P, N47S, and F114N in Pseudomonas aeruginosa azurin (Az)—which modulate hydrogen bonding to and protein derived dipoles nearby the Cu-S(Cys) bond. Density functional theory (DFT) calculations correlated to the experimental data allow for the fractionation of the contributions to tuning E0 into covalent and non-local electrostatic components. These are found to be significant, comparable in magnitude, and additive for active H-bonds, while passive H-bonds are mostly non-local electrostatic in nature. For dipoles, these terms can be additive to or oppose one another. This study provides a methodology for uncoupling covalency from non-local electrostatics, which, when coupled to X-ray crystallographic data, distinguishes specific local interactions from more long range protein/active interactions, while affording further insight into the second sphere mechanisms available to the protein to tune the E0 of electron transfer sites in biology. PMID:22985400

Geology and Mineral Resources of the East Mojave National Scenic Area, San Bernardino County, California

USGS Publications Warehouse

Theodore, Ted G.

2007-01-01

From our evaluations that largely used model-based criteria, we conclude that much of the East Mojave National Scenic Area (EMNSA) contains significant indications of epigenetic mineralization of various types. Economically significant concentrations of many metals may possibly remain to be discovered in many parts of the EMNSA (see also Wetzel and others, 1992). We have discussed specific types of metallic deposits that are known to be present in the EMNSA. Some mountain ranges that have widespread occurrences are the Providence Mountains, Clark Mountain Range, Ivanpah Mountains, and New York Mountains; the area of Hackberry Mountain is included in a tract that is judged to be favorable for the discovery of epithermal, volcanic-hosted gold deposits (pl. 2). These ranges make up a broad, roughly north-south-trending region in the central part of the EMNSA. Much less endowed with known occurrences of all of the various types of deposits considered above are the Granite Mountains, the central parts of the Piute Range, the Fenner Valley area, the general area of Cima Dome, the Cima volcanic field, and areas west to Soda Lake. We have attempted to make some judgments concerning the gravel-covered areas in the EMNSA (pl. 3), including the areal extent of bedrock apparently covered only by thin veneers of gravel. But few data are available to us for the overwhelming bulk of the covered areas. The presence of any mineralization, the type of mineralization, and the extent and intensity of mineralization in the covered areas is essentially unknown. The likelihood is high, however, that those areas in the EMNSA covered only by a thin cap of gravels could host mineralization similar to that known in the adjoining mountain ranges. Most buried epigenetic-mineral deposits do not respond to standard geophysical methods, particularly at the coarse spacing of the data-collection points available for our evaluation. Restricting judgments concerning the presence of undiscovered metal resources in the EMNSA only to currently known types of deposits and to regionally representative tonnages for such deposits would undoubtedly yield small estimates for volumes of many metals that might be exploited. Metals from most newly discovered, base- and ferrous-metal deposits of the types presently known in the EMNSA probably would be insignificant from the standpoint of national needs. For example, copper from a newly discovered skarn deposit in the EMNSA would have roughly a 25 percent chance of being in excess of approximately 10,000 tonnes contained Cu, if the grade-and-tonnage distribution curves of Jones and Menzie (1986b) for copper skarns are applicable to copper skarn in the EMNSA. Most copper in the United States is produced in the Southwest from much larger open-pit operations than those associated with the typical copper skarn; the former operations exploit large-tonnage porphyry-type systems. Historically, the EMNSA has been the site of minor production of many metals from a large number of sites. Since 1985, however, a small number of sites in the EMNSA whose gold production and reserves are much greater than that of the preceding discoveries have been developed (see U.S. Bureau of Mines, 1990a). Nonetheless, widespread distribution of numerous types of deposits (including copper skarn, lead-zinc skarn, tin-tungsten skarn, polymetallic vein, gold-silver quartz-pyrite vein, low-fluorine porphyry molybdenum, gold breccia pipe, and volcanic-hosted gold) that are petrogenetically associated with igneous rock in many parts of the EMNSA is indicative of a metallogenic environment that may be the site of future discoveries of mineral-deposit types that are not now recognized by the exploration community. The science, art, and, yes, even luck of exploration procedures continually evolve, and this evolution is one of the most important aspects of currently employed methods of exploration (Bailly, 1981; Hutchinson and Grauch, 1991).

Engineering Copper Carboxylate Functionalities on Water Stable Metal–Organic Frameworks for Enhancement of Ammonia Removal Capacities

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

Joshi, Jayraj N.; Garcia-Gutierrez, Erika Y.; Moran, Colton M.

Functionalization of copper carboxylate groups on a series of UiO-66 metal organic framework (MOF) analogues and their corresponding impact on humid and dry ammonia adsorption behavior were studied. Relative locations of possible carboxylic acid binding sites for copper on the MOF analogues were varied on ligand and missing linker defect sites. Materials after copper incorporation exhibited increased water vapor and ammonia affinity during isothermal adsorption and breakthrough experiments, respectively. The introduction of copper markedly increased ammonia adsorption capacities for all adsorbents possessing carboxyl binding sites. In particular, the new MOF UiO-66-(COOCu)2 displayed the highest ammonia breakthrough capacities of 6.38 andmore » 6.84 mmol g–1 under dry and humid conditions, respectively, while retaining crystallinity and porosity. Relative carboxylic acid site locations were also found to impact sorbent stability, as missing linker defect functionalized materials degraded under humid conditions after copper incorporation. Postsynthetic metal insertion provides a method for adding sites that are analogous to open metal sites while maintaining good structural stability.« less

Discovery and characterization of a new family of lytic polysaccharide monooxygenases.

PubMed

Hemsworth, Glyn R; Henrissat, Bernard; Davies, Gideon J; Walton, Paul H

2014-02-01

Lytic polysaccharide monooxygenases (LPMOs) are a recently discovered class of enzymes capable of oxidizing recalcitrant polysaccharides. They are attracting considerable attention owing to their potential use in biomass conversion, notably in the production of biofuels. Previous studies have identified two discrete sequence-based families of these enzymes termed AA9 (formerly GH61) and AA10 (formerly CBM33). Here, we report the discovery of a third family of LPMOs. Using a chitin-degrading exemplar from Aspergillus oryzae, we show that the three-dimensional structure of the enzyme shares some features of the previous two classes of LPMOs, including a copper active center featuring the 'histidine brace' active site, but is distinct in terms of its active site details and its EPR spectroscopy. The newly characterized AA11 family expands the LPMO clan, potentially broadening both the range of potential substrates and the types of reactive copper-oxygen species formed at the active site of LPMOs.

Determination of an organic-acid analog of DOC for use in copper toxicity studies on salmonids

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

MacRae, R.K.; Meyer, J.S.; Hansen, J.A.

1995-12-31

Concentrations of dissolved copper in streams draining mine sites often exceed concentrations shown to cause acute and chronic mortality in salmonids. However, toxicity and impaired behaviors may be modified by dissolved organic carbon (DOC) and other inorganic components present in the site water. The effects of DOC on copper speciation, and thus bioavailability and toxicity, were determined by titrating stream waters with copper, using a cupric ion-specific electrode to detect free copper concentrations. Effects of various competing cations (e.g., Ca{sup +2}, Co{sup +2}) on copper-DOC binding were also evaluated. Titration results were evaluated using Scatchard and non-linear regression analyses tomore » quantify the strength and capacity of copper-DOC binding. Inorganic speciation was determined using the geochemical model MINEQL{sup +}. Results of these titrations indicated the presence of two or three distinct copper binding components in site water DOC. Three commercially available organic acids where then chosen to mimic the binding characteristics of natural DOC. This DOC-analog was used successfully in fish toxicity studies to evaluate the influence of DOC on copper bioavailability. Geochemical models were developed to predict copper speciation in both laboratory test waters and site waters, for any typical combination of water chemistry parameters (pH, alkalinity, [DOC], etc.). A combined interpretation of fish toxicity and modeling results indicate that some DOC-bound copper was bioavailable.« less

Communication between the N and C Termini Is Required for Copper-stimulated Ser/Thr Phosphorylation of Cu(I)-ATPase (ATP7B)*

PubMed Central

Braiterman, Lelita T.; Gupta, Arnab; Chaerkady, Raghothama; Cole, Robert N.; Hubbard, Ann L.

2015-01-01

The Wilson disease protein ATP7B exhibits copper-dependent trafficking. In high copper, ATP7B exits the trans-Golgi network and moves to the apical domain of hepatocytes where it facilitates elimination of excess copper through the bile. Copper levels also affect ATP7B phosphorylation. ATP7B is basally phosphorylated in low copper and becomes more phosphorylated (“hyperphosphorylated”) in elevated copper. The functional significance of hyperphosphorylation remains unclear. We showed that hyperphosphorylation occurs even when ATP7B is restricted to the trans-Golgi network. We performed comprehensive phosphoproteomics of ATP7B in low versus high copper, which revealed that 24 Ser/Thr residues in ATP7B could be phosphorylated, and only four of these were copper-responsive. Most of the phosphorylated sites were found in the N- and C-terminal cytoplasmic domains. Using truncation and mutagenesis, we showed that inactivation or elimination of all six N-terminal metal binding domains did not block copper-dependent, reversible, apical trafficking but did block hyperphosphorylation in hepatic cells. We showed that nine of 15 Ser/Thr residues in the C-terminal domain were phosphorylated. Inactivation of 13 C-terminal phosphorylation sites reduced basal phosphorylation and eliminated hyperphosphorylation, suggesting that copper binding at the N terminus propagates to the ATP7B C-terminal region. C-terminal mutants with either inactivating or phosphomimetic substitutions showed little effect upon copper-stimulated trafficking, indicating that trafficking does not depend on phosphorylation at these sites. Thus, our studies revealed that copper-dependent conformational changes in the N-terminal region lead to hyperphosphorylation at C-terminal sites, which seem not to affect trafficking and may instead fine-tune copper sequestration. PMID:25666620

Copper tolerance in clones of Agrostis gigantea from a mine waste site

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

Hogan, G.D.; Courtin, G.M.; Rauser, W.E.

1977-04-15

A mine waste site from Sudbury, Ontario, contaminated with heavy metals is described. The dominant vegetative cover was formed by two grasses: Agrostis gigantea Roth. and Agrostis scabra Willd. Testing of 10 clones of A. gigantea from the roast bed and an adjoining area for copper tolerance showed that two clones collected from the roast bed were tolerant to increased copper levels. Copper tolerance was found in clones growing on soils with high copper contents and low pHs. The combination of high copper content and low pH brought about a high level of extractable copper within the soil. Soils withmore » equally high copper levels but higher pHs and therefore low extractable-copper levels did not support copper-tolerant clones.« less

Crystallography with online optical and X-ray absorption spectroscopies demonstrates an ordered mechanism in copper nitrite reductase.

PubMed

Hough, Michael A; Antonyuk, Svetlana V; Strange, Richard W; Eady, Robert R; Hasnain, S Samar

2008-04-25

Nitrite reductases are key enzymes that perform the first committed step in the denitrification process and reduce nitrite to nitric oxide. In copper nitrite reductases, an electron is delivered from the type 1 copper (T1Cu) centre to the type 2 copper (T2Cu) centre where catalysis occurs. Despite significant structural and mechanistic studies, it remains controversial whether the substrates, nitrite, electron and proton are utilised in an ordered or random manner. We have used crystallography, together with online X-ray absorption spectroscopy and optical spectroscopy, to show that X-rays rapidly and selectively photoreduce the T1Cu centre, but that the T2Cu centre does not photoreduce directly over a typical crystallographic data collection time. Furthermore, internal electron transfer between the T1Cu and T2Cu centres does not occur, and the T2Cu centre remains oxidised. These data unambiguously demonstrate an 'ordered' mechanism in which electron transfer is gated by binding of nitrite to the T2Cu. Furthermore, the use of online multiple spectroscopic techniques shows their value in assessing radiation-induced redox changes at different metal sites and demonstrates the importance of ensuring the correct status of redox centres in a crystal structure determination. Here, optical spectroscopy has shown a very high sensitivity for detecting the change in T1Cu redox state, while X-ray absorption spectroscopy has reported on the redox status of the T2Cu site, as this centre has no detectable optical absorption.

Regional mapping of hydrothermally altered igneous rocks along the Urumieh-Dokhtar, Chagai, and Alborz Belts of western Asia using Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) data and Interactive Data Language (IDL) logical operators: a tool for porphyry copper exploration and assessment: Chapter O in Global mineral resource assessment

USGS Publications Warehouse

Mars, John L.; Zientek, M.L.; Hammarstrom, J.M.; Johnson, K.M.; Pierce, F.W.

2014-01-01

The ASTER alteration map and corresponding geologic maps were used to select circular to elliptical patterns of argillic- and phyllic-altered volcanic and intrusive rocks as potential porphyry copper sites. One hundred and seventy eight potential porphyry copper sites were mapped along the UDVB, and 23 sites were mapped along the CVB. The potential sites were selected to assist in further exploration and assessments of undiscovered porphyry copper deposits.

Surface-Water Hydrology and Quality at the Pike Hill Superfund Site, Corinth, Vermont, October 2004 to December 2005

USGS Publications Warehouse

Kiah, Richard G.; Deacon, Jeffrey R.; Piatak, Nadine M.; Seal, Robert R.; Coles, James F.; Hammarstrom, Jane M.

2007-01-01

The hydrology and quality of surface water in and around the Pike Hill Brook watershed, in Corinth, Vermont, was studied from October 2004 to December 2005 by the U.S. Geological Survey in cooperation with the U.S. Environmental Protection Agency (USEPA). Pike Hill was mined intermittently for copper from 1847 to 1919 and the site is known to be contributing trace elements and acidity to Pike Hill Brook and an unnamed tributary to Cookville Brook. The site has been listed as a Superfund site since 2004. Streamflow, specific conductance, pH, and water temperature were measured continuously and monthly at three sites on Pike Hill Brook to determine the variation in these parameters over an annual cycle. Synoptic water-quality sampling was done at 10 stream sites in October 2004, April 2005, and June 2005 and at 13 stream sites in August 2005 to characterize the quality of surface water in the watershed on a seasonal and spatial basis, as well as to assess the effects of wetlands on water quality. Samples for analysis of benthic macroinvertebrate populations were collected at 11 stream sites in August 2005. Water samples were analyzed for 5 major ions and 32 trace elements. Concentrations of trace elements at sites in the Pike Hill Brook watershed exceeded USEPA National Recommended Water Quality Criteria acute and chronic toxicity standards for aluminum, iron, cadmium, copper, and zinc. Concentrations of copper exceeded the chronic criteria in an unnamed tributary to Cookville Brook in one sample. Concentrations of sulfate, calcium, aluminum, iron, cadmium, copper, and zinc decreased with distance from a site directly downstream from the mine (site 1), as a result of dilution and through sorption and precipitation of the trace elements. Maximum concentrations of aluminum, iron, cadmium, copper, and zinc were observed during spring snowmelt. Concentrations of sulfate, calcium, cadmium, copper, and zinc, and instantaneous loads of calcium and aluminum were statistically different (p<0.05) among the three continuously monitored sites (sites 1, 4, and 5). Instantaneous loads of aluminum, iron, and copper decreased by one to three orders of magnitude from site 1 to a site 1.1 mi downstream (site 4). Instantaneous loads of sulfate were similar between sites 1, 4, and at a site 3 mi downstream (site 5). Instantaneous loads of cadmium and zinc were similar between sites 1 and 4, and loads of iron and copper were similar between sites 4 and 5. Loads of chemical constituents were compared at site 1 (closest to the mine waste piles) and site 5 (near the mouth of Pike Hill Brook and below a majority of the wetlands). Annually, the loads of dissolved cadmium and zinc at site 1 were about five times greater than loads at site 5, and the load of dissolved copper at site 1 was about 17 times greater than at site 5. The ratio of loads for dissolved cadmium, copper, and zinc to total cadmium, copper, and zinc at site 1 was about 1. Samples collected in Pike Hill Brook upstream and downstream from the wetlands during low flows in August 2005 showed that oxidation of ferrous iron and precipitation of iron-hydroxides were probably not affecting trace metals in the wetlands through sorption; however, a significant portion of the iron entering the wetlands was in particulate form and may have transported sorbed copper and other trace metals. Thus, aerobic activity in the wetlands was probably not affecting metal cycling in the watershed. Concentrations and loads of sulfate may be unlikely to define unequivocally the role of the wetlands with regard to anaerobic bacterial sulfate reduction; however, bacterial sulfate removal may have affected loads of sulfate. Loads of copper increased downstream from the wetlands and may reflect the reductive dissolution of ferric hydroxide particulates in anaerobic parts of the wetlands.Concentrations of dissolved iron increased downstream from the wetlands. The most apparent effects on the macroinvertebr

Lead and Copper Tap Sample Site Plan Instructions

EPA Pesticide Factsheets

This document may be used by public water systems in Wyoming and on EPA R8 Tribal Lands as a guide for how to properly complete their lead and copper tap sample site plans to comply with the Lead and Copper Rule.

Bio-mimicking galactose oxidase and hemocyanin, two dioxygen-processing copper proteins.

PubMed

Gamez, Patrick; Koval, Iryna A; Reedijk, Jan

2004-12-21

The modelling of the active sites of metalloproteins is one of the most challenging tasks in bio-inorganic chemistry. Copper proteins form part of this stimulating field of research as copper enzymes are mainly involved in oxidation bio-reactions. Thus, the understanding of the structure-function relationship of their active sites will allow the design of effective and environmental friendly oxidation catalysts. This perspective illustrates some outstanding structural and functional synthetic models of the active site of copper proteins, with special attention given to models of galactose oxidase and hemocyanin.

Metal stabilization of collagen and de novo designed mimetic peptides

PubMed Central

Parmar, Avanish S.; Xu, Fei; Pike, Douglas H.; Belure, Sandeep V.; Hasan, Nida F.; Drzewiecki, Kathryn E.; Shreiber, David I.; Nanda, Vikas

2017-01-01

We explore the design of metal binding sites to modulate triple-helix stability of collagen and collagen-mimetic peptides. Globular proteins commonly utilize metals to connect tertiary structural elements that are well separated in sequence, constraining structure and enhancing stability. It is more challenging to engineer structural metals into fibrous protein scaffolds, which lack the extensive tertiary contacts seen in globular proteins. In the collagen triple helix, the structural adjacency of the carboxy-termini of the three chains makes this region an attractive target for introducing metal binding sites. We engineered His3 sites based on structural modeling constraints into a series of designed homotrimeric and heterotrimeric peptides, assessing the capacity of metal binding to improve stability and in the case of heterotrimers, affect specificity of assembly. Notable enhancements in stability for both homo and heteromeric systems were observed upon addition of zinc(II) and several other metal ions only when all three histidine ligands were present. Metal binding affinities were consistent with the expected Irving-Williams series for imidazole. Unlike other metals tested, copper(II) also bound to peptides lacking histidine ligands. Acetylation of the peptide N-termini prevented copper binding, indicating proline backbone amide metal-coordination at this site. Copper similarly stabilized animal extracted Type I collagen in a metal specific fashion, highlighting the potential importance of metal homeostasis within the extracellular matrix. PMID:26225466

Metal Stabilization of Collagen and de Novo Designed Mimetic Peptides.

PubMed

Parmar, Avanish S; Xu, Fei; Pike, Douglas H; Belure, Sandeep V; Hasan, Nida F; Drzewiecki, Kathryn E; Shreiber, David I; Nanda, Vikas

2015-08-18

We explore the design of metal binding sites to modulate triple-helix stability of collagen and collagen-mimetic peptides. Globular proteins commonly utilize metals to connect tertiary structural elements that are well separated in sequence, constraining structure and enhancing stability. It is more challenging to engineer structural metals into fibrous protein scaffolds, which lack the extensive tertiary contacts seen in globular proteins. In the collagen triple helix, the structural adjacency of the carboxy-termini of the three chains makes this region an attractive target for introducing metal binding sites. We engineered His3 sites based on structural modeling constraints into a series of designed homotrimeric and heterotrimeric peptides, assessing the capacity of metal binding to improve stability and in the case of heterotrimers, affect specificity of assembly. Notable enhancements in stability for both homo- and heteromeric systems were observed upon addition of zinc(II) and several other metal ions only when all three histidine ligands were present. Metal binding affinities were consistent with the expected Irving-Williams series for imidazole. Unlike other metals tested, copper(II) also bound to peptides lacking histidine ligands. Acetylation of the peptide N-termini prevented copper binding, indicating proline backbone amide metal-coordination at this site. Copper similarly stabilized animal extracted Type I collagen in a metal-specific fashion, highlighting the potential importance of metal homeostasis within the extracellular matrix.

MX Siting Investigation. Mineral Resources Survey, Seven Additional Valleys, Nevada/Utah Siting Area. Volume IV.

DTIC Science & Technology

1981-06-23

Lead, copper , silver In brecciated Devonian (?) limestone at the contact with altered grane* Porphyry (507). Silver, lead, copper , gold. Silver, lead...rhyolite and latite. Molybdenum- quartz yamns and disseminated in quartz monaonilte porphyry ( 402) Silveir, gold, lead, Silver, gold, lead, copper ...in parentheses ) Canyon) Tfungsten, gold. silver Tungsten -irregular pipelike bodies in brocaiated and silicified copper , lead. flourspar liniestone

CorA Is a Copper Repressible Surface-Associated Copper(I)-Binding Protein Produced in Methylomicrobium album BG8

PubMed Central

Johnson, Kenneth A.; Ve, Thomas; Larsen, Øivind; Pedersen, Rolf B.; Lillehaug, Johan R.; Jensen, Harald B.; Helland, Ronny; Karlsen, Odd A.

2014-01-01

CorA is a copper repressible protein previously identified in the methanotrophic bacterium Methylomicrobium album BG8. In this work, we demonstrate that CorA is located on the cell surface and binds one copper ion per protein molecule, which, based on X-ray Absorption Near Edge Structure analysis, is in the reduced state (Cu(I)). The structure of endogenously expressed CorA was solved using X-ray crystallography. The 1.6 Å three-dimensional structure confirmed the binding of copper and revealed that the copper atom was coordinated in a mononuclear binding site defined by two histidines, one water molecule, and the tryptophan metabolite, kynurenine. This arrangement of the copper-binding site is similar to that of its homologous protein MopE* from Metylococcus capsulatus Bath, confirming the importance of kynurenine for copper binding in these proteins. Our findings show that CorA has an overall fold similar to MopE, including the unique copper(I)-binding site and most of the secondary structure elements. We suggest that CorA plays a role in the M. album BG8 copper acquisition. PMID:24498370

Use of Fatty Acid Methyl Ester Profiles to Compare Copper-Tolerant and Copper-Sensitive Strains of Pantoea ananatis.

PubMed

Nischwitz, C; Gitaitis, R; Sanders, H; Langston, D; Mullinix, B; Torrance, R; Boyhan, G; Zolobowska, L

2007-10-01

ABSTRACT A survey was conducted to evaluate differences in fatty acid methyl ester (FAME) profiles among strains of Pantoea ananatis, causal agent of center rot of onion (Allium cepa), isolated from 15 different onion cultivars in three different sites in Georgia. Differences in FAME composition were determined by plotting principal components (PCs) in two-dimensional plots. Euclidean distance squared (ED(2)) values indicated a high degree of similarity among strains. Plotting of PCs calculated from P. ananatis strains capable of growing on media amended with copper sulfate pentahydrate (200 mug/ml) indicated that copper-tolerant strains grouped into tight clusters separate from clusters formed by wild-type strains. However, unlike copper-sensitive strains, the copper-tolerant strains tended to cluster by location. A total of 80, 60, and 73% of the strains from Tift1, Tift2, and Tattnall, respectively, exhibited either confluent growth or partial growth on copper-amended medium. However, all strains were sensitive to a mixture of copper sulfate pentahydrate (200 mug/ml) and maneb (40 mug/ml). When copper-tolerant clones were analyzed and compared with their wild-type parents, in all cases the plotting of PCs developed from copper-tolerant clones formed tight clusters separate from clusters formed by the parents. Eigenvalues generated from these tests indicated that two components provided a good summary of the data, accounting for 98, 98, and 96% of the standardized variance for strains Pna 1-15B, Pna 1-12B, and Pna 2-5A, respectively. Furthermore, feature 4 (cis-9-hexadecenoic acid/2-hydroxy-13-methyltetradecanoic acid) and feature 7 (cis-9/trans-12/cis-7-octadecenoic acid) were the highest or second highest absolute values for PC1 in all three strains of the parents versus copper-tolerant clones, and hexadecanoic acid was the highest absolute value for PC2 in all three strains. Along with those fatty acids, dodecanoic acid and feature 3 (3-hydroxytetradecanoic acid/14-methylpentadecenoic acid) also had an impact on the differences observed between copper-sensitive parents and copper-resistant mutants. Finding these changes in bacterial fatty acid composition could lead to the development of a laboratory assay to identify copper-tolerant strains using gas chromatography as well as providing clues to further elucidate the mode of action of copper tolerance.

N Deposition Effects on Hermes Copper Butterfly (Lycaena hermes) Habitat in Southern California

NASA Astrophysics Data System (ADS)

Malter, L. I.; Vourlitis, G. L.

2017-12-01

Atmospheric nitrogen (N) deposition has become a global concern over the past few decades as population sizes have increased. San Diego County, CA, USA, with a high population density, Mediterranean-type climate, and high biodiversity, is an ideal site for an extensive N deposition study. Chronic anthropogenic N deposition is one of the main contributing factors to affect plant species diversity (Vourlitis and Pasquini 2009) and invasive species encroachment (Minnich and Dezzani 1998). It is also the location of the rare endemic Hermes copper butterfly (Lycaena hermes), which has received minimal research and remains a mystery to many ecologists. We hypothesized that N deposition will impact Hermes abundance; however, there is limited research on the effects of N deposition on butterfly habitat. Thus, this study aims to determine the effect of increased N on the alterations to plant-insect interactions. These effects are being measured at five sites throughout San Diego County in current or historical Hermes copper habitat. N deposition collectors have been placed under the canopy of spiny redberry shrubs (Rhamnus crocea) to accumulate N throughfall at each site. Soil and redberry stem fragments are being used to analyze total N and Carbon (C), water potential, and shrub growth throughout the course of this study. Despite the preliminary nature of our results, we show a number of trends between data groups, such as large differences in soil and tissue N and C between the study sites, suggesting differences in atmospheric N inputs. These variations in soil N availability lead to variations in leaf tissue chemistry, which can ultimately impact the performance of the Hermes copper larvae. Our current data demonstrate some clear trends, but whether these trends remain consistent and interpretable remains to be seen. We anticipate this research will increase our understanding of spatial variation patterns of N deposition in southern California and how that N input might affect the rare Hermes copper butterfly and its host plant, Rhamnus crocea. Furthermore, these data are important because they might help us understand why Hermes is in decline and which sites should be prioritized for management.

INS studies of Cobalt-Copper Catalyst for the Conversion of Syngas to Higher Oxygenates

NASA Astrophysics Data System (ADS)

Sprunger, Phillip; Wang, Zi; Patterson, Matthew; Kurtz, Richard; Spivey, James

Cobalt-copper catalysts have been proposed for the synthesis of ethanol and higher oxygenates as a substitute of Rh and other high-cost noble metal catalysts. Two types of sites with atomic proximity are needed to form higher oxygenates: one to dissociate CO and a second to insert CO to the intermediates to form the CHxCO intermediate. Metallic cobalt is responsible for CO dissociation, while the nature of the site for CO insertion is still under study. We have utilized inelastic neutron scattering (INS) at the VISION beamline at SNS to probe intermediate surface species of this cobalt-copper catalyst. This unique technique allows for elucidation of mechanistic details of the CO insertion and subsequent CHxCO intermediate formation on the metal surfaces (Co0, Co2C and/or Cu0) . In addition to XRD and EXAFS which show a unique surface Co-C carbide formation, a combination of both INS and computational modeling indicate that the active site for CHxCO intermediates. Sponsored through the Louisiana Consortium for Neutron Scattering, DOE No. DE-SC0012432 with additional support from the LA BOR; also ORNL's Spallation Neutron Source (VISION Beamline), DOE-BES under Contract No. DE-AC0500OR22725.

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

[Spatiotemporal variation characteristics of heavy metals pollution in the water, soil and sediments environment of the Lean River-Poyang Lake Wetland].

PubMed

Jian, Min-Fei; Li, Ling-Yu; Xu, Peng-Fei; Chen, Pu-Qing; Xiong, Jian-Qiu; Zhou, Xue-Ling

2014-05-01

Overlying water, sediments, surface soils in the typical wetland areas of Lean River and Poyang Lake which were rich in non-ferrous metal mineral resources on both sides of the river, were chosen for monitoring heavy metals including copper, lead and cadmium of base flow in average season, flood season, and dry season in 2012. Statistical analysis methods were coupled to characterize the spatiotemporal variation of heavy metals pollution and identify the main sources. The results indicated that the concentrations of copper were the highest in all samples of each sampling sites in the Lean River-Poyang Lake wetland. And the content values of copper, lead and cadmium in different samples of different sampling sites also showed that the content values of copper were higher than those of lead, and the content values of lead were also higher than those of cadmium. The results also showed that the heavy metals pollution of copper, lead and cadmium in flood season was the heaviest whereas the heavy metals pollution in dry season was comparatively light. The results of the contents of the three kinds of heavy metals elements in different sampling sites of the watersheds of lean River showed that the contents of copper in the samples from the upstream sampling sites of Lean River were higher than those of other samples from other sites. And the contents of lead in the samples from the downstream sampling sites of Lean River were higher than those of other samples from other sampling sites. The contents of cadmium in the samples from the midstream sampling sites of Lean River were higher than those of other samples from other sites. The first principal component representing copper pollution explained 36. 99% of the total variance of water quality. The second principal component concerning representing lead pollution explained 30. 12% of the total variance. The correlation analysis results showed that there were significant positive correlations among the contents of copper in sediments and the contents of copper in overlying water. And there was also significant positive correlation between the contents of copper in sediments and the contents of copper in the surface soils. And the correlation analysis showed that there were significant positive correlations among the contents of cadmium in sediments and the contents of cadmium in surface soils. The above results reflected that the copper pollution or cadmium sources of water, soil and sediments were consistent, which were mainly from heavy metal acidic waste of mining emissions. The correlations between other components were not very obvious, which reflected the sources of pollutants were different.

Pulse-radiolysis studies on the interaction of one-electron reduced species with blue oxidases. Reduction of type-2-copper-depleted ascorbate oxidase.

PubMed

O'Neill, P; Fielden, E M; Avigliano, L; Marcozzi, G; Ballini, A; Agrò, F

1984-08-15

The interaction of one-electron reduced metronidazole (ArNO2.-) with native and Type-2-copper-depleted ascorbate oxidase were studied in buffered aqueous solution at pH 6.0 and 7.4 by using the technique of pulse radiolysis. With ArNO2.-, reduction of Type 1 copper of the native enzyme and of the Type-2-copper-depleted ascorbate oxidase occurs via a bimolecular step and at the same rate. Whereas the native protein accepts, in the absence of O2, 6-7 reducing equivalents, Type-2-copper-depleted ascorbate oxidase accepts only 3 reducing equivalents with stoichiometric reduction of Type 1 copper. On reaction of O2.- with ascorbate oxidase under conditions of [O2.-] much greater than [ascorbate oxidase], removal of Type 2 copper results in reduction of all the Type 1 copper atoms, in contrast with reduction of the equivalent of only one Type 1 copper atom in the holoprotein. From observations at 610 nm, the rate of reduction of ascorbate oxidase by O2.- is not dependent on the presence of Type 2 copper. For the holoprotein, no significant optical-absorption changes were observed at 330 nm. It is proposed that electrons enter the protein via Type 1 copper in a rate-determining step followed by a fast intramolecular transfer of electrons within the protein. For the Type-2-copper-depleted protein, intramolecular transfer within the protein, however, is slow or does not occur. In the presence of O2, it is also suggested that re-oxidation of the partially reduced holoprotein occurs at steady state, as inferred from the observations at 330 nm and 610 nm. The role of Type 2 copper in ascorbate oxidase is discussed in terms of its involvement in redistribution of electrons within the protein or structural considerations.

Optimizing the performance of catalytic traps for hydrocarbon abatement during the cold-start of a gasoline engine.

PubMed

Puértolas, B; Navlani-García, M; García, T; Navarro, M V; Lozano-Castelló, D; Cazorla-Amorós, D

2014-08-30

A key target to reduce current hydrocarbon emissions from vehicular exhaust is to improve their abatement under cold-start conditions. Herein, we demonstrate the potential of factorial analysis to design a highly efficient catalytic trap. The impact of the synthesis conditions on the preparation of copper-loaded ZSM-5 is clearly revealed by XRD, N2 sorption, FTIR, NH3-TPD, SEM and TEM. A high concentration of copper nitrate precursor in the synthesis improves the removal of hydrocarbons, providing both strong adsorption sites for hydrocarbon retention at low temperature and copper oxide nanoparticles for full hydrocarbon catalytic combustion at high temperature. The use of copper acetate precursor leads to a more homogeneous dispersion of copper oxide nanoparticles also providing enough catalytic sites for the total oxidation of hydrocarbons released from the adsorption sites, although lower copper loadings are achieved. Thus, synthesis conditions leading to high copper loadings jointly with highly dispersed copper oxide nanoparticles would result in an exceptional catalytic trap able to reach superior hydrocarbon abatement under highly demanding operational conditions. Copyright © 2014 Elsevier B.V. All rights reserved.

Discovery and characterization of a new family of lytic polysaccharide mono-oxygenases

PubMed Central

Hemsworth, Glyn R.; Henrissat, Bernard; Davies, Gideon J.; Walton, Paul H.

2014-01-01

Lytic polysaccharide mono-oxygenases (LPMOs) are a recently discovered class of enzymes capable of oxidizing recalcitrant polysaccharides. They currently attract much attention due to their potential use in biomass conversion, notably in the production of biofuels. Past work has identified two discrete sequence-based families of these enzymes termed AA9 (formerly GH61) and AA10 (formerly CBM33). Here we report the discovery of a third family of LPMOs. Using a chitin-degrading exemplar from Aspergillus oryzae, we show that the 3-D structure of the enzyme shares some features of the previous two classes of LPMOs, including a copper active centre featuring the histidine brace active site, but is distinct in terms of its active site details and its EPR spectroscopy. The new AA11 family expands the LPMO clan with the potential to broaden both the range of potential substrates and the types of reactive copper-oxygen species formed at the active site of LPMOs. PMID:24362702

Using XAS and SXRF to Study Copper in Wilson Disease at the Molecular and Tissue Level

NASA Astrophysics Data System (ADS)

Ralle, Martina; Blackburn, Ninian J.; Lutsenko, Svetlana

2007-02-01

Wilson disease (WD) is a genetic disorder of copper metabolism associated with severe hepatic, neurological, and psychiatric abnormalities. In WD, the billiary copper excretion is impaired and copper accumulates in tissues, particularly in the liver and the brain. The affected gene, ATP7B, encodes the copper transporting ATPase, Wilson disease protein (WNDP). WNDP has six copper binding sites in the N-terminal portion of the molecule. Each site includes the conserved amino acid sequence MXCXXC, and binds 1 Cu(I) through its 2 cysteine residues. We performed X-ray absorption studies at the Cu Kα-edge on the recombinant N-terminal domain of WNDP (N-WNDP). Copper was bound to N-WNDP either in vivo or in vitro in the presence of different reducing agents. We found that in N-WNDP copper is predominantly coordinated in a linear fashion by two cysteines, with the appearance of a Cu-Cu interaction when all metal binding sites are filled. Increasing amounts of reducing agents containing sulfide or phosphine groups led to binding of the exogenous ligands to copper thereby increasing the coordination number of copper from two to three. To better understand the role of copper in WD, we utilized livers of the 6-weeks-old Atp7b-/- mice (an animal model for WD) in which the copper concentration was 10-20-fold higher compared to that of the control mice. The distribution of copper in hepatocytes was evaluated by synchrotron based X-ray fluorescence microprobe (SXRF). We demonstrate that we can prepare liver slices that retain copper and can detect copper with subcellular resolution. On the same sections μ-XANES (spot size: 5 micron) was used to determine the oxidation state of copper.

Pulse-radiolysis studies on the interaction of one-electron reduced species with blue oxidases. Reduction of native and type-2-copper-depleted Vietnamese-lacquer-tree and Japanese-lacquer-tree laccases.

PubMed

O'Neill, P; Fielden, E M; Morpurgo, L; Agostinelli, E

1984-08-15

The interactions of one-electron reduced metronidazole (ArNO2.-) and O2.- with native and Type-2-copper-depleted Vietnamese- and Japanese-lacquer-tree laccases were studied in aqueous solution at pH 6.0 and 7.4 by using the technique of pulse radiolysis. On reaction with ArNO2.-, in the absence of O2, the holo- and the Type-2-copper-depleted proteins accept, with reduction of Type 1 copper, 2 and 1 reducing equivalents respectively. On reaction with O2.- of both holo- and Type-2-copper-depleted Vietnamese-lacquer-tree laccase, almost complete reduction of Type 1 copper was observed and, after completion of the reaction, some (less than 20%) reoxidation of Type 1 copper occurs. Reduction of Type 1 copper of the laccases by these one-electron donors occurs via a bimolecular step; however, the rate of reduction of Vietnamese-lacquer-tree laccase is over 10 times that of Japanese-lacquer-tree laccase. It is inferred that electrons enter the protein via Type 1 copper with, in the case of the holoprotein, subsequent rapid intramolecular transfer of 1 reducing equivalent within the protein. Furthermore it is suggested that intra-molecular electron transfer to Type 3 copper atoms is slow and, in the case of Type-2-copper-depleted protein, may not occur. This slow process may partially account for the variation of the catalytic activities of 'blue' oxidases.

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

Fluorescence properties and conformational stability of the beta-hemocyanin of Helix pomatia.

PubMed

Idakieva, Krassimira; Siddiqui, Nurul I; Parvanova, Katja; Nikolov, Peter; Gielens, Constant

2006-04-01

The beta-hemocyanin (beta-HpH) is one of the three dioxygen-binding proteins found freely dissolved in the hemolymph of the gastropodan mollusc Helix pomatia. The didecameric molecule (molecular mass 9 MDa) is built up of only one type of subunits. The fluorescence properties of the oxygenated and apo-form (copper-deprived) of the didecamer and its subunits were characterized. Upon excitation of the hemocyanins at 295 or 280 nm, tryptophyl residues buried in the hydrophobic interior of the protein determine the fluorescence emission. This is confirmed by quenching experiments with acrylamide, cesium chloride and potassium iodide. The copper-dioxygen system at the binuclear active site quenches the tryptophan emission of the oxy-beta-HpH. The removal of this system increases the fluorescence quantum yield and causes structural rearrangement of the microenvironment of the emitting tryptophyl residues in the apo-form. Time-resolved fluorescence measurements show that the oxygenated and copper-deprived forms of the beta-HpH and its subunits exist in different conformations. The thermal stability of the oxy- and apo-beta-HpH is characterized by a transition temperature (Tm) of 84 degrees C and 63 degrees C, respectively, obtained by differential scanning calorimetry. Increase of the temperature influences the active site at lower temperatures than the environments of tryptophans and tyrosines causing a loss of oxygen bound to the copper atoms. This process is, at least partially, reversible as after cooling of the protein samples, around 60% reinstatement of the copper-peroxide band has been observed. The results confirm the role of the copper-dioxygen complex for the stabilization of the hemocyanin structure in solution. The other important stabilizing factor is oligomerization of the hemocyanin molecule.

Recognition of the geologic framework of porphyry deposits on ERTS-1 imagery. [copper/molybdenum porphyrys

NASA Technical Reports Server (NTRS)

Wilson, J. C. (Principal Investigator)

1974-01-01

The author has identified the following significant results. Three major tectonic provinces have been mapped by geologic photointerpretation of ERTS-1 imagery over the Ok Tedi test site. These areas can be characterized as follows: (1) A broad area of low relief and mature topography suggesting a history of relative tectonic stability. (2) A narrow belt of moderate to high relief, broad open folds and prominent linear features. The Mount Fubilan-type porphyry copper deposits and recent volcanic effusive centers occur in this province. (3) A heterogeneous zone of high relief and high drainage density suggestive of relative structural complexity.

Conformational exchange in pseudoazurin: different kinds of microsecond to millisecond dynamics characterized by their pH and buffer dependence using 15N NMR relaxation.

PubMed

Hass, Mathias A S; Vlasie, Monica D; Ubbink, Marcellus; Led, Jens J

2009-01-13

The dynamics of the reduced form of the blue copper protein pseudoazurin from Alcaligenes faecalis S-6 was investigated using (15)N relaxation measurements with a focus on the dynamics of the micro- to millisecond time scale. Different types of conformational exchange processes are observed in the protein on this time scale. At low pH, the protonation of the C-terminal copper-ligated histidine, His81, is observed. A comparison of the exchange rates in the presence and absence of added buffers shows that the protonation is the rate-limiting step at low buffer concentrations. This finding agrees with previous observations for other blue copper proteins, e.g., amicyanin and plastocyanin. However, in contrast to plastocyanin but similar to amicyanin, a second conformational exchange between different conformations of the protonated copper site is observed at low pH, most likely triggered by the protonation of His81. This process has been further characterized using CPMG dispersion methods and is found to occur with a rate of a few thousands per second. Finally, micro- to millisecond motions are observed in one of the loop regions and in the alpha-helical regions. These motions are unaffected by pH and are unrelated to the conformational changes in the active site of pseudoazurin.

Complexation of copper by aquatic humic substances from different environments

USGS Publications Warehouse

McKnight, Diane M.; Feder, Gerald L.; Thurman, E. Michael; Wershaw, Robert L.

1983-01-01

The copper-complexing properties of aquatic humic substances isolated from eighteen different environments were characterized by potentiometric titration, using a cupric ion selective electrode. Potentiometric data were analyzed using FITEQL, a computer program for the determination of chemical equilibrium constants from experimental data. All the aquatic humic substances could be modelled as having two types of Cu(II)-binding sites: one with K equal to about 106 and a concentration of 1.0 ± 0.4 × 10−6 M(mg C)−1 and another with K equal to about 108 and a concentration of 2.6 ± 1.6 × 10−7 M(mg C)−1.A method is described for estimating the Cu(II)-binding sites associated with dissolved humic substances in natural water based on a measurement of dissolved organic carbon, which may be helpful in evaluating chemical processes controlling speciation of Cu and bioavailability of Cu to aquatic organisms.

Polyhydrido Copper Clusters: Synthetic Advances, Structural Diversity, and Nanocluster-to-Nanoparticle Conversion.

PubMed

Dhayal, Rajendra S; van Zyl, Werner E; Liu, C W

2016-01-19

Metal hydride clusters have historically been studied to unravel their aesthetically pleasing molecular structures and interesting properties, especially toward hydrogen related applications. Central to this work is the hydride ligand, H¯, the smallest closed-shell spherical anion known. Two new developments in polyhydrido nanocluster chemistry include the determination of heretofore unknown hydride coordination modes and novel structural constructs, and conversion from the molecular entities to rhombus-shaped copper nanoparticles (CuNPs). These advances, together with hydrogen evolution and catalysis, have provided both experimentalists and theorists with a rich scientific directive to further explore. The isolation of hexameric [{(Ph3P)CuH}6] (Stryker reagent) could be regarded as the springboard for the recent emergence of polyhydrido copper cluster chemistry due to its utilization in a variety of organic chemical transformations. The stability of clusters of various nuclearity was improved through phosphine, pyridine, and carbene type ligands. Our focus lies with the isolation of novel copper (poly)hydride clusters using mostly the phosphor-1,1-dithiolato type ligands. We found such chalcogen-stabilized clusters to be exceptionally air and moisture stable over a wide range of nuclearities (Cu7 to Cu32). In this Account, we (i) report on state-of-the-art copper hydride cluster chemistry, especially with regards to the diverse and novel structural types generally, and newly discovered hydride coordination modes in particular, (ii) demonstrate the indispensable power of neutron diffraction for the unambiguous assignment and location of hydride ligand(s) within a cluster, and (iii) prove unique transformations that can occur not only between well characterized high nuclearity clusters, but also how such clusters can transform to uniquely shaped nanoparticles of several nanometers in diameter through copper hydride reduction. The increase in the number of low- to high-nuclearity hydride clusters allows for different means by which they can be classified. We chose a classification based on the coordination mode of hydride ligand within the cluster. This includes copper clusters associated with bridging (μ2-H) and capping (μ3-H) hydride modes, followed by an interstitial (μ4-H) hydride mode that was introduced for the first time into octa- and hepta-nuclear copper clusters stabilized by dichalcogen-type ligands. This breakthrough provided a means to explore higher nuclearity polyhydrido nanoclusters, which contain both capping (μ3-H) and interstitial (μ(4-6)-H) hydrides. The presence of bidentate ligands having mixed S/P dative sites led to air- and moisture-stable copper hydride nanoclusters. The formation of rhombus-shaped nanoparticles (CuNPs) from copper polyhydrides in the presence of excess borohydrides suggests the presence of metal hydrides as intermediates during the formation of nanoparticles.

Regulation of extracellular copper-binding proteins in copper-resistant and copper-sensitive mutants of Vibrio alginolyticus.

PubMed Central

Harwood, V J; Gordon, A S

1994-01-01

Extracellular proteins of wild-type Vibrio alginolyticus were compared with those of copper-resistant and copper-sensitive mutants. One copper-resistant mutant (Cu40B3) constitutively produced an extracellular protein with the same apparent molecular mass (21 kDa) and chromatographic behavior as copper-binding protein (CuBP), a copper-induced supernatant protein which has been implicated in copper detoxification in wild-type V. alginolyticus. Copper-sensitive V. alginolyticus mutants displayed a range of alterations in supernatant protein profiles. CuBP was not detected in supernatants of one copper-sensitive mutant after cultures had been stressed with 50 microM copper. Increased resistance to copper was not induced by preincubation with subinhibitory levels of copper in the wild type or in the copper-resistant mutant Cu40B3. Copper-resistant mutants maintained the ability to grow on copper-amended agar after 10 or more subcultures on nonselective agar, demonstrating the stability of the phenotype. A derivative of Cu40B3 with wild-type sensitivity to copper which no longer constitutively expressed CuBP was isolated. The simultaneous loss of both constitutive CuBP production and copper resistance in Cu40B3 indicates that constitutive CuBP production is necessary for copper resistance in this mutant. These data support the hypothesis that the extracellular, ca. 20-kDa protein(s) of V. alginolyticus is an important factor in survival and growth of the organism at elevated copper concentrations. The range of phenotypes observed in copper-resistant and copper-sensitive V. alginolyticus indicate that altered sensitivity to copper was mediated by a variety of physiological changes. Images PMID:8031076

Systematic Perturbation of the Trinuclear Copper Cluster in the Multicopper Oxidases: The Role of Active Site Asymmetry in its Reduction of O2 to H2O

PubMed Central

Augustine, Anthony J.; Kjaergaard, Christian; Qayyum, Munzarin; Ziegler, Lynn; Kosman, Daniel J.; Hodgson, Keith O.; Hedman, Britt; Solomon, Edward I.

2010-01-01

The multicopper oxidase Fet3p catalyzes the four-electron reduction of dioxygen to water, coupled to the one-electron oxidation of four equivalents of substrate. To carry out this process the enzyme utilizes four Cu atoms: a type 1, a type 2, and a coupled binuclear, type 3 site. Substrates are oxidized at the T1 Cu, which rapidly transfers electrons, 13 Å away, to a trinuclear copper cluster composed of the T2 and T3 sites where dioxygen is reduced to water in two sequential 2e− steps. This study focuses on two variants of Fet3p, H126Q and H483Q, that perturb the two T3 Cu's, T3α and T3β, respectively. The variants have been isolated in both holo and type 1 depleted (T1D) forms, T1DT3αQ and T1DT3βQ, and their trinuclear copper clusters have been characterized in their oxidized and reduced states. While the variants are only mildly perturbed relative to T1D in the resting oxidized state, in contrast to T1D they are both found to have lost a ligand in their reduced states. Importantly, T1DT3αQ reacts with O2 but T1DT3βQ does not. Thus loss of a ligand at T3β, but not at T3α, turns off O2 reactivity, indicating that T3β and T2 are required for the 2e− reduction of O2 to form the peroxide intermediate (PI), whereas T3α remains reduced. This is supported by the spectroscopic features of PI in T1DT3αQ, which are identical to T1D PI. This selective redox activity of one edge of the trinuclear cluster demonstrates its asymmetry in O2 reactivity. The structural origin of this asymmetry between the T3α and T3β is discussed as is its contribution to reactivity. PMID:20377263

Relations of benthic macroinvertebrates to concentrations of trace elements in water, streambed sediments, and transplanted bryophytes and stream habitat conditions in nonmining and mining areas of the upper Colorado River basin, Colorado, 1995-98

USGS Publications Warehouse

Mize, Scott V.; Deacon, Jeffrey R.

2002-01-01

Intensive mining activity and highly mineralized rock formations have had significant impacts on surface-water and streambed-sediment quality and aquatic life within the upper reaches of the Uncompahgre River in western Colorado. A synoptic study by the U.S. Geological Survey National Water-Quality Assessment Program was completed in the upper Uncompahgre River Basin in 1998 to better understand the relations of trace elements (with emphasis on aluminum, arsenic, copper, iron, lead, and zinc concentrations) in water, streambed sediment, and aquatic life. Water-chemistry, streambed-sediment, and benthic macroinvertebrate samples were collected during low-flow conditions between October 1995 and July 1998 at five sites on the upper Uncompahgre River, all downstream from historical mining, and at three sites in drainage basins of the Upper Colorado River where mining has not occurred. Aquatic bryophytes were transplanted to all sites for 15 days of exposure to the water column during which time field parameters were measured and chemical water-quality and benthic macroinvertebrate samples were collected. Stream habitat characteristics also were documented at each site. Certain attributes of surface-water chemistry among streams were significantly different. Concentrations of total aluminum, copper, iron, lead, and zinc in the water column and concentrations of dissolved aluminum, copper, and zinc were significantly different between nonmining and mining sites. Some sites associated with mining exceeded Colorado acute aquatic-life standards for aluminum, copper, and zinc and exceeded Colorado chronic aquatic-life standards for aluminum, copper, iron, lead, and zinc. Concentrations of copper, lead, and zinc in streambed sediments were significantly different between nonmining and mining sites. Generally, concentrations of arsenic, copper, lead, and zinc in streambed sediments at mining sites exceeded the Canadian Sediment Quality Guidelines probable effect level (PEL), except at two mining sites where concentrations of copper and zinc were below the PEL. Concentrations of arsenic, copper, iron, and lead in transplanted bryophytes were significantly different between nonmining and mining sites. Bioconcentration factors calculated for 15-day exposure using one-half of the minimum reporting level were significantly different between nonmining and mining sites. In general, concentrations of trace elements in streambed sediment and transplanted bryophytes were more closely correlated than were the concentrations of trace elements in the water column with streambed sediments or concentrations in the water column with transplanted bryophytes. Stream habitat was rated as optimal to suboptimal using the U.S. Environmental Protection Agency Rapid Bioassessment Protocols for all sites in the study area. Generally, stream habitat conditions were similar at nonmining compared to mining sites and were suitable for diverse macroinvertebrate communities. All study sites had optimal instream habitat except two mining sites with suboptimal instream habitat because of disturbances in stream habitat. The benthic macroinvertebrate community composition at nonmining sites and mining sites differed. Mining sites had significantly lower total abundance of macroinvertebrates, fewer numbers of taxa, and lower dominance of Ephemeroptera (mayflies), Plecoptera (stoneflies), and Trichoptera (caddisflies), and a larger percentage of tolerant species than did nonmining sites. The predominance of Baetis sp. (mayflies), Hydropsychidae (caddisflies), and large percentage of Orthocladiinae chironomids (midges) at mining sites indicated that these species may be tolerant to elevated trace-element concentrations. The absence of Heptageniidae (mayflies), Chloroperlidae (stoneflies), and Rhyacophila sp. (caddisflies) at mining sites indicated that these species may be sensitive to elevated trace-element concentrations. Comparison of field parameters and

A Study of Knowledge-Based Systems for Photo Interpretation.

DTIC Science & Technology

1980-06-01

special models have been developed by V. F. Hollister and A. N. Campbell to aid in the selection of drilling targets for porphyry copper and...type lead/zinc N. Campbell 20 Kuroko-type massive sulfide C. F. Park, Jr. 34 Komatiitic-type nickel sulfide A. J. Naldrett 72 Butte-type porphyry copper ...M. T. Einaudi 104 Yerington-type porphyry copper M. T. Einaudi 143 Island-arc-type porphyry copper D. Cox 116 Roll-front sandstone uranium R. I

Methanobactin and the Link between Copper and Bacterial Methane Oxidation

PubMed Central

Semrau, Jeremy D.; Murrell, J. Colin; Gallagher, Warren H.; Dennison, Christopher; Vuilleumier, Stéphane

2016-01-01

SUMMARY Methanobactins (mbs) are low-molecular-mass (<1,200 Da) copper-binding peptides, or chalkophores, produced by many methane-oxidizing bacteria (methanotrophs). These molecules exhibit similarities to certain iron-binding siderophores but are expressed and secreted in response to copper limitation. Structurally, mbs are characterized by a pair of heterocyclic rings with associated thioamide groups that form the copper coordination site. One of the rings is always an oxazolone and the second ring an oxazolone, an imidazolone, or a pyrazinedione moiety. The mb molecule originates from a peptide precursor that undergoes a series of posttranslational modifications, including (i) ring formation, (ii) cleavage of a leader peptide sequence, and (iii) in some cases, addition of a sulfate group. Functionally, mbs represent the extracellular component of a copper acquisition system. Consistent with this role in copper acquisition, mbs have a high affinity for copper ions. Following binding, mbs rapidly reduce Cu2+ to Cu1+. In addition to binding copper, mbs will bind most transition metals and near-transition metals and protect the host methanotroph as well as other bacteria from toxic metals. Several other physiological functions have been assigned to mbs, based primarily on their redox and metal-binding properties. In this review, we examine the current state of knowledge of this novel type of metal-binding peptide. We also explore its potential applications, how mbs may alter the bioavailability of multiple metals, and the many roles mbs may play in the physiology of methanotrophs. PMID:26984926

Demystifying Controlling Copper Corrosion

EPA Science Inventory

The LCR systematically misses the highest health and corrosion risk sites for copper. Additionally, there are growing concerns for WWTP copper in sludges and discharge levels. There are many corrosion control differences between copper and lead. This talk explains the sometimes c...

Why do nickel-titanium archwires fracture intraorally? Fractographic analysis and failure mechanism of in-vivo fractured wires.

PubMed

Zinelis, Spiros; Eliades, Theodore; Pandis, Nikolaos; Eliades, George; Bourauel, Christoph

2007-07-01

The aim of this study was to characterize intraorally fractured nickel-titanium (Ni-Ti) archwires, determine the type of fracture, assess changes in the alloy's hardness and structure, and propose a mechanism of failure. Eleven Ni-Ti SE 200 and 19 copper-Ni-Ti (both, Ormco, Glendora, Calif) intraorally fractured archwires were collected. The location of fracture (anterior or posterior), wire type, cross section, and period of service before fracture were recorded. The retrieved wires and brand-, type-, and size-matched specimens of unused wires were subjected to scanning electron microscopy to assess the fracture type and morphological variation of fracture site of retrieved specimens, and to Vickers hardness (HV200) testing to investigate the hardness of as-received and in-vivo fractured specimens. Fracture site distribution was statistically analyzed with the chi-square test (alpha = 0.05), whereas the results of the hardness testing were analyzed with 2-way ANOVA with state (control vs in-vivo fractured) and composition (Ni-Ti SE vs copper-Ni-Ti) serving as discriminating variables and the Student-Newman-Keuls test at the 95% confidence level. The fracture site distribution showed a preferential location at the midspan between the premolar and the molar, suggesting that masticatory forces and complex loading during engagement of the wire to the bracket slot and potential intraoral aging might account for fracture incidence. All retrieved wires had the distinct features of brittle fracture without plastic deformation or crack propagation, whereas no increase in hardness was observed for the retrieved specimens. Most fractures sites were in the posterior region of the arch, probably because of the high-magnitude masticatory forces. Brittle fracture without plastic deformation was observed in most Ni-Ti wires regardless of archwire composition. There was no increase in the hardness of the intraorally exposed specimens regardless of wire type. This contradicts previous in-vitro studies and rules out hydrogen embrittlement as the cause of fracture.

Cephradine as corrosion inhibitor for copper in 0.9% NaCl solution

NASA Astrophysics Data System (ADS)

Tasić, Žaklina Z.; Petrović Mihajlović, Marija B.; Radovanović, Milan B.; Simonović, Ana T.; Antonijević, Milan M.

2018-05-01

The effect of (6R,7R)-7-[[(2R)-2-amino-2-cyclohexa-1,4-dien-1-ylacetyl]amino]-3-methyl-8-oxo-5-thia-1-azobicyclo[4.2.0]oct-2-ene-2-carboxylic acid (cephradine) on corrosion behavior of copper in 0.9% NaCl solution was investigated. The electrochemical methods including the open circuit potential measurements, potentiodynamic polarization and electrochemical impedance spectroscopy measurements, scanning electron microscopy with energy dispersive X-ray spectroscopy and quantum chemical calculations were used for this investigation. According to the results obtained by potentiodynamic polarization, cephradine acts as mixed type inhibitor. Also, the results obtained by electrochemical impedance spectroscopy indicate that cephradine provides good copper protection in 0.9% NaCl solution. The inhibition efficiency of cephradine increases with increasing its concentration. The scanning electron microscopy with energy dispersive X-ray spectroscopy confirms that a protective layer is formed on the copper surface due to the adsorption of cephradine on the active sites on the copper surface. Adsorption of cephradine in 0.9% NaCl solution follows the Langmuir adsorption isotherm. Quantum chemical calculations are in agreement with results obtained by electrochemical measurements.

Cytoplasmic CopZ-Like Protein and Periplasmic Rusticyanin and AcoP Proteins as Possible Copper Resistance Determinants in Acidithiobacillus ferrooxidans ATCC 23270

PubMed Central

Navarro, Claudio A.; von Bernath, Diego; Martínez-Bussenius, Cristóbal; Castillo, Rodrigo A.

2015-01-01

Acidophilic organisms, such as Acidithiobacillus ferrooxidans, possess high-level resistance to copper and other metals. A. ferrooxidans contains canonical copper resistance determinants present in other bacteria, such as CopA ATPases and RND efflux pumps, but these components do not entirely explain its high metal tolerance. The aim of this study was to find other possible copper resistance determinants in this bacterium. Transcriptional expression of A. ferrooxidans genes coding for a cytoplasmic CopZ-like copper-binding chaperone and the periplasmic copper-binding proteins rusticyanin and AcoP, which form part of an iron-oxidizing supercomplex, was found to increase when the microorganism was grown in the presence of copper. All of these proteins conferred more resistance to copper when expressed heterologously in a copper-sensitive Escherichia coli strain. This effect was absent when site-directed-mutation mutants of these proteins with altered copper-binding sites were used in this metal sensitivity assay. These results strongly suggest that the three copper-binding proteins analyzed here are copper resistance determinants in this extremophile and contribute to the high-level metal resistance of this industrially important biomining bacterium. PMID:26637599

Effect of copper oxide concentration on the formation and persistency of environmentally persistent free radicals (EPFRs) in particulates.

PubMed

Kiruri, Lucy W; Khachatryan, Lavrent; Dellinger, Barry; Lomnicki, Slawo

2014-02-18

Environmentally persistent free radicals (EPFRs) are formed by the chemisorption of substituted aromatics on metal oxide surfaces in both combustion sources and superfund sites. The current study reports the dependency of EPFR yields and their persistency on metal loading in particles (0.25, 0.5, 0.75, 1, 2, and 5% CuO/silica). The EPFRs were generated through exposure of particles to three adsorbate vapors at 230 °C: phenol, 2-monochlorophenol (2-MCP), and dichlorobenzene (DCBz). Adsorption resulted in the formation of surface-bound phenoxyl- and semiquinoine-type radicals with characteristic EPR spectra displaying a g value ranging from ∼ 2.0037 to 2.006. The highest EPFR yield was observed for CuO concentrations between 1 and 3% in relation to MCP and phenol adsorption. However, radical density, which is expressed as the number of radicals per copper atom, was highest at 0.75-1% CuO loading. For 1,2-dichlorobenzene adsorption, radical concentration increased linearly with decreasing copper content. At the same time, a qualitative change in the radicals formed was observed--from semiquinone to chlorophenoxyl radicals. The two longest lifetimes, 25 and 23 h, were observed for phenoxyl-type radicals on 0.5% CuO and chlorophenoxyl-type radicals on 0.75% CuO, respectively.

Active-site copper reduction promotes substrate binding of fungal lytic polysaccharide monooxygenase and reduces stability.

PubMed

Kracher, Daniel; Andlar, Martina; Furtmüller, Paul G; Ludwig, Roland

2018-02-02

Lytic polysaccharide monooxygenases (LPMOs) are a class of copper-containing enzymes that oxidatively degrade insoluble plant polysaccharides and soluble oligosaccharides. Upon reductive activation, they cleave the substrate and promote biomass degradation by hydrolytic enzymes. In this study, we employed LPMO9C from Neurospora crassa , which is active toward cellulose and soluble β-glucans, to study the enzyme-substrate interaction and thermal stability. Binding studies showed that the reduction of the mononuclear active-site copper by ascorbic acid increased the affinity and the maximum binding capacity of LPMO for cellulose. The reduced redox state of the active-site copper and not the subsequent formation of the activated oxygen species increased the affinity toward cellulose. The lower affinity of oxidized LPMO could support its desorption after catalysis and allow hydrolases to access the cleavage site. It also suggests that the copper reduction is not necessarily performed in the substrate-bound state of LPMO. Differential scanning fluorimetry showed a stabilizing effect of the substrates cellulose and xyloglucan on the apparent transition midpoint temperature of the reduced, catalytically active enzyme. Oxidative auto-inactivation and destabilization were observed in the absence of a suitable substrate. Our data reveal the determinants of LPMO stability under turnover and non-turnover conditions and indicate that the reduction of the active-site copper initiates substrate binding. © 2018 by The American Society for Biochemistry and Molecular Biology, Inc.

Effects of an aged copper contamination on distribution of earthworms, reproduction and cocoon hatchability.

PubMed

Mirmonsef, Hassan; Hornum, Hanne D; Jensen, John; Holmstrup, Martin

2017-01-01

Contaminated soil is a problem throughout the industrialized world, and a significant proportion of these sites are polluted with heavy metals such as copper. Ecological risk assessment of contaminated sites requires ecotoxicological studies with spiked soils as well as in-situ ecological observations. Here, we report laboratory and field assessment of copper toxicity for earthworms at a Danish site (Hygum) exclusively contaminated with an increasing gradient in copper from background to highly toxic levels (>1000mgkg -1 dry soil). More specifically, we report effects on field populations, body contents of copper, hatching of earthworm cocoons and reproduction of the common species Aporrectodea tuberculata. Abundance of earthworms and cocoons decreased significantly from about 400-150m -2 along the gradient as the soil copper concentration increased from ca. 50 to ca. 1000mgkg -1 . At lower concentrations, the population was dominated by endogeic species, whereas at high concentrations the population was dominated by epigeic species. At high copper contents the internal concentration of copper was in the range 100-160mgkg -1 dry tissue. Despite the high internal copper contents, hatchability of field collected cocoons was not impaired in any species. The EC50 reproduction value of A. tuberculata was about 220mg copper kg -1 dry soil in the first two exposure periods, but nearly doubled in the third period suggesting that an acclimation response had occurred. Also in the laboratory reproduction test, cocoon hatchability was not reduced, but rather slightly stimulated by copper. Based on these results we discuss the possibility that acute exposure in laboratory experiments is more detrimental than exposure in a field situation, perhaps because increased tolerance may be acquired through natural selection and genetic adaptation through increased use of defense mechanisms such as metallothioneins. Further, we discuss that the rather high tissue copper level of earthworms from the Hygum site may have smaller effects in these free-ranging worms than it would have in acute-exposure laboratory tests because the copper is more efficiently sequestered and detoxified in the field situation where populations have been exposed for many generations. Copyright © 2016 Elsevier Inc. All rights reserved.

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.

Anisotropic Covalency Contributions to Superexchange Pathways in Type One Copper Active Sites

PubMed Central

2015-01-01

Type one (T1) Cu sites deliver electrons to catalytic Cu active sites: the mononuclear type two (T2) Cu site in nitrite reductases (NiRs) and the trinuclear Cu cluster in the multicopper oxidases (MCOs). The T1 Cu and the remote catalytic sites are connected via a Cys-His intramolecular electron-transfer (ET) bridge, which contains two potential ET pathways: P1 through the protein backbone and P2 through the H-bond between the Cys and the His. The high covalency of the T1 Cu–S(Cys) bond is shown here to activate the T1 Cu site for hole superexchange via occupied valence orbitals of the bridge. This covalency-activated electronic coupling (HDA) facilitates long-range ET through both pathways. These pathways can be selectively activated depending on the geometric and electronic structure of the T1 Cu site and thus the anisotropic covalency of the T1 Cu–S(Cys) bond. In NiRs, blue (π-type) T1 sites utilize P1 and green (σ-type) T1 sites utilize P2, with P2 being more efficient. Comparing the MCOs to NiRs, the second-sphere environment changes the conformation of the Cys-His pathway, which selectively activates HDA for superexchange by blue π sites for efficient turnover in catalysis. These studies show that a given protein bridge, here Cys-His, provides different superexchange pathways and electronic couplings depending on the anisotropic covalencies of the donor and acceptor metal sites. PMID:25310460

Trace copper measurements and electrical effects in LPE HgCdTe

NASA Astrophysics Data System (ADS)

Tower, J. P.; Tobin, S. P.; Norton, P. W.; Bollong, A. B.; Socha, A.; Tregilgas, J. H.; Ard, C. K.; Arlinghaus, H. F.

1996-08-01

Recent improvements in sputter initiated resonance ionization spectroscopy (SIRIS) have now made it possible to measure copper in HgCdTe films into the low 1013 cm-3 range. We have used this technique to show that copper is responsible for type conversion in n-type HgCdTe films. Good n-type LPE films were found to have less than 1 x 1014 cm-3 copper, while converted p-type samples were found to have copper concentrations approximately equal to the hole concentrations. Some compensated n-type samples with low mobilities have copper concentrations too low to account for the amount of compensation and the presence of a deep acceptor level is suggested. In order to study diffusion of copper from substrates into LPE layers, a CdTe boule was grown intentionally spiked with copper at approximately 3 x 1016 cm-3. Annealing HgCdTe films at 360°C was found to greatly increase the amount of copper that diffuses out of the substrates and a substrate screening technique was developed based on this phenomenon. SIRIS depth profiles showed much greater copper in HgCdTe films than in the substrates, indicating that copper is preferentially attracted to HgCdTe over Cd(Zn)Te. SIRIS spatial mapping showed that copper is concentrated in substrate tellurium inclusions 5 25 times greater than in the surrounding CdZnTe matrix.

In vitro and in vivo corrosion evaluation of nickel-chromium- and copper-aluminum-based alloys.

PubMed

Benatti, O F; Miranda, W G; Muench, A

2000-09-01

The low resistance to corrosion is the major problem related to the use of copper-aluminum alloys. This in vitro and in vivo study evaluated the corrosion of 2 copper-aluminum alloys (Cu-Al and Cu-Al-Zn) compared with a nickel-chromium alloy. For the in vitro test, specimens were immersed in the following 3 corrosion solutions: artificial saliva, 0.9% sodium chloride, and 1.0% sodium sulfide. For the in vivo test, specimens were embedded in complete dentures, so that one surface was left exposed. The 3 testing sites were (1) close to the oral mucosa (partial self-cleaning site), (2) surface exposed to the oral cavity (self-cleaning site), and (3) specimen bottom surface exposed to the saliva by means of a tunnel-shaped perforation (non-self-cleaning site). Almost no corrosion occurred with the nickel-chromium alloy, for either the in vitro or in vivo test. On the other hand, the 2 copper-aluminum-based alloys exhibited high corrosion in the sulfide solution. These same alloys also underwent high corrosion in non-self-cleaning sites for the in vivo test, although minimal attack was observed in self-cleaning sites. The nickel-chromium alloy presented high resistance to corrosion. Both copper-aluminum alloys showed considerable corrosion in the sulfide solution and clinically in the non-self-cleaning site. However, in self-cleaning sites these 2 alloys did not show substantial corrosion.

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.

LONG-TERM IMPACTS OF ORTHOPHOSPHATE TREATMENT ON COPPER

EPA Science Inventory

Laboratory, pilot, and field data collected support the theoretical "cupric hydroxide" copper solubility model. For the short time frames inherent in laboratory and pilot studies of copper solubility and in initial field monitoring for the LCR from Tier 1 soldered copper sites, c...

Lead and Copper Rule Tier Schedule

EPA Pesticide Factsheets

The Lead and Copper Rule Tier Schedule may be used by public water systems in Wyoming and on EPA R8 Tribal Lands as a guide to properly identify their lead and copper tap sample sites to comply with the Lead and Copper Rule.

The Phylogeny and Active Site Design of Eukaryotic Copper-only Superoxide Dismutases*

PubMed Central

Peterson, Ryan L.; Galaleldeen, Ahmad; Villarreal, Johanna; Taylor, Alexander B.; Cabelli, Diane E.; Hart, P. John; Culotta, Valeria C.

2016-01-01

In eukaryotes the bimetallic Cu/Zn superoxide dismutase (SOD) enzymes play important roles in the biology of reactive oxygen species by disproportionating superoxide anion. Recently, we reported that the fungal pathogen Candida albicans expresses a novel copper-only SOD, known as SOD5, that lacks the zinc cofactor and electrostatic loop (ESL) domain of Cu/Zn-SODs for substrate guidance. Despite these abnormalities, C. albicans SOD5 can disproportionate superoxide at rates limited only by diffusion. Here we demonstrate that this curious copper-only SOD occurs throughout the fungal kingdom as well as in phylogenetically distant oomycetes or “pseudofungi” species. It is the only form of extracellular SOD in fungi and oomycetes, in stark contrast to the extracellular Cu/Zn-SODs of plants and animals. Through structural biology and biochemical approaches we demonstrate that these copper-only SODs have evolved with a specialized active site consisting of two highly conserved residues equivalent to SOD5 Glu-110 and Asp-113. The equivalent positions are zinc binding ligands in Cu/Zn-SODs and have evolved in copper-only SODs to control catalysis and copper binding in lieu of zinc and the ESL. Similar to the zinc ion in Cu/Zn-SODs, SOD5 Glu-110 helps orient a key copper-coordinating histidine and extends the pH range of enzyme catalysis. SOD5 Asp-113 connects to the active site in a manner similar to that of the ESL in Cu/Zn-SODs and assists in copper cofactor binding. Copper-only SODs are virulence factors for certain fungal pathogens; thus this unique active site may be a target for future anti-fungal strategies. PMID:27535222

The Phylogeny and Active Site Design of Eukaryotic Copper-only Superoxide Dismutases

DOE PAGES

Peterson, Ryan L.; Galaleldeen, Ahmad; Villarreal, Johanna; ...

2016-08-17

In eukaryotes the bimetallic Cu/Zn superoxide dismutase (SOD) enzymes play important roles in the biology of reactive oxygen species by disproportionating superoxide anion. We reported that the fungal pathogen Candida albicans expresses a novel copper-only SOD, known as SOD5, that lacks the zinc cofactor and electrostatic loop (ESL) domain of Cu/Zn-SODs for substrate guidance. In spite of these abnormalities, C. albicans SOD5 can disproportionate superoxide at rates limited only by diffusion. Here we demonstrate that this curious copper-only SOD occurs throughout the fungal kingdom as well as in phylogenetically distant oomycetes or “pseudofungi” species. It is the only form ofmore » extracellular SOD in fungi and oomycetes, in stark contrast to the extracellular Cu/Zn-SODs of plants and animals. Through structural biology and biochemical approaches we demonstrate that these copper-only SODs have evolved with a specialized active site consisting of two highly conserved residues equivalent to SOD5 Glu-110 and Asp-113. The equivalent positions are zinc binding ligands in Cu/Zn-SODs and have evolved in copper-only SODs to control catalysis and copper binding in lieu of zinc and the ESL. Similar to the zinc ion in Cu/Zn-SODs, SOD5 Glu-110 helps orient a key copper-coordinating histidine and extends the pH range of enzyme catalysis. Furthermore, SOD5 Asp-113 connects to the active site in a manner similar to that of the ESL in Cu/Zn-SODs and assists in copper cofactor binding. Copper-only SODs are virulence factors for certain fungal pathogens; thus this unique active site may be a target for future anti-fungal strategies.« less

Long distance electron-transfer mechanism in peptidylglycine alpha-hydroxylating monooxygenase: a perfect fitting for a water bridge.

PubMed

de la Lande, Aurélien; Martí, Sergio; Parisel, Olivier; Moliner, Vicent

2007-09-26

The active sites of copper enzymes have been the subject of many theoretical and experimental investigations from a number of years. Such studies have embraced topics devoted to the modeling of the first coordination sphere at the metallic cations up to the development of biomimetic, or bioinspired, catalytic systems. At least from the theoretical viewpoint, fewer efforts have been dedicated to elucidate how the two copper cations act concertedly in noncoupled dicopper enzymes such as peptidylglycine alpha-hydroxylating monooxygenase (PHM) and dopamine beta-monooxygenase (DbetaM). In these metalloenzymes, an electronic transfer is assumed between the two distant copper cations (11 A). Recent experimental results suggest that this transfer occurs through water molecules, a phenomenon which has been theoretically evidenced to be of high efficiency in the case of cytochrome b5 (Science, 2005, 310, 1311). In the present contribution dedicated to PHM, we overpass the common theoretical approaches dedicated to the electronic and geometrical structures of sites CuM or CuH restricted to their first coordination spheres and aim at directly comparing theoretical results to the experimentally measured activity of the PHM enzyme. To achieve this goal, molecular dynamics simulations were performed on wild-type and various mutants of PHM. More precisely, we provide an estimate of the electron-transfer efficiency between the CuM and CuH sites by means of such molecular dynamics simulations coupled to Marcus theory joined to the Beratan model to approximate the required coupling matrix elements. The theoretical results are compared to the kinetics measurements performed on wild and mutated PHM. The present work, the dynamic aspects of which are essential, accounts for the experimental results issued from mutagenesis. It supports the conclusion that an electronic transfer can occur between two copper(I) sites along a bridge involving a set of hydrogen and chemical bonds. Residue Gln170 is evidenced to be the keystone of this water-mediated pathway.

Four second-sphere residues of Thermus thermophilus SG0.5JP17-16 laccase tune the catalysis by hydrogen-bonding networks.

PubMed

Liu, Huiping; Zhu, Yanyun; Yang, Xiaorong; Lin, Ying

2018-05-01

The multicopper oxidases catalyze 1-electron oxidation of four substrate molecules and concomitantly 4-electron reduction of dioxygen to water. The substrate loses the electrons at the type 1 copper (T1 Cu) site of the enzyme, while the dioxygen is reduced to water at the trinuclear copper center. A highly conserved Glu residue, which is at the dioxygen-entering channel, shuttles the proton to break the O-O bond of dioxygen. At the water-leaving channel, an Asp residue was found to be important in the protonation mechanism. In this study, laccase from Thermus thermophilus SG0.5JP17-16 (lacTT) was investigated to address how four second-sphere residues E356, E456, D106, and D423 affect the activity of the enzyme. Kinetic data indicate that catalytic activities of the enzyme are altered by site-directed mutagenesis on four second-sphere residues. The structural model of lacTT was generated by homology modeling. Structural and spectral data indicate that the E356 residue is situated at the substrate-binding site, responsible for the binding of the substrate and the geometry of the T1 Cu site by hydrogen-bonding networks; the E456 residue, located at the dioxygen-entering channel, plays a critical role in stabilizing the structure of all active copper centers and shuttling the proton to the trinuclear copper cluster (TNC) for the reductive reaction of dioxygen; the D106 and D423 residues are at the water-leaving channel, and they are important for the essential geometry of the TNC and the release of the water molecules. Altogether, this study contributes to the further understanding of the basic mechanism involving the oxidation of the substrate, electron transfer, and the reduction of dioxygen in lacTT.

An Expanding Range of Functions for the Copper Chaperone/Antioxidant Protein Atox1

PubMed Central

Hatori, Yuta

2013-01-01

Abstract Significance: Antioxidant protein 1 (Atox1 in human cells) is a copper chaperone for the copper export pathway with an essential role in cellular copper distribution. In vitro, Atox1 binds and transfers copper to the copper-transporting ATPases, stimulating their catalytic activity. Inactivation of Atox1 in cells inhibits maturation of secreted cuproenzymes as well as copper export from cells. Recent Advances: Accumulating data suggest that cellular functions of Atox1 are not limited to its copper-trafficking role and may include storage of labile copper, modulation of transcription, and antioxidant defense. The conserved metal binding site of Atox1, CxGC, differs from the metal-binding sites of copper-transporting ATPases and has a physiologically relevant redox potential that equilibrates with the GSH:GSSG pair. Critical Issues: Tight relationship appears to exist between intracellular copper levels and glutathione (GSH) homeostasis. The biochemical properties of Atox1 place it at the intersection of cellular networks that regulate copper distribution and cellular redox balance. Mechanisms through which Atox1 facilitates copper export and contributes to oxidative defense are not fully understood. Future Directions: The current picture of cellular redox homeostasis and copper physiology will be enhanced by further mechanistic studies of functional interactions between the GSH:GSSG pair and copper-trafficking machinery. Antioxid. Redox Signal. 19, 945–957. PMID:23249252

Copper Tolerance and Characterization of a Copper-Responsive Operon, copYAZ, in an M1T1 Clinical Strain of Streptococcus pyogenes

PubMed Central

Gordon, Lily D.; Fang, Zhong; Holder, Robert C.; Reid, Sean D.

2015-01-01

ABSTRACT Infection with Streptococcus pyogenes is associated with a breadth of clinical manifestations ranging from mild pharyngitis to severe necrotizing fasciitis. Elevated levels of intracellular copper are highly toxic to this bacterium, and thus, the microbe must tightly regulate the level of this metal ion by one or more mechanisms, which have, to date, not been clearly defined. In this study, we have identified two virulence mechanisms by which S. pyogenes protects itself against copper toxicity. We defined a set of putative genes, copY (for a regulator), copA (for a P1-type ATPase), and copZ (for a copper chaperone), whose expression is regulated by copper. Our results indicate that these genes are highly conserved among a range of clinical S. pyogenes isolates. The copY, copA, and copZ genes are induced by copper and are transcribed as a single unit. Heterologous expression assays revealed that S. pyogenes CopA can confer copper tolerance in a copper-sensitive Escherichia coli mutant by preventing the accumulation of toxic levels of copper, a finding that is consistent with a role for CopA in copper export. Evaluation of the effect of copper stress on S. pyogenes in a planktonic or biofilm state revealed that biofilms may aid in protection during initial exposure to copper. However, copper stress appears to prevent the shift from the planktonic to the biofilm state. Therefore, our results indicate that S. pyogenes may use several virulence mechanisms, including altered gene expression and a transition to and from planktonic and biofilm states, to promote survival during copper stress. IMPORTANCE Bacterial pathogens encounter multiple stressors at the host-pathogen interface. This study evaluates a virulence mechanism(s) utilized by S. pyogenes to combat copper at sites of infection. A better understanding of pathogen tolerance to stressors such as copper is necessary to determine how host-pathogen interactions impact bacterial survival during infections. These insights may lead to the identification of novel therapeutic targets that can be used to address antibiotic resistance. PMID:26013489

Copper Tolerance and Characterization of a Copper-Responsive Operon, copYAZ, in an M1T1 Clinical Strain of Streptococcus pyogenes.

PubMed

Young, Christie A; Gordon, Lily D; Fang, Zhong; Holder, Robert C; Reid, Sean D

2015-08-01

Infection with Streptococcus pyogenes is associated with a breadth of clinical manifestations ranging from mild pharyngitis to severe necrotizing fasciitis. Elevated levels of intracellular copper are highly toxic to this bacterium, and thus, the microbe must tightly regulate the level of this metal ion by one or more mechanisms, which have, to date, not been clearly defined. In this study, we have identified two virulence mechanisms by which S. pyogenes protects itself against copper toxicity. We defined a set of putative genes, copY (for a regulator), copA (for a P1-type ATPase), and copZ (for a copper chaperone), whose expression is regulated by copper. Our results indicate that these genes are highly conserved among a range of clinical S. pyogenes isolates. The copY, copA, and copZ genes are induced by copper and are transcribed as a single unit. Heterologous expression assays revealed that S. pyogenes CopA can confer copper tolerance in a copper-sensitive Escherichia coli mutant by preventing the accumulation of toxic levels of copper, a finding that is consistent with a role for CopA in copper export. Evaluation of the effect of copper stress on S. pyogenes in a planktonic or biofilm state revealed that biofilms may aid in protection during initial exposure to copper. However, copper stress appears to prevent the shift from the planktonic to the biofilm state. Therefore, our results indicate that S. pyogenes may use several virulence mechanisms, including altered gene expression and a transition to and from planktonic and biofilm states, to promote survival during copper stress. Bacterial pathogens encounter multiple stressors at the host-pathogen interface. This study evaluates a virulence mechanism(s) utilized by S. pyogenes to combat copper at sites of infection. A better understanding of pathogen tolerance to stressors such as copper is necessary to determine how host-pathogen interactions impact bacterial survival during infections. These insights may lead to the identification of novel therapeutic targets that can be used to address antibiotic resistance. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

LONG-TERM IMPACTS OF ORTHOPHOSPHATE TREATMENT ON COPPER LEVELS - PRESENTATION

EPA Science Inventory

Laboratory, pilot, and field data collected support the theoretical "cupric hydroxide" copper solubility model. For the short time frames inherent in laboratory and pilot studies of copper solubility and in initial field monitoring for the LCR from Tier 1 soldered copper sites, c...

Long-Term Effects of Orthophosphate Treatment on Copper Concentration

EPA Science Inventory

Laboratory, pilot, and field data collected support the theoretical “cupric hydroxide” copper solubility model. For the short time frames inherent in laboratory and pilot studies of copper solubility, and in initial field monitoring for the LCR from Tier 1 soldered copper sites,...

LONG-TERM IMPACTS OF ORTHOPHOSPHATE TREATMENT ON COPPER LEVELS

EPA Science Inventory

Laboratory, pilot, and field data collected support the theoretical “cupric hydroxide” copper solubility model. For the short time frames inherent in laboratory and pilot studies of copper solubility and in initial field monitoring for the LCR from Tier 1 soldered copper sites,...

In vitro release of cupric ion from intrauterine devices: influence of frame, shape, copper surface area and indomethacin.

PubMed

Zhang, Shuangshuang; Li, Ying; Yu, Panpan; Chen, Tong; Zhou, Weisai; Zhang, Wenli; Liu, Jianping

2015-02-01

The release of cupric ion from copper intrauterine device (Cu-IUD) in human uterus is essential for contraception. However, excessive cupric ion will cause cytotoxic effect. In this paper, we investigated the influence of device characteristics (frame, copper surface area, shape, copper type and indomethacin) on copper release for the efficacy and adverse effects vary with IUD types which may correlate to their different release behaviors. Nine types of Cu-IUDs were selected and incubated in simulated uterine fluid. They were paired for comparison based on the device properties and the release of cupric ion was determined by flame atomic absorption spectrometer for about 160 days. The result showed that there was a burst release during the first month and the release rate tends to slow down and become steady afterwards. In addition, the copper release was mainly influenced by frame, indomethacin and copper type (copper wire and copper sleeve) while the shape variation had little effect on copper release throughout the experiment. Moreover, the influence of copper surface area was only noticeable during the first month. These findings were seldom reported before and may provide some useful information for the design of Cu-IUDs.

Copper Hazards to Fish, Wildlife, and Invertebrates: A Synoptic Review.

DTIC Science & Technology

1998-01-01

species; Brazil; November 1989; whole Alga, Ascophyllum nodosum England; polluted bay vs. reference site Norway; polluted fjord vs. reference site...concentra- tions of copper are sometimes fatal to ducklings (Wood and Worden 1973) and livestock when fed for extended periods. Domestic sheep ...is widely used in veterinary clinics in medical products (Roncero et al. 1992). Copper sulfate is used by veterinarians to treat cattle and sheep

A Study on the Thermomechanical Reliability Risks of Through-Silicon-Vias in Sensor Applications

PubMed Central

Shao, Shuai; Liu, Dapeng; Niu, Yuling; O’Donnell, Kathy; Sengupta, Dipak; Park, Seungbae

2017-01-01

Reliability risks for two different types of through-silicon-vias (TSVs) are discussed in this paper. The first is a partially-filled copper TSV, if which the copper layer covers the side walls and bottom. A polymer is used to fill the rest of the cavity. Stresses in risk sites are studied and ranked for this TSV structure by FEA modeling. Parametric studies for material properties (modulus and thermal expansion) of TSV polymer are performed. The second type is a high aspect ratio TSV filled by polycrystalline silicon (poly Si). Potential risks of the voids in the poly Si due to filling defects are studied. Fracture mechanics methods are utilized to evaluate the risk for two different assembly conditions: package assembled to printed circuit board (PCB) and package assembled to flexible substrate. The effect of board/substrate/die thickness and the size and location of the void are discussed. PMID:28208758

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

Cytoplasmic CopZ-Like Protein and Periplasmic Rusticyanin and AcoP Proteins as Possible Copper Resistance Determinants in Acidithiobacillus ferrooxidans ATCC 23270.

PubMed

Navarro, Claudio A; von Bernath, Diego; Martínez-Bussenius, Cristóbal; Castillo, Rodrigo A; Jerez, Carlos A

2016-02-15

Acidophilic organisms, such as Acidithiobacillus ferrooxidans, possess high-level resistance to copper and other metals. A. ferrooxidans contains canonical copper resistance determinants present in other bacteria, such as CopA ATPases and RND efflux pumps, but these components do not entirely explain its high metal tolerance. The aim of this study was to find other possible copper resistance determinants in this bacterium. Transcriptional expression of A. ferrooxidans genes coding for a cytoplasmic CopZ-like copper-binding chaperone and the periplasmic copper-binding proteins rusticyanin and AcoP, which form part of an iron-oxidizing supercomplex, was found to increase when the microorganism was grown in the presence of copper. All of these proteins conferred more resistance to copper when expressed heterologously in a copper-sensitive Escherichia coli strain. This effect was absent when site-directed-mutation mutants of these proteins with altered copper-binding sites were used in this metal sensitivity assay. These results strongly suggest that the three copper-binding proteins analyzed here are copper resistance determinants in this extremophile and contribute to the high-level metal resistance of this industrially important biomining bacterium. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

Ionic Diffusion in Cu6PS5Br Studied by 63Cu NMR

NASA Astrophysics Data System (ADS)

Ohki, H.; Harazono, K.; Erata, T.; Tasaki, A.; Ikeda, R.

1993-10-01

Applying 63Cu NMR technique, we observed exchange between the nonequivalent copper sites in crystalline Cu6PS5Br, known as a member of the mineral "argyrodite". Below 200 K, where the motion of the copper (I) ion is slow, we could distinguish several nonequivalent copper sites. On increasing the temperature, the chemical exchange between the nonequivalent cation sites was seen on the 63Cu NMR spectra. We could determine the activation energy for this motion to be 35 kJ mol-1 , in good agreement with the published ionic conductivity.

Binding of copper to lysozyme: Spectroscopic, isothermal titration calorimetry and molecular docking studies

NASA Astrophysics Data System (ADS)

Jing, Mingyang; Song, Wei; Liu, Rutao

2016-07-01

Although copper is essential to all living organisms, its potential toxicity to human health have aroused wide concerns. Previous studies have reported copper could alter physical properties of lysozyme. The direct binding of copper with lysozyme might induce the conformational and functional changes of lysozyme and then influence the body's resistance to bacterial attack. To better understand the potential toxicity and toxic mechanisms of copper, the interaction of copper with lysozyme was investigated by biophysical methods including multi-spectroscopic measurements, isothermal titration calorimetry (ITC), molecular docking study and enzyme activity assay. Multi-spectroscopic measurements proved that copper quenched the intrinsic fluorescence of lysozyme in a static process accompanied by complex formation and conformational changes. The ITC results indicated that the binding interaction was a spontaneous process with approximately three thermodynamical binding sites at 298 K and the hydrophobic force is the predominant driven force. The enzyme activity was obviously inhibited by the addition of copper with catalytic residues Glu 35 and Asp 52 locating at the binding sites. This study helps to elucidate the molecular mechanism of the interaction between copper and lysozyme and provides reference for toxicological studies of copper.

Evaluation of copper resistant bacteria from vineyard soils and mining waste for copper biosorption

PubMed Central

Andreazza, R.; Pieniz, S.; Okeke, B.C.; Camargo, F.A.O

2011-01-01

Vineyard soils are frequently polluted with high concentrations of copper due application of copper sulfate in order to control fungal diseases. Bioremediation is an efficient process for the treatment of contaminated sites. Efficient copper sorption bacteria can be used for bioremoval of copper from contaminated sites. In this study, a total of 106 copper resistant bacteria were examined for resistance to copper toxicity and biosorption of copper. Eighty isolates (45 from vineyard Mollisol, 35 from Inceptisol) were obtained from EMBRAPA (Empresa Brasileira de Pesquisa Agropecuária) experimental station, Bento Gonçalves, RS, Brazil (29°09′53.92″S and 51°31′39.40″W) and 26 were obtained from copper mining waste from Caçapava do Sul, RS, Brazil (30°29′43.48″S and 53′32′37.87W). Based on resistance to copper toxicity and biosorption, 15 isolates were identified by 16S rRNA gene sequencing. Maximal copper resistance and biosorption at high copper concentration were observed with isolate N2 which removed 80 mg L−1 in 24 h. Contrarily isolate N11 (Bacillus pumilus) displayed the highest specific copper biosorption (121.82 mg/L/OD unit in 24 h). GenBank MEGABLAST analysis revealed that isolate N2 is 99% similar to Staphylococcus pasteuri. Results indicate that several of our isolates have potential use for bioremediation treatment of vineyards soils and mining waste contaminated with high copper concentration. PMID:24031606

Temporal assessment of copper speciation, bioavailability and toxicity in UK freshwaters using chemical equilibrium and biotic ligand models: Implications for compliance with copper environmental quality standards.

PubMed

Lathouri, Maria; Korre, Anna

2015-12-15

Although significant progress has been made in understanding how environmental factors modify the speciation, bioavailability and toxicity of metals such as copper in aquatic environments, the current methods used to establish water quality standards do not necessarily consider the different geological and geochemical characteristics of a given site and the factors that affect copper fate, bioavailability potential and toxicity. In addition, the temporal variation in the concentration and bioavailable metal fraction is also important in freshwater systems. The work presented in this paper illustrates the temporal and seasonal variability of a range of water quality parameters, and Cu speciation, bioavailability and toxicity at four freshwaters sites in the UK. Rivers Coquet, Cree, Lower Clyde and Eden (Kent) were selected to cover a broad range of different geochemical environments and site characteristics. The monitoring data used covered a period of around six years at almost monthly intervals. Chemical equilibrium modelling was used to study temporal variations in Cu speciation and was combined with acute toxicity modelling to assess Cu bioavailability for two aquatic species, Daphnia magna and Daphnia pulex. The estimated copper bioavailability, toxicity levels and the corresponding ecosystem risks were analysed in relation to key water quality parameters (alkalinity, pH and DOC). Although copper concentrations did not vary much during the sampling period or between the seasons at the different sites; copper bioavailability varied markedly. In addition, through the chronic-Cu BLM-based on the voluntary risk assessment approach, the potential environmental risk in terms of the chronic toxicity was assessed. A much higher likelihood of toxicity effects was found during the cold period at all sites. It is suggested that besides the metal (copper) concentration in the surface water environment, the variability and seasonality of other important water quality parameters should be considered in setting appropriately protective environmental quality standards for metals. Copyright © 2015 Elsevier B.V. All rights reserved.

The N-terminus of the human copper transporter 1 (hCTR1) is localized extracellularly, and interacts with itself.

PubMed Central

Klomp, Adriana E M; Juijn, Jenneke A; van der Gun, Linda T M; van den Berg, Inge E T; Berger, Ruud; Klomp, Leo W J

2003-01-01

We have used indirect immunofluorescense studies and glycosylation-site insertion and deletion mapping to characterize the topology of human copper transporter 1 (hCTR1), the putative human high-affinity copper-import protein. Both approaches indicated that hCTR1 contains three transmembrane domains and that the N-terminus of hCTR1, which contains several putative copper-binding sites, is localized extracellularly, whereas the C-terminus is exposed to the cytosol. Based on previous observations that CTR1 proteins form high-molecular-mass complexes, we investigated directly whether CTR1 proteins interact with themselves. Yeast two-hybrid studies showed that interaction of yeast, mouse, rat and human CTR1 occurs at the sites of their N-terminal domains, and is not dependent on the copper concentration in the growth media. Analysis of deletion constructs indicated that multiple regions in the N-terminus are essential for this self-interaction. In contrast, the N-terminal tail of the presumed low-affinity copper transporter, hCTR2, does not interact with itself. Taken together, these results suggest that CTR1 spans the membrane at least six times, permitting formation of a channel, which is consistent with its proposed role as a copper transporter. PMID:12466020

Determination of the Bridging Ligand in the Active Site of Tyrosinase.

PubMed

Zou, Congming; Huang, Wei; Zhao, Gaokun; Wan, Xiao; Hu, Xiaodong; Jin, Yan; Li, Junying; Liu, Junjun

2017-10-28

Tyrosinase is a type-3 copper enzyme that is widely distributed in plants, fungi, insects, and mammals. Developing high potent inhibitors against tyrosinase is of great interest in diverse fields including tobacco curing, food processing, bio-insecticides development, cosmetic development, and human healthcare-related research. In the crystal structure of Agaricus bisporus mushroom tyrosinase, there is an oxygen atom bridging the two copper ions in the active site. It is unclear whether the identity of this bridging oxygen is a water molecule or a hydroxide anion. In the present study, we theoretically determine the identity of this critical bridging oxygen by performing first-principles hybrid quantum mechanics/molecular mechanics/Poisson-Boltzmann-surface area (QM/MM-PBSA) calculations along with a thermodynamic cycle that aim to improve the accuracy. Our results show that the binding with water molecule is energy favored and the QM/MM-optimized structure is very close to the crystal structure, whereas the binding with hydroxide anions causes the increase of energy and significant structural changes of the active site, indicating that the identity of the bridging oxygen must be a water molecule rather than a hydroxide anion. The different binding behavior between water and hydroxide anions may explain why molecules with a carboxyl group or too many negative charges have lower inhibitory activity. In light of this, the design of high potent active inhibitors against tyrosinase should satisfy both the affinity to the copper ions and the charge neutrality of the entire molecule.

Host and Pathogen Copper-Transporting P-Type ATPases Function Antagonistically during Salmonella Infection.

PubMed

Ladomersky, Erik; Khan, Aslam; Shanbhag, Vinit; Cavet, Jennifer S; Chan, Jefferson; Weisman, Gary A; Petris, Michael J

2017-09-01

Copper is an essential yet potentially toxic trace element that is required by all aerobic organisms. A key regulator of copper homeostasis in mammalian cells is the copper-transporting P-type ATPase ATP7A, which mediates copper transport from the cytoplasm into the secretory pathway, as well as copper export across the plasma membrane. Previous studies have shown that ATP7A-dependent copper transport is required for killing phagocytosed Escherichia coli in a cultured macrophage cell line. In this investigation, we expanded on these studies by generating Atp7a LysMcre mice, in which the Atp7a gene was specifically deleted in cells of the myeloid lineage, including macrophages. Primary macrophages isolated from Atp7a LysMcre mice exhibit decreased copper transport into phagosomal compartments and a reduced ability to kill Salmonella enterica serovar Typhimurium compared to that of macrophages isolated from wild-type mice. The Atp7a LysMcre mice were also more susceptible to systemic infection by S Typhimurium than wild-type mice. Deletion of the S Typhimurium copper exporters, CopA and GolT, was found to decrease infection in wild-type mice but not in the Atp7a LysMcre mice. These studies suggest that ATP7A-dependent copper transport into the phagosome mediates host defense against S Typhimurium, which is counteracted by copper export from the bacteria via CopA and GolT. These findings reveal unique and opposing functions for copper transporters of the host and pathogen during infection. Copyright © 2017 American Society for Microbiology.

Structural evidence for a copper-bound carbonate intermediate in the peroxidase and dismutase activities of superoxide dismutase.

PubMed

Strange, Richard W; Hough, Michael A; Antonyuk, Svetlana V; Hasnain, S Samar

2012-01-01

Copper-zinc superoxide dismutase (SOD) is of fundamental importance to our understanding of oxidative damage. Its primary function is catalysing the dismutation of superoxide to O(2) and H(2)O(2). SOD also reacts with H(2)O(2), leading to the formation of a strong copper-bound oxidant species that can either inactivate the enzyme or oxidise other substrates. In the presence of bicarbonate (or CO(2)) and H(2)O(2), this peroxidase activity is enhanced and produces the carbonate radical. This freely diffusible reactive oxygen species is proposed as the agent for oxidation of large substrates that are too bulky to enter the active site. Here, we provide direct structural evidence, from a 2.15 Å resolution crystal structure, of (bi)carbonate captured at the active site of reduced SOD, consistent with the view that a bound carbonate intermediate could be formed, producing a diffusible carbonate radical upon reoxidation of copper. The bound carbonate blocks direct access of substrates to Cu(I), suggesting that an adjunct to the accepted mechanism of SOD catalysed dismutation of superoxide operates, with Cu(I) oxidation by superoxide being driven via a proton-coupled electron transfer mechanism involving the bound carbonate rather than the solvent. Carbonate is captured in a different site when SOD is oxidised, being located in the active site channel adjacent to the catalytically important Arg143. This is the probable route of diffusion from the active site following reoxidation of the copper. In this position, the carbonate is poised for re-entry into the active site and binding to the reduced copper.

Structural Evidence for a Copper-Bound Carbonate Intermediate in the Peroxidase and Dismutase Activities of Superoxide Dismutase

PubMed Central

Strange, Richard W.; Hough, Michael A.; Antonyuk, Svetlana V.; Hasnain, S. Samar

2012-01-01

Copper-zinc superoxide dismutase (SOD) is of fundamental importance to our understanding of oxidative damage. Its primary function is catalysing the dismutation of superoxide to O2 and H2O2. SOD also reacts with H2O2, leading to the formation of a strong copper-bound oxidant species that can either inactivate the enzyme or oxidise other substrates. In the presence of bicarbonate (or CO2) and H2O2, this peroxidase activity is enhanced and produces the carbonate radical. This freely diffusible reactive oxygen species is proposed as the agent for oxidation of large substrates that are too bulky to enter the active site. Here, we provide direct structural evidence, from a 2.15 Å resolution crystal structure, of (bi)carbonate captured at the active site of reduced SOD, consistent with the view that a bound carbonate intermediate could be formed, producing a diffusible carbonate radical upon reoxidation of copper. The bound carbonate blocks direct access of substrates to Cu(I), suggesting that an adjunct to the accepted mechanism of SOD catalysed dismutation of superoxide operates, with Cu(I) oxidation by superoxide being driven via a proton-coupled electron transfer mechanism involving the bound carbonate rather than the solvent. Carbonate is captured in a different site when SOD is oxidised, being located in the active site channel adjacent to the catalytically important Arg143. This is the probable route of diffusion from the active site following reoxidation of the copper. In this position, the carbonate is poised for re-entry into the active site and binding to the reduced copper. PMID:22984565

Molecular Cloning and Characteristic Features of a Novel Extracellular Tyrosinase from Aspergillus niger PA2.

PubMed

Agarwal, Pragati; Singh, Jyoti; Singh, R P

2017-05-01

Aspergillus niger PA2, a novel strain isolated from waste effluents of food industry, is a potential extracellular tyrosinase producer. Enzyme activity and L-DOPA production were maximum when glucose and peptone were employed as C source and nitrogen source respectively in the medium and enhanced notably when the copper was supplemented, thus depicting the significance of copper in tyrosinase activity. Tyrosinase-encoding gene from the fungus was cloned, and amplification of the tyrosinase gene yielded a 1127-bp DNA fragment and 374 amino acid residue long product that encoded for a predicted protein of 42.3 kDa with an isoelectric point of 4.8. Primary sequence analysis of A. niger PA2 tyrosinase had shown that it had approximately 99% identity with that of A. niger CBS 513.88, which was further confirmed by phylogenetic analysis. The inferred amino acid sequence of A. niger tyrosinase contained two putative copper-binding sites comprising of six histidines, a characteristic feature for type-3 copper proteins, which were highly conserved in all tyrosinases throughout the Aspergillus species. When superimposed onto the tertiary structure of A. oryzae tyrosinase, the conserved residues from both the organisms occupied same spatial positions to provide a di-copper-binding peptide groove.

Copper in the sediment and sea surface microlayer near a fallowed, open-net fish farm.

PubMed

Loucks, Ronald H; Smith, Ruth E; Fisher, Clyde V; Fisher, E Brian

2012-09-01

Sediment and sea surface microlayer samples near an open-net salmon farm in Nova Scotia, were analysed for copper. Copper is a constituent of the feed and is an active ingredient of anti-foulants. The salmon farm was placed in fallow after 15 years of production. Sampling was pursued over 27 months. Elevated copper concentrations in the sediments indicated the farm site as a source. Bubble flotation due to gas-emitting sediments from eutrophication is a likely process for accumulating copper in the sea surface microlayer at enriched concentrations. Elevated and enriched concentrations in the sea surface microlayer over distance from the farm site led, as a result of wind-drift, to an enlarged farm footprint. The levels of copper in both sediments and sea surface microlayer exceeded guidelines for protection of marine life. Over the 27 months period, copper levels persisted in the sediments and decreased gradually in the sea surface microlayer. Copyright © 2012 Elsevier Ltd. All rights reserved.

Seasonal and spatial patterns of metals at a restored copper mine site. I. Stream copper and zinc

USGS Publications Warehouse

Bambic, D.G.; Alpers, Charles N.; Green, P.G.; Fanelli, E.; Silk, W.K.

2006-01-01

Seasonal and spatial variations in metal concentrations and pH were found in a stream at a restored copper mine site located near a massive sulfide deposit in the Foothill copper-zinc belt of the Sierra Nevada, California. At the mouth of the stream, copper concentrations increased and pH decreased with increased streamflow after the onset of winter rain and, unexpectedly, reached extreme values 1 or 2 months after peaks in the seasonal hydrographs. In contrast, aqueous zinc and sulfate concentrations were highest during low-flow periods. Spatial variation was assessed in 400 m of reach encompassing an acidic, metal-laden seep. At this seep, pH remained low (2-3) throughout the year, and copper concentrations were highest. In contrast, the zinc concentrations increased with downstream distance. These spatial patterns were caused by immobilization of copper by hydrous ferric oxides in benthic sediments, coupled with increasing downstream supply of zinc from groundwater seepage.

Surface-rain interactions: differences in copper runoff for copper sheet of different inclination, orientation, and atmospheric exposure conditions.

PubMed

Hedberg, Yolanda S; Goidanich, Sara; Herting, Gunilla; Wallinder, Inger Odnevall

2015-01-01

Predictions of the diffuse dispersion of metals from outdoor constructions such as roofs and facades are necessary for environmental risk assessment and management. An existing predictive model has been compared with measured data of copper runoff from copper sheets exposed at four different inclinations facing four orientations at two different urban sites (Stockholm, Sweden, and Milan, Italy) during a 4-year period. Its applicability has also been investigated for copper sheet exposed at two marine sites(Cadiz, Spain, for 5 years, and Brest, France, for 9 years). Generally the model can be used for all given conditions. However, vertical surfaces should be considered as surfaces inclined 60-80 due to wind driven effects. The most important parameters that influence copper runoff, and not already included in the model, are the wind and rain characteristics that influence the actual rainfall volume impinging the surface of interest.

c-Type Cytochrome Assembly Is a Key Target of Copper Toxicity within the Bacterial Periplasm

PubMed Central

Durand, Anne; Azzouzi, Asma; Bourbon, Marie-Line; Steunou, Anne-Soisig; Liotenberg, Sylviane; Maeshima, Akinori; Astier, Chantal; Argentini, Manuela; Saito, Shingo

2015-01-01

ABSTRACT In the absence of a tight control of copper entrance into cells, bacteria have evolved different systems to control copper concentration within the cytoplasm and the periplasm. Central to these systems, the Cu+ ATPase CopA plays a major role in copper tolerance and translocates copper from the cytoplasm to the periplasm. The fate of copper in the periplasm varies among species. Copper can be sequestered, oxidized, or released outside the cells. Here we describe the identification of CopI, a periplasmic protein present in many proteobacteria, and show its requirement for copper tolerance in Rubrivivax gelatinosus. The ΔcopI mutant is more susceptible to copper than the Cu+ ATPase copA mutant. CopI is induced by copper, localized in the periplasm and could bind copper. Interestingly, copper affects cytochrome c membrane complexes (cbb3 oxidase and photosystem) in both ΔcopI and copA-null mutants, but the causes are different. In the copA mutant, heme and chlorophyll synthesis are affected, whereas in ΔcopI mutant, the decrease is a consequence of impaired cytochrome c assembly. This impact on c-type cytochromes would contribute also to the copper toxicity in the periplasm of the wild-type cells when they are exposed to high copper concentrations. PMID:26396241

Biodiversity of rocky intertidal benthic communities associated with copper mine tailing discharges in northern Chile.

PubMed

Medina, M; Andrade, S; Faugeron, S; Lagos, N; Mella, D; Correa, J A

2005-04-01

Copper mine tailings have been discharged around the city of Chanaral, in northern Chile, for more than 60 years. This report summarizes a 17-month long monitoring study of species richness and biodiversity at five intertidal sites around the point of the tailing discharge. Total dissolved copper in sites close to the point of discharge varied between 8.72 microg/l and 34.15 microg/l, showing that there has not been a significant reduction since 1994. However, species richness has increased, suggesting a possible recovery of the system. While diversity of sessile organisms correlates negatively with dissolved copper, diversity of mobile invertebrates did not correlate with the metal concentration. To explain the observed results we discuss the role of algal turf interference on the distribution of mobile invertebrates at reference sites, a top-down effect caused by the absence of carnivores at impacted sites, and an avoidance strategy by some species to reduce their contact with contaminated seawater.

Trace elements and organic compounds in streambed sediment and aquatic biota from the Sacramento River Basin, California, October and November 1995

USGS Publications Warehouse

MacCoy, Dorene E.; Domagalski, Joseph L.

1999-01-01

Elevated levels of trace elements and hydrophobic organic compounds were detected in streambed sediments and aquatic biota [Asiatic clam (Corbicula fluminea) or bottom-feeding fish] of the Sacramento River Basin, California, during October and November 1995. Trace elements detected included cadmium, copper, mercury, lead, and zinc. Elevated levels of cadmium, copper, and zinc in the upper Sacramento River are attributed to a mining land use, and elevated levels of zinc and lead in an urban stream, and possibly in the lower Sacramento River, are attributed to urban runoff processes. Elevated levels of mercury in streambed sediment are attributed to either past mercury mining or to the use of mercury in past gold mining operations. Mercury mining was an important land use within the Coast Ranges in the past and gold mining was an important land use of the Sierra Nevada in the past. Mercury was the only trace element found in elevated levels in the tissue of aquatic biota, and those levels also could be attributed to either mining or urban runoff. Hydrophobic organic compounds also were detected in streambed sediments and aquatic biota. The most frequently detected compounds were DDT and its breakdown products, dieldrin, oxychlordane, and toxaphene. Differences were found in the types of compounds detected at agricultural sites and the urban site. Although both types of sites had measurable concentrations of DDT or its breakdown products, the urban site also had measurable concentrations of pesticides used for household pest control. Few semivolatile compounds were detected in the streambed sediments of any site. The semivolatile compound p-cresol, a coal-tar derivative associated with road maintenance, was found in the highest concentration.

Effect of Copper Oxide Concentration on the Formation and Persistency of Environmentally Persistent Free Radicals (EPFRs) in Particulates

PubMed Central

2015-01-01

Environmentally persistent free radicals (EPFRs) are formed by the chemisorption of substituted aromatics on metal oxide surfaces in both combustion sources and superfund sites. The current study reports the dependency of EPFR yields and their persistency on metal loading in particles (0.25, 0.5, 0.75, 1, 2, and 5% CuO/silica). The EPFRs were generated through exposure of particles to three adsorbate vapors at 230 °C: phenol, 2-monochlorophenol (2-MCP), and dichlorobenzene (DCBz). Adsorption resulted in the formation of surface-bound phenoxyl- and semiquinoine-type radicals with characteristic EPR spectra displaying a g value ranging from ∼2.0037 to 2.006. The highest EPFR yield was observed for CuO concentrations between 1 and 3% in relation to MCP and phenol adsorption. However, radical density, which is expressed as the number of radicals per copper atom, was highest at 0.75–1% CuO loading. For 1,2-dichlorobenzene adsorption, radical concentration increased linearly with decreasing copper content. At the same time, a qualitative change in the radicals formed was observed—from semiquinone to chlorophenoxyl radicals. The two longest lifetimes, 25 and 23 h, were observed for phenoxyl-type radicals on 0.5% CuO and chlorophenoxyl-type radicals on 0.75% CuO, respectively. PMID:24437381

Substitutions of PrP N-terminal histidine residues modulate scrapie disease pathogenesis and incubation time in transgenic mice

PubMed Central

Eigenbrod, Sabina; Frick, Petra; Bertsch, Uwe; Mitteregger-Kretzschmar, Gerda; Mielke, Janina; Maringer, Marko; Piening, Niklas; Hepp, Alexander; Daude, Nathalie; Windl, Otto; Levin, Johannes; Giese, Armin; Sakthivelu, Vignesh; Tatzelt, Jörg

2017-01-01

Prion diseases have been linked to impaired copper homeostasis and copper induced-oxidative damage to the brain. Divalent metal ions, such as Cu2+ and Zn2+, bind to cellular prion protein (PrPC) at octapeptide repeat (OR) and non-OR sites within the N-terminal half of the protein but information on the impact of such binding on conversion to the misfolded isoform often derives from studies using either OR and non-OR peptides or bacterially-expressed recombinant PrP. Here we created new transgenic mouse lines expressing PrP with disrupted copper binding sites within all four histidine-containing OR's (sites 1–4, H60G, H68G, H76G, H84G, "TetraH>G" allele) or at site 5 (composed of residues His-95 and His-110; "H95G" allele) and monitored the formation of misfolded PrP in vivo. Novel transgenic mice expressing PrP(TetraH>G) at levels comparable to wild-type (wt) controls were susceptible to mouse-adapted scrapie strain RML but showed significantly prolonged incubation times. In contrast, amino acid replacement at residue 95 accelerated disease progression in corresponding PrP(H95G) mice. Neuropathological lesions in terminally ill transgenic mice were similar to scrapie-infected wt controls, but less severe. The pattern of PrPSc deposition, however, was not synaptic as seen in wt animals, but instead dense globular plaque-like accumulations of PrPSc in TgPrP(TetraH>G) mice and diffuse PrPSc deposition in (TgPrP(H95G) mice), were observed throughout all brain sections. We conclude that OR and site 5 histidine substitutions have divergent phenotypic impacts and that cis interactions between the OR region and the site 5 region modulate pathogenic outcomes by affecting the PrP globular domain. PMID:29220360

Critical review: Copper runoff from outdoor copper surfaces at atmospheric conditions.

PubMed

Hedberg, Yolanda S; Hedberg, Jonas F; Herting, Gunilla; Goidanich, Sara; Odnevall Wallinder, Inger

2014-01-01

This review on copper runoff dispersed from unsheltered naturally patinated copper used for roofing and facades summarizes and discusses influencing factors, available literature, and predictive models, and the importance of fate and speciation for environmental risk assessment. Copper runoff from outdoor surfaces is predominantly governed by electrochemical and chemical reactions and is highly dependent on given exposure conditions (size, inclination, geometry, degree of sheltering, and orientation), surface parameters (age, patina composition, and thickness), and site-specific environmental conditions (gaseous pollutants, chlorides, rainfall characteristics (amount, intensity, pH), wind direction, temperature, time of wetness, season). The corrosion rate cannot be used to assess the runoff rate. The extent of released copper varies largely between different rain events and is related to dry and wet periods, dry deposition prior to the rain event and prevailing rain and patina characteristics. Interpretation and use of copper runoff data for environmental risk assessment and management need therefore to consider site-specific factors and focus on average data of long-term studies (several years). Risk assessments require furthermore that changes in copper speciation, bioavailability aspects, and potential irreversible retention on solid surfaces are considered, factors that determine the environmental fate of copper runoff from outdoor surfaces.

Talitrid amphipods (Crustacea) as biomonitors for copper and zinc

NASA Astrophysics Data System (ADS)

Rainbow, P. S.; Moore, P. G.; Watson, D.

1989-06-01

Data are presented on the copper and zinc concentrations of four talitrid amphipod species (standard dry weight 10 mg), i.e. Orchestia gammarellus (Pallas), O. mediterranea Costa, Talitrus saltator Montagu and Talorchestia deshayesii (Audouin), from 31 sites in S.W. Scotland, N. Wales and S.W. England. More limited data are also presented for cadmium in O. gammarellus (three sites) and T. deshayesii (one site). In S.W. Scotland, copper concentrations were raised significantly in O. gammarellus from Whithorn and Auchencairn (Solway) and Loch Long and Holy Loch (Clyde). In S.W. England, copper concentrations were highest at Restronguet Creek, Torpoint and Gannel (Cornwall). Samples of O. gammarellus from Islay (inner Hebrides) taken adjacent to the effluent outfalls of local whisky distilleries fell into two groups based on copper concentrations (presumably derived from copper stills), the higher copper levels deriving from the more productive distilleries. High copper levels were found in T. saltator and Tal. deshayesii from Dulas Bay (Wales). Zinc levels in O. gammarellus were high in Holy Loch and Auchencairn (Scotland), Gannel and Torpoint (England) but extremely elevated (as was Zn in O. mediterranea) at Restronguet Creek. Zinc was also high in T. saltator from Dulas Bay (Wales), but not in Tal. deshayesii. Cadmium levels in O. gammarellus from Kilve (Bristol Channel) were much raised. These differences (a) conform with expectations of elevated bioavailability of these metals from well researched areas (S.W. England & N. Wales), and (b) identify hitherto unappreciated areas of enrichment in S.W. Scotland. Orchestia gammarellus is put forward as a suitable biomonitor for copper and zinc in British coastal waters.

Geochemical Characteristics of TP3 Mine Wastes at the Elizabeth Copper Mine Superfund Site, Orange County, Vermont

USGS Publications Warehouse

Hammarstrom, Jane M.; Piatak, Nadine M.; Seal, Robert R.; Briggs, Paul H.; Meier, Allen L.; Muzik, Timothy L.

2003-01-01

Remediation of the Elizabeth mine Superfund site in the Vermont copper belt poses challenges for balancing environmental restoration goals with issues of historic preservation while adopting cost-effective strategies for site cleanup and long-term maintenance. The waste-rock pile known as TP3, at the headwaters of Copperas Brook, is especially noteworthy in this regard because it is the worst source of surface- and ground-water contamination identified to date, while also being the area of greatest historical significance. The U.S. Geological Survey (USGS) conducted a study of the historic mine-waste piles known as TP3 at the Elizabeth mine Superfund site near South Strafford, Orange County, VT. TP3 is a 12.3-acre (49,780 m2) subarea of the Elizabeth mine site. It is a focus area for historic preservation because it encompasses an early 19th century copperas works as well as waste from late 19th- and 20th century copper mining (Kierstead, 2001). Surface runoff and seeps from TP3 form the headwaters of Copperas Brook. The stream flows down a valley onto flotation tailings from 20th century copper mining operations and enters the West Branch of the Ompompanoosuc River approximately 1 kilometer downstream from the mine site. Shallow drinking water wells down gradient from TP3 exceed drinking water standards for copper and cadmium (Hathaway and others, 2001). The Elizabeth mine was listed as a Superfund site in 2001, mainly because of impacts of acid-mine drainage on the Ompompanoosuc River.

The metal-insulator transition in Fe(1.01-x)Cu(x)Se.

PubMed

Williams, A J; McQueen, T M; Ksenofontov, V; Felser, C; Cava, R J

2009-07-29

Iron selenide, Fe(1.01)Se, the layered parent compound of the recently discovered superconducting arsenide family, has previously been shown to be non-magnetic and superconducting with a critical temperature of 8 K. Here we show that copper can be substituted at the iron site in Fe(1.01)Se up to a solubility limit of 20-30%, after which a first-order transition to the three-dimensional CuFeSe(2) structure type is observed. As little as 1.5% copper is sufficient to suppress the superconductivity, and 4% drives the system through a metal-insulator transition. A local magnetic moment is introduced, which maximizes near 12% doping, where a spin-glass transition near 15 K is observed.

Synthesis and characterization of copper zinc oxide nanoparticles obtained via metathesis process

NASA Astrophysics Data System (ADS)

Phoohinkong, Weerachon; Foophow, Tita; Pecharapa, Wisanu

2017-09-01

Copper-doped zinc oxide nanoparticles were successfully synthesized by grinding copper acetate and zinc acetate powder with different starting molar ratios in combined with sodium hydroxide. The effect of initial copper and zinc molar ratios on the product samples was investigated and discussed. Relevant ligand coordination type of reactant acetate salt precursors and product samples were investigated by Fourier transform infrared spectroscopy (FTIR). The particle shapes and surface morphologies were characterized by field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). Phase structures of prepared samples were studied by x-ray powder diffraction (XRD) and x-ray absorption near-edge spectroscopy (XANES) was applied to investigate the local structure of Cu and Zn environment atoms. The results demonstrate that the, particle size of as-synthesized products affected by copper concentration in the precursor trend to gradually decreases from nanorod shape with diameter around 50-100 nm to irregular particle structure around 5 nm associated with an increase in the concentration of copper in precursor. Moreover, it is noticed that shape and morphology of the products are strongly dependent on Cu:Zn ratios during the synthesis. Nanocrystallines Cu-doped ZnO by the substitution in Zn site with a high crystallization degree of hexagonal wurtzite structure were obtained. This synthesis technique is suggested as a potential effective technique for preparing copper zinc oxide nanoparticles with various atomic ratio in wide range of applications. Contribution at the 4th Southeast Asia Conference on Thermoelectrics 2016 (SACT 2016), 15-18 December 2016, Da Nang City, Vietnam.

CopZ from Bacillus subtilis interacts in vivo with a copper exporting CPx-type ATPase CopA.

PubMed

Radford, David S; Kihlken, Margaret A; Borrelly, Gilles P M; Harwood, Colin R; Le Brun, Nick E; Cavet, Jennifer S

2003-03-14

The structure of the hypothetical copper-metallochaperone CopZ from Bacillus subtilis and its predicted partner CopA have been studied but their respective contributions to copper export, -import, -sequestration and -supply are unknown. DeltacopA was hypersensitive to copper and contained more copper atoms cell(-1) than wild-type. Expression from the copA operator-promoter increased in elevated copper (not other metals), consistent with a role in copper export. A bacterial two-hybrid assay revealed in vivo interaction between CopZ and the N-terminal domain of CopA but not that of a related transporter, YvgW, involved in cadmium-resistance. Activity of copper-requiring cytochrome caa(3) oxidase was retained in deltacopZ and deltacopA. DeltacopZ was only slightly copper-hypersensitive but deltacopZ/deltacopA was more sensitive than deltacopA, implying some action of CopZ that is independent of CopA. Significantly, deltacopZ contained fewer copper atoms cell(-1) than wild-type under these conditions. CopZ makes a net contribution to copper sequestration and/or recycling exceeding any donation to CopA for export.

The effect of iron and copper impurities on the wettability of sphalerite (110) surface.

PubMed

Simpson, Darren J; Bredow, Thomas; Chandra, Anand P; Cavallaro, Giuseppe P; Gerson, Andrea R

2011-07-15

The effect of impurities in the zinc sulfide mineral sphalerite on surface wettability has been investigated theoretically to shed light on previously reported conflicting results on sphalerite flotation. The effect of iron and copper impurities on the sphalerite (110) surface energy and on the water adsorption energy was calculated with the semi-empirical method modified symmetrically orthogonalized intermediate neglect of differential overlap (MSINDO) using the cyclic cluster model. The effect of impurities or dopants on surface energies is small but significant. The surface energy increases with increasing surface iron concentration while the opposite effect is reported for increasing copper concentration. The effect on adsorption energies is much more pronounced with water clearly preferring to adsorb on an iron site followed by a zinc site, and copper site least favorable. The theoretical results indicate that a sphalerite (110) surface containing iron is more hydrophilic than the undoped zinc sulfide surface. In agreement with the literature, the surface containing copper (either naturally or by activation) is more hydrophobic than the undoped surface. Copyright © 2011 Wiley Periodicals, Inc.

Bioaccumulation Using Surrogate Samplers (Bass): Evaluation Of A Passive Sampler As An Alternative Monitoring Tool For Environmental Contaminants At The Savannah River Site

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

Paller, M.; Knox, A.; Kuhne, W.

2015-10-15

DOE sites conduct traditional environmental monitoring programs that require collecting, processing, and analyzing water, sediment, and fish samples. However, recently developed passive sampling technologies, such as Diffusive Gradient in Thin films (DGT), may measure the chemical phases that are available and toxic to organisms (the bioavailable fraction), thereby producing more accurate and economical results than traditional methods.  Our laboratory study showed that dissolved copper concentrations measured by DGT probes were strongly correlated with the uptake of copper by Lumbriculus variegatus, an aquatic worm, and with concentrations of copper measured by conventional methods.  Dissolved copper concentrations in DGT probes increased with timemore » of exposure, paralleling the increase in copper with time that ocurred in Lumbriculus.  Additional studies with a combination of seven dissolved metals showed similar results.  These findings support the use of DGT as a biomimetic monitoring tool and provide a basis for refinement of these methods for cost-effective environmental monitoring at DOE sites.« less

Eukaryotic copper-only superoxide dismutases (SODs): A new class of SOD enzymes and SOD-like protein domains.

PubMed

Robinett, Natalie G; Peterson, Ryan L; Culotta, Valeria C

2018-03-30

The copper-containing superoxide dismutases (SODs) represent a large family of enzymes that participate in the metabolism of reactive oxygen species by disproportionating superoxide anion radical to oxygen and hydrogen peroxide. Catalysis is driven by the redox-active copper ion, and in most cases, SODs also harbor a zinc at the active site that enhances copper catalysis and stabilizes the protein. Such bimetallic Cu,Zn-SODs are widespread, from the periplasm of bacteria to virtually every organelle in the human cell. However, a new class of copper-containing SODs has recently emerged that function without zinc. These copper-only enzymes serve as extracellular SODs in specific bacteria ( i.e. Mycobacteria), throughout the fungal kingdom, and in the fungus-like oomycetes. The eukaryotic copper-only SODs are particularly unique in that they lack an electrostatic loop for substrate guidance and have an unusual open-access copper site, yet they can still react with superoxide at rates limited only by diffusion. Copper-only SOD sequences similar to those seen in fungi and oomycetes are also found in the animal kingdom, but rather than single-domain enzymes, they appear as tandem repeats in large polypeptides we refer to as CSRPs (copper-only SOD-repeat proteins). Here, we compare and contrast the Cu,Zn versus copper-only SODs and discuss the evolution of copper-only SOD protein domains in animals and fungi. © 2018 by The American Society for Biochemistry and Molecular Biology, Inc.

Ground-dwelling ant fauna of sites with high levels of copper.

PubMed

Diehl, E; Sanhudo, C E; Diehl-Fleig, Ed

2004-02-01

Richness and diversity of ant species are related to environmental factors such as vegetation, soil, presence of heavy metals, and insecticides, which allow the use of the assemblage members as terrestrial indicators of environmental conservation status. This study presents the results of ground ants surveyed in Minas do Camaquã in the municipality of Cacapava do Sul (Camaquã Basin), State of Rio Grande do Sul. Collections were performed in four sites, which high levels of copper in the soil, three of which--a mine, a liquid reject, and a solid reject-, had sparse or no plant cover, and one site where Pinus has been used for rehabilitation. Parque das Guaritas was the control site, since it presented normal levels of copper and a dense savanna cover. For each site, three transect lines extending 100 m were draw, and at each 10 m sardine baits were distributed; after two hours the ants present were collected. Hand collections in all five sites were performed during one hour (capture effort). A total of 51 species belonging to 17 genera were collected. The control site was the richest in ant species (r = 45). Sites with high level of copper and poor plant cover presented the lowest richness: mine (r = 14), solid reject (r = 15), and liquid reject (r = 16). In contrast, the site planted with Pinus presented an increment in richness (r = 24) of ground-dwelling ants, suggesting a reahabilitation process.

Laccase versus Laccase-Like Multi-Copper Oxidase: A Comparative Study of Similar Enzymes with Diverse Substrate Spectra

PubMed Central

Reiss, Renate; Ihssen, Julian; Richter, Michael; Eichhorn, Eric; Schilling, Boris; Thöny-Meyer, Linda

2013-01-01

Laccases (EC 1.10.3.2) are multi-copper oxidases that catalyse the one-electron oxidation of a broad range of compounds including substituted phenols, arylamines and aromatic thiols to the corresponding radicals. Owing to their broad substrate range, copper-containing laccases are versatile biocatalysts, capable of oxidizing numerous natural and non-natural industry-relevant compounds, with water as the sole by-product. In the present study, 10 of the 11 multi-copper oxidases, hitherto considered to be laccases, from fungi, plant and bacterial origin were compared. A substrate screen of 91 natural and non-natural compounds was recorded and revealed a fairly broad but distinctive substrate spectrum amongst the enzymes. Even though the enzymes share conserved active site residues we found that the substrate ranges of the individual enzymes varied considerably. The EC classification is based on the type of chemical reaction performed and the actual name of the enzyme often refers to the physiological substrate. However, for the enzymes studied in this work such classification is not feasible, even more so as their prime substrates or natural functions are mainly unknown. The classification of multi-copper oxidases assigned as laccases remains a challenge. For the sake of simplicity we propose to introduce the term “laccase-like multi-copper oxidase” (LMCO) in addition to the term laccase that we use exclusively for the enzyme originally identified from the sap of the lacquer tree Rhus vernicifera. PMID:23755261

Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol.

PubMed

Grundner, Sebastian; Markovits, Monica A C; Li, Guanna; Tromp, Moniek; Pidko, Evgeny A; Hensen, Emiel J M; Jentys, Andreas; Sanchez-Sanchez, Maricruz; Lercher, Johannes A

2015-06-25

Copper-exchanged zeolites with mordenite structure mimic the nuclearity and reactivity of active sites in particulate methane monooxygenase, which are enzymes able to selectively oxidize methane to methanol. Here we show that the mordenite micropores provide a perfect confined environment for the highly selective stabilization of trinuclear copper-oxo clusters that exhibit a high reactivity towards activation of carbon-hydrogen bonds in methane and its subsequent transformation to methanol. The similarity with the enzymatic systems is also implied from the similarity of the reversible rearrangements of the trinuclear clusters occurring during the selective transformations of methane along the reaction path towards methanol, in both the enzyme system and copper-exchanged mordenite.

A Robust Analytical Approach for the Identification of Specific Protein Carbonylation Sites: Metal-Catalyzed Oxidations of Human Serum Albumin

PubMed Central

Ugur, Zafer; Gronert, Scott

2017-01-01

The formation of protein carbonyls in the metal-catalyzed oxidation of human serum albumin (HSA) is characterized using a new analytical approach that involves tagging the modification site with multiple hydrazide reagents. Protein carbonyl formation at lysine and arginine residues was catalyzed with copper and iron ions, and the resulting oxidation patterns in HSA are contrasted. A total of 18 modification sites were identified with iron ion catalysis and 14 with copper ion catalysis. However, with the more stringent requirement of identification with at least two tagging reagents, the number of validated modification sites drops to 10 for iron and 9 for copper. Of the 14 total validated sites, there were only five in common for the two metal ions. The results illustrate the value of using multiple tagging agents and highlight the selective and specific nature of metal-catalyzed protein oxidations. PMID:28303033

Subsurface Oxygen in Oxide-Derived Copper Electrocatalysts for Carbon Dioxide Reduction

DOE PAGES

Eilert, Andre; Cavalca, Filippo; Roberts, F. Sloan; ...

2016-12-16

Copper electrocatalysts derived from an oxide have shown extraordinary electrochemical properties for the carbon dioxide reduction reaction (CO 2RR). Using in situ ambient pressure X-ray photoelectron spectroscopy and quasi in situ electron energy-loss spectroscopy in a transmission electron microscope, we show that there is a substantial amount of residual oxygen in nanostructured, oxide-derived copper electrocatalysts but no residual copper oxide. On the basis of these findings in combination with density functional theory simulations, we propose that residual subsurface oxygen changes the electronic structure of the catalyst and creates sites with higher carbon monoxide binding energy. If such sites are stablemore » under the strongly reducing conditions found in CO 2RR, these findings would explain the high efficiencies of oxide-derived copper in reducing carbon dioxide to multicarbon compounds such as ethylene.« less

Copper-catalyst-controlled site-selective allenylation of ketones and aldehydes with propargyl boronates.

PubMed

Fandrick, Keith R; Ogikubo, Junichi; Fandrick, Daniel R; Patel, Nitinchandra D; Saha, Jaideep; Lee, Heewon; Ma, Shengli; Grinberg, Nelu; Busacca, Carl A; Senanayake, Chris H

2013-03-15

A practical and highly site-selective copper-PhBPE-catalyst-controlled allenylation with propargyl boronates has been developed. The methodology has shown to be tolerant of diverse ketones and aldehydes providing the allenyl adducts in high selectivity. The BPE ligand and boronate substituents were shown to direct the site selectivity for which either propargyl or allenyl adducts can be acquired in high selectivity. A model is proposed that explains the origin of the site selectivity.

The delivery of copper for thylakoid import observed by NMR

PubMed Central

Banci, Lucia; Bertini, Ivano; Ciofi-Baffoni, Simone; Kandias, Nikolaos G.; Robinson, Nigel J.; Spyroulias, Georgios A.; Su, Xun-Cheng; Tottey, Stephen; Vanarotti, Murugendra

2006-01-01

The thylakoid compartments of plant chloroplasts are a vital destination for copper. Copper is needed to form holo-plastocyanin, which must shuttle electrons between photosystems to convert light into biologically useful chemical energy. Copper can bind tightly to proteins, so it has been hypothesized that copper partitions onto ligand-exchange pathways to reach intracellular locations without inflicting damage en route. The copper metallochaperone Atx1 of chloroplast-related cyanobacteria (ScAtx1) engages in bacterial two-hybrid interactions with N-terminal domains of copper-transporting ATPases CtaA (cell import) and PacS (thylakoid import). Here we visualize copper delivery. The N-terminal domain PacSN has a ferredoxin-like fold that forms copper-dependent heterodimers with ScAtx1. Removal of copper, by the addition of the cuprous-ion chelator bathocuproine disulfonate, disrupts this heterodimer, as shown from a reduction of the overall tumbling rate of the protein mixture. The NMR spectral changes of the heterodimer versus the separate proteins reveal that loops 1, 3, and 5 (the carboxyl tail) of the ScAtx1 Cu(I) site switch to an apo-like configuration in the heterodimer. NMR data (2JNH couplings in the imidazole ring of 15N ScAtx1 His-61) also show that His-61, bound to copper(I) in [Cu(I)ScAtx1]2, is not coordinated to copper in the heterodimer. A model for the PacSN/Cu(I)/ScAtx1 complex is presented. Contact with PacSN induces change to the ScAtx1 copper-coordination sphere that drives copper release for thylakoid import. These data also elaborate on the mechanism to keep copper(I) out of the ZiaAN ATPase zinc sites. PMID:16707580

Long-term trends of metal content and water quality in the Belaya River Basin

NASA Astrophysics Data System (ADS)

Fashchevskaia, Tatiana; Motovilov, Yuri

2017-04-01

The aim of this research is to identify the spatiotemporal regularities of iron, copper and zinc contents in the streams of the Belaya River basin. The Belaya River is situated in the South Ural region and it is one of the biggest tributary in the Volga River basin with catchment area of 142 000 km2. More than sixty years the diverse economic activities are carried out in the Belaya River basin, the intensity of this activity is characterized by high temporal variability. The leading industries in the region are metallurgy, oil production, petroleum processing, chemistry and petro chemistry, mechanical engineering, power industry. The dynamics of human activities in the catchment and intra and inter-annual changes in the water quality were analyzed for the period 1969-2007 years. Inter-annual dynamics of the metal content in the river waters was identified on the basis of the long-term hydrological monitoring statistics at the 32 sites. It was found that the dynamics of intensity of economic activities in the Belaya River basin was the cause statistically significant changes in the metal content of the river network. Statistically homogeneous time intervals have been set for each monitoring site. Within these time intervals there were obtained averaged reliable quantitative estimations of water quality. Calculations showed that the content of iron, copper and zinc did not change during the analyzed period at the sites, located in the mountain and foothill parts of the basin. At other sites, located on the plains areas of the Belaya River Basin and in the areas of functioning of large industrial facilities, metal content varies. A period of increased concentrations of metals is since the second half of 1970 until the end of the 1990s. From the end of 1990 to 2007 the average metal content for a long-term period in the river waters is reduced in comparison with the previous period: iron - to 7.4 times, copper - to 6.7 times, zinc - to 15 times. As a result, by the end of the test period the average long-term metal content in the river waters is: iron 0.07-1.21 mg/l, copper 0.9-7.0 μg/l, zinc 2,0-12.5 μg/l. Empirical probability distributions of iron, copper and zinc concentrations for various phases of the water regime in all investigated monitoring sites were approximated by Pearson type III curves and the average of the concentration values, the coefficient of variation and asymmetry, as well as the values of the concentrations of metal in the range of 1-95% of frequency were estimated. It was found that by the end of the test period, the average long-term concentrations for iron and copper exceed MAC for fishery use, for zinc become smaller MAC in many streams of Belaya River basin. The probability of exceeding the iron and copper content of MAC level increases during floods, the zinc content of MAC level increases during the winter low. Acknowledgements. The work was financially supported by the Russian Foundation for Basic Research (Grant 15-05-09022)

Molecular dynamics simulations of apocupredoxins: insights into the formation and stabilization of copper sites under entatic control.

PubMed

Abriata, Luciano A; Vila, Alejandro J; Dal Peraro, Matteo

2014-06-01

Cupredoxins perform copper-mediated long-range electron transfer (ET) in biological systems. Their copper-binding sites have evolved to force copper ions into ET-competent systems with decreased reorganization energy, increased reduction potential, and a distinct electronic structure compared with those of non-ET-competent copper complexes. The entatic or rack-induced state hypothesis explains these special properties in terms of the strain that the protein matrix exerts on the metal ions. This idea is supported by X-ray structures of apocupredoxins displaying "closed" arrangements of the copper ligands like those observed in the holoproteins; however, it implies completely buried copper-binding atoms, conflicting with the notion that they must be exposed for copper loading. On the other hand, a recent work based on NMR showed that the copper-binding regions of apocupredoxins are flexible in solution. We have explored five cupredoxins in their "closed" apo forms through molecular dynamics simulations. We observed that prearranged ligand conformations are not stable as the X-ray data suggest, although they do form part of the dynamic landscape of the apoproteins. This translates into variable flexibility of the copper-binding regions within a rigid fold, accompanied by fluctuations of the hydrogen bonds around the copper ligands. Major conformations with solvent-exposed copper-binding atoms could allow initial binding of the copper ions. An eventual subsequent incursion to the closed state would result in binding of the remaining ligands, trapping the closed conformation thanks to the additional binding energy and the fastening of noncovalent interactions that make up the rack.

Combined copper/zinc attachment to prion protein

NASA Astrophysics Data System (ADS)

Hodak, Miroslav; Bernholc, Jerry

2013-03-01

Misfolding of prion protein (PrP) is responsible for diseases such as ``mad-cow disease'' in cattle and Creutzfeldt-Jacob in humans. Extensive experimental investigation has established that this protein strongly interacts with copper ions, and this ability has been linked to its still unknown function. Attachment of other metal ions (zinc, iron, manganese) have been demonstrated as well, but none of them could outcompete copper. Recent finding, however, indicates that at intermediate concentrations both copper and zinc ions can attach to the PrP at the octarepeat region, which contains high affinity metal binding sites. Based on this evidence, we have performed density functional theory simulations to investigate the combined Cu/Zn attachment. We consider all previously reported binding modes of copper at the octarepeat region and examine a possibility simultaneous Cu/Zn attachment. We find that this can indeed occur for only one of the known binding sites, when copper changes its coordination mode to allow for attachment of zinc ion. The implications of the simultaneous attachment on neural function remain to be explored.

Typing mineral deposits using their associated rocks, grades and tonnages using a probabilistic neural network

USGS Publications Warehouse

Singer, D.A.

2006-01-01

A probabilistic neural network is employed to classify 1610 mineral deposits into 18 types using tonnage, average Cu, Mo, Ag, Au, Zn, and Pb grades, and six generalized rock types. The purpose is to examine whether neural networks might serve for integrating geoscience information available in large mineral databases to classify sites by deposit type. Successful classifications of 805 deposits not used in training - 87% with grouped porphyry copper deposits - and the nature of misclassifications demonstrate the power of probabilistic neural networks and the value of quantitative mineral-deposit models. The results also suggest that neural networks can classify deposits as well as experienced economic geologists. ?? International Association for Mathematical Geology 2006.

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.

Formation of copper precipitates in silicon

NASA Astrophysics Data System (ADS)

Flink, Christoph; Feick, Henning; McHugo, Scott A.; Mohammed, Amna; Seifert, Winfried; Hieslmair, Henry; Heiser, Thomas; Istratov, Andrei A.; Weber, Eicke R.

1999-12-01

The formation of copper precipitates in silicon was studied after high-temperature intentional contamination of p- and n-type FZ and Cz-grown silicon and quench to room temperature. With the Transient Ion Drift (TID) technique on p-type silicon a critical Fermi level position at EC-0.2 eV was found. Only if the Fermi level position, which is determined by the concentrations of the acceptors and the copper donors, surpasses this critical value precipitation takes place. If the Fermi level is below this level the supersaturated interstitial copper diffuses out. An electrostatic precipitation model is introduced that correlates the observed precipitation behavior with the electrical activity of the copper precipitates as detected with Deep Level Transient Spectroscopy (DLTS) on n-type and with Minority Carrier Transient Spectroscopy (MCTS) on p-type silicon.

Olympic Dam copper-uranium-gold deposit, South Australia

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

Lalor, J.H.

1986-07-01

The Olympic Dam copper-uranium-gold deposit was discovered in July 1975. It is located 650 km north-northwest of Adelaide on Roxby Downs Station in South Australia. The first diamond drill hole, RD1, intersected 38 m of 1.05% copper. A further eight holes were drilled with only marginal encouragement to November 1976, when RD10 cored 170 m of 2.12% copper and 0.06% of uranium oxide, thus confirming an economic discovery. The discovery of Olympic Dam is an excellent example applying broad-scale, scientifically based conceptual studies to area selection. Exploration management supported its exploration scientists in testing their ideas with stratigraphic drilling. Geologicmore » modeling, supported by geophysical interpretations and tectonic studies, was used to site the first hole. The discovery also illustrates the persistence required in mineral exploration. The deposit appears to be a new type of stratabound sediment-hosted ore. It has an areal extent exceeding 20 km/sup 2/ with vertical thicknesses of mineralization up to 350 m. It is estimated to contain more than 2000 million MT of mineralized material with an average grade of 1.6% copper, 0.06% uranium oxide, and 0.6 g/MT gold. The deposit occurs in middle Proterozoic basement beneath 350 m of unmineralized, flat upper Proterozoic sediments. The sediments comprising the local basement sequence are predominantly sedimentary breccias controlled by a northwest-trending graben.« less

Environmental concentrations of copper, chromium, and arsenic released from a chromated-copper-arsenate-(CCA-C-) treated wetland boardwalk

Treesearch

Stan T. Lebow; Daniel Foster

2005-01-01

A study was conducted to evaluate environmental accumulation and mobility of total copper, chromium, and arsenic adjacent to a chromated-copper-arsenate-(CCA-C-) treated wetland boardwalk. The study was considered a severe test because it included a large volume of treated wood in a site with high annual rainfall. Soil and sediment samples were collected before...

Insect prophenoloxidase: the view beyond immunity

PubMed Central

Lu, Anrui; Zhang, Qiaoli; Zhang, Jie; Yang, Bing; Wu, Kai; Xie, Wei; Luan, Yun-Xia; Ling, Erjun

2014-01-01

Insect prophenoloxidase (PPO) is an important innate immunity protein due to its involvement in cellular and humoral defense. It belongs to a group of type-3 copper-containing proteins that occurs in almost all organisms. Insect PPO has been studied for over a century, and the PPO activation cascade is becoming clearer. The insect PPO activation pathway incorporates several important proteins, including pattern-recognition receptors (PGRP, β GRP, and C-type lectins), serine proteases, and serine protease inhibitors (serpins). Due to their complexity, PPO activation mechanisms vary among insect species. Activated phenoloxidase (PO) oxidizes phenolic molecules to produce melanin around invading pathogens and wounds. The crystal structure of Manduca sexta PPO shows that a conserved amino acid, phenylalanine (F), can block the active site pocket. During activation, this blocker must be dislodged or even cleaved at the N-terminal sequence to expose the active site pockets and allow substrates to enter. Thanks to the crystal structure of M. sexta PPO, some domains and specific amino acids that affect PPO activities have been identified. Further studies of the relationship between PPO structure and enzyme activities will provide an opportunity to examine other type-3 copper proteins, and trace when and why their various physiological functions evolved. Recent researches show that insect PPO has a relationship with neuron activity, longevity, feces melanization (phytophagous insects) and development, which suggests that it is time for us to look back on insect PPO beyond the view of immunity in this review. PMID:25071597

Effect of the components' interface on the synthesis of methanol over Cu/ZnO from CO2/H2: a microkinetic analysis based on DFT + U calculations.

PubMed

Tang, Qian-Lin; Zou, Wen-Tian; Huang, Run-Kun; Wang, Qi; Duan, Xiao-Xuan

2015-03-21

The elucidation of chemical reactions occurring on composite systems (e.g., copper (Cu)/zincite (ZnO)) from first principles is a challenging task because of their very large sizes and complicated equilibrium geometries. By combining the density functional theory plus U (DFT + U) method with microkinetic modeling, the present study has investigated the role of the phase boundary in CO2 hydrogenation to methanol over Cu/ZnO. The absence of hydrogenation locations created by the interface between the two catalyst components was revealed based on the calculated turnover frequency under realistic conditions, in which the importance of interfacial copper to provide spillover hydrogen for remote Cu(111) sites was stressed. Coupled with the fact that methanol production on the binary catalyst was recently believed to predominantly involve the bulk metallic surface, the spillover of interface hydrogen atoms onto Cu(111) facets facilitates the production process. The cooperative influence of the two different kinds of copper sites can be rationalized applying the Brönsted-Evans-Polanyi (BEP) relationship and allows us to find that the catalytic activity of ZnO-supported Cu catalysts is of volcano type with decrease in the particle size. Our results here may have useful implications in the future design of new Cu/ZnO-based materials for CO2 transformation to methanol.

Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol

DOE PAGES

Grundner, Sebastian; Markovits, Monica A. C.; Li, Guanna; ...

2015-06-25

Copper-exchanged zeolites with mordenite structure mimic the nuclearity and reactivity of active sites in particulate methane monooxygenase, which are enzymes able to selectively oxidize methane to methanol. Here we show that the mordenite micropores provide a perfect confined environment for the highly selective stabilization of trinuclear copper-oxo clusters that exhibit a high reactivity towards activation of carbon–hydrogen bonds in methane and its subsequent transformation to methanol. In conclusion, the similarity with the enzymatic systems is also implied from the similarity of the reversible rearrangements of the trinuclear clusters occurring during the selective transformations of methane along the reaction path towardsmore » methanol, in both the enzyme system and copper-exchanged mordenite.« less

Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol

PubMed Central

Grundner, Sebastian; Markovits, Monica A.C.; Li, Guanna; Tromp, Moniek; Pidko, Evgeny A.; Hensen, Emiel J.M.; Jentys, Andreas; Sanchez-Sanchez, Maricruz; Lercher, Johannes A.

2015-01-01

Copper-exchanged zeolites with mordenite structure mimic the nuclearity and reactivity of active sites in particulate methane monooxygenase, which are enzymes able to selectively oxidize methane to methanol. Here we show that the mordenite micropores provide a perfect confined environment for the highly selective stabilization of trinuclear copper-oxo clusters that exhibit a high reactivity towards activation of carbon–hydrogen bonds in methane and its subsequent transformation to methanol. The similarity with the enzymatic systems is also implied from the similarity of the reversible rearrangements of the trinuclear clusters occurring during the selective transformations of methane along the reaction path towards methanol, in both the enzyme system and copper-exchanged mordenite. PMID:26109507

Bacterial populations within copper mine tailings: long-term effects of amendment with Class A biosolids

USDA-ARS?s Scientific Manuscript database

This study evaluates the effect of surface application of dried Class A biosolids on microbial populations within copper mine tailings. Methods and Results: Mine tailing sites were established at ASARCO Mission Mine close to Sahuarita, Arizona. Site 1 (Dec. 1998) was amended with 248 tons ha-1 of C...

A sediment quality triad assessment of the impact of copper mine tailings disposal on the littoral sedimentary environment in the Atacama region of northern Chile.

PubMed

Lee, Matthew R; Correa, Juan A; Seed, Ray

2006-11-01

A sediment quality triad (SQT) assessment was made of the impact of copper mine tailings disposal on littoral meiofaunal assemblages in the Atacama region of northern Chile. This situation is unusual in that the disposal is direct into the high-energy coastal system and not via a river estuary or other low-energy environment. This situation also allows for the examination of the impact of copper mine tailings in the absence of confounding effects from other pollutants. The three components of the SQT were: 1. an analysis of the bioavailable metals in both the sedimentary porewater and the adjacent seawater, 2. a microcosm bioassay of both sediments and seawaters using meiofaunal assemblages, and 3. quantitative field samples of the meiofaunal assemblages. Twelve study sites with varying degrees of impact were used, including three reference sites. The study identified that both the meiofaunal assemblage densities and taxa diversities decrease with increasing levels of bioavailable copper, that the Foraminifera and Harpacticoida are sensitive to copper, and that otoplanid Turbellaria are often characteristic of impacted sites; tailings also have both chemical and physical impacts on the environment. In some cases the physical impact of tailings is more important in excluding some organisms e.g. the interstitial polychaete, Saccocirrus sonomacus, from a site than is their chemical impact.

Water-quality trends and constituent-transport analysis for selected sampling sites in the Milltown Reservoir/Clark Fork River Superfund Site in the upper Clark Fork Basin, Montana, water years 1996–2015

USGS Publications Warehouse

Sando, Steven K.; Vecchia, Aldo V.

2016-07-20

During the extended history of mining in the upper Clark Fork Basin in Montana, large amounts of waste materials enriched with metallic contaminants (cadmium, copper, lead, and zinc) and the metalloid trace element arsenic were generated from mining operations near Butte and milling and smelting operations near Anaconda. Extensive deposition of mining wastes in the Silver Bow Creek and Clark Fork channels and flood plains had substantial effects on water quality. Federal Superfund remediation activities in the upper Clark Fork Basin began in 1983 and have included substantial remediation near Butte and removal of the former Milltown Dam near Missoula. To aid in evaluating the effects of remediation activities on water quality, the U.S. Geological Survey began collecting streamflow and water-quality data in the upper Clark Fork Basin in the 1980s.Trend analysis was done on specific conductance, selected trace elements (arsenic, copper, and zinc), and suspended sediment for seven sampling sites in the Milltown Reservoir/Clark Fork River Superfund Site for water years 1996–2015. The most upstream site included in trend analysis is Silver Bow Creek at Warm Springs, Montana (sampling site 8), and the most downstream site is Clark Fork above Missoula, Montana (sampling site 22), which is just downstream from the former Milltown Dam. Water year is the 12-month period from October 1 through September 30 and is designated by the year in which it ends. Trend analysis was done by using a joint time-series model for concentration and streamflow. To provide temporal resolution of changes in water quality, trend analysis was conducted for four sequential 5-year periods: period 1 (water years 1996–2000), period 2 (water years 2001–5), period 3 (water years 2006–10), and period 4 (water years 2011–15). Because of the substantial effect of the intentional breach of Milltown Dam on March 28, 2008, period 3 was subdivided into period 3A (October 1, 2005–March 27, 2008) and period 3B (March 28, 2008–September 30, 2010) for the Clark Fork above Missoula (sampling site 22). Trend results were considered statistically significant when the statistical probability level was less than 0.01.In conjunction with the trend analysis, estimated normalized constituent loads (hereinafter referred to as “loads”) were calculated and presented within the framework of a constituent-transport analysis to assess the temporal trends in flow-adjusted concentrations (FACs) in the context of sources and transport. The transport analysis allows assessment of temporal changes in relative contributions from upstream source areas to loads transported past each reach outflow.Trend results indicate that FACs of unfiltered-recoverable copper decreased at the sampling sites from the start of period 1 through the end of period 4; the decreases ranged from large for one sampling site (Silver Bow Creek at Warm Springs [sampling site 8]) to moderate for two sampling sites (Clark Fork near Galen, Montana [sampling site 11] and Clark Fork above Missoula [sampling site 22]) to small for four sampling sites (Clark Fork at Deer Lodge, Montana [sampling site 14], Clark Fork at Goldcreek, Montana [sampling site 16], Clark Fork near Drummond, Montana [sampling site 18], and Clark Fork at Turah Bridge near Bonner, Montana [sampling site 20]). For period 4 (water years 2011–15), the most notable changes indicated for the Milltown Reservoir/Clark Fork River Superfund Site were statistically significant decreases in FACs and loads of unfiltered-recoverable copper for sampling sites 8 and 22. The period 4 changes in FACs of unfiltered-recoverable copper for all other sampling sites were not statistically significant.Trend results indicate that FACs of unfiltered-recoverable arsenic decreased at the sampling sites from period 1 through period 4 (water years 1996–2015); the decreases ranged from minor (sampling sites 8–20) to small (sampling site 22). For period 4 (water years 2011–15), the most notable changes indicated for the Milltown Reservoir/Clark Fork River Superfund Site were statistically significant decreases in FACs and loads of unfiltered-recoverable arsenic for sampling site 8 and near statistically significant decreases for sampling site 22. The period 4 changes in FACs of unfiltered-recoverable arsenic for all other sampling sites were not statistically significant.Trend results indicate that FACs of suspended sediment decreased at the sampling sites from period 1 through period 4 (water years 1996–2015); the decreases ranged from moderate (sampling site 8) to small (sampling sites 11–22). For period 4 (water years 2011–15), the changes in FACs of suspended sediment were not statistically significant for any sampling sites.The reach of the Clark Fork from Galen to Deer Lodge is a large source of metallic contaminants and suspended sediment, which strongly affects downstream transport of those constituents. Mobilization of copper and suspended sediment from flood-plain tailings and the streambed of the Clark Fork and its tributaries within the reach results in a contribution of those constituents that is proportionally much larger than the contribution of streamflow from within the reach. Within the reach from Galen to Deer Lodge, unfiltered-recoverable copper loads increased by a factor of about 4 and suspended-sediment loads increased by a factor of about 5, whereas streamflow increased by a factor of slightly less than 2. For period 4 (water years 2011–15), unfiltered-recoverable copper and suspended-sediment loads sourced from within the reach accounted for about 41 and 14 percent, respectively, of the loads at Clark Fork above Missoula (sampling site 22), whereas streamflow sourced from within the reach accounted for about 4 percent of the streamflow at sampling site 22. During water years 1996–2015, decreases in FACs and loads of unfiltered-recoverable copper and suspended sediment for the reach generally were proportionally smaller than for most other reaches.Unfiltered-recoverable copper loads sourced within the reaches of the Clark Fork between Deer Lodge and Turah Bridge near Bonner (just upstream from the former Milltown Dam) were proportionally smaller than contributions of streamflow sourced from within the reaches; these reaches contributed proportionally much less to copper loading in the Clark Fork than the reach between Galen and Deer Lodge. Although substantial decreases in FACs and loads of unfiltered-recoverable copper and suspended sediment were indicated for Silver Bow Creek at Warm Springs (sampling site 8), those substantial decreases were not translated to downstream reaches between Deer Lodge and Turah Bridge near Bonner. The effect of the reach of the Clark Fork from Galen to Deer Lodge as a large source of copper and suspended sediment, in combination with little temporal change in those constituents for the reach, contributes to this pattern.With the removal of the former Milltown Dam in 2008, substantial amounts of contaminated sediments that remained in the Clark Fork channel and flood plain in reach 9 (downstream from Turah Bridge near Bonner) became more available for mobilization and transport than before the dam removal. After the removal of the former Milltown Dam, the Clark Fork above Missoula (sampling site 22) had statistically significant decreases in FACs of unfiltered-recoverable copper in period 3B (March 28, 2008, through water year 2010) that continued in period 4 (water years 2011–15). Also, decreases in FACs of unfiltered-recoverable arsenic and suspended sediment were indicated for period 4 at this site. The decrease in FACs of unfiltered-recoverable copper for sampling site 22 during period 4 was proportionally much larger than the decrease for the Clark Fork at Turah Bridge near Bonner (sampling site 20). Net mobilization of unfiltered-recoverable copper and arsenic from sources within reach 9 are smaller for period 4 than for period 1 when the former Milltown Dam was in place, providing evidence that contaminant source materials have been substantially reduced in reach 9.

Assimilation of zinc, cadmium, lead, copper, and iron by the spider Dysdera crocata, a predator of woodlice

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

Hopkin, S.P.; Martin, M.H.

1985-02-01

In this paper, an experiment is described on the assimilation of zinc, cadmium, lead, copper and iron by Dysdera crocata collected from a site in central Bristol. The spiders were fed on woodlice from their own site, and on woodlice from a site contaminated by a smelting works which contained much higher levels of zinc, cadmium and lead than the spiders would have been used to in their normal diet.

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.

DJ-1 Is a Copper Chaperone Acting on SOD1 Activation*

PubMed Central

Girotto, Stefania; Cendron, Laura; Bisaglia, Marco; Tessari, Isabella; Mammi, Stefano; Zanotti, Giuseppe; Bubacco, Luigi

2014-01-01

Lack of oxidative stress control is a common and often prime feature observed in many neurodegenerative diseases. Both DJ-1 and SOD1, proteins involved in familial Parkinson disease and amyotrophic lateral sclerosis, respectively, play a protective role against oxidative stress. Impaired activity and modified expression of both proteins have been observed in different neurodegenerative diseases. A potential cooperative action of DJ-1 and SOD1 in the same oxidative stress response pathway may be suggested based on a copper-mediated interaction between the two proteins reported here. To investigate the mechanisms underlying the antioxidative function of DJ-1 in relation to SOD1 activity, we investigated the ability of DJ-1 to bind copper ions. We structurally characterized a novel copper binding site involving Cys-106, and we investigated, using different techniques, the kinetics of DJ-1 binding to copper ions. The copper transfer between the two proteins was also examined using both fluorescence spectroscopy and specific biochemical assays for SOD1 activity. The structural and functional analysis of the novel DJ-1 copper binding site led us to identify a putative role for DJ-1 as a copper chaperone. Alteration of the coordination geometry of the copper ion in DJ-1 may be correlated to the physiological role of the protein, to a potential failure in metal transfer to SOD1, and to successive implications in neurodegenerative etiopathogenesis. PMID:24567322

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

Peterson, Ryan L.; Galaleldeen, Ahmad; Villarreal, Johanna

In eukaryotes the bimetallic Cu/Zn superoxide dismutase (SOD) enzymes play important roles in the biology of reactive oxygen species by disproportionating superoxide anion. We reported that the fungal pathogen Candida albicans expresses a novel copper-only SOD, known as SOD5, that lacks the zinc cofactor and electrostatic loop (ESL) domain of Cu/Zn-SODs for substrate guidance. In spite of these abnormalities, C. albicans SOD5 can disproportionate superoxide at rates limited only by diffusion. Here we demonstrate that this curious copper-only SOD occurs throughout the fungal kingdom as well as in phylogenetically distant oomycetes or “pseudofungi” species. It is the only form ofmore » extracellular SOD in fungi and oomycetes, in stark contrast to the extracellular Cu/Zn-SODs of plants and animals. Through structural biology and biochemical approaches we demonstrate that these copper-only SODs have evolved with a specialized active site consisting of two highly conserved residues equivalent to SOD5 Glu-110 and Asp-113. The equivalent positions are zinc binding ligands in Cu/Zn-SODs and have evolved in copper-only SODs to control catalysis and copper binding in lieu of zinc and the ESL. Similar to the zinc ion in Cu/Zn-SODs, SOD5 Glu-110 helps orient a key copper-coordinating histidine and extends the pH range of enzyme catalysis. Furthermore, SOD5 Asp-113 connects to the active site in a manner similar to that of the ESL in Cu/Zn-SODs and assists in copper cofactor binding. Copper-only SODs are virulence factors for certain fungal pathogens; thus this unique active site may be a target for future anti-fungal strategies.« less

Design, synthesis and fluorescence property evaluation of blue emitting triazole-linked chromene peptidomimetics.

PubMed

Mohan, T Jency; Bahulayan, D

2017-08-01

A highly efficient "Click with MCR" strategy for the three-step synthesis of two types of blue emitting chromene peptidomimetics is described. The peptidomimetics were synthesized via a copper-catalyzed [3[Formula: see text]2] azide-alkyne cycloaddition between chromene alkynes obtained from a three-component reaction and the peptide azides obtained from Ugi or Mannich type multicomponent reactions. The photophysical properties of the peptidomimetics are comparable with commercial fluorophores. Computational studies using drug property descriptors support the possibility of using these molecules for modulating difficult target classes having large, flat, and groove-shaped binding sites.

Copper Root Pruning and Container Cavity Size Influence Longleaf Pine Growth through Five Growing Seasons

Treesearch

James D. Haywood; Shi-Jean Susana Sung; Mary Anne Sword Sayer

2012-01-01

However, type and size of container can influence field performance. In this study, longleaf pine seedlings were grown in Beaver Plastics Styroblocks either without a copper treatment (Superblock) or with a copper oxychloride coating (Copperblock) and with three sizes of cavities that were 60, 108, and 164 ml. Seedlings from the six container types (two types of...

Small mammal-heavy metal concentrations from mined and control sites

USGS Publications Warehouse

Smith, G.J.; Rongstad, O.J.

1982-01-01

Total body concentrations of zinc, copper, cadmium, lead, nickel, mercury and arsenic were determined for Peromyscus maniculatus and Microtus pennsylvanicus from an active zinc-copper mine near Timmins, Ontario, Canada, and a proposed zinc-copper mine near Crandon, Wisconsin, USA. Metal concentrations were evaluated with respect to area, species, sex and age groups. Metal concentrations in Peromyscus from the proposed mine site were not different from those collected in a third area where no mine or deposit exists. This is probably due to the 30 m of glacial material over the proposed mine site deposit. A statistical interaction between area, species, sex and age was observed for zinc and copper concentrations in small mammals we examined. Peromyscus from the mine site had consistently higher metal concentrations than Peromyscus from the control site. Greater total body cadmium and lead concentrations in adult?compared with juvenile?Peromyscus collected at the mine site suggests age-dependent accumulation of these toxic metals. Microtus did not exhibit this age-related response, and responded to other environmental metals more erratically and to a lesser degree. Differences in the response of these two species to environmental metal exposure may be due to differences in food habits. Nickel, mercury and arsenic concentrations in small mammals from the mine site were not different from controls. Heavy metal concentrations are also presented for Sorex cinereus, Blarina brevicauda and Zapus hudsonicus without respect to age and sex cohorts. Peromyscus may be a potentially important species for the monitoring of heavy metal pollution.

The CopRS Two-Component System Is Responsible for Resistance to Copper in the Cyanobacterium Synechocystis sp. PCC 68031[C][W][OA

PubMed Central

Giner-Lamia, Joaquín; López-Maury, Luis; Reyes, José C.; Florencio, Francisco J.

2012-01-01

Photosynthetic organisms need copper for cytochrome oxidase and for plastocyanin in the fundamental processes of respiration and photosynthesis. However, excess of free copper is detrimental inside the cells and therefore organisms have developed homeostatic mechanisms to tightly regulate its acquisition, sequestration, and efflux. Herein we show that the CopRS two-component system (also known as Hik31-Rre34) is essential for copper resistance in Synechocystis sp. PCC 6803. It regulates expression of a putative heavy-metal efflux-resistance nodulation and division type copper efflux system (encoded by copBAC) as well as its own expression (in the copMRS operon) in response to the presence of copper in the media. Mutants in this two-component system or the efflux system render cells more sensitive to the presence of copper in the media and accumulate more intracellular copper than the wild type. Furthermore, CopS periplasmic domain is able to bind copper, suggesting that CopS could be able to detect copper directly. Both operons (copMRS and copBAC) are also induced by the photosynthetic inhibitor 2,5-dibromo-3-methyl-6-isopropyl-p-benzoquinone but this induction requires the presence of copper in the media. The reduced response of two mutant strains to copper, one lacking plastocyanin and a second one impaired in copper transport to the thylakoid, due to the absence of the PI-type ATPases PacS and CtaA, suggests that CopS can detect intracellular copper. In addition, a tagged version of CopS with a triple HA epitope localizes to both the plasma and the thylakoid membranes, suggesting that CopS could be involved in copper detection in both the periplasm and the thylakoid lumen. PMID:22715108

The CopRS two-component system is responsible for resistance to copper in the cyanobacterium Synechocystis sp. PCC 6803.

PubMed

Giner-Lamia, Joaquín; López-Maury, Luis; Reyes, José C; Florencio, Francisco J

2012-08-01

Photosynthetic organisms need copper for cytochrome oxidase and for plastocyanin in the fundamental processes of respiration and photosynthesis. However, excess of free copper is detrimental inside the cells and therefore organisms have developed homeostatic mechanisms to tightly regulate its acquisition, sequestration, and efflux. Herein we show that the CopRS two-component system (also known as Hik31-Rre34) is essential for copper resistance in Synechocystis sp. PCC 6803. It regulates expression of a putative heavy-metal efflux-resistance nodulation and division type copper efflux system (encoded by copBAC) as well as its own expression (in the copMRS operon) in response to the presence of copper in the media. Mutants in this two-component system or the efflux system render cells more sensitive to the presence of copper in the media and accumulate more intracellular copper than the wild type. Furthermore, CopS periplasmic domain is able to bind copper, suggesting that CopS could be able to detect copper directly. Both operons (copMRS and copBAC) are also induced by the photosynthetic inhibitor 2,5-dibromo-3-methyl-6-isopropyl-p-benzoquinone but this induction requires the presence of copper in the media. The reduced response of two mutant strains to copper, one lacking plastocyanin and a second one impaired in copper transport to the thylakoid, due to the absence of the P(I)-type ATPases PacS and CtaA, suggests that CopS can detect intracellular copper. In addition, a tagged version of CopS with a triple HA epitope localizes to both the plasma and the thylakoid membranes, suggesting that CopS could be involved in copper detection in both the periplasm and the thylakoid lumen.

Mechanisms of Contact-Mediated Killing of Yeast Cells on Dry Metallic Copper Surfaces▿

PubMed Central

Quaranta, Davide; Krans, Travis; Santo, Christophe Espírito; Elowsky, Christian G.; Domaille, Dylan W.; Chang, Christopher J.; Grass, Gregor

2011-01-01

Surfaces made of copper or its alloys have strong antimicrobial properties against a wide variety of microorganisms. However, the molecular mode of action responsible for the antimicrobial efficacy of metallic copper is not known. Here, we show that dry copper surfaces inactivate Candida albicans and Saccharomyces cerevisiae within minutes in a process called contact-mediated killing. Cellular copper ion homeostasis systems influenced the kinetics of contact-mediated killing in both organisms. Deregulated copper ion uptake through a hyperactive S. cerevisiae Ctr1p (ScCtr1p) copper uptake transporter in Saccharomyces resulted in faster inactivation of mutant cells than of wild-type cells. Similarly, lack of the C. albicans Crp1p (CaCrp1p) copper-efflux P-type ATPase or the metallothionein CaCup1p caused more-rapid killing of Candida mutant cells than of wild-type cells. Candida and Saccharomyces took up large quantities of copper ions as soon as they were in contact with copper surfaces, as indicated by inductively coupled plasma mass spectroscopy (ICP-MS) analysis and by the intracellular copper ion-reporting dye coppersensor-1. Exposure to metallic copper did not cause lethality through genotoxicity, deleterious action on a cell's genetic material, as indicated by a mutation assay with Saccharomyces. Instead, toxicity mediated by metallic copper surfaces targeted membranes in both yeast species. With the use of Live/Dead staining, onset of rapid and extensive cytoplasmic membrane damage was observed in cells from copper surfaces. Fluorescence microscopy using the indicator dye DiSBaC2(3) indicated that cell membranes were depolarized. Also, during contact-mediated killing, vacuoles first became enlarged and then disappeared from the cells. Lastly, in metallic copper-stressed yeasts, oxidative stress in the cytoplasm and in mitochondria was elevated. PMID:21097600

The development of a site-specific water-quality standard for copper

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

Sinclair, R.M.

This dissertation proposes to determine, for one toxic chemical, copper, if the Federal water quality standard and the state interpretation of that standard are appropriate for the Duck River, some 50 miles south of Nashville, Tennessee. This involved conducting toxicity tests in Duck River water, and the use of the computer metal speciation program MINTEQA1 to predict instream impact. The speciation model chosen for the determination of chemical equilibria in this study was MINTEQA1. To test the validity of the MINTEQA1 speciation model, water chemistry from the Duck River was entered into the model. At the typical site pH ofmore » 7.8, 55.7% of the copper is bound as Cu(OH){sub 2}, 29.8% is bound as copper humate, and 12.7% is found as CuCO{sub 3}. Of extreme importance to the toxicity of copper in the site water is the complete absence of the most toxic species, ionic copper. The test species were the brook silversides minnow (Labidesthes sicculus), mosquitofish (Gambusia affinis), caddisfly larvae (Cheumatopsyche sp.), fathead minnow (Pimephales promelas), geniculate river snail (Lithasia geniculata), sunfish (Lepomis sp.), and the amphipod (Hyalella azeca). The test concentrations were confirmed by atomic absorption spectroscopy on selected concentrations. The caddisfly larvae was the single most tolerant species observed during this study, while the amphipod and snail were the two most sensitive species tested.« less

Copper attachment to prion protein at a non-octarepeat site

NASA Astrophysics Data System (ADS)

Hodak, Miroslav; Bernholc, Jerry

2011-03-01

Prion protein (PrP) plays a causative role in a group of neurodegenerative diseases, which include ``mad cow disease'' or its human form variant Creutzfeld-Jacob disease. Normal function of PrP remains unknown, but it is now well established that PrP can efficiently bind copper ions and this ability has been linked to its function. The primary binding sites are located in the so-called octarepeat region located between residues 60-91. While these are by now well characterized, the sites located outside these region remain mostly undetermined. In this work, we investigate the properties of Cu binding site located at His 111 using recently developed hybrid Kohn-Sham/orbital-free density functional simulations. Experimental data indicate that copper is coordinated by either four nitrogens or three nitrogens and one oxygen. We investigate both possibilities, comparing their energetics and attachment geometries. Similarities and differences with other binding sites and implications for PrP function will also be discussed.

Independent University Study to Assess the Performance of a Humate Amendment for Copper Detoxification at the H-12 Outfall at Savannah River Site

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

Looney, B.; Harmon, S.; King, J.

2016-09-06

The overarching objective of this study was to evaluate the effectiveness of the copper detoxification process that is in place at the Savannah River Site H-12 Outfall. The testing was performed in two phases; Phase 1 assessed the safety and potential for intrinsic toxicity of the humate amendment being used at the H-12 Outfall, Borregro HA-1, as well as an alternative amendment sodium humic acid. The second phase assessed the effectiveness of Borregro HA-1 in mitigating and reducing toxic effects of copper.

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.

Characterization of commercially cold sprayed copper coatings and determination of the effects of impacting copper powder velocities

NASA Astrophysics Data System (ADS)

Jakupi, P.; Keech, P. G.; Barker, I.; Ramamurthy, S.; Jacklin, R. L.; Shoesmith, D. W.; Moser, D. E.

2015-11-01

Copper coated steel containers are being developed for the disposal of high level nuclear waste using processes such as cold spray and electrodeposition. Electron Back-Scatter Diffraction has been used to determine the microstructural properties and the quality of the steel-copper coating interface. The influence of the nature of the cold-spray carrier gas as well as its temperature and pressure (velocity) on the coating's plastic strain and recrystallization behaviour have been investigated, and one commercially-produced electrodeposited coating characterized. The quality of the coatings was assessed using the coincident site lattice model to analyse the properties of the grain boundaries. For cold spray coatings the grain size and number of coincident site lattice grain boundaries increased, and plastic strain decreased, with carrier gas velocity. In all cases annealing improved the quality of the coatings by increasing texture and coincidence site-lattices, but also increased the number of physical voids, especially when a low temperature cold spray carrier gas was used. Comparatively, the average grain size and number of coincident site-lattices was considerably larger for the strongly textured electrodeposited coating. Tensile testing showed the electrodeposited coating was much more strongly adherent to the steel substrate.

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

Eilert, Andre; Cavalca, Filippo; Roberts, F. Sloan

Copper electrocatalysts derived from an oxide have shown extraordinary electrochemical properties for the carbon dioxide reduction reaction (CO 2RR). Using in situ ambient pressure X-ray photoelectron spectroscopy and quasi in situ electron energy-loss spectroscopy in a transmission electron microscope, we show that there is a substantial amount of residual oxygen in nanostructured, oxide-derived copper electrocatalysts but no residual copper oxide. On the basis of these findings in combination with density functional theory simulations, we propose that residual subsurface oxygen changes the electronic structure of the catalyst and creates sites with higher carbon monoxide binding energy. If such sites are stablemore » under the strongly reducing conditions found in CO 2RR, these findings would explain the high efficiencies of oxide-derived copper in reducing carbon dioxide to multicarbon compounds such as ethylene.« less

The Features of Copper Metabolism in the Rat Liver during Development

PubMed Central

2015-01-01

Strong interest in copper homeostasis is due to the fact that copper is simultaneously a catalytic co-factor of the vital enzymes, a participant in signaling, and a toxic agent provoking oxidative stress. In mammals, during development copper metabolism is conformed to two types. In embryonic type copper metabolism (ETCM), newborns accumulate copper to high level in the liver because its excretion via bile is blocked; and serum copper concentration is low because ceruloplasmin (the main copper-containing protein of plasma) gene expression is repressed. In the late weaning, the ETCM switches to the adult type copper metabolism (ATCM), which is manifested by the unlocking of copper excretion and the induction of ceruloplasmin gene activity. The considerable progress has been made in the understanding of the molecular basis of copper metabolic turnover in the ATCM, but many aspects of the copper homeostasis in the ETCM remain unclear. The aim of this study was to investigate the copper metabolism during transition from the ETCM (up to 12-days-old) to the ATCM in the rats. It was shown that in the liver, copper was accumulated in the nuclei during the first 5 days of life, and then it was re-located to the mitochondria. In parallel with the mitochondria, copper bulk bound with cytosolic metallothionein was increased. All compartments of the liver cells rapidly lost most of their copper on the 13th day of life. In newborns, serum copper concentration was low, and its major fraction was associated with holo-Cp, however, a small portion of copper was bound to extracellular metallothionein and a substance that was slowly eluted during gel-filtration. In adults, serum copper concentration increased by about a factor of 3, while metallothionein-bound copper level decreased by a factor of 2. During development, the expression level of Cp, Sod1, Cox4i1, Atp7b, Ctr1, Ctr2, Cox17, and Ccs genes was significantly increased, and metallothionein was decreased. Atp7a gene’s activity was fully repressed. The copper routes in newborns are discussed. PMID:26474410

Effects of stimulation of copper bioleaching on microbial community in vineyard soil and copper mining waste.

PubMed

Andreazza, Robson; Okeke, Benedict C; Pieniz, Simone; Bortolon, Leandro; Lambais, Márcio R; Camargo, Flávio A O

2012-04-01

Long-term copper application in vineyards and copper mining activities cause heavy metal pollution sites. Such sites need remediation to protect soil and water quality. Bioremediation of contaminated areas through bioleaching can help to remove copper ions from the contaminated soils. Thus, the aim of this work was to evaluate the effects of different treatments for copper bioleaching in two diverse copper-contaminated soils (a 40-year-old vineyard and a copper mining waste) and to evaluate the effect on microbial community by applying denaturing gradient gel electrophoresis (DGGE) of 16S ribosomal DNA amplicons and DNA sequence analysis. Several treatments with HCl, H(2)SO(4), and FeSO(4) were evaluated by stimulation of bioleaching of copper in the soils. Treatments and extractions using FeSO(4) and H(2)SO(4) mixture at 30°C displayed more copper leaching than extractions with deionized water at room temperature. Treatment with H(2)SO(4) supported bioleaching of as much as 120 mg kg(-1) of copper from vineyard soil after 115 days of incubation. DGGE analysis of the treatments revealed that some treatments caused greater diversity of microorganisms in the vineyard soil compared to the copper mining waste. Nucleotide Blast of PCR-amplified fragments of 16S rRNA gene bands from DGGE indicated the presence of Rhodobacter sp., Silicibacter sp., Bacillus sp., Paracoccus sp., Pediococcus sp., a Myxococcales, Clostridium sp., Thiomonas sp., a firmicute, Caulobacter vibrioides, Serratia sp., and an actinomycetales in vineyard soil. Contrarily, Sphingomonas was the predominant genus in copper mining waste in most treatments. Paracoccus sp. and Enterobacter sp. were also identified from DGGE bands of the copper mining waste. Paracoccus species is involved in the copper bioleaching by sulfur oxidation system, liberating the copper bounded in the soils and hence promoting copper bioremediation. Results indicate that stimulation of bioleaching with a combination of FeSO(4) and H(2)SO(4) promoted bioleaching in the soils and can be employed ex situ to remediate copper-impacted soils.

DFT study of the effect of substitution on the molecular structure of copper phthalocyanine

NASA Astrophysics Data System (ADS)

Kaur, Prabhjot; Sachdeva, Ritika; Singh, Sukhwinder; Saini, G. S. S.

2016-05-01

To study the effect of sulfonic acid group as substituent on the molecular structure of an organic compound copper Phthalocyanine, the optimized geometry, mulliken charges, energies and dipole momemts of copper phthalocyanine and copper phthalocyaninetetrasulfonic acid tetra sodium salt have been investigated using density functional theory. Also to predict the change in reactive sites after substitution, molecular electrostatic potential maps for both the molecules have been calculated.

Human cytoplasmic copper chaperones Atox1 and CCS exchange copper ions in vitro.

PubMed

Petzoldt, Svenja; Kahra, Dana; Kovermann, Michael; Dingeldein, Artur P G; Niemiec, Moritz S; Ådén, Jörgen; Wittung-Stafshede, Pernilla

2015-06-01

After Ctr1-mediated copper ion (Cu) entry into the human cytoplasm, chaperones Atox1 and CCS deliver Cu to P1B-type ATPases and to superoxide dismutase, respectively, via direct protein-protein interactions. Although the two Cu chaperones are presumed to work along independent pathways, we here assessed cross-reactivity between Atox1 and the first domain of CCS (CCS1) using biochemical and biophysical methods in vitro. By NMR we show that CCS1 is monomeric although it elutes differently from Atox1 in size exclusion chromatography (SEC). This property allows separation of Atox1 and CCS1 by SEC and, combined with the 254/280 nm ratio as an indicator of Cu loading, we demonstrate that Cu can be transferred from one protein to the other. Cu exchange also occurs with full-length CCS and, as expected, the interaction involves the metal binding sites since mutation of Cu-binding cysteine in Atox1 eliminates Cu transfer from CCS1. Cross-reactivity between CCS and Atox1 may aid in regulation of Cu distribution in the cytoplasm.

Validation of a biotic ligand model on site-specific copper toxicity to Daphnia magna in the Yeongsan River, Korea.

PubMed

Park, Jinhee; Ra, Jin-Sung; Rho, Hojung; Cho, Jaeweon; Kim, Sang Don

2018-03-01

The objective of this study was to determine whether the water effect ratio (WER) or biotic ligand model (BLM) could be applied to efficiently develop water quality criteria (WQC) in Korea. Samples were collected from 12 specific sites along the Yeongsan River (YSR), Korea, including two sewage treatment plants and one estuary lake. A copper toxicity test using Daphnia magna was performed to determine the WER and to compare to the BLM prediction. The results of the WER from YSR samples also indicated significantly different copper toxicities in all sites. The model-based predictions showed that effluent and estuary waters had significantly different properties in regard to their ability to be used to investigate water characteristics and copper toxicity. It was supposed that the slight water characteristics changes, such as pH, DOC, hardness, conductivity, among others, influence copper toxicity, and these variable effects on copper toxicity interacted with the water composition. The 38% prediction was outside of the validation range by a factor of two in all sites, showing a poor predictive ability, especially in STPs and streams adjacent to the estuary, while the measured toxicity was more stable. The samples that ranged from pH 7.3-7.7 generated stable predictions, while other samples, including those with lower and the higher pH values, led to more unstable predictions. The results also showed that the toxicity of Cu in sample waters to D. magna was closely proportional to the amounts of acidity, including the carboxylic and phenolic groups, as well as the DOC concentrations. Consequently, the acceptable prediction of metal toxicity in various water samples needs the site-specific results considering the water characteristics such as pH and DOC properties particularly in STPs and estuary regions. Copyright © 2017 Elsevier Inc. All rights reserved.

Gold-Copper Nanoparticles: Nanostructural Evolution and Bifunctional Catalytic Sites

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

Yin, Jun; Shan, Shiyao; Yang, Lefu

2012-12-12

Understanding of the atomic-scale structure is essential for exploiting the unique catalytic properties of any nanoalloy catalyst. This report describes novel findings of an investigation of the nanoscale alloying of gold-copper (AuCu) nanoparticles and its impact on the surface catalytic functions. Two pathways have been explored for the formation of AuCu nanoparticles of different compositons, including wet chemical synthesis from mixed Au- and Cu-precursor molecules, and nanoscale alloying via an evolution of mixed Au- and Cu-precursor nanoparticles near the nanoscale melting temperatures. For the evolution of mixed precursor nanoparticles, synchrotron x-ray based in-situ real time XRD was used to monitormore » the structural changes, revealing nanoscale alloying and reshaping towards an fcc-type nanoalloy (particle or cube) via a partial melting–resolidification mechanism. The nanoalloys supported on carbon or silica were characterized by in-situ high-energy XRD/PDFs, revealing an intriguing lattice "expanding-shrinking" phenomenon depending on whether the catalyst is thermochemically processed under oxidative or reductive atmosphere. This type of controllable structural changes is found to play an important role in determining the catalytic activity of the catalysts for carbon monoxide oxidation reaction. The tunable catalytic activities of the nanoalloys under thermochemically oxidative and reductive atmospheres are also discussed in terms of the bifunctional sites and the surface oxygenated metal species for carbon monoxide and oxygen activation.« less

Geochemical characterization of slags, other mines wastes, and their leachates from the Elizabeth and Ely mines (Vermont), the Ducktown mining district (Tennessee), and the Clayton smelter site (Idaho)

USGS Publications Warehouse

Piatak, Nadine M.; Seal, Robert R.; Hammarstrom, Jane M.; Meier, Allen L.; Briggs, Paul H.

2003-01-01

Waste-rock material produced at historic metal mines contains elevated concentrations of potentially toxic trace elements. Two types of mine waste were examined in this study: sintered waste rock and slag. The samples were collected from the Elizabeth and Ely mines in the Vermont copper belt (Besshi-type massive sulfide deposits), from the Copper Basin mining district near Ducktown, Tennessee (Besshi-type massive sulfide deposits), and from the Clayton silver mine in the Bayhorse mining district, Idaho (polymetallic vein and replacement deposits). The data in this report are presented as a compilation with minimal interpretation or discussion. A detailed discussion and interpretation of the slag data are presented in a companion paper. Data collected from sintered waste rock and slag include: (1) bulk rock chemistry, (2) mineralogy, (3) and the distribution of trace elements among phases for the slag samples. In addition, the reactivity of the waste material under surficial conditions was assessed by examining secondary minerals formed on slag and by laboratory leaching tests using deionized water and a synthetic solution approximating precipitation in the eastern United States.

Estimate of undiscovered copper resources of the world, 2013

USGS Publications Warehouse

Johnson, Kathleen M.; Hammarstrom, Jane M.; Zientek, Michael L.; Dicken, Connie L.

2014-01-01

Using a geology-based assessment methodology, the U.S. Geological Survey estimated a mean of 3,500 million metric tons (Mt) of undiscovered copper among 225 tracts around the world. Annual U.S. copper consumption is 2 Mt; global consumption is 20 Mt. The USGS assessed undiscovered copper in two deposit types that account for about 80 percent of the world's copper supply. Results of the assessment are provided by deposit type for 11 regions. Approximately 50 percent of the global total occurs in South America, South Central Asia and Indochina, and North America combined.

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.

Molecular Characterization of CTR-type Copper Transporters in an Oceanic Diatom, Thalassiosira oceanica 1005

NASA Astrophysics Data System (ADS)

Kong, L.; Price, N. M.

2016-02-01

Copper is an essential micronutrient for phytoplankton growth because of its role as a redox cofactor in electron transfer proteins in photosynthesis and respiration, and a potentially limiting resource in parts of the open sea. Thalassiosira oceanica 1005 can grow at inorganic copper concentrations varying from 10 fmol/L to 10 nmol/L by regulating copper uptake across plasma membrane. Four putative CTR-type copper transporter genes (ToCTR1, ToCTR2, ToCTR3.1 and ToCTR3.2) were identified by BLASTP search against the T. oceanica genome. Predicted gene models were revised by assembled mRNA sequencing transcripts and updated gene models contained all conserved features of characterized CTR-type copper transporters. ToCTR3.1 and ToCTR3.2 may arise from one another by gene duplication as they shared a sequence similarity of 97.6% with a peptide insertion of 5 amino acids at N-terminus of ToCTR3.1. The expression of ToCTR1, ToCTR2 and ToCTR3.1/3.2 was upregulated in low copper concentrations, but only ToCTR3.1/3.2 showed a significant increase (2.5 fold) in copper-starved cells. Both ToCTR3.1 and ToCTR3.2 restored growth of a yeast double mutant, Saccharomyces cerevisiae ctr1Δctr3Δ, in copper deficient medium. GFP-fused ToCTR expression showed that some ToCTR3.1 localized to the plasma membrane but a large portion was retained in the endoplasmic reticulum. Inefficient targeting of ToCTR3.1 to the yeast outer membrane may explain poorer growth compared to the Saccharomyces native ScCTR1 transformant. Thus, diatom CTR genes encoding CTR-type copper transporters show high-affinity copper uptake and their regulation may enable diatoms to survive in ocean environments containing a wide range of copper concentrations.

Liver mitochondrial dysfunction and electron transport chain defect induced by high dietary copper in broilers.

PubMed

Yang, Fan; Cao, Huabin; Su, Rongsheng; Guo, Jianying; Li, Chengmei; Pan, Jiaqiang; Tang, Zhaoxin

2017-09-01

Copper is an important trace mineral in the diet of poultry due to its biological activity. However, limited information is available concerning the effects of high copper on mitochondrial dysfunction. In this study, 72 broilers were used to investigate the effects of high dietary copper on liver mitochondrial dysfunction and electron transport chain defect. Birds were fed with different concentrations [11, 110, 220, and 330 mg of copper/kg dry matter (DM)] of copper from tribasic copper chloride (TBCC). The experiment lasted for 60 d. Liver tissues on d 60 were subjected to histopathological observation. Additionally, liver mitochondrial function was recorded on d 12, 36, and 60. Moreover, a site-specific defect in the electron transport chain in liver mitochondria was also identified by using various chemical inhibitors of mitochondrial respiration. The results showed different degrees of degeneration, mitochondrial swelling, and high-density electrons in hepatocytes. In addition, the respiratory control ratio (RCR) and oxidative phosphorylation rate (OPR) in liver mitochondria increased at first and then decreased in high-dose groups. Moreover, hydrogen peroxide (H2O2) generation velocity in treated groups was higher than that in control group, which were magnified by inhibiting electron transport at Complex IV. The results indicated that high dietary copper could decline liver mitochondrial function in broilers. The presence of a site-specific defect at Complex IV in liver mitochondria may be responsible for liver mitochondrial dysfunction caused by high dietary copper. © 2017 Poultry Science Association Inc.

Elucidating the mechanism for the reduction of nitrite by copper nitrite reductase--a contribution from quantum chemical studies.

PubMed

De Marothy, S A; Blomberg, M R A; Siegbahn, P E M

2007-01-30

Density functional methods have been applied to investigate the properties of the active site of copper-containing nitrite reductases and possible reaction mechanisms for the enzyme catalysis. The results for a model of the active site indicate that a hydroxyl intermediate is not formed during the catalytic cycle, but rather a state with a protonated nitrite bound to the reduced copper. Electron affinity calculations indicate that reduction of the T2 copper site does not occur immediately after nitrite binding. Proton affinity calculations are indicative of substantial pK(a) differences between different states of the T2 site. The calculations further suggest that the reaction does not proceed until uptake of a second proton from the bulk solution. They also indicate that Asp-92 may play both a key role as a proton donor to the substrate, and a structural role in promoting catalysis. In the D92N mutant another base, presumably a nearby histidine (His-249) may take the role as the proton donor. On the basis of these model calculations and available experimental evidence, an ordered reaction mechanism for the reduction of nitrite is suggested. An investigation of the binding modes of the nitric oxide product and the nitrite substrate to the model site has also been made, indicating that nitric oxide prefers to bind in an end-on fashion to the reduced T2 site.

Mitochondrial Copper Metabolism and Delivery to Cytochrome c Oxidase

PubMed Central

Horn, Darryl; Barrientos, Antoni

2010-01-01

Summary Metals are essential elements of all living organisms. Among them, copper is required for a multiplicity of functions including mitochondrial oxidative phosphorylation and protection against oxidative stress. Here we will focus on describing the pathways involved in the delivery of copper to cytochrome c oxidase (COX), a mitochondrial metalloenzyme acting as the terminal enzyme of the mitochondrial respiratory chain. The catalytic core of COX is formed by three mitochondrially-encoded subunits and contains three copper atoms. Two copper atoms bound to subunit 2 constitute the CuA site, the primary acceptor of electrons from ferrocytochrome c. The third copper, CuB, is associated with the high-spin heme a3 group of subunit 1. Recent studies, mostly performed in the yeast Saccharomyces cerevisiae, have provided new clues about 1- the source of the copper used for COX metallation; 2- the roles of Sco1p and Cox11p, the proteins involved in the direct delivery of copper to the CuA and CuB sites, respectively; 3- the action mechanism of Cox17p, a copper chaperone that provides copper to Sco1p and Cox11p; 4- the existence of at least four Cox17p homologues carrying a similar twin CX9C domain suggestive of metal binding, Cox19p, Cox23p, Pet191p and Cmc1p, that could be part of the same pathway; and 5- the presence of a disulfide relay system in the intermembrane space of mitochondria that mediates import of proteins with conserved cysteines motifs such as the CX9C characteristic of Cox17p and its homologues. The different pathways are reviewed and discussed in the context of both mitochondrial COX assembly and copper homeostasis. PMID:18459161

Influence of clay on the adsorption of heavy metals like copper and cadmium on chitosan.

PubMed

Prakash, Nagan; Latha, Srinivasan; Sudha, Persu N; Renganathan, N Gopalan

2013-02-01

The influence of clay on the adsorption of heavy metals like copper and cadmium on chitosan from simulated industrial wastewater is evaluated. Chitosan-clay blend with ratio of (1:1), (1:2), and (2:1) have been prepared, and these were used as membranes to remove copper and cadmium ions from synthetic industrial wastewater. The chemical parameters for quantities of adsorption of heavy metal contamination have been done, and the kinetics of adsorption has also been carried out. Clay provides enough absorbable sites to overcome mass transfer limitations. The number of absorbable sites for cadmium is more compared to copper, and thus the rate of recovery of cadmium is faster than copper, and the percentage removal of cadmium is more than copper at all times on clay over nylon 6. This difference indicates the influence of clay in the adsorption of heavy metals in comparison to synthetic polymer nylon 6. Rate constant for first-order kinetics of adsorption, k (1), for copper and cadmium is less than that of clay, which clearly indicates that clay, which is a natural polymer, is more kinetically favored compared to synthetic polymer. The difference in the intraparticle diffusion in both the natural and synthetic polymer is not much, and it suggests that the particle diffusion mechanism is the same in both cases. Copper and cadmium recovery is parallel at all times. The percentage of removal of copper increased with an increase in pH from 3 to 5. In the case of cadmium containing wastewater, the maximum removal of metal occurred at pH 5. The uptake amount of Cu(2+) ions on chitosan increased rapidly with increasing the contact time from 0 to 360 min and then reaches equilibrium after 360 min, and the equilibrium constant for copper and cadmium ions are more or less the same for the adsorption reaction. There are more adsorption sites for cadmium in the presence of clay and mass transfer limitation is avoided without resorting to rotation, which is the highlight of the present work. And more so, this is pronounced in the case of natural polymer compared to synthetic polymer.

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

PubMed Central

Elguindi, Jutta; Moffitt, Stuart; Hasman, Henrik; Andrade, Cassandra; Raghavan, Srini; Rensing, Christopher

2013-01-01

The rapid killing of various bacteria in contact with metallic copper is thought to be influenced by influx of copper ions into the cells but the exact mechanism is not fully understood. This study showed that the kinetics of contact-killing of copper surfaces depended greatly on the amount of moisture present, copper content of alloys, type of medium used, and type of bacteria. We examined antibiotic- and copper-ion resistant strains of Escherichia coli and Enterococcus faecium isolated from pig farms following the use of copper sulfate as feed supplement. The results showed rapid killing of both copper-ion resistant E. coli and E. faecium strains when samples in rich medium were spread in a thin, moist layer on copper alloys with 85% or greater copper content. E. coli strains were rapidly killed under dry conditions while E. faecium strains were less affected. Electroplated copper surface corrosion rates were determined from electro-chemical polarization tests using the Stern-Geary method and revealed decreased corrosion rates with benzotriazole and thermal oxide coating. Copper-ion resistant E. coli and E. faecium cells suspended in 0.8% NaCl showed prolonged survival rates on electroplated copper surfaces with benzotriazole coating and thermal oxide coating compared to surfaces without anti-corrosion treatment. Control of surface corrosion affected the level of copper ion influx into bacterial cells which contributed directly to bacterial killing. PMID:21085951

Quantum mechanical calculations suggest that lytic polysaccharide monooxygenases use a copper-oxyl, oxygen-rebound mechanism

PubMed Central

Kim, Seonah; Ståhlberg, Jerry; Sandgren, Mats; Paton, Robert S.; Beckham, Gregg T.

2014-01-01

Lytic polysaccharide monooxygenases (LPMOs) exhibit a mononuclear copper-containing active site and use dioxygen and a reducing agent to oxidatively cleave glycosidic linkages in polysaccharides. LPMOs represent a unique paradigm in carbohydrate turnover and exhibit synergy with hydrolytic enzymes in biomass depolymerization. To date, several features of copper binding to LPMOs have been elucidated, but the identity of the reactive oxygen species and the key steps in the oxidative mechanism have not been elucidated. Here, density functional theory calculations are used with an enzyme active site model to identify the reactive oxygen species and compare two hypothesized reaction pathways in LPMOs for hydrogen abstraction and polysaccharide hydroxylation; namely, a mechanism that employs a η1-superoxo intermediate, which abstracts a substrate hydrogen and a hydroperoxo species is responsible for substrate hydroxylation, and a mechanism wherein a copper-oxyl radical abstracts a hydrogen and subsequently hydroxylates the substrate via an oxygen-rebound mechanism. The results predict that oxygen binds end-on (η1) to copper, and that a copper-oxyl–mediated, oxygen-rebound mechanism is energetically preferred. The N-terminal histidine methylation is also examined, which is thought to modify the structure and reactivity of the enzyme. Density functional theory calculations suggest that this posttranslational modification has only a minor effect on the LPMO active site structure or reactivity for the examined steps. Overall, this study suggests the steps in the LPMO mechanism for oxidative cleavage of glycosidic bonds. PMID:24344312

Use of the Biotic Ligand Model to predict metal toxicity to aquatic biota in areas of differing geology

USGS Publications Warehouse

Smith, Kathleen S.

2005-01-01

This work evaluates the use of the biotic ligand model (BLM), an aquatic toxicity model, to predict toxic effects of metals on aquatic biota in areas underlain by different rock types. The chemical composition of water, soil, and sediment is largely derived from the composition of the underlying rock. Geologic source materials control key attributes of water chemistry that affect metal toxicity to aquatic biota, including: 1) potentially toxic elements, 2) alkalinity, 3) total dissolved solids, and 4) soluble major elements, such as Ca and Mg, which contribute to water hardness. Miller (2002) compiled chemical data for water samples collected in watersheds underlain by ten different rock types, and in a mineralized area in western Colorado. He found that each rock type has a unique range of water chemistry. In this study, the ten rock types were grouped into two general categories, igneous and sedimentary. Water collected in watersheds underlain by sedimentary rock has higher mean pH, alkalinity, and calcium concentrations than water collected in watersheds underlain by igneous rock. Water collected in the mineralized area had elevated concentrations of calcium and sulfate in addition to other chemical constituents. Miller's water-chemistry data were used in the BLM (computer program) to determine copper and zinc toxicity to Daphnia magna. Modeling results show that waters from watersheds underlain by different rock types have characteristic ranges of predicted LC 50 values (a measurement of aquatic toxicity) for copper and zinc, with watersheds underlain by igneous rock having lower predicted LC 50 values than watersheds underlain by sedimentary rock. Lower predicted LC 50 values suggest that aquatic biota in watersheds underlain by igneous rock may be more vulnerable to copper and zinc inputs than aquatic biota in watersheds underlain by sedimentary rock. For both copper and zinc, there is a trend of increasing predicted LC 50 values with increasing dissolved organic carbon (DOC) concentrations. Predicted copper LC 50 values are extremely sensitive to DOC concentrations, whereas alkalinity appears to have an influence on zinc toxicity at alkalinities in excess of about 100 mg/L CaCO 3 . These findings show promise for coupling the BLM (computer program) with measured water-chemistry data to predict metal toxicity to aquatic biota in different geologic settings and under different scenarios. This approach may ultimately be a useful tool for mine-site planning, mitigation and remediation strategies, and ecological risk assessment.

pH-regulated metal-ligand switching in the HM loop of ATP7A: a new paradigm for metal transfer chemistry.

PubMed

Kline, Chelsey D; Gambill, Benjamin F; Mayfield, Mary; Lutsenko, Svetlana; Blackburn, Ninian J

2016-08-01

Cuproproteins such as PHM and DBM mature in late endosomal vesicles of the mammalian secretory pathway where changes in vesicle pH are employed for sorting and post-translational processing. Colocation with the P1B-type ATPase ATP7A suggests that the latter is the source of copper and supports a mechanism where selectivity in metal transfer is achieved by spatial colocation of partner proteins in their specific organelles or vesicles. In previous work we have suggested that a lumenal loop sequence located between trans-membrane helices TM1 and TM2 of the ATPase, and containing five histidines and four methionines, acts as an organelle-specific chaperone for metallation of the cuproproteins. The hypothesis posits that the pH of the vesicle regulates copper ligation and loop conformation via a mechanism which involves His to Met ligand switching induced by histidine protonation. Here we report the effect of pH on the HM loop copper coordination using X-ray absorption spectroscopy (XAS), and show via selenium substitution of the Met residues that the HM loop undergoes similar conformational switching to that found earlier for its partner PHM. We hypothesize that in the absence of specific chaperones, HM motifs provide a template for building a flexible, pH-sensitive transfer site whose structure and function can be regulated to accommodate the different active site structural elements and pH environments of its partner proteins.

Effects of ionizing radiations on the optical properties of ionic copper-activated sol-gel silica glasses

NASA Astrophysics Data System (ADS)

Al Helou, Nissrine; El Hamzaoui, Hicham; Capoen, Bruno; Ouerdane, Youcef; Boukenter, Aziz; Girard, Sylvain; Bouazaoui, Mohamed

2018-01-01

Studying the impact of radiations on doped silica glasses is essential for several technological applications. Herein, bulk silica glasses, activated with various concentrations of luminescent monovalent copper (Cu+), have been prepared using the sol-gel technique. Thereafter, these glasses were subjected to X- or γ-rays irradiation at 1 MGy(SiO2) accumulated dose. The effect of these ionizing radiations on the optical properties of these glasses, as a function of the Cu-doping content, were investigated using optical absorption and photoluminescence spectroscopies. Before any irradiation, the glass with the lowest copper concentration exhibits blue and green luminescence bands under UV excitation, suggesting that Cu+ ions occupy both cubic and tetragonal symmetry sites. However, at higher Cu-doping level, only the green emission band exists. Moreover, we showed that the hydroxyl content decreases with increasing copper doping concentration. Both X and γ radiation exposures induced visible absorption due to HC1 color centers in the highly Cu-doped glasses. In the case of the lower Cu-doped glass, the Cu+ sites with a cubic symmetry are transformed into sites with tetragonal symmetry.

Neuronal differentiation is associated with a redox-regulated increase of copper flow to the secretory pathway

PubMed Central

Hatori, Yuta; Yan, Ye; Schmidt, Katharina; Furukawa, Eri; Hasan, Nesrin M.; Yang, Nan; Liu, Chin-Nung; Sockanathan, Shanthini; Lutsenko, Svetlana

2016-01-01

Brain development requires a fine-tuned copper homoeostasis. Copper deficiency or excess results in severe neuro-pathologies. We demonstrate that upon neuronal differentiation, cellular demand for copper increases, especially within the secretory pathway. Copper flow to this compartment is facilitated through transcriptional and metabolic regulation. Quantitative real-time imaging revealed a gradual change in the oxidation state of cytosolic glutathione upon neuronal differentiation. Transition from a broad range of redox states to a uniformly reducing cytosol facilitates reduction of the copper chaperone Atox1, liberating its metal-binding site. Concomitantly, expression of Atox1 and its partner, a copper transporter ATP7A, is upregulated. These events produce a higher flux of copper through the secretory pathway that balances copper in the cytosol and increases supply of the cofactor to copper-dependent enzymes, expression of which is elevated in differentiated neurons. Direct link between glutathione oxidation and copper compartmentalization allows for rapid metabolic adjustments essential for normal neuronal function. PMID:26879543

Neuronal differentiation is associated with a redox-regulated increase of copper flow to the secretory pathway.

PubMed

Hatori, Yuta; Yan, Ye; Schmidt, Katharina; Furukawa, Eri; Hasan, Nesrin M; Yang, Nan; Liu, Chin-Nung; Sockanathan, Shanthini; Lutsenko, Svetlana

2016-02-16

Brain development requires a fine-tuned copper homoeostasis. Copper deficiency or excess results in severe neuro-pathologies. We demonstrate that upon neuronal differentiation, cellular demand for copper increases, especially within the secretory pathway. Copper flow to this compartment is facilitated through transcriptional and metabolic regulation. Quantitative real-time imaging revealed a gradual change in the oxidation state of cytosolic glutathione upon neuronal differentiation. Transition from a broad range of redox states to a uniformly reducing cytosol facilitates reduction of the copper chaperone Atox1, liberating its metal-binding site. Concomitantly, expression of Atox1 and its partner, a copper transporter ATP7A, is upregulated. These events produce a higher flux of copper through the secretory pathway that balances copper in the cytosol and increases supply of the cofactor to copper-dependent enzymes, expression of which is elevated in differentiated neurons. Direct link between glutathione oxidation and copper compartmentalization allows for rapid metabolic adjustments essential for normal neuronal function.

A comparative study of stream water and stream sediment as geochemical exploration media in the Rio Tanama porphyry copper district, Puerto Rico

USGS Publications Warehouse

Learned, R.E.; Chao, T.T.; Sanzolone, R.F.

1985-01-01

To test the relative effectiveness of stream water and sediment as geochemical exploration media in the Rio Tanama porphyry copper district of Puerto Rico, we collected and subsequently analyzed samples of water and sediment from 29 sites in the rivers and tributaries of the district. Copper, Mo, Pb, Zn, SO42-, and pH were determined in the waters; Cu, Mo, Pb, and Zn were determined in the sediments. In addition, copper in five partial extractions from the sediments was determined. Geochemical contrast (anomaly-to-background quotient) was the principal criterion by which the effectiveness of the two media and the five extractions were judged. Among the distribution patterns of metals in stream water, that of copper most clearly delineates the known porphyry copper deposits and yields the longest discernable dispersion train. The distribution patterns of Mo, Pb, and Zn in water show little relationship to the known mineralization. The distribution of SO42- in water delineates the copper deposits and also the more extensive pyrite alteration in the district; its recognizable downstream dispersion train is substantially longer than those of the metals, either in water or sediment. Low pH values in small tributaries delineate areas of known sulfide mineralization. The distribution patterns of copper in sediments clearly delineate the known deposits, and the dispersion trains are longer than those of copper in water. The partial determinations of copper related to secondary iron and manganese oxides yield the strongest geochemical contrasts and longest recognizable dispersion trains. Significantly high concentrations of molybdenum in sediments were found at only three sites, all within one-half km downstream of the known copper deposits. The distribution patterns of lead and zinc in sediments are clearly related to the known primary lead-zinc haloes around the copper deposits. The recognizable downstream dispersion trains of lead and zinc are shorter than those of copper. ?? 1985.

The effectiveness of surface liming in ameliorating the phytotoxic effects of soil contaminated by copper acid leach pad solution in an arid ecosystem

NASA Astrophysics Data System (ADS)

Golos, Peter

2016-04-01

Revegetation of sites following soil contamination can be challenging especially in identifying the most effective method for ameliorating phytotoxic effects in arid ecosystems. This study at a copper mine in the Great Sandy Desert of Western Australia investigated vegetation restoration of a site contaminated by acid (H2SO4) leach pad solution. Elevated soil copper at low soil pH is phytotoxic to plant roots inhibiting root elongation. In arid ecosystems where rapid root growth is crucial for seedling survival post germination physical or chemical barriers to root growth need to be identified and ameliorated. Initial attempt at rehabilitation of contaminated site with hydrated lime (CaOH2) at 2 tonnes/ha followed by ripping to 30 cm depth then seeding was ineffective as successful seedling emergence was followed by over 90% seedling mortality which was 10-fold greater than seedling mortality in an uncontaminated reference site. High mortality was attributed to seedling roots being impededed as soil water was more than 3-fold greater at 5 to 40 cm depth in contaminated site than reference site. In response to high seedling mortality after emergence test pits were dug to 1 m deep to collect soil samples at 10 cm intervals for phytotoxicity testing and to measure soil pH-CaCl2, copper (DPTA ion extraction), electrical conductivity and gravimetric water content in three replicate pits at three replicate sites. Also, soil impedance was measured down the soil profile at 5 cm intervals at six replicate points/pit. For phytotoxicity testing soil samples were placed into three replicate plastic pots/sample and seeded with 10 seeds of Avena sativa and watered daily. Seedlings were harvested after at least two weeks after seedling emergence and rooting depth in pots measured. There was no difference in seedling emergence and survival of seedlings between contaminated and uncontaminated soil samples however mean seedling root growth was significantly lower in soil samples collected at >10 cm depth than the control. Mean soil pH at 0-10 cm was higher (>7.2) at all sites treated with lime compared to uncontaminated soil (5.5). At depths greater than 10 cm soil pH was <4.6. Soil copper was >16 mg/kg in all contaminated soil samples compared to 0.5 mg/kg in control. High seedling mortality in contaminated site is attributed to low soil pH and elevated soil copper levels which inhibited plant root growth and hence access to soil water. While surface liming of soil increased soil pH ameliorating the effect of elevated soil copper, this was only effective in the top 10 cm due to low solubility of hydrated lime. To improve seedling survival lime will need to be incorporated into the contaminated soil profile to allow plants to access soil water at depth. This study highlights the importance of the need to assess the phytotoxic effects of soil contamination and the effectiveness of amelioration treatments and with proper reference to its ecological context. To improve the success of vegetation restoration of sites contaminated with acidic copper solution, lime needs to be incorporated into the contaminated soil profile to allow plant roots to access soil water at depth. This study highlights the importance of the need to assess the phytotoxic effects of soil contamination and the effectiveness of amelioration treatments and with proper reference to its ecological context.

Phytostabilization potential of evening primrose (Oenothera glazioviana) for copper-contaminated sites.

PubMed

Guo, Pan; Wang, Ting; Liu, Yanli; Xia, Yan; Wang, Guiping; Shen, Zhenguo; Chen, Yahua

2014-01-01

A field investigation, field experiment, and hydroponic experiment were conducted to evaluate feasibility of using Oenothera glazioviana for phytostabilization of copper-contaminated soil. In semiarid mine tailings in Tongling, Anhui, China, O. glazioviana, a copper excluder, was a dominant species in the community, with a low bioaccumulation factor, the lowest copper translocation factor, and the lowest copper content in seed (8 mg kg(-1)). When O. glazioviana was planted in copper-polluted farmland soil in Nanjing, Jiangsu, China, its growth and development improved and the level of γ-linolenic acid in seeds reached 17.1%, compared with 8.73% in mine tailings. A hydroponic study showed that O. glazioviana had high tolerance to copper, low upward transportation capacity of copper, and a high γ-linolenic acid content. Therefore, it has great potential for the phytostabilization of copper-contaminated soils and a high commercial value without risk to human health.

Using water-quality profiles to characterize seasonal water quality and loading in the upper Animas River basin, southwestern Colorado

USGS Publications Warehouse

Leib, Kenneth J.; Mast, M. Alisa; Wright, Winfield G.

2003-01-01

One of the important types of information needed to characterize water quality in streams affected by historical mining is the seasonal pattern of toxic trace-metal concentrations and loads. Seasonal patterns in water quality are estimated in this report using a technique called water-quality profiling. Water-quality profiling allows land managers and scientists to assess priority areas to be targeted for characterization and(or) remediation by quantifying the timing and magnitude of contaminant occurrence. Streamflow and water-quality data collected at 15 sites in the upper Animas River Basin during water years 1991?99 were used to develop water-quality profiles. Data collected at each sampling site were used to develop ordinary least-squares regression models for streamflow and constituent concentrations. Streamflow was estimated by correlating instantaneous streamflow measured at ungaged sites with continuous streamflow records from streamflow-gaging stations in the subbasin. Water-quality regression models were developed to estimate hardness and dissolved cadmium, copper, and zinc concentrations based on streamflow and seasonal terms. Results from the regression models were used to calculate water-quality profiles for streamflow, constituent concentrations, and loads. Quantification of cadmium, copper, and zinc loads in a stream segment in Mineral Creek (sites M27 to M34) was presented as an example application of water-quality profiling. The application used a method of mass accounting to quantify the portion of metal loading in the segment derived from uncharacterized sources during different seasonal periods. During May, uncharacterized sources contributed nearly 95 percent of the cadmium load, 0 percent of the copper load (or uncharacterized sources also are attenuated), and about 85 percent of the zinc load at M34. During September, uncharacterized sources contributed about 86 percent of the cadmium load, 0 percent of the copper load (or uncharacterized sources also are attenuated), and about 52 percent of the zinc load at M34. Characterized sources accounted for more of the loading gains estimated in the example reach during September, possibly indicating the presence of diffuse inputs during snowmelt runoff. The results indicate that metal sources in the upper Animas River Basin may change substantially with season, regardless of the source.

Long-term passive restoration following fluvial deposition of sulphidic copper tailings: nature filters out the solutions.

PubMed

Nikolic, Nina; Böcker, Reinhard; Nikolic, Miroslav

2016-07-01

Despite the growing popularity of ecological restoration approach, data on primary succession on toxic post-mining substrates, under site environmental conditions which considerably differ from the surrounding environment, are still scarce. Here, we studied the spontaneous vegetation development on an unusual locality created by long-term and large-scale fluvial deposition of sulphidic tailings from a copper mine in a pronouncedly xerothermic, calcareous surrounding. We performed multivariate analyses of soil samples (20 physical and chemical parameters) and vegetation samples (floristic and structural parameters in three types of occurring forests), collected along the pollution gradients throughout the affected floodplain. The nature can cope with two types of imposed constraints: (a) excessive Cu concentrations and (b) very low pH, combined with nutrient deficiency. The former will still allow convergence to the original vegetation, while the latter will result in novel, depauperate assemblages of species typical for cooler and moister climate. Our results for the first time demonstrate that with the increasing severity of environmental filtering, the relative importance of the surrounding vegetation for primary succession strongly decreases.

The Myxococcus xanthus two-component system CorSR regulates expression of a gene cluster involved in maintaining copper tolerance during growth and development.

PubMed

Sánchez-Sutil, María Celestina; Pérez, Juana; Gómez-Santos, Nuria; Shimkets, Lawrence J; Moraleda-Muñoz, Aurelio; Muñoz-Dorado, José

2013-01-01

Myxococcus xanthus is a soil-dwelling member of the δ-Proteobacteria that exhibits a complex developmental cycle upon starvation. Development comprises aggregation and differentiation into environmentally resistant myxospores in an environment that includes fluctuations in metal ion concentrations. While copper is essential for M. xanthus cells because several housekeeping enzymes use it as a cofactor, high copper concentrations are toxic. These opposing effects force cells to maintain a tight copper homeostasis. A plethora of paralogous genes involved in copper detoxification, all of which are differentially regulated, have been reported in M. xanthus. The use of in-frame deletion mutants and fusions with the reporter gene lacZ has allowed the identification of a two-component system, CorSR, that modulates the expression of an operon termed curA consisting of nine genes whose expression slowly increases after metal addition, reaching a plateau. Transcriptional regulation of this operon is complex because transcription can be initiated at different promoters and by different types of regulators. These genes confer copper tolerance during growth and development. Copper induces carotenoid production in a ΔcorSR mutant at lower concentrations than with the wild-type strain due to lack of expression of a gene product resembling subunit III of cbb3-type cytochrome c oxidase. This data may explain why copper induces carotenoid biosynthesis at suboptimal rather than optimal growth conditions in wild-type strains.

The Myxococcus xanthus Two-Component System CorSR Regulates Expression of a Gene Cluster Involved in Maintaining Copper Tolerance during Growth and Development

PubMed Central

Sánchez-Sutil, María Celestina; Pérez, Juana; Gómez-Santos, Nuria; Shimkets, Lawrence J.; Moraleda-Muñoz, Aurelio; Muñoz-Dorado, José

2013-01-01

Myxococcus xanthus is a soil-dwelling member of the δ–Proteobacteria that exhibits a complex developmental cycle upon starvation. Development comprises aggregation and differentiation into environmentally resistant myxospores in an environment that includes fluctuations in metal ion concentrations. While copper is essential for M. xanthus cells because several housekeeping enzymes use it as a cofactor, high copper concentrations are toxic. These opposing effects force cells to maintain a tight copper homeostasis. A plethora of paralogous genes involved in copper detoxification, all of which are differentially regulated, have been reported in M. xanthus. The use of in-frame deletion mutants and fusions with the reporter gene lacZ has allowed the identification of a two-component system, CorSR, that modulates the expression of an operon termed curA consisting of nine genes whose expression slowly increases after metal addition, reaching a plateau. Transcriptional regulation of this operon is complex because transcription can be initiated at different promoters and by different types of regulators. These genes confer copper tolerance during growth and development. Copper induces carotenoid production in a ΔcorSR mutant at lower concentrations than with the wild-type strain due to lack of expression of a gene product resembling subunit III of cbb3-type cytochrome c oxidase. This data may explain why copper induces carotenoid biosynthesis at suboptimal rather than optimal growth conditions in wild-type strains. PMID:23874560

Ground-contact durability of wood treated with borax-copper preservative

Treesearch

Stan T. Lebow; Bessie Woodward; Patricia K. Lebow

2007-01-01

This study evaluated the ability of a borax-copper(BC) preservative to protect wood exposed in ground contact. Southern pine sapwood stakes were pressure-treated with 0.9%, 1.4%, 2.3%, and 4.7% BC solution concentrations and placed into the ground at test sites near Mississippi, or Madison, Wisconsin. Untreated stakes and stakes treated with 1% chromated copper...

On-site infiltration of a copper roof runoff: role of clinoptilolite as an artificial barrier material.

PubMed

Athanasiadis, Konstantinos; Helmreich, Brigitte; Horn, Harald

2007-08-01

On-site infiltration may be considered as a promising way of managing rainwater runoffs in urban areas, provided the hydrological and ecological conditions allow infiltration, and provided there is adequate treatment of the contaminants to avoid a risk of soil and groundwater pollution. The aim of this study was to evaluate the feasibility of the application of a new technical infiltration system equipped with clinoptilolite as an artificial barrier material for the treatment of the copper roof runoff of the Academy of Fine Arts in Munich, Germany. During the 2-yr sampling period, 30 rain events were examined. The cover material of the roof and the drainage system was responsible for the high copper concentrations in the roof runoff. The rain height and the rain intensity were of great significance regarding the establishment of the copper runoff rate. The technical infiltration system applied was able to reduce the copper from the roof runoff by a factor up to 96%. The mean measured copper concentration in percolation water was lower than the critical value of 50 microg/l set by the German Federal Soil Protection Act and Ordinance, indicating no risk for soil and groundwater contamination.

Migration and stopover strategies of individual Dunlin along the Pacific coast of North America

USGS Publications Warehouse

Warnock, N.; Takekawa, John Y.; Bishop, M.A.

2004-01-01

We radio-marked 18 Dunlin, Calidris alpina (L., 1758), at San Francisco Bay, California, and 11 Dunlin at Grays Harbor, Washington, and relocated 90% of them along the 4200 km long coastline from north of San Francisco Bay to the Yukon-Kuskokwim Delta, Alaska. The Copper River Delta, Alaska, was the single most important stopover site, with 79% of the marked birds detected there. Our second most important site was the Willapa Bay and Grays Harbor complex of wetlands in Washington. The mean length of stay past banding sites ranged from 1.0 to 3.8 days. Controlling for date of departure, birds banded at San Francisco Bay had higher rates of travel to the Copper River Delta than those banded at Grays Harbor. The later a bird left a capture site, the faster it traveled to the Copper River Delta. Length of stay at the Copper River Delta was inversely related to arrival date. We did not find any effect of sex on travel rate or length of stay. Combining the results of this study with our previous work on Western Sandpipers, Calidris mauri (Cabanis, 1875), reveals variation of migration strategies used within and among shorebird species along the eastern Pacific Flyway. ?? 2004 NRC.

Zinc Deficiency Impacts CO2 Assimilation and Disrupts Copper Homeostasis in Chlamydomonas reinhardtii*

PubMed Central

Malasarn, Davin; Kropat, Janette; Hsieh, Scott I.; Finazzi, Giovanni; Casero, David; Loo, Joseph A.; Pellegrini, Matteo; Wollman, Francis-André; Merchant, Sabeeha S.

2013-01-01

Zinc is an essential nutrient because of its role in catalysis and in protein stabilization, but excess zinc is deleterious. We distinguished four nutritional zinc states in the alga Chlamydomonas reinhardtii: toxic, replete, deficient, and limited. Growth is inhibited in zinc-limited and zinc-toxic cells relative to zinc-replete cells, whereas zinc deficiency is visually asymptomatic but distinguished by the accumulation of transcripts encoding ZIP family transporters. To identify targets of zinc deficiency and mechanisms of zinc acclimation, we used RNA-seq to probe zinc nutrition-responsive changes in gene expression. We identified genes encoding zinc-handling components, including ZIP family transporters and candidate chaperones. Additionally, we noted an impact on two other regulatory pathways, the carbon-concentrating mechanism (CCM) and the nutritional copper regulon. Targets of transcription factor Ccm1 and various CAH genes are up-regulated in zinc deficiency, probably due to reduced carbonic anhydrase activity, validated by quantitative proteomics and immunoblot analysis of Cah1, Cah3, and Cah4. Chlamydomonas is therefore not able to grow photoautotrophically in zinc-limiting conditions, but supplementation with 1% CO2 restores growth to wild-type rates, suggesting that the inability to maintain CCM is a major consequence of zinc limitation. The Crr1 regulon responds to copper limitation and is turned on in zinc deficiency, and Crr1 is required for growth in zinc-limiting conditions. Zinc-deficient cells are functionally copper-deficient, although they hyperaccumulate copper up to 50-fold over normal levels. We suggest that zinc-deficient cells sequester copper in a biounavailable form, perhaps to prevent mismetallation of critical zinc sites. PMID:23439652

Role of the P-Type ATPases, ATP7A and ATP7B in brain copper homeostasis.

PubMed

Telianidis, Jonathon; Hung, Ya Hui; Materia, Stephanie; Fontaine, Sharon La

2013-01-01

Over the past two decades there have been significant advances in our understanding of copper homeostasis and the pathological consequences of copper dysregulation. Cumulative evidence is revealing a complex regulatory network of proteins and pathways that maintain copper homeostasis. The recognition of copper dysregulation as a key pathological feature in prominent neurodegenerative disorders such as Alzheimer's, Parkinson's, and prion diseases has led to increased research focus on the mechanisms controlling copper homeostasis in the brain. The copper-transporting P-type ATPases (copper-ATPases), ATP7A and ATP7B, are critical components of the copper regulatory network. Our understanding of the biochemistry and cell biology of these complex proteins has grown significantly since their discovery in 1993. They are large polytopic transmembrane proteins with six copper-binding motifs within the cytoplasmic N-terminal domain, eight transmembrane domains, and highly conserved catalytic domains. These proteins catalyze ATP-dependent copper transport across cell membranes for the metallation of many essential cuproenzymes, as well as for the removal of excess cellular copper to prevent copper toxicity. A key functional aspect of these copper transporters is their copper-responsive trafficking between the trans-Golgi network and the cell periphery. ATP7A- and ATP7B-deficiency, due to genetic mutation, underlie the inherited copper transport disorders, Menkes and Wilson diseases, respectively. Their importance in maintaining brain copper homeostasis is underscored by the severe neuropathological deficits in these disorders. Herein we will review and update our current knowledge of these copper transporters in the brain and the central nervous system, their distribution and regulation, their role in normal brain copper homeostasis, and how their absence or dysfunction contributes to disturbances in copper homeostasis and neurodegeneration.

Role of the P-Type ATPases, ATP7A and ATP7B in brain copper homeostasis

PubMed Central

Telianidis, Jonathon; Hung, Ya Hui; Materia, Stephanie; Fontaine, Sharon La

2013-01-01

Over the past two decades there have been significant advances in our understanding of copper homeostasis and the pathological consequences of copper dysregulation. Cumulative evidence is revealing a complex regulatory network of proteins and pathways that maintain copper homeostasis. The recognition of copper dysregulation as a key pathological feature in prominent neurodegenerative disorders such as Alzheimer’s, Parkinson’s, and prion diseases has led to increased research focus on the mechanisms controlling copper homeostasis in the brain. The copper-transporting P-type ATPases (copper-ATPases), ATP7A and ATP7B, are critical components of the copper regulatory network. Our understanding of the biochemistry and cell biology of these complex proteins has grown significantly since their discovery in 1993. They are large polytopic transmembrane proteins with six copper-binding motifs within the cytoplasmic N-terminal domain, eight transmembrane domains, and highly conserved catalytic domains. These proteins catalyze ATP-dependent copper transport across cell membranes for the metallation of many essential cuproenzymes, as well as for the removal of excess cellular copper to prevent copper toxicity. A key functional aspect of these copper transporters is their copper-responsive trafficking between the trans-Golgi network and the cell periphery. ATP7A- and ATP7B-deficiency, due to genetic mutation, underlie the inherited copper transport disorders, Menkes and Wilson diseases, respectively. Their importance in maintaining brain copper homeostasis is underscored by the severe neuropathological deficits in these disorders. Herein we will review and update our current knowledge of these copper transporters in the brain and the central nervous system, their distribution and regulation, their role in normal brain copper homeostasis, and how their absence or dysfunction contributes to disturbances in copper homeostasis and neurodegeneration. PMID:23986700

Spatial variability of total dissolved copper and copper speciation in the inshore waters of Bermuda.

PubMed

Oldham, V E; Swenson, M M; Buck, K N

2014-02-15

Total dissolved copper (Cu) and Cu speciation were examined from inshore waters of Bermuda, in October 2009 and July-August 2010, to determine the relationship between total dissolved Cu, Cu-binding ligands and bioavailable, free, hydrated Cu(2+) concentrations. Speciation was performed using competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV). Mean total dissolved Cu concentrations ranged from 1.4 nM to 19.2 nM, with lowest concentrations at sites further from shore, consistent with previous measurements in the Sargasso Sea, and localized Cu enrichment inshore in enclosed harbors. Ligand concentrations exceeded dissolved [Cu] at most sites, and [Cu(2+)] were correspondingly low at those sites, typically <10(-13) M. One site, Hamilton Harbour, was found to have [Cu] in excess of ligands, resulting in [Cu(2+)] of 10(-10.7) M, and indicating that Cu may be toxic to phytoplankton here. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

Frankaer, Christian Grundahl; Mossin, Susanne; Ståhl, Kenny

The level of structural detail around the metal sites in Ni{sup 2+} and Cu{sup 2+} T{sub 6} insulin derivatives was significantly improved by using a combination of single-crystal X-ray crystallography and X-ray absorption spectroscopy. Photoreduction and subsequent radiation damage of the Cu{sup 2+} sites in Cu insulin was followed by XANES spectroscopy. Using synchrotron radiation (SR), the crystal structures of T{sub 6} bovine insulin complexed with Ni{sup 2+} and Cu{sup 2+} were solved to 1.50 and 1.45 Å resolution, respectively. The level of detail around the metal centres in these structures was highly limited, and the coordination of water inmore » Cu site II of the copper insulin derivative was deteriorated as a consequence of radiation damage. To provide more detail, X-ray absorption spectroscopy (XAS) was used to improve the information level about metal coordination in each derivative. The nickel derivative contains hexacoordinated Ni{sup 2+} with trigonal symmetry, whereas the copper derivative contains tetragonally distorted hexacoordinated Cu{sup 2+} as a result of the Jahn–Teller effect, with a significantly longer coordination distance for one of the three water molecules in the coordination sphere. That the copper centre is of type II was further confirmed by electron paramagnetic resonance (EPR). The coordination distances were refined from EXAFS with standard deviations within 0.01 Å. The insulin derivative containing Cu{sup 2+} is sensitive towards photoreduction when exposed to SR. During the reduction of Cu{sup 2+} to Cu{sup +}, the coordination geometry of copper changes towards lower coordination numbers. Primary damage, i.e. photoreduction, was followed directly by XANES as a function of radiation dose, while secondary damage in the form of structural changes around the Cu atoms after exposure to different radiation doses was studied by crystallography using a laboratory diffractometer. Protection against photoreduction and subsequent radiation damage was carried out by solid embedment of Cu insulin in a saccharose matrix. At 100 K the photoreduction was suppressed by ∼15%, and it was suppressed by a further ∼30% on cooling the samples to 20 K.« less

Rupture testing for the quality control of electrodeposited copper interconnections in high-speed, high-density circuits

NASA Technical Reports Server (NTRS)

Zakraysek, Louis

1987-01-01

Printed Wiring Multilayer Board (PWMLB) structures for high speed, high density circuits are prone to failure due to the microcracking of electrolytic copper interconnections. The failure can occur in the foil that makes up the inner layer traces or in the plated through holes (PTH) deposit that forms the layer to layer interconnections. It is shown that there are some distinctive differences in the quality of Type E copper and that these differences can be detected before its use in a PWMLB. It is suggested that the strength of some Type E copper can be very low when the material is hot and that it is the use of this poor quality material in a PWMLB that results in PTH and inner layer microcracking. Since the PWMLB failure in question are induced by a thermal stress, and since the poorer grades of Type E materials used in these structures are susceptible to premature failure under thermal stress, the use of elevated temperature rupture and creep rupture testing is proposed as a means for screening copper foil, or its PTH equivalent, in order to eliminate the problem of Type E copper microcracking in advanced PWMLBs.

Factors controlling peat chemistry and vegetation composition in Sudbury peatlands after 30 years of pollution emission reductions.

PubMed

Barrett, Sophie E; Watmough, Shaun A

2015-11-01

The objective of this research was to assess factors controlling peat and plant chemistry, and vegetation composition in 18 peatlands surrounding Sudbury after more than 30 years of large (>95%) pollution emission reductions. Sites closer to the main Copper Cliff smelter had more humified peat and the surface horizons were greatly enriched in copper (Cu) and nickel (Ni). Copper and Ni concentrations in peat were significantly correlated with that in the plant tissue of Chamaedaphne calyculata. The pH of peat was the strongest determining factor for species richness, diversity, and community composition, although percent vascular plant cover was strongly negatively correlated with surface Cu and Ni concentrations in peat. Sphagnum frequency was also negatively related to peat Cu and Ni concentrations indicating sites close to Copper Cliff smelter remain adversely impacted by industrial activities. Copyright © 2015 Elsevier Ltd. All rights reserved.

Influence of feedstock on the copper removal capacity of waste-derived biochars.

PubMed

Arán, Diego; Antelo, Juan; Fiol, Sarah; Macías, Felipe

2016-07-01

Biochar samples were generated by low temperature pyrolysis of different types of waste. The physicochemical characteristics of the different types of biochar affected the copper retention capacity, by determining the main mechanism involved. The capacity of the biochar to retain copper present in solution depended on the size of the inorganic fraction and varied in the following order: rice biochar>chicken manure biochar>olive mill waste biochar>acacia biochar>eucalyptus biochar>corn cob biochar. The distribution of copper between the forms bound to solid biochar, dissolved organic matter and free organic matter in solution also depended on the starting material. However, the effect of pH on the adsorption capacity was independent of the nature of the starting material, and the copper retention of all types of biochar increased with pH. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ionic configuration of copper ferrimanganites Cu 0.5Mn xFe 2.5- xO 4

NASA Astrophysics Data System (ADS)

Lenglet, M.; Kasperek, J.; Hannoyer, B.; Lopitaux, J.; d'Huysser, A.; Tellier, J. C.

1992-06-01

Mössbauer spectrometry, neutron diffraction, XANES, and XPS have led to the determination of the cation distributions of the system Cu 0.5Mn xFe 2.5- xO 4 (0≤ x≤1.5). The three cations are present in both tetrahedral and octahedral sites, and the relative number of Fe ions on A- and B-sites remains nearly constant in the whole range of x. It appears that for x≤0.5 manganese is divalent and copper is in its two oxidation states. For x>0.5 copper and iron are respectively divalent and trivalent; the manganese is in +2 and +3 oxydation states.

Paired Magmatic-Metallogenic Belts in Myanmar - an Andean Analogue?

NASA Astrophysics Data System (ADS)

Gardiner, Nicholas; Robb, Laurence; Searle, Michael; Morley, Christopher

2015-04-01

Myanmar (Burma) is richly endowed in precious and base metals, having one of the most diverse collections of natural resources in SE Asia. Its geological history is dominated by the staged closing of Tethys and the suturing of Gondwana-derived continental fragments onto the South China craton during the Mesozoic-Cenozoic. The country is located at a crucial geologic juncture where the main convergent Tethyan collision zone swings south around the Namche Barwa Eastern Himalayan syntaxis. However, despite recent work, the geological and geodynamic history of Myanmar remains enigmatic. Plate margin processes, magmatism, metasomatism and the genesis of mineral deposits are intricately linked, and there has long been recognized a relationship between the distribution of certain mineral deposit types, and the tectonic settings which favour their genesis. A better knowledge of the regional tectonic evolution of a potential exploration jurisdiction is therefore crucial to understanding its minerals prospectivity. This strong association between tectonics and mineralization can equally be applied in reverse. By mapping out the spatial, and temporal, distribution of presumed co-genetic mineral deposits, coupled with an understanding of their collective metallogenetic origin, a better appreciation of the tectonic evolution of a terrane may be elucidated. Identification and categorization of metallotects within a geodynamically-evolving terrane thus provides a complimentary tool to other methodologies (e.g. geochemical, geochronological, structural, geophysical, stratigraphical), for determining the tectonic history and inferred geodynamic setting of that terrane through time. Myanmar is one such study area where this approach can be undertaken. Here are found two near-parallel magmatic belts, which together contain a significant proportion of that country's mineral wealth of tin, tungsten, copper, gold and silver. Although only a few 100 km's apart, these belts exhibit a contrasting minerals endowment. The Mogok-Mandalay-Mergui (MMM) Belt hosts crustal-melt S-type granites with significant tin-tungsten mineralization, and contains the historically major tungsten deposit of Mawchi. The Wuntho-Popa Arc comprises I-type granites and granodiorites with porphyry-type copper-gold and epithermal gold mineralization, and includes the world-class Monywa copper mine. Recent U-Pb radiometric age dating has shown the potential for the two belts to be both active from the Late Cretaceous to Eocene. The spatial juxtaposition of these two sub-parallel belts, the implication of contemporary magmatism, and their distinct but consistent metallogenic endowment bears strong similarities to the metallogenic belts of the South American Cordillera. Here we investigate whether they together represent the magmatic and metallogenic expression of an Andean-type setting in Myanmar during the subduction of Neo-Tethys. In this analogue the Wuntho-Popa Arc represents a proximal I-type magmatic belt sited immediately above the eastwards-verging Neo-Tethys subduction zone. Exhibiting porphyry-type copper-gold and epithermal gold mineralization, this would therefore be the Myanmar equivalent of the Andean coastal copper belts. Conversely, the parallel MMM Belt, comprised of more distal crustal-melt S-type tin granites, would have an analogue in the Bolivian tin belt.

Synergy and Diffusion with a Borax-Copper Hydroxide Groundline Preservative: 20 Year Update

Treesearch

Stan Lebow; Bessie Woodward; Bill Abbott; Mike West

2014-01-01

A groundline remedial treatment containing 3.1% copper hydroxide (2% elemental copper) and 40% sodium tetraborate decahydrate (borax) was applied to unseasoned pine posts prior to placement in a test site in southern Mississippi. The soundness of the posts was periodically evaluated using a push test. After 3.5, 6.5, 10, 15 and 20 years, sections were taken from two...

The effects of metal ions on the DNA damage induced by hydrogen peroxide.

PubMed

Kobayashi, S; Ueda, K; Komano, T

1990-01-01

The effects of metal ions on DNA damage induced by hydrogen peroxide were investigated using two methods, agarose-gel electrophoretic analysis of supercoiled DNA and sequencing-gel analysis of single end-labeled DNA fragments of defined sequences. Hydrogen peroxide induced DNA damage when iron or copper ion was present. At least two classes of DNA damage were induced, one being direct DNA-strand cleavage, and the other being base modification labile to hot piperidine. The investigation of the damaged sites and the inhibitory effects of radical scavengers revealed that hydroxyl radical was the species which attacked DNA in the reaction of H2O2/Fe(II). On the other hand, two types of DNA damage were induced by H2O2/Cu(II). Type I damage was predominant and inhibited by potassium iodide, but type II was not. The sites of the base-modification induced by type I damage were similar to those by lipid peroxidation products and by ascorbate in the presence of Cu(II), suggesting the involvement of radical species other than free hydroxyl radical in the damaging reactions.

Splitting of the O–O bond at the heme-copper catalytic site of respiratory oxidases

PubMed Central

Poiana, Federica; von Ballmoos, Christoph; Gonska, Nathalie; Blomberg, Margareta R. A.; Ädelroth, Pia; Brzezinski, Peter

2017-01-01

Heme-copper oxidases catalyze the four-electron reduction of O2 to H2O at a catalytic site that is composed of a heme group, a copper ion (CuB), and a tyrosine residue. Results from earlier experimental studies have shown that the O–O bond is cleaved simultaneously with electron transfer from a low-spin heme (heme a/b), forming a ferryl state (PR; Fe4+=O2−, CuB2+–OH−). We show that with the Thermus thermophilus ba3 oxidase, at low temperature (10°C, pH 7), electron transfer from the low-spin heme b to the catalytic site is faster by a factor of ~10 (τ ≅ 11 μs) than the formation of the PR ferryl (τ ≅110 μs), which indicates that O2 is reduced before the splitting of the O–O bond. Application of density functional theory indicates that the electron acceptor at the catalytic site is a high-energy peroxy state [Fe3+–O−–O−(H+)], which is formed before the PR ferryl. The rates of heme b oxidation and PR ferryl formation were more similar at pH 10, indicating that the formation of the high-energy peroxy state involves proton transfer within the catalytic site, consistent with theory. The combined experimental and theoretical data suggest a general mechanism for O2 reduction by heme-copper oxidases. PMID:28630929

3D local structure around copper site of rabbit prion-related protein: Quantitative determination by XANES spectroscopy combined with multiple-scattering calculations

NASA Astrophysics Data System (ADS)

Cui, P. X.; Lian, F. L.; Wang, Y.; Wen, Yi; Chu, W. S.; Zhao, H. F.; Zhang, S.; Li, J.; Lin, D. H.; Wu, Z. Y.

2014-02-01

Prion-related protein (PrP), a cell-surface copper-binding glycoprotein, is considered to be responsible for a number of transmissible spongiform encephalopathies (TSEs). The structural conversion of PrP from the normal cellular isoform (PrPC) to the post-translationally modified form (PrPSc) is thought to be relevant to Cu2+ binding to histidine residues. Rabbits are one of the few mammalian species that appear to be resistant to TSEs, because of the structural characteristics of the rabbit prion protein (RaPrPC) itself. Here we determined the three-dimensional local structure around the C-terminal high-affinity copper-binding sites using X-ray absorption near-edge structure combined with ab initio calculations in the framework of the multiple-scattering (MS) theory. Result shows that two amino acid resides, Gln97 and Met108, and two histidine residues, His95 and His110, are involved in binding this copper(II) ion. It might help us understand the roles of copper in prion conformation conversions, and the molecular mechanisms of prion-involved diseases.

Dielectric Properties of Reduced Graphene Oxide/Copper Phthalocyanine Nanocomposites Fabricated Through π- π Interaction

NASA Astrophysics Data System (ADS)

Wang, Zicheng; Wei, Renbo; Liu, Xiaobo

2017-01-01

Reduced graphene oxide/copper phthalocyanine nanocomposites are successfully prepared through a simple and effective two-step method, involving preferential reduction of graphene oxide and followed by self-assembly with copper phthalocyanine. The results of photographs, ultraviolet visible, x-ray diffraction, x-ray photoelectron spectroscopy, and scanning electron microscopy show that the in situ blending method can effectively facilitate graphene sheets to disperse homogenously in the copper phthalocyanine matrix through π- π interactions. As a result, the reduction of graphene oxide and restoration of the sp 2 carbon sites in graphene can enhance the dielectric properties and alternating current conductivity of copper phthalocyanine effectively.

Non-nucleoside building blocks for copper-assisted and copper-free click chemistry for the efficient synthesis of RNA conjugates.

PubMed

Jayaprakash, K N; Peng, Chang Geng; Butler, David; Varghese, Jos P; Maier, Martin A; Rajeev, Kallanthottathil G; Manoharan, Muthiah

2010-12-03

Novel non-nucleoside alkyne monomers compatible with oligonucleotide synthesis were designed, synthesized, and efficiently incorporated into RNA and RNA analogues during solid-phase synthesis. These modifications allowed site-specific conjugation of ligands to the RNA oligonucleotides through copper-assisted (CuAAC) and copper-free strain-promoted azide-alkyne cycloaddition (SPAAC) reactions. The SPAAC click reactions of cyclooctyne-oligonucleotides with various classes of azido-functionalized ligands in solution phase and on solid phase were efficient and quantitative and occurred under mild reaction conditions. The SPAAC reaction provides a method for the synthesis of oligonucleotide-ligand conjugates uncontaminated with copper ions.

Rapid Analysis of Copper Ore in Pre-Smelter Head Flow Slurry by Portable X-ray Fluorescence.

PubMed

Burnett, Brandon J; Lawrence, Neil J; Abourahma, Jehad N; Walker, Edward B

2016-05-01

Copper laden ore is often concentrated using flotation. Before the head flow slurry can be smelted, it is important to know the concentration of copper and contaminants. The concentration of copper and other elements fluctuate significantly in the head flow, often requiring modification of the concentrations in the slurry prior to smelting. A rapid, real-time analytical method is needed to support on-site optimization of the smelter feedstock. A portable, handheld X-ray fluorescence spectrometer was utilized to determine the copper concentration in a head flow suspension at the slurry origin. The method requires only seconds and is reliable for copper concentrations of 2.0-25%, typically encountered in such slurries. © The Author(s) 2016.

Effect of copper on the properties of Pr-Dy-Fe-Co-B sintered magnets

NASA Astrophysics Data System (ADS)

Kablov, E. N.; Piskorskii, V. P.; Valeev, R. A.; Volkov, N. V.; Davydova, E. A.; Shaikhutdinov, K. A.; Balaev, D. A.; Semenov, S. V.

2014-01-01

The effect of copper on the properties of magnets (Pr0.52Dy0.48)13(Fe65Co0.35)80.3 - x Cu x B6.7 ( x = 0-10) has been studied. Alloying with copper is shown to decrease the sintering temperature and to increase the content of the principal (Pr,Dy)2(Fe,Co)14B magnetic phase. For compositions with x = 1.3-3.3, copper is found to affect the value and sign of the temperature induction coefficient (TIC). It is shown that the effect of copper on the TIC is determined by the substitution of copper ions for iron ions in lattice sites, which are coupled via an antiferromagnetic exchange interaction.

ATP7B mediates vesicular sequestration of copper: insight into biliary copper excretion.

PubMed

Cater, Michael A; La Fontaine, Sharon; Shield, Kristy; Deal, Yolanda; Mercer, Julian F B

2006-02-01

The Wilson protein (ATP7B) regulates levels of systemic copper by excreting excess copper into bile. It is not clear whether ATP7B translocates excess intrahepatic copper directly across the canalicular membrane or sequesters this copper into exocytic vesicles, which subsequently fuse with canalicular membrane to expel their contents into bile. The aim of this study was to clarify the mechanism underlying ATP7B-mediated copper detoxification by investigating endogenous ATP7B localization in the HepG2 hepatoma cell line and its ability to mediate vesicular sequestration of excess intracellular copper. Immunofluorescence microscopy was used to investigate the effect of copper concentration on the localization of endogenous ATP7B in HepG2 cells. Copper accumulation studies to determine whether ATP7B can mediate vesicular sequestration of excess intracellular copper were performed using Chinese hamster ovary cells that exogenously expressed wild-type and mutant ATP7B proteins. In HepG2 cells, elevated copper levels stimulated trafficking of ATP7B to pericanalicular vesicles and not to the canalicular membrane as previously reported. Mutation of an endocytic retrieval signal in ATP7B caused the protein to constitutively localize to vesicles and not to the plasma membrane, suggesting that a vesicular compartment(s) is the final trafficking destination for ATP7B. Expression of wild-type and mutant ATP7B caused Chinese hamster ovary cells to accumulate copper in vesicles, which subsequently undergo exocytosis, releasing copper across the plasma membrane. This report provides compelling evidence that the primary mechanism of biliary copper excretion involves ATP7B-mediated vesicular sequestration of copper rather than direct copper translocation across the canalicular membrane.

The Potential for Prophyry Copper-Molybdenum Deposits in the Eastern United States

USGS Publications Warehouse

Schmidt, Robert Gordon

1978-01-01

Several significant porphyry-type deposits of Paleozoic age are known in New England and eastern Canada. Disseminated copper-molybdenum deposits of Paleozoic age are in the Southeastern United States, and copper is produced from porphyry-type deposits of both Precambrian and Paleozoic age in eastern Canada. Although these old deposits are surely less abundant than those in Cenozoic and Tertiary porphyry belts, the known Precrambrian and Paleozoic deposits in Eastern North America appear to be valid exploration targets. The difficult of 'prospecting in drift-covered and saprolite-mantled terrains suggests that all such deposits probably have not been discovered. Although such deposits are more costly to discover in this region than a massive sulfide deposit, the total amount of copper in even a medium-sized porphyry copper deposit is much greater than in most massive sulfide deposits. This report summarizes current knowledge of porphyry copper-molybdenum-type deposits in the Eastern United States and suggests more favorable areas for mineral exploration. Selected Canadian deposits are discussed because of their bearing on planning exploration in this country.

Copper uptake by the water hyacinth. [Eichornia crassipes

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

Lee, T.A.; Hardy, J.K.

1987-01-01

Factors affecting Cu/sup +2/ uptake by the water hyacinth (Eichornia crassipes) were examined. Two phases of copper uptake were observed throughout the uptake range (1-1000 mg/1). An initial rapid uptake phase of 4 hours followed by a slower, near linear uptake phase extending past 48 hours was observed. Stirring the solution enhanced uptake, suggesting copper removal is partially diffusion limited. Variations in pH over the range of 3 to 10 did not significantly affect uptake. Increasing the root mass of the plant increased the amount of copper taken up. As solution volume was increased more copper was removed. The presencemore » of complexing agents during the uptake phase reduced copper uptake. The inability of complexing agents to recover all copper initially removed by a plant suggests a migration to sites within the plant.« less

Genotoxicity of mercury used in chromosome aberration tests.

PubMed

Akiyama, M; Oshima, H; Nakamura, M

2001-01-01

The purpose of this study was to investigate the genotoxic effects of Hg released from dental amalgams. The chromosome aberration test was conducted using original extracts and their diluted solutions of conventional type amalgam and high copper amalgam. The concentrations of Hg, Cu and Ag in the original extract of high copper amalgam were 17.64, 7.97 and 43.90 microM, respectively. Those in the original extract of conventional type amalgam were 20.63, 7.87 and 14.79 microM, respectively. 10 and 30 microM Hg(2+) were also used for comparison. The frequency of chromosome aberrations was below 5% with 0 microM Hg(2+) and with a triple dilution of high copper amalgam extract, containing 5.88 microM Hg, 14.63 microM Cu and 2.65 microM Ag. However, 9.5% of the cells showed chromosome aberrations with a quadruple dilution of conventional type amalgam, containing 5.15 microM Hg, 3.69 microM Cu and 1.96 microM Ag. The amount of Hg in the quadruple dilution of conventional type amalgam was less than that in the triple dilution of high copper amalgam extract and 10 microM Hg(2+). A concentration of 30 microM Hg(2+) caused 34.5% of the cells to show chromosome aberrations while with a two-thirds dilution of high copper amalgam extract, containing 11.76 microM Hg, 29.26 microM Cu and 5.31 microM Ag, 58.5% of the cells showed chromosome aberrations. A two-thirds dilution of high copper amalgam extract induced more chromosome aberrations than 30 microM Hg(2+), although the amount of Hg was less than 30 microM Hg(2+). A triple dilution of conventional type amalgam extract, original extracts of conventional type amalgam and high copper amalgam and 100 microM Hg(2+) were induced few metaphases. It was revealed that the conventional type amalgam induced chromosome aberrations with quadruple dilution where cell viability was about 80% and that the high copper amalgam induced a high level of chromosome aberrations with the two-thirds dilution. The effects of low level Hg on humans are not clear.

Increased sensitivity of apolipoprotein E knockout mice to copper-induced oxidative injury to the liver.

PubMed

Chen, Yuan; Li, Bin; Zhao, Ran-ran; Zhang, Hui-feng; Zhen, Chao; Guo, Li

2015-04-10

Apolipoprotein E (ApoE) genotypes are related to clinical presentations in patients with Wilson's disease, indicating that ApoE may play an important role in the disease. However, our understanding of the role of ApoE in Wilson's disease is limited. High copper concentration in Wilson's disease induces excessive generation of free oxygen radicals. Meanwhile, ApoE proteins possess antioxidant effects. We therefore determined whether copper-induced oxidative damage differ in the liver of wild-type and ApoE knockout (ApoE(-/-)) mice. Both wild-type and ApoE(-/-) mice were intragastrically administered with 0.2 mL of copper sulfate pentahydrate (200 mg/kg; a total dose of 4 mg/d) or the same volume of saline daily for 12 weeks, respectively. Copper and oxidative stress markers in the liver tissue and in the serum were assessed. Our results showed that, compared with the wild-type mice administered with copper, TBARS as a marker of lipid peroxidation, the expression of oxygenase-1 (HO-1), NAD(P)H dehydrogenase, and quinone 1 (NQO1) significantly increased in the ApoE(-/-) mice administered with copper, meanwhile superoxide dismutase (SOD) activity significantly decreased. Thus, it is concluded that ApoE may protect the liver from copper-induced oxidative damage in Wilson's disease. Copyright © 2015 Elsevier Inc. All rights reserved.

Geochemical Characterization of Mine Waste, Mine Drainage, and Stream Sediments at the Pike Hill Copper Mine Superfund Site, Orange County, Vermont

USGS Publications Warehouse

Piatak, Nadine M.; Seal, Robert R.; Hammarstrom, Jane M.; Kiah, Richard G.; Deacon, Jeffrey R.; Adams, Monique; Anthony, Michael W.; Briggs, Paul H.; Jackson, John C.

2006-01-01

The Pike Hill Copper Mine Superfund Site in the Vermont copper belt consists of the abandoned Smith, Eureka, and Union mines, all of which exploited Besshi-type massive sulfide deposits. The site was listed on the U.S. Environmental Protection Agency (USEPA) National Priorities List in 2004 due to aquatic ecosystem impacts. This study was intended to be a precursor to a formal remedial investigation by the USEPA, and it focused on the characterization of mine waste, mine drainage, and stream sediments. A related study investigated the effects of the mine drainage on downstream surface waters. The potential for mine waste and drainage to have an adverse impact on aquatic ecosystems, on drinking- water supplies, and to human health was assessed on the basis of mineralogy, chemical concentrations, acid generation, and potential for metals to be leached from mine waste and soils. The results were compared to those from analyses of other Vermont copper belt Superfund sites, the Elizabeth Mine and Ely Copper Mine, to evaluate if the waste material at the Pike Hill Copper Mine was sufficiently similar to that of the other mine sites that USEPA can streamline the evaluation of remediation technologies. Mine-waste samples consisted of oxidized and unoxidized sulfidic ore and waste rock, and flotation-mill tailings. These samples contained as much as 16 weight percent sulfides that included chalcopyrite, pyrite, pyrrhotite, and sphalerite. During oxidation, sulfides weather and may release potentially toxic trace elements and may produce acid. In addition, soluble efflorescent sulfate salts were identified at the mines; during rain events, the dissolution of these salts contributes acid and metals to receiving waters. Mine waste contained concentrations of cadmium, copper, and iron that exceeded USEPA Preliminary Remediation Goals. The concentrations of selenium in mine waste were higher than the average composition of eastern United States soils. Most mine waste was potentially acid generating because of paste-pH values of less than 4 and negative net-neutralization potentials (NNP). The processed flotation-mill tailings, however, had a near neutral paste pH, positive NNP, and a few weight percent calcite. Leachate tests indicated that elements and compounds such as Al, Cd, Cu, Fe, Mn, Se, SO4, and Zn were leached from mine waste in concentrations that exceeded aquatic ecosystem and drinking-water standards. Mine waste from the Pike Hill mines was chemically and mineralogically similar to that from the Elizabeth and Ely mines. In addition, metals were leached and acid was produced from mine waste from the Pike Hill mines in comparable concentrations to those from the Elizabeth and Ely mines, although the host rock of the Pike Hill deposits contains significant amounts of carbonate minerals and, thus, a greater acid-neutralizing capacity when compared to the host rocks of the Elizabeth and Ely deposits. Water samples collected from unimpacted parts of the Waits River watershed generally contained lower amounts of metals compared to water samples from mine drainage, were alkaline, and had a neutral pH, which was likely because of calcareous bedrock. Seeps and mine pools at the mine site had acidic to neutral pH, ranged from oxic to anoxic, and generally contained concentrations of metals, for example, aluminum, cadmium, copper, iron, and zinc, that exceeded aquatic toxicity standards or drinking-water standards, or both. Surface waters directly downstream of the Eureka and Union mines were acidic, as indicated by pH values from 3.1 to 4.2, and contained high concentrations of some elements including as much as 11,400 micrograms per liter (?g/L) Al, as much as 22.9 ?g/L Cd, as much as 6,790 ?g/L Cu, as much as 23,300 ?g/L Fe, as much as 1,400 ?g/L Mn, and as much as 3,570 ?g/L Zn. The concentrations of these elements exceeded water-quality guidelines. Generally, in surface waters, the pH increased and the concentrations of these elemen

Direct Measurement of the Nanomechanical Stability of a Redox Protein Active Site and Its Dependence upon Metal Binding.

PubMed

Giannotti, Marina I; Cabeza de Vaca, Israel; Artés, Juan M; Sanz, Fausto; Guallar, Victor; Gorostiza, Pau

2015-09-10

The structural basis of the low reorganization energy of cupredoxins has long been debated. These proteins reconcile a conformationally heterogeneous and exposed metal-chelating site with the highly rigid copper center required for efficient electron transfer. Here we combine single-molecule mechanical unfolding experiments with statistical analysis and computer simulations to show that the metal-binding region of apo-azurin is mechanically flexible and that high mechanical stability is imparted by copper binding. The unfolding pathway of the metal site depends on the pulling residue and suggests that partial unfolding of the metal-binding site could be facilitated by the physical interaction with certain regions of the redox protein.

Anaconda Copper Mine, Yerington, NV; Proposed Settlement Agreement and Order on Consent

EPA Pesticide Factsheets

This notice announces the availability for review and comment of an administrative Settlement Agreement and Order on Consent under CERCLA between the EPA and Atlantic Richfield Company regarding the Anaconda Copper Mine Site in Yerington, Nevada.

A Recyclable Cu-MOF-74 Catalyst for the Ligand-Free O-Arylation Reaction of 4-Nitrobenzaldehyde and Phenol

PubMed Central

Leo, Pedro; Orcajo, Gisela; Briones, David; Calleja, Guillermo; Sánchez-Sánchez, Manuel; Martínez, Fernando

2017-01-01

The activity and recyclability of Cu-MOF-74 as a catalyst was studied for the ligand-free C–O cross-coupling reaction of 4-nitrobenzaldehyde (NB) with phenol (Ph) to form 4-formyldiphenyl ether (FDE). Cu-MOF-74 is characterized by having unsaturated copper sites in a highly porous metal-organic framework. The influence of solvent, reaction temperature, NB/Ph ratio, catalyst concentration, and basic agent (type and concentration) were evaluated. High conversions were achieved at 120 °C, 5 mol % of catalyst, NB/Ph ratio of 1:2, DMF as solvent, and 1 equivalent of K2CO3 base. The activity of Cu-MOF-74 material was higher than other ligand-free copper catalytic systems tested in this study. This catalyst was easily separated and reused in five successive runs, achieving a remarkable performance without significant porous framework degradation. The leaching of copper species in the reaction medium was negligible. The O-arylation between NB and Ph took place only in the presence of Cu-MOF-74 material, being negligible without the solid catalyst. The catalytic advantages of using nanostructured Cu-MOF-74 catalyst were also proven. PMID:28621710

A Recyclable Cu-MOF-74 Catalyst for the Ligand-Free O-Arylation Reaction of 4-Nitrobenzaldehyde and Phenol.

PubMed

Leo, Pedro; Orcajo, Gisela; Briones, David; Calleja, Guillermo; Sánchez-Sánchez, Manuel; Martínez, Fernando

2017-06-16

The activity and recyclability of Cu-MOF-74 as a catalyst was studied for the ligand-free C-O cross-coupling reaction of 4-nitrobenzaldehyde (NB) with phenol (Ph) to form 4-formyldiphenyl ether (FDE). Cu-MOF-74 is characterized by having unsaturated copper sites in a highly porous metal-organic framework. The influence of solvent, reaction temperature, NB/Ph ratio, catalyst concentration, and basic agent (type and concentration) were evaluated. High conversions were achieved at 120 °C, 5 mol % of catalyst, NB/Ph ratio of 1:2, DMF as solvent, and 1 equivalent of K₂CO₃ base. The activity of Cu-MOF-74 material was higher than other ligand-free copper catalytic systems tested in this study. This catalyst was easily separated and reused in five successive runs, achieving a remarkable performance without significant porous framework degradation. The leaching of copper species in the reaction medium was negligible. The O-arylation between NB and Ph took place only in the presence of Cu-MOF-74 material, being negligible without the solid catalyst. The catalytic advantages of using nanostructured Cu-MOF-74 catalyst were also proven.

Phenotypic Characterization of a copA Mutant of Neisseria gonorrhoeae Identifies a Link between Copper and Nitrosative Stress

PubMed Central

Djoko, Karrera Y.; Franiek, Jessica A.; Edwards, Jennifer L.; Falsetta, Megan L.; Kidd, Stephen P.; Potter, Adam J.; Chen, Nathan H.; Apicella, Michael A.; Jennings, Michael P.

2012-01-01

NGO0579 is annotated copA in the Neisseria gonorrhoeae chromosome, suggesting that it encodes a cation-transporting ATPase specific for copper ions. Compared to wild-type cells, a copA mutant was more sensitive to killing by copper ions but not to other transition metals. The mutant also accumulated a greater amount of copper, consistent with the predicted role of CopA as a copper efflux pump. The copA mutant showed a reduced ability to invade and survive within human cervical epithelial cells, although its ability to form a biofilm on the surface of these cells was not significantly different from that of the wild type. In the presence of copper, the copA mutant exhibited increased sensitivity to killing by nitrite or nitric oxide. Therefore, we concluded that copper ion efflux catalyzed by CopA is linked to the nitrosative stress defense system of Neisseria gonorrhoeae. These observations suggest that copper may exert its effects as an antibacterial agent in the innate immune system via an interaction with reactive nitrogen species. PMID:22184419

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.

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.

Potential of copper-tolerant grasses to implement phytostabilisation strategies on polluted soils in South D. R. Congo : Poaceae candidates for phytostabilisation.

PubMed

Boisson, Sylvain; Le Stradic, Soizig; Collignon, Julien; Séleck, Maxime; Malaisse, François; Ngoy Shutcha, Mylor; Faucon, Michel-Pierre; Mahy, Grégory

2016-07-01

Phytostabilisation (i.e. using plants to immobilise contaminants) represents a well-known technology to hamper heavy metal spread across landscapes. Southeastern D.R. Congo, Microchloa altera, a tolerant grass from the copper hills, was recently identified as a candidate species to stabilise copper in the soil. More than 50 grasses compose this flora, which may be studied to implement phytostabilisation strategies. However, little is known about their phenology, tolerance, reproductive strategy or demography. The present study aims to characterize the Poaceae that may be used in phytostabilisation purposes based on the following criteria: their ecological distribution, seed production at two times, abundance, soil coverage and the germination percentage of their seeds. We selected seven perennial Poaceae that occur on the copper hills. Their ecological distributions (i.e. species response curves) have been modelled along copper or cobalt gradients with generalised additive models using logic link based on 172 presence-absence samples on three sites. For other variables, a total of 69 quadrats (1 m(2)) were randomly placed across three sites and habitats. For each species, we compared the number of inflorescence-bearing stems (IBS) by plot, the percentage of cover, the number of seeds by IBS and the estimated number of seeds by plot between sites and habitat. Three species (Andropogon schirensis, Eragrostis racemosa and Loudetia simplex) were very interesting for phytostabilisation programs. They produced a large quantity of seeds and had the highest percentage of cover. However, A. schirensis and L. simplex presented significant variations in the number of seeds and the percentage of cover according to site.

Hypoxia induces copper stable isotope fractionation in hepatocellular carcinoma, in a HIF-independent manner.

PubMed

Bondanese, Victor P; Lamboux, Aline; Simon, Melanie; Lafont, Jérôme E; Albalat, Emmanuelle; Pichat, Sylvain; Vanacker, Jean-Marc; Telouk, Philippe; Balter, Vincent; Oger, Philippe; Albarède, Francis

2016-11-09

Hepatocellular carcinoma (HCC) is the most frequent type of primary liver cancer, with increasing incidence worldwide. The unrestrained proliferation of tumour cells leads to tumour hypoxia which in turn promotes cancer aggressiveness. While changes in the concentration of copper (Cu) have long been observed upon cancerization, we have recently reported that the isotopic composition of copper is also altered in several types of cancer. In particular, we showed that in hepatocellular carcinoma, tumour tissue contains heavier copper compared to the surrounding parenchyma. However, the reasons behind such isotopic signature remained elusive. Here we show that hypoxia causes heavy copper enrichment in several human cell lines. We also demonstrate that this effect of hypoxia is pH, HIF-1 and -2 independent. Our data identify a previously unrecognized cellular process associated with hypoxia, and suggests that in vivo tumour hypoxia determines copper isotope fractionation in HCC and other solid cancers.

COPPER COMPLEXATION BY NATURAL ORGANIC MATTER IN CONTAMINATED AND UNCOMTAINATED GROUND WATER

EPA Science Inventory

Ground-water samples were collected from an uncontaminated and a contaminated site. Copper complexation was characterized by ion-selective electrode (ISE), fluorescence quenching (FQ), and cathodic stripping voltammetric (CSV) titrations. All of the samples were titrated at their...

Nanostructures formed by displacement of porous silicon with copper: from nanoparticles to porous membranes

PubMed Central

2012-01-01

The application of porous silicon as a template for the fabrication of nanosized copper objects is reported. Three different types of nanostructures were formed by displacement deposition of copper on porous silicon from hydrofluoric acid-based solutions of copper sulphate: (1) copper nanoparticles, (2) quasi-continuous copper films, and (3) free porous copper membranes. Managing the parameters of porous silicon (pore sizes, porosity), deposition time, and wettability of the copper sulphate solution has allowed to achieve such variety of the copper structures. Elemental and structural analyses of the obtained structures are presented. Young modulus measurements of the porous copper membrane have been carried out and its modest activity in surface enhanced Raman spectroscopy is declared. PMID:22916840

Synthesis, crystal structure investigation and magnetism of the complex metal-rich boride series Crx(Rh1-yRuy)7-xB3 (x=0.88-1; y=0-1) with Th7Fe3-type structure

NASA Astrophysics Data System (ADS)

Misse, Patrick R. N.; Mbarki, Mohammed; Fokwa, Boniface P. T.

2012-08-01

Powder samples and single crystals of the new complex boride series Crx(Rh1-yRuy)7-xB3 (x=0.88-1; y=0-1) have been synthesized by arc-melting the elements under purified argon atmosphere on a water-cooled copper crucible. The products, which have metallic luster, were structurally characterized by single-crystal and powder X-ray diffraction as well as EDX measurements. Within the whole solid solution range the hexagonal Th7Fe3 structure type (space group P63mc, no. 186, Z=2) was identified. Single-crystal structure refinement results indicate the presence of chromium at two sites (6c and 2b) of the available three metal Wyckoff sites, with a pronounced preference for the 6c site. An unexpected Rh/Ru site preference was found in the Ru-rich region only, leading to two different magnetic behaviors in the solid solution: The Rh-rich region shows a temperature-independent (Pauli) paramagnetism whereas an additional temperature-dependent paramagnetic component is found in the Ru-rich region.

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.

Cost-benefit analysis of copper recovery in remediation projects: A case study from Sweden.

PubMed

Volchko, Yevheniya; Norrman, Jenny; Rosén, Lars; Karlfeldt Fedje, Karin

2017-12-15

Contamination resulting from past industrial activity is a problem throughout the world and many sites are severely contaminated by metals. Advances in research in recent years have resulted in the development of technologies for recovering metal from metal-rich materials within the framework of remediation projects. Using cost-benefit analysis (CBA), and explicitly taking uncertainties into account, this paper evaluates the potential social profitability of copper recovery as part of four remediation alternatives at a Swedish site. One alternative involves delivery of copper-rich ash to a metal production company for refining. The other three alternatives involve metal leaching from materials and sale of the resulting metal sludge for its further processing at a metal production company using metallurgical methods. All the alternatives are evaluated relative to the conventional excavation and disposal method. Metal recovery from the ash, metal sludge sale, and disposal of the contaminated soil and the ash residue at the local landfill site, was found to be the best remediation alternative. However, given the present conditions, its economic potential is low relative to the conventional excavation and disposal method but higher than direct disposal of the copper-rich ash for refining. Volatile copper prices, the high cost of processing equipment, the highly uncertain cost of the metal leaching and washing process, coupled with the substantial project risks, contribute most to the uncertainties in the CBA results for the alternatives involving metal leaching prior to refining. However, investment in processing equipment within the framework of a long-term investment project, production of safe, reusable soil residue, and higher copper prices on the metal market, can make metal recovery technology socially profitable. Copyright © 2017 Elsevier B.V. All rights reserved.

Effects of cell condition, pH, and temperature on lead, zinc, and copper sorption to Acidithiobacillus caldus strain BC13

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

John E. Aston; William A. Apel; Brady D. Lee

2010-12-01

This study describes the effects of cell condition, pH, and temperature on lead, zinc, and copper sorption to Acidithiobacillus caldus strain BC13 with a Langmuir model. Copper exhibited the highest loading capacity, 4.76 ± 0.28 mmol g-1, to viable cells at pH 5.5. The highest kL (binding-site affinity) observed was 61.2 ± 3.0 L mmol-1 to dehydrated cells at pH 4.0. The pHs that maximized loading capacities and binding-site affinities were generally between 4.0 and 5.5, where the sum of free-proton and complexed-metal concentrations was near a minimum. Of additional importance, lead, zinc, and copper sorbed to viable cells atmore » pH values as low as 1.5. Previous studies with other acidithiobacilli did not measure viable-cell sorption below pH 4.0. In separate experiments, desorption studies showed that far less copper was recovered from viable cells than any other metal or cell condition, suggesting that uptake may play an important role in copper sorption by At. caldus strain BC13. To reflect an applied system, the sorption of metal mixtures was also studied. In these experiments, lead, zinc, and copper sorption from a tertiary mixture were 40.2 ± 4.3%, 28.7 ± 3.8%, and 91.3 ± 3.0%, respectively, of that sorbed in single-metal systems.« less

Neutron activation analysis traces copper artifacts to geographical point of origin

NASA Technical Reports Server (NTRS)

Conway, M.; Fields, P.; Friedman, A.; Kastner, M.; Metta, D.; Milsted, J.; Olsen, E.

1967-01-01

Impurities remaining in the metallic copper are identified and quantified by spectrographic and neutron activation analysis. Determination of the type of ore used for the copper artifact places the geographic point of origin of the artifact.

The application of PGNAA borehole logging for copper grade estimation at Chuquicamata mine.

PubMed

Charbucinski, J; Duran, O; Freraut, R; Heresi, N; Pineyro, I

2004-05-01

The field trials of a prompt gamma neutron activation (PGNAA) spectrometric logging method and instrumentation (SIROLOG) for copper grade estimation in production holes of a porphyry type copper ore mine, Chuquicamata in Chile, are described. Examples of data analysis, calibration procedures and copper grade profiles are provided. The field tests have proved the suitability of the PGNAA logging system for in situ quality control of copper ore.

Direct ROS scavenging activity of CueP from Salmonella enterica serovar Typhimurium.

PubMed

Yoon, Bo-Young; Yeom, Ji-Hyun; Kim, Jin-Sik; Um, Si-Hyeon; Jo, Inseong; Lee, Kangseok; Kim, Yong-Hak; Ha, Nam-Chul

2014-02-01

Salmonella enterica serovar Typhimurium (S. Typhimurium) is an intracellular pathogen that has evolved to survive in the phagosome of macrophages. The periplasmic copper-binding protein CueP was initially known to confer copper resistance to S. Typhimurium. Crystal structure and biochemical studies on CueP revealed a putative copper binding site surrounded by the conserved cysteine and histidine residues. A recent study reported that CueP supplies copper ions to periplasmic Cu, Zn-superoxide dismutase (SodCII) at a low copper concentration and thus enables the sustained SodCII activity in the periplasm. In this study, we investigated the role of CueP in copper resistance at a high copper concentration. We observed that the survival of a cueP-deleted strain of Salmonella in macrophage phagosome was significantly reduced. Subsequent biochemical experiments revealed that CueP specifically mediates the reduction of copper ion using electrons released during the formation of the disulfide bond. We observed that the copper ion-mediated Fenton reaction in the presence of hydrogen peroxide was blocked by CueP. This study provides insight into how CueP confers copper resistance to S. Typhimurium in copper-rich environments such as the phagosome of macrophages.

Testing the Underlying Chemical Principles of the Biotic Ligand Model (BLM) to Marine Copper Systems: Measuring Copper Speciation Using Fluorescence Quenching.

PubMed

Tait, Tara N; McGeer, James C; Smith, D Scott

2018-01-01

Speciation of copper in marine systems strongly influences the ability of copper to cause toxicity. Natural organic matter (NOM) contains many binding sites which provides a protective effect on copper toxicity. The purpose of this study was to characterize copper binding with NOM using fluorescence quenching techniques. Fluorescence quenching of NOM with copper was performed on nine sea water samples. The resulting stability constants and binding capacities were consistent with literature values of marine NOM, showing strong binding with [Formula: see text] values from 7.64 to 10.2 and binding capacities ranging from 15 to 3110 nmol mg [Formula: see text] Free copper concentrations estimated at total dissolved copper concentrations corresponding to previously published rotifer effect concentrations, in the same nine samples, were statistically the same as the range of free copper calculated for the effect concentration in NOM-free artificial seawater. These data confirms the applicability of fluorescence spectroscopy techniques for NOM and copper speciation characterization in sea water and demonstrates that such measured speciation is consistent with the chemical principles underlying the biotic ligand model approach for bioavailability-based metals risk assessment.

Diffuse emission and control of copper in urban surface runoff.

PubMed

Boller, M A; Steiner, M

2002-01-01

Copper washed off from roofs and roads is considered to be a major contribution to diffuse copper pollution of urban environments. In order to guarantee sustainable protection of soils and water, the long-term strategy is to avoid or replace copper containing materials on roofs and fagades. Until achievement of this goal, a special adsorber system is suggested to control the diffuse copper fluxes by retention of copper by a mixture of granulated iron-hydroxide (GEH) and calcium carbonate. Since future stormwater runoff concepts are based on decentralised runoff infiltration into the underground, solutions are proposed which provide for copper retention in infiltration sites using GEH adsorption layers. The example of a large copper façade of which the runoff is treated in an adsorption trench reveals the first full-scale data on façade runoff and adsorber performance. During the first year of investigation average façade runoff concentrations in the range of 1-10 mg Cu/l are reduced by 96-99% in the adsorption ditch.

Copper-silver deposits of the Revett Formation, Montana and Idaho: origin and resource potential

USGS Publications Warehouse

Frost, Thomas P.; Zientek, Michael L.

2006-01-01

The Revett Formation of northern Idaho and western Montana contains major stratabound copper-silver deposits near Troy, Rock Creek, and Rock Lake, Montana. To help the U.S. Forest Service (USFS) meet its goal of integrating geoscience information into the land-planning process, U.S. Geological Survey (USGS) scientists recently completed a compilation of regional stratigraphy and mineralogy of the Revett Formation and a mineral resource assessment of Revett-type copper-silver deposits. The USGS assessment indicates that a large area of USFS-administered land in northwestern Montana and northern Idaho may contain significant undiscovered Revett-type copper-silver deposits.

Spatial and temporal variations of metal content and water quality in the Belaya River Basin

NASA Astrophysics Data System (ADS)

Fashchevskaia, T. B.; Motovilov, Y.

2016-12-01

The aim of this research is to identify the spatiotemporal regularities of iron, copper and zinc contents dynamics in the streams of the Belaya River basin. The Belaya River is situated in the South Ural region and is one of the biggest tributary in the Volga River basin with catchment area of 142 000 km2. More than sixty years the diverse economic activities are carried out in the Belaya River basin, the intensity of this activity is characterized by high temporal variability. The leading industries in the region are oil, mining, petroleum processing, chemistry and petro chemistry, mechanical engineering, metallurgy, power industry. The dynamics of human activities in the catchment and intra and inter-annual changes in the water quality are analyzed for the period 1969-2007 years. Inter-annual dynamics of the metal content in the river waters was identified on the basis of the long-term hydrological monitoring statistics at the 32 sites. It was found that the dynamics of intensity of economic activities in the Belaya River basin is the cause statistically significant changes in the metal content of the river network. Statistically homogeneous time intervals have been set for each monitoring site. Within these time intervals there were obtained averaged reliable quantitative estimations of water quality. Empirical probability distributions of iron, copper and zinc concentrations for various phases of the water regime in all investigated monitoring sites were approximated by Pearson type III curves and the averages of the concentration values, the coefficient of variation and asymmetry, as well as the values of the concentrations of metal in the range of 1-95% of frequency were estimated. It was found that by the end of the test period, the average long-term concentrations for iron and copper exceed MAC for fishery use, for zinc become smaller MAC in many streams of Belaya River basin. Acknowledgements. The work was financially supported by the Russian Foundation for Basic Research (Grant 15-05-09022)

Laramide alteration of proterozoic diabase: A likely contributor of copper to porphyry systems in the dripping spring mountains area, Southeastern Arizona

USGS Publications Warehouse

Force, E.R.

1998-01-01

Proterozoic diabase of the Dripping Spring range occurs as sills in the Proterozoic Apache Group and the Troy Quartzite and as intrusive sheets in basement rocks. The aggregate thickness of the diabase sills and intrusive sheets averages about 450 m in the part of the range showing little mid-Tertiary extension. Laramide alteration is of two types, dominated by chlorite and actinolite, respectively, and formed mostly from clinopyroxene. Actinolite-dominated assemblages are higher in Na and Ca. Hydrothermal biotite is common in the central areas of both alteration types. Laramide alteration forms two distribution patterns: a subequant pattern centered on Laramide intrusions and small porphyry deposits, characterized by actinolitic alteration, and a more extensive branching linear pattern that follows Laramide structures, centered on the larger Ray porphyry deposit, extending toward other Laramide districts and showing both alteration types. Alteration has apparently mobilized copper and other metals from diabase. The freshest diabase samples average about 120 ppm copper with little variation. In chloritic alteration, about 100 ppm of this copper is expelled in the most completely altered rocks. In actinolitic alteration, diabase may either gain or lose copper during alteration. Chloritic alteration constitutes roughly 70 percent of the diabase alteration in the study area, where alteration averages 41 percent complete. This implies liberation of about 9 ?? 106 tons (t) copper from diabase alteration, significantly less than the 16 ?? 106 t copper in Laramide mineral deposits of the superdistrict (Ray, Superior, Chilito, Christmas). However, diabase alteration may have been a significant component of the supply of copper to the Laramide mineral districts of the area. Synmineral magmatic sources of copper are not documented in this area. The distribution of Proterozoic diabase coincides with the central part of the southeastern Arizona copper province, which may thus owe much copper availability to an unusual abundance of diabase. However, many unanswered questions remain about metal supply from altering diabase.

CsoR Is Essential for Maintaining Copper Homeostasis in Mycobacterium tuberculosis

PubMed Central

Marcus, Sarah A.; Sidiropoulos, Sarah W.; Steinberg, Howard; Talaat, Adel M.

2016-01-01

Mycobacterium tuberculosis, a pathogen infecting one third of the world population, faces numerous challenges within the host, including high levels of copper. We have previously shown that M. tuberculosis CsoR is a copper inducible transcriptional regulator. Here we examined the hypothesis that csoR is necessary for maintaining copper homeostasis and surviving under various stress conditions. With an unmarked csoR knockout strain, we were able to characterize the role of csoR in M. tuberculosis as it faced copper and host stress. Growth under high levels of copper demonstrated that M. tuberculosis survives copper stress significantly better in the absence of csoR. Yet under minimal levels of copper, differential expression analysis revealed that the loss of csoR results in a cell wide hypoxia-type stress response with the induction of the DosR regulon. Despite the stress placed on M. tuberculosis by the loss of csoR, survival of the knockout strain was increased compared to wild type during the early chronic stages of mouse infection, suggesting that csoR could play an active role in modulating M. tuberculosis fitness within the host. Overall, analysis of CsoR provided an increased understanding of the M. tuberculosis copper response with implications for other intracellular pathogens harboring CsoR. PMID:26999439

Geology, geochemistry, and geophysics of the Fry Canyon uranium/copper project site, southeastern Utah - Indications of contaminant migration

USGS Publications Warehouse

Otton, James K.; Zielinski, Robert A.; Horton, Robert J.

2010-01-01

The Fry Canyon uranium/copper project site in San Juan County, southeastern Utah, was affected by the historical (1957-68) processing of uranium and copper-uranium ores. Relict uranium tailings and related ponds, and a large copper heap-leach pile at the site represent point sources of uranium and copper to local soils, surface water, and groundwater. This study was designed to establish the nature, extent, and pathways of contaminant dispersion. The methods used in this study are applicable at other sites of uranium mining, milling, or processing. The uranium tailings and associated ponds sit on a bench that is as much as 4.25 meters above the level of the adjacent modern channel of Fry Creek. The copper heap leach pile sits on bedrock just south of this bench. Contaminated groundwater from the ponds and other nearby sites moves downvalley and enters the modern alluvium of adjacent Fry Creek, its surface water, and also a broader, deeper paleochannel that underlies the modern creek channel and adjacent benches and stream terraces. The northern extent of contaminated groundwater is uncertain from geochemical data beyond an area of monitoring wells about 300 meters north of the site. Contaminated surface water extends to the State highway bridge. Some uranium-contaminated groundwater may also enter underlying bedrock of the Permian Cedar Mesa Sandstone along fracture zones. Four dc-resistivity surveys perpendicular to the valley trend were run across the channel and its adjacent stream terraces north of the heap-leach pile and ponds. Two surveys were done in a small field of monitoring wells and two in areas untested by borings to the north of the well field. Bedrock intercepts, salt distribution, and lithologic information from the wells and surface observations in the well field aided interpretation of the geophysical profiles there and allowed interpretation of the two profiles not tested by wells. The geophysical data for the two profiles to the north of the well field suggest that the paleochannel persists at least 900 m to the north of the heap leach and pond sites. Contamination of groundwater beneath the stream terraces may extend at least that far. Fry Creek surface water (six samples), seeps and springs (six samples), and wells (eight samples) were collected during a dry period of April 16-19, 2007. The most uranium-rich (18.7 milligrams per liter) well water on the site displays distinctive Ca-Mg-SO4-dominant chemistry indicating the legacy of heap leaching copper-uranium ores with sulfuric acid. This same water has strongly negative d34S of sulfate (-13.3 per mil) compared to most local waters of -2.4 to -5.4 per mil. Dissolved uranium species in all sampled waters are dominantly U(VI)-carbonate complexes. All waters are undersaturated with respect to U(VI) minerals. The average 234U/238U activity ratio (AR) in four well waters from the site (0.939 + or ? 0.011) is different from that of seven upstream waters (1.235 + or ? 0.069). This isotopic contrast permits quantitative estimates of mixing of site-derived uranium with natural uranium in waters collected downstream. At the time of sampling, uranium in downstream surface water was mostly (about 67 percent) site-derived and subject to further concentration by evaporation. Three monitoring wells located approximately 0.4 kilometer downstream contained dominantly (78-87 percent) site-derived uranium. Distinctive particles of chalcopyrite (CuFeS) and variably weathered pyrite (FeS2) are present in tailings at the stream edge on the site and are identified in stream sediments 1.3 kilometers downstream, based on inspection of polished grain mounts of magnetic mineral separates.

Dynamics of the metal binding domains and regulation of the human copper transporters ATP7B and ATP7A.

PubMed

Yu, Corey H; Dolgova, Natalia V; Dmitriev, Oleg Y

2017-04-01

Copper transporters ATP7A and ATP7B regulate copper levels in the human cells and deliver copper to the biosynthetic pathways. ATP7A and ATP7B belong to the P-type ATPases and share much of the domain architecture and the mechanism of ATP hydrolysis with the other, well-studied, enzymes of this type. A unique structural feature of the copper ATPases is the chain of six cytosolic metal-binding domains (MBDs), which are believed to be involved in copper-dependent regulation of the activity and intracellular localization of these enzymes. Although the structures of all the MBDs have been solved, the mechanism of copper-dependent regulation of ATP7B and ATP7A, the roles of individual MBDs, and the relationship between the regulatory and catalytic copper binding are still unknown. We describe the structure and dynamics of the MBDs, review the current knowledge about their functional roles and propose a mechanism of regulation of ATP7B by copper-dependent changes in the dynamics and conformation of the MBD chain. Transient interactions between the MBDs, rather than transitions between distinct static conformations are likely to form the structural basis of regulation of the ATP-dependent copper transporters in human cells. © 2016 IUBMB Life, 69(4):226-235, 2017. © 2017 International Union of Biochemistry and Molecular Biology.

Nature of the Active Sites for CO Reduction on Copper Nanoparticles; Suggestions for Optimizing Performance.

PubMed

Cheng, Tao; Xiao, Hai; Goddard, William A

2017-08-30

Recent experiments show that the grain boundaries (GBs) of copper nanoparticles (NPs) lead to an outstanding performance in reducing CO 2 and CO to alcohol products. We report here multiscale simulations that simulate experimental synthesis conditions to predict the structure of a 10 nm Cu NP (158 555 atoms). To identify active sites, we first predict the CO binding at a large number of sites and select four exhibiting CO binding stronger than the (211) step surface. Then, we predict the formation energy of the *OCCOH intermediate as a descriptor for C-C coupling, identifying two active sites, both of which have an under-coordinated surface square site adjacent to a subsurface stacking fault. We then propose a periodic Cu surface (4 by 4 supercell) with a similar site that substantially decreases the formation energy of *OCCOH, by 0.14 eV.

A tectonic model for the spatial occurrence of porphyry copper and polymetallic vein deposits - applications to Central Europe

USGS Publications Warehouse

Drew, Lawrence J.

2006-01-01

A structural-tectonic model, which was developed to assess the occurrence of undiscovered porphyry copper deposits and associated polymetallic vein systems for the Matra Mountains, Hungary, has been expanded here and applied to other parts of central Europe. The model explains how granitoid stocks are emplaced and hydrothermal fluids flow within local strain features (duplexes) within strike-slip fault systems that develop in continental crust above subducting plates. Areas of extension that lack shear at the corners and along the edges of the fault duplexes are structural traps for the granitoid stocks associated with porphyry copper deposits. By contrast, polymetallic vein deposits are emplaced where shear and extension are prevalent in the interior of the duplexes. This model was applied to the Late Cretaceous-age porphyry copper and polymetallic vein deposits in the Banat-Timok-Srednogorie region of Romania-Serbia-Bulgaria and the middle Miocene-age deposits in Romania and Slovakia. In the first area, porphyry copper deposits are most commonly located at the corners, and occasionally along the edges, of strike-slip fault duplexes, and the few polymetallic vein deposits identified are located at interior sites of the duplexes. In the second area, the model accounts for the preferred sites of porphyry copper and polymetallic vein deposits in the Apuseni Mountains (Romania) and central Slovakian volcanic field (Slovakia).

Copper Homeostasis in Escherichia coli and Other Enterobacteriaceae.

PubMed

Rensing, Christopher; Franke, Sylvia

2007-04-01

An interesting model for studying environmental influences shaping microbial evolution is provided by a multitude of copper resistance and copper homeostasis determinants in enteric bacteria. This review describes these determinants and tries to relate their presence to the habitat of the respective organism, as a current hypothesis predicts that the environment should determine an organism's genetic makeup. In Escherichia coli there are four regulons that are induced in the presence of copper. Two, the CueR and the CusR regulons, are described in detail. A central component regulating intracellular copper levels, present in all free-living enteric bacteria whose genomes have so far been sequenced, is a Cu(I)translocating P-type ATPase. The P-type ATPase superfamily is a ubiquitous group of proteins involved in the transport of charged substrates across biological membranes. Whereas some components involved in copper homeostasis can be found in both anaerobes and aerobes, multi-copper oxidases (MCOs) implicated in copper tolerance in E. coli, such as CueO and the plasmid-based PcoA, can be found only in aerobic organisms. Several features indicate that CueO, PcoA, and other related MCOs are specifically adapted to combat copper-mediated oxidative damage. In addition to these well-characterized resistance operons, there are numerous other genes that appear to be involved in copper binding and trafficking that have not been studied in great detail. SilE and its homologue PcoE, for example, are thought to effect the periplasmic binding and sequestration of silver and copper, respectively.

Copper Resistance of the Emerging Pathogen Acinetobacter baumannii

PubMed Central

Williams, Caitlin L.; Neu, Heather M.; Gilbreath, Jeremy J.; Michel, Sarah L. J.; Zurawski, Daniel V.

2016-01-01

ABSTRACT Acinetobacter baumannii is an important emerging pathogen that is capable of causing many types of severe infection, especially in immunocompromised hosts. Since A. baumannii can rapidly acquire antibiotic resistance genes, many infections are on the verge of being untreatable, and novel therapies are desperately needed. To investigate the potential utility of copper-based antibacterial strategies against Acinetobacter infections, we characterized copper resistance in a panel of recent clinical A. baumannii isolates. Exposure to increasing concentrations of copper in liquid culture and on solid surfaces resulted in dose-dependent and strain-dependent effects; levels of copper resistance varied broadly across isolates, possibly resulting from identified genotypic variation among strains. Examination of the growth-phase-dependent effect of copper on A. baumannii revealed that resistance to copper increased dramatically in stationary phase. Moreover, A. baumannii biofilms were more resistant to copper than planktonic cells but were still susceptible to copper toxicity. Exposure of bacteria to subinhibitory concentrations of copper allowed them to better adapt to and grow in high concentrations of copper; this copper tolerance response is likely achieved via increased expression of copper resistance mechanisms. Indeed, genomic analysis revealed numerous putative copper resistance proteins that share amino acid homology to known proteins in Escherichia coli and Pseudomonas aeruginosa. Transcriptional analysis revealed significant upregulation of these putative copper resistance genes following brief copper exposure. Future characterization of copper resistance mechanisms may aid in the search for novel antibiotics against Acinetobacter and other highly antibiotic-resistant pathogens. IMPORTANCE Acinetobacter baumannii causes many types of severe nosocomial infections; unfortunately, some isolates have acquired resistance to almost every available antibiotic, and treatment options are incredibly limited. Copper is an essential nutrient but becomes toxic at high concentrations. The inherent antimicrobial properties of copper give it potential for use in novel therapeutics against drug-resistant pathogens. We show that A. baumannii clinical isolates are sensitive to copper in vitro, both in liquid and on solid metal surfaces. Since bacterial resistance to copper is mediated though mechanisms of efflux and detoxification, we identified genes encoding putative copper-related proteins in A. baumannii and showed that expression of some of these genes is regulated by the copper concentration. We propose that the antimicrobial effects of copper may be beneficial in the development of future therapeutics that target multidrug-resistant bacteria. PMID:27520808

Inhibition and oxygen activation in copper amine oxidases.

PubMed

Shepard, Eric M; Dooley, David M

2015-05-19

Copper-containing amine oxidases (CuAOs) use both copper and 2,4,5-trihydroxyphenylalanine quinone (TPQ) to catalyze the oxidative deamination of primary amines. The CuAO active site is highly conserved and comprised of TPQ and a mononuclear type II copper center that exhibits five-coordinate, distorted square pyramidal coordination geometry with histidine ligands and equatorially and axially bound water in the oxidized, resting state. The active site is buried within the protein, and CuAOs from various sources display remarkable diversity with respect to the composition of the active site channel and cofactor accessibility. Structural and mechanistic factors that influence substrate preference and inhibitor sensitivity and selectivity have been defined. This Account summarizes the strategies used to design selective CuAO inhibitors based on active site channel characteristics, leading to either enhanced steric fits or the trapping of reactive electrophilic products. These findings provide a framework to support the future development of candidate molecules aimed at minimizing the negative side effects associated with drugs containing amine functionalities. This is vital given the existence of human diamine oxidase and vascular adhesion protein-1, which have distinct amine substrate preferences and are associated with different metabolic processes. Inhibition of these enzymes by antifungal or antiprotozoal agents, as well as classic monoamine oxidase (MAO) inhibitors, may contribute to the adverse side effects associated with drug treatment. These observations provide a rationale for the limited clinical value associated with certain amine-containing pharmaceuticals and emphasize the need for more selective AO inhibitors. This Account also discusses the novel roles of copper and TPQ in the chemistry of O2 activation and substrate oxidation. Reduced CuAOs exist in a redox equilibrium between the Cu(II)-TPQAMQ (aminoquinol) and Cu(I)-TPQSQ (semiquinone). Elucidating the roles of Cu(I), TPQSQ, and TPQAMQ in O2 activation, for example, distinguishing inner-sphere versus outer-sphere electron transfer mechanisms, has been actively investigated since the discovery of TPQSQ in 1991 and has only recently been clarified. Kinetics and spectroscopic studies encompassing metal substitution, stopped-flow and temperature-jump relaxation methods, and oxygen kinetic isotope experiments have provided strong support for an inner-sphere electron transfer step from Cu(I) to O2. Data for two enzymes support a mechanism wherein O2 prebinds to a three-coordinate Cu(I) site, yielding a [Cu(II)(η(1)-O2(-1))](+) intermediate, with H2O2 generated from ensuing rate-determining proton coupled electron transfer from TPQSQ. While kinetics data from the cobalt-substituted yeast enzyme indicated that O2 is reduced through an outer-sphere process involving TPQAMQ, new findings with a bacterial CuAO demonstrate that both the Cu(II) and Co(II) forms of the enzyme operate via parallel mechanisms involving metal-superoxide intermediates. Structural observations of a coordinated TPQSQ-Cu(I) complex in two CuAOs supports previous indications that Cu(II)/(I) ligand substitution chemistry may be mechanistically relevant. Substantial evidence indicates that rapid and reversible inner-sphere reduction of O2 at a three-coordinate Cu(I) site occurs, but the existence of a coordinated semiquinone in some AOs suggests that, in these enzymes, an outer-sphere reaction between O2 and TPQSQ may also be possible, since this is expected to be energetically favorable compared with outer-sphere electron transfer from TPQAMQ to O2.

Copper speciation in highway stormwater runoff as related to bioavailability and toxicity to ESA-listed salmon.

DOT National Transportation Integrated Search

2011-04-01

The objectives of this study were to 1) identify the effects of site location, storm hydrology, and water quality parameters on the concentration of dissolved copper (Cu2+diss) in Oregon highway runoff; 2) establish an analytical technique suitable f...

Copper clusters capture and convert carbon dioxide to make fuel | Argonne

Science.gov Websites

Photos Videos Fact Sheets, Brochures and Reports Summer Science Writing Internship Careers Education Photos Videos Fact Sheets, Brochures and Reports Summer Science Writing Internship Copper clusters sites, the current method of reduction creates high-pressure conditions to facilitate stronger bonds

Antibiotic and heavy metal resistance in enterococci from coastal marine sediment.

PubMed

Vignaroli, Carla; Pasquaroli, Sonia; Citterio, Barbara; Di Cesare, Andrea; Mangiaterra, Gianmarco; Fattorini, Daniele; Biavasco, Francesca

2018-06-01

Sediment samples from three coastal sites - two beach resorts (Beach 1 and Beach 2 sites) and an area lying between an oil refinery and a river estuary (Estuarine site) - were analyzed for antibiotic- and heavy metal (HM)-resistant enterococci. A total of 123 enterococci, 36 E. faecium, 34 E. casseliflavus, 33 E. hirae, 5 E. faecalis, 3 E. durans, 3 E. gallinarum, and 9 Enterococcus spp, were recovered. Strains resistant to erythromycin, tetracycline and quinupristin/dalfopristin (Q/D) were recovered from all sites, whereas multidrug-resistant isolates were recovered only from "Beach 2" (14%) and "Estuarine" (3.7%). As regards HM resistance, the strains showed a high frequency (68%) of cadmium and/or copper resistance and uniform susceptibility to mercury. The prevalence of cadmium-resistant strains was significantly higher among erythromycin-resistant than among erythromycin-susceptible strains. A significant association between cadmium or copper resistance and Q/D resistance was also observed at "Estuarine" site. The levels of the two HMs in sediment from all sites were fairly low, ranging from 0.070 to 0.126 μg/g, for cadmium and from 1.00 to 7.64 μg/g for copper. Mercury was always undetectable. These findings are consistent with reports that low HM concentrations may contribute to co-selection of antibiotic-resistant bacterial strains, including enterococci. Copyright © 2018 Elsevier Ltd. All rights reserved.

Antibacterial Properties of Copper Nanoparticle Dispersions: Influence of Synthesis Conditions and Physicochemical Characteristics

NASA Astrophysics Data System (ADS)

Godymchuk, A.; Frolov, G.; Gusev, A.; Zakharova, O.; Yunda, E.; Kuznetsov, D.; Kolesnikov, E.

2015-11-01

The production of bactericidal plasters, bandages and medicines with the inclusion of copper nanoparticles and copper ions may have a great potential in terms of their biomedical application. The work considers the influence of the synthesis conditions, size, aggregation status, and charge of nanoparticles in aqueous solutions as well as the type of microorganisms to the antibacterial properties of water suspensions of electroexplosive copper nanoparticles in the conditions in vitro in relation to strains Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, and Bacillus cereus. Water dispersions of copper nanoparticles were shown to inhibit the growth of test cells for both G+ and G- microbacteria but the degree of such an influence strongly depended on the type of a test strain. The authors have demonstrated that use of deeply purified water and alcohol-containing stabilizers at the synthesis of nanoparticles via metals electric erosion in the liquid prevents the copper nanoparticles coagulation and significantly influences on their physicochemical characteristics and, consequently, antibacterial properties.

The copYAZ Operon Functions in Copper Efflux, Biofilm Formation, Genetic Transformation, and Stress Tolerance in Streptococcus mutans

PubMed Central

Singh, Kamna; Senadheera, Dilani B.; Lévesque, Céline M.

2015-01-01

ABSTRACT In bacteria, copper homeostasis is closely monitored to ensure proper cellular functions while avoiding cell damage. Most Gram-positive bacteria utilize the copYABZ operon for copper homeostasis, where copA and copB encode copper-transporting P-type ATPases, whereas copY and copZ regulate the expression of the cop operon. Streptococcus mutans is a biofilm-forming oral pathogen that harbors a putative copper-transporting copYAZ operon. Here, we characterized the role of copYAZ operon in the physiology of S. mutans and delineated the mechanisms of copper-induced toxicity in this bacterium. We observed that copper induced toxicity in S. mutans cells by generating oxidative stress and disrupting their membrane potential. Deletion of the copYAZ operon in S. mutans strain UA159 resulted in reduced cell viability under copper, acid, and oxidative stress relative to the viability of the wild type under these conditions. Furthermore, the ability of S. mutans to form biofilms and develop genetic competence was impaired under copper stress. Briefly, copper stress significantly reduced cell adherence and total biofilm biomass, concomitantly repressing the transcription of the gtfB, gtfC, gtfD, gbpB, and gbpC genes, whose products have roles in maintaining the structural and/or functional integrity of the S. mutans biofilm. Furthermore, supplementation with copper or loss of copYAZ resulted in significant reductions in transformability and in the transcription of competence-associated genes. Copper transport assays revealed that the ΔcopYAZ strain accrued significantly large amounts of intracellular copper compared with the amount of copper accumulation in the wild-type strain, thereby demonstrating a role for CopYAZ in the copper efflux of S. mutans. The complementation of the CopYAZ system restored copper expulsion, membrane potential, and stress tolerance in the copYAZ-null mutant. Taking these results collectively, we have established the function of the S. mutans CopYAZ system in copper export and have further expanded knowledge on the importance of copper homeostasis and the CopYAZ system in modulating streptococcal physiology, including stress tolerance, membrane potential, genetic competence, and biofilm formation. IMPORTANCE S. mutans is best known for its role in the initiation and progression of human dental caries, one of the most common chronic diseases worldwide. S. mutans is also implicated in bacterial endocarditis, a life-threatening inflammation of the heart valve. The core virulence factors of S. mutans include its ability to produce and sustain acidic conditions and to form a polysaccharide-encased biofilm that provides protection against environmental insults. Here, we demonstrate that the addition of copper and/or deletion of copYAZ (the copper homeostasis system) have serious implications in modulating biofilm formation, stress tolerance, and genetic transformation in S. mutans. Manipulating the pathways affected by copper and the copYAZ system may help to develop potential therapeutics to prevent S. mutans infection in and beyond the oral cavity. PMID:26013484

Factors affecting catalysis of copper corrosion products in NDMA formation from DMA in simulated premise plumbing.

PubMed

Zhang, Hong; Andrews, Susan A

2013-11-01

This study investigated the effects of corrosion products of copper, a metal commonly employed in household plumbing systems, on N-nitrosodimethylamine (NDMA) formation from a known NDMA precursor, dimethylamine (DMA). Copper-catalyzed NDMA formation increased with increasing copper concentrations, DMA concentrations, alkalinity and hardness, but decreased with increasing natural organic matter (NOM) concentration. pH influenced the speciation of chloramine and the interactions of copper with DMA. The transformation of monochloramine (NH2Cl) to dichloramine and complexation of copper with DMA were involved in elevating the formation of NDMA by copper at pH 7.0. The inhibiting effect of NOM on copper catalysis was attributed to the rapid consumption of NH2Cl by NOM and/or the competitive complexation of NOM with copper to limit the formation of DMA-copper complexes. Hardness ions, as represented by Ca(2+), also competed with copper for binding sites on NOM, thereby weakening the inhibitory effect of NOM on NDMA formation. Common copper corrosion products also participated in these reactions but in different ways. Aqueous copper released from malachite [Cu2CO3(OH)2] was shown to promote NDMA formation while NDMA formation decreased in the presence of CuO, most likely due to the adsorption of DMA. Copyright © 2013 Elsevier Ltd. All rights reserved.

Modeling of light-induced degradation due to Cu precipitation in p-type silicon. II. Comparison of simulations and experiments

NASA Astrophysics Data System (ADS)

Vahlman, H.; Haarahiltunen, A.; Kwapil, W.; Schön, J.; Inglese, A.; Savin, H.

2017-05-01

The presence of copper impurities is known to deteriorate the bulk minority carrier lifetime of silicon. In p-type silicon, the degradation occurs only under carrier injection (e.g., illumination), but the reason for this phenomenon called copper-related light-induced degradation (Cu-LID) has long remained uncertain. To clarify the physics of this problem, a mathematical model of Cu-LID was introduced in Paper I of this article. Within the model, kinetic precipitation simulations are interlinked with a Schottky junction model for electric behavior of metallic precipitates. As this approach enables simulating precipitation directly at the minority carrier lifetime level, the model is verified in this second part with a direct comparison to the corresponding degradation experiments and literature data. Convincing agreement is found with different doping and Cu concentrations as well as at increased temperature, and in the dark, both simulated degradation and measured degradation are very slow. In addition, modeled final lifetimes after illumination are very close to experimental final lifetimes, and a correlation with the final precipitate size is found. However, the model underestimates experimentally observed differences in the degradation rate at different illumination intensities. Nevertheless, the results of this work support the theory of Cu-LID as a precipitate formation process. Part of the results also imply that heterogeneous nucleation sites play a role during precipitate nucleation. The model reveals fundamental aspects of the physics of Cu-LID including how doping and heterogeneous nucleation site concentrations can considerably influence the final recombination activity.

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.

A cadmium-transporting P1B-type ATPase in yeast Saccharomyces cerevisiae.

PubMed

Adle, David J; Sinani, Devis; Kim, Heejeong; Lee, Jaekwon

2007-01-12

Detoxification and homeostatic acquisition of metal ions are vital for all living organisms. We have identified PCA1 in yeast Saccharomyces cerevisiae as an overexpression suppressor of copper toxicity. PCA1 possesses signatures of a P1B-type heavy metal-transporting ATPase that is widely distributed from bacteria to humans. Copper resistance conferred by PCA1 is not dependent on catalytic activity, but it appears that a cysteine-rich region located in the N terminus sequesters copper. Unexpectedly, when compared with two independent natural isolates and an industrial S. cerevisiae strain, the PCA1 allele of the common laboratory strains we have examined possesses a missense mutation in a predicted ATP-binding residue conserved in P1B-type ATPases. Consistent with a previous report that identifies an equivalent mutation in a copper-transporting P1B-type ATPase of a Wilson disease patient, the PCA1 allele found in laboratory yeast strains is nonfunctional. Overexpression or deletion of the functional allele in yeast demonstrates that PCA1 is a cadmium efflux pump. Cadmium as well as copper and silver, but not other metals examined, dramatically increase PCA1 protein expression through post-transcriptional regulation and promote subcellular localization to the plasma membrane. Our study has revealed a novel metal detoxification mechanism in yeast mediated by a P1B-type ATPase that is unique in structure, substrate specificity, and mode of regulation.

Distribution and Fate of Energetics on DoD Test and Training Ranges: Interim Report 5

DTIC Science & Technology

2005-04-01

aluminum, arsenic, and iron were naturally elevated (Ampleman et al. 2003). A cadmium concentration at 0.3 ppb was observed in one sample. Copper...copper concentration was twice the CCME criterion. Iron was also observed in the Shaver River sample at three times the CCME criterion. Concentrations...mainly in C-295, the first site visited. Copper and iron were found at high concentrations in almost all samples; however, only one or two samples showed

Tracking metal ions through a Cu/Ag efflux pump assigns the functional roles of the periplasmic proteins

DOE PAGES

Chacon, Kelly N.; Mealman, Tiffany D.; McEvoy, Megan M.; ...

2014-10-13

Copper is an essential nutrient for all aerobic organisms but is toxic in excess. At the host–pathogen interface, macrophages respond to bacterial infection by copper-dependent killing mechanisms, whereas the invading bacteria are thought to counter with an up-regulation of copper transporters and efflux pumps. The tripartite efflux pump CusCBA and its metallochaperone CusF are vital to the detoxification of copper and silver ions in the periplasm of Escherichia coli. However, the mechanism of efflux by this complex, which requires the activation of the inner membrane pump CusA, is poorly understood. In this paper, we use selenomethionine (SeM) active site labelsmore » in a series of biological X-ray absorption studies at the selenium, copper, and silver edges to establish a “switch” role for the membrane fusion protein CusB. We determine that metal-bound CusB is required for activation of cuprous ion transfer from CusF directly to a site in the CusA antiporter, showing for the first time (to our knowledge) the in vitro activation of the Cus efflux pump. This metal-binding site of CusA is unlike that observed in the crystal structures of the CusA protein and is composed of one oxygen and two sulfur ligands. Finally, our results suggest that metal transfer occurs between CusF and apo-CusB, and that, when metal-loaded, CusB plays a role in the regulation of metal ion transfer from CusF to CusA in the periplasm.« less

Tracking metal ions through a Cu/Ag efflux pump assigns the functional roles of the periplasmic proteins.

PubMed

Chacón, Kelly N; Mealman, Tiffany D; McEvoy, Megan M; Blackburn, Ninian J

2014-10-28

Copper is an essential nutrient for all aerobic organisms but is toxic in excess. At the host-pathogen interface, macrophages respond to bacterial infection by copper-dependent killing mechanisms, whereas the invading bacteria are thought to counter with an up-regulation of copper transporters and efflux pumps. The tripartite efflux pump CusCBA and its metallochaperone CusF are vital to the detoxification of copper and silver ions in the periplasm of Escherichia coli. However, the mechanism of efflux by this complex, which requires the activation of the inner membrane pump CusA, is poorly understood. Here, we use selenomethionine (SeM) active site labels in a series of biological X-ray absorption studies at the selenium, copper, and silver edges to establish a "switch" role for the membrane fusion protein CusB. We determine that metal-bound CusB is required for activation of cuprous ion transfer from CusF directly to a site in the CusA antiporter, showing for the first time (to our knowledge) the in vitro activation of the Cus efflux pump. This metal-binding site of CusA is unlike that observed in the crystal structures of the CusA protein and is composed of one oxygen and two sulfur ligands. Our results suggest that metal transfer occurs between CusF and apo-CusB, and that, when metal-loaded, CusB plays a role in the regulation of metal ion transfer from CusF to CusA in the periplasm.

Organochlorines and heavy metals in 17-year cicadas pose no apparent dietary threat to birds

USGS Publications Warehouse

Clark, D.R.

1992-01-01

Organochlorine and heavy metal concentrations in 17-year cicadas from Prince Georges and Anne Arundel Counties, Maryland, were well below levels known to be harmful to birds. Cicadas contained concentrations of metals similar to or less than other local invertebrates except they contained more copper than did earthworms. Copper and lead concentrations in cicadas from one site may have been elevated by sewage plant effluent deposited during river floodings. Cicadas from the median of a major highway did not contain more lead than cicadas from non-traffic sites.

MX Siting Investigation. Mineral Resources Survey, Seven Additional Valleys, Nevada/Utah Siting Area. Volume II.

DTIC Science & Technology

1981-06-23

Minerals Inc. Box 90 W. Grace #100 Reno NV 89509 Anaconda Copper Co. 555 17th Street Denver CO 80217 Argus Resources Inc. Box 56 Austin NV 93099 Armenian...Donald F. 7272 Lindale Drive Sacramento CA 95828 Combined Metals Red. 1865 S. Main St. Salt Lake City UT 84115 Conlan, Mary Helen N/A Copper Range Co...hApl. Co. Mineral Services co. N/A Miragliotta, Vito 1184 S. 1000 E. Clearfield UT 84015 Neeser, Earl Francis Box 495 Goldfield NV 89013 Nev. Porphyry

Comment on "Active sites for CO2 hydrogenation to methanol on Cu/ZnO catalysts".

PubMed

Nakamura, Junji; Fujitani, Tadahiro; Kuld, Sebastian; Helveg, Stig; Chorkendorff, Ib; Sehested, Jens

2017-09-01

Kattel et al (Reports, 24 March 2017, p. 1296) report that a zinc on copper (Zn/Cu) surface undergoes oxidation to zinc oxide/copper (ZnO/Cu) during carbon dioxide (CO 2 ) hydrogenation to methanol and conclude that the Cu-ZnO interface is the active site for methanol synthesis. Similar experiments conducted two decades ago by Fujitani and Nakamura et al demonstrated that Zn is attached to formate rather than being fully oxidized. Copyright © 2017, American Association for the Advancement of Science.

Corrosive effect of the type of soil in the systems of grounding more used (copper and stainless steel) for local soil samples from the city of Tunja (Colombia), by means of electrochemical techniques

NASA Astrophysics Data System (ADS)

Guerrero, L.; Salas, Y.; Blanco, J.

2016-02-01

In this work electrochemical techniques were used to determine the corrosion behaviour of copper and stainless steel electrodes, used in grounding varying soil type with which they react. A slight but significant change in the corrosion rate, linear polarization resistance and equivalent parameters in the technique of electrochemical impedance spectroscopy circuit was observed. Electrolytes in soils are slightly different depending on laboratory study, but the influence was noted in the retention capacity of water, mainly due to clays, affecting ion mobility and therefore measures such as the corrosion rate. Behaviour was noted in lower potential for copper corrosion, though the corrosion rate regardless of the type of soil, was much higher for electrodes based on copper, by several orders of magnitude.

Spinons and holons for the one-dimensional three-band Hubbard models of high-temperature superconductors.

PubMed Central

Tahir-Kheli, J; Goddard, W A

1993-01-01

The one-dimensional three-band Hubbard Hamiltonian is shown to be equivalent to an effective Hamiltonian that has independent spinon and holon quasiparticle excitations plus a weak coupling of the two. The spinon description includes both copper sites and oxygen hole sites leading to a one-dimensional antiferromagnet incommensurate with the copper lattice. The holons are spinless noninteracting fermions in a simple cosine band. Because the oxygen sites are in the Hamiltonian, the quasiparticles are much simpler than in the exact solution of the t-J model for 2t = +/- J. If a similar description is correct for two dimensions, then the holons will attract in a p-wave potential. PMID:11607436

Activation of dioxygen by copper metalloproteins and insights from model complexes

PubMed Central

Quist, David A.; Diaz, Daniel E.; Liu, Jeffrey J.; Karlin, Kenneth D.

2017-01-01

Nature uses dioxygen as a key oxidant in the transformation of biomolecules. Among the enzymes that are utilized for these reactions are copper-containing met-alloenzymes, which are responsible for important biological functions such as the regulation of neurotransmitters, dioxygen transport, and cellular respiration. Enzymatic and model system studies work in tandem in order to gain an understanding of the fundamental reductive activation of dioxygen by copper complexes. This review covers the most recent advancements in the structures, spectroscopy, and reaction mechanisms for dioxygen-activating copper proteins and relevant synthetic models thereof. An emphasis has also been placed on cofactor biogenesis, a fundamentally important process whereby biomolecules are post-translationally modified by the pro-enzyme active site to generate cofactors which are essential for the catalytic enzymatic reaction. Significant questions remaining in copper-ion-mediated O2-activation in copper proteins are addressed. PMID:27921179

Activation of dioxygen by copper metalloproteins and insights from model complexes.

PubMed

Quist, David A; Diaz, Daniel E; Liu, Jeffrey J; Karlin, Kenneth D

2017-04-01

Nature uses dioxygen as a key oxidant in the transformation of biomolecules. Among the enzymes that are utilized for these reactions are copper-containing metalloenzymes, which are responsible for important biological functions such as the regulation of neurotransmitters, dioxygen transport, and cellular respiration. Enzymatic and model system studies work in tandem in order to gain an understanding of the fundamental reductive activation of dioxygen by copper complexes. This review covers the most recent advancements in the structures, spectroscopy, and reaction mechanisms for dioxygen-activating copper proteins and relevant synthetic models thereof. An emphasis has also been placed on cofactor biogenesis, a fundamentally important process whereby biomolecules are post-translationally modified by the pro-enzyme active site to generate cofactors which are essential for the catalytic enzymatic reaction. Significant questions remaining in copper-ion-mediated O 2 -activation in copper proteins are addressed.

Crystal structure of human lysyl oxidase-like 2 (hLOXL2) in a precursor state.

PubMed

Zhang, Xi; Wang, Qifan; Wu, Jianping; Wang, Jiawei; Shi, Yigong; Liu, Minhao

2018-04-10

Lysyl oxidases (LOXs), a type of copper- and lysyl tyrosylquinone (LTQ) -dependent amine oxidase, catalyze the oxidative deamination of lysine residues of extracellular matrix (ECM) proteins such as elastins and collagens and generate aldehyde groups. The oxidative deamination of lysine represents the foundational step for the cross-linking of elastin and collagen and thus is crucial for ECM modeling. Despite their physiological significance, the structure of this important family of enzymes remains elusive. Here we report the crystal structure of human lysyl oxidase-like 2 (hLOXL2) at 2.4-Å resolution. Unexpectedly, the copper-binding site of hLOXL2 is occupied by zinc, which blocks LTQ generation and the enzymatic activity of hLOXL2 in our in vitro assay. Biochemical analysis confirms that copper loading robustly activates hLOXL2 and supports LTQ formation. Furthermore, the LTQ precursor residues in the structure are distanced by 16.6 Å, corroborating the notion that the present structure may represent a precursor state and that pronounced conformational rearrangements would be required for protein activation. The structure presented here establishes an important foundation for understanding the structure-function relationship of LOX proteins and will facilitate LOX-targeting drug discovery. Copyright © 2018 the Author(s). Published by PNAS.

Response to copper of Acidithiobacillus ferrooxidans ATCC 23270 grown in elemental sulfur.

PubMed

Almárcegui, Rodrigo J; Navarro, Claudio A; Paradela, Alberto; Albar, Juan Pablo; von Bernath, Diego; Jerez, Carlos A

2014-11-01

The response of Acidithiobacillus ferrooxidans ATCC 23270 to copper was analyzed in sulfur-grown cells by using quantitative proteomics. Forty-seven proteins showed altered levels in cells grown in the presence of 50 mM copper sulfate. Of these proteins, 24 were up-regulated and 23 down-regulated. As seen before in ferrous iron-grown cells, there was a notorious up-regulation of RND-type Cus systems and different RND-type efflux pumps, indicating that these proteins are very important in copper resistance. Copper also triggered the down-regulation of the major outer membrane porin of A. ferrooxidans in sulfur-grown bacteria, suggesting they respond to the metal by decreasing the influx of cations into the cell. On the contrary, copper in sulfur-grown cells caused an overexpression of putative TadA and TadB proteins known to be essential for biofilm formation in bacteria. Surprisingly, sulfur-grown microorganisms showed increased levels of proteins related with energy generation (rus and petII operons) in the presence of copper. Although rus operon is overexpressed mainly in cells grown in ferrous iron, the up-regulation of rusticyanin in sulfur indicates a possible role for this protein in copper resistance as well. Finally, copper response in A. ferrooxidans appears to be influenced by the substrate being oxidized by the microorganism. Copyright © 2014 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.

Sustainable p-type copper selenide solar material with ultra-large absorption coefficient

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

Chen, Erica M.; Williams, Logan; Olvera, Alan

We report the synthesis of CTSe, a p-type titanium copper selenide semiconductor. Its band gap (1.15 eV) and its ultra-large absorption coefficient (10 5 cm −1 ) in the entire visible range make it a promising Earth-abundant solar absorber material.

Sustainable p-type copper selenide solar material with ultra-large absorption coefficient

DOE PAGES

Chen, Erica M.; Williams, Logan; Olvera, Alan; ...

2018-01-01

We report the synthesis of CTSe, a p-type titanium copper selenide semiconductor. Its band gap (1.15 eV) and its ultra-large absorption coefficient (10 5 cm −1 ) in the entire visible range make it a promising Earth-abundant solar absorber material.

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).

Inhibitory effect of brazilein on tyrosinase and melanin synthesis: Kinetics and in silico approach.

PubMed

Hridya, Hemachandran; Amrita, Anantharaman; Sankari, Mohan; George Priya Doss, C; Gopalakrishnan, Mohan; Gopalakrishnan, Chandrasekaran; Siva, Ramamoorthy

2015-11-01

In our present study, the inhibitory effect of brazilein from Caesalpinia sappan on tyrosinase activity was investigated through multi-spectroscopic and molecular docking techniques. The result has shown that brazilein reversibly inhibited tyrosinase in a mixed type manner. The interaction of brazilein with the amino acid residues of tyrosinase has been validated through fluorescence quenching studies. Copper interaction studies suggested that brazilein could bind with copper ions of the enzyme. Circular dichroism analysis confirmed that brazilein induced secondary structural changes in tyrosinase. Docking studies further authenticate that brazilein forms hydrophobic and hydrogen bonding with the active site residues of tyrosinase. Moreover, in vitro studies confirmed that the inhibitory mechanism of cellular tyrosinase and melanin synthesis by brazilein in B16F0 melanoma cells. These results suggested that brazilein act as a potential tyrosinase inhibitor and it would contribute as a of novel tyrosinase inhibitor in food, cosmetic and pharmaceutical industry. Copyright © 2015 Elsevier B.V. All rights reserved.

Characterization of the recombinant copper chaperone (CCS) from the plant Glycine (G.) max.

PubMed

Sagasti, Sara; Yruela, Inmaculada; Bernal, Maria; Lujan, Maria A; Frago, Susana; Medina, Milagros; Picorel, Rafael

2011-02-01

The goal of the present work was to characterize the recombinant copper chaperone (CCS) from soybean. Very little is known about plant copper chaperones, which makes this study of current interest, and allows for a comparison with the better known homologues from yeast and humans. To obtain sizeable amounts of pure protein suitable for spectroscopic characterization, we cloned and overexpressed the G. max CCS chaperone in E. coli in the presence of 0.5 mM CuSO(4) and 0.5 mM ZnSO(4) in the broth. A pure protein preparation was obtained by using two IMAC steps and pH gradient chromatography. Most of the proteins were obtained as apo-form, devoid of copper atoms. The chaperone showed a high content (i.e., over 40%) of loops, turns and random coil as determined both by circular dichroism and homology modelling. The homology 3-D structural model suggests the protein might fold in three structural protein domains. The 3-D model along with the primary structure and spectroscopic data may suggest that copper atoms occupy the two metal binding sites, MKCEGC and CTC, within the N-terminal domain I and C-terminal domain III, respectively. But only one Zn-binding site was obtained spectroscopically.

Synthesis of Large and Few Atomic Layers of Hexagonal Boron Nitride on Melted Copper

PubMed Central

Khan, Majharul Haque; Huang, Zhenguo; Xiao, Feng; Casillas, Gilberto; Chen, Zhixin; Molino, Paul J.; Liu, Hua Kun

2015-01-01

Hexagonal boron nitride nanosheets (h-BNNS) have been proposed as an ideal substrate for graphene-based electronic devices, but the synthesis of large and homogeneous h-BNNS is still challenging. In this contribution, we report a facile synthesis of few-layer h-BNNS on melted copper via an atmospheric pressure chemical vapor deposition process. Comparative studies confirm the advantage of using melted copper over solid copper as a catalyst substrate. The former leads to the formation of single crystalline h-BNNS that is several microns in size and mostly in mono- and bi-layer forms, in contrast to the polycrystalline and mixed multiple layers (1–10) yielded by the latter. This difference is likely to be due to the significantly reduced and uniformly distributed nucleation sites on the smooth melted surface, in contrast to the large amounts of unevenly distributed nucleation sites that are associated with grain boundaries and other defects on the solid surface. This synthesis is expected to contribute to the development of large-scale manufacturing of h-BNNS/graphene-based electronics. PMID:25582557

Synthesis of large and few atomic layers of hexagonal boron nitride on melted copper.

PubMed

Khan, Majharul Haque; Huang, Zhenguo; Xiao, Feng; Casillas, Gilberto; Chen, Zhixin; Molino, Paul J; Liu, Hua Kun

2015-01-13

Hexagonal boron nitride nanosheets (h-BNNS) have been proposed as an ideal substrate for graphene-based electronic devices, but the synthesis of large and homogeneous h-BNNS is still challenging. In this contribution, we report a facile synthesis of few-layer h-BNNS on melted copper via an atmospheric pressure chemical vapor deposition process. Comparative studies confirm the advantage of using melted copper over solid copper as a catalyst substrate. The former leads to the formation of single crystalline h-BNNS that is several microns in size and mostly in mono- and bi-layer forms, in contrast to the polycrystalline and mixed multiple layers (1-10) yielded by the latter. This difference is likely to be due to the significantly reduced and uniformly distributed nucleation sites on the smooth melted surface, in contrast to the large amounts of unevenly distributed nucleation sites that are associated with grain boundaries and other defects on the solid surface. This synthesis is expected to contribute to the development of large-scale manufacturing of h-BNNS/graphene-based electronics.

Accumulation of heavy metals and As in liver, hair, femur, and lung of Persian jird (Meriones persicus) in Darreh Zereshk copper mine, Iran.

PubMed

Khazaee, Manoochehr; Hamidian, Amir Hossein; Alizadeh Shabani, Afshin; Ashrafi, Sohrab; Mirjalili, Seyyed Ali Ashghar; Esmaeilzadeh, Esmat

2016-02-01

Rodents frequently serve as bioindicator to monitor the quality of the environment. Concentrations of 11 elements (Cd, Co, Ti, Fe, Mn, Cu, Sb, As, Sr, Ni, and Cr) were investigated and compared in liver, hair, femur, and lung of the Persian jird (Meriones persicus) from Darreh Zereshk copper mine, Iran. Metals were determined in different tissues of 39 individuals of Persian jird, collected by snap trap in 2014 from five areas of Darreh Zereshk copper mine. Samples were prepared by wet digestion method, and the contents of elements were analyzed with ICP-OES (VARIAN, 725-ES) instrument. Cadmium, Sb, and Co were below the limit of detection, and Mn and As were found only in hair and liver tissues. We detected the highest concentration of Cu, As, Ti, Fe, Mn, Cr, and Ni in hair in comparison with other tissues. Significant higher levels of Ti in femur and hair; Fe in liver and hair; Mn in liver; As in hair; Sr in lung; Cr in lung, hair, femur, and liver; Cu in femur; and Ni in liver and lung tissues were observed in females. Nearly all element concentrations in the tissues of Persian jird from flotation site, Darreh Zereshk and Hasan Abad villages and leaching site (mining areas) were higher than those from tailing dump site (reference site). We found the highest concentrations of As in liver and hair; Ni and Cr in liver, hair, and lung; and Sr in lung and hair tissues of Persian jird in leaching site. We tried to specify the status of elements before fully exploitation of Darreh Zereshk copper mine by using bioindicator species. Based on our achievements, initial activities did not strongly pollute the surrounded environment of the mine. The high abundance of Persian jird as well as their several proper features makes them a suitable species for biomonitoring programs especially for further studies will be performed after full exploitation of Darreh Zereshk copper mine.

Relation of precipitation quality to storm type, and deposition of dissolved chemical constituents from precipitation in Massachusetts, 1983-85

USGS Publications Warehouse

Gay, F.B.; Melching, C.S.

1995-01-01

Precipitation samples were collected for 83 storms at a rural inland site in Princeton, Mass., and 73 storms at a rural coastal site in Truro, Mass., to examine the quality of precipitation from storms and relate quality to three storm types (oceanic cyclone, continental cyclone, and cold front). At the inland site, Princeton, ranked-means of precipitation depth, storm duration, specific conductance, and concentrations and loads of hydrogen, sulfate, aluminum, bromide, and copper ions were affected by storm type. At the coastal site, Truro, ranked means of precipitation depth, storm duration, and concentrations and loads of calcium, chloride, magnesium, potassium, and sodium ions were affected by storm type. Precipitation chemistry at the coastal site was 85 percent oceanic in orgin, whereas precipitation 72 kilometers inland was 60 percent hydrogen, nitrate, and sulfate ions, reflecting fossil-fuel combustion. Concentrations and loads for specific conductance and 9 chemical constituents on an annual and seasonal basis were determined from National Atmospheric Deposition Program data for spring 1983 through winter 1985 at Quabbin (rural, inland), Waltham (suburban, inland) and Truro (rural, coastal), Massachusetts. Concentrations of magnesium, potassium, sodium, and chloride concentrations were highest at the coast and much lower inland, with very little difference between Waltham and Quabbin. Loads of ammonium, nitrate, sulfate, and hydrogen are highest at Quabbin and are about equal at Waltham and Truro. About twice as much nitrate and hydrogen and about 35 percent more sulfate is deposited at Quabbin than at Waltham or Truro; this pattern indicates that the interior of Massachusetts receives more acidic precipitation than do the eastern or the coastal areas of Massachusetts.

New copper resistance determinants in the extremophile acidithiobacillus ferrooxidans: a quantitative proteomic analysis.

PubMed

Almárcegui, Rodrigo J; Navarro, Claudio A; Paradela, Alberto; Albar, Juan Pablo; von Bernath, Diego; Jerez, Carlos A

2014-02-07

Acidithiobacillus ferrooxidans is an extremophilic bacterium used in biomining processes to recover metals. The presence in A. ferrooxidans ATCC 23270 of canonical copper resistance determinants does not entirely explain the extremely high copper concentrations this microorganism is able to stand, suggesting the existence of other efficient copper resistance mechanisms. New possible copper resistance determinants were searched by using 2D-PAGE, real time PCR (qRT-PCR) and quantitative proteomics with isotope-coded protein labeling (ICPL). A total of 594 proteins were identified of which 120 had altered levels in cells grown in the presence of copper. Of this group of proteins, 76 were up-regulated and 44 down-regulated. The up-regulation of RND-type Cus systems and different RND-type efflux pumps was observed in response to copper, suggesting that these proteins may be involved in copper resistance. An overexpression of most of the genes involved in histidine synthesis and several of those annotated as encoding for cysteine production was observed in the presence of copper, suggesting a possible direct role for these metal-binding amino acids in detoxification. Furthermore, the up-regulation of putative periplasmic disulfide isomerases was also seen in the presence of copper, suggesting that they restore copper-damaged disulfide bonds to allow cell survival. Finally, the down-regulation of the major outer membrane porin and some ionic transporters was seen in A. ferrooxidans grown in the presence of copper, indicating a general decrease in the influx of the metal and other cations into the cell. Thus, A. ferrooxidans most likely uses additional copper resistance strategies in which cell envelope proteins are key components. This knowledge will not only help to understand the mechanism of copper resistance in this extreme acidophile but may help also to select the best fit members of the biomining community to attain more efficient industrial metal leaching processes.

Variation in whole DNA methylation in red maple (Acer rubrum) populations from a mining region: association with metal contamination and cation exchange capacity (CEC) in podzolic soils.

PubMed

Kalubi, K N; Mehes-Smith, M; Spiers, G; Omri, A

2017-04-01

Although a number of publications have provided convincing evidence that abiotic stresses such as drought and high salinity are involved in DNA methylation reports on the effects of metal contamination, pH, and cation exchange on DNA modifications are limited. The main objective of the present study is to determine the relationship between metal contamination and Cation exchange capacity (CEC) on whole DNA modifications. Metal analysis confirms that nickel and copper are the main contaminants in sampled sites within the Greater Sudbury Region (Ontario, Canada) and liming has increased soil pH significantly even after 30 years following dolomitic limestone applications. The estimated CEC values varied significantly among sites, ranging between 1.8 and 10.5 cmol(+) kg -1 , with a strong relationship being observed between CEC and pH (r = 0.96**). Cation exchange capacity, significantly lower in highly metal contaminated sites compared to both reference and less contaminated sites, was higher in the higher organic matter limed compared to unlimed sites. There was a significant variation in the level of cytosine methylation among the metal-contaminated sites. Significant and strong negative correlations between [5mdC]/[dG] and bioavailable nickel (r = -0.71**) or copper (r = -0.72**) contents were observed. The analysis of genomic DNA for adenine methylation in this study showed a very low level of [6N-mdA]/dT] in Acer rubrum plants analyzed ranging from 0 to 0.08%. Significant and very strong positive correlation was observed between [6N-mdA]/dT] and soil bioavailable nickel (r = 0.78**) and copper (r = 0.88**) content. This suggests that the increased bioavailable metal levels associated with contamination by nickel and copper particulates are associated with cytosine and adenine methylation.

Copper speciation in variably toxic sediments at the Ely Copper Mine, Vermont, United States

USGS Publications Warehouse

Kimball, Bryn E.; Foster, Andrea L.; Seal, Robert R.; Piatak, Nadine M.; Webb, Samuel M.; Hammarstrom, Jane M.

2016-01-01

At the Ely Copper Mine Superfund site, Cu concentrations exceed background values in both streamwater (160–1200 times) and sediments (15–79 times). Previously, these sediment samples were incubated with laboratory test organisms, and they exhibited variable toxicity for different stream sites. In this study we combined bulk- and microscale techniques to determine Cu speciation and distribution in these contaminated sediments on the basis of evidence from previous work that Cu was the most important stressor in this environment and that variable observed toxicity could have resulted from differences in Cu speciation. Copper speciation results were similar at microscopic and bulk scales. The major Cu species in the more toxic samples were sorbed or coprecipitated with secondary Mn (birnessite) and Fe minerals (jarosite and goethite), which together accounted for nearly 80% of the total Cu. The major Cu species in the less toxic samples were Cu sulfides (chalcopyrite and a covellite-like phase), making up about 80–95% of the total Cu, with minor amounts of Cu associated with jarosite or goethite. These Cu speciation results are consistent with the toxicity results, considering that Cu sorbed or coprecipitated with secondary phases at near-neutral pH is relatively less stable than Cu bound to sulfide at lower pH. The more toxic stream sediment sites were those that contained fewer detrital sulfides and were upstream of the major mine waste pile, suggesting that removal and consolidation of sulfide-bearing waste piles on site may not eliminate all sources of bioaccessible Cu.

Determination of instream metal loads using tracer-injection and synoptic-sampling techniques in Wightman Fork, southwestern Colorado, September 1997

USGS Publications Warehouse

Ortiz, Roderick F.; Bencala, Kenneth E.

2001-01-01

Spatial determinations of the metal loads in Wightman Fork can be used to identify potential source areas to the stream. In September 1997, a chloride tracer-injection study was done concurrently with synoptic water-quality sampling in Wightman Fork near the Summitville Mine site. Discharge was determined and metal concentrations at 38 sites were used to generate mass-load profiles for dissolved aluminum, copper, iron, manganese, and zinc. The U.S. Environmental Protection Agency had previously identified these metals as contaminants of concern.Metal loads increased substantially in Wightman Fork near the Summitville Mine. A large increase occurred along a 60-meter reach that is north of the North Waste Dump and generally corresponds to a region of radial faults. Metal loading from this reach was equivalent to 50 percent or more of the dissolved aluminum, copper, iron, manganese, and zinc load upstream from the outfall of the Summitville Water Treatment Facility (SWTF). Overall, sources along the entire reach upstream from the SWTF were equivalent to 15 percent of the iron, 33 percent of the copper and manganese, 58 percent of the zinc, and 66 percent of the aluminum load leaving the mine site. The largest increases in metal loading to Wightman Fork occurred as a result of inflow from Cropsy Creek. Aluminum, iron, manganese, and zinc loads from Cropsy Creek were equivalent to about 40 percent of the specific metal load leaving the mine site. Copper, iron, and manganese loads from Cropsy Creek were nearly as large or larger than the load from sources upstream from the SWTF.

Combining -Omics to Unravel the Impact of Copper Nutrition on Alfalfa (Medicago sativa) Stem Metabolism.

PubMed

Printz, Bruno; Guerriero, Gea; Sergeant, Kjell; Audinot, Jean-Nicolas; Guignard, Cédric; Renaut, Jenny; Lutts, Stanley; Hausman, Jean-Francois

2016-02-01

Copper can be found in the environment at concentrations ranging from a shortage up to the threshold of toxicity for plants, with optimal growth conditions situated in between. The plant stem plays a central role in transferring and distributing minerals, water and other solutes throughout the plant. In this study, alfalfa is exposed to different levels of copper availability, from deficiency to slight excess, and the impact on the metabolism of the stem is assessed by a non-targeted proteomics study and by the expression analysis of key genes controlling plant stem development. Under copper deficiency, the plant stem accumulates specific copper chaperones, the expression of genes involved in stem development is decreased and the concentrations of zinc and molybdenum are increased in comparison with the optimum copper level. At the optimal copper level, the expression of cell wall-related genes increases and proteins playing a role in cell wall deposition and in methionine metabolism accumulate, whereas copper excess imposes a reduction in the concentration of iron in the stem and a reduced abundance of ferritins. Secondary ion mass spectrometry (SIMS) analysis suggests a role for the apoplasm as a copper storage site in the case of copper toxicity. © The Author 2016. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists.

Combining -Omics to Unravel the Impact of Copper Nutrition on Alfalfa (Medicago sativa) Stem Metabolism

PubMed Central

Printz, Bruno; Guerriero, Gea; Sergeant, Kjell; Audinot, Jean-Nicolas; Guignard, Cédric; Renaut, Jenny; Lutts, Stanley; Hausman, Jean-Francois

2016-01-01

Copper can be found in the environment at concentrations ranging from a shortage up to the threshold of toxicity for plants, with optimal growth conditions situated in between. The plant stem plays a central role in transferring and distributing minerals, water and other solutes throughout the plant. In this study, alfalfa is exposed to different levels of copper availability, from deficiency to slight excess, and the impact on the metabolism of the stem is assessed by a non-targeted proteomics study and by the expression analysis of key genes controlling plant stem development. Under copper deficiency, the plant stem accumulates specific copper chaperones, the expression of genes involved in stem development is decreased and the concentrations of zinc and molybdenum are increased in comparison with the optimum copper level. At the optimal copper level, the expression of cell wall-related genes increases and proteins playing a role in cell wall deposition and in methionine metabolism accumulate, whereas copper excess imposes a reduction in the concentration of iron in the stem and a reduced abundance of ferritins. Secondary ion mass spectrometry (SIMS) analysis suggests a role for the apoplasm as a copper storage site in the case of copper toxicity. PMID:26865661

Metabolic crossroads of iron and copper

PubMed Central

Collins, James F; Prohaska, Joseph R; Knutson, Mitchell D

2013-01-01

Interactions between the essential dietary metals, iron and copper, have been known for many years. This review highlights recent advances in iron-copper interactions with a focus on tissues and cell types important for regulating whole-body iron and copper homeostasis. Cells that mediate dietary assimilation (enterocytes) and storage and distribution (hepatocytes) of iron and copper are considered, along with the principal users (erythroid cells) and recyclers of red cell iron (reticuloendothelial macrophages). Interactions between iron and copper in the brain are also discussed. Many unanswered questions regarding the role of these metals and their interactions in health and disease emerge from this synopsis, highlighting extensive future research opportunities. PMID:20384844

Molecular Features of the Copper Binding Sites in the Octarepeat Domain of the Prion Protein†

PubMed Central

Burns, Colin S.; Aronoff-Spencer, Eliah; Dunham, Christine M.; Lario, Paula; Avdievich, Nikolai I.; Antholine, William E.; Olmstead, Marilyn M.; Vrielink, Alice; Gerfen, Gary J.; Peisach, Jack; Scott, William G.; Millhauser, Glenn L.

2010-01-01

Recent evidence suggests that the prion protein (PrP) is a copper binding protein. The N-terminal region of human PrP contains four sequential copies of the highly conserved octarepeat sequence PHGGGWGQ spanning residues 60–91. This region selectively binds Cu2+ in vivo. In a previous study using peptide design, EPR, and CD spectroscopy, we showed that the HGGGW segment within each octarepeat comprises the fundamental Cu2+ binding unit [Aronoff-Spencer et al. (2000) Biochemistry 40, 13760–13771]. Here we present the first atomic resolution view of the copper binding site within an octarepeat. The crystal structure of HGGGW in a complex with Cu2+ reveals equatorial coordination by the histidine imidazole, two deprotonated glycine amides, and a glycine carbonyl, along with an axial water bridging to the Trp indole. Companion S-band EPR, X-band ESEEM, and HYSCORE experiments performed on a library of 15N-labeled peptides indicate that the structure of the copper binding site in HGGGW and PHGGGWGQ in solution is consistent with that of the crystal structure. Moreover, EPR performed on PrP(23–28, 57–91) and an 15N-labeled analogue demonstrates that the identified structure is maintained in the full PrP octarepeat domain. It has been shown that copper stimulates PrP endocytosis. The identified Gly–Cu linkage is unstable below pH ≈6.5 and thus suggests a pH-dependent molecular mechanism by which PrP detects Cu2+ in the extracellular matrix or releases PrP-bound Cu2+ within the endosome. The structure also reveals an unusual complementary interaction between copper-structured HGGGW units that may facilitate molecular recognition between prion proteins, thereby suggesting a mechanism for transmembrane signaling and perhaps conversion to the pathogenic form. PMID:11900542

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.

Developing on-site paper colorimetric monitoring technique for quick evaluating copper ion concentration in mineral wastewater

NASA Astrophysics Data System (ADS)

Liu, Guokun; Peng, Jingji; Zheng, Hong; Yuan, Dongxing

2018-05-01

With the reinforce of the copper mining, the on-site monitoring of the accompanied effluent discharge is highly demanded for the emergency response to minimize the negative effect of the effluent on the surrounding ecosystem. On the basis of the specific interaction between Cu2+ and L-Cysteine (L-Cys), which was modified on gold nanoparticles (Au NPs), and the aggregation dependent surface plasmon resonance (SPR) of Au NPs, we developed an easy-on-going paper colorimetric method for the quick evaluating the copper ion concentration in the waste water excreted from the copper mine. The color change of L-Cys modified Au NPs (L-Cys-Au NPs)immobilized on a filter paper was very sensitive to the Cu2+ concentration and free of interference from other metal ions typically in waste water. The proposed paper colorimetry has the LOD of 0.09 mg/L and the linear range of 0.1-10 mg/L, respectively, with the RSD (n = 5) was 6.6% for 1 mg/L Cu2+ and 3.5% for 5 mg/L Cu2+. The quantitative analysis results for the mineral wastewater is in good agreement the China National Environmental Protection Standards HJ485-2009, which indicates the current method could be developed to the on-site detection technique for the emergency response in monitoring Cu2+ in industrial wastewater or polluted water.

Elucidation of the factors affecting the oxidative activity of Acremonium sp. HI-25 ascorbate oxidase by an electrochemical approach

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

Murata, Kenichi; Nakamura, Nobuhumi; Ohno, Hiroyuki

Steady-state kinetics of Acremonium sp. HI-25 ascorbate oxidase toward p-hydroquinone derivatives have been examined by using an electrochemical analysis based on the theory of steady-state bioelectrocatalysis. The electrochemical technique has enabled one to examine the influence of electronic and chemical properties of substrates on the activity. It was proven that the oxidative activity of ascorbate oxidase was dominated by the highly selective substrate-binding affinity based on electrostatic interaction beyond the one-electron redox potential difference between ascorbate oxidase's type 1 copper site and substrate.

Electrochemical properties and structures of the mixed-valence lithium cuprates Li 3Cu 2O 4 and Li 2NaCu 2O 4

NASA Astrophysics Data System (ADS)

Raekelboom, E. A.; Hector, A. L.; Weller, M. T.; Owen, J. R.

The electrochemical performances of Li 3Cu 2O 4 and Li 2NaCu 2O 4 as cathode materials in lithium coin type batteries have been studied. In Li 3Cu 2O 4, the copper was oxidised to the III level when cycling. The replacement of the lithium by the sodium ions in the octahedral sites in Li 2NaCu 2O 4 might have an effect on the pathway of the lithium ions during the (de)intercalations.

Spectrum sensitivity, energy yield, and revenue prediction of PV and CPV modules

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

Kinsey, Geoffrey S., E-mail: Geoffrey.kinsey@ee.doe.gov

2015-09-28

Impact on module performance of spectral irradiance variation has been determined for III-V multijunctions compared against the four most common flat-plate module types (cadmium telluride, multicrystalline silicon, copper indium gallium selenide, and monocrystalline silicon. Hour-by-hour representative spectra were generated using atmospheric variables for Albuquerque, New Mexico, USA. Convolution with published values for external quantum efficiency gave the predicted current output. When combined with specifications of commercial PV modules, energy yield and revenue were predicted. This approach provides a means for optimizing PV module design based on various site-specific temporal variables.

Spectrum sensitivity, energy yield, and revenue prediction of PV and CPV modules

NASA Astrophysics Data System (ADS)

Kinsey, Geoffrey S.

2015-09-01

Impact on module performance of spectral irradiance variation has been determined for III-V multijunctions compared against the four most common flat-plate module types (cadmium telluride, multicrystalline silicon, copper indium gallium selenide, and monocrystalline silicon. Hour-by-hour representative spectra were generated using atmospheric variables for Albuquerque, New Mexico, USA. Convolution with published values for external quantum efficiency gave the predicted current output. When combined with specifications of commercial PV modules, energy yield and revenue were predicted. This approach provides a means for optimizing PV module design based on various site-specific temporal variables.

Porins Increase Copper Susceptibility of Mycobacterium tuberculosis

PubMed Central

Speer, Alexander; Rowland, Jennifer L.; Haeili, Mehri; Niederweis, Michael

2013-01-01

Copper resistance mechanisms are crucial for many pathogenic bacteria, including Mycobacterium tuberculosis, during infection because the innate immune system utilizes copper ions to kill bacterial intruders. Despite several studies detailing responses of mycobacteria to copper, the pathways by which copper ions cross the mycobacterial cell envelope are unknown. Deletion of porin genes in Mycobacterium smegmatis leads to a severe growth defect on trace copper medium but simultaneously increases tolerance for copper at elevated concentrations, indicating that porins mediate copper uptake across the outer membrane. Heterologous expression of the mycobacterial porin gene mspA reduced growth of M. tuberculosis in the presence of 2.5 μM copper by 40% and completely suppressed growth at 15 μM copper, while wild-type M. tuberculosis reached its normal cell density at that copper concentration. Moreover, the polyamine spermine, a known inhibitor of porin activity in Gram-negative bacteria, enhanced tolerance of M. tuberculosis for copper, suggesting that copper ions utilize endogenous outer membrane channel proteins of M. tuberculosis to gain access to interior cellular compartments. In summary, these findings highlight the outer membrane as the first barrier against copper ions and the role of porins in mediating copper uptake in M. smegmatis and M. tuberculosis. PMID:24013632

Bioleaching of two different genetic types of chalcopyrite and their comparative mineralogical assessment.

PubMed

Deng, Sha; Gu, Guohua; Ji, Jing; Xu, Baoke

2018-02-01

The bioleaching of two different genetic types of chalcopyrite by the moderate thermophile Sulfobacillus thermosulfidooxidans was investigated by leaching behaviors elucidation and their comparative mineralogical assessment. The leaching experiment showed that the skarn-type chalcopyrite (STC) revealed a much faster leaching rate with 33.34% copper extracted finally, while only 23.53% copper was bioleached for the porphyry-type chalcopyrite (PTC). The mineralogical properties were analyzed by XRD, SEM, XPS, and Fermi energy calculation. XRD indicated that the unit cell volume of STC was a little larger than that of PTC. SEM indicated that the surface of STC had more steps and ridges. XPS spectra showed that Cu(I) was the dominant species of copper on the surfaces of the two chalcopyrite samples, and STC had much more copper with lower Cu 2p 3/2 binding energy. Additionally, the Fermi energy of STC was much higher than that of PTC. These mineralogical differences were in good agreement with the bioleaching behaviors of chalcopyrite. This study will provide some new information for evaluating the oxidation kinetics of chalcopyrite.

Spectroscopic characterization and O2 reactivity of the trinuclear Cu cluster of mutants of the multicopper oxidase Fet3p.

PubMed

Palmer, Amy E; Quintanar, Liliana; Severance, Scott; Wang, Tzu-Pin; Kosman, Daniel J; Solomon, Edward I

2002-05-21

Fet3p is a multicopper oxidase that uses four copper ions (one type 1, one type 2, and one type 3 binuclear site) to couple substrate oxidation to the reduction of O(2) to H(2)O. The type 1 Cu site shuttles electrons between the substrate and the type 2/type 3 Cu sites which form a trinuclear Cu cluster that is the active site for O(2) reduction. This study extends the spectroscopic and reactivity studies that have been conducted with type 1-substituted Hg (T1Hg) laccase to Fet3p and a mutant of Fet3p in which the trinuclear Cu cluster is perturbed. To examine the reaction between the trinuclear Cu cluster and O(2), the type 1 Cu Cys(484) was mutated to Ser, resulting in a type 1-depleted (T1D) form of the enzyme. Additional His to Gln mutations were made at the trinuclear cluster to further probe specific contributions to reactivity. One of these mutants (His(126)Gln) produces the first stable but perturbed trinuclear Cu cluster (T1DT3' Fet3p). Spectroscopic characterization (absorption, circular dichroism, magnetic circular dichroism, and electron paramagnetic resonance) of the resting trinuclear sites in T1D and T1DT3' Fet3p reveal that the His(126)Gln mutation changes the electronic structure of both the type 3 and type 2 Cu sites. The trinuclear clusters in T1D and T1DT3' Fet3p react with O(2) to produce peroxide intermediates analogous to that observed in T1Hg laccase. Spectroscopic data on the peroxide intermediates in the three forms provide further insight into the structure of this intermediate. In T1D Fet3p, the decay of this peroxide intermediate is pH-dependent, and the rate of decay is 10-fold higher at low pH. In T1DT3' Fet3p, the decay of the peroxide intermediate is pH-independent and is slow at all pH's. This change in the pH dependence provides new insight into the mechanism of intermediate decay involving reductive cleavage of the O-O bond.

Role of plastic deformation in wear of copper and copper - 10-percent-aluminum alloy in cryogenic fuels

NASA Technical Reports Server (NTRS)

Bill, R. C.; Wisander, D. W.

1973-01-01

High-purity copper specimens and a copper-aluminum (10%) alloy specimen were subjected to sliding against Type 440 C in cryogenic fuel environments. It was found that virtually all wear occurred by the plastic deformation of a recrystallized layer extending to about 10 micrometers below the wear scar surface of the copper or copper alloy. The wear debris was in the form of a layered structure adhering to the exit region of the wear scar. Measurements on the high purity copper specimens indicated that the wear rate was proportional to the applied load and to the sliding velocity squared. A physical model of the wear process is proposed to account for these observations.

The california poppy (eschscholtzia mexicana) as a copper indicator plant - a new example

USGS Publications Warehouse

Chaffee, M.A.; Gale, C.W.

1976-01-01

The abundance and distribution of the California poppy (Eschscholtzia mexicana) correlates closely with the copper-rich outcrop of a small porphyry-type deposit in Arizona. Chemical factors are probably more important than physical factors in determining why this species is sometimes found as a copper indicator plant. ?? 1976.

Elevated copper impairs hepatic nuclear receptor function in Wilson's disease

USDA-ARS?s Scientific Manuscript database

Wilson's disease (WD) is an autosomal recessive disorder that results in accumulation of copper in the liver as a consequence of mutations in the gene encoding the copper-transporting P-type ATPase (ATP7B). WD is a chronic liver disorder, and individuals with the disease present with a variety of co...

Antimicrobial and bone-forming activity of a copper coated implant in a rabbit model.

PubMed

Prinz, Cornelia; Elhensheri, Mohamed; Rychly, Joachim; Neumann, Hans-Georg

2017-08-01

Current strategies in implant technology are directed to generate bioactive implants that are capable to activate the regenerative potential of the surrounding tissue. On the other hand, implant-related infections are a common problem in orthopaedic trauma patients. To meet both challenges, i.e. to generate a bone implant with regenerative and antimicrobial characteristics, we tested the use of copper coated nails for surgical fixation in a rabbit model. Copper acetate was galvanically deposited with a copper load of 1 µg/mm 2 onto a porous oxide layer of Ti6Al4V nails, which were used for the fixation of a tibia fracture, inoculated with bacteria. After implantation of the nail the concentration of copper ions did not increase in blood which indicates that copper released from the implant was locally restricted to the fracture site. After four weeks, analyses of the extracted implants revealed a distinct antimicrobial effect of copper, because copper completely prevented both a weak adhesion and firm attachment of biofilm-forming bacteria on the titanium implant. To evaluate fracture healing, radiographic examination demonstrated an increased callus index in animals with copper coated nails. This result indicates a stimulated bone formation by releasing copper ions. We conclude that the use of implants with a defined load of copper ions enables both prevention of bacterial infection and the stimulation of regenerative processes.

Cadmium-free junction fabrication process for CuInSe.sub.2 thin film solar cells

DOEpatents

Ramanathan, Kannan V.; Contreras, Miguel A.; Bhattacharya, Raghu N.; Keane, James; Noufi, Rommel

1999-01-01

The present invention provides an economical, simple, dry and controllable semiconductor layer junction forming process to make cadmium free high efficiency photovoltaic cells having a first layer comprised primarily of copper indium diselenide having a thin doped copper indium diselenide n-type region, generated by thermal diffusion with a group II(b) element such as zinc, and a halide, such as chlorine, and a second layer comprised of a conventional zinc oxide bilayer. A photovoltaic device according the present invention includes a first thin film layer of semiconductor material formed primarily from copper indium diselenide. Doping of the copper indium diselenide with zinc chloride is accomplished using either a zinc chloride solution or a solid zinc chloride material. Thermal diffusion of zinc chloride into the copper indium diselenide upper region creates the thin n-type copper indium diselenide surface. A second thin film layer of semiconductor material comprising zinc oxide is then applied in two layers. The first layer comprises a thin layer of high resistivity zinc oxide. The second relatively thick layer of zinc oxide is doped to exhibit low resistivity.

Conformational and thermodynamic hallmarks of DNA operator site specificity in the copper sensitive operon repressor from Streptomyces lividans

PubMed Central

Tan, Benedict G.; Vijgenboom, Erik; Worrall, Jonathan A. R.

2014-01-01

Metal ion homeostasis in bacteria relies on metalloregulatory proteins to upregulate metal resistance genes and enable the organism to preclude metal toxicity. The copper sensitive operon repressor (CsoR) family is widely distributed in bacteria and controls the expression of copper efflux systems. CsoR operator sites consist of G-tract containing pseudopalindromes of which the mechanism of operator binding is poorly understood. Here, we use a structurally characterized CsoR from Streptomyces lividans (CsoRSl) together with three specific operator targets to reveal the salient features pertaining to the mechanism of DNA binding. We reveal that CsoRSl binds to its operator site through a 2-fold axis of symmetry centred on a conserved 5′-TAC/GTA-3′ inverted repeat. Operator recognition is stringently dependent not only on electropositive residues but also on a conserved polar glutamine residue. Thermodynamic and circular dichroic signatures of the CsoRSl–DNA interaction suggest selectivity towards the A-DNA-like topology of the G-tracts at the operator site. Such properties are enhanced on protein binding thus enabling the symmetrical binding of two CsoRSl tetramers. Finally, differential binding modes may exist in operator sites having more than one 5′-TAC/GTA-3′ inverted repeat with implications in vivo for a mechanism of modular control. PMID:24121681

Identification and partial characterization of a low affinity metal-binding site in the light chain of tetanus toxin.

PubMed

Wright, J F; Pernollet, M; Reboul, A; Aude, C; Colomb, M G

1992-05-05

Tetanus toxin was shown to contain a metal-binding site for zinc and copper. Equilibrium dialysis binding experiments using 65Zn indicated an association constant of 9-15 microM, with one zinc-binding site/toxin molecule. The zinc-binding site was localized to the toxin light chain as determined by binding of 65Zn to the light chain but not to the heavy chain after separation by sodium dodecyl sulfate-polyacrylamide gel electrophoresis and transfer to Immobilon membranes. Copper was an efficient inhibitor of 65Zn binding to tetanus toxin and caused two peptide bond cleavages in the toxin light chain in the presence of ascorbate. These metal-catalyzed oxidative cleavages were inhibited by the presence of zinc. Partial characterization of metal-catalyzed oxidative modifications of a peptide based on a putative metal-binding site (HELIH) in the toxin light chain was used to map the metal-binding site in the protein.

Elucidation of the Human Serum Albumin (HSA) Binding Site for the Cu-PTSM and Cu-ATSM Radiopharmaceuticals

PubMed Central

Basken, Nathan E.; Mathias, Carla J.; Green, Mark A.

2008-01-01

The Cu-PTSM (pyruvaldehyde bis(N4-methylthiosemicarbazonato)copper(II)) and Cu-ATSM (diacetyl bis(N4-methylthiosemicarbazonato)copper(II)) radiopharmaceuticals exhibit strong, species-dependent binding to human serum albumin (HSA), while Cu-ETS (ethylglyoxal bis(thiosemicarbazonato)copper(II)) appears to only exhibit non-specific binding to human and animal serum albumins. This study examines the structural basis for HSA binding of Cu-PTSM and Cu-ATSM via competition with drugs having known albumin binding sites. Warfarin, furosemide, ibuprofen, phenylbutazone, benzylpenicillin, and cephmandole were added to HSA solutions at drug:HSA mole ratios from 0 to 8:1, followed by quantification of radiopharmaceutical binding to HSA by ultrafiltration. Warfarin, a site IIA drug, progressively displaced both [64Cu]Cu-PTSM and [64Cu]Cu-ATSM from HSA. At 8:1 warfarin:HSA mole ratios, free [64Cu]Cu-PTSM and [64Cu]Cu-ATSM levels increased 300–500%. This was in contrast to solutions containing ibuprofen, a site IIIA drug; no increase in free [64Cu]Cu-PTSM or [64Cu]Cu-ATSM was observed except at high ibuprofen:HSA ratios, where secondary ibuprofen binding to the IIA site may cause modest radiopharmaceutical displacement. By contrast, and consistent with earlier findings suggesting Cu-ETS exhibits only non-specific associations, [64Cu]Cu-ETS binding to HSA was unaffected by the addition of drugs that bind in either site. We conclude that the species-dependence of Cu-PTSM and Cu-ATSM albumin binding arises from interaction(s) with the IIA site of HSA. PMID:18937368

Crystal Structures of Copper-depleted and Copper-bound Fungal Pro-tyrosinase

PubMed Central

Fujieda, Nobutaka; Yabuta, Shintaro; Ikeda, Takuya; Oyama, Takuji; Muraki, Norifumi; Kurisu, Genji; Itoh, Shinobu

2013-01-01

Tyrosinase, a dinuclear copper monooxygenase/oxidase, plays a crucial role in the melanin pigment biosynthesis. The structure and functions of tyrosinase have so far been studied extensively, but the post-translational maturation process from the pro-form to the active form has been less explored. In this study, we provide the crystal structures of Aspergillus oryzae full-length pro-tyrosinase in the holo- and the apo-forms at 1.39 and 2.05 Å resolution, respectively, revealing that Phe513 on the C-terminal domain is accommodated in the substrate-binding site as a substrate analog to protect the dicopper active site from substrate access (proteolytic cleavage of the C-terminal domain or deformation of the C-terminal domain by acid treatment transforms the pro-tyrosinase to the active enzyme (Fujieda, N., Murata, M., Yabuta, S., Ikeda, T., Shimokawa, C., Nakamura, Y., Hata, Y., and Itoh, S. (2012) ChemBioChem. 13, 193–201 and Fujieda, N., Murata, M., Yabuta, S., Ikeda, T., Shimokawa, C., Nakamura, Y., Hata, Yl, and Itoh, S. (2013) J. Biol. Inorg. Chem. 18, 19–26). Detailed crystallographic analysis and structure-based mutational studies have shown that the copper incorporation into the active site is governed by three cysteines as follows: Cys92, which is covalently bound to His94 via an unusual thioether linkage in the holo-form, and Cys522 and Cys525 of the CXXC motif located on the C-terminal domain. Molecular mechanisms of the maturation processes of fungal tyrosinase involving the accommodation of the dinuclear copper unit, the post-translational His-Cys thioether cross-linkage formation, and the proteolytic C-terminal cleavage to produce the active tyrosinase have been discussed on the basis of the detailed structural information. PMID:23749993

Hazard evaluation of inorganics, singly and in mixtures, to Flannelmouth Sucker Catostomus latipinnis in the San Juan River, New Mexico

USGS Publications Warehouse

Hamilton, S.J.; Buhl, K.J.

1997-01-01

Larval flannelmouth sucker (Catostomus latipinnis) were exposed to arsenate, boron, copper, molybdenum, selenate, selenite, uranium, vanadium, and zinc singly, and to five mixtures of five to nine inorganics. The exposures were conducted in reconstituted water representative of the San Juan River near Shiprock, New Mexico. The mixtures simulated environmental ratios reported for sites along the San Juan River (San Juan River backwater, Fruitland marsh, Hogback East Drain, Mancos River, and McElmo Creek). The rank order of the individual inorganics, from most to least toxic, was: copper > zinc > vanadium > selenite > selenate > arsenate > uranium > boron > molybdenum. All five mixtures exhibited additive toxicity to flannelmouth sucker. In a limited number of tests, 44-day-old and 13-day-old larvae exhibited no difference in sensitivity to three mixtures. Copper was the major toxic component in four mixtures (San Juan backwater, Hogback East Drain, Mancos River, and McElmo Creek), whereas zinc was the major toxic component in the Fruitland marsh mixture, which did not contain copper. The Hogback East Drain was the most toxic mixture tested. Comparison of 96-h LC50values with reported environmental water concentrations from the San Juan River revealed low hazard ratios for arsenic, boron, molybdenum, selenate, selenite, uranium, and vanadium, moderate hazard ratios for zinc and the Fruitland marsh mixture, and high hazard ratios for copper at three sites and four environmental mixtures representing a San Juan backwater, Hogback East Drain, Mancos River, and McElmo Creek. The high hazard ratios suggest that inorganic contaminants could adversely affect larval flannelmouth sucker in the San Juan River at four sites receiving elevated inorganics.

The Hydrogenase Activity of the Molybdenum/Copper-containing Carbon Monoxide Dehydrogenase of Oligotropha carboxidovorans*

PubMed Central

Wilcoxen, Jarett; Hille, Russ

2013-01-01

The reaction of the air-tolerant CO dehydrogenase from Oligotropha carboxidovorans with H2 has been examined. Like the Ni-Fe CO dehydrogenase, the enzyme can be reduced by H2 with a limiting rate constant of 5.3 s−1 and a dissociation constant Kd of 525 μm; both kred and kred/Kd, reflecting the breakdown of the Michaelis complex and the reaction of free enzyme with free substrate in the low [S] regime, respectively, are largely pH-independent. During the reaction with H2, a new EPR signal arising from the Mo/Cu-containing active site of the enzyme is observed which is distinct from the signal seen when the enzyme is reduced by CO, with greater g anisotropy and larger hyperfine coupling to the active site 63,65Cu. The signal also exhibits hyperfine coupling to at least two solvent-exchangeable protons of bound substrate that are rapidly exchanged with solvent. Proton coupling is also evident in the EPR signal seen with the dithionite-reduced native enzyme, and this coupling is lost in the presence of bicarbonate. We attribute the coupled protons in the dithionite-reduced enzyme to coordinated water at the copper site in the native enzyme and conclude that bicarbonate is able to displace this water from the copper coordination sphere. On the basis of our results, a mechanism for H2 oxidation is proposed which involves initial binding of H2 to the copper of the binuclear center, displacing the bound water, followed by sequential deprotonation through a copper-hydride intermediate to reduce the binuclear center. PMID:24165123

Copper-coated textiles: armor against MDR nosocomial pathogens.

PubMed

Irene, Galani; Georgios, Priniotakis; Ioannis, Chronis; Anastasios, Tzerachoglou; Diamantis, Plachouras; Marianthi, Chatzikonstantinou; Philippe, Westbroek; Maria, Souli

2016-06-01

Soft surfaces in the health-care setting harbor potentially pathogenic bacteria and fungi that can be transferred to patients and personnel. We evaluated the in vitro antimicrobial efficacy of two types of innovative copper-coated textiles against a variety of nosocomial multi-drug resistant (MDR) pathogens. Five isolates each of MDR Staphylococcus aureus, Klebsiella pneumoniae, Pseudomonas aeruginosa, Acinetobacter baumannii and Enterococcus faecium as well as three Candida parapsilosis were tested. The antimicrobial activity of copper-coated para-aramide and copper-coated polyester swatches was compared to that of non-copper coated controls using a quantitative method. Reduction of viable colonies by >3log10 from starting inoculum was characterized as bactericidal activity. No viable colonies of S. aureus, P. aeruginosa, E. faecium and C. parapsilosis were recovered after the first hour of contact while for A. baumannii, no viable colonies were recovered after only 15min of contact with either type of copper-coated textiles. Copper-coated para-aramide exhibited a bactericidal effect at 15min of contact with A. baumannii, at 1h with S. aureus, P. aeruginosa, E. faecium and C. parapsilosis and at 3h with K. pneumoniae. Copper-coated polyester was bactericidal at 15min of contact for A. baumannii and at 1h for the other species tested. Both copper-coated textiles exhibited a rapid and significant antimicrobial effect. Antimicrobial textiles may have a role in the arsenal of strategies aiming to reduce environmental contamination in the health-care setting. Copyright © 2016 Elsevier Inc. All rights reserved.

Metals transport in the Sacramento River, California, 1996-1997; Volume 2: Interpretation of metal loads

USGS Publications Warehouse

Alpers, Charles N.; Antweiler, Ronald C.; Taylor, Howard E.; Dileanis, Peter D.; Domagalski, Joseph L.

2000-01-01

Metals transport in the Sacramento River, northern California, from July 1996 to June 1997 was evaluated in terms of metal loads from samples of water and suspended colloids that were collected on up to six occasions at 13 sites in the Sacramento River Basin. Four of the sampling periods (July, September, and November 1996; and May-June 1997) took place during relatively low-flow conditions and two sampling periods (December 1996 and January 1997) took place during high-flow and flooding conditions, respectively. This study focused primarily on loads of cadmium, copper, lead, and zinc, with secondary emphasis on loads of aluminum, iron, and mercury.Trace metals in acid mine drainage from abandoned and inactive base-metal mines, in the East and West Shasta mining districts, enter the Sacramento River system in predominantly dissolved form into both Shasta Lake and Keswick Reservoir. The proportion of trace metals that was dissolved (as opposed to colloidal) in samples collected at Shasta and Keswick dams decreased in the order zinc ≈ cadmium > copper > lead. At four sampling sites on the Sacramento River--71, 256, 360, and 412 kilometers downstream of Keswick Dam--trace-metal loads were predominantly colloidal during both high- and low-flow conditions. The proportion of total cadmium, copper, lead, and zinc loads transported to San Francisco Bay and the Sacramento-San Joaquin Delta estuary (referred to as the Bay-Delta) that is associated with mineralized areas was estimated by dividing loads at Keswick Dam by loads 412 kilometers downstream at Freeport and the Yolo Bypass. During moderately high flows in December 1996, mineralization-related total (dissolved + colloidal) trace-metal loads to the Bay-Delta (as a percentage of total loads measured downstream) were cadmium, 87 percent; copper, 35 percent; lead, 10 percent; and zinc, 51 percent. During flood conditions in January 1997 loads were cadmium, 22 percent; copper, 11 percent; lead, 2 percent; and zinc, 15 percent. During irrigation drainage season from rice fields (May-June 1997) loads were cadmium, 53 percent; copper, 42 percent; lead, 20 percent; and zinc, 75 percent. These estimates must be qualified by the following factors: (1) metal loads at Colusa in December 1996 and at Verona in May-June 1997 generally exceeded those determined at Freeport during those sampling periods. Therefore, the above percentages represent maximum estimates of the apparent total proportion of metals from mineralized areas upstream of Keswick Dam; and (2) for logistics reasons, the Sacramento River was sampled at Tower Bridge instead of at Freeport during January 1997.Available data suggest that trace metal loads from agricultural drainage may be significant during certain flow conditions in areas where metals such as copper and zinc are added as agricultural amendments. Copper loads for sampling periods in July and September 1996 and in May-June 1997 show increases of dissolved and colloidal copper and in colloidal zinc between Colusa and Verona, the reach of the Sacramento River along which the Colusa Basin Drain, the Sacramento Slough, and other agricultural return flows are tributaries. Monthly sampling of these two agricultural drains by the USGS National Water-Quality Assessment Program shows seasonal variations in metal concentrations, reaching maximum concentrations of 4 to 6 micrograms per liter in "dissolved" (0.45-micrometer filtrate) copper concentrations in May 1996, December 1996, and June 1997. The total (dissolved plus colloidal) load of copper from the Colusa Basin Drain in June 1997 was 18 kilograms per day, whereas the copper load in Spring Creek, which drains the inactive mines on Iron Mountain, was 20 kilograms per day during the same sampling period. For comparison, during the January 1997 flood, the copper load in Spring Creek was about 1,100 kilograms per day and the copper load in the Yolo Bypass was about 7,300 kilograms per day. The data clearly indicate that most copper and zinc loads during the January 1997 flood entered the Sacramento River upstream of Colusa, and upstream of the influence of the most intense agricultural drainage return flows in the Sacramento River watershed.This study has demonstrated that some trace metals of environmental significance (cadmium, copper, and zinc) in the Sacramento River are transported largely in dissolved form at upstream sites (below Shasta Dam, below Keswick Dam, and at Bend Bridge) proximal to the mineralized areas of the West Shasta and East Shasta mining districts. In contrast, these trace metals are transported largely in colloidal form at downstream sites (Colusa, Verona, Freeport, and Yolo Bypass). Aluminum, iron, and lead were observed to be transported predominantly in the colloidal phase at all mainstem Sacramento River sampling sites during all sampling periods in this study. Despite continuous water treatment, which has removed 85 to 90 percent of the cadmium, copper, and zinc from the mine drainage at Iron Mountain, Spring Creek remains a significant source of these metals to the Sacramento River system.

40 CFR 141.86 - Monitoring requirements for lead and copper in tap water.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 23 2014-07-01 2014-07-01 false Monitoring requirements for lead and... § 141.86 Monitoring requirements for lead and copper in tap water. (a) Sample site location. (1) By the applicable date for commencement of monitoring under paragraph (d)(1) of this section, each water system...

40 CFR 141.86 - Monitoring requirements for lead and copper in tap water.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 24 2013-07-01 2013-07-01 false Monitoring requirements for lead and... § 141.86 Monitoring requirements for lead and copper in tap water. (a) Sample site location. (1) By the applicable date for commencement of monitoring under paragraph (d)(1) of this section, each water system...

40 CFR 141.86 - Monitoring requirements for lead and copper in tap water.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 24 2012-07-01 2012-07-01 false Monitoring requirements for lead and... § 141.86 Monitoring requirements for lead and copper in tap water. (a) Sample site location. (1) By the applicable date for commencement of monitoring under paragraph (d)(1) of this section, each water system...

Active-Site Environment of Copper-Bound Human Amylin Relevant to Type 2 Diabetes.

PubMed

Seal, Manas; Dey, Somdatta Ghosh

2018-01-02

Type 2 diabetes mellitus (T2Dm) is characterized by reduced β cell mass and amyloid deposits of human islet amyloid polypeptide (hIAPP) or amylin, a 37 amino acid containing peptide around pancreatic β cells. The interaction of copper (Cu) with amylin and its mutants has been studied in detail using absorption, circular dichroism, electron paramagnetic resonance spectroscopy, and cyclic voltammetry. Cu binds amylin in a 1:1 ratio, and the binding domain lies within the first 19 amino acid residues of the peptide. Depending on the pH of the medium, Cu-amylin shows the formation of five pH-dependent components (component IV at pH 4.0, component III at pH 5.0, component II at pH 6.0, component I at pH 8.0, and another higher pH component above pH 9.0). The terminal amine, His18, and amidates are established as key residues in the peptide that coordinate the Cu center. The physiologically relevant components I and II can generate H 2 O 2 , which can possibly account for the enhanced toxicity of amylin in the presence of Cu, causing damage of the β cells of the pancreas via oxidative stress.

Sources of variation in concentrations of nickel and copper in mountain birch foliage near a nickel-copper smelter at Monchegorsk, north-western Russia: results of long-term monitoring.

PubMed

Kozlov, Mikhail V

2005-05-01

Concentrations of nickel and copper, two principal metal pollutants of the 'Severonikel' smelter at Monchegorsk, NW Russia, were measured in unwashed leaves of mountain birch, Betula pubescens subsp. czerepanovii, collected in eight study sites along the pollution gradient during 1991-2003. In spite of significant decline in metal emissions, concentrations of foliar metals in most of the study sites did not decrease, indicating that soil contamination remains extremely high. Multiyear mean values peaked at 6.6 km S of the smelter, where they were 20-25 times higher than in the most distant study site. Concentrations of both metals demonstrated pronounced annual variation, which was explained by the meteorological conditions of early summer: higher precipitation in May increased foliar concentrations of both metals, whereas higher precipitation in June resulted in lower foliar concentrations of nickel. These data suggest that ecotoxicological situation in metal-contaminated areas can be modified by the expected climate change. In heavily polluted sites individual birch trees generally retained their ranks in terms of metal contamination during 1995-2003, demonstrating that the use of the same set of trees can significantly increase the accuracy of the monitoring data.

Storm water runoff measurements of copper from a naturally patinated roof and from a parking space. Aspects on environmental fate and chemical speciation.

PubMed

Odnevall Wallinder, I; Hedberg, Y; Dromberg, P

2009-12-01

Release of copper from a naturally aged copper roof on a shopping centre building in a suburban site of Stockholm has been measured during different rain events after its interaction with the internal drainage system and storm drains made of cast iron and concrete. Concentrations of copper removed by means of urban storm water from a nearby parking space have been determined for comparison. Predictions and measurements of the chemical speciation of released copper are discussed compared to the total concentration, and to threshold values for freshwater and drinking water. The results clearly illustrate that the major part of the released copper from the roof is readily retained already during transport through the internal drainage system of the building, a pathway that also changes the chemical speciation of released copper and its bioavailable fraction. Most copper, not retained by cast iron and concrete surfaces, was strongly complexed to organic matter. The median concentration of free cupric ions and weak copper complexes was less than, or within the range of reported no effect concentrations, NOECs, of copper in surface waters. The parking space contributed with significantly higher and time-dependent concentrations of total copper compared to measured concentrations of copper from the roof after the interaction with the drainage system. Most copper in the surface runoff water was strongly complexed with organic matter, hence reducing the bioavailable fraction significantly to concentrations within the NOEC range. Dilution with other sources of urban storm water will reduce the released concentration of copper even further. The results illustrate that already the internal drainage system and the storm drains made of cast iron and concrete act as efficient sinks for released copper which means that any installation of additional infiltration devices is redundant.

Responses of Lyngbya wollei to exposures of copper-based algaecides: the critical burden concept.

PubMed

Bishop, W M; Rodgers, J H

2012-04-01

The formulation of a specific algaecide can greatly influence the bioavailability, uptake, and consequent control of the targeted alga. In this research, three copper-based algaecide formulations were evaluated in terms of copper sorption to a specific problematic alga and amount of copper required to achieve control. The objectives of this study were (1) to compare the masses of copper required to achieve control of Lyngbya wollei using the algaecide formulations Algimycin-PWF, Clearigate, and copper sulfate pentahydrate in laboratory toxicity experiments; (2) to relate the responses of L. wollei to the masses of copper adsorbed and absorbed (i.e., dose) as well as the concentrations of copper in the exposure water; and (3) to discern the relation between the mass of copper required to achieve control of a certain mass of L. wollei among different algaecide formulations. The critical burden of copper (i.e., threshold algaecide concentration that must be absorbed or adsorbed to achieve control) for L. wollei averaged 3.3 and 1.9 mg Cu/g algae for Algimycin-PWF and Clearigate, respectively, in experiments with a series of aqueous copper concentrations, water volumes, and masses of algae. With reasonable exposures in these experiments, control was not achieved with single applications of copper sulfate despite copper sorption >13 mg Cu/g algae in one experiment. Factors governing the critical burden of copper required for control of problematic cyanobacteria include algaecide formulation and concentration, volume of water, and mass of algae. By measuring the critical burden of copper from an algaecide formulation necessary to achieve control of the targeted algae, selection of an effective product and treatment rate can be calculated at a given field site.

Temporal and spatial variations of copper, cadmium, lead, and zinc in Ten Mile Creek in South Florida, USA.

PubMed

Yang, Yuangen; He, Zhenli; Lin, Youjian; Phlips, Edward J; Stoffella, Peter J; Powell, Charles A

2009-01-01

Lead (Pb), zinc (Zn), copper (Cu), and cadmium (Cd) often seriously deteriorate water quality. Spatial and temporal fluctuations of the metal concentrations in the Ten Mile Creek (Florida) (TMC) were monitored on a weekly basis at 7 sampling sites, from June 2005 to September 2007. River sediment samples were also collected from these sites in April, June, and October 2006 and January 2007, and analyzed for water, Mehlich 1 (M1), and Mehlich 3 (M3)-extractable metals (Mehlich, 1953, 1984), to examine the role of sediments as sources or sinks of the metals. The concentrations of lead, zinc, copper, and cadmium in the water samples were

Adsorption of xenon on vicinal copper and platinum surfaces

NASA Astrophysics Data System (ADS)

Baker, Layton

The adsorption of xenon was studied on Cu(111), Cu(221), Cu(643) and on Pt(111), Pt(221), and Pt(531) using low energy electron diffraction (LEED), temperature programmed desorption (TPD) of xenon, and ultraviolet photoemission of adsorbed xenon (PAX). These experiments were performed to study the atomic and electronic structure of stepped and step-kinked, chiral metal surfaces. Xenon TPD and PAX were performed on each surface in an attempt to titrate terrace, step edge, and kink adsorption sites by adsorption energetics (TPD) and local work function differences (PAX). Due to the complex behavior of xenon on the vicinal copper and platinum metal surfaces, adsorption sites on these surfaces could not be adequately titrated by xenon TPD. On Cu(221) and Cu(643), xenon desorption from step adsorption sites was not apparent leading to the conclusion that the energy difference between terrace and step adsorption is minuscule. On Pt(221) and Pt(531), xenon TPD indicated that xenon prefers to bond at step edges and that the xenon-xenon interaction at step edges in repulsive but no further indication of step-kink adsorption was observed. The Pt(221) and Pt(531) TPD spectra indicated that the xenon overlayer undergoes strong compression near monolayer coverage on these surfaces due to repulsion between step-edge adsorbed xenon and other encroaching xenon atoms. The PAX experiments on the copper and platinum surfaces demonstrated that the step adsorption sites have lower local work functions than terrace adsorption sites and that higher step density leads to a larger separation in the local work function of terrace and step adsorption sites. The PAX spectra also indicated that, for all surfaces studied at 50--70 K, step adsorption is favored at low coverage but the step sites are not saturated until monolayer coverage is reached; this observation is due to the large entropy difference between terrace and step adsorption states and to repulsive interactions between xenon atoms adsorbed at step edges (on the platinum surfaces). The results herein provide several novel observations regarding the adsorptive behavior of xenon on vicinal copper and platinum surfaces.

Growth of tropical tree species and absorption of copper in soil artificially contaminated.

PubMed

Silva, R F; Andreazza, R; Da Ros, C; Dellai, A; Jacques, R J S; Scheid, D

2015-11-01

Reclamation of copper contaminated sites using forest species may be an efficient alternative to reduce the negative impact. The aim of this study was to quantify the growth and evaluate the quality of seedlings of native species at different doses of copper in the soil. The experimental design was completely randomized, with seven replications in a factorial arrangement (3×9), using three indigenous species of plants (Anadenanthera macrocarpa, Mimosa scabrella and Apuleia leiocarpa) and nine doses of copper in the soil (0, 60, 120, 180, 240, 300, 360, 420 and 480 mg kg-1).The experiment was carried out in a greenhouse which the seedlings were grown for 180 days. The experimental units were plastic pots of 125 cm3 filled with Oxisol. The results indicated that the levels of copper applied to the soil decreased the quality of seedlings and growth of Apuleia leiocarpato a lesser extent compared with Mimosa scabrella and Anadenanthera macrocarpa. Anadenanthera macrocarpa was the forest species that resulted in the lowest copper translocation from roots to shoots. In addition, the Apuleia leiocarpa exhibited high resistance and tolerance for copper in the soil and also, it is highlighted an ability for copper phytoremediation.

Iron Oxide-Supported Copper Oxide Nanoparticles (Nanocat-Fe-CuO): Magnetically Recyclable Catalysts for the Synthesis of Pyrazole Derivatives, 4-Methoxyaniline, and Ullmann-type Condensation Reactions

EPA Science Inventory

An efficient and benign protocol is reported for the synthesis of 4-methoxyaniline, medicinally important pyrazole derivatives, and Ullmann-type condensation reaction using magnetically separable and reusable magnetite-supported copper (nanocat-Fe-CuO) nanoparticles under mild co...

Colorimetric assay of copper ions based on the inhibition of peroxidase-like activity of MoS2 nanosheets

NASA Astrophysics Data System (ADS)

Chen, Huan; Li, Zhihong; Liu, Xueting; Zhong, Jianhai; Lin, Tianran; Guo, Liangqia; Fu, Fengfu

2017-10-01

The peroxidase-like catalytic activity of MoS2 nanomaterials has been utilized for colorimetric bioassays and medical diagnostics. However, the application of peroxidase-like catalytic activity of MoS2 nanomaterials in environmental analysis was seldom explored. Herein, copper ions were found to inhibit the peroxidase-like catalytic activity of MoS2 nanosheets, which can catalyze the oxidation of 3, 3‧, 5, 5‧-tetramethylbenzidine by H2O2 to produce a colorimetric product. Based on this finding, a simple sensitive colorimetric method for the detection of copper ions was developed. In the presence of copper ions, the absorbance and color of the solution decreased with the increasing concentration of copper ions. The color of the solution can be used to semi-quantitative on-site assay of copper ions by naked eyes. A linear relationship between the absorbance and the concentration of copper ions was observed in the range of 0.4-4.0 μmol L- 1 with a detection limit of 92 nmol L- 1, which was much lower than the maximum contaminant level of copper in drinking water legislated by the Environmental Protection Agency of USA and the World Health Organization. The method was applied to detect copper ions in environmental water samples with satisfactory results.

Characterization of polycyclic aromatic hydrocarbons in soil close to secondary copper and aluminum smelters.

PubMed

Hu, Jicheng; Wu, Jing; Zha, Xiaoshuo; Yang, Chen; Hua, Ying; Wang, Ying; Jin, Jun

2017-04-01

A total of 35 surface soil samples around two secondary copper smelters and one secondary aluminum smelter were collected and analyzed for 16 USEPA priority polycyclic aromatic hydrocarbons (PAHs). The concentrations of PAHs were highest when the soil sample sites were closest to the secondary copper smelters. And, a level gradient of PAHs was observed in soil samples according to the distance from two secondary copper smelters, respectively. The results suggested that PAH concentrations in surrounding soils may be influenced by secondary copper smelters investigated, whereas no such gradient was observed in soils around the secondary aluminum smelter. Further analysis revealed that PAH patterns in soil samples also showed some difference between secondary copper and aluminum smelter, which may be attributed to the difference in their fuel and smelting process. PAH patterns and diagnostic ratios indicated that biomass burning may be also an important source of PAHs in the surrounding soil in addition to the emissions from the plants investigated.

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

Exopolysaccharides favor the survival of Erwinia amylovora under copper stress through different strategies.

PubMed

Ordax, Mónica; Marco-Noales, Ester; López, María M; Biosca, Elena G

2010-09-01

Erwinia amylovora causes fire blight, a destructive disease of rosaceous plants very difficult to control. We demonstrated that copper, employed to control plant diseases, induces the "viable-but-nonculturable" (VBNC) state in E. amylovora. Moreover, it was previously reported that copper increases production of its main exopolysaccharide (EPS), amylovoran. In this work, the copper-complexing ability of amylovoran and levan, other major EPS of E. amylovora, was demonstrated. Following this, EPS-deficient mutants were used to determine the role of these EPSs in survival of this bacterium in AB mineral medium with copper, compared to their wild type strain and AB without copper. Total, viable and culturable counts of all strains were monitored for six months. With copper, a larger fraction of the viable population of EPS mutants entered into the VBNC state, and earlier than their wild type strain, showing the contribution of both EPSs to long-term survival in a culturable state. Further, we demonstrated that both EPSs can be used as carbon source by E. amylovora under deprivation conditions. Overall, these previously unreported functions of amylovoran and levan provide survival advantages for E. amylovora, which could contribute to its enhanced persistence in nature. Copyright 2010 Elsevier Masson SAS. All rights reserved.

Molecular control of copper homeostasis in filamentous fungi: increased expression of a metallothionein gene during aging of Podospora anserina.

PubMed

Averbeck, N B; Borghouts, C; Hamann, A; Specke, V; Osiewacz, H D

2001-01-01

The lifespan of the ascomycete Podospora anserina was previously demonstrated to be significantly increased in a copper-uptake mutant, suggesting that copper is a potential stressor involved in degenerative processes. In order to determine whether changes in copper stress occur in the cells during normal aging of cultures, we cloned and characterized a gene coding for a component of the molecular machinery involved in the control of copper homeostasis. This gene, PaMt1, is a single-copy gene that encodes a metallothionein of 26 amino acids. The coding sequence of PaMt1 is interrupted by a single intron. The deduced amino acid sequence shows a high degree of sequence identity to metallothioneins of the filamentous ascomycete Neurospora crassa and the basidiomycete Agaricus bisporus, and to the N-terminal portion of mammalian metallothioneins. Levels of PaMt1 transcript increase in response to elevated amounts of copper in the growth medium and during aging of wild-type cultures. In contrast, in the long-lived mutant grisea, transcript levels first increase but then decrease again. The ability of wild-type cultures to respond to exogenous copper stress via the induction of PaMt1 transcription is not affected as they grow older.

Intermittent use of copper-silver ionization for Legionella control in water distribution systems: a potential option in buildings housing individuals at low risk of infection.

PubMed

Liu, Z; Stout, J E; Boldin, M; Rugh, J; Diven, W F; Yu, V L

1998-01-01

One copper-silver ionization system was sequentially installed onto the hot-water recirculation lines of two hospital buildings colonized with Legionella pneumophila, serogroup 1. A third building with the same water supply and also colonized with Legionella served as a control. Four weeks after activation of the system, distal site positivity for Legionella in the first test building dropped to zero. After operating for 16 weeks, the system was disconnected and installed onto the second test building. Twelve weeks of disinfection reduced the distal site positivity for Legionella in the second test building to zero. Legionella recolonization did not occur in the first test building for 6-12 weeks and in the second test building for 8-12 weeks after inactivation of the system. The control building remained Legionella-positive throughout the experimental period. A significantly higher copper concentration was found in the biofilm taken from a sampling device than in that from water. This is likely to be the reason that the copper-silver ionization system had the residual effect of preventing early recolonization. Our study raises the possibility that one copper-silver unit could be rotated among several buildings to maintain a Legionella-free environment. Such an approach may be cost-effective for buildings housing individuals at low risk for contracting legionnaires' disease.

A Copper(II)-Paddlewheel Metal-Organic Framework with Exceptional Hydrolytic Stability and Selective Adsorption and Detection Ability of Aniline in Water.

PubMed

Chen, Ya; Wang, Bin; Wang, Xiaoqing; Xie, Lin-Hua; Li, Jinping; Xie, Yabo; Li, Jian-Rong

2017-08-16

Copper(II)-paddlewheel-based metal-organic frameworks (CP-MOFs) represent a unique subclass of MOFs with highly predictable porous structures, facile syntheses, and functional open metal sites. However, the lack of high hydrolytic stability is an obstacle for CP-MOFs in many practical applications. In this work, we report a new CP-MOF, [Cu 4 (tdhb)] (BUT-155), which is constructed from a judiciously designed carboxylate ligand with high coordination connectivity (octatopic), abundant hydrophobic substituents (six methyl groups), and substituent constrained geometry (tetrahedral backbone), tdhb 8- [H 8 tdhb = 3,3',5,5'-tetrakis(3,5-dicarboxyphenyl)-2,2',4,4',6,6'-hexamethylbiphenyl)]. BUT-155 shows high porosity with a Brunauer-Emmett-Teller surface area of 2070 m 2 /g. Quite interestingly, this CP-MOF retains its structural integrity after being treated in water for 10 days at room temperature or in boiling water for 24 h. To the best of our knowledge, BUT-155 represents the first CP-MOF that is demonstrated to retain its structural integrity in boiling water. The high hydrolytic stability of BUT-155 allowed us to carry out adsorption studies of water vapor and aqueous organic pollutants on it. Water-vapor adsorption reveals a sigmoidal isotherm and a high uptake (46.7 wt %), which is highly reversible and regenerable. In addition, because of the availability of soft-acid-type open Cu(II) sites, BUT-155 shows a high performance for selective adsorption of soft-base-type aniline over water or phenol, and a naked-eye detectable color change for the MOF sample accompanies this. The adsorption selectivity and high adsorption capacity of aniline in BUT-155 are also well-interpreted by single-crystal structures of the water- and aniline-included phases of BUT-155.

Serial crystallography captures enzyme catalysis in copper nitrite reductase at atomic resolution from one crystal.

PubMed

Horrell, Sam; Antonyuk, Svetlana V; Eady, Robert R; Hasnain, S Samar; Hough, Michael A; Strange, Richard W

2016-07-01

Relating individual protein crystal structures to an enzyme mechanism remains a major and challenging goal for structural biology. Serial crystallography using multiple crystals has recently been reported in both synchrotron-radiation and X-ray free-electron laser experiments. In this work, serial crystallography was used to obtain multiple structures serially from one crystal (MSOX) to study in crystallo enzyme catalysis. Rapid, shutterless X-ray detector technology on a synchrotron MX beamline was exploited to perform low-dose serial crystallography on a single copper nitrite reductase crystal, which survived long enough for 45 consecutive 100 K X-ray structures to be collected at 1.07-1.62 Å resolution, all sampled from the same crystal volume. This serial crystallography approach revealed the gradual conversion of the substrate bound at the catalytic type 2 Cu centre from nitrite to nitric oxide, following reduction of the type 1 Cu electron-transfer centre by X-ray-generated solvated electrons. Significant, well defined structural rearrangements in the active site are evident in the series as the enzyme moves through its catalytic cycle, namely nitrite reduction, which is a vital step in the global denitrification process. It is proposed that such a serial crystallography approach is widely applicable for studying any redox or electron-driven enzyme reactions from a single protein crystal. It can provide a 'catalytic reaction movie' highlighting the structural changes that occur during enzyme catalysis. The anticipated developments in the automation of data analysis and modelling are likely to allow seamless and near-real-time analysis of such data on-site at some of the powerful synchrotron crystallographic beamlines.

Structure of a Thermobifida fusca lytic polysaccharide monooxygenase and mutagenesis of key residues

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

Kruer-Zerhusen, Nathan; Alahuhta, Markus; Lunin, Vladimir V.

Auxiliary activity (AA) enzymes are produced by numerous bacterial and fungal species to assist in the degradation of biomass. These enzymes are abundant but have yet to be fully characterized. Here, we report the X-ray structure of Thermobifida fusca AA10A (TfAA10A), investigate mutational characterization of key surface residues near its active site, and explore the importance of the various domains of Thermobifida fusca AA10B (TfAA10B). The structure of TfAA10A is similar to other bacterial LPMOs (lytic polysaccharide monooxygenases), including signs of photo-reduction and a distorted active site, with mixed features showing both type I and II copper coordination. The pointmore » mutation experiments of TfAA10A show that Trp82 and Asn83 are needed for binding, but only Trp82 affects activity. The TfAA10B domain truncation mutants reveal that CBM2 is crucial for the binding of substrate, but that the X1 module does not affect binding or activity. In TfAA10A, Trp82 and Asn83 are needed for binding, but only Trp82 affects activity. The TfAA10B domain truncation mutants reveal that CBM2 is crucial for substrate binding, but that the X1 module does not affect binding or activity. The structure of TfAA10A is similar to other bacterial lytic polysaccharide monooxygenases with mixed features showing both type I and II copper coordination. The role of LPMOs and the variability of abundance in genomes are not fully explored. LPMOs likely perform initial attacks into crystalline cellulose to allow larger processive cellulases to bind and attack, but the precise nature of their synergistic behavior remains to be definitively characterized.« less

Structure of a Thermobifida fusca lytic polysaccharide monooxygenase and mutagenesis of key residues

DOE PAGES

Kruer-Zerhusen, Nathan; Alahuhta, Markus; Lunin, Vladimir V.; ...

2017-11-30

Auxiliary activity (AA) enzymes are produced by numerous bacterial and fungal species to assist in the degradation of biomass. These enzymes are abundant but have yet to be fully characterized. Here, we report the X-ray structure of Thermobifida fusca AA10A (TfAA10A), investigate mutational characterization of key surface residues near its active site, and explore the importance of the various domains of Thermobifida fusca AA10B (TfAA10B). The structure of TfAA10A is similar to other bacterial LPMOs (lytic polysaccharide monooxygenases), including signs of photo-reduction and a distorted active site, with mixed features showing both type I and II copper coordination. The pointmore » mutation experiments of TfAA10A show that Trp82 and Asn83 are needed for binding, but only Trp82 affects activity. The TfAA10B domain truncation mutants reveal that CBM2 is crucial for the binding of substrate, but that the X1 module does not affect binding or activity. In TfAA10A, Trp82 and Asn83 are needed for binding, but only Trp82 affects activity. The TfAA10B domain truncation mutants reveal that CBM2 is crucial for substrate binding, but that the X1 module does not affect binding or activity. The structure of TfAA10A is similar to other bacterial lytic polysaccharide monooxygenases with mixed features showing both type I and II copper coordination. The role of LPMOs and the variability of abundance in genomes are not fully explored. LPMOs likely perform initial attacks into crystalline cellulose to allow larger processive cellulases to bind and attack, but the precise nature of their synergistic behavior remains to be definitively characterized.« less

Neutropenia restores virulence to an attenuated Cu,Zn superoxide dismutase-deficient Haemophilus ducreyi strain in the swine model of chancroid.

PubMed

San Mateo, L R; Toffer, K L; Orndorff, P E; Kawula, T H

1999-10-01

Haemophilus ducreyi causes chancroid, a sexually transmitted cutaneous genital ulcer disease associated with increased heterosexual transmission of human immunodeficiency virus. H. ducreyi expresses a periplasmic copper-zinc superoxide dismutase (Cu, Zn SOD) that protects the bacterium from killing by exogenous superoxide in vitro. We hypothesized that the Cu,Zn SOD would protect H. ducreyi from immune cell killing, enhance survival, and affect ulcer development in vivo. In order to test this hypothesis and study the role of the Cu,Zn SOD in H. ducreyi pathogenesis, we compared a Cu,Zn SOD-deficient H. ducreyi strain to its isogenic wild-type parent with respect to survival and ulcer development in immunocompetent and immunosuppressed pigs. The Cu,Zn SOD-deficient strain was recovered from significantly fewer inoculated sites and in significantly lower numbers than the wild-type parent strain or a merodiploid (sodC+ sodC) strain after infection of immunocompetent pigs. In contrast, survival of the wild-type and Cu,Zn SOD-deficient strains was not significantly different in pigs that were rendered neutropenic by treatment with cyclophosphamide. Ulcer severity in pigs was not significantly different between sites inoculated with wild type and sites inoculated with Cu,Zn SOD-deficient H. ducreyi. Our data suggest that the periplasmic Cu,Zn SOD is an important virulence determinant in H. ducreyi, protecting the bacterium from host immune cell killing and contributing to survival and persistence in the host.

Neutropenia Restores Virulence to an Attenuated Cu,Zn Superoxide Dismutase-Deficient Haemophilus ducreyi Strain in the Swine Model of Chancroid

PubMed Central

San Mateo, Lani R.; Toffer, Kristen L.; Orndorff, Paul E.; Kawula, Thomas H.

1999-01-01

Haemophilus ducreyi causes chancroid, a sexually transmitted cutaneous genital ulcer disease associated with increased heterosexual transmission of human immunodeficiency virus. H. ducreyi expresses a periplasmic copper-zinc superoxide dismutase (Cu,Zn SOD) that protects the bacterium from killing by exogenous superoxide in vitro. We hypothesized that the Cu,Zn SOD would protect H. ducreyi from immune cell killing, enhance survival, and affect ulcer development in vivo. In order to test this hypothesis and study the role of the Cu,Zn SOD in H. ducreyi pathogenesis, we compared a Cu,Zn SOD-deficient H. ducreyi strain to its isogenic wild-type parent with respect to survival and ulcer development in immunocompetent and immunosuppressed pigs. The Cu,Zn SOD-deficient strain was recovered from significantly fewer inoculated sites and in significantly lower numbers than the wild-type parent strain or a merodiploid (sodC+ sodC) strain after infection of immunocompetent pigs. In contrast, survival of the wild-type and Cu,Zn SOD-deficient strains was not significantly different in pigs that were rendered neutropenic by treatment with cyclophosphamide. Ulcer severity in pigs was not significantly different between sites inoculated with wild type and sites inoculated with Cu,Zn SOD-deficient H. ducreyi. Our data suggest that the periplasmic Cu,Zn SOD is an important virulence determinant in H. ducreyi, protecting the bacterium from host immune cell killing and contributing to survival and persistence in the host. PMID:10496915

A horizontally gene transferred copper resistance locus confers hyper‐resistance to antibacterial copper toxicity and enables survival of community acquired methicillin resistant Staphylococcus aureus USA300 in macrophages

PubMed Central

Purves, Joanne; Thomas, Jamie; Riboldi, Gustavo P.; Zapotoczna, Marta; Tarrant, Emma; Andrew, Peter W.; Londoño, Alejandra; Planet, Paul J.; Geoghegan, Joan A.; Waldron, Kevin J.

2018-01-01

Summary Excess copper is highly toxic and forms part of the host innate immune system's antibacterial arsenal, accumulating at sites of infection and acting within macrophages to kill engulfed pathogens. We show for the first time that a novel, horizontally gene transferred copper resistance locus (copXL), uniquely associated with the SCCmec elements of the highly virulent, epidemic, community acquired methicillin resistant Staphylococcus aureus (CA‐MRSA) USA300, confers copper hyper‐resistance. These genes are additional to existing core genome copper resistance mechanisms, and are not found in typical S. aureus lineages, but are increasingly identified in emerging pathogenic isolates. Our data show that CopX, a putative P1B‐3‐ATPase efflux transporter, and CopL, a novel lipoprotein, confer copper hyper‐resistance compared to typical S. aureus strains. The copXL genes form an operon that is tightly repressed in low copper environments by the copper regulator CsoR. Significantly, CopX and CopL are important for S. aureus USA300 intracellular survival within macrophages. Therefore, the emergence of new S. aureus clones with the copXL locus has significant implications for public health because these genes confer increased resistance to antibacterial copper toxicity, enhancing bacterial fitness by altering S. aureus interaction with innate immunity. PMID:29521441

Localization and Specification of Copper Ions in Biofilms on Corroding Copper Surfaces.

DTIC Science & Technology

1994-01-01

WW~nhi~. OC ;mmS 1 . Agency use unay (L-mUv umia. IA. "O" ,.ie. $3. Report Type and Dates Covered. I 1994 Final - Proceedings 4. Title and Subtitle. S...structure (XANES) techniques can be used to differentiate Cu’ 1 and Cu+2 species within biofilms attached to surfaces. Copper ions , uld not be... 1 The organism with associated polymer has been shown to bind copper ions from solution. Geesey et al.2 demonstrated that exopolymers produced by

Remediation System Evaluation, Peerless Plating Site

EPA Pesticide Factsheets

The Peerless Plating Superfund Site is located at 2554 South Getty Street, north of the intersection of South Getty Street and East Sherman Boulevard in Muskegon, Michigan. Copper, nickel, chromium, cadmium, and zinc electroplating operations as well as...

Redox control of copper homeostasis in cyanobacteria.

PubMed

López-Maury, Luis; Giner-Lamia, Joaquín; Florencio, Francisco J

2012-12-01

Copper is essential for all living organisms but is toxic when present in excess. Therefore organisms have developed homeostatic mechanism to tightly regulate its cellular concentration. In a recent study we have shown that CopRS two-component system is essential for copper resistance in the cyanobacterium Synechocystis sp PCC 6803. This two-component regulates expression of a heavy-metal RND type copper efflux system (encoded by copBAC) as well as its own expression (in the copMRS operon) in response to an excess of copper in the media. We have also observed that both operons are induced under condition that reduces the photosynthetic electron flow and this induction depends on the presence of the copper-protein, plastocyanin. These findings, together with CopS localization to the thylakoid membrane and its periplasmic domain being able to bind copper directly, suggest that CopS could be involved in copper detection in both the periplasm and the thylakoid lumen.

Copper Tube Pitting in Santa Fe Municipal Water Caused by Microbial Induced Corrosion.

PubMed

Burleigh, Thomas D; Gierke, Casey G; Fredj, Narjes; Boston, Penelope J

2014-06-05

Many copper water lines for municipal drinking water in Santa Fe, New Mexico USA, have developed pinhole leaks. The pitting matches the description of Type I pitting of copper, which has historically been attributed to water chemistry and to contaminants on the copper tubing surface. However, more recent studies attribute copper pitting to microbial induced corrosion (MIC). In order to test for microbes, the copper tubing was fixed in hexamethyldisilazane (HMDS), then the tops of the corrosion mounds were broken open, and the interior of the corrosion pits were examined with scanning electron microscopy (SEM). The analysis found that microbes resembling actinobacteria were deep inside the pits and wedged between the crystallographic planes of the corroded copper grains. The presence of actinobacteria confirms the possibility that the cause of this pitting corrosion was MIC. This observation provides better understanding and new methods for preventing the pitting of copper tubing in municipal water.

Copper Tube Pitting in Santa Fe Municipal Water Caused by Microbial Induced Corrosion

PubMed Central

Burleigh, Thomas D.; Gierke, Casey G.; Fredj, Narjes; Boston, Penelope J.

2014-01-01

Many copper water lines for municipal drinking water in Santa Fe, New Mexico USA, have developed pinhole leaks. The pitting matches the description of Type I pitting of copper, which has historically been attributed to water chemistry and to contaminants on the copper tubing surface. However, more recent studies attribute copper pitting to microbial induced corrosion (MIC). In order to test for microbes, the copper tubing was fixed in hexamethyldisilazane (HMDS), then the tops of the corrosion mounds were broken open, and the interior of the corrosion pits were examined with scanning electron microscopy (SEM). The analysis found that microbes resembling actinobacteria were deep inside the pits and wedged between the crystallographic planes of the corroded copper grains. The presence of actinobacteria confirms the possibility that the cause of this pitting corrosion was MIC. This observation provides better understanding and new methods for preventing the pitting of copper tubing in municipal water. PMID:28788679

Multiple approaches to assess the safety of artisanal marine food in a tropical estuary.

PubMed

Padovan, A C; Neave, M J; Munksgaard, N C; Gibb, K S

2017-03-01

In this study, metal and metalloid concentrations and pathogens were measured in shellfish at different locations in a tropical estuary, including sites impacted by sewage and industry. Oyster, mangrove snails and mud snails did not exceed Australian and New Zealand Food Standards maximum levels for copper, lead or estimated inorganic arsenic at any site although copper concentrations in oysters and mud snails exceeded generally expected levels at some locations. Bacterial community composition in shellfish was species-specific regardless of location and different to the surrounding water and sediment. In the snails Telescopium telescopium, Terebralia palustris and Nerita balteata, some bacterial taxa differed between sites, but not in Saccostrea cucullata oysters. The abundance of potential human pathogens was very low and pathogen abundance or diversity was not associated with site classification, i.e. sewage impact, industry impact and reference.

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.

Strong coupling diagram technique for the three-band Hubbard model

NASA Astrophysics Data System (ADS)

Sherman, A.

2016-03-01

Strong coupling diagram technique equations are derived for hole Green’s functions of the three-band Hubbard model, which describes Cu-O planes of high-Tc cuprates. The equations are self-consistently solved in the approximation, in which the series for the irreducible part in powers of the oxygen-copper hopping constant is truncated to two lowest-order terms. For parameters used for hole-doped cuprates, the calculated energy spectrum consists of lower and upper Hubbard subbands of predominantly copper nature, oxygen bands with a small admixture of copper states and the Zhang-Rice states of mixed nature, which are located between the lower Hubbard subband and oxygen bands. The spectrum contains also pseudogaps near transition frequencies of Hubbard atoms on copper sites.

Copper removal using a heavy-metal resistant microbial consortium in a fixed-bed reactor.

PubMed

Carpio, Isis E Mejias; Machado-Santelli, Glaucia; Sakata, Solange Kazumi; Ferreira Filho, Sidney Seckler; Rodrigues, Debora Frigi

2014-10-01

A heavy-metal resistant bacterial consortium was obtained from a contaminated river in São Paulo, Brazil and utilized for the design of a fixed-bed column for the removal of copper. Prior to the design of the fixed-bed bioreactor, the copper removal capacity by the live consortium and the effects of copper in the consortium biofilm formation were investigated. The Langmuir model indicated that the sorption capacity of the consortium for copper was 450.0 mg/g dry cells. The biosorption of copper into the microbial biomass was attributed to carboxyl and hydroxyl groups present in the microbial biomass. The effect of copper in planktonic cells to form biofilm under copper rich conditions was investigated with confocal microscopy. The results revealed that biofilm formed after 72 h exposure to copper presented a reduced thickness by 57% when compared to the control; however 84% of the total cells were still alive. The fixed-bed bioreactor was set up by growing the consortium biofilm on granular activated carbon (GAC) and analyzed for copper removal. The biofilm-GAC (BGAC) column retained 45% of the copper mass present in the influent, as opposed to 17% in the control column that contained GAC only. These findings suggest that native microbial communities in sites contaminated with heavy metals can be immobilized in fixed-bed bioreactors and used to treat metal contaminated water. Copyright © 2014 Elsevier Ltd. All rights reserved.

Second-Generation Difluorinated Cyclooctynes for Copper-Free Click Chemistry

PubMed Central

2008-01-01

The 1,3-dipolar cycloaddition of azides and activated alkynes has been used for site-selective labeling of biomolecules in vitro and in vivo. While copper catalysis has been widely employed to activate terminal alkynes for [3 + 2] cycloaddition, this method, often termed “click chemistry”, is currently incompatible with living systems because of the toxicity of the metal. We recently reported a difluorinated cyclooctyne (DIFO) reagent that rapidly reacts with azides in living cells without the need for copper catalysis. Here we report a novel class of DIFO reagents for copper-free click chemistry that are considerably more synthetically tractable. The new analogues maintained the same elevated rates of [3 + 2] cycloaddition as the parent compound and were used for imaging glycans on live cells. These second-generation DIFO reagents should expand the use of copper-free click chemistry in the hands of biologists. PMID:18680289

Second-generation difluorinated cyclooctynes for copper-free click chemistry.

PubMed

Codelli, Julian A; Baskin, Jeremy M; Agard, Nicholas J; Bertozzi, Carolyn R

2008-08-27

The 1,3-dipolar cycloaddition of azides and activated alkynes has been used for site-selective labeling of biomolecules in vitro and in vivo. While copper catalysis has been widely employed to activate terminal alkynes for [3 + 2] cycloaddition, this method, often termed "click chemistry", is currently incompatible with living systems because of the toxicity of the metal. We recently reported a difluorinated cyclooctyne (DIFO) reagent that rapidly reacts with azides in living cells without the need for copper catalysis. Here we report a novel class of DIFO reagents for copper-free click chemistry that are considerably more synthetically tractable. The new analogues maintained the same elevated rates of [3 + 2] cycloaddition as the parent compound and were used for imaging glycans on live cells. These second-generation DIFO reagents should expand the use of copper-free click chemistry in the hands of biologists.

Copper, lead and zinc concentrations of human breast milk as affected by maternal dietary practices

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

Umoren, J.; Kies, C.

1986-03-01

Maternal dietary practices have been found to affect the concentrations of some nutrients in human breast milk. Lead toxicity is a concern in young children. Lead, copper and zinc are thought to compete for intestinal absorption sites. The objective of the current project was to compare copper, lead and zinc contents of breast milk from practicing lacto-vegetarian and omnivore, lactating women at approximately four months post-partum. Analyses were done by atomic absorption spectrophotometry using a carbon rod attachment. Copper concentrations were higher in milk samples from lacto-ovo-vegetarians. Milk samples from the omnivores had the highest lead and zinc concentrations. Leadmore » and copper concentrations in milk were negatively correlated. The higher zinc concentrations in the milk of the omnivore women may have been related to better utilization of zinc from meat than from plant food sources.« less

Internal electron transfer between hemes and Cu(II) bound at cysteine beta93 promotes methemoglobin reduction by carbon monoxide.

PubMed

Bonaventura, C; Godette, G; Tesh, S; Holm, D E; Bonaventura, J; Crumbliss, A L; Pearce, L L; Peterson, J

1999-02-26

Previous studies showed that CO/H2O oxidation provides electrons to drive the reduction of oxidized hemoglobin (metHb). We report here that Cu(II) addition accelerates the rate of metHb beta chain reduction by CO by a factor of about 1000. A mechanism whereby electron transfer occurs via an internal pathway coupling CO/H2O oxidation to Fe(III) and Cu(II) reduction is suggested by the observation that the copper-induced rate enhancement is inhibited by blocking Cys-beta93 with N-ethylmaleimide. Furthermore, this internal electron-transfer pathway is more readily established at low Cu(II) concentrations in Hb Deer Lodge (beta2His --> Arg) and other species lacking His-beta2 than in Hb A0. This difference is consistent with preferential binding of Cu(II) in Hb A0 to a high affinity site involving His-beta2, which is ineffective in promoting electron exchange between Cu(II) and the beta heme iron. Effective electron transfer is thus affected by Hb type but is not governed by the R left arrow over right arrow T conformational equilibrium. The beta hemes in Cu(II)-metHb are reduced under CO at rates close to those observed for cytochrome c oxidase, where heme and copper are present together in the oxygen-binding site and where internal electron transfer also occurs.

Quality of ground water in the Puget sound region, Washington, 1981

USGS Publications Warehouse

Turney, G.L.

1986-01-01

Groundwater from more than 100 sites in the Puget Sound region, Washington, was sampled and analyzed in 1981 for pH, specific conductance, and concentrations of fecal coliform bacteria, major ions, and dissolved iron, manganese, and nitrate. 20% of the samples were analyzed for concentrations of dissolved trace metals including aluminum, arsenic, barium, cadmium, chromium, copper, lead, mercury, selenium, silver, and zinc. The predominant water types were calcium bicarbonate and calcium-magnesium bicarbonate. Some wells in San Juan and Island Counties contained sodium chloride as a result of seawater intrusion. Dissolved solids concentrations were generally < 150 mg/L. Iron concentrations > 300 micrograms/L in 14% of all samples. Manganese concentrations > 50 micrograms/L in 40% of all samples. Trace-metal concentrations were generally < 10 mg/L , except for barium, copper, lead, and zinc. Nitrate concentrations were < 1.0 mg/L in water for over 75% of the sites. Concentrations > 1.0 mg/L in samples from Skagit, Whatcom , and Pierce Counties, were probably due to agricultural activities or septic tanks. Fecal coliform bacteria were detected in isolated instances. EPA drinking water regulations were exceeded only in isolated instances, except for widespread excessive iron and manganese concentrations. The historical data for the region were also evaluated for the same constituents. There are quantitative differences between historical and 1981 data, but they may be due to inconsistencies in data collection and analytical methods. (Author 's abstract)

In long-term bedridden elderly patients with dietary copper deficiency, biochemical markers of bone resorption are increased with copper supplementation during 12 weeks.

PubMed

Kawada, Etsuo; Moridaira, Kazuaki; Itoh, Katsuhiko; Hoshino, Ayami; Tamura, Jun'ichi; Morita, Toyoho

2006-01-01

Although the effect of copper on bone has been tested in animals and healthy subjects, no studies concerning the effect of copper supplementation on bone metabolism in patients with copper deficiency have been reported because of the rarity of these patients. This study was conducted to investigate the effect of copper supplementation on bone metabolism in copper-deficient patients. This study included 10 patients (83.7 +/- 8.3 years) with dietary copper deficiency under long-term bed rest for more than 12 months. They had their diets supplemented with copper sulfate (3 mg/day) over 12 weeks in addition to their diet of only one kind of enteral food with a low concentration of copper. Serum copper and ceruloplasmin, urinary deoxypyridinoline (DPD) and collagen-type 1 N-telopeptide (NTX) (biomarkers of bone resorption), serum osteocalcin (OC) and bone-specific alkaline phosphatase (Bone ALP) (biomarkers of bone formation) were analyzed at baseline, 4 and 12 weeks after copper supplementation. DPD and NTX excretion were significantly increased 4 weeks after copper supplementation (p = 0.009 and p = 0.013, respectively). Serum bone ALP and OC were not significantly changed 12 weeks after copper supplementation (p = 0.051 and p = 0.594). In patients with nutritional copper deficiency, bone resorption markers are increased with copper supplementation. Copyright (c) 2006 S. Karger AG, Basel.

CELLULAR MULTITASKING: THE DUAL ROLE OF HUMAN CU-ATPASES IN COFACTOR DELIVERY AND INTRACELLULAR COPPER BALANCE

PubMed Central

Lutsenko, Svetlana; Gupta, Arnab; Burkhead, Jason L.; Zuzel, Vesna

2008-01-01

Summary The human copper-transporting ATPases (Cu-ATPases) are essential for dietary copper uptake, normal development and function of the CNS, and regulation of copper homeostasis in the body. In a cell, Cu-ATPases maintain the intracellular concentration of copper by transporting copper into intracellular exocytic vesicles. In addition, these P-type ATPases mediate delivery of copper to copper-dependent enzymes in the secretory pathway and in specialized cell compartments such as secretory granules or melanosomes. The multiple functions of human Cu-ATPase necessitate complex regulation of these transporters that is mediated through the presence of regulatory domains in their structure, posttranslational modification and intracellular trafficking, as well as interactions with the copper chaperone Atox1 and other regulatory molecules. In this review, we summarize the current information on the function and regulatory mechanisms acting on human Cu-ATPases ATP7A and ATP7B. Brief comparison with the Cu-ATPase orthologues from other species is included. PMID:18534184

Chalcopyrite—bearer of a precious, non-precious metal

USGS Publications Warehouse

Kimball, Bryn E.

2013-01-01

The mineral chalcopyrite (CuFeS2) is the world's most abundant source of copper, a metal component in virtually every piece of electrical equipment. It is the main copper mineral in several different ore deposit types, the most important of which are porphyry deposits. Chalcopyrite is unstable at the Earth's surface, so it weathers from sulphide outcrops and mine waste piles, contributing acid and dissolved copper to what is known as acid rock drainage. If not prevented, dissolved copper from chalcopyrite weathering will be transported downstream, potentially harming ecosystems along the way. Pristine areas are becoming targets for future copper supply as we strive to meet ever-increasing demands for copper by developed and developing nations. Additionally, our uses for copper are expanding to include technology such as solar energy production. This has lead to the processing of increasingly lower grade ores, which is possible, in part, due to advances in bio-leaching (i.e. metal extraction catalysed by micro-organisms). Although copper is plentiful, it is still a nonrenewable resource. Future copper supply promises to fall short of demand and the volatility of the copper market may continue if we do not prioritize copper use and improve copper recycling and ore extraction efficiency.

Increased mercury emissions from modern dental amalgams.

PubMed

Bengtsson, Ulf G; Hylander, Lars D

2017-04-01

All types of dental amalgams contain mercury, which partly is emitted as mercury vapor. All types of dental amalgams corrode after being placed in the oral cavity. Modern high copper amalgams exhibit two new traits of increased instability. Firstly, when subjected to wear/polishing, droplets rich in mercury are formed on the surface, showing that mercury is not being strongly bonded to the base or alloy metals. Secondly, high copper amalgams emit substantially larger amounts of mercury vapor than the low copper amalgams used before the 1970s. High copper amalgams has been developed with focus on mechanical strength and corrosion resistance, but has been sub-optimized in other aspects, resulting in increased instability and higher emission of mercury vapor. This has not been presented to policy makers and scientists. Both low and high copper amalgams undergo a transformation process for several years after placement, resulting in a substantial reduction in mercury content, but there exist no limit for maximum allowed emission of mercury from dental amalgams. These modern high copper amalgams are nowadays totally dominating the European, US and other markets, resulting in significant emissions of mercury, not considered when judging their suitability for dental restoration.

Electrochemical Behavior of Pure Copper in Phosphate Buffer Solutions: A Comparison Between Micro- and Nano-Grained Copper

NASA Astrophysics Data System (ADS)

Imantalab, O.; Fattah-alhosseini, A.; Keshavarz, M. K.; Mazaheri, Y.

2016-02-01

In this work, electrochemical behavior of annealed (micro-) and nano-grained pure copper (fabricated by accumulative roll bonding process) in phosphate buffer solutions of various pH values ranging from 10.69 to 12.59 has been studied. Before any electrochemical measurements, evaluation of microstructure was obtained by optical microscope and transmission electron microscopy. To investigate the electrochemical behavior of the samples, the potentiodynamic polarization, Mott-Schottky analysis, and electrochemical impedance spectroscopy (EIS) were carried out. Potentiodynamic polarization plots and EIS measurements revealed that as a result of grain refinement, the passive behavior of the nano-grained sample was improved compared to that of annealed pure copper. Also, Mott-Schottky analysis indicated that the passive films behaved as p-type semiconductors and grain refinement did not change the semiconductor type of passive films.

Phenotypic convergence of Menkes and Wilson disease.

PubMed

Bansagi, Boglarka; Lewis-Smith, David; Pal, Endre; Duff, Jennifer; Griffin, Helen; Pyle, Angela; Müller, Juliane S; Rudas, Gabor; Aranyi, Zsuzsanna; Lochmüller, Hanns; Chinnery, Patrick F; Horvath, Rita

2016-12-01

Menkes disease is an X-linked multisystem disorder with epilepsy, kinky hair, and neurodegeneration caused by mutations in the copper transporter ATP7A . Other ATP7A mutations have been linked to juvenile occipital horn syndrome and adult-onset hereditary motor neuropathy. 1,2 About 5%-10% of the patients present with "atypical Menkes disease" characterized by longer survival, cerebellar ataxia, and developmental delay. 2 The intracellular copper transport is regulated by 2 P type ATPase copper transporters ATP7A and ATP7B. These proteins are expressed in the trans-Golgi network that guides copper to intracellular compartments, and in copper excess, it relocates copper to the plasma membrane to pump it out from the cells. 3 ATP7B mutations cause Wilson disease with dystonia, ataxia, tremor, and abnormal copper accumulation in the brain, liver, and other organs. 4 .

Transaction Design Specification Medical Exam Databases System (MED) update Transaction

DTIC Science & Technology

1986-12-01

8217RECOFD IN 51) 73. CORONARY SFAS1 SITE ;CHAR X(6) IN 7:) 74* CORONARY FLAQUES (RECO D IN 51) 75. CCFONARY PLAOUE 3ITE ,CHAR K(60 IN 74) 76* FCT DIAMETER...KETOSTEROIDS YE HYDROXYCARTICOSTEROIDS YO 24 HR URINE TOTAL VOLUME MA URINE OSMOLALITY MB SERUM OSMOLALITY MC 24HR URINE TOTAL VOLUME ZE SERUM COPPER FBS TO...RHEUMATOID FACTOR PA N P -2 2 ANTINUCLEAR ANTIBODY PB N P -2 2 0 FREE FATTY ACIDS QA 5 9 57 200 MG% SERUM COPPER RA 30 70 130 300 JG% URINE COPPER RBM 10 30 90

The role of mineral surface chemistry in modified dextrin adsorption.

PubMed

Beaussart, Audrey; Mierczynska-Vasilev, Agnieszka M; Harmer, Sarah L; Beattie, David A

2011-05-15

The adsorption of two modified dextrins (phenyl succinate dextrin--PS Dextrin; styrene oxide dextrin--SO Dextrin) on four different mineral surfaces has been studied using X-ray photoelectron spectroscopy (XPS), in situ atomic force microscopy (AFM) imaging, and captive bubble contact angle measurements. The four surfaces include highly orientated pyrolytic graphite (HOPG), freshly cleaved synthetic sphalerite (ZnS), and two surfaces produced through surface reactions of sphalerite: one oxidized in alkaline solution (pH 9, 1 h immersion); and one subjected to metal ion exchange between copper and zinc (i.e. copper activation: exposed to 1×10(-3) M CuSO(4) solution for 1 h). XPS measurements indicate that the different sphalerite surfaces contain varying amounts of sulfur, zinc, oxygen, and copper, producing substrates for polymer adsorption with a range of possible binding sites. AFM imaging has shown that the two polymers adsorb to a similar extent on HOPG, and that the two polymers display very different propensities for adsorption on the three sphalerite surface types, with freshly cleaved sphalerite encouraging the least adsorption, and copper activated and oxidized sphalerite encouraging significantly more adsorption. Contact angle measurements of the four surfaces indicate that synthetic sphalerite has a low contact angle upon fracture, and that oxidation on the timescale of one hour substantially alters the hydrophobicity. HOPG and copper-activated sphalerite were the most hydrophobic, as expected due to the carbon and di/poly-sulfide rich surfaces of the two samples, respectively. SO Dextrin is seen to have a significant impact on the wettability of HOPG and the surface reacted sphalerite samples, highlighting the difficulty in selectively separating sphalerite from carbonaceous unwanted minerals in flotation. PS Dextrin has the least effect on the hydrophobicity of the reacted sphalerite surfaces, whilst still significantly increasing the wettability of graphite, and thus has more potential for use as a polymer depressant in this separation. Copyright © 2011 Elsevier Inc. All rights reserved.

Predicting toxic effects of copper on aquatic biota in mineralized areas by using the Biotic Ligand Model

USGS Publications Warehouse

Smith, Kathleen S.; Ranville, James F.; Adams, M.; Choate, LaDonna M.; Church, Stan E.; Fey, David L.; Wanty, Richard B.; Crock, James G.

2006-01-01

The chemical speciation of metals influences their biological effects. The Biotic Ligand Model (BLM) is a computational approach to predict chemical speciation and acute toxicological effects of metals on aquatic biota. Recently, the U.S. Environmental Protection Agency incorporated the BLM into their regulatory water-quality criteria for copper. Results from three different laboratory copper toxicity tests were compared with BLM predictions for simulated test-waters. This was done to evaluate the ability of the BLM to accurately predict the effects of hardness and concentrations of dissolved organic carbon (DOC) and iron on aquatic toxicity. In addition, we evaluated whether the BLM and the three toxicity tests provide consistent results. Comparison of BLM predictions with two types of Ceriodaphnia dubia toxicity tests shows that there is fairly good agreement between predicted LC50 values computed by the BLM and LC50 values determined from the two toxicity tests. Specifically, the effect of increasing calcium concentration (and hardness) on copper toxicity appears to be minimal. Also, there is fairly good agreement between the BLM and the two toxicity tests for test solutions containing elevated DOC, for which the LC50 is 3-to-5 times greater (less toxic) than the LC50 for the lower-DOC test water. This illustrates the protective effects of DOC on copper toxicity and demonstrates the ability of the BLM to predict these protective effects. In contrast, for test solutions with added iron there is a decrease in LC50 values (increase in toxicity) in results from the two C. dubia toxicity tests, and the agreement between BLM LC50 predictions and results from these toxicity tests is poor. The inability of the BLM to account for competitive iron binding to DOC or DOC fractionation may be a significant shortcoming of the BLM for predicting site- specific water-quality criteria in streams affected by iron-rich acidic drainage in mined and mineralized areas.

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.

Trialkylphosphine-stabilized copper(I) gallium(III) phenylchalcogenolate complexes: crystal structures and generation of ternary semiconductors by thermolysis.

PubMed

Kluge, Oliver; Krautscheid, Harald

2012-06-18

A series of organometallic trialkylphosphine-stabilized copper gallium phenylchalcogenolate complexes [(R(3)P)(m)Cu(n)Me(2-x)Ga(EPh)(n+x+1)] (R = Me, Et, (i)Pr, (t)Bu; E = S, Se, Te; x = 0, 1) has been prepared and structurally characterized by X-ray diffraction. From their molecular structures three groups of compounds can be distinguished: ionic compounds, ring systems, and cage structures. All these complexes contain one gallium atom bound to one or two methyl groups, whereas the number of copper atoms, and therefore the nuclearity of the complexes, is variable and depends mainly on size and amount of phosphine ligand used in synthesis. The Ga-E bonds are relatively rigid, in contrast to flexible Cu-E bonds. The lengths of the latter are controlled by the coordination number and steric influences. The Ga-E bond lengths depend systematically on the number of methyl groups bound to the gallium atom, with somewhat shorter bonds in monomethyl compounds compared to dimethyl compounds. Quantum chemical computations reproduce this trend and show furthermore that the rotation of one phenyl group around the Ga-E bond is a low energy process with two distinct minima, corresponding to two different conformations found experimentally. Mixtures of different types of chalcogen atoms on molecular scale are possible, and then ligand exchange reactions in solution lead to mixed site occupation. In thermogravimetric studies the complexes were converted into the ternary semiconductors CuGaE(2). The thermolysis reaction is completed at temperatures between 250 and 400 °C, typically with lower temperatures for the heavier chalcogens. Because of significant release of Me(3)Ga during the thermolysis process, and especially in case of copper excess in the precursor complexes, binary copper chalcogenides are obtained as additional thermolysis products. Quaternary semiconductors can be obtained from mixed chalcogen precursors.

Copper speciation and binding by organic matter in copper-contaminated streamwater

USGS Publications Warehouse

Breault, R.F.; Colman, J.A.; Aiken, G.R.; McKnight, D.

1996-01-01

Fulvic acid binding sites (1.3-70 ??M) and EDTA (0.0017-0.18 ??M) accounted for organically bound Cu in seven stream samples measured by potentiometric titration. Cu was 84-99% organically bound in filtrates with 200 nM total Cu. Binding of Cu by EDTA was limited by competition from other trace metals. Water hardness was inversely related to properties of dissolved organic carbon (DOC) that enhance fulvic acid binding: DOC concentration, percentage of DOC that is fulvic acid, and binding sites per fulvic acid carbon. Dissolved trace metals, stabilized by organic binding, occurred at increased concentration in soft water as compared to hard water.

Growth of nitrogen-doped graphene on copper: Multiscale simulations

NASA Astrophysics Data System (ADS)

Gaillard, P.; Schoenhalz, A. L.; Moskovkin, P.; Lucas, S.; Henrard, L.

2016-02-01

We used multiscale simulations to model the growth of nitrogen-doped graphene on a copper substrate by chemical vapour deposition (CVD). Our simulations are based on ab-initio calculations of energy barriers for surface diffusion, which are complemented by larger scale Kinetic Monte Carlo (KMC) simulations. Our results indicate that the shape of grown doped graphene flakes depends on the temperature and deposition flux they are submitted during the process, but we found no significant effect of nitrogen doping on this shape. However, we show that nitrogen atoms have a preference for pyridine-like sites compared to graphite-like sites, as observed experimentally.

Impacts of air pollution on cultural heritage corrosion at European level: What has been achieved and what are the future scenarios.

PubMed

Di Turo, Francesca; Proietti, Chiara; Screpanti, Augusto; Fornasier, M Francesca; Cionni, Irene; Favero, Gabriele; De Marco, Alessandra

2016-11-01

The interaction of pollutants with Cultural Heritage materials leads to artworks and materials degradation and loss, causing an unpriceless damage. This works aims to estimate the impacts of air pollution and meteorological conditions on limestone, copper and bronze and represents the European risk assessment for corrosion of Cultural Heritage materials. The measures and policies for atmospheric pollution reduction have cut off the SO 2 concentration and consequently its impact on materials is drastically reduced. Indeed, in 1980 the number of UNESCO sites in danger was extremely high (94% for limestone, 54% for copper and 1% for bronze) while in 2010 these sites did not exceed the tolerable value of surface recession and corrosion. However, some problem related to air pollution persists. In particular, Random Forest Analysis (RFA), highlights PM 10 as the main responsible for materials corrosion, in 2010. Two scenarios in 2030 have been tested, highlighting that the corrosion levels of limestone, copper and bronze exceed the tolerable limits only in the Balkan area and Turkey. Our results show the importance in the air quality modelling as a powerful tool for the UNESCO sites conservation. Copyright © 2016 Elsevier Ltd. All rights reserved.

Water-quality trends for selected sites in the Boulder River and Tenmile Creek watersheds, Montana, based on data collected during water years 1997-2013

USGS Publications Warehouse

Sando, Steven K.; Clark, Melanie L.; Cleasby, Thomas E.; Barnhart, Elliott P.

2015-01-01

Trend results for sites in the Tenmile Creek watershed generally are more variable and difficult to interpret than for sites in the Boulder River watershed. Trend results for Tenmile Creek above City Diversion (site 11) and Minnehaha Creek near Rimini (site 12) for water years 2000–13 indicate decreasing trends in FACs of cadmium, copper, and zinc. The magnitudes of the decreasing trends in FACs of copper generally are moderate and statistically significant for sites 11 and 12. The magnitudes of the decreasing trends in FACs of cadmium and zinc for site 11 are minor to small and not statistically significant; however, the magnitudes for site 12 are moderate and statistically significant. In general, patterns in FACs for Tenmile Creek near Rimini (site 13) are not well represented by fitted trends within the short data collection period, which might indicate that the trend-analysis structure of the study is not appropriate for describing trends in FACs for site 13. The large decreasing trend in FACs of suspended sediment is the strongest indication of change in water quality during the short period of record for site 13; however, this trend is not statistically significant.

Competition between Metals for Binding to Methanobactin Enables Expression of Soluble Methane Monooxygenase in the Presence of Copper

PubMed Central

Kalidass, Bhagyalakshmi; Ul-Haque, Muhammad Farhan; Baral, Bipin S.; DiSpirito, Alan A.

2014-01-01

It is well known that copper is a key factor regulating expression of the two forms of methane monooxygenase found in proteobacterial methanotrophs. Of these forms, the cytoplasmic, or soluble, methane monooxygenase (sMMO) is expressed only at low copper concentrations. The membrane-bound, or particulate, methane monooxygenase (pMMO) is constitutively expressed with respect to copper, and such expression increases with increasing copper. Recent findings have shown that copper uptake is mediated by a modified polypeptide, or chalkophore, termed methanobactin. Although methanobactin has high specificity for copper, it can bind other metals, e.g., gold. Here we show that in Methylosinus trichosporium OB3b, sMMO is expressed and active in the presence of copper if gold is also simultaneously present. Such expression appears to be due to gold binding to methanobactin produced by M. trichosporium OB3b, thereby limiting copper uptake. Such expression and activity, however, was significantly reduced if methanobactin preloaded with copper was also added. Further, quantitative reverse transcriptase PCR (RT-qPCR) of transcripts of genes encoding polypeptides of both forms of MMO and SDS-PAGE results indicate that both sMMO and pMMO can be expressed when copper and gold are present, as gold effectively competes with copper for binding to methanobactin. Such findings suggest that under certain geochemical conditions, both forms of MMO may be expressed and active in situ. Finally, these findings also suggest strategies whereby field sites can be manipulated to enhance sMMO expression, i.e., through the addition of a metal that can compete with copper for binding to methanobactin. PMID:25416758

Cell density dependence of Microcystis aeruginosa responses to copper algaecide concentrations: Implications for microcystin-LR release.

PubMed

Kinley, Ciera M; Iwinski, Kyla J; Hendrikse, Maas; Geer, Tyler D; Rodgers, John H

2017-11-01

Along with mechanistic models, predictions of exposure-response relationships for copper are often derived from laboratory toxicity experiments with standardized experimental exposures and conditions. For predictions of copper toxicity to algae, cell density is a critical factor often overlooked. For pulse exposures of copper-based algaecides in aquatic systems, cell density can significantly influence copper sorbed by the algal population, and consequent responses. A cyanobacterium, Microcystis aeruginosa, was exposed to a copper-based algaecide over a range of cell densities to model the density-dependence of exposures, and effects on microcystin-LR (MC-LR) release. Copper exposure concentrations were arrayed to result in a gradient of MC-LR release, and masses of copper sorbed to algal populations were measured following exposures. While copper exposure concentrations eliciting comparable MC-LR release ranged an order of magnitude (24-h EC50s 0.03-0.3mg Cu/L) among cell densities of 10 6 through 10 7 cells/mL, copper doses (mg Cu/mg algae) were similar (24-h EC50s 0.005-0.006mg Cu/mg algae). Comparisons of MC-LR release as a function of copper exposure concentrations and doses provided a metric of the density dependence of algal responses in the context of copper-based algaecide applications. Combined with estimates of other site-specific factors (e.g. water characteristics) and fate processes (e.g. dilution and dispersion, sorption to organic matter and sediments), measuring exposure-response relationships for specific cell densities can refine predictions for in situ exposures and algal responses. These measurements can in turn decrease the likelihood of amending unnecessary copper concentrations to aquatic systems, and minimize risks for non-target aquatic organisms. Copyright © 2017 Elsevier Inc. All rights reserved.

Competition between metals for binding to methanobactin enables expression of soluble methane monooxygenase in the presence of copper.

PubMed

Kalidass, Bhagyalakshmi; Ul-Haque, Muhammad Farhan; Baral, Bipin S; DiSpirito, Alan A; Semrau, Jeremy D

2015-02-01

It is well known that copper is a key factor regulating expression of the two forms of methane monooxygenase found in proteobacterial methanotrophs. Of these forms, the cytoplasmic, or soluble, methane monooxygenase (sMMO) is expressed only at low copper concentrations. The membrane-bound, or particulate, methane monooxygenase (pMMO) is constitutively expressed with respect to copper, and such expression increases with increasing copper. Recent findings have shown that copper uptake is mediated by a modified polypeptide, or chalkophore, termed methanobactin. Although methanobactin has high specificity for copper, it can bind other metals, e.g., gold. Here we show that in Methylosinus trichosporium OB3b, sMMO is expressed and active in the presence of copper if gold is also simultaneously present. Such expression appears to be due to gold binding to methanobactin produced by M. trichosporium OB3b, thereby limiting copper uptake. Such expression and activity, however, was significantly reduced if methanobactin preloaded with copper was also added. Further, quantitative reverse transcriptase PCR (RT-qPCR) of transcripts of genes encoding polypeptides of both forms of MMO and SDS-PAGE results indicate that both sMMO and pMMO can be expressed when copper and gold are present, as gold effectively competes with copper for binding to methanobactin. Such findings suggest that under certain geochemical conditions, both forms of MMO may be expressed and active in situ. Finally, these findings also suggest strategies whereby field sites can be manipulated to enhance sMMO expression, i.e., through the addition of a metal that can compete with copper for binding to methanobactin. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

A cytosolic copper storage protein provides a second level of copper tolerance in Streptomyces lividans.

PubMed

Straw, Megan L; Chaplin, Amanda K; Hough, Michael A; Paps, Jordi; Bavro, Vassiliy N; Wilson, Michael T; Vijgenboom, Erik; Worrall, Jonathan A R

2018-01-24

Streptomyces lividans has a distinct dependence on the bioavailability of copper for its morphological development. A cytosolic copper resistance system is operative in S. lividans that serves to preclude deleterious copper levels. This system comprises of several CopZ-like copper chaperones and P 1 -type ATPases, predominantly under the transcriptional control of a metalloregulator from the copper sensitive operon repressor (CsoR) family. In the present study, we discover a new layer of cytosolic copper resistance in S. lividans that involves a protein belonging to the newly discovered family of copper storage proteins, which we have named Ccsp (cytosolic copper storage protein). From an evolutionary perspective, we find Ccsp homologues to be widespread in Bacteria and extend through into Archaea and Eukaryota. Under copper stress Ccsp is upregulated and consists of a homotetramer assembly capable of binding up to 80 cuprous ions (20 per protomer). X-ray crystallography reveals 18 cysteines, 3 histidines and 1 aspartate are involved in cuprous ion coordination. Loading of cuprous ions to Ccsp is a cooperative process with a Hill coefficient of 1.9 and a CopZ-like copper chaperone can transfer copper to Ccsp. A Δccsp mutant strain indicates that Ccsp is not required under initial copper stress in S. lividans, but as the CsoR/CopZ/ATPase efflux system becomes saturated, Ccsp facilitates a second level of copper tolerance.

(Pt1-xCux)3Cu2B and Pt9Cu3B5, the first examples of copper platinum borides. Observation of superconductivity in a novel boron filled β-Mn-type compound

NASA Astrophysics Data System (ADS)

Salamakha, Leonid P.; Sologub, Oksana; Stöger, Berthold; Michor, Herwig; Bauer, Ernst; Rogl, Peter F.

2015-09-01

New ternary copper platinum borides have been synthesized by arc melting of pure elements followed by annealing at 600 °C. The structures have been studied by X-ray single crystal and powder diffraction. (Pt1-xCux)3Cu2B (x=0.33) forms a B-filled β-Mn-type structure (space group P4132; a=0.6671(1) nm). Cu atoms are distributed preferentially on the 8c atom sites, whereas the 12d site is randomly occupied by Pt and Cu atoms (0.670(4) Pt±0.330(4) Cu). Boron is located in octahedral voids of the parent β-Mn-type structure. Pt9Cu3B5 (space group P-62m; a=0.9048(3) nm, c=0.2908(1) nm) adopts the Pt9Zn3B5-δ-type structure. It has a columnar architecture along the short translation vector exhibiting three kinds of [Pt6] trigonal prism columns (boron filled, boron semi-filled and empty) and Pt channels with a pentagonal cross section filled with Cu atoms. The striking structural feature is a [Pt6] cluster in form of an empty trigonal prism at the origin of the unit cell, which is surrounded by coupled [BPt6] and [Pt6] trigonal prisms, rotated perpendicularly to the central one. There is no B-B contact as well as Cu-B contact in the structure. The relationships of Pt9Cu3B5 structure with the structure of Ti1+xOs2-xRuB2 as well as with the structure families of metal sulfides and aluminides have been elucidated. (Pt1-xCux)3Cu2B (x=0.3) (B-filled β-Mn-type structure) is a bulk superconductor with a transition temperature of about 2.06 K and an upper critical field μ0HC2(0)WHH of 1.2 T, whereas no superconducting transition has been observed up to 0.3 K in Pt9Cu3B5 (Pt9Zn3B5-δ-type structure) from electrical resistivity measurements.

Spectroscopic and Theoretical Study of CuI Binding to His111 in the Human Prion Protein Fragment 106–115

PubMed Central

2016-01-01

The ability of the cellular prion protein (PrPC) to bind copper in vivo points to a physiological role for PrPC in copper transport. Six copper binding sites have been identified in the nonstructured N-terminal region of human PrPC. Among these sites, the His111 site is unique in that it contains a MKHM motif that would confer interesting CuI and CuII binding properties. We have evaluated CuI coordination to the PrP(106–115) fragment of the human PrP protein, using NMR and X-ray absorption spectroscopies and electronic structure calculations. We find that Met109 and Met112 play an important role in anchoring this metal ion. CuI coordination to His111 is pH-dependent: at pH >8, 2N1O1S species are formed with one Met ligand; in the range of pH 5–8, both methionine (Met) residues bind to CuI, forming a 1N1O2S species, where N is from His111 and O is from a backbone carbonyl or a water molecule; at pH <5, only the two Met residues remain coordinated. Thus, even upon drastic changes in the chemical environment, such as those occurring during endocytosis of PrPC (decreased pH and a reducing potential), the two Met residues in the MKHM motif enable PrPC to maintain the bound CuI ions, consistent with a copper transport function for this protein. We also find that the physiologically relevant CuI-1N1O2S species activates dioxygen via an inner-sphere mechanism, likely involving the formation of a copper(II) superoxide complex. In this process, the Met residues are partially oxidized to sulfoxide; this ability to scavenge superoxide may play a role in the proposed antioxidant properties of PrPC. This study provides further insight into the CuI coordination properties of His111 in human PrPC and the molecular mechanism of oxygen activation by this site. PMID:26930130

Synthesis of pyrrole-imidazole polyamide oligomers based on a copper-catalyzed cross-coupling strategy.

PubMed

Shiga, Naoki; Takayanagi, Shihori; Muramoto, Risa; Murakami, Tasuku; Qin, Rui; Suzuki, Yuta; Shinohara, Ken-Ichi; Kaneda, Atsushi; Nemoto, Tetsuhiro

2017-05-15

Pyrrole-imidazole (Py-Im) polyamides are useful tools for chemical biology and medicinal chemistry studies due to their unique binding properties to the minor groove of DNA. We developed a novel method of synthesizing Py-Im polyamide oligomers based on a Cu-catalyzed cross-coupling strategy. All four patterns of dimer fragments could be synthesized using a Cu-catalyzed Ullmann-type cross-coupling with easily prepared monomer units. Moreover, we demonstrated that pyrrole dimer, trimer, and tetramer building blocks for Py-Im polyamide synthesis were accessible by combining site selective iodination of the pyrrole/pyrrole coupling adduct. Copyright © 2017 Elsevier Ltd. All rights reserved.

Utilization of Copper Alloys for Marine Applications

NASA Astrophysics Data System (ADS)

Drach, Andrew

Utilization of copper alloy components in systems deployed in marine environment presents potential improvements by reducing maintenance costs, prolonging service life, and increasing reliability. However, integration of these materials faces technological challenges, which are discussed and addressed in this work, including characterization of material performance in seawater environment, hydrodynamics of copper alloy components, and design procedures for systems with copper alloys. To characterize the hydrodynamic behavior of copper alloy nets, mesh geometry of the major types of copper nets currently used in the marine aquaculture are analyzed and formulae for the solidity and strand length are proposed. Experimental studies of drag forces on copper alloy net panels are described. Based on these studies, empirical values for normal drag coefficients are proposed for various types of copper netting. These findings are compared to the previously published data on polymer nets. It is shown that copper nets exhibit significantly lower resistance to normal currents, which corresponds to lower values of normal drag coefficient. The seawater performance (corrosion and biofouling) of copper alloys is studied through the field trials of tensioned and untensioned specimens in a one-year deployment in the North Atlantic Ocean. The corrosion behavior is characterized by weight loss, optical microscopy, and SEM/EDX analyses. The biofouling performance is quantified in terms of the biomass accumulation. To estimate the effects of stray electrical currents on the seawater corrosion measurements, a low cost three-axis stray electric current monitoring device is designed and tested both in the lab and in the 30-day field deployment. The system consists of a remotely operated PC with a set of pseudo-electrodes and a digital compass. The collected data is processed to determine magnitudes of AC and DC components of electric field and dominant AC frequencies. Mechanical behavior of copper alloys is investigated through a series of uniaxial tension tests on virgin and weathered (after one-year deployment in the ocean) specimens. The changes in mechanical properties are quantified in terms of differences in Young's modulus, Poisson's ratio, ultimate strength, and ultimate strain. The obtained stress-strain data is used for numerical modeling of the mechanical behavior of chain-link nets. The simulations are compared with the experimental data on stiffness and strength of the nets. The available information on seawater performance of copper alloys (corrosion, biofouling, mechanics) and copper alloy nets (hydrodynamics) is used to develop engineering procedures for marine aquaculture fish cage systems with copper alloy netting. The design, analysis, and fabrication procedures are illustrated on a commercial size gravity-type offshore fish cage deployed in the Pacific Ocean near Isla Italia (Patagonia, Chile). The funding for this work was provided by the International Copper Association. This work was also supported through two UNH Fellowships: CEPS UNH Graduate Fellowship to Outstanding PhD Program Applicants and Dissertation Year Fellowship.

Dry atmospheric deposition rates of metals along a coastal transect in southern California

NASA Astrophysics Data System (ADS)

Sabin, Lisa D.; Schiff, Kenneth C.

While recent studies indicate atmospheric deposition is a significant source of metals to the Santa Monica Bay and coastal river systems of the Los Angeles area, the spatial extent of the atmospheric source along the entire southern California coast has not been measured in 30 years. This study provides measurements of dry atmospheric deposition of chromium, copper, lead, nickel and zinc at eight sites located along the coast between Santa Barbara and San Diego, and compares these data to historic measurements from the 1970s. Median dry deposition fluxes across sites ranged between 0.23 and 3.6 (chromium), 0.21 and 5.4 (nickel), 0.52 and 14 (lead), 0.89 and 29 (copper), and 4.8 and 160 (zinc) μg m -2 day -1. Differences in metal dry deposition rates observed between sites were dominated by proximity to urban areas and/or other nearby sources, with the highest metal fluxes observed near the Los Angeles Harbor (LAH) and San Diego Bay (SDB) sites. Compared with data from the 1970s, lead fluxes were typically one to two orders of magnitude lower in the present study (2006), indicating atmospheric sources of this metal have decreased over the past three decades in southern California. Chromium fluxes were also lower in 2006 compared with the 1970s, although to a lesser extent than for lead. In contrast, copper and zinc fluxes were typically within the same order of magnitude between the two time periods, with some higher measurements observed in 2006 compared with the 1970s at the LAH and SDB sites. This result indicates atmospheric sources of copper and zinc have not decreased over the past three decades in southern California, and have increased near our harbor/urban sites. Differences in sampling conditions (e.g., Santa Ana winds) and measurement techniques may also explain, in part, the differences observed in metal flux rates for these time periods. However, these limitations were most important for those metals with the smallest difference in flux rates measured in the 1970s vs. 2006 (e.g., chromium).

Distribution of trace metals at Hopewell Furnace National Historic Site, Berks and Chester Counties, Pennsylvania

USGS Publications Warehouse

Sloto, Ronald A.; Reif, Andrew G.

2011-01-01

Hopewell Furnace, located approximately 50 miles northwest of Philadelphia, was a cold-blast, charcoal iron furnace that operated for 113 years (1771 to 1883). The purpose of this study by the U.S. Geological Survey, in cooperation with the National Park Service, was to determine the distribution of trace metals released to the environment from an historical iron smelter at Hopewell Furnace National Historic Site (NHS). Hopewell Furnace used iron ore from local mines that contained abundant magnetite and accessory sulfide minerals enriched in arsenic, cobalt, copper, and other metals. Ore, slag, cast iron furnace products, soil, groundwater, stream base flow, streambed sediment, and benthic macroinvertebrates were sampled for this study. Soil samples analyzed in the laboratory had concentrations of trace metals low enough to meet Pennsylvania Department of Environmental Protection standards for non-residential use. Groundwater samples from the supply well met U.S. Environmental Protection Agency drinking-water regulations. Concentrations of metals in surface-water base flow at the five stream sampling sites were below continuous concentration criteria for protection of aquatic organisms. Concentrations of metals in sediment at the five stream sites were below probable effects level guidelines for protection of aquatic organisms except for copper at site HF-3. Arsenic, copper, lead, zinc, and possibly cobalt were incorporated into the cast iron produced by Hopewell Furnace. Manganese was concentrated in slag along with iron, nickel, and zinc. The soil near the furnace has elevated concentrations of chromium, copper, iron, lead, and zinc compared to background soil concentrations. Concentrations of toxic elements were not present at concentrations of concern in water, soil, or stream sediments, despite being elevated in ore, slag, and cast iron furnace products. The base-flow surface-water samples indicated good overall quality. The five sampled sites generally had low concentrations of nutrients and major ions but had elevated concentrations of iron, manganese, and strontium when compared to sites sampled in adjacent watersheds. The background site on Baptism Creek generally had the lowest concentrations and yields of constituents. Low concentrations of nutrients and major ions at all five sites indicate that measured concentrations can be attributed to general land use and geology and not to point sources. Streambed-sediment sampling results indicated higher concentrations of all metals except nickel at sites on French Creek compared to the background site on Baptism Creek. Concentrations of aluminum, cadmium, and nickel were highest in sediment from the sampling site upstream from Hopewell Furnace. The highest concentrations of arsenic, boron, cobalt, copper, iron, lead, manganese, mercury, and zinc were detected at the site just below Hopewell Furnace, which indicates that the source of these metals may be in Hopewell Furnace NHS. The invertebrate community at the background site on Baptism Creek was dominated by pollution sensitive taxa indicating a healthy, diverse benthic-macroinvertebrate community. Benthic-macroinvertebrate communities at sampling sites on French Creek indicated disturbed communities when compared to the background site on Baptism Creek and that the overall stream quality immediately above and below Hopewell Furnace NHS is degraded. The benthic-macroinvertebrate communities were dominated by pollution-tolerant taxa, and taxa were less diverse than at the background site. Habitat conditions at the upstream site on French Creek were good but were degraded at downstream sites on French Creek. The major habitat issues at these sites were related to a lack of stable substrate, erosion, and deposition. Water quality and streambed-sediment quality do not indicate that the degraded benthic-macroinvertebrate communities are the result of poor water quality. Habitat conditions (erosion and sedimentation) and physical alterations (water temperature) from the outfall of Hopewell Lake are the most likely causes of the impaired communities.

Cytoplasmic Copper Detoxification in Salmonella Can Contribute to SodC Metalation but Is Dispensable during Systemic Infection

PubMed Central

Fenlon, Luke A.

2017-01-01

ABSTRACT Salmonella enterica serovar Typhimurium is a leading cause of foodborne disease worldwide. Severe infections result from the ability of S. Typhimurium to survive within host immune cells, despite being exposed to various host antimicrobial factors. SodCI, a copper-zinc-cofactored superoxide dismutase, is required to defend against phagocytic superoxide. SodCII, an additional periplasmic superoxide dismutase, although produced during infection, does not function in the host. Previous studies suggested that CueP, a periplasmic copper binding protein, facilitates acquisition of copper by SodCII. CopA and GolT, both inner membrane ATPases that pump copper from the cytoplasm to the periplasm, are a source of copper for CueP. Using in vitro SOD assays, we found that SodCI can also utilize CueP to acquire copper. However, both SodCI and SodCII have a significant fraction of activity independent of CueP and cytoplasmic copper export. We utilized a series of mouse competition assays to address the in vivo role of CueP-mediated SodC activation. A copA golT cueP triple mutant was equally as competitive as the wild type, suggesting that sufficient SodCI is active to defend against phagocytic superoxide independent of CueP and cytoplasmic copper export. We also confirmed that a strain containing a modified SodCII, which is capable of complementing a sodCI deletion, was fully virulent in a copA golT cueP background competed against the wild type. These competitions also address the potential impact of cytoplasmic copper toxicity within the phagosome. Our data suggest that Salmonella does not encounter inhibitory concentrations of copper during systemic infection. IMPORTANCE Salmonella is a leading cause of gastrointestinal disease worldwide. In severe cases, Salmonella can cause life-threatening systemic infections, particularly in very young children, the elderly, or people who are immunocompromised. To cause disease, Salmonella must survive the hostile environment inside host immune cells, a location in which most bacteria are killed. Our work examines how one particular metal, copper, is acquired by Salmonella to activate a protein important for survival within immune cells. At high levels, copper itself can inhibit Salmonella. Using a strain of Salmonella that cannot detoxify intracellular copper, we also addressed the in vivo role of copper as an antimicrobial agent. PMID:28924031

Cytoplasmic Copper Detoxification in Salmonella Can Contribute to SodC Metalation but Is Dispensable during Systemic Infection.

PubMed

Fenlon, Luke A; Slauch, James M

2017-12-15

Salmonella enterica serovar Typhimurium is a leading cause of foodborne disease worldwide. Severe infections result from the ability of S Typhimurium to survive within host immune cells, despite being exposed to various host antimicrobial factors. SodCI, a copper-zinc-cofactored superoxide dismutase, is required to defend against phagocytic superoxide. SodCII, an additional periplasmic superoxide dismutase, although produced during infection, does not function in the host. Previous studies suggested that CueP, a periplasmic copper binding protein, facilitates acquisition of copper by SodCII. CopA and GolT, both inner membrane ATPases that pump copper from the cytoplasm to the periplasm, are a source of copper for CueP. Using in vitro SOD assays, we found that SodCI can also utilize CueP to acquire copper. However, both SodCI and SodCII have a significant fraction of activity independent of CueP and cytoplasmic copper export. We utilized a series of mouse competition assays to address the in vivo role of CueP-mediated SodC activation. A copA golT cueP triple mutant was equally as competitive as the wild type, suggesting that sufficient SodCI is active to defend against phagocytic superoxide independent of CueP and cytoplasmic copper export. We also confirmed that a strain containing a modified SodCII, which is capable of complementing a sodCI deletion, was fully virulent in a copA golT cueP background competed against the wild type. These competitions also address the potential impact of cytoplasmic copper toxicity within the phagosome. Our data suggest that Salmonella does not encounter inhibitory concentrations of copper during systemic infection. IMPORTANCE Salmonella is a leading cause of gastrointestinal disease worldwide. In severe cases, Salmonella can cause life-threatening systemic infections, particularly in very young children, the elderly, or people who are immunocompromised. To cause disease, Salmonella must survive the hostile environment inside host immune cells, a location in which most bacteria are killed. Our work examines how one particular metal, copper, is acquired by Salmonella to activate a protein important for survival within immune cells. At high levels, copper itself can inhibit Salmonella Using a strain of Salmonella that cannot detoxify intracellular copper, we also addressed the in vivo role of copper as an antimicrobial agent. Copyright © 2017 American Society for Microbiology.

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

PubMed

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

2014-01-01

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

Synthetic fluorescent probes for studying copper in biological systems

PubMed Central

Cotruvo, Joseph A.; Aron, Allegra T.; Ramos-Torres, Karla M.; Chang, Christopher J.

2015-01-01

The potent redox activity of copper is required for sustaining life. Mismanagement of its cellular pools, however, can result in oxidative stress and damage connected to aging, neurodegenerative diseases, and metabolic disorders. Therefore, copper homeostasis is tightly regulated by cells and tissues. Whereas copper and other transition metal ions are commonly thought of as static cofactors buried within protein active sites, emerging data points to the presence of additional loosely bound, labile pools that can participate in dynamic signalling pathways. Against this backdrop, we review advances in sensing labile copper pools and understanding their functions using synthetic fluorescent indicators. Following brief introductions to cellular copper homeostasis and considerations in sensor design, we survey available fluorescent copper probes and evaluate their properties in the context of their utility as effective biological screening tools. We emphasize the need for combined chemical and biological evaluation of these reagents, as well as the value of complementing probe data with other techniques for characterizing the different pools of metal ions in biological systems. This holistic approach will maximize the exciting opportunities for these and related chemical technologies in the study and discovery of novel biology of metals. PMID:25692243

Synthetic fluorescent probes for studying copper in biological systems.

PubMed

Cotruvo, Joseph A; Aron, Allegra T; Ramos-Torres, Karla M; Chang, Christopher J

2015-07-07

The potent redox activity of copper is required for sustaining life. Mismanagement of its cellular pools, however, can result in oxidative stress and damage connected to aging, neurodegenerative diseases, and metabolic disorders. Therefore, copper homeostasis is tightly regulated by cells and tissues. Whereas copper and other transition metal ions are commonly thought of as static cofactors buried within protein active sites, emerging data points to the presence of additional loosely bound, labile pools that can participate in dynamic signalling pathways. Against this backdrop, we review advances in sensing labile copper pools and understanding their functions using synthetic fluorescent indicators. Following brief introductions to cellular copper homeostasis and considerations in sensor design, we survey available fluorescent copper probes and evaluate their properties in the context of their utility as effective biological screening tools. We emphasize the need for combined chemical and biological evaluation of these reagents, as well as the value of complementing probe data with other techniques for characterizing the different pools of metal ions in biological systems. This holistic approach will maximize the exciting opportunities for these and related chemical technologies in the study and discovery of novel biology of metals.

Reactivity Study of Unsymmetrical β-Diketiminato Copper(I) Complexes: Effect of the Chelating Ring.

PubMed

Chuang, Wan-Jung; Hsu, Sung-Po; Chand, Kuldeep; Yu, Fu-Lun; Tsai, Cheng-Long; Tseng, Yu-Hsuan; Lu, Yuh-Hsiu; Kuo, Jen-Yu; Carey, James R; Chen, Hsuan-Ying; Chen, Hsing-Yin; Chiang, Michael Y; Hsu, Sodio C N

2017-03-06

β-Diketiminato copper(I) complexes play important roles in bioinspired catalytic chemistry and in applications to the materials industry. However, it has been observed that these complexes are very susceptible to disproportionation. Coordinating solvents or Lewis bases are typically used to prevent disproportionation and to block the coordination sites of the copper(I) center from further decomposition. Here, we incorporate this coordination protection directly into the molecule in order to increase the stability and reactivity of these complexes and to discover new copper(I) binding motifs. Here we describe the synthesis, structural characterization, and reactivity of a series of unsymmetrical N-aryl-N'-alkylpyridyl β-diketiminato copper(I) complexes and discuss the structures and reactivity of these complexes with respect to the length of the pyridyl arm. All of the aforementioned unsymmetrical ß-diketiminato copper(I) complexes bind CO reversibly and are stable to disproportionation. The binding ability of CO and the rate of pyridyl ligand decoordination of these copper(I) complexes are directly related to the competition between the degree of puckering of the chelate system and the steric demands of the N-aryl substituent.

Binuclear Cu A formation in biosynthetic models of Cu A in azurin proceeds via a novel Cu(Cys) 2His mononuclear copper intermediate

DOE PAGES

Chakraborty, Saumen; Polen, Michael J.; Chacon, Kelly N.; ...

2015-09-09

Cu A is a binuclear electron transfer (ET) center found in cytochrome c oxidases (C cOs), nitrous oxide reductases (N 2ORs), and nitric oxide reductase (NOR). In these proteins, the Cu A centers facilitate efficient ET ( k ET > 10 4 s –1) under low thermodynamic driving forces (10–90 mV). While the structure and functional properties of Cu A are well understood, a detailed mechanism of the incorporation of copper into the protein and the identity of the intermediates formed during the Cu A maturation process are still lacking. Previous studies of the Cu A assembly mechanism in vitromore » using a biosynthetic model Cu A center in azurin (Cu AAz) identified a novel intermediate X (I x) during reconstitution of the binuclear site. However, because of the instability of I x and the coexistence of other Cu centers, such as Cu A' and type 1 copper centers, the identity of this intermediate could not be established. In this paper, we report the mechanism of Cu A assembly using variants of Glu114XCu AAz (X = Gly, Ala, Leu, or Gln), the backbone carbonyl of which acts as a ligand to the Cu A site, with a major focus on characterization of the novel intermediate I x. We show that Cu A assembly in these variants proceeds through several types of Cu centers, such as mononuclear red type 2 Cu, the novel intermediate I x, and blue type 1 Cu. Our results show that the backbone flexibility of the Glu114 residue is an important factor in determining the rates of T2Cu → I x formation, suggesting that Cu A formation is facilitated by swinging of the ligand loop, which internalizes the T2Cu capture complex to the protein interior. The kinetic data further suggest that the nature of the Glu114 side chain influences the time scales on which these intermediates are formed, the wavelengths of the absorption peaks, and how cleanly one intermediate is converted to another. Through careful understanding of these mechanisms and optimization of the conditions, we have obtained I x in ~80–85% population in these variants, which allowed us to employ ultraviolet–visible, electron paramagnetic resonance, and extended X-ray absorption fine structure spectroscopic techniques to identify the I x as a mononuclear Cu(Cys) 2(His) complex. Finally, because some of the intermediates have been proposed to be involved in the assembly of native Cu A, these results shed light on the structural features of the important intermediates and mechanism of Cu A formation.« less

Effect of copper on the recombination activity of extended defects in silicon

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

Feklisova, O. V., E-mail: feklisov@iptm.ru; Yakimov, E. B.

2015-06-15

The effect of copper atoms introduced by high-temperature diffusion on the recombination properties of dislocations and dislocation trails in p-type single-crystal silicon is studied by the electron-beam-induced current technique. It is shown that, in contrast to dislocations, dislocation trails exhibit an increase in recombination activity after the introduction of copper. Bright contrast appearance in the vicinity of dislocation trails is detected after the diffusion of copper and quenching of the samples. The contrast depends on the defect density in these trails.

An Index to PGE-Ni-Cr Deposits and Occurrences in Selected Mineral-Occurrence Databases

USGS Publications Warehouse

Causey, J. Douglas; Galloway, John P.; Zientek, Michael L.

2009-01-01

Databases of mineral deposits and occurrences are essential to conducting assessments of undiscovered mineral resources. In the USGS's (U.S. Geological Survey) global assessment of undiscovered resources of copper, potash, and the platinum-group elements (PGE), only a few mineral deposit types will be evaluated. For example, only porphyry-copper and sediment-hosted copper deposits will be considered for the copper assessment. To support the global assessment, the USGS prepared comprehensive compilations of the occurrences of these two deposit types in order to develop grade and tonnage models and delineate permissive areas for undiscovered deposits of those types. This publication identifies previously published databases and database records that describe PGE, nickel, and chromium deposits and occurrences. Nickel and chromium were included in this overview because of the close association of PGE with nickel and chromium mineralization. Users of this database will need to refer to the original databases for detailed information about the deposits and occurrences. This information will be used to develop a current and comprehensive global database of PGE deposits and occurrences.

Macroscopic Streamer Growths in Acidic, Metal-Rich Mine Waters in North Wales Consist of Novel and Remarkably Simple Bacterial Communities

PubMed Central

Hallberg, Kevin B.; Coupland, Kris; Kimura, Sakurako; Johnson, D. Barrie

2006-01-01

The microbial composition of acid streamers (macroscopic biofilms) in acidic, metal-rich waters in two locations (an abandoned copper mine and a chalybeate spa) in north Wales was studied using cultivation-based and biomolecular techniques. Known chemolithotrophic and heterotrophic acidophiles were readily isolated from disrupted streamers, but they accounted for only <1 to 7% of the total microorganisms present. Fluorescent in situ hybridization (FISH) revealed that 80 to 90% of the microbes in both types of streamers were β-Proteobacteria. Terminal restriction fragment length polymorphism analysis of the streamers suggested that a single bacterial species was dominant in the copper mine streamers, while two distinct bacteria (one of which was identical to the bacterium found in the copper mine streamers) accounted for about 90% of the streamers in the spa water. 16S rRNA gene clone libraries showed that the β-proteobacterium found in both locations was closely related to a clone detected previously in acid mine drainage in California and that its closest characterized relatives were neutrophilic ammonium oxidizers. Using a modified isolation technique, this bacterium was isolated from the copper mine streamers and shown to be a novel acidophilic autotrophic iron oxidizer. The β-proteobacterium found only in the spa streamers was closely related to the neutrophilic iron oxidizer Gallionella ferruginea. FISH analysis using oligonucleotide probes that targeted the two β-proteobacteria confirmed that the biodiversity of the streamers in both locations was very limited. The microbial compositions of the acid streamers found at the two north Wales sites are very different from the microbial compositions of the previously described acid streamers found at Iron Mountain, California, and the Rio Tinto, Spain. PMID:16517651

Chemical Data for Rock, Sediment, Biological, Precipitate, and Water Samples from Abandoned Copper Mines in Prince William Sound, Alaska

USGS Publications Warehouse

Koski, Randolph A.; Munk, LeeAnn

2007-01-01

In the early 20th century, approximately 6 million metric tons of copper ore were mined from numerous deposits located along the shorelines of fjords and islands in Prince William Sound, Alaska. At the Beatson, Ellamar, and Threeman mine sites (fig. 1), rocks containing Fe, Cu, Zn, and Pb sulfide minerals are exposed to chemical weathering in abandoned mine workings and remnant waste piles that extend into the littoral zone. Field investigations in 2003 and 2005 as well as analytical data for rock, sediment, precipitate, water, and biological samples reveal that the oxidation of sulfides at these sites is resulting in the generation of acid mine drainage and the transport of metals into the marine environment (Koski and others, 2008; Stillings and others, 2008). At the Ellamar and Threeman sites, plumes of acidic and metal-enriched water are flowing through beach gravels into the shallow offshore environment. Interstitial water samples collected from beach sediment at Ellamar have low pH levels (to ~3) and high concentrations of metals including iron, copper, zinc, cobalt, lead, and mercury. The abundant precipitation of the iron sulfate mineral jarosite in the Ellamar gravels also signifies a low-pH environment. At the Beatson mine site (the largest copper mine in the region) seeps containing iron-rich microbial precipitates drain into the intertidal zone below mine dumps (Foster and others, 2008). A stream flowing down to the shoreline from underground mine workings at Beatson has near-neutral pH, but elevated levels of zinc, copper, and lead (Stillings and others, 2008). Offshore sediment samples at Beatson are enriched in these metals. Preliminary chemical data for tissue from marine mussels collected near the Ellamar, Threeman, and Beatson sites reveal elevated levels of copper, zinc, and lead compared to tissue in mussels from other locations in Prince William Sound (Koski and others, 2008). Three papers presenting results of this ongoing investigation of sulfide oxidation in Prince William Sound are in press. Koski and others (2008) provide an overview of rock alteration, surface water chemistry, and the distribution of metals at the Ellamar, Threeman, and Beatson mine sites. Based on a 60-day, stream-discharge experiment at Beatson in 2005, Stillings and others (2008) analyze changes in water chemistry during storm events and the flux of metals to the shoreline. Foster and others (2008) investigate the biomass and diversity of microbial communities present in surface waters (streams, seeps, pore waters) using fatty acid methyl ester (FAMES) data and principal component analysis. The publications cited above contain a subset of the total chemical data for rock, sediment, biological, precipitate, and water samples collected from the three mine sites in 2003 and 2005. The purpose of this report is the presentation of complete chemical data sets for all samples collected during the two field periods of fieldwork. Data for a small number of samples collected at two other mines (Schlosser and Fidalgo, fig. 1), visited in 2003, are also included in the tables.

Chemical Data for Rock, Sediment, Biological, Precipitate, and Water Samples from Abandoned Copper Mines in Prince William Sound, Alaska

USGS Publications Warehouse

Koski, Randolph A.; Munk, LeeAnn

2007-01-01

Introduction In the early 20th century, approximately 6 million metric tons of copper ore were mined from numerous deposits located along the shorelines of fjords and islands in Prince William Sound, Alaska. At the Beatson, Ellamar, and Threeman mine sites (fig. 1), rocks containing Fe, Cu, Zn, and Pb sulfide minerals are exposed to chemical weathering in abandoned mine workings and remnant waste piles that extend into the littoral zone. Field investigations in 2003 and 2005 as well as analytical data for rock, sediment, precipitate, water, and biological samples reveal that the oxidation of sulfides at these sites is resulting in the generation of acid mine drainage and the transport of metals into the marine environment (Koski and others, 2008; Stillings and others, 2008). At the Ellamar and Threeman sites, plumes of acidic and metal-enriched water are flowing through beach gravels into the shallow offshore environment. Interstitial water samples collected from beach sediment at Ellamar have low pH levels (to ~3) and high concentrations of metals including iron, copper, zinc, cobalt, lead, and mercury. The abundant precipitation of the iron sulfate mineral jarosite in the Ellamar gravels also signifies a low-pH environment. At the Beatson mine site (the largest copper mine in the region) seeps containing iron-rich microbial precipitates drain into the intertidal zone below mine dumps (Foster and others, 2008). A stream flowing down to the shoreline from underground mine workings at Beatson has near-neutral pH, but elevated levels of zinc, copper, and lead (Stillings and others, 2008). Offshore sediment samples at Beatson are enriched in these metals. Preliminary chemical data for tissue from marine mussels collected near the Ellamar, Threeman, and Beatson sites reveal elevated levels of copper, zinc, and lead compared to tissue in mussels from other locations in Prince William Sound (Koski and others, 2008). Three papers presenting results of this ongoing investigation of sulfide oxidation in Prince William Sound are in press. Koski and others (2008) provide an overview of rock alteration, surface water chemistry, and the distribution of metals at the Ellamar, Threeman, and Beatson mine sites. Based on a 60-day, stream-discharge experiment at Beatson in 2005, Stillings and others (2008) analyze changes in water chemistry during storm events and the flux of metals to the shoreline. Foster and others (2008) investigate the biomass and diversity of microbial communities present in surface waters (streams, seeps, pore waters) using fatty acid methyl ester (FAMES) data and principal component analysis. The publications cited above contain a subset of the total chemical data for rock, sediment, biological, precipitate, and water samples collected from the three mine sites in 2003 and 2005. The purpose of this report is the presentation of complete chemical data sets for all samples collected during the two field periods of fieldwork. Data for a small number of samples collected at two other mines (Schlosser and Fidalgo, fig. 1), visited in 2003, are also included in the tables.

Assessment of the Bioaccessibility of Micronized Copper Wood on Simulated Stomach Fluid

EPA Pesticide Factsheets

The widespread use of copper-treated lumber has increased the potential for human exposure. Moreover, there is a lack of information on the fate and behavior of copper-treated wood particles following oral ingestion. In this study, the in vitro bioaccessibility of copper from copper-treated wood dust in simulated stomach fluid and DI water was determined. Three copper-treated wood products, liquid alkali copper quaternary and two micronized copper quarternary from different manufacturers, were incubated in the extraction media then fractionated by centrifugation and filtration through 0.45 ?m and 10 kDa filters. The copper concentrations from isolated fractions were measured using Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES). Total amounts of copper from each wood product were also determined using microwave-assisted acid digestion of dried wood samples and quantification using ICP-OES. The percent in vitro bioaccessible copper was between 83 and 90 % for all treated wood types. However, the percent of copper released in DI water was between 14 and 25 % for all wood products. This data suggests that copper is highly bioaccessible at low pH and may pose a potential human exposure risk upon ingestion. This dataset is associated with the following publication:Santiago-Rodrigues, L., J.L. Griggs, K. Bradham , C. Nelson , T. Luxton , W. Platten , and K. Rogers. Assessment of the bioaccessibility of micronized copper wood in synthetic stomach flu

Effects of acidic recharge on groundwater at the St. Kevin Gulch site, Leadville, Colorado

USGS Publications Warehouse

Paschke, S.S.; Harrison, W.J.; Walton-Day, K.

2001-01-01

The acid rock drainage-affected stream of St. Kevin Gulch recharges the Quaternary sand and gravel aquifer of Tennessee Park, near Leadville, Colorado, lowering pH and contributing iron, cadmium, copper, zinc and sulphate to the ground-water system. Dissolved metal mobility is controlled by the seasonal spring runoff as well as oxidation/reduction (redox) reactions in the aquifer. Oxidizing conditions occur in the unconfined portions of the aquifer whilst sulphate-reducing conditions are found down gradient where semi-confined groundwater flow occurs beneath a natural wetland. Iron-reducing conditions occur in the transition from unconfined to semi-confined groundwater flow. Dissolved iron concentrations are low to not detectable in the alluvial fan recharge zone and increase in a down gradient direction. The effects of low-pH, metal-rich recharge are pronounced during low-flow in the fall when there is a defined area of low pH groundwater with elevated concentrations of dissolved zinc, cadmium, copper and sulphate adjacent to St. Kevin Gulch. Dissolved metal and sulphate concentrations in the recharge zone are diluted during spring runoff, although the maximum concentrations of dissolved zinc, cadmium, copper and sulphate occur at selected down gradient locations during high flow. Dissolved zinc, cadmium and copper concentrations are low to not detectable, whereas dissolved iron concentrations are greatest, in groundwater samples from the sulphate-reducing zone. Attenuation of zinc, cadmium and copper beneath the wetland suggests sulphide mineral precipitation is occurring in the semi-confined aquifer, in agreement with previous site investigations and saturation index calculations. Adsorption of dissolved zinc, cadmium and copper onto iron hydroxides is a minor attenuation process due to the low pH of the groundwater system.

Highly efficient aerobic oxidation of alcohols by using less-hindered nitroxyl-radical/copper catalysis: optimum catalyst combinations and their substrate scope.

PubMed

Sasano, Yusuke; Kogure, Naoki; Nishiyama, Tomohiro; Nagasawa, Shota; Iwabuchi, Yoshiharu

2015-04-01

The oxidation of alcohols into their corresponding carbonyl compounds is one of the most fundamental transformations in organic chemistry. In our recent report, 2-azaadamantane N-oxyl (AZADO)/copper catalysis promoted the highly chemoselective aerobic oxidation of unprotected amino alcohols into amino carbonyl compounds. Herein, we investigated the extension of the promising AZADO/copper-catalyzed aerobic oxidation of alcohols to other types of alcohol. During close optimization of the reaction conditions by using various alcohols, we found that the optimum combination of nitroxyl radical, copper salt, and solution concentration was dependent on the type of substrate. Various alcohols, including highly hindered and heteroatom-rich ones, were efficiently oxidized into their corresponding carbonyl compounds under mild conditions with lower amounts of the catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural effects of Cu(II)-coordination in the octapeptide region of the human prion protein.

PubMed

Riihimäki, Eva-Stina; Martínez, José Manuel; Kloo, Lars

2008-05-14

The copper-binding ability of the prion protein is thought to be central to its function. The structural effects of copper coordination in the octapeptide region of the human prion protein have been investigated by molecular dynamics simulations. Simulations were performed with the apo state, in order to investigate the behavior of the region without copper ions, as well as with the octapeptide region in the presence of copper ions. While the structure of the apo state is greatly influenced by the interaction between the rings in the histidine, tryptophan and proline residues, the region shows evidence of highly ordered coordination sites in the presence of copper ions. The position of the tryptophan indole ring is stabilized by cation-pi interactions. Two stable orientations of the indole ring with respect to the equatorial coordination plane of copper were observed, which showed that the indole ring can reside on both sides of the coordination plane. The interaction with the indole ring was found to occur without a mediating axial water molecule.

Quick Access Rocket Exhaust Rig Testing of Coated GRCop-84 Sheets Used to Aid Coating Selection for Reusable Launch Vehicles

NASA Technical Reports Server (NTRS)

Raj, Sai V.; Robinson, Raymond C.; Ghosn, Louis J.

2005-01-01

The design of the next generation of reusable launch vehicles calls for using GRCop-84 copper alloy liners based on a composition1 invented at the NASA Glenn Research Center: Cu-8(at.%)Cr-4%Nb. Many of the properties of this alloy have been shown to be far superior to those of other conventional copper alloys, such as NARloy-Z. Despite this considerable advantage, it is expected that GRCop-84 will suffer from some type of environmental degradation depending on the type of rocket fuel utilized. In a liquid hydrogen (LH2), liquid oxygen (LO2) booster engine, copper alloys undergo repeated cycles of oxidation of the copper matrix and subsequent reduction of the copper oxide, a process termed "blanching". Blanching results in increased surface roughness and poor heat-transfer capabilities, local hot spots, decreased engine performance, and premature failure of the liner material. This environmental degradation coupled with the effects of thermomechanical stresses, creep, and high thermal gradients can distort the cooling channel severely, ultimately leading to its failure.

Fate and forms of Cu in a reservoir ecosystem following copper sulfate treatment (Saint Germain les Belles, France)

NASA Astrophysics Data System (ADS)

van Hullebusch, E.; Chatenet, P.; Deluchat, V.; Chazal, P. M.; Froissard, D.; Lens, P. N. L.; Baudu, M.

2003-05-01

Copper sulfate (CuSO4) addition to freshwater for phytoplankton control has been practiced for decades, and remains the most effective algicidal treatment for numerous managed water bodies. A reservoir in the centre of France was the site for an investigation of copper distribution in aquatic systems after a copper sulfate treatment Results of copper monitoring showed a rapid conversion of dissolved Cu to particulate forms, with significant accumulation in the sediments/83% of total copper added). Total sediment Cu content increasedfrom approximately 37.7 to 45.4 μg.g^{-1} dry weight after the first treatment. Sequential extraction suggested that a significanl portion of the sediment-borne Cu was associated with the organic fraction which may release Cu to the water column, although significant release would occur only under extreme changes in water chemistry. Based upon measured Cu concentrations, flows at the down-stream water, and known mass applied during treatment, mass balance calculations indicated that approximately 17% of the Cu was exported from the reservoir over a 70 day period following a 196 μg.L^{-l} Cu^{2+} (as CuSO4, 5 H2O) treatment. The largest amount of copper was probably adsorbed on downstream sediment or lost in running water, Copper bioaccumulation by a moss, Fontinalis antipyretica, in the down-stream water showed that it was possible to distinguish between a treated and an untreated area. The impact of copper treatment in the down-stream reservoir could be followed using mosses. The bioaccumulation data further showed that there is a distance effect which could be exploited to determine potential copper impact on receiving water bodies. Thirty days after copper sulfate addition, Fontinalis still indicated copper exposure.

Impact of the rainfall pattern on synthetic pesticides and copper runoff from a vineyard catchment

NASA Astrophysics Data System (ADS)

Payraudeau, Sylvain; Meite, Fatima; Wiegert, Charline; Imfeld, Gwenaël

2017-04-01

Runoff is a major process of pesticide transport from agricultural land to downstream aquatic ecosystems. The impact of rainfall characteristics on the transport of runoff-related pesticide is rarely evaluated at the catchment scale. Here, we evaluate the influence of rainfall pattern on the mobilization of synthetic pesticides and copper fungicides in runoff from a small vineyard catchment, both at the plot and catchment scales. During two vineyard growing seasons in 2015 and 2016 (from March to October), we monitored rainfall, runoff, and concentrations of copper and 20 fungicides and herbicides applied by winegrowers at the Rouffach vineyard catchment (France, Alsace; 42.5 ha). Rainfall data were recorded within the catchment while runoff measurement and flow-proportional water sampling were carried out at the outlet of the plot (1486 m2; 87.5 × 17 m) and the catchment. In total, discharges of the 14 runoff events were continuously monitored between March and October 2015 using bubbler flow modules combined with Venturi channels. Detailed and distributed dataset on pesticide applications were extracted from survey (copper formulations and type of pesticides, amount and application dates). Pools of copper and synthetic pesticides were quantified weekly in the topsoil (0-3 cm) by systematic sampling across the catchment. The concentrations of copper (10 mg.kg-1 dried soil) and synthetic pesticides (close to the quantification limit, i.e. 0.05 µg.L-1) available in the top soil for off-site transport largely differed over time. Between March and October, an accumulation of copper of 10% was observed in the top-soil while pesticide concentration decreased below the quantification limits after a few days or weeks following application, depending of the compounds. The average runoff generated at the plot scale was very low (0.13% ± 0.30). The maximum runoff reached 1.37% during the storm of July 22, 2015. Synthetic pesticides exported by runoff was less than 1‰ of the applications. The copper mass exported represented about 1% (i.e. 2,085 g at the plot's scale) of the seasonal input, and mainly occurred during the major storm event. Copper were mainly exported in association with suspended particulate matter (SPM) (>80% of the total load). The partitioning between dissolved and SPM phases differs for the synthetic pesticides as expected by their properties. The rainfall pattern influences concentrations and loads of copper and the pesticides. Dissolved pesticide loads normalized by the pesticide mass in soil varied with larger rainfall intensities, runoff discharges and volumes. Contrasted relationships between rainfall characteristics (i.e. intensity, duration and total amount) and the load exported suggest that mechanisms of contaminant delivery from the vineyard soil differs among the pesticides and for copper. The results support the idea that, even in small catchment areas, the rainfall pattern (i.e. rainfall intensity and duration) partly controls the transport of pesticide and copper loads in runoff. Though other factors, such as the chemical characteristics and the amount and timing of applications, are important drivers for pesticide runoff, the rainfall patterns also determine the transport of pesticides from catchment to downstream aquatic ecosystems, and thus the ecotoxicological risk.

Source identification of uranium-containing materials at mine legacy sites in Portugal.

PubMed

Keatley, A C; Martin, P G; Hallam, K R; Payton, O D; Awbery, R; Carvalho, F P; Oliveira, J M; Silva, L; Malta, M; Scott, T B

2018-03-01

Whilst prior nuclear forensic studies have focused on identifying signatures to distinguish between different uranium deposit types, this paper focuses on providing a scientific basis for source identification of materials from different uranium mine sites within a single region, which can then be potentially used within nuclear forensics. A number of different tools, including gamma spectrometry, alpha spectrometry, mineralogy and major and minor elemental analysis, have been utilised to determine the provenance of uranium mineral samples collected at eight mine sites, located within three different uranium provinces, in Portugal. A radiation survey was initially conducted by foot and/or unmanned aerial vehicle at each site to assist sample collection. The results from each mine site were then compared to determine if individual mine sites could be distinguished based on characteristic elemental and isotopic signatures. Gamma and alpha spectrometry were used to differentiate between samples from different sites and also give an indication of past milling and mining activities. Ore samples from the different mine sites were found to be very similar in terms of gangue and uranium mineralogy. However, rarer minerals or specific impurity elements, such as calcium and copper, did permit some separation of the sites examined. In addition, classification rates using linear discriminant analysis were comparable to those in the literature. Crown Copyright © 2018. Published by Elsevier Ltd. All rights reserved.

Characterization and growth analysis of two types of thin films formed on copper surfaces: An inorganic chromium containing film and an organic film formed via reduction of diazonium ions

NASA Astrophysics Data System (ADS)

Hurley, Belinda Louise

Surface enhanced Raman scattering was used to observe interactions of dilute CrVI solutions with silver and copper surfaces in situ. Using silver as a model surface, CrIII was observed at the near monolayer level, and the spectra were compared to those from CrIII oxyhydroxide species and CrIII/Cr VI mixed oxide. Similar experiments were conducted with copper surfaces and 785 nm excitation. Upon exposure of a copper surface to CrVI solution, the characteristic copper oxide Raman bands disappeared, and a Cr III band increased in intensity over a period of ˜20 hours. The intensity of the CrIII band on copper became self limiting after the formation of several CrIII monolayers, as supported by chronoamperometry experiments. This CrIII spectrum was stable after CrVI was removed from the solution provided the potential remained negative of -200 mV vs. Ag/AgCl. The results support the conclusion that CrVI is reductively adsorbed to copper at the near neutral pH and open circuit potentials expected for Cu/Al alloys in field applications. The CrIII film is stable and strongly inhibits oxygen reduction at the treated copper surface. Copper surfaces and polished Aluminum Alloy 2024 T3 substrates were derivatized at open circuit potential with arenediazonium salts in both aprotic and aqueous media. Raman spectroscopy confirmed the presence of a derivatized film on the substrates before and after exposure to boiling water and sonication in acetone. Preliminary experiments to test these films for corrosion inhibition proved unsuccessful. Aluminum and copper substrates were prepared and used for x-ray photoelectron spectroscopy (XPS) analysis of the derivatization results. In the copper experiments, one surface was native oxide copper, predominantly in the form of Cu2O, and one surface was predominantly Cu 0. Results of the XPS analysis indicate the presence of a Cu-O-C linkage and possibly a Cu-C covalent bond between the aryl ring and the copper substrate. XPS results also indicate the formation of multilayers on both types of copper surfaces with different percentages of azo coupling within the multilayers on the two surfaces. These easily prepared, covalently bonded organic films could be used for applications currently fulfilled with self-absorbed monolayers and Langmuir Blodgett films.

Evaluation of four rapid methods for hemoglobin screening of whole blood donors in mobile collection settings.

PubMed

Gómez-Simón, Antonia; Navarro-Núñez, Leyre; Pérez-Ceballos, Elena; Lozano, María L; Candela, María J; Cascales, Almudena; Martínez, Constantino; Corral, Javier; Vicente, Vicente; Rivera, José

2007-06-01

Predonation hemoglobin measurement is a problematic requirement in mobile donation settings, where accurate determination of venous hemoglobin by hematology analyzers is not available. We have evaluated hemoglobin screening in prospective donors by the semiquantitative copper sulphate test and by capillary blood samples analyzed by three portable photometers, HemoCue, STAT-Site MHgb, and the CompoLab HB system. Capillary blood samples were obtained from 380 donors and tested by the copper sulphate test and by at least one of the named portable photometers. Predonation venous hemoglobin was also determined in all donors using a Coulter Max-M analyzer. The three photometers provided acceptable reproducibility (CV below 5%), and displayed a significant correlation between the capillary blood samples and the venous hemoglobin (R2 0.5-0.8). HemoCue showed the best agreement with venous hemoglobin determination, followed by STAT-Site MHgb, and the CompoLab HB system. The copper sulphate test provided the highest rate of donors acceptance (83%) despite unacceptable hemoglobin levels, and the lowest rate for donor deferral (1%) despite acceptable hemoglobin levels. The percentage of donors correctly categorized for blood donation by the portable hemoglobinometers was 85%, 82%, and 76% for CompoLab HB system, HemoCue and STAT-Site, respectively. Our data suggest that hemoglobin determination remains a conflictive issue in donor selection in the mobile setting. Without appropriate performance control, capillary hemoglobin screening by either the copper sulphate method or by the novel portable hemoglobinometers could be inaccurate, thus potentially affecting both donor safety and the blood supply.

Combined Mini-Cylex & Disk Acceleration Tests in Type K Copper

DOE PAGES

Maines, Warren Russell; Kittell, David E.; Hobbs, Michael L.

2018-04-16

In this work, we combined the miniature cylinder expansion test (Mini-Cylex), with the Disk Acceleration Test (DAX) using Type K copper, Picatinny Liquid Explosive, and photonic Doppler velocimetry. We estimated the CJ state using plate reverberation methods at the test cap. We extracted velocities at 2, 7, and 10 volume expansions to fit Jones-Wilkins-Lee Equation of State and estimated Gurney velocity at the tube wall. The test also provides an additional method to estimate reaction products Hugoniot through knowledge of the copper test cap. Our experiments and simulations are within expected uncertainty. Lastly, the test and the analysis effectively reducemore » costs while keeping or increasing fidelity.« less

Combined Mini-Cylex & Disk Acceleration Tests in Type K Copper

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

Maines, Warren Russell; Kittell, David E.; Hobbs, Michael L.

In this work, we combined the miniature cylinder expansion test (Mini-Cylex), with the Disk Acceleration Test (DAX) using Type K copper, Picatinny Liquid Explosive, and photonic Doppler velocimetry. We estimated the CJ state using plate reverberation methods at the test cap. We extracted velocities at 2, 7, and 10 volume expansions to fit Jones-Wilkins-Lee Equation of State and estimated Gurney velocity at the tube wall. The test also provides an additional method to estimate reaction products Hugoniot through knowledge of the copper test cap. Our experiments and simulations are within expected uncertainty. Lastly, the test and the analysis effectively reducemore » costs while keeping or increasing fidelity.« less

Electronic structure of the organic semiconductor copper phthalocyanine: experiment and theory.

PubMed

Aristov, V Yu; Molodtsova, O V; Maslyuk, V V; Vyalikh, D V; Zhilin, V M; Ossipyan, Yu A; Bredow, T; Mertig, I; Knupfer, M

2008-01-21

The electronic structure of the organic semiconductor copper-phthalocyanine (CuPc) has been determined by a combination of conventional and resonant photoemission, near-edge x-ray absorption, as well as by the first-principles calculations. The experimentally obtained electronic valence band structure of CuPc is in very good agreement with the calculated density of states results, allowing the derivation of detailed site specific information.

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.

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

Streltsov, Victor A.; Titmuss, Stephen J.; Epa, V. Chandana

Neurodegeneration observed in Alzheimer disease (AD) is believed to be related to the toxicity from reactive oxygen species (ROS) produced in the brain by the amyloid-{beta} (A{beta}) protein bound primarily to copper ions. The evidence for an oxidative stress role of A{beta}-Cu redox chemistry is still incomplete. Details of the copper binding site in A{beta} may be critical to the etiology of AD. Here we present the structure determined by combining x-ray absorption spectroscopy (XAS) and density functional theory analysis of A{beta} peptides complexed with Cu{sup 2+} in solution under a range of buffer conditions. Phosphate-buffered saline buffer salt (NaCl)more » concentration does not affect the high-affinity copper binding mode but alters the second coordination sphere. The XAS spectra for truncated and full-length A{beta}-Cu{sup 2+} peptides are similar. The novel distorted six-coordinated (3N3O) geometry around copper in the A{beta}-Cu{sup 2+} complexes include three histidines: glutamic, or/and aspartic acid, and axial water. The structure of the high-affinity Cu{sup 2+} binding site is consistent with the hypothesis that the redox activity of the metal ion bound to A{beta} can lead to the formation of dityrosine-linked dimers found in AD.« less

Short-term dietary copper deficiency does not inhibit angiogenesis in tumours implanted in striated muscle.

PubMed Central

Schuschke, D. A.; Reed, M. W.; Saari, J. T.; Olson, M. D.; Ackermann, D. M.; Miller, F. N.

1992-01-01

The effect of dietary copper deficiency on tumour growth, neovascularisation and microvascular integrity was studied in the rat cremaster muscle. Male, weanling Sprague-Dawley rats were fed purified diets which were copper deficient (< 0.5 micrograms g-1 of diet) or copper adequate (5 micrograms g-1 of diet). Seven days after initiation of diets, a chondrosarcoma was implanted in the cremaster muscle of each rat. Five, 10 or 20 days after tumour implantation, rats were anesthetised and their cremasters prepared for observation by intravital microscopy. Intraarterial injection of fluorescein isothiocyanate-conjugated albumin and subsequent observation of fluorescence in the perivascular space indicated no difference in microvascular albumin leakage between the tumour vasculature of copper deficient and copper adequate rats. Neither tumour growth (assessed by wet weight), vascular density (assessed by light microscopy), nor any ultrastructural characteristics of the tumour or its vasculature (assessed by electron microscopy) were affected by copper deficiency. In view of findings by others which indicate changes in tumour characteristics with copper deficiency, we conclude that the copper dependency of tumour growth and vascularisation is a function of the type of tumour, the host tissue, or the conditions of copper depletion. PMID:1280989

Substitution of Li for Cu in Cu2ZnSnS4: Toward Wide Band Gap Absorbers with Low Cation Disorder for Thin Film Solar Cells.

PubMed

Lafond, A; Guillot-Deudon, C; Vidal, J; Paris, M; La, C; Jobic, S

2017-03-06

The substitution of lithium for copper in Cu 2 ZnSnS 4 (CZTS) has been experimentally and theoretically investigated. Formally, the (Cu 1-x Li x )ZnSnS 4 system exhibits two well-defined solid solutions. Indeed, single crystal structural analyses demonstrate that the low (x < 0.4) and high (x > 0.6) lithium-content compounds adopt the kesterite structure and the wurtz-kesterite structure, respectively. For x between 0.4 and 0.6, the two aforementioned structure types coexist. Moreover, 119 Sn NMR analyses carried out on a (Cu 0.7 Li 0.3 ) 2 ZnSnS 4 sample clearly indicate that lithium replaces copper preferentially on two of the three available 2-fold crystallographic sites commonly occupied by Cu and Zn in disordered kesterite. Furthermore, the observed individual lines in the NMR spectrum suggest that the propensity of Cu and Zn atoms to be randomly distributed over the 2c and 2d crystallographic sites is lowered when lithium is partially substituted for copper. Additionally, the first-principles calculations provide insights into the arrangement of Li atoms as a function of the Cu/Zn disorder and its effect on the structural (lattice parameters) and optical properties of CZTS (band gap evolution). Those calculations agree with the experimental observations and account for the evolutions of the unit cell parameters as well as for the increase of band gap when the Li-content increases. The calculation of the formation enthalpy of point defect unambiguously indicates that Li modifies the Cu/Zn disorder in a manner similar to the change of Cu/Zn disorder induced by Ag alloying. Overall, it was found that Li alloying is a versatile way of tuning the optoelectronic properties of CZTS making it a good candidate as wide band gap materials for the top cells of tandem solar cells.

Cobalt—Styles of deposits and the search for primary deposits

USGS Publications Warehouse

Hitzman, Murray W.; Bookstrom, Arthur A.; Slack, John F.; Zientek, Michael L.

2017-11-30

Cobalt (Co) is a potentially critical mineral. The vast majority of cobalt is a byproduct of copper and (or) nickel production. Cobalt is increasingly used in magnets and rechargeable batteries. More than 50 percent of primary cobalt production is from the Central African Copperbelt. The Central African Copperbelt is the only sedimentary rock-hosted stratiform copper district that contains significant cobalt. Its presence may indicate significant mafic-ultramafic rocks in the local basement. The balance of primary cobalt production is from magmatic nickel-copper and nickel laterite deposits. Cobalt is present in several carbonate-hosted lead-zinc and copper districts. It is also variably present in Besshi-type volcanogenic massive sulfide and siliciclastic sedimentary rock-hosted deposits in back arc and rift environments associated with mafic-ultramafic rocks. Metasedimentary cobalt-copper-gold deposits (such as Blackbird, Idaho), iron oxide-copper-gold deposits, and the five-element vein deposits (such as Cobalt, Ontario) contain different amounts of cobalt. None of these deposit types show direct links to mafic-ultramafic rocks; the deposits may result from crustal-scale hydrothermal systems capable of leaching and transporting cobalt from great depths. Hydrothermal deposits associated with ultramafic rocks, typified by the Bou Azzer district of Morocco, represent another type of primary cobalt deposit.In the United States, exploration for cobalt deposits may focus on magmatic nickel-copper deposits in the Archean and Proterozoic rocks of the Midwest and the east coast (Pennsylvania) and younger mafic rocks in southeastern and southern Alaska; also, possibly basement rocks in southeastern Missouri. Other potential exploration targets include—The Belt-Purcell basin of British Columbia (Canada), Idaho, Montana, and Washington for different styles of sedimentary rock-hosted cobalt deposits;Besshi-type VMS deposits, such as the Greens Creek (Alaska) deposit and the Ducktown (Tennessee) waste and tailings; andKnown five-element vein districts in Arizona and New Mexico, as well as in the Yukon-Tanana terrane of Alaska; and hydrothermal deposits associated with ultramafic rocks along the west coast, in Alaska, and in the Appalachian Mountains.

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).

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

Highly porous non-precious bimetallic electrocatalysts for efficient hydrogen evolution

DOE PAGES

Lu, Qi; Hutchings, Gregory S.; Yu, Weiting; ...

2015-03-16

One of the key components of carbon dioxide-free hydrogen production is a robust and efficient non-precious metal catalyst for the hydrogen evolution reaction. We report that a hierarchical nanoporous copper-titanium bimetallic electrocatalyst is able to produce hydrogen from water under a mild overpotential at more than twice the rate of state-of-the- art carbon-supported platinum catalyst. Although both copper and titanium are known to be poor hydrogen evolution catalysts, the combination of these two elements creates unique copper-copper-titanium hollow sites, which have a hydrogen-binding energy very similar to that of platinum, resulting in an exceptional hydrogen evolution activity. Moreover, the hierarchicalmore » porosity of the nanoporous-copper titanium catalyst also contributes to its high hydrogen evolution activity, because it provides a large-surface area for electrocatalytic hydrogen evolution, and improves the mass transport properties. Moreover, the catalyst is self-supported, eliminating the overpotential associated with the catalyst/support interface.« less

Evidence for the role of copper in the injury process of coliform bacteria in drinking water. [Escherichia coli

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

Domek, M.J.; LeChevallier, M.W.; Cameron, S.C.

1984-08-01

Low levels of copper in chlorine-free distribution water caused injury of coliform populations. Monitoring of 44 drinking water samples indicated that 64% of the coliform population was injured. Physical and chemical parameters were measured, including three heavy metals (Cu, Cd, and Pb). Copper concentrations were important, ranging from 0.007 to 0.54 mg/liter. Statistical analyses of these factors were used to develop a model to predict coliform injury. The model predicted almost 90% injury with a copper concentration near the mean observed value (0.158 mg/liter) in distribution waters. Laboratory studies with copper concentrations of 0.025 and 0.050 mg/liter in an inorganicmore » carbon buffer under controlled conditions of temperature and pH caused over 90% injury within 6 and 2 days, respectively. Studies of the metabolism of injured Escherichia coli cells indicated that the respiratory chain is at least one site of damage in injured cells.« less

Genomic and Transcriptomic Analyses to Identify Pathways Involved in Nanoparticle Generation in the Ubiquitous Marine Bacterium Alteromonas macleodii Under Elevated Copper Conditions

NASA Astrophysics Data System (ADS)

Cusick, K. D.; Dale, J.; Little, B.; Cockrell, A.; Biffinger, J.

2016-02-01

Alteromonas macleodii is a ubiquitous marine bacterium that clusters by molecular analyses into two ecotypes: surface and deep-water. Our group isolated a marine bacterium from copper coupons that generates nanoparticles (NPs) at elevated copper concentrations. Sequencing of the 16S rRNA gene identified it as an A. macleodii strain. In phylogenetic analyses based on the gyrB gene, it clustered with other surface isolates; however, it formed a unique cluster separate from that of other surface isolates based on rpoB gene sequences. Copper is commonly employed as an antifouling agent on the hulls of ships, and so copper tolerance and NP generation is under investigation in this strain. The overall goals of this study were: (1) to determine if copper tolerance is the result of changes at the genetic or transcriptional level and (2) to identify the genes involved in NP formation. Sub-cultures were established from the initial isolate in which copper concentrations were increased in .25 mM increments through multiple generations. These sub-cultures were assayed for NP formation in seawater medium supplemented with 3-4 mM copper. Scanning electron microscopy revealed large aggregates of NPs on the exterior surface of all sub-cultures. Additionally, a portion of the cells in all sub-cultures displayed an elongated morphology in comparison to the wild-type. No NPs were observed in wild-type controls grown without the addition of increased copper. Metagenomic sequencing of natural populations of A. macleodii revealed extreme divergence in several large genomic regions whose content includes genes coding for exopolysaccharide production and metal resistance. High-throughput sequencing is being used to determine whether copper tolerance and NP generation is the result of genetic or transcriptional changes. These results will be extended to natural communities to gain insights into the role of bacterial NPs during conditions of elevated metal concentrations in coastal systems.

Metals transport in the Sacramento River, California, 1996-1997; Volume 1, Methods and data

USGS Publications Warehouse

Alpers, Charles N.; Taylor, Howard E.; Domagalski, Joseph L.

2000-01-01

Metals transport in the Sacramento River, northern California, was evaluated on the basis of samples of water, suspended colloids, streambed sediment, and caddisfly larvae that were collected on one to six occasions at 19 sites in the Sacramento River Basin from July 1996 to June 1997. Four of the sampling periods (July, September, and November 1996; and May-June 1997) took place during relatively low-flow conditions and two sampling periods (December 1996 and January 1997) took place during high-flow and flooding conditions; respectively. Tangential-flow ultrafiltration with 10,000 nominal molecular weight limit, or daltons (0.005 micrometer equivalent), pore-size membranes was used to separate metals in streamwater into ultrafiltrate (operationally defined dissolved fraction) and retentate (colloidal fraction) components, respectively. Conventional filtration with capsule filters (0.45 micrometer pore-size) and membrane filters (0.40 micrometer pore-size) and total-recoverable analysis of unfiltered (whole-body) samples were done for comparison at all sites. Because the total-recoverable analysis involves an incomplete digestion of particulate matter, a more reliable measurement of whole-water concentrations is derived from the sum of the dissolved component that is based on the ultrafiltrate plus the suspended component that is based on a total digestion of colloid concentrates from the ultra-filtration retentate. Metals in caddisfly larvae were determined for whole-body samples and cytosol extracts, which are intercellular solutions that provide a more sensitive indication of the metals that have been bioaccumulated. Trace metals in acidic, metal-rich drainage from abandoned and inactive sulfide mines were observed to enter the Sacramento River system (specifically, into both Shasta Lake and Keswick Reservoir) in predominantly dissolved form, as operationally defined using ultrafiltrates. The predominant source of acid mine drainage to Keswick Reservoir is Spring Creek, which drains the Iron Mountain mine area. Copper concentrations in filtered samples from Spring Creek taken during December 1996, January 1997, and May 1997 ranged from 420 to 560 micrograms per liter. Below Keswick Dam, copper concentrations in conventionally filtered samples ranged from 0.5 micrograms per liter during September 1996 to 9.4 micrograms per liter during January 1997; the latter concentration exceeded the applicable water-quality standard. The proportion of trace metals that was dissolved (versus colloidal) in samples collected at Shasta and Keswick dams decreased in the order cadmium zinc > copper > aluminum iron lead mercury. At four sampling sites on the Sacramento River at various distances downstream of Keswick Dam (Bend Bridge, 71 kilometers; Colusa, 256 kilometers; Verona, 360 kilometers; and Freeport, 412 kilometers) concentrations of these seven metals were predominantly colloidal during both high- and low-flow conditions. Because copper compounds are used extensively as algaecides in rice farming, agricultural drainage at the Colusa Basin Drain was sampled in June 1997 during a period shortly after copper applications to newly planted rice fields. Copper concentrations ranged from 1.3 to 3.0 micrograms per liter in filtered samples and from 12 to 13 micrograms per liter in whole-water samples (total recoverable analysis). These results are consistent with earlier work by the U.S. Geological Survey indicating that copper in rice-field drainage likely represents a detectable, but relatively minor source of copper to the Sacramento River. Lead isotope data from suspended colloids and streambed sediments collected during October and November 1996 indicate that lead from acid mine drainage sources became a relatively minor component of the total lead at the site located 71 kilometers downstream of Keswick Dam and beyond. Cadmium, copper, and zinc concentrations in caddisfly larvae were elevated at several sites downstream of Keswick Dam,

Effect of copper chloride on the emissions of PCDD/Fs and PAHs from PVC combustion.

PubMed

Wang, Dongli; Xu, Xiaobai; Zheng, Minghui; Chiu, Chung H

2002-09-01

The influences of temperature, air flow and the amount of copper chloride upon the types and amount of the toxic emissions such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) during combustion of polyvinyl chloride (PVC) were investigated. The mechanism concerning the effect of temperature and copper chloride on the PCDD/Fs and PAHs formation was discussed. The results shown that without copper chloride, trace amounts of PCDD/Fs and large amounts of PAHs were found in the emissions from the pure PVC combustion under various combustion conditions. The addition of copper chloride enhanced PCDD/Fs formation, but it seems that the formation of PAHs decreased with increasing amount of copper chloride, and greater total amount of PAHs were produced at the higher temperature under our experimental conditions.

Bioleaching of two different types of chalcopyrite by Acidithiobacillus ferrooxidans

NASA Astrophysics Data System (ADS)

Dong, Ying-bo; Lin, Hai; Fu, Kai-bin; Xu, Xiao-fang; Zhou, Shan-shan

2013-02-01

Two different types of chalcopyrite (pyritic chalcopyrite and porphyry chalcopyrite) were bioleached with Acidithiobacillus ferrooxidans ATF6. The bioleaching of the pyritic chalcopyrite and porphyry chalcopyrite is quite different. The copper extraction reaches 46.96% for the pyritic chalcopyrite after 48-d leaching, but it is only 14.50% for the porphyry chalcopyrite. Proper amounts of initial ferrous ions can improve the efficiency of copper extraction for the two different types of chalcopyrite. The optimum dosage of ferrous ions for the pyritic chalcopyrite and porphyry chalcopyrite is different. The adsorption of ATF6 on the pyritic chalcopyrite and porphyry chalcopyrite was also studied in this paper. It is found that ATF6 is selectively adsorbed by the two different types of chalcopyrite; the higher adsorption onto the pyritic chalcopyrite than the porphyry chalcopyrite leads to the higher copper dissolution rate of the pyritic chalcopyrite. In addition, the zeta-potential of chalcopyrite before and after bioleaching further confirms that ATF6 is more easily adsorbed onto the pyritic chalcopyrite.

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

Fusaric acid induces a notochord malformation in zebrafish via copper chelation.

PubMed

Yin, Emily S; Rakhmankulova, Malika; Kucera, Kaury; de Sena Filho, Jose Guedes; Portero, Carolina E; Narváez-Trujillo, Alexandra; Holley, Scott A; Strobel, Scott A

2015-08-01

Over a thousand extracts were tested for phenotypic effects in developing zebrafish embryos to identify bioactive molecules produced by endophytic fungi. One extract isolated from Fusarium sp., a widely distributed fungal genus found in soil and often associated with plants, induced an undulated notochord in developing zebrafish embryos. The active compound was isolated and identified as fusaric acid. Previous literature has shown this phenotype to be associated with copper chelation from the active site of lysyl oxidase, but the ability of fusaric acid to bind copper ions has not been well described. Isothermal titration calorimetry revealed that fusaric acid is a modest copper chelator with a binding constant of 4.4 × 10(5) M(-1). These results shed light on the toxicity of fusaric acid and the potential teratogenic effects of consuming plants infected with Fusarium sp.

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

Oxidation Potentials in Matte Smelting of Copper and Nickel

NASA Astrophysics Data System (ADS)

Matousek, Jan W.

2014-09-01

The oxidation potential, given as the base-ten logarithm of the oxygen partial pressure in bars and the temperature [log pO2/ T, °C], defines the state of oxidation of pyrometallurgical extraction and refining processes. This property varies from copper making, [-6/1150]; to lead/zinc smelting, [-10/1200]; to iron smelting, [-13/1600]. The current article extends the analysis to the smelting of copper and nickel/copper sulfide concentrates to produce mattes of the type Cu(Ni)FeS(O) and iron silicate slags, FeOxSiO2—with oxidation potentials of [-7.5/1250].

Sub-cellular damage by copper in the cnidarian Zoanthus robustus.

PubMed

Grant, A; Trompf, K; Seung, D; Nivison-Smith, L; Bowcock, H; Kresse, H; Holmes, S; Radford, J; Morrow, P

2010-09-01

Sessile organisms may experience chronic exposure to copper that is released into the marine environment from antifoulants and stormwater runoff. We have identified the site of damage caused by copper to the symbiotic cnidarian, Zoanthus robustus (Anthozoa, Hexacorallia). External changes to the zoanthids were apparent when compared with controls. The normally flexible bodies contracted and became rigid. Histological examination of the zoanthid tissue revealed that copper had caused sub-cellular changes to proteins within the extracellular matrix (ECM) of the tubular body. Collagen in the ECM and the internal septa increased in thickness to five and seven times that of controls respectively. The epithelium, which stained for elastin, was also twice as thick and tough to cut, but exposure to copper did not change the total amount of desmosine which is found only in elastin. We conclude that copper stimulated collagen synthesis in the ECM and also caused cross-linking of existing proteins. However, there was no expulsion of the symbiotic algae (Symbiodinium sp.) and no effect on algal pigments or respiration (44, 66 and 110 microg Cu L(-1)). A decrease in net photosynthesis was observed only at the highest copper concentration (156 microg Cu L(-1)). These results show that cnidarians may be more susceptible to damage by copper than their symbiotic algae. Copyright (c) 2010 Elsevier Inc. All rights reserved.

Cover crops influence soil microorganisms and phytoextraction of copper from a moderately contaminated vineyard.

PubMed

Mackie, K A; Schmidt, H P; Müller, T; Kandeler, E

2014-12-01

We investigated the ability of summer (Avena sativa [oat], Trifolium incarnatum [crimson clover], Chenopodium [goosefoot]) and winter (Vicia villosa [hairy vetch], Secale Cereale L. [Rye], Brassica napus L. partim [rape]) cover crops, including a mixed species treatment, to extract copper from an organic vineyard soil in situ and the microbial communities that may support it. Clover had the highest copper content (14.3mgCukg(-1) DM). However, it was the amount of total biomass production that determined which species was most effective at overall copper removal per hectare. The winter crop rye produced significantly higher amounts of biomass (3532kgDMha(-1)) and, therefore, removed significantly higher amounts of copper (14,920mgCuha(-1)), despite less accumulation of copper in plant shoots. The maximum annual removal rate, a summation of best performing summer and winter crops, would be 0.033kgCuha(-1)y(-1). Due to this low annual extraction efficiency, which is less than the 6kgCuha(-1)y(-1) permitted for application, phytoextraction cannot be recommended as a general method of copper extraction from vineyards. Copper concentration did not influence aboveground or belowground properties, as indicated by sampling at two distances from the grapevine row with different soil copper concentrations. Soil microorganisms may have become tolerant to the copper levels at this site. Microbial biomass and soil enzyme activities (arylsulfatase and phosphatase) were instead driven by seasonal fluxes of resource pools. Gram+ bacteria were associated with high soil moisture, while fungi seemed to be driven by extractable carbon, which was linked to high plant biomass. There was no microbial group associated with the increased phytoextraction of copper. Moreover, treatment did not influence the abundance, activity or community structure of soil microorganisms. Copyright © 2014 Elsevier B.V. All rights reserved.

Terrestrial Eco-Toxicological Tests as Screening Tool to Assess Soil Contamination in Krompachy Area

NASA Astrophysics Data System (ADS)

Ol'ga, Šestinová; Findoráková, Lenka; Hančuľák, Jozef; Fedorová, Erika; Tomislav, Špaldon

2016-10-01

In this study, we present screening tool of heavy metal inputs to agricultural and permanent grass vegetation of the soils in Krompachy. This study is devoted to Ecotoxicity tests, Terrestrial Plant Test (modification of OECD 208, Phytotoxkit microbiotest on Sinapis Alba) and chronic tests of Earthworm (Dendrobaena veneta, modification of OECD Guidelines for the testing of chemicals 317, Bioaccumulation in Terrestrial Oligochaetes) as practical and sensitive screening method for assessing the effects of heavy metals in Krompachy soils. The total Cu, Zn, As, Pb and Hg concentrations and eco-toxicological tests of soils from the Krompachy area were determined of 4 sampling sites in 2015. An influence of the sampling sites distance from the copper smeltery on the absolutely concentrations of metals were recorded for copper, lead, zinc, arsenic and mercury. The highest concentrations of these metals were detected on the sampling sites up to 3 km from the copper smeltery. The samples of soil were used to assess of phytotoxic effect. Total mortality was established at earthworms using chronic toxicity test after 7 exposure days. The results of our study confirmed that no mortality was observed in any of the study soils. Based on the phytotoxicity testing, phytotoxic effects of the metals contaminated soils from the samples 3KR (7-9) S.alba seeds was observed.

Utilization of Seismic and Infrasound Signals for Characterizing Mining Explosions

DTIC Science & Technology

2001-10-01

different types of mining operations exist, ranging from surface coal cast blasting to hard rock fragmentation blasting in porphyry copper mines. The study...both seismic and infrasound signals. The seismic coupling of large-scale cast blasts in Wyoming, copper fragmentation blasts in Arizona and New Mexico...mining explosions from the copper fragmentation blasts in SE Arizona were observed at Los Alamos. Detected events were among the largest of the blasts

High-resolution, cryogenic, side-entry type specimen stage

DOEpatents

King, Wayne E.; Merkle, Karl L.

1979-01-01

A high-resolution, cryogenic side-entry type specimen stage includes a copper block within which a specimen can be positioned in the electron beam of an electron microscope, one end of the copper block constituting a specimen heat exchanger, means for directing a flow of helium at cryogenic temperature into the heat exchanger, and electrical leads running from the specimen to the exterior of the microscope for four point D.C. electrical resistivity measurements.

Effective removal of coordinated copper from wastewater using a new dithiocarbamate-type supramolecular heavy metal precipitant.

PubMed

Fu, Fenglian; Zeng, Haiyan; Cai, Qinhong; Qiu, Rongliang; Yu, Jimmy; Xiong, Ya

2007-11-01

A new dithiocarbamate-type heavy metal precipitant, sodium 1,3,5-hexahydrotriazinedithiocarbamate (HTDC), was prepared and used to remove coordinated copper from wastewater. In the reported dithiocarbamate-type precipitants, HTDC possesses the highest percentage of the effective functional groups. It could effectively precipitate copper to less than 0.5mgl(-1) from both synthetic and actual industrial wastewater containing CuEDTA in the range of pH 3-9. UV-vis spectral investigation and elemental analysis suggested that the precipitate was a kind of coordination supramolecular compound, [Cu(3)(HTDC)(2)](n). The toxicity characteristic leaching procedure (TCLP) and semi-dynamic leaching test (SDLT) indicated that the supramolecular precipitate was non-hazardous and stable in weak acid and alkaline conditions. Tests of an anion exchange resin D231 provided a clue to simultaneously remove excess HTDC and residual CuEDTA in practical process of wastewater treatment.

Core Sulphate-Reducing Microorganisms in Metal-Removing Semi-Passive Biochemical Reactors and the Co-Occurrence of Methanogens

PubMed Central

Rezadehbashi, Maryam; Baldwin, Susan A.

2018-01-01

Biochemical reactors (BCRs) based on the stimulation of sulphate-reducing microorganisms (SRM) are emerging semi-passive remediation technologies for treatment of mine-influenced water. Their successful removal of metals and sulphate has been proven at the pilot-scale, but little is known about the types of SRM that grow in these systems and whether they are diverse or restricted to particular phylogenetic or taxonomic groups. A phylogenetic study of four established pilot-scale BCRs on three different mine sites compared the diversity of SRM growing in them. The mine sites were geographically distant from each other, nevertheless the BCRs selected for similar SRM types. Clostridia SRM related to Desulfosporosinus spp. known to be tolerant to high concentrations of copper were members of the core microbial community. Members of the SRM family Desulfobacteraceae were dominant, particularly those related to Desulfatirhabdium butyrativorans. Methanogens were dominant archaea and possibly were present at higher relative abundances than SRM in some BCRs. Both hydrogenotrophic and acetoclastic types were present. There were no strong negative or positive co-occurrence correlations of methanogen and SRM taxa. Knowing which SRM inhabit successfully operating BCRs allows practitioners to target these phylogenetic groups when selecting inoculum for future operations. PMID:29473875

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

PubMed

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

2016-05-01

Copper surfaces possess efficient antimicrobial effect. Here, we reported that copper surfaces could inactivate Candida albicans biofilms within 40 min. The intracellular reactive oxygen species in C. albicans biofilms were immediately stimulated during the contact of copper surfaces, which might be an important factor for killing the mature biofilms. Copper release assay demonstrated that the copper ions automatically released from the surface of 1 mm thick copper coupons with over 99.9% purity are not the key determinant for the copper-mediated killing action. The susceptibility test to copper surfaces by using C. albicans mutant strains, which were involved in efflux pumps, adhesins, biofilms formation or osmotic stress response showed that als1/als1 and als3/als3 displayed higher resistance to the copper surface contact than other mutants did. The intracellular concentration of copper ions was lower in als1/als1 and als3/als3 than that in wild-type strain. Transcriptional analysis revealed that the expression of copper transporter-related gene, CRP1, was significantly increased in als1/als1, als3/als3, suggesting a potential role of ALS1 and ALS3 in absorbing ions by regulating the expression of CRP1 This study provides a potential application in treating pathogenic fungi by using copper surfaces and uncovers the roles of ALS1 and ALS3 in absorbing copper ions for C. albicans. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Copper induction and differential expression of laccase in Aspergillus flavus

PubMed Central

Gomaa, Ola M.; Momtaz, Osama A.

2015-01-01

Aspergillus flavus was isolated from soil and exhibited laccase activity under both constitutive and copper induced conditions. Spiking the medium with 1 mM copper sulfate resulted in an increase in the activity which reached 51.84 U/mL, a distinctive protein band was detected at 60 kDa. The extracellular enzyme was purified 81 fold using gel filtration chromatography and resulted in two different laccase fractions L1 and L2, the latter had a higher enzymatic activity which reached 79.57 U/mL and specific activity of 64.17 U/μg protein. The analysis of the spectrum of the L2 fraction showed a shoulder at 330 nm which is characteristic for T2/T3 copper centers; both copper and zinc were detected suggesting that this is an unconventional white laccase. Primers of laccase gene were designed and synthesized to recover specific gene from A. flavus . Sequence analysis indicated putative laccase (Genbank ID: JF683612) at the amino acid level suggesting a close identity to laccases from other genera containing the copper binding site. Decolorization of textile waste water under different conditions showed possible application in bioremediation within a short period of time. The effect of copper on A. flavus was concentration dependent. PMID:26221119

Copper removal from contaminated soils by soil washing process using camellian-derived saponin

NASA Astrophysics Data System (ADS)

Reyes, Arturo; Fernanda Campos, Maria; Videla, Álvaro; Letelier, María Victoria; Fuentes, Bárbara

2015-04-01

Antofagasta Region in North of Chile has been the main copper producer district in the world. As a consequence of a lack of mining closure regulation, a large number of abandon small-to-medium size metal-contaminated sites have been identified in the last survey performed by the Chilean Government. Therefore, more research development on sustainable reclamation technologies must be made in this extreme arid-dry zone. The objective of this study is to test the effectiveness of soil remediation by washing contaminated soil using camellian-derived saponin for the mobilization of copper. Soil samples were taken from an abandoned copper mine site located at 30 km North Antofagasta city. They were dried and sieved at 75 µm for physico-chemical characterization. A commercial saponin extracted from camellias seed was used as biosurfactant. The soil used contains 67.4 % sand, 26.3 % silt and 6.3 % clay. The soil is highly saline (electric conductivity, 61 mScm-1), with low organic matter content (0.41%), with pH 7.30, and a high copper concentration (2200 mg Kg-1 soil). According to the sequential extraction procedure of the whole soil, copper species are mainly as exchangeable fraction (608.2 mg Kg-1 soil) and reducible fraction (787.3 mg Kg-1 soil), whereas the oxidizable and residual fractions are around 205.7 and 598.8 mg Kg-1 soil, respectively. Soil particles under 75 µm contain higher copper concentrations (1242 mg Kg-1 soil) than the particle fraction over 75 µm (912 mg Kg-1 soil). All washing assays were conducted in triplicate using a standard batch technique with and without pH adjustment. The testing protocols includes evaluation of four solid to liquid ratio (0.5:50; 1.0:50; 2.0:50, and 5.0:50) and three saponin concentrations (0, 1, and 4 mg L-1). After shaking (24 h, 20±1 °C) and subsequently filtration (0.45 µm), the supernatants were analyzed for copper and pH. The removal efficiencies of copper by saponin solutions were calculated in according to the concentrations of copper in aqueous solution and its initial concentration on contaminated soil. It was found along this study that the washing of soils reaches a maximum performance when a 0.5:50 ratio soil:water, and 4 mg L-1 of saponin solution were used, in comparison with any other ratios and saponin dosage evaluated. Moreover, when saponin solution (4 mg L-1) was adjusted at pH 4.0, the efficiency of copper removal increased more than three times (98.3 mg Kg-1 soil) in comparison with the washing without pH adjustment (27.7 mg Kg-1 soil soil). Copper removal was found to be dependent on saponin concentration. The carboxyl group of the saponin hydrophilic head molecule could form copper-aquo complexes, which contribute to the mobilization of copper. However, a low pH is also necessary to solubilize and release copper from soil allowing interaction with saponin. It can be concluded that the use of saponin for washing soils containing copper is a cost-effective and environmental friendly alternative for cleaning and remediation of contaminated soils in the Antofagasta Region.

Crystal structure of Agaricus bisporus mushroom tyrosinase: identity of the tetramer subunits and interaction with tropolone.

PubMed

Ismaya, Wangsa T; Rozeboom, Henriëtte J; Weijn, Amrah; Mes, Jurriaan J; Fusetti, Fabrizia; Wichers, Harry J; Dijkstra, Bauke W

2011-06-21

Tyrosinase catalyzes the conversion of phenolic compounds into their quinone derivatives, which are precursors for the formation of melanin, a ubiquitous pigment in living organisms. Because of its importance for browning reactions in the food industry, the tyrosinase from the mushroom Agaricus bisporus has been investigated in depth. In previous studies the tyrosinase enzyme complex was shown to be a H(2)L(2) tetramer, but no clues were obtained of the identities of the subunits, their mode of association, and the 3D structure of the complex. Here we unravel this tetramer at the molecular level. Its 2.3 Å resolution crystal structure is the first structure of the full fungal tyrosinase complex. The complex comprises two H subunits of ∼392 residues and two L subunits of ∼150 residues. The H subunit originates from the ppo3 gene and has a fold similar to other tyrosinases, but it is ∼100 residues larger. The L subunit appeared to be the product of orf239342 and has a lectin-like fold. The H subunit contains a binuclear copper-binding site in the deoxy-state, in which three histidine residues coordinate each copper ion. The side chains of these histidines have their orientation fixed by hydrogen bonds or, in the case of His85, by a thioether bridge with the side chain of Cys83. The specific tyrosinase inhibitor tropolone forms a pre-Michaelis complex with the enzyme. It binds near the binuclear copper site without directly coordinating the copper ions. The function of the ORF239342 subunits is not known. Carbohydrate binding sites identified in other lectins are not conserved in ORF239342, and the subunits are over 25 Å away from the active site, making a role in activity unlikely. The structures explain how calcium ions stabilize the tetrameric state of the enzyme.

THE CHEMISTRY OF NEW COPPER PLUMBING

EPA Science Inventory

The presence of sulfate, bicarbonate and orthophosphate can change the type of solid present in systems containing cupric ion or cupric hydroxide solids. In some cases, a short term reduction in copper solubility is realized, but over longer periods of time formation of basic cup...

Soil management of copper mine tailing soils--sludge amendment and tree vegetation could improve biological soil quality.

PubMed

Asensio, Verónica; Covelo, Emma F; Kandeler, Ellen

2013-07-01

Mine soils at the depleted copper mine in Touro (Northwest Spain) are physico-chemically degraded and polluted by chromium and copper. To increase the quality of these soils, some areas at this mine have been vegetated with eucalyptus or pines, amended with sludges, or received both treatments. Four sites were selected at the Touro mine tailing in order to evaluate the effect of these different reclamation treatments on the biological soil quality: (1) Control (untreated), (2) Forest (vegetated), (3) Sludge (amended with sludges) and (4) Forest+Sludge (vegetated and amended). The new approach of the present work is that we evaluated the effect of planting trees or/and amending with sludges on the biological soil quality of mine sites polluted by metals under field conditions. The addition of sludges to mine sites recovered the biological quality of the soil, while vegetating with trees did not increase microbial biomass and function to the level of unpolluted sites. Moreover, amending with sludges increased the efficiency of the soil's microbial community to metabolize C and N, which was indicated by the decrease of the specific enzyme activities and the increase in the ratio Cmic:Nmic (shift towards predominance of fungi instead of bacteria). However, the high Cu and Cr concentrations still have negative influence on the microorganisms in all the treated soils. For the future remediation of mine soils, we recommend periodically adding sludge and planting native legume species. Copyright © 2013 Elsevier B.V. All rights reserved.

Study of the effect of varying core diameter, shell thickness and strain velocity on the tensile properties of single crystals of Cu-Ag core-shell nanowire using molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Sarkar, Jit; Das, D. K.

2018-01-01

Core-shell type nanostructures show exceptional properties due to their unique structure having a central solid core of one type and an outer thin shell of another type which draw immense attention among researchers. In this study, molecular dynamics simulations are carried out on single crystals of copper-silver core-shell nanowires having wire diameter ranging from 9 to 30 nm with varying core diameter, shell thickness, and strain velocity. The tensile properties like yield strength, ultimate tensile strength, and Young's modulus are studied and correlated by varying one parameter at a time and keeping the other two parameters constant. The results obtained for a fixed wire size and different strain velocities were extrapolated to calculate the tensile properties like yield strength and Young's modulus at standard strain rate of 1 mm/min. The results show ultra-high tensile properties of copper-silver core-shell nanowires, several times than that of bulk copper and silver. These copper-silver core-shell nanowires can be used as a reinforcing agent in bulk metal matrix for developing ultra-high strength nanocomposites.

Metallic corrosion in the polluted urban atmosphere of Hong Kong.

PubMed

Liu, Bo; Wang, Da-Wei; Guo, Hai; Ling, Zhen-Hao; Cheung, Kalam

2015-01-01

This study aimed to explore the relationship between air pollutants, particularly acidic particles, and metallic material corrosion. An atmospheric corrosion test was carried out in spring-summer 2012 at a polluted urban site, i.e., Tung Chung in western Hong Kong. Nine types of metallic materials, namely iron, Q235 steel, 20# steel, 16Mn steel, copper, bronze, brass, aluminum, and aluminum alloy, were selected as specimens for corrosion tests. Ten sets of the nine materials were all exposed to ambient air, and then each set was collected individually after exposure to ambient air for consecutive 6, 13, 20, 27, 35, 42, 49, 56, 63, and 70 days, respectively. After the removal of the corrosion products on the surface of the exposed specimens, the corrosion rate of each material was determined. The surface structure of materials was observed using scanning electron microscopy (SEM) before and after the corrosion tests. Environmental factors including temperature, relative humidity, concentrations of gaseous pollutants, i.e., sulfur dioxide (SO₂), nitrogen dioxide (NO₂), carbon monoxide (CO), ozone (O₃), and particulate-phase pollutants, i.e., PM₂.₅ (FSP) and PM₁₀ (RSP), were monitored. Correlation analysis between environmental factors and corrosion rate of materials indicated that iron and carbon steel were damaged by both gaseous pollutants (SO₂ and NO₂) and particles. Copper and copper alloys were mainly corroded by gaseous pollutants (SO₂ and O₃), while corrosion of aluminum and aluminum alloy was mainly attributed to NO₂ and particles.

Adsorption of aqueous copper on peanut hulls

NASA Astrophysics Data System (ADS)

Davis, Kanika Octavia

A method was established for measuring the adsorption of Cu(II) from aqueous solution to unmodified and modified peanut hulls at constant temperature and pH. Modification of the hulls was performed by oxidation with alkaline hydrogen peroxide. During the modification process, the hydrogen peroxide solubilizes the lignin component, making the surface more porous which increases the availability of binding sites, while simultaneously oxidizing the cellulose. The oxidation of alcohol groups creates more binding sites by creating functional groups such as COO-, which increases chelation to metal ions. Fourier transform infrared spectroscopy confirms delignification of the peanut hulls by the disappearance of carboxyl peaks of the modified hulls, which were originally produced from the lignin content. Although, oxidation is not fully confirmed, it is not ruled out because the expected carboxylate peak (1680 cm-1) maybe overshadowed by a broad peak due to OH bending of water adsorbed to the hulls. Hulls adsorbed copper from solutions in the concentration range of 50-1000 ppm of CuCl2. Concentrations of pre- and post-adsorption solutions were determined using inductively coupled plasma optical emission spectroscopy. The adsorption isotherms were fit to known two and three-parameter models, evaluated and the binding mechanism was inferred. Maximum surface coverage was 3.5 +/- 0.6 mg Cu2+ /g hull for unmodified hulls and 11 +/- 1 mg Cu2+/g hull for modified hulls. The adsorption for the hulls is best described by the Langmuir model, suggesting monolayer, homogeneous adsorption. With a free energy of adsorption of 10.5 +/- 0.9 kJ/mol for unmodified hulls and 14.5 +/-0.4 kJ/mol for modified hulls, the process is categorized as chemisorption for both types of hulls. The adsorption for both hulls is also described by the Redlich-Peterson model, giving beta nearer to 1 than 0, which further suggests homogeneous adsorption described by the Langmuir model. After rinsing the hulls, scanning electron microscopy images coupled with energy dispersive X-ray spectroscopy showed that the percentage of copper on the modified hulls (2.5 %) was greater than on the unmodified hulls (1.6 %). This study concluded that the adsorption of copper using peanut hulls is a potential method for wastewater treatment and delignification and oxidation of the hulls increases the adsorption capacity approximately three-fold.

(Pt{sub 1–x}Cu{sub x}){sub 3}Cu{sub 2}B and Pt{sub 9}Cu{sub 3}B{sub 5}, the first examples of copper platinum borides. Observation of superconductivity in a novel boron filled β-Mn-type compound

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

Salamakha, Leonid P.; Sologub, Oksana, E-mail: oksana.sologub@univie.ac.at; Stöger, Berthold

New ternary copper platinum borides have been synthesized by arc melting of pure elements followed by annealing at 600 °C. The structures have been studied by X-ray single crystal and powder diffraction. (Pt{sub 1−x}Cu{sub x}){sub 3}Cu{sub 2}B (x=0.33) forms a B-filled β-Mn-type structure (space group P4{sub 1}32; a=0.6671(1) nm). Cu atoms are distributed preferentially on the 8c atom sites, whereas the 12d site is randomly occupied by Pt and Cu atoms (0.670(4) Pt±0.330(4) Cu). Boron is located in octahedral voids of the parent β-Mn-type structure. Pt{sub 9}Cu{sub 3}B{sub 5} (space group P-62m; a=0.9048(3) nm, c=0.2908(1) nm) adopts the Pt{sub 9}Zn{submore » 3}B{sub 5–δ}-type structure. It has a columnar architecture along the short translation vector exhibiting three kinds of [Pt{sub 6}] trigonal prism columns (boron filled, boron semi-filled and empty) and Pt channels with a pentagonal cross section filled with Cu atoms. The striking structural feature is a [Pt{sub 6}] cluster in form of an empty trigonal prism at the origin of the unit cell, which is surrounded by coupled [BPt{sub 6}] and [Pt{sub 6}] trigonal prisms, rotated perpendicularly to the central one. There is no B–B contact as well as Cu–B contact in the structure. The relationships of Pt{sub 9}Cu{sub 3}B{sub 5} structure with the structure of Ti{sub 1+x}Os{sub 2−x}RuB{sub 2} as well as with the structure families of metal sulfides and aluminides have been elucidated. (Pt{sub 1–x}Cu{sub x}){sub 3}Cu{sub 2}B (x=0.3) (B-filled β-Mn-type structure) is a bulk superconductor with a transition temperature of about 2.06 K and an upper critical field μ{sub 0}H{sub C2}(0){sup WHH} of 1.2 T, whereas no superconducting transition has been observed up to 0.3 K in Pt{sub 9}Cu{sub 3}B{sub 5} (Pt{sub 9}Zn{sub 3}B{sub 5–δ}-type structure) from electrical resistivity measurements. - Highlights: • First two copper platinum borides, (Pt{sub 0.67}Cu{sub 0.33}){sub 3}Cu{sub 2}B and Pt{sub 9}Cu{sub 3}B{sub 5} were obtained. • (Pt{sub 0.67}Cu{sub 0.33}){sub 3}Cu{sub 2}B forms a B-filled β-Mn-type structure. • Pt{sub 9}Cu{sub 3}B{sub 5} adopts a Pt{sub 9}Zn{sub 3}B{sub 5–δ}-type structure. • Boron atoms exhibit octahedral and trigonal prismatic coordination. • (Pt{sub 1–x}Cu{sub x})3Cu{sub 2}B (x=0.3) is a bulk superconductor with T{sub c} 2.06 K.« less

Demonstration and Validation of a Regenerated Cellulose Dialysis Membrane Diffusion Sampler for Monitoring Groundwater Quality and Remediation Progress at DoD Sites

DTIC Science & Technology

2007-02-01

years if kept refrigerated in its preservative solution of ethanol, sodium benzoate , and ethylene diamine tetra-acetic acid (EDTA). Alternatively... sodium bicarbonate solution, EDTA, and sodium azide solution to remove residual gylcerol, sulfide, cadmium, chromium, copper, iron, nickel, zinc, and lead...Magnesium Cadmium Nickel Potassium Chromium Selenium Sodium Copper Vanadium Aluminum Iron Zinc Arsenic Lead Antimony Manganese Anions (1-3 days

Effect of the mechanical activation of a cathode on the structure of electrolytic copper single crystals

NASA Astrophysics Data System (ADS)

Gryzunova, N. N.; Vikarchuk, A. A.; Gryzunov, A. M.; Denisova, A. G.

2017-10-01

The morphology of the electrolytic copper single crystals formed under the mechanical activation of a cathode is described. Pentagonal pyramids and conical microcrystals with high growth steps are shown to form during electrocrystallization under these conditions. It is experimentally found that microcrystals grow on disclination defects, in particular, at the sites of termination of twin growth boundaries, and mechanical activation causes the formation of such defects.

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.

Comparative contraceptive effectiveness of levonorgestrel-releasing and copper intrauterine devices: the European Active Surveillance Study for Intrauterine Devices.

PubMed

Heinemann, Klaas; Reed, Suzanne; Moehner, Sabine; Minh, Thai Do

2015-04-01

The objective was to measure the rate of unintended pregnancies in women using levonorgestrel-releasing intrauterine systems (LNG IUSs, releasing 20 mcg LNG daily) and copper intrauterine devices (IUDs) in a typical population of IUD users and to describe associated complications. A multinational, prospective, non-interventional cohort study of new users of LNG IUS and copper IUDs was performed. Following a baseline survey, study participants and their physicians completed one follow-up questionnaire after 12 months. A multifaceted four-level follow-up procedure minimized loss to follow-up. Patient-reported outcomes were validated by the treating physicians. A total of 61,448 women with a newly inserted IUD were enrolled in six European countries between 2006 and 2012. The copper IUD cohort contained more than 30 different types. Validated 1-year follow-up information for 58,324 users between 18 and 50 years of age (70% using LNG IUS, 30% using copper IUDs) was collected. A total of 118 contraceptive failures occurred (26 LNG, 92 copper). Both types of IUD were highly effective, with overall Pearl indices of 0.06 [95% confidence interval (CI): 0.04-0.09] and 0.52 (95% CI: 0.42-0.64) for LNG IUS and copper IUDs, respectively. The adjusted hazard ratio for LNG IUS vs. copper IUDs was 0.16 (95% CI: 0.10-0.25). Tenty-one pregnancies (7 LNG IUS, 14 copper IUD) were ectopic, yielding an adjusted hazard ratio for ectopic pregnancy of 0.26 (95% CI: 0.10-0.66). The contraceptive failure rate was low with both IUDs. However, the LNG IUS was associated with a significantly lower risk of pregnancy, including ectopic pregnancy, than the copper IUDs. To our knowledge, this is the first large-scale, multinational, prospective epidemiological study to measure and compare the contraceptive effectiveness of LNG IUSs and copper IUDs during routine clinical practice. Clinicians and patients should be aware of differences in rates of unintended pregnancies and associated complications in relation to IUD us. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

Characterization of the role of copCD in copper uptake and the 'copper-switch' in Methylosinus trichosporium OB3b.

PubMed

Gu, Wenyu; Farhan Ul Haque, Muhammad; Semrau, Jeremy D

2017-05-01

Methanotrophs or methane-oxidizing bacteria exhibit a unique 'copper-switch' where expression of two forms of methane monooxygenase (MMO) is controlled by the availability of copper. In the absence of copper, a cytoplasmic or soluble methane monooxygenase (sMMO) is expressed. In the presence of copper, a membrane-bound or particulate methane monooxygenase (pMMO) is expressed. These two forms of MMO have very different properties, and elucidation of the basis of the copper-switch is of significant interest as methanotrophs are becoming increasingly popular for the valorization of methane. Recently, it was suggested via characterization of a mutant of Methylosinus trichosporium OB3b that expresses sMMO in the presence of copper (smmoC mutant) that the copper-switch may be based on copCD. These genes encode for a periplasmic copper-binding protein and an inner membrane protein, respectively, and are used by other bacteria for copper uptake. Specific knockouts of copCD in M. trichosporium OB3b wild type, however, show that these genes are not part of the copper-switch in methanotrophs, nor do they appear to be critical for copper uptake. Rather, it appears that the constitutive expression of sMMO in the smmoC mutant of M. trichosporium OB3b may be due to multiple lesions as smmoC was generated via random chemical mutagenesis. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Stratabound copper-silver deposits of the Mesoproterozoic Revett formation, Montana and Idaho

USGS Publications Warehouse

Boleneus, David E.; Appelgate, Larry M.; Stewart, John H.; Zientek, Michael L.

2005-01-01

The western Montana copper belt in western Montana and northern Idaho contains several large stratabound copper-silver deposits in fine- to medium-grained quartzite beds of the Revett Formation of the Mesoproterozoic (1,470-1,401 Ma) Belt Supergroup. Production from the deposits at the Troy Mine and lesser production from the Snowstorm Mine has yielded 222,237 tons Cu and 1,657.4 tons Ag. Estimates of undeveloped resources, mostly from the world-class Rock Creek-Montanore deposits, as well as lesser amounts at the Troy Mine, total more than 2.9 million tons Cu and 2,600 tons Ag in 406 million tons of ore.The Rock Creek-Montanore and Troy deposits, which are currently the most significant undeveloped resources identified in the copper belt, are also among the largest stratabound copper-silver deposits in North America and contain about 15 percent of the copper in such deposits in North America. Worldwide, stratabound copper-silver deposits contain 23 percent of all copper resources and are the second-most important global source of the metal after porphyry copper deposits.The Revett Formation, which consists of subequal amounts of argillite, siltite, and quartzite, is informally divided into lower, middle, and upper members on the basis of the proportions of the dominant rock types. The unit thickness increases from north to south, from 1,700 ft near the Troy Mine, 55 mi north of Wallace, Idaho, to more than 5,300 ft at Wallace, Idaho, in the Coeur d'Alene Trough south of the Osburn Fault, a major right-lateral strike-slip fault.Mineral deposits in the Revett Formation occur mostly in the A-D beds of the lower member and in the middle quartzite of the upper member. The deposits are concentrated along a preore pyrite/hematite interface in relatively coarse grained, thick quartzite beds that acted as paleoaquifers for ore fluids. The deposits are characterized by mineral zones (alteration-mineral assemblages) that are a useful guide to the locations of mineral deposits. In particular, the gradational zone between the chalcopyrite-ankerite and pyrite-calcite zones is the site of most mineral deposits. Detailed information on the geology and mineral deposits of the Revett Formation is presented in the accompanying files that include (1) a tab-delimited text file providing details of the geologic and mineral-resource data for 57 Revett-subtype stratabound copper-silver deposits, occurrences, and prospects; (2) the stratigraphic records of 40 diamond-drill cores and 86 measured sections, totaling 150,752 ft of true thickness, which are provided in Excel spreadsheet and Adobe Portable Document Format files; and (3) spatial geologic data consisting of geologic maps of the Revett Formation, the subsurface locations of resources in Revett-subtype stratabound copper-silver deposits based on diamond-drill-core data, and the locations of diamond-drill holes and measured sections. The spatial data are contained in Arc/Info interchange files. Spatial information derived from these data includes the locations of mineral zones, a digital database showing untested exploration areas, and a digital database of permissive tracts for undiscovered mineral deposits.

Reversible and nonvolatile ferroelectric control of two-dimensional electronic transport properties of ZrCuSiAs-type copper oxyselenide thin films with a layered structure

NASA Astrophysics Data System (ADS)

Zhao, Xu-Wen; Gao, Guan-Yin; Yan, Jian-Min; Chen, Lei; Xu, Meng; Zhao, Wei-Yao; Xu, Zhi-Xue; Guo, Lei; Liu, Yu-Kuai; Li, Xiao-Guang; Wang, Yu; Zheng, Ren-Kui

2018-05-01

Copper-based ZrCuSiAs-type compounds of LnCuChO (Ln =Bi and lanthanides, Ch =S , Se, Te) with a layered crystal structure continuously attract worldwide attention in recent years. Although their high-temperature (T ≥ 300 K) electrical properties have been intensively studied, their low-temperature electronic transport properties are little known. In this paper, we report the integration of ZrCuSiAs-type copper oxyselenide thin films of B i0.94P b0.06CuSeO (BPCSO) with perovskite-type ferroelectric Pb (M g1 /3N b2 /3 ) O3-PbTi O3 (PMN-PT) single crystals in the form of ferroelectric field effect devices that allow us to control the electronic properties (e.g., carrier density, magnetoconductance, dephasing length, etc.) of BPCSO films in a reversible and nonvolatile manner by polarization switching at room temperature. Combining ferroelectric gating and magnetotransport measurements with the Hikami-Larkin-Nagaoka theory, we demonstrate two-dimensional (2D) electronic transport characteristics and weak antilocalization effect as well as strong carrier-density-mediated competition between weak antilocalization and weak localization in BPCSO films. Our results show that ferroelectric gating using PMN-PT provides an effective and convenient approach to probe the carrier-density-related 2D electronic transport properties of ZrCuSiAs-type copper oxyselenide thin films.

Rhenium

USGS Publications Warehouse

John, David A.; Seal, Robert R.; Polyak, Désirée E.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

2017-12-19

Rhenium is one of the rarest elements in Earth’s continental crust; its estimated average crustal abundance is less than 1 part per billion. Rhenium is a metal that has an extremely high melting point and a heat-stable crystalline structure. More than 80 percent of the rhenium consumed in the world is used in high-temperature superalloys, especially those used to make turbine blades for jet aircraft engines. Rhenium’s other major application is in platinum-rhenium catalysts used in petroleum refining.Rhenium rarely occurs as a native element or as its own sulfide mineral; most rhenium is present as a substitute for molybdenum in molybdenite. Annual world mine production of rhenium is about 50 metric tons. Nearly all primary rhenium production (that is, rhenium produced by mining rather than through recycling) is as a byproduct of copper mining, and about 80 percent of the rhenium obtained through mining is recovered from the flue dust produced during the roasting of molybdenite concentrates from porphyry copper deposits. Molybdenite in porphyry copper deposits can contain hundreds to several thousand grams per metric ton of rhenium, although the estimated rhenium grades of these deposits range from less than 0.1 gram per metric ton to about 0.6 gram per metric ton.Continental-arc porphyry copper-(molybdenum-gold) deposits supply most of the world’s rhenium production and have large inferred rhenium resources. Porphyry copper mines in Chile account for about 55 percent of the world’s mine production of rhenium; rhenium is also recovered from porphyry copper deposits in the United States, Armenia, Kazakhstan, Mexico, Peru, Russia, and Uzbekistan. Sediment-hosted strata-bound copper deposits in Kazakhstan (of the sandstone type) and in Poland (of the reduced-facies, or Kupferschiefer, type) account for most other rhenium produced by mining. These types of deposits also have large amounts of identified rhenium resources. The future supply of rhenium is likely to depend largely on the capacity of the specialized processing facilities needed to recover rhenium from molybdenite concentrates.The environmental consequences of rhenium recovery are closely linked to the consequences of mining large porphyry copper and strata-bound copper deposits; no additional environmental impact from recovery of rhenium from these deposits has been identified. No information is available regarding the potential toxic effects of rhenium on humans, partly because of the low natural abundance of rhenium.

Lingual dyskinesia and tics: a novel presentation of copper-metabolism disorder.

PubMed

Goez, Helly R; Jacob, Francois D; Yager, Jerome Y

2011-02-01

Copper is a trace element that is required for cellular respiration, neurotransmitter biosynthesis, pigment formation, antioxidant defense, peptide amidation, and formation of connective tissue. Abnormalities of copper metabolism have been linked with neurologic disorders that affect movement, such as Wilson disease and Menkes disease; however, the diagnosis of non-Wilson, non-Menkes-type copper-metabolism disorders has been more elusive, especially in cases with atypical characteristics. We present here the case of an adolescent with a novel presentation of copper-metabolism disorder who exhibited acute severe hemilingual dyskinesia and prominent tics, with ballismus of the upper limbs, but had normal brain and spinal MRI results and did not show any signs of dysarthria or dysphagia. His serum copper and ceruloplasmin levels were low, but his urinary copper level was elevated after penicillamine challenge. We conclude that copper-metabolism disorders should be included in the differential diagnosis for movement disorders, even in cases with highly unusual presentations, because many of them are treatable. Moreover, a connection between copper-metabolism disorders and tics is presented, to our knowledge, for the first time in humans; further investigation is needed to better establish this connection and understand its underlying pathophysiology.

Transcription factor Afmac1 controls copper import machinery in Aspergillus fumigatus.

PubMed

Kusuya, Yoko; Hagiwara, Daisuke; Sakai, Kanae; Yaguchi, Takashi; Gonoi, Tohru; Takahashi, Hiroki

2017-08-01

Copper (Cu) is an essential metal for all living organisms, although it is toxic in excess. Filamentous fungus must acquire copper from its environment for growth. Despite its essentiality for growth, the mechanisms that maintain copper homeostasis are not fully understood in filamentous fungus. To gain insights into copper homeostasis, we investigated the roles of a copper transcription factor Afmac1 in the life-threatening fungus Aspergillus fumigatus, a homolog of the yeast MAC1. We observed that the Afmac1 deletion mutant exhibited not only significantly slower growth, but also incomplete conidiation including a short chain of conidia and defective melanin. Moreover, the expressions of the copper transporters, ctrA1, ctrA2, and ctrC, and metalloreductases, Afu8g01310 and fre7, were repressed in ∆Afmac1 cells, while those expressions were induced under copper depletion conditions in wild-type. The expressions of pksP and wetA, which are, respectively, involved in biosynthesis of conidia-specific melanin and the late stage of conidiogenesis, were decreased in the ∆Afmac1 strain under minimal media condition. Taken together, these results indicate that copper acquisition through AfMac1 functions in growth as well as conidiation.

Copper emissions from a high volume air sampler

NASA Technical Reports Server (NTRS)

King, R. B.; Toma, J.

1975-01-01

High volume air samplers (hi vols) are described which utilize a brush-type electric motor to power the fans used for pulling air through the filter. Anomalously high copper values were attributed to removal of copper from the commutator into the air stream due to arcing of the brushes and recirculation through the filter. Duplicate hi vols were set up under three operating conditions: (1) unmodified; (2) gasketed to prevent internal recirculation; and (3) gasketed and provided with a pipe to transport the motor exhaust some 20 feet away. The results of 5 days' operation demonstrate that hi vols can suddenly start emitting increased amounts of copper with no discernible operational indication, and that recirculation and capture on the filter can take place. Copper levels found with hi vols whose exhaust was discharged at a distance downwind were among the lowest found, and apparently provides a satisfactory solution to copper contamination.

Patterned self-assembled monolayers of alkanethiols on copper nanomembranes by submerged laser ablation

NASA Astrophysics Data System (ADS)

Rhinow, Daniel; Hampp, Norbert A.

2012-06-01

Self-assembled monolayers (SAMs) of alkanethiols are major building blocks for nanotechnology. SAMs provide a functional interface between electrodes and biomolecules, which makes them attractive for biochip fabrication. Although gold has emerged as a standard, copper has several advantages, such as compatibility with semiconductors. However, as copper is easily oxidized in air, patterning SAMs on copper is a challenging task. In this work we demonstrate that submerged laser ablation (SLAB) is well-suited for this purpose, as thiols are exchanged in-situ, avoiding air exposition. Using different types of ω-substituted alkanethiols we show that alkanethiol SAMs on copper surfaces can be patterned using SLAB. The resulting patterns were analyzed by atomic force microscopy (AFM) and scanning electron microscopy (SEM). Both methods indicate that the intense laser beam promotes the exchange of thiols at the copper surface. Furthermore, we present a procedure for the production of free-standing copper nanomembranes, oxidation-protected by alkanethiol SAMs. Incubation of copper-coated mica in alkanethiol solutions leads to SAM formation on both surfaces of the copper film due to intercalation of the organic molecules. Corrosion-protected copper nanomembranes were floated onto water, transferred to electron microscopy grids, and subsequently analyzed by electron energy loss spectroscopy (EELS).

Experimental Evaluation of the Taylor-Type Polycrystal Model for the Finite Deformation of an FCC Metal (OFHC Copper)

DTIC Science & Technology

1991-05-01

was received as bar stocks in the work hardened condition. Before machining, the copper rods were annealed at 400 °C in argon for one hour. This...ABSTRACT Large deformation uniaxial compression and fixed-end torsion (simple shear) experiments were conducted on annealed OFHC Copper to obtain its... annealing treatment produced an average grain diameter of 45 jim. Experimental Procedure Compression Tests All the compression tests were conducted with

Military Jet Fuels, 1944-1987

DTIC Science & Technology

1987-11-01

first high density, synthetic hydrocarbon missile fuel. Developed by the US Navy, RJ-4 was used in the mid-1960s in the ramjet-powered Tales missile...High Density Synthetic Hydrocarbon Type. Grades 7P-9 and JP-10, covers two fuels currently in use in the Air Launched Cruise Missile (ALCM). JP-9...revealed that a significant quantity of copper was in the fuel, carried over from a copper- sweetening process. The copper was chelated by the metal

IN-HOUSE COPPER AND LEAD SOLUBILITY/CORROSION STUDIES

EPA Science Inventory

Understanding and predicting metal release from pipes of all sizes and types from the treatment plant to the consumer’s tap is critical, specifically for regulatory compliance with the Lead and Copper Rule, as well as the performance, corrosion morphology, and longevity of infras...

Advances in copper-catalyzed C-C coupling reactions and related domino reactions based on active methylene compounds.

PubMed

Liu, Yunyun; Wan, Jie-Ping

2012-06-01

Active methylene compounds are a major class of reaction partners for C-C bond formation with sp(2) C-X (X = halide) fragments. As one of the most-classical versions of the Ullmann-type coupling reaction, activated-methylene-based C-C coupling reactions have been efficiently employed in a large number of syntheses. Although this type of reaction has long relied on noble-metal catalysis, the renaissance of copper catalysis at the end of last century has led to dramatic developments in Ullmann C-C coupling reactions. Owing to its low cost, abundance, as well as excellent catalytic activity, the exceptional atom economy of copper catalysis is gaining widespread attention in various organic synthesis. This review summarizes the advances in copper-catalyzed intermolecular and intramolecular C-C coupling reactions that use activated methylene species as well as in tandem reactions that are initiated by this transformation. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Health safety of main water pipe materials supplied in China market.

PubMed

Lu, Kai; Ding, Liang; Wang, Hong-Wei; Jing, Hai-Ning; Zhao, Xiao-Ning; Lin, Shao-Bin; Li, Ya-Dong; Jin, Yin-Long; Liu, Feng-Mao; Jiang, Shu-Ren

2006-04-01

To assess the health safety of copper, steel and plastic water pipes by field water quality investigations. Four consumers were randomly selected for each type of water pipes. Two consumers of every type of the water pipes had used the water pipes for more than 1 year and the other 2 consumers had used the water pipes for less than 3 months. The terminal volume of tap water in copper and steel water pipes should be not less than 0.1 liter, whereas that in plastic water pipes should be not less than 1 liter. The mean values of the experimental results in the second field water quality investigation of the copper and steel water pipes met the Sanitary Standards for Drinking Water Quality. The items of water sample of the plastic water pipes met the requirements of the Sanitary Standards for Drinking Water Quality. Copper, steel, and plastic pipes can be used as drinking water pipes.

Checking Studies on Zones of Siting Feasibility for Dredged Material in Puget Sound.

DTIC Science & Technology

1986-01-01

priority pollutants in the ZSFs including copper, lead, mercury , HPAH, LPAH, PCBs and DDT. The area around Fourmile Rock dump site was classified in a...sediment contains ferric hydroxide (an olive color when associated with organic particles), while the reduced hydrogen sulphide sediments below this

Hazardous Waste Cleanup: Square D Company in Bordentown, New Jersey

EPA Pesticide Factsheets

Square D Company is located at 90 US Highway 130 in Bordentown, New Jersey. The site was formerly used for clay mining in the 1930's and then for a municipal landfill. The site was originally used as for a copper-foil manufacturing process under a company

My Spring with Graphene

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

O'Leary, Timothy Sean

2015-06-08

Graphene is a two-dimensional structure, one atom thick, with many uses in the world of technology. It has many useful electrical properties, is a very strong and durable material, and can be used to protect different types of substances. The world would be able to use these properties to further the strength of cars, protect metals from oxidation, increase computer speeds, use to improve superconductors, and whatever future uses that scientist invent or discover. We sought to optimize the growth and transfer of graphene. We grew graphene on copper foils by heating the foil in a furnace, and having variousmore » gases flow through a tube, where the copper foil was placed. We varied some of the concentrations of gases, along with having different times for heating the copper foil, different times for graphene growth, or a combination of the two. The focus of our experiment was to specifically grow monolayer single crystal graphene, which means that we do not want multiplayers of graphene, and do not want multiple crystals growing to form a bigger crystal. Our goal was to grow large single crystals from the growth experiment. We used a few different types of transfer methods that ranged from: using heat and pressure to press the graphene on different materials, using a polymer to cover the graphene with a method to destroy the copper, but leave the graphene and polymer intact, and using a type of heat tape with a combination of varying pressures to transfer the graphene, and then destroy the copper foil. To discover if we grew graphene we used different techniques involving lasers and microscopes to take different types of measurements. Discovering the best way of growing and transferring graphene will help with managing the cost of the future uses of graphene.« less

Simultaneous Measurement of Zinc, Copper, Lead and Cadmium in Baby Weaning Food and Powder Milk by DPASV.

PubMed

Sadeghi, Naficeh; Oveisi, Mohammad Reza; Jannat, Behrooz; Hajimahmoodi, Mannan; Behfar, Abdolazim; Behzad, Masoomeh; Norouzi, Narges; Oveisi, Morvarid; Jannat, Behzad

2014-01-01

Apart from the breast milk, infant formula and baby weaning food have a special role in infant diet. Infants and young children are very susceptible to amount of trace elements. Copper and zinc are two elements that add in infant food. Lead and cadmium are heavy metals that enter to food chain unavoidably. DPASV is a benefit and applicable method for measurement of trace elements in food products. In this study, concentration of zinc, copper, lead and cadmium in four brands of baby food (rice and wheat based) and powder milk was analyzed with DPASV and polarograph set. Total Mean ± SE of zinc, copper, lead and cadmium in baby foods (n = 240) were 11.86 ± 1.474 mg/100g, 508.197 ± 83.154 μg/100g, 0.445 ± 0.006, 0.050 ± 0.005 mg/Kg respectively. Also these amount in powder milk (n = 240) were 3.621± 0.529 mg/100g, 403.822 ± 133.953 μg/100g, 0.007 ± 0.003, 0.060 ± 0.040 mg/Kg respectively. Zinc level in baby food type I was higher than lablled value (P = 0.030), but in other brands was not difference. Concentration of copper in all of samples was in labeled range (P > 0.05). In each four products, level of lead and cadmium were lower than the standard limit (P < 0.05). Amount of zinc and lead in baby food I, had difference versus other products. Concentration of zinc, camium in baby food type I, was higher than type II (P = 0.043, 0.001 respectively). Concentration of lead and cadmium in baby food type II, was higher than infant formulas, but are in standard limit.

Insights into the role of the unusual disulfide bond in copper-zinc superoxide dismutase.

PubMed

Sea, Kevin; Sohn, Se Hui; Durazo, Armando; Sheng, Yuewei; Shaw, Bryan F; Cao, Xiaohang; Taylor, Alexander B; Whitson, Lisa J; Holloway, Stephen P; Hart, P John; Cabelli, Diane E; Gralla, Edith Butler; Valentine, Joan Selverstone

2015-01-23

The functional and structural significance of the intrasubunit disulfide bond in copper-zinc superoxide dismutase (SOD1) was studied by characterizing mutant forms of human SOD1 (hSOD) and yeast SOD1 lacking the disulfide bond. We determined x-ray crystal structures of metal-bound and metal-deficient hC57S SOD1. C57S hSOD1 isolated from yeast contained four zinc ions per protein dimer and was structurally very similar to wild type. The addition of copper to this four-zinc protein gave properly reconstituted 2Cu,2Zn C57S hSOD, and its spectroscopic properties indicated that the coordination geometry of the copper was remarkably similar to that of holo wild type hSOD1. In contrast, the addition of copper and zinc ions to apo C57S human SOD1 failed to give proper reconstitution. Using pulse radiolysis, we determined SOD activities of yeast and human SOD1s lacking disulfide bonds and found that they were enzymatically active at ∼10% of the wild type rate. These results are contrary to earlier reports that the intrasubunit disulfide bonds in SOD1 are essential for SOD activity. Kinetic studies revealed further that the yeast mutant SOD1 had less ionic attraction for superoxide, possibly explaining the lower rates. Saccharomyces cerevisiae cells lacking the sod1 gene do not grow aerobically in the absence of lysine, but expression of C57S SOD1 increased growth to 30-50% of the growth of cells expressing wild type SOD1, supporting that C57S SOD1 retained a significant amount of activity. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Insights into the Role of the Unusual Disulfide Bond in Copper-Zinc Superoxide Dismutase*

PubMed Central

Sea, Kevin; Sohn, Se Hui; Durazo, Armando; Sheng, Yuewei; Shaw, Bryan F.; Cao, Xiaohang; Taylor, Alexander B.; Whitson, Lisa J.; Holloway, Stephen P.; Hart, P. John; Cabelli, Diane E.; Gralla, Edith Butler; Valentine, Joan Selverstone

2015-01-01

The functional and structural significance of the intrasubunit disulfide bond in copper-zinc superoxide dismutase (SOD1) was studied by characterizing mutant forms of human SOD1 (hSOD) and yeast SOD1 lacking the disulfide bond. We determined x-ray crystal structures of metal-bound and metal-deficient hC57S SOD1. C57S hSOD1 isolated from yeast contained four zinc ions per protein dimer and was structurally very similar to wild type. The addition of copper to this four-zinc protein gave properly reconstituted 2Cu,2Zn C57S hSOD, and its spectroscopic properties indicated that the coordination geometry of the copper was remarkably similar to that of holo wild type hSOD1. In contrast, the addition of copper and zinc ions to apo C57S human SOD1 failed to give proper reconstitution. Using pulse radiolysis, we determined SOD activities of yeast and human SOD1s lacking disulfide bonds and found that they were enzymatically active at ∼10% of the wild type rate. These results are contrary to earlier reports that the intrasubunit disulfide bonds in SOD1 are essential for SOD activity. Kinetic studies revealed further that the yeast mutant SOD1 had less ionic attraction for superoxide, possibly explaining the lower rates. Saccharomyces cerevisiae cells lacking the sod1 gene do not grow aerobically in the absence of lysine, but expression of C57S SOD1 increased growth to 30–50% of the growth of cells expressing wild type SOD1, supporting that C57S SOD1 retained a significant amount of activity. PMID:25433341

Assessment of the Toxicity of CuO Nanoparticles by Using Saccharomyces cerevisiae Mutants with Multiple Genes Deleted

PubMed Central

Bao, Shaopan; Lu, Qicong; Dai, Heping; Zhang, Chao

2015-01-01

To develop applicable and susceptible models to evaluate the toxicity of nanoparticles, the antimicrobial effects of CuO nanoparticles (CuO-NPs) on various Saccharomyces cerevisiae (S. cerevisiae) strains (wild type, single-gene-deleted mutants, and multiple-gene-deleted mutants) were determined and compared. Further experiments were also conducted to analyze the mechanisms associated with toxicity using copper salt, bulk CuO (bCuO), carbon-shelled copper nanoparticles (C/Cu-NPs), and carbon nanoparticles (C-NPs) for comparisons. The results indicated that the growth inhibition rates of CuO-NPs for the wild-type and the single-gene-deleted strains were comparable, while for the multiple-gene deletion mutant, significantly higher toxicity was observed (P < 0.05). When the toxicity of the CuO-NPs to yeast cells was compared with the toxicities of copper salt and bCuO, we concluded that the toxicity of CuO-NPs should be attributed to soluble copper rather than to the nanoparticles. The striking difference in adverse effects of C-NPs and C/Cu-NPs with equivalent surface areas also proved this. A toxicity assay revealed that the multiple-gene-deleted mutant was significantly more sensitive to CuO-NPs than the wild type. Specifically, compared with the wild-type strain, copper was readily taken up by mutant strains when cell permeability genes were knocked out, and the mutants with deletions of genes regulated under oxidative stress (OS) were likely producing more reactive oxygen species (ROS). Hence, as mechanism-based gene inactivation could increase the susceptibility of yeast, the multiple-gene-deleted mutants should be improved model organisms to investigate the toxicity of nanoparticles. PMID:26386067

Estimating risks for water-quality exceedances of total-copper from highway and urban runoff under predevelopment and current conditions with the Stochastic Empirical Loading and Dilution Model (SELDM)

USGS Publications Warehouse

Granato, Gregory E.; Jones, Susan C.; Dunn, Christopher N.; Van Weele, Brian

2017-01-01

The stochastic empirical loading and dilution model (SELDM) was used to demonstrate methods for estimating risks for water-quality exceedances of event-mean concentrations (EMCs) of total-copper. Monte Carlo methods were used to simulate stormflow, total-hardness, suspended-sediment, and total-copper EMCs as stochastic variables. These simulations were done for the Charles River Basin upstream of Interstate 495 in Bellingham, Massachusetts. The hydrology and water quality of this site were simulated with SELDM by using data from nearby, hydrologically similar sites. Three simulations were done to assess the potential effects of the highway on receiving-water quality with and without highway-runoff treatment by a structural best-management practice (BMP). In the low-development scenario, total copper in the receiving stream was simulated by using a sediment transport curve, sediment chemistry, and sediment-water partition coefficients. In this scenario, neither the highway runoff nor the BMP effluent caused concentration exceedances in the receiving stream that exceed the once in three-year threshold (about 0.54 percent). In the second scenario, without the highway, runoff from the large urban areas in the basin caused exceedances in the receiving stream in 2.24 percent of runoff events. In the third scenario, which included the effects of the urban runoff, neither the highway runoff nor the BMP effluent increased the percentage of exceedances in the receiving stream. Comparison of the simulated geometric mean EMCs with data collected at a downstream monitoring site indicates that these simulated values are within the 95-percent confidence interval of the geometric mean of the measured EMCs.

Bioavailability and Environmental Regulation - Integrating a Fate & Effects Model with a Biotic Ligand Model for Copper in Seawater

NASA Astrophysics Data System (ADS)

Rivera, I.; Chadwick, B.; Rosen, G.; Wang, P. F.; Paquin, P.; Santore, R.; Ryan, A.

2015-12-01

Understanding the bioavailability of metals in the aquatic environment is important for defining appropriate regulatory constraints. A failure to recognize the importance of bioavailability factors on metal toxicity can result in criteria that are over- or under-protective. USEPA addresses the tendency of the national Water Quality Criterion (WQC) for regulation of copper in marine waters to underestimate the natural attenuation of copper toxicity in harbors by the application of site-specific Water Quality Standards (WQS). Which provides the level of protection intended by the WQC, and establishes realistic regulatory objectives. However, development of site-specific WQS involves a long-term effort, and does not account for temporal variation. The toxicity model seawater-Biotic Ligand Model (BLM) was developed and integrated with the existing Curvilinear Hydrodynamics in 3 Dimensions (CH3D) transport & fate model to create an efficient tool for development of site-specific WQS in harbors. The integrated model was demonstrated at a harbor-wide scale in San Diego Bay and Pearl Harbor, and accounted for the natural physical, chemical, biological and toxicological characteristics of the harbor to achieve more scientifically based compliance. In both harbors the spatial and temporal distributions of copper species, toxic effects, and Water Effect Ratio predicted by the integrated model are comparable to previous data. The model was further demonstrated in Shelter Island Yacht Basin (SIYB) marina in San Diego Bay. The integrated model agreed with toxicological and chemical approaches by indicating negligible bioavailability as well as no toxicity; but for a single event, even though an increasing gradient in Cu was observed both horizontally and vertically, with concentrations that reached levels well above current regulatory thresholds. These results support the incorporation by USEPA of the seawater-BLM in a full-strength seawater criterion.

Characterisation of [Cu4S], the catalytic site in nitrous oxide reductase, by EPR spectroscopy.

PubMed

Oganesyan, Vasily S; Rasmussen, Tim; Fairhurst, Shirley; Thomson, Andrew J

2004-04-07

The enzyme nitrous oxide reductase (N(2)OR) has a unique tetranuclear copper centre [Cu(4)S], called Cu(Z), at the catalytic site for the two-electron reduction of N(2)O to N(2). The X- and Q-band EPR spectra have been recorded from two forms of the catalytic site of the enzyme N(2)OR from Paracoccus pantotrophus, namely, a form prepared anaerobically, Cu(Z), that undergoes a one-electron redox cycle and Cu(Z)*, prepared aerobically, which cannot be redox cycled. The spectra of both species are axial with that of Cu(Z) showing a rich hyperfine splitting in the g||-region at X-band. DFT calculations were performed to gain insight into the electronic configuration and ground-state properties of Cu(Z) and to calculate EPR parameters. The results for the oxidation state [Cu(+1)(3)Cu(+2)(1)S](3+) are in good agreement with values obtained from the fitting of experimental spectra, confirming the absolute oxidation state of Cu(Z). The unpaired spin density in this configuration is delocalised over four copper ions, thus, Cu(I) 20.1%, Cu(II) 9.5%, Cu(III) 4.8% and Cu(IV) 9.2%, the mu(4)-sulfide ion and oxygen ligand. The three copper ions carrying the highest spin density plus the sulfide ion lie approximately in the same plane while the fourth copper ion is perpendicular to this plane and carries only 4.8% spin density. It is suggested that the atoms in this plane represent the catalytic core of Cu(Z), allowing electron redistribution within the plane during interaction with the substrate, N(2)O.

Nevus Removal

MedlinePlus

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Cost-Effective Fabrication of Wettability Gradient Copper Surface by Screen Printing and its Application to Condensation Heat Transfer

NASA Astrophysics Data System (ADS)

Leu, Tzong-Shyng; Huang, Hung-Ming; Huang, Ding-Jun

2016-06-01

In this paper, wettability gradient pattern is applied to condensation heat transfer on a copper tube surface. For this application, the vital issue is how to fabricate gradient patterns on a curve tube surface to accelerate the droplet collection efficiently. For this purpose, novel fabrication processes are developed to form wettability gradient patterns on a curve copper tube surface by using roller screen printing surface modification techniques. The roller screen printing surface modification techniques can easily realize wettability gradient surfaces with superhydrophobicity and superhydrophilicity on a copper tube surface. Experimental results show the droplet nucleation sites, movement and coalescence toward the collection areas can be effectively controlled which can assist in removing the condensation water from the surface. The effectiveness of droplet collection is appropriate for being applied to condensation heat transfer in the foreseeable future.

Surface structure. Subatomic resolution force microscopy reveals internal structure and adsorption sites of small iron clusters.

PubMed

Emmrich, Matthias; Huber, Ferdinand; Pielmeier, Florian; Welker, Joachim; Hofmann, Thomas; Schneiderbauer, Maximilian; Meuer, Daniel; Polesya, Svitlana; Mankovsky, Sergiy; Ködderitzsch, Diemo; Ebert, Hubert; Giessibl, Franz J

2015-04-17

Clusters built from individual iron atoms adsorbed on surfaces (adatoms) were investigated by atomic force microscopy (AFM) with subatomic resolution. Single copper and iron adatoms appeared as toroidal structures and multiatom clusters as connected structures, showing each individual atom as a torus. For single adatoms, the toroidal shape of the AFM image depends on the bonding symmetry of the adatom to the underlying structure [twofold for copper on copper(110) and threefold for iron on copper(111)]. Density functional theory calculations support the experimental data. The findings correct our previous work, in which multiple minima in the AFM signal were interpreted as a reflection of the orientation of a single front atom, and suggest that dual and triple minima in the force signal are caused by dimer and trimer tips, respectively. Copyright © 2015, American Association for the Advancement of Science.

The potential for portable X-ray fluorescence determination of soil copper at ancient metallurgy sites, and considerations beyond measurements of total concentrations.

PubMed

Tighe, M; Rogan, G; Wilson, S C; Grave, P; Kealhofer, L; Yukongdi, P

2018-01-15

Copper (Cu) at ancient metallurgy sites represents the earliest instance of anthropogenically generated metal pollution. Such sites are spread across a wide range of environments from Eurasia to South America, and provide a unique opportunity to investigate the past and present extent and impact of metalworking contamination. Establishing the concentration and extent of soil Cu at archaeometallurgy sites can enhance archaeological interpretations of site use but can also, more fundamentally, provide an initial indication of contamination risk from such sites. Systematic evaluations of total soil Cu concentrations at ancient metalworking sites have not been conducted, due in part to the limitations of conventional laboratory-based protocols. In this paper, we first review what is known about Cu soil concentrations at ancient metallurgy sites. We then assess the benefits and challenges of portable X-ray fluorescence spectrometry (pXRF) as an alternative, rapid technique for the assessment of background and contaminant levels of Cu in soils. We conclude that pXRF is an effective tool for identifying potential contamination. Finally, we provide an overview of some major considerations beyond total Cu concentrations, such as bioavailability assessments, that will need to be considered at such sites to move toward a complete assessment of environmental and human risk. Copyright © 2017 Elsevier Ltd. All rights reserved.

Transfer of Metals in Food Chain: An Example with Copper and Lettuce

NASA Astrophysics Data System (ADS)

Vincevica-Gaile, Zane; Klavins, Maris

2012-12-01

Present study investigated the possible transfer of metals in the food chain (from soil to edible plants). The experiment was done with lettuce Lactuca sativa grown in different types of soil contaminated with copper (Cu2+) in various concentrations, with or without addition of humic substances. The highest content of copper was detected in lettuce samples grown in soils with lower levels of organic matter, thus indicating the importance of soil organics in metal transfer routes and accumulation rates in plants. It was found that copper accumulation in lettuce grown in contaminated soils can be significantly reduced by the addition of humic substances.

The ropAe gene encodes a porin-like protein involved in copper transit in Rhizobium etli CFN42.

PubMed

González-Sánchez, Antonio; Cubillas, Ciro A; Miranda, Fabiola; Dávalos, Araceli; García-de Los Santos, Alejandro

2017-12-27

Copper (Cu) is an essential micronutrient for all aerobic forms of life. Its oxidation states (Cu + /Cu 2+ ) make this metal an important cofactor of enzymes catalyzing redox reactions in essential biological processes. In gram-negative bacteria, Cu uptake is an unexplored component of a finely regulated trafficking network, mediated by protein-protein interactions that deliver Cu to target proteins and efflux surplus metal to avoid toxicity. Rhizobium etliCFN42 is a facultative symbiotic diazotroph that must ensure its appropriate Cu supply for living either free in the soil or as an intracellular symbiont of leguminous plants. In crop fields, rhizobia have to contend with copper-based fungicides. A detailed deletion analysis of the pRet42e (505 kb) plasmid from an R. etli mutant with enhanced CuCl 2 tolerance led us to the identification of the ropAe gene, predicted to encode an outer membrane protein (OMP) with a β-barrel channel structure that may be involved in Cu transport. In support of this hypothesis, the functional characterization of ropAe revealed that: (I) gene disruption increased copper tolerance of the mutant, and its complementation with the wild-type gene restored its wild-type copper sensitivity; (II) the ropAe gene maintains a low basal transcription level in copper overload, but is upregulated when copper is scarce; (III) disruption of ropAe in an actP (copA) mutant background, defective in copper efflux, partially reduced its copper sensitivity phenotype. Finally, BLASTP comparisons and a maximum likelihood phylogenetic analysis highlight the diversification of four RopA paralogs in members of the Rhizobiaceae family. Orthologs of RopAe are highly conserved in the Rhizobiales order, poorly conserved in other alpha proteobacteria and phylogenetically unrelated to characterized porins involved in Cu or Mn uptake. © 2017 The Authors. MicrobiologyOpen published by John Wiley & Sons Ltd.

Functional and Biochemical Characterization of Cucumber Genes Encoding Two Copper ATPases CsHMA5.1 and CsHMA5.2*

PubMed Central

Migocka, Magdalena; Posyniak, Ewelina; Maciaszczyk-Dziubinska, Ewa; Papierniak, Anna; Kosieradzaka, Anna

2015-01-01

Plant copper P1B-type ATPases appear to be crucial for maintaining copper homeostasis within plant cells, but until now they have been studied mostly in model plant systems. Here, we present the molecular and biochemical characterization of two cucumber copper ATPases, CsHMA5.1 and CsHMA5.2, indicating a different function for HMA5-like proteins in different plants. When expressed in yeast, CsHMA5.1 and CsHMA5.2 localize to the vacuolar membrane and are activated by monovalent copper or silver ions and cysteine, showing different affinities to Cu+ (Km ∼1 or 0.5 μm, respectively) and similar affinity to Ag+ (Km ∼2.5 μm). Both proteins restore the growth of yeast mutants sensitive to copper excess and silver through intracellular copper sequestration, indicating that they contribute to copper and silver detoxification. Immunoblotting with specific antibodies revealed the presence of CsHMA5.1 and CsHMA5.2 in the tonoplast of cucumber cells. Interestingly, the root-specific CsHMA5.1 was not affected by copper stress, whereas the widely expressed CsHMA5.2 was up-regulated or down-regulated in roots upon copper excess or deficiency, respectively. The copper-induced increase in tonoplast CsHMA5.2 is consistent with the increased activity of ATP-dependent copper transport into tonoplast vesicles isolated from roots of plants grown under copper excess. These data identify CsHMA5.1 and CsHMA5.2 as high affinity Cu+ transporters and suggest that CsHMA5.2 is responsible for the increased sequestration of copper in vacuoles of cucumber root cells under copper excess. PMID:25963145

Inhibition of cyclin-dependent kinase CDK1 by oxindolimine ligands and corresponding copper and zinc complexes.

PubMed

Miguel, Rodrigo Bernardi; Petersen, Philippe Alexandre Divina; Gonzales-Zubiate, Fernando A; Oliveira, Carla Columbano; Kumar, Naresh; do Nascimento, Rafael Rodrigues; Petrilli, Helena Maria; da Costa Ferreira, Ana Maria

2015-10-01

Oxindolimine-copper(II) and zinc(II) complexes that previously have shown to induce apoptosis, with DNA and mitochondria as main targets, exhibit here significant inhibition of kinase CDK1/cyclin B protein. Copper species are more active than the corresponding zinc, and the free ligand shows to be less active, indicating a major influence of coordination in the process, and a further modulation by the coordinated ligand. Molecular docking and classical molecular dynamics provide a better understanding of the effectiveness and kinase inhibition mechanism by these compounds, showing that the metal complex provides a stronger interaction than the free ligand with the ATP-binding site. The metal ion introduces charge in the oxindole species, giving it a more rigid conformation that then becomes more effective in its interactions with the protein active site. Analogous experiments resulted in no significant effect regarding phosphatase inhibition. These results can explain the cytotoxicity of these metal complexes towards different tumor cells, in addition to its capability of binding to DNA, and decreasing membrane potential of mitochondria.

Joint simulation of stationary grade and non-stationary rock type for quantifying geological uncertainty in a copper deposit

NASA Astrophysics Data System (ADS)

Maleki, Mohammad; Emery, Xavier

2017-12-01

In mineral resources evaluation, the joint simulation of a quantitative variable, such as a metal grade, and a categorical variable, such as a rock type, is challenging when one wants to reproduce spatial trends of the rock type domains, a feature that makes a stationarity assumption questionable. To address this problem, this work presents methodological and practical proposals for jointly simulating a grade and a rock type, when the former is represented by the transform of a stationary Gaussian random field and the latter is obtained by truncating an intrinsic random field of order k with Gaussian generalized increments. The proposals concern both the inference of the model parameters and the construction of realizations conditioned to existing data. The main difficulty is the identification of the spatial correlation structure, for which a semi-automated algorithm is designed, based on a least squares fitting of the data-to-data indicator covariances and grade-indicator cross-covariances. The proposed models and algorithms are applied to jointly simulate the copper grade and the rock type in a Chilean porphyry copper deposit. The results show their ability to reproduce the gradual transitions of the grade when crossing a rock type boundary, as well as the spatial zonation of the rock type.

Phosphorylation of amyloid precursor protein at threonine 668 is essential for its copper-responsive trafficking in SH-SY5Y neuroblastoma cells.

PubMed

Acevedo, Karla M; Opazo, Carlos M; Norrish, David; Challis, Leesa M; Li, Qiao-Xin; White, Anthony R; Bush, Ashley I; Camakaris, James

2014-04-18

Amyloid precursor protein (APP) undergoes post-translational modification, including O- and N-glycosylation, ubiquitination, and phosphorylation as it traffics through the secretory pathway. We have previously reported that copper promotes a change in the cellular localization of APP. We now report that copper increases the phosphorylation of endogenous APP at threonine 668 (Thr-668) in SH-SY5Y neuronal cells. The level of APPT668-p (detected using a phospho-site-specific antibody) exhibited a copper-dependent increase. Using confocal microscopy imaging we demonstrate that the phospho-deficient mutant, Thr-668 to alanine (T668A), does not exhibit detectable copper-responsive APP trafficking. In contrast, mutating a serine to an alanine at residue 655 does not affect copper-responsive trafficking. We further investigated the importance of the Thr-668 residue in copper-responsive trafficking by treating SH-SY5Y cells with inhibitors for glycogen synthase kinase 3-β (GSK3β) and cyclin-dependent kinases (Cdk), the main kinases that phosphorylate APP at Thr-668 in neurons. Our results show that the GSK3β kinase inhibitors LiCl, SB 216763, and SB 415286 prevent copper-responsive APP trafficking. In contrast, the Cdk inhibitors Purvalanol A and B had no significant effect on copper-responsive trafficking in SH-SY5Y cells. In cultured primary hippocampal neurons, copper promoted APP re-localization to the axon, and this effect was inhibited by the addition of LiCl, indicating that a lithium-sensitive kinase(s) is involved in copper-responsive trafficking in hippocampal neurons. This is consistent with APP axonal transport to the synapse, where APP is involved in a number of functions. We conclude that copper promotes APP trafficking by promoting a GSK3β-dependent phosphorylation in SH-SY5Y cells.

Relationship among aqueous copper half-lives and responses of Pimephales promelas to a series of copper sulfate pentahydrate concentrations.

PubMed

Calomeni, Alyssa J; Kinley, Ciera M; Geer, Tyler D; Iwinski, Kyla J; Hendrikse, Maas; Rodgers, John H

2018-04-01

Copper algaecide exposures in situ are often of shorter duration than exposures for static toxicity experiments because aqueous concentrations in situ dissipate as a function of site-specific fate processes. Consequently, responses of organisms to static copper exposures may overestimate effects following in situ exposures. To understand the role of exposure duration for altering responses, Pimephales promelas survival was compared following static (96 h) and pulse (1.5, 4, 8, and 15 h half-lives) exposures of CuSO 4 •5H 2 O. Copper concentrations sorbed by fry indicated a consequence of different exposures. Responses of P. promelas to static exposures resulted in 96 h LC 50 s of 166 µgCu/L (95% confidence interval [CI], 142-189 µgCu/L) as soluble copper and 162 µgCu/L (CI, 140-183 µgCu/L) as acid soluble copper. Relative to static 96 h LC 50 s, exposures with half-lives of 1.5, 4 and 8 h resulted in LC 50 s 10, 3 and 2 times greater, respectively, for responses measured 96 h after exposure initiation. Copper concentrations extracted from fry exposed for 1.5, 4 and 8 h half-lives were less than the static experiment. However, copper sorbed by fry in the 15 h half-life experiment was not different than the static experiment. The relationship between 96 h LC 50 and 1/half-life was expressed using the equations y = 116 + 1360 × (R 2  = 0.97) for soluble copper and y = 147 + 1620 × (R 2  = 0.98) for acid soluble copper. Incorporation of exposure duration for predictions of P. promelas responses to copper pulse exposures increases prediction accuracy by an order of magnitude.

Phosphorylation of Amyloid Precursor Protein at Threonine 668 Is Essential for Its Copper-responsive Trafficking in SH-SY5Y Neuroblastoma Cells*

PubMed Central

Acevedo, Karla M.; Opazo, Carlos M.; Norrish, David; Challis, Leesa M.; Li, Qiao-Xin; White, Anthony R.; Bush, Ashley I.; Camakaris, James

2014-01-01

Amyloid precursor protein (APP) undergoes post-translational modification, including O- and N-glycosylation, ubiquitination, and phosphorylation as it traffics through the secretory pathway. We have previously reported that copper promotes a change in the cellular localization of APP. We now report that copper increases the phosphorylation of endogenous APP at threonine 668 (Thr-668) in SH-SY5Y neuronal cells. The level of APPT668-p (detected using a phospho-site-specific antibody) exhibited a copper-dependent increase. Using confocal microscopy imaging we demonstrate that the phospho-deficient mutant, Thr-668 to alanine (T668A), does not exhibit detectable copper-responsive APP trafficking. In contrast, mutating a serine to an alanine at residue 655 does not affect copper-responsive trafficking. We further investigated the importance of the Thr-668 residue in copper-responsive trafficking by treating SH-SY5Y cells with inhibitors for glycogen synthase kinase 3-β (GSK3β) and cyclin-dependent kinases (Cdk), the main kinases that phosphorylate APP at Thr-668 in neurons. Our results show that the GSK3β kinase inhibitors LiCl, SB 216763, and SB 415286 prevent copper-responsive APP trafficking. In contrast, the Cdk inhibitors Purvalanol A and B had no significant effect on copper-responsive trafficking in SH-SY5Y cells. In cultured primary hippocampal neurons, copper promoted APP re-localization to the axon, and this effect was inhibited by the addition of LiCl, indicating that a lithium-sensitive kinase(s) is involved in copper-responsive trafficking in hippocampal neurons. This is consistent with APP axonal transport to the synapse, where APP is involved in a number of functions. We conclude that copper promotes APP trafficking by promoting a GSK3β-dependent phosphorylation in SH-SY5Y cells. PMID:24610780

Risk assessment of water quality in three North Carolina, USA, streams supporting federally endangered freshwater mussels (Unionidae)

USGS Publications Warehouse

Ward, S.; Augspurger, T.; Dwyer, F.J.; Kane, C.; Ingersoll, C.G.

2007-01-01

Water quality data were collected from three drainages supporting the endangered Carolina heelsplitter (Lasmigona decorata) and dwarf wedgemussel (Alasmidonta heterodon) to determine the potential for impaired water quality to limit the recovery of these freshwater mussels in North Carolina, USA. Total recoverable copper, total residual chlorine, and total ammonia nitrogen were measured every two months for approximately a year at sites bracketing wastewater sources and mussel habitat. These data and state monitoring datasets were compared with ecological screening values, including estimates of chemical concentrations likely to be protective of mussels, and federal ambient water quality criteria to assess site risks following a hazard quotient approach. In one drainage, the site-specific ammonia ecological screening value for acute exposures was exceeded in 6% of the samples, and 15% of samples exceeded the chronic ecological screening value; however, ammonia concentrations were generally below levels of concern in other drainages. In all drainages, copper concentrations were higher than ecological screening values most frequently (exceeding the ecological screening values for acute exposures in 65-94% of the samples). Chlorine concentrations exceeding the acute water quality criterion were observed in 14 and 35% of samples in two of three drainages. The ecological screening values were exceeded most frequently in Goose Creek and the Upper Tar River drainages; concentrations rarely exceeded ecological screening values in the Swift Creek drainage except for copper. The site-specific risk assessment approach provides valuable information (including site-specific risk estimates and ecological screening values for protection) that can be applied through regulatory and nonregulatory means to improve water quality for mussels where risks are indicated and pollutant threats persist. ?? 2007 SETAC.

Structural and electronic snapshots during the transition from a Cu(II) to Cu(I) metal center of a lytic polysaccharide monooxygenase by X-ray photoreduction.

PubMed

Gudmundsson, Mikael; Kim, Seonah; Wu, Miao; Ishida, Takuya; Momeni, Majid Hadadd; Vaaje-Kolstad, Gustav; Lundberg, Daniel; Royant, Antoine; Ståhlberg, Jerry; Eijsink, Vincent G H; Beckham, Gregg T; Sandgren, Mats

2014-07-04

Lytic polysaccharide monooxygenases (LPMOs) are a recently discovered class of enzymes that employ a copper-mediated, oxidative mechanism to cleave glycosidic bonds. The LPMO catalytic mechanism likely requires that molecular oxygen first binds to Cu(I), but the oxidation state in many reported LPMO structures is ambiguous, and the changes in the LPMO active site required to accommodate both oxidation states of copper have not been fully elucidated. Here, a diffraction data collection strategy minimizing the deposited x-ray dose was used to solve the crystal structure of a chitin-specific LPMO from Enterococcus faecalis (EfaCBM33A) in the Cu(II)-bound form. Subsequently, the crystalline protein was photoreduced in the x-ray beam, which revealed structural changes associated with the conversion from the initial Cu(II)-oxidized form with two coordinated water molecules, which adopts a trigonal bipyramidal geometry, to a reduced Cu(I) form in a T-shaped geometry with no coordinated water molecules. A comprehensive survey of Cu(II) and Cu(I) structures in the Cambridge Structural Database unambiguously shows that the geometries observed in the least and most reduced structures reflect binding of Cu(II) and Cu(I), respectively. Quantum mechanical calculations of the oxidized and reduced active sites reveal little change in the electronic structure of the active site measured by the active site partial charges. Together with a previous theoretical investigation of a fungal LPMO, this suggests significant functional plasticity in LPMO active sites. Overall, this study provides molecular snapshots along the reduction process to activate the LPMO catalytic machinery and provides a general method for solving LPMO structures in both copper oxidation states. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc.

Assessment of the Environmental Effects Associated With Wooden Bridges Preserved With Creosote, Pentachlorophenol, or Chromated Copper Arsenate

DOT National Transportation Integrated Search

2000-09-01

Timber bridge components are treated with chromated copper arsenate type C (CCA), pentachlorophenol or creosote to preserve the life of the structure from a few years to many decades, resulting in reduced transportation infrastructure costs and incre...

The Underpotential Deposition of Copper on Pt(311): Site Selective Deposition and Anion Effects

DTIC Science & Technology

1994-03-14

water (18 MOhms Millipore Milli-Q water). Aqueous acid solutions were prepared from high-purity (ULTREX) sulfuric acid . Copper ion solutions were...prepared by dissolution of CuSO 4 .5H 2 0 (Aldrich Gold Label 5N5) in sulfuric acid solutions. Chloride and bromide containing solutions were prepared by...Voltammetric characteristics of a Pt(311) electrode in acidic solutions containing chloride and bromide. Fig. 1 shows cyclic voltammograxns for the

Spectroscopic properties and conformational stability of Concholepas concholepas hemocyanin.

PubMed

Idakieva, Krassimira; Nikolov, Peter; Chakarska, Irena; Genov, Nicolay; Shnyrov, Valery L

2008-01-01

The structure in solution and conformational stability of the hemocyanin from the Chilean gastropod mollusk Concholepas concholepas (CCH) and its structural subunits, CCH-A and CCH-B, were studied using fluorescence spectroscopy and differential scanning calorimetry (DSC). The fluorescence properties of the oxygenated and apo-form (copper-deprived) of the didecamer and its subunits were characterized. Besides tryptophan residues buried in the hydrophobic interior of the protein molecule also exposed fluorophores determine the fluorescence emission of the oxy- and apo-forms of the investigated hemocyanins. The copper-dioxygen system at the binuclear active site quenches the tryptophan emission of the oxy-forms of CCH and its subunits. The removal of this system increases the fluorescence quantum yield and causes structural rearrangement of the microenvironment of the emitting tryptophan residues in the respective apo-forms. Time-resolved fluorescence measurements show that the oxygenated and copper-deprived forms of the CCH and its subunits exist in different conformations. The thermal denaturation of the hemocyanin is an irreversible process, under kinetic control. A successive annealing procedure was applied to obtain the experimental deconvolution of the irreversible thermal transitions. Arrhenius equation parameter for the two-state irreversible model of the thermal denaturation of oxy-CCH at pH 7.2 was estimated. Both factors, oligomerization and the copper-dioxygen system at the active site, are important for stabilizing the structure of the hemocyanin molecule.

Effects of land use on water quality and transport of selected constituents in streams in Mecklenburg County, North Carolina, 1994–98

USGS Publications Warehouse

Ferrell, Gloria M.

2001-01-01

Transport rates for total solids, total nitrogen, total phosphorus, biochemical oxygen demand, chromium, copper, lead, nickel, and zinc during 1994–98 were computed for six stormwater-monitoring sites in Mecklenburg County, North Carolina. These six stormwater-monitoring sites were operated by the Mecklenburg County Department of Environmental Protection, in cooperation with the City of Charlotte, and are located near the mouths of major streams. Constituent transport at the six study sites generally was dominated by nonpoint sources, except for nitrogen and phosphorus at two sites located downstream from the outfalls of major municipal wastewater-treatment plants.To relate land use to constituent transport, regression equations to predict constituent yield were developed by using water-quality data from a previous study of nine stormwater-monitoring sites on small streams in Mecklenburg County. The drainage basins of these nine stormwater sites have relatively homogeneous land-use characteristics compared to the six study sites. Mean annual construction activity, based on building permit files, was estimated for all stormwater-monitoring sites and included as an explanatory variable in the regression equations. These regression equations were used to predict constituent yield for the six study sites. Predicted yields generally were in agreement with computed yields. In addition, yields were predicted by using regression equations derived from a national urban water-quality database. Yields predicted from the regional regression equations generally were about an order of magnitude lower than computed yields.Regression analysis indicated that construction activity was a major contributor to transport of the constituents evaluated in this study except for total nitrogen and biochemical oxygen demand. Transport of total nitrogen and biochemical oxygen demand was dominated by point-source contributions. The two study basins that had the largest amounts of construction activity also had the highest total solids yields (1,300 and 1,500 tons per square mile per year). The highest total phosphorus yields (3.2 and 1.7 tons per square mile per year) attributable to nonpoint sources also occurred in these basins. Concentrations of chromium, copper, lead, nickel, and zinc were positively correlated with total solids concentrations at most of the study sites (Pearson product-moment correlation >0.50). The site having the highest median concentrations of chromium, copper, and nickel also was the site having the highest computed yield for total solids.

Characterization of binding site heterogeneity for copper within dissolved organic matter fractions using two-dimensional correlation fluorescence spectroscopy.

PubMed

Hur, Jin; Lee, Bo-Mi

2011-06-01

The heterogeneity of copper binding characteristics for dissolved organic matter (DOM) fractions was investigated based on the fluorescence quenching of the synchronous fluorescence spectra upon the addition of copper and two-dimensional correlation spectroscopy (2D-COS). Hydrophobic acid (HoA) and hydrophilic (Hi) fractions of two different DOM (algal and leaf litter DOM) were used for this study. For both DOM, fluorescence quenching occurred at a wider range of wavelengths for the HoA fractions compared to the Hi fractions. The combined information of the synchronous and asynchronous maps derived from 2D-COS provided a clear picture of the heterogeneous distribution of the copper binding sites within each DOM fraction, which was not readily recognized by a simple comparison of the changes in the synchronous fluorescence spectra upon the addition of copper. For the algal DOM, higher stability constants were exhibited for the HoA versus the Hi fractions. The logarithms of the stability constants ranged from 4.8 to 6.1 and from 4.5 to 5.0 for the HoA and the Hi fractions of the algal DOM, respectively, depending on the associated wavelength and the fitted models. In contrast, no distinctive difference in the binding characteristics was found between the two fractions of the leaf litter DOM. This suggests that influences of the structural and chemical properties of DOM on copper binding may differ for DOM from different sources. The relative difference of the calculated stability constants within the DOM fractions were consistent with the sequential orders interpreted from the asynchronous 2D-COS. It is expected that 2D-COS will be widely applied to other DOM studies requiring detailed information on the heterogeneous nature and subsequent effects under a range of environmental conditions. Copyright © 2011 Elsevier Ltd. All rights reserved.

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.